‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Engineering
2022/2023 Chemistry 2022/2023 2022/2023

30504101603434
By
30504101603434 30504101603434

Professor Doctor Doctor

Mona Ahmed Darweesh Wafaa Ahmed Hamad

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫‪Gases‬‬
‫‪2022/2023‬‬

‫‪Chapter 1‬‬
‫‪2022/2023‬‬ ‫‪2022/2023‬‬

‫‪30504101603434‬‬ ‫‪30504101603434‬‬ ‫‪30504101603434‬‬

 Gases

The gas laws

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

The gas law we will study in this chapter are the product of countless experiments on the
physical properties of gases that were carried out over several centuries. Each of these
generalizations regarding the macroscopic behavior of gaseous substances represents a milestone
in the history of science . Together they have played a major mole in the development of many
ideas in chemistry.

The Pressure –Volume Relationship:

Boyle’s law:

In the seventeenth century, Robert Boyle studied the behavior Of gases systematically and
quantitatively. In one series of studies. Boyle investigated the pressure volume relationship of a
gas sample
2022/2023. 2022/2023 2022/2023

Typical data collected by Boyle are shown in the following table:

P(mmHg) V(arbitrary units) PV

724 1.50 1.09x103

869 1.33 1.16x103

951 1.22 1.16x103

998 1.18 1.18x103

30504101603434 30504101603434 30504101603434

1230 0.94 1.20x103

1893 0.61 1.20x103

2250 0.58 1.30x103

Table(1): Pressure volume Relationship taken by Boyle

 That table shows that as the pressure (P) is increased at constant temperature , the volume (V)
occupied by a given amount of gas decreases . Compare the first data point with a

pressure of 724 mmHg and a volume of 1.50( in arbitrary unit ) to the last data point with a
pressure of 2250 mmHg and a volume of 0.58 . Clearly there is an inverse relationship between
pressure and volume of a gas at constant temperature , As the pressure is increased , the volume
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

occupied by the gas decreased conversely .

If the applied pressure is decreased the volume the gas occupies increases . This relationship
is now known as Boyle's law which states that the pressure of a fixed amount of gas
at a constant temperature is inversely proportional to the volume of the gas .

The apparatus used by Boyle in this experiment was very simple the pressure exerted on the
gas is equal to atmospheric pressure and the volume of the gas is 100 ml. (Note that the tube is
open at the top and is therefore exposed to atmospheric pressure) , more mercury has been
added to double the pressure on the gas , and the gas volume decreases to 50 ml. tripling the
pressure on the gas decreases its volume to a third of the original value .

We can write a mathematical expression showing

2022/2023 2022/2023the inverse relationship between pressure and
2022/2023

volume:

𝟏
𝝆∝
𝒗

𝟏
𝝆=𝒌
𝒗

𝝆𝒗 = 𝒌

Where: k is a constant called proportionality constant .

30504101603434 30504101603434 30504101603434

 Figure (1) : shows two conventional ways of expressing Boyle's findings graphically .

Figure (1-a ) is a graph of the equation 𝜌𝑣 = 𝑘1 . figure (1-b) is a graph of `the equivalent equation
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

𝜌 = 𝑘1 × 1⁄ 𝑁ote that the latter is a linear equation of the form = 𝑦 = 𝑚𝑥 + 𝑏,

𝑉.

𝑊ℎ𝑒𝑟𝑒: 𝑏=0 𝑎𝑛𝑑 𝑚 = 𝑘1 .

Although the individual values of pressure and volume can vary greatly for a given sample of gas,
as long as the temperature is held constant and the amount of the gas does not change p time V
is an always equal to the same constant. Therefore, for a given sample of gas under two different
sets of conditions at constant temperature, we have

𝑝1 𝑣1 = 𝑘1 = 𝑝2 𝑣2
Or
𝑝1 𝑣1 = 𝑝2 𝑣2
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Where:

𝑣1 and 𝑣2 are the volumes at pressures 𝑝1 and 𝑝2 respectively.

The Temperature – Volume Relationship:

Charles’s and Gay – Lussac,s law :
Boyle, s law depends on the temperature of the system remaining constant. But suppose the
temperature changes; How does a change in temperature affect the volume and pressure of a
gas?
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Let us first look at the effect of temperature on the volume of the gas. The earliest investigators
of this relationship were French scientists, Jacques Charles and Joseph Gay –Lussac's .
Their studies showed that:
at constant pressure, the volume of a gas sample
expands when heated and contracts when cooled
figure(2). The quantitative relations involved in
changes in gas temperature and volume turn out
 to be remarkably consistent.
For example, we observe an interesting phenomenon
when we study the temperature –volume relationship
at various pressures. At any given pressure, the plot of
volume versus temperature yields a straight line.
By extending the line to zero volume. , we find the intercept on the temperature axis to be -
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

273.15℃. At any other pressure, we obtain a different straight line for the volume –temperature
plot, but we get the same zero-volume temperature intercept at-273.15℃ figure ( 3 )

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. In practice, we can measure the volume of a gas over only a limited temperature range,
because all gases condense at low temperature to form liquids.)

In 1848 Lond Kelvin realized the significance of this phenomenon. He identified -237.15℃as
absolute zero, theoretically the lowest attainable temperature. He set up an absolute temperature
scale, now called the Kelvin temperature scale, with absolute zero as the starting point.

On the Kelvin scale, one Kelvin (K) is equal in magnitude to one degree Celsius scale. The only
difference between the absolute temperature scale and the Celsius scale is that the zero position
is shifted.
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 Important points on the two scales match up as follows:

Kelvin scale Celsius scale

Absolute zero 0K -273.15℃

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Freezing point of 273.15 K 0℃

water

Boiling point of 373.15 K 100℃

water

The conversion between ℃ and K is as follows:

𝑡(℃) + 273 = 𝑇( K)

In most calculations we will use 273 instead of 273.15 as the term relating K and ℃ . By
convention, we use T to denote absolute (Kelvin) temperature and t to indicate temperature on
the Celsius scale
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The dependence of the volume of a gas on temperature is given by

V ∝T

V= 𝑘2 T

𝑉
or 𝑇
=𝑘2

Where 𝑘2 : is the proportionality constant .

k

The last Equation is known as Charles’s and Gay-Lussac,s law , or simply Charles’s law , which
30504101603434 30504101603434 30504101603434
states that the volume of a fixed amount of gas maintained at constant pressure is directly
proportional to the absolute temperature of the gas , Charles’s law is also illustrated in figure
we see that the proportionality constant 𝑘2 is equal to n R ⁄ p
 Just as we did for pressure –volume relationships at constant temperature. we can compare two
sets of volume-temperature for a given sample of gas at constant pressure. We can write:
𝑣1 𝑣2
= 𝐾2 =
𝑇1 𝑇2
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

𝑉1 𝑉2
Or =
𝑇1 𝑇2

Where: V1 and V2 are the volumes, f the gas at temperatures T1 and 𝑇2

(Both in Kelvin) respectively.

Another form of Charles’s law shows that at constant amount of gas and volume the pressure of
a gas is proportional to temperature

P∝𝑇

2022/2023 𝑃 = 𝑘3 𝑇
2022/2023 2022/2023

𝑃
or = 𝐾3
𝑇

we see that V&Tk are directly proportional

𝑃1 𝑃2
= 𝐾3 =
𝑇1 𝑇2

𝑃1 𝑃2
Or =
𝑇1 𝑇2

Where 𝑝1and 𝑝2 are the pressures of the gas at temperatures 𝑇1 𝑎𝑛𝑑 𝑇2 respectively.
30504101603434 30504101603434 30504101603434

The volume –amount Relationship:

Avogadro’s law:

The work of the Italian scientist Amedeo Avogadro complemented the studies of Boyle, Charles,
and Gay-Lussac . In 1811 he published a hypothesis stating that:

1- At the same temperature and pressure, equal volumes of different gases contain
the same number of molecules ( or atoms if the gas is monatomic ) .
 2- It follows that the volume of any given gas must be proportional to the number of
moles of molecules present.

that is ,

𝑉∝n
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

𝑉 = 𝑘4 n

Where:

n: represents the number of moles and

𝑘4 : is the proportionality constant.

And the Equation is the mathematical e expression of Avogadro’s law , which states that at
constant pressure and temperature the volume of a gas is directly proportional to the number of
moles of the gas present .

According to Avogadro’s law we see that when two gases react with each other, their
reacting volumes have a simple ratio to each2022/2023
2022/2023 other. If the product is a gas its volume is related to
2022/2023

the volume of the reactants by a simple ratio (a fact demonstrated earlier by Gay – Lussac)

for example, consider the synthesis of ammonia from molecular hydrogen and molecular
nitrogen:

3𝐻2 (𝑔) + 𝑁2 (𝑔) 2NH3(𝑔)

3mole 1mole 2mole

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Because at the same temperature and pressure, the volumes of gases are directly proportional to
the number of moles of the gases present we can now write
 3𝐻2 (𝑔) + 𝑁2 (𝑔) 2NH3(𝑔)

3 volume 1 volume 2 volume

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

The volume ratio of molecular hydrogen to molecular nitrogen is 3:1 . and that of ammonia ( the
product ) to the sum of the volumes of molecular hydrogen and molecular nitrogen ( the
reactants ) is 2:4 or 1:2

The ideal Gas Equation:

Let us summarize the gas laws we have discussed so far :

1
Boyle's : 𝑉 ∝ ( at constant n and T )
𝑝

Charles’s: 𝑉 ∝ 𝑇 ( at constant n and P )

Avogadro’s law:
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𝑉 ∝ 𝑛 ( at constant P and T)
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We can combine all three expressions to form a single master equation for the behavior of gases:

𝑛𝑇
𝑉∝
𝑝

𝑛𝑇
𝑉=𝑅
𝑝

Or

𝑃𝑉 = 𝑛𝑅𝑇
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Where:

R : the proportionality constant , is called the gas constant , and the equation

𝑃𝑉 = 𝑛𝑅𝑇

is called the ideal gas equation describes the relationship among the four variables P,V,T and n .
an ideal gas is a hypothetical gas whose pressure-volume-temperature behavior can be
completely accounted for by the ideals gas equation .
 The molecules of an ideal gas do not attract or repel one another , and their volume is
negligible compared with the volume of the container although three is no such thing in nature
as an ideal gas , the ideals gas , The ideal gas approximation works rather well for most
reasonable temperature and pressure ranges thus, we can safely use the ideal gas equation to
solve many gas problems.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Figure (5) comparison of the moler volume at STP

( whichis approimately 224 L) with a basketball

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Before we can apply the ideal gas equation to a real system, we must evaluate the gas
constant R. At 0 ℃ ( 273.15 K ) and I atm pressure many real gases behave like an ideal gas.

Experiments show that under these conditions , 1 mole of an ideal gas occupies
22.414L , which is somewhat greater than the volume of a basketball, as shown in figure(5) . the
conditions 0℃ and 1 atm are called standar temperature and pressure , often abbreviated STP ,
from30504101603434
the ideal gas equation . We can write :
30504101603434 30504101603434

𝑃𝑉
𝑅=
𝑛𝑇

(1 𝑎𝑡𝑚 )( 22.414𝐿)
R= ( 1 𝑚𝑜𝑙)(273.15𝑘)

𝐿 .𝑎𝑡𝑚
R=0.082057𝐾. 𝑚𝑜𝑙

R=0.082057 L . atm /k. mol

 The dots between L and atm and between K and mol remind us that both L and atm are
in the numerator and both K and mol are in the denominator for most calcuations , we will
round off the value of R to three significant figures (0.082)L. Atm / K . mol ) and use 22.41 L for
the molar volume of a gas at STP.

Example(1):
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Sulfur hexafluoride (SF6 ) is a colorless , odorless , very unreactive gas . Calculate the pressure (
in atm ) exerted by 1.82 moles of the gas in a steel vessel of volume 5.43L at 69.5℃

Solution :

Because no changes in gas properties occur 2022/2023

2022/2023 , we can use the ideal gas equation
2022/2023 to calculate the

pressure from the following Equation .

𝑛𝑅𝑇
𝑃=
𝑉

(1.82 𝑚𝑜𝑙)(0.0821𝐿 .𝑎𝑡𝑚𝐾 .𝑚𝑜𝑙 )( 69.5+237)𝑘

P=
5.43𝐿

P = 9.42 atm

By using
30504101603434 the fact that the moler volume of a gas occupies 22.4130504101603434
30504101603434 L at STP, we calculate the
volume of a gas at STP without using the ideal gas equation .
 Example(2):
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Calculate the volume ( in liters ) occupied by 7.80 g of NH3 at STP

Soulation:

recognizing that 1 mole of an ideal gas occupies 22.40 L at STP and using the molar mass of NH 3
( 17.03 g) we write the sequence of conversions as

Grams of NH3 moles of NH3 liters of NH3 at STP

So the volume of NH3 is given by

1 𝑚𝑜𝑙 𝑁𝐻3 22.41𝐿

2022/2023 𝑉 = 7.40𝑔 NH3 x × 2022/2023 2022/2023
17.03 𝑔 𝑁𝐻3 1 𝑚𝑜𝑙 𝑁𝐻3

V=9.74L

It is often true in chemistry , particulary in gas –law calculations , that a problem can be solved in
more than one way . Here the problem can also be solved by first converting 7.40 g of NH 3 to
number of moles of NH3and then applying the ideal gas equation (v= nRT/p ) try it .

------------------------------------------------------------------------------------
30504101603434 30504101603434 30504101603434
The ideal gas equation is useful for problem not involve change in P .V.T and n for a
gas sample . Thus . if we know any three of the variables we can calculate the fourth one using
the equation . At times , however , we need to deal with changes in pressure , volume , and
temperature , or even in the amount of gas . when conditions change , we must employ a
modified from of the ideal gas equation that takes into account the intial and final conditions . We
derive the modified equation as follows :
 𝑃1 𝑉1
𝑅= ( 𝑏𝑒𝑓𝑜𝑟𝑒 𝑐ℎ𝑎𝑛𝑔𝑒 )
𝑛1 𝑇1

𝑎𝑛𝑑

𝑃2 𝑉2
𝑅 = ( after change )
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

𝑛2 𝑇2

therefore

𝑃1 𝑉1 𝑃2 𝑉2
=
𝑛1 𝑇1 𝑛2 𝑇2

If n 1 = n2 as is usally the case because the amount of gas normally does not change ,
the equation then becomes :

𝑃1 𝑉1 𝑃2 𝑉2
=
𝑇1 𝑇2

Exanple(3):
2022/2023 2022/2023 2022/2023
An inflated helium balloon with a volume of 0.55 L at sea level( 1.0 atm ) is allowed to rise to a
height of 6,5 km, where the pressure is about 0.40 atm Assuming that the temperature remains
constant , what is the final volume of the ballon ?
Strategy the amount of gas inside the balloon and its temperature remain constant , but both the
pressure and the volume change . What gas law do you need ?
Solution:
We start with the following equation :
𝑷𝟏 𝑽𝟏 𝑷𝟐 𝑽𝟐
=
𝒏 𝟏 𝑻𝟏 𝒏 𝟐 𝑻𝟐

30504101603434 30504101603434 30504101603434

because n 1 = n2 and T1 = T2
 The given information is tabulated as follows :
𝐢𝐧𝐢𝐭𝐢𝐚𝐥 𝐜𝐨𝐧𝐝𝐢𝐭𝐢𝐨𝐧𝐬 𝐅𝐢𝐧𝐚𝐥 𝐜𝐨𝐧𝐝𝐢𝐭𝐢𝐨𝐧𝐬
𝑝1=1.0 𝑎𝑡𝑚 𝑝2=0.40 𝑎𝑡𝑚
𝑉1 =0.55 𝑉2=?
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

therefore ,
𝑃1
𝑉2 = 𝑉1 ×
𝑃2
1.0𝑎𝑡𝑚
𝑉2 =0.55 L x 0.40 𝑎𝑡𝑚

𝑉2 =1.4 L

check When pressure applied on the ballon is reduced ( at constant temperature ) the helium
gas expands , and the ballon,s volume increase . The final volume is greater than the intial
volume , so the answer is reasonable .

Example(4):
2022/2023 2022/2023 2022/2023

Electrical lightbulbs are usually filled with argon

30504101603434 30504101603434 30504101603434

Argon is an inert gas used in lightbulbs to retard the vaporization of the tungsten filament .

A certain lightbulb containing argon at 1.20 atm and 18℃ is heated to 85℃ at constant volume .
Calculate its final pressure ( in atm ) .
 Solution :

The temperature and pressure of argon change but the amount and volume of gas remain the
same .What equation would you use to solve for the final pressure ?
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

What temperature unit should you use ?

Because n1 = n2 and V1 = V2

Equation
𝑷𝟏 𝑽𝟏 𝑷𝟐 𝑽𝟐
=
𝒏 𝟏 𝑻𝟏 𝒏 𝟐 𝑻𝟐

Becomes

𝑃1 𝑃2
=
𝑇1 𝑇2

Next we write
2022/2023 2022/2023 2022/2023
𝐢𝐧𝐢𝐭𝐢𝐚𝐥 𝐜𝐨𝐧𝐝𝐢𝐭𝐢𝐨𝐧𝐬 𝐅𝐢𝐧𝐚𝐥 𝐜𝐨𝐧𝐝𝐢𝐭𝐢𝐨𝐧𝐬
𝑝1=1.20 𝑎𝑡𝑚 𝑝2=?
𝑻𝟏 =(𝟏𝟖+𝟐𝟕𝟑)𝒌=𝟐𝟗𝟏𝒌 𝑻𝟐=(𝟖𝟓+𝟐𝟕𝟑)𝒌=𝟑𝟓𝟖 𝒌

the final pressure is given by

𝑻𝟐
𝑷𝟐= 𝑷 .
𝑻𝟏
358𝐾
P 2= 1.20 𝑎𝑡𝑚 𝑥 291𝐾
= 1.48 𝑎𝑡𝑚
Check at constant volume , the pressure of a given amount of gas is directly proportional to
30504101603434 30504101603434 30504101603434
its absolute temperature . Therefore the increase in pressure is reasonable .

Example(5):

A small bubble rises from the bottom of a lake , where the temperature and pressure are
8℃ 𝑎𝑛𝑑 6.4 𝑎𝑡𝑚 to water,s surface where the temperature is
25℃ 𝑎𝑛𝑑 𝑡ℎ𝑒 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑖𝑠 1.0 𝑎𝑡𝑚 (Calculate its final volume ( in mL ) of the bubble if its intial
volume was 2.1 mL.
 Solution:
In solving this kind of problem , where a lot of information is given it is sometimes helpful to
make a sketch of the situation as shown here :

𝐢𝐧𝐢𝐭𝐢𝐚𝐥 𝐜𝐨𝐧𝐝𝐢𝐭𝐢𝐨𝐧𝐬 𝐅𝐢𝐧𝐚𝐥 𝐜𝐨𝐧𝐝𝐢𝐭𝐢𝐨𝐧𝐬

𝑝1=6.4 𝑎𝑡𝑚 𝑝2=1.0 𝑎𝑡𝑚
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

𝑣1 =2.1 𝑚𝑙 𝒗𝟐=?

N1= n2
T1 = 8℃ T2 = 25℃

What temperature unit should be used in the calculation ?

According to Equation :

𝑷𝟏 𝑽𝟏 𝑷𝟐 𝑽𝟐
=
𝒏 𝟏 𝑻𝟏 𝒏 𝟐 𝑻𝟐

We assume that amount of air in the bubble remains constant ,

2022/2023 2022/2023 2022/2023

that is , n1= n2

so that

𝑷𝟏 𝑽𝟏 𝑷𝟐 𝑽𝟐
=
𝑻𝟏 𝑻𝟐

The given information is summarized :

𝐢𝐧𝐢𝐭𝐢𝐚𝐥 𝐜𝐨𝐧𝐝𝐢𝐭𝐢𝐨𝐧𝐬 𝐅𝐢𝐧𝐚𝐥 𝐜𝐨𝐧𝐝𝐢𝐭𝐢𝐨𝐧𝐬

𝑝1=6.4 𝑎𝑡𝑚 𝑝2=1.0 𝑎𝑡𝑚

30504101603434
𝑣1 =2.130504101603434
𝑚𝑙 𝒗𝟐=? 30504101603434

n1= n2
T1 = 8(8 + 273 )𝑘 = 381𝑘
T2 = (25+273) 𝑘 = 298𝑘
Rearranging Equation gives

𝑃1 𝑇2
𝑉2 = 𝑉1 × x
𝑃2 𝑇1
 6.4 𝑎𝑡𝑚 298 𝑘
𝑉2 =2.1 mL . .
1.0 𝑎𝑡𝑚 281 𝑘

𝑉2 = 14 ml
Check your result :

we see that the final volume involves multiplying the intial volume by a ratio of pressures
(𝑃1 /𝑃2 ) and a ratio of temperature (𝑇2 / 𝑇1 ) Recall that volume is inversety proportional to
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

pressure decreases and temperature increases as the bubble rises we expect the bubble,s volume
to increase in fact , here the change in pressure plays a greater role in the volume change .
Assume the number of moles remains unchanged .

Density Calculations:
If we rearrange the idea gas equation ., we can calculate the density of agas

𝑛 𝑃
=
𝑉 𝑅𝑇

The number of moles of the gas , n. is given by

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n= m/µ

where m is th mass of the gas in grams and u is its moler mass

therefore

𝑚 𝑃
=
µ𝑉 𝑅𝑇

Because density . d. is mass per unit volume , we can write

𝒎 𝑷µ
30504101603434 30504101603434 30504101603434
d =𝑽 = 𝑹𝑻

Unlike molecules in condensed matter ( that is , in liquids and solids ) , gaseous molecules are
separated by distances that are large compared with their size . consequently the density of
gases is very low under atmospheric conditions . for this reason , gas densities are usually
expressed in grams per liter ( g /L) rather than grams per mililiter ( g / mL ) , as the
following Example .
 Example(6):
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Calculate the density of carbon dioxide ( CO2) in grams per liter ( g /L ) at 0.990 atm and 55℃

Solution:

we need Equation

𝒎 𝑷µ
d= =
𝑽 𝑹𝑻

to calculate gas density . Is sufficient information provided in the problem ? What temperature
unit should be used ?

we convert temperature to kelvins ( T = 273+ 55 = 328 k ) and use 44.01 g for the moler
mass of CO2
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𝑷µ
d=
𝑹𝑻

(𝟎.𝟗𝟗𝟎𝒂𝒕𝒎 )( 𝟒𝟒.𝟎𝟏 𝒈𝒎𝒐𝒍 )

d= = 1.62 g / L
(𝟎.𝟎𝟖𝟐𝟏 𝑳 .𝒂𝒕𝒎𝒌 .𝒎𝒐𝒍 )( 𝟑𝟐𝟖 𝒌 )

Alternatively , we can solve for the density by writing

𝒎𝒂𝒔𝒔
density =
𝒗𝒐𝒍𝒖𝒎𝒆

Assurming that we have I mole of CO2 the mass is 44.01 g . The volume of the gas can be
obtained from the ideal gas equation
30504101603434 30504101603434 30504101603434

𝑛𝑅𝑇
𝑃=
𝑉
(1 𝑚𝑜𝑙𝑒)(0.08210𝐿 .𝑎𝑡𝑚𝑘 .𝑚𝑜𝑙 ) ( 328𝑘))
𝑃= = 27.2 L
0.990 𝑎𝑡𝑚

Therefore , the density of CO2 is given by

44.010𝑔
d= = 1.62 g / L
27.2 𝐿
 Comment in units of grames per millilier , the gas density is 1.62 x 10 -3 g ⁄ ml. which is avery
small number to comparison . the density of water is g ⁄ ml . and that of gold is 19.3 g ⁄ cm2

The Molar Mass of a Gaseous Substance:

from what we have seen so far ,ay have the impression that the molar mass of a substance is
found by examining its formula and summing the molar masses of its component atoms .
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

However . this procedure works only if actual formula of the substance is known In practice ,
chemists often deal with substance of unknown at only partially defined composition . If the
unknown substance is gaseous , its molar mass can nevertheless be found thanks to the ideal gas
equation . all that is needed is an experimentally determind density value ( or mass and volume
data ) for the gas at a known temperature and pressure .

By rearranging equation :.

𝑷µ
d=
𝑹𝑻

we get:

2022/2023 𝑑𝑅𝑇
2022/2023 2022/2023
𝜇=
𝑃

in a typical experiment a buth of known volume is filled with the gaseous substande under study .
The temperature and pressure of the gas sample are recorded and the total mass of the buth
plus gas sample is determind

( figure 6 ).

The bulb is then evacuated (emptied ) and weighed again . the difference in mass is the mass of
the gas . The density of the gas is equal to its mass divied by the volume of the bulh once we
know the density of the gas ,
30504101603434 30504101603434 30504101603434
 we can calculate the molar of the substance using the previous equation of course , a mass
spectrometer would be the ideal instrumen to determine the molar mass , but not every chemist
can afford one ..

The following example shows the density method for molar mass determination .
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Example(7):

A chemist has synthesized a greenish –yellow gaseous compound of chlorine and oxygen and
finds that its density is density is 7.71 g ⁄ L at 36℃ and 2.88 atm . Calculate the molar mass of
the compound and determine its molecular formula ?

Solution:

𝑷µ 𝑑𝑅𝑇
Because Equations (d = ) and ( 𝜇 = ) are rearrangements of each other , we can
𝑹𝑻 𝑃

calculate the molar mass of a gas if a gas if we know its density , temerature and pressure the
molecular formula of the compound must be consistent with its molar mass , What temperature
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unit should we use ?

From the following Equation:

𝑑𝑅𝑇
𝜇=
𝑃
(7.71 𝑔 ⁄ 𝐿 ) ( 0.0821 𝐿 .𝑎𝑡𝑚 𝐾 ,𝑚𝑜𝑙 )( 36=273 )𝑘
𝜇=
2.88 𝑎𝑡𝑚

𝜇 = 67.9 g ⁄ mol
30504101603434 30504101603434 30504101603434
Alternatively we can solve for the molar mass by writing

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑
moar mass of compound = 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑

from the given densitly we know there are 7.71 g of the gas in 1 L . the number of moles of the
gas in this volume can be obtafrom the ideal gas equation

𝑷𝑽
n= 𝑹𝑻
 ( 2.88 𝑎𝑡𝑚 )( 1.00𝐿 )
n= ( 0.0821 𝐿 .𝑎𝑡𝑚⁄ 𝑘.𝑚𝑜𝑙)( 309𝑘)

n =0.1135 mol

therefore the molar mass is given by

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

𝑚𝑎𝑠𝑠 7.71𝑔
µ= = = 67.9g ⁄ mol
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 0,1135 𝑚𝑜𝑙

we can determine the molecular formula of the compound by trial and error , using only the
knowledge of the molar masses of chlorine ( 35.45g ) and oxygen ( 16.oo g) we know
that a compound containing one Cl atom and one O atom would have a molar mass of 51.45 g
which is too low while the molar mass of a compound made up of two Cl atoms and one O atom
is 86.90 g . Which is too high . thus , the compound must contain one Cl atom and two O atom
and have the formula ClO2 , which has a molar mass of 67.45 g

-----------------------------------------------------------------------------------------
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𝑑𝑅𝑇
Because Equation ( 𝜇 = ) is derived from the ideal gas equation , we can also
𝑃

calculate the molar mass of a gaseous substance using the ideal gas equation , as shown in the
following example:

Example(8):

30504101603434 30504101603434 30504101603434

Si2F6

Chemical analysis of a gaseous compound showed that it contained 33.0 precent silicon ( Si) and
67.0 precent fluorine (F) by mass. At 35℃ , 0.21 L of the compound exerted a pressure of 1.70
atm .

If the mass of 0.210 L of the compound was 2.38 g . calculate the molecular formula of the
compound? .
 Solution:

To calculate the empirical formula by assuming that we have 100 g of the compound so the
percentages are comverted to grams . the number of moles of Si and F qre given by

1 𝑚𝑜𝑙 𝑆𝑖
𝑛Si = 33.0 g Si . = 1.17 mol Si
28.09 𝑔 𝑆𝑖
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

1 𝑚𝑜𝑙 𝐹
𝑛𝐹 = 67.0 g F = 3.53 mol F
28.09 𝑔 𝐹

Therefore , the empirical formula is Si 1.17 F3.53 or dividing by the smaller subscript (1.17) we
obtain SiF3

To calculate the molar mass of the compound , we need first to calculate the number of moles
contained in 2.38 g of the compound from the ideal gas equation

𝑃𝑉
𝑛=
𝑅𝑇

( 1.70𝑎𝑡𝑚 )(0.210𝐿)
n= 2022/2023
(0.0821𝐿.𝑎𝑡𝑚/𝑘.𝑚𝑜𝑙)(308𝑘)
= 0.0141 mol 2022/2023 2022/2023

Beacause there are 2.38 g in 0.0141 mole of the compound , the mass in 1 mole , or the molar
mass , is given by

2.38𝑔
µ = 0.0141 𝑚𝑜𝑙 = 169 g / mol

The molar mass of the empirical formula SiF3 is 85.09 g . recall that the ratio ( molar mass/
empirical molar mass ) is always an integer ( 169/85.09 ≅ 2).

Therefore , the molecular formula of the compound

30504101603434 30504101603434must be ( SiF3)2 or30504101603434
Si2F6.

Gas stoichiometry:

We used relationship between amounts ( in moles ) and masses ( in grams) of reactants and
products to solve stoichiometry . When the reactants and /or products are gases , we can also
use the relationship between amounts( mole ,n ) and volume (V) to solve such problems .

Examples 9, 10 and 11 show how the gas laws are used in these calculations .
 Example(9):

Calculate the volume of O2 ( in liters) required for the complete combustion of 7.64 of acetylene
( C2 H2) measured at the same temperature and pressure.

2𝐶2 𝐻2 (𝑔) + 5O2 (𝑔) → 4𝐶O2 (𝑔) + 2𝐻2 O(1)

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Soulation:

Note that the temperature and pressure of O2 and C2H2 are the same . which gas law do we need
to relate the volume of the gases to the moles of gases ?

According to avogardro's Law , at the same temperature and pressure ,the number of moles of
gases are directly related to their volumes.

From the equation , we have

5 mol O2 ≅ 2mol C2H2

2022/2023 2022/2023 2022/2023

therefore , we can also write

5L O2≅ 2L C2H2 .

The volume Of O2 that will react with 7.64 L C2H2 is given By

5𝐿𝑂2
Volume of O2 = 7.64LC2H2 x =19.1L
2𝑙𝐶2 𝐻2

Amount of reactant ( Moles OF Moles of Amount of

grams or volume) reactant product product ( grams
30504101603434 30504101603434 or volume)
30504101603434

Figure (7): Stoichiometric calculations involving gases

Example(10):

Sodium azide (NaN3) is used in some, automobile air bags . the impact of a collision triggers the
decomposition of NaN3 as follows:
 the nitrogen gas produvt quickly inflates the bag between the driver and the windshield and
dashhorad.

Calculate the volume of N2 generated at 80℃ and 823 mmHg by the decomosition of 60.0 g of
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

NaN3. ?

Solution:

From the balanced equation we see that:

2 mol NaN3 ≅ 3 mol N2

so the conversion factor between NaN3 and N2 is

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Because the mass of NaN3 is given , we can calculate the number of moles of NaN3 and
hence the number of moles of N2 produced Finaly , we can calculate the volume of N2 using the
ideal gas equation.

First we calculate number of moles of N2 produced by 60.0 g NaN3 using the following
sequence of conversions

30504101603434 30504101603434 30504101603434

so that

The volume of 1.38 moles of N2 can be obtained by using the ideal gas equation :
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Example(11):

Aqueous lithium hydroxide solution is used to purify air in spacerafts and submarines because it
absorbs carbon dioxide , which is an end product of metabolism, according to the equation

2𝐿𝑖𝑂𝐻(𝑎) + 𝐶𝑂2(g) L𝑖2 C𝑂3(aq) + 𝐻2 O(l)

The pressure of carbon dioxide inside thee cabin a submarine having a volume of 2.4 x
105L is 7.9 x 10-3 atm at 312 oK.

A solution of lithium hydroxide (LiOH) of negligible volume is introduced into the cabin.
2022/2023 2022/2023 2022/2023
Eventually the pressure of Co2falls to 1.2 x 10-4 atm . How many grams of lithium
carbonate are formed bt this process?

Solution:

How do we calculate the number of moles of co2 reacted from the drop in CO2 pressure ?

From the ideal gas equation we write

30504101603434 30504101603434 30504101603434

At constant T and V , the change in pressure of CO2 . ∆ 𝑃, corresponds to the change in the
number of moles of CO2 , ∆ n . Thus

What is the conversion factor between CO2 and Li2CO3- ?

 The drop in Co2 pressure is 97.9 x 10 -3 atm ) – ( 1.2 x 10-4 atm ) or 7.8 x 10-3 atm
therefore the number of moles of CO2 reacted is given by

2.4 𝑥 105 𝐿
∆𝑛 = 7.8 x 10−3 atm x ( 𝑜.𝑜821 𝐿 .𝑎𝑡𝑚⁄𝑘.𝑚𝑜𝑙 )(312 𝐾 )

=73 mol
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

From the chemical equation we see that 1 mol CO2 ~ 1 𝑚𝑜𝑙 𝐿𝑖2 𝐶𝑂3 so the amount of 𝐿𝑖2 𝐶𝑂3
formed is also 73 moles . Then , with the molar mass of 𝐿𝑖2 𝐶𝑂3 (73.89 g) we calculate its mass:

Dalton's law of partial pressures

Thus far have concentrated on the behavior

2022/2023 2022/2023
of pure gaseous substances
2022/2023
, but
experimental studies very often involve mixtures of gases For example , for a study of air
pollution , we may be interested in the pressure-volume- temperature relationship of a sample of
air , which contains several gases . in this cases involving mixtures of gases , the total gas
pressure is related to partial pressures , that is the pressures of individual gas
components in the mixture .

In 1801 Dalton formulated a law now known as Dalton's law of partial pressure
which states that the total pressure of amixture of gases is just the sum of the
pressures that each gas would exert if it were present alone .

Figure(8) illustrates Dalton,s law of partial pressures.

30504101603434 30504101603434 30504101603434

 Consider a case in which two gases , A and B , are in a container of volume V .

The pressure exerted by gas A , according to the ideal gas equation , is

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

where :

nA : is the number of moles of A present. Similarly , the pressure exerted by gas B is :

In a mixture of gases A and B , the total pressure PT is the result of the collisions of
both types of molecules , A and B, with the walls of the container .

Thus according to Dalton's law

2022/2023 2022/2023 2022/2023

where:

n: the total number of moles of gases present , is given by

30504101603434 30504101603434 30504101603434

n = nA + n B

PAand PB : are the partial pressures of gases A and B respectively

For a mixture of gases then , PT depends only on the total number of moles of the gas present
, not on the nature of the gas molecules.

In general . the tatal pressure of a mixture of gases given by :

PT = P1+ P2 + P3+ ………

 Where :

P1 , P2 , P3,……the partial pressure of the components 1,2,3,…..

𝑃𝐴 𝑛𝐴 𝑅𝑇/𝑉
=
𝑃𝑇 (𝑛𝐴 + 𝑛𝐵)𝑅𝑇/𝑉
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

𝑛𝐴 𝑃𝐴
=
𝑛𝐴+𝑛𝐵 𝑃𝑇

𝑃𝐴
= XA
𝑃𝑇

Where:

XA : is called the mole fraction of A .

The mole Fraction is a dimensionless Quantity that expresses the ratio of the number of moles of
one component
2022/2023 to the number of moles of all components present .
2022/2023 2022/2023

In general , the mole fraction of componenti in a mixture is given by :

30504101603434 30504101603434 30504101603434

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

How are partial pressures determined ? A manometer can measure only the total
pressure of a gaseous mixture . To obtain the partial pressures , we need to know the mole
fractions of the components , which would involve elaborate chemical analyses . The most direct
method of measuring partial pressures is using a mass spectrometer . The relative intensities of
the peaks in a mass spectrum are directly proportional to the amounts , and hence to the mole
fractions , of the gases present.

From mole fractions and total pressure , we can calculate the partial pressuress of individual
components , as Example (12) shows .
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Example (12):

A mixture of gases contains 4.46 moles of neaon (Ne) . 0.74 mole of argon ( Ar) and 2.15
moles of xenon ( Xe) . Calculate the partial pressures of the gases if the total pressure is 2.00
atm at a certain temperature.

Solution:

According to the following Equation:

Pi = Xi PT
30504101603434 30504101603434 30504101603434
The partial pressure of Ne is equal to the product of its mole fraction XNe

And the total pressure (PT)

PNe = XNe PT

We can calculate the mole fraction of the Ne as follows :

 nNe nNe 4.46 mol
XNe = = =
nT nNe+nAr+ nXe 4.46 mol+0.74 mol+ 2.15mol

= 0.607

Therefore

PNe = XNe PT
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

=0.607 * 2.00 =1.21 atm

Similary

PAr = XAr PT

=0.10 * 2.00 =0.20 atm

And

PXe = XXe PT

=0.293 * 2.00 = 0.586 atm

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Dalton's law of partial pressures is useful for calculating volumes of gases collected
over water . For example ,where potassium chlorate ( KCIO3 ) is heated it composes to KCL and
O2

2𝐾𝐶𝐼O3 (s)→2KCL(s) + 3O2 (g)

The Oxygen gas can be collected over water , as shown in figure(9).

Initially , the inverterd bottle is completely filed with water . As oxygen gas is generated ,
the gas bubbles rise to the top and displace water from the bottle .

30504101603434 30504101603434 30504101603434

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

This method of collecting a gas is based on the assurmptions that the gas does not react
with water and that it is not appreciably soluble in it . theses assumptions are valid for oxygen
gas , but not for gases such as NH3+ which dissolves readily in water . The oxygen gas collected
in this way is not pure , however , because water vapor is also present in the bottle . the total
gas pressure is equal to the sum of the pressures exerted by the oxygen gas and the water vapor
:

Table ( 2 )

consequently , we must allow for the pressure caused by the

2022/2023 2022/2023 2022/2023

presence of water vapor when we calculate the amount of O2

generated . Table(2) shows the pressure of water vapor at

various temperatures , These data are plotted in figure .

Example (13) shows how to use Dalton,s law to calculated

the amount of a gas collected over water.

30504101603434 30504101603434 30504101603434

Example(13):

Oxygen gas generated by the decomposition of potassium

chlorate is collected as shown in figure (9) .

The volume of oxygen collected at24 ℃ and atmospheric

pressure of 762 mmHg is 128 mL . Calculate the mass

 ( in grams ) of oxygen gas obtained . The pressure of

the water vapor at 24℃ is 22.4 mmHg.

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Solultion:

To solve for the mass of O2 generated , we must first calculate the partial pressure of O2 in the
mixture . What gas law do we need ? How do convert pressure of O2 gas to mass of O2 in grams
?

From Dalton 's Law of partial pressure we know that

Figure (10)the pressure of water vapor as a function of temperature, Note that at the
boiling2022/2023
point of water (100℃ ) the pressure is 760 mmHg. which is exactly
2022/2023 equal to 1 atm.
2022/2023

therfore

from the ideal gas equation we write

m
PV= nRT= RT
µ

30504101603434 30504101603434 30504101603434

where m and µ are the mass of O2 and the moler mass of O2 respectively :

Rearraging the equation we obtain

Check The density of the oxygen gas is (0.164g/0.128L) or 1.28 g/L , which is a reasonable value
for gases under atmosheric conditions .
 The kinetic Molecular theory of gases

The gas laws help us to predict the behavior of gases , but they do not explain what
happens at the molecular level to cause the changes we observe in the macroscopic world . For
example , why does a gas expand on heating ?
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Chemistry in Action

Scuba Diving and the gas laws

Scuba diving is an exhilarating sport , and thanks in part to the gas laws, it is also a safe activity
for trained individuals who are in good health (”Scuba” is an acronym for selfcontained
underwater breathing apparatus.) Two applications of the gas laws to this popular
pastime are the development of guidelines for returming safely to the surface after a dive and the
determination of the proper mix of gases to prevent a potentially fatal condition during a dive .

A typical dive might be 40 to 65 ft , but dives to 90 ft are not uncommon . Because seawater has
a slightly density than fresh water – about 1.03
2022/2023 g/mL, compared with 1.00
2022/2023 g/mL – the pressure
2022/2023

exerted by a column of 33 ft of seawater is equivalent to 1 am pressure . Pressure increases with

increasing depth , so at a depth of 66 ft the pressure of the water will be 2 atm, and so o What
would happen if a diver rose to the surface from a depth of , say 20 ft rather quickly without
breathing ? The total decrease in pressure for this change in depth would be (20ft /33ft) 1 atm ,
or 0.6 atm . when the diver reached the surace , the volume of air trapped in lungs would have
increased by a factor of (1+0.6) atm . or 1.6 times this sudden expansion of air can faraly
rupture the membranes of the lungs . Another serious possibility is that an air embolism might
develop . As air expands in the lungs , it is forced into tiny blood vessels called cpillaries . The
presence of air bubbles in these vessels can
30504101603434
block normal blood flow to30504101603434
30504101603434
the brain. As\a resulat ,
the diver might lose consciousness before reaching the surface .The only cure for an air
embolism is reacompression . for this painful process , the vicim is placed in a chamber filled
with compressed air .Here bubbles in the blood are slowly squeezed down to hamless sizover the
course of several hours to a day .To avoid these umpleasant complications , divers know they
must assend slowly pausing at certain points to give their bodies time to adjust to the falling
pressure.
 Our second example is a direct application of Dalton,s law Oxygen gas is essential for our
survival, so it is hard to believe that an excess of Oxygen could be harmful . Nevertheless , the
toxicity of too much oxygen is well established .for example newborn infants placed in oxygen
tents often sustain damage to the retinal lissue , which can cause partial or total blindness .
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Our bodies function best when oxygen gas has a partial pressure of about 0.20 atm ,as it does
in the air we breathe .the oxygen partial pressure is given by

where Pt is the total pressure . However , because volume is directly proportional to the number
of moles of gas present (at Constant temperature and pressure ) we can now write

thus the composition of air is 20 precent oxygen gas and 80 percent introgen gas by volume .
2022/2023 2022/2023 2022/2023
when a driver is submerged the pressure of the water on the driver is greater than atmospheric
pressure . The air pressure inside the body cavities ( for example lings , sinuses ) must be the
same as the pressure of the surrounding water , otherwise they would collapse . A special valve
automatically adjusts the pressure of the air breathed from a cubu tank to ensure that the air air
pressure equals the water pressure at all times . For example at a depth where the total pressure
is 2.0 atm the oxygen content in air should be reduced to 10 percent by volume to maintain the
same partial pressure of 0.20atm , that is

30504101603434 30504101603434 30504101603434

Although nitrogen gas may seem to be the obvious choice in mix with oxygen gas , there is a
serious problem with it . when the partial pressure of nitrogen gas exceeds . 1 atm , enough of
the gas disolves in the blood to cause a condition known as nitrogen narcosis . the effects on the
 diver resemble those associated with alcohol intoxication divers suffering from nitrogen narcosis
have been known to do strange things , such as dancing on the seafloor and chasing sharks , for
this reason , helium is often used to dilute oxygen gas . An inert gas , helium is much less soluble
in blood than nitrogen and produces no narcotic narcotic effects.

in the nineteenth century , a number of physicists , notably Ludwing Boltzman and James Clerk
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Maxwell . found that the physical of gases can be explained in terms of the motion of individual
molecules . this molecular is a form of energy which we define as the capacity to do work or to
produce change . in mechanics , work is defined as force times disr=tance . because energy can
be measured as work , we can write

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alrenatively energy can be expresses in kilojoules ( KJ)

1 KL = 1000J

as we will see in chapter there are many different Kinds of energy . Kinetic energy ( KE) is the
type of energy expended by a moving object , or energy of motion .

the findings of Maxwell , Boltzmann , and others resulat in a number of generolizations about gas
behavior that have since bneen known as the Kinetic molecular theory of gases or simply the
kinetic theory of gases central to the kinetic
30504101603434 theory are the following assumpitions.
30504101603434 30504101603434

1- A gas is composed of molecules that are separated fromeach other by distances far greater
than their own dimensions . the moleculed can be considered to be “ point” that is they possess
mass but have negligible volume .
2- Gas molecules are in constant motion in random direction and they frequantly colide with one
another Collisions among molecules are perfectly elastic . In other words energy can be
 transferred from one molecule to anther as a resultof a collision Nevertheless , the total energy of
all the molecules in a system remains the same .
3- gas molecules exert neither attactive nor requisive forces on one another
4- the average kinetic energy of the molecules is proportionalto the temperature of the gas in
kelvins . Any two gases at the same temperature will have the same average kinetic energy . The
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

5- average kinetic energy of a molecules is given by

where m is the mass of the molecule and u is its speed . The horizontal bar denotes an average
value . The quantity u2 is called mean square speed : it is the average of the square of the speed
of all the molecules :

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Where : C is the proportionality constant and T is the absolue temperature .

according to the Kinetic molecular theory ,30504101603434

30504101603434 gas pressure is the result of30504101603434
collisions between
molecules and the walls of their container . it depends on the frequency of collision per unit area
and on how “ hard” the molecules strike the wall . The theory also provides a molecular
interpreation of temperature .According to Equation the absolute temperature of a gas is
ameasure of the average kinetic energy of the molecules .Inother words , the absolute
temperature is an indication of the random motion of the molecules – the higher the temperature
. the more energetic the molecules . Because it is the related to the temperature of the gas
sample , random molecular motion is sometimes referred to as thermal motion .
 Application to the Gas Laws

although the kinetic theory of gases is based on a rather simple model , the mathematical details
involved are very complex . However, on a qualitative basis , it is possible to use the theory to
account for the general properties of substances in the gaseous state . the following examples
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

illusr=trate the range of its utility.

• Comressibility of gases . Because molecules in the gas phase are separated by large
distances (assumption 1) , gases can be compressed easily to occupy less volume.
• Boyle's Law . The pressure exerted by a gas results from the impact of its molecules on the
walls of the container . The collision rate , or the number of molecular collisions with the walls
per second , is proportional to the number density ( that is , number of molecules per unit
volume ) of the gas . Decreasing the volume of a given amount of gas increases its number
dendity and hence its collision rate for this reason , the pressure of a gas is inversely proportional
to the volume it occupies : as volume decreases , pressure increases and vice versa.
• Charles's
2022/2023 law . Because the average kinetic
2022/2023energy of gas molecules is proportional to the
2022/2023

sample,s absolute temperature ( assumtion 4 ) . raising the temperature increases the average
kinetic energy . Consequently , molecules will colide with the walls of the container more
frequently and with greater impact if the gas is heated and thus the pressure increases . The
volume of gas will expand unitl the gas pressure is balanced by the constant external pressure (
see figure )
• Avogadro's law . we have shown that the pressure of a gas is directly proportional to both
the density and the temperature of the gas .
Because the mass of the gas is directly proportional to the number of moles (n) of the gas , we
can 30504101603434
represent density by n ⁄ V . therefore 30504101603434 30504101603434
 where C is the proportionality constant . thus , for two gases unde the same conditions of
pressure , volume and temperature ( that is , when P1= P2+ T1 = T 2+ and V1 = V2 ) it follows
that n1 = n2-which is a mathematical expression of avogadro,s law.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

• Dalton's law of partial pressures . If molecules do not attract or repel one another
( assumtion 3 ) then the pressure exerted by one of molecule is unaffected by the pressure of
another gas consequently . the total pressure is given by the sum of individual gas pressures .

Distiribution of molecular speeds

The kinetic theory of gases enables us to investigate molecular motion in more detail
suppose we have a large number of gas molecules , say I mole, in a container . As long as we
hold the temperature constant , the average2022/2023
2022/2023 kinetic energy and the meansquare
2022/2023 speed will
remain unchanged as time passes . As you might expect , the motion if the molecules is totally
random and unpredictable . At a given instant , how many molecules are moving at a particular ?
To answer this question Maxwell analyzed the behavior of gas molecules at different
temperatures .

Figure (11-a) shows typical Maxwellspeed distribution curves for nitrogen gas at three different
temperatures . At a given temperature , the distribution curve tells us the number of molecules
moving at a certain speed.thepeak of each curve represents the most probable speed , that is ,
the speed of the largest number of molecules note that the most probable speed increases as
temperature increases ( the peak shifts toward
30504101603434 the right ) furthermore30504101603434
30504101603434 , the curve also begins to
flatten out with increasing temperature , indicating that larger numbers of molecules are moving
at greater speed .

Figure (11-b) shows the speed distributions of three gases at the same temperature .

The different in the curves can be explined by noting that lighter molecules move faster on
average than heavier ones.
 The distribution of molecular speeds can be demonstrated with the apparatus shown in figure
(12) A beam of atoms ( or molecules ) exits from an oven at a known temperature and passes
through a inhole ( to collimate the beam ) . Two circular plates mounted om the same shaft are
rotaed by amotor . The first plate is called the “ chopper” and the second is the dector .The
purpose of the chopper is to allow amall bursts of atoms ( or molecules ) to pas through it
whnever the slit is aligned with the beam . within each burst , the faster-moving molecules will
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

reach the detector earlier Than the slower –moving ones .Eventually . a layer of deposit will
accumulate on the detector . Because the two plates are rotating at the same speed , molecules
in the next burst will hit the detector plate at approximately the same place as molecules from
the previous burst having the same speed . In time , the molecular deposition will become visible
. the density of the deposition indicates the distribution of molecular speeds at that particular
temperature.

2022/2023 2022/2023 2022/2023

Figure (11) (a) The distribuation of speeds for nitrogen gas at three different temperatures. At
the higher temperatures, more molecules aremoving at faster speeds (b) The distibution of
speeds for three gasses at 3000 K, At a given temperature , the lighter molecules are moving
30504101603434 30504101603434 30504101603434
faster , on the average.

Root –mean-square speed:

How fast does a molecule move on the average at any temperature T?One way to estimate
molecular speed is to calculate the root-mean-square (rms) speed (urms) , which ia sn average
molecular speed . one of the resulats of the kinetic theory of gases is that total kinetic energy of
a mole of any gas equals 3/2 RT . Earlier we saw that the average kinetic energy of one molecule
 is ½ mu and so we can write
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Where NA is avogardo,s number and m the mass of a single molecule . Because

NAm = u . the above equation can be rearranged to give :

2022/2023 2022/2023 2022/2023

The previous equation shows that the root-mean-square speed of agas increases with the square
root of its temperature ( in kelvins) : Because .M appears in the denominator , it follows that the
heavier the gas , the more slowly its molecules
30504101603434 move . If we substitue 30504101603434
30504101603434 8.314 J/K mol for R ( see
Appendix2) and convert the molar mass to kg/mol. Then urmswillbe calculated in meters per
second ( m/s) . this procedure is illustrated in example

Example(14 ):

Calculate the root –mean-square speeds of helium atoms and nitrogen molecules in m/s at
 25 ℃

Solution :

To calculate urms the units of R should be 8.314 J/K . mol and because 1J = 1JK m2/s2 the
mo;ar mass must be in Kg/mol . the molar mass of he is 4.003 g/mol, or 4.003 x 10 -3 Kg/mol .
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

30504101603434 30504101603434 30504101603434

Check Because he is a lighter gas we expect it to move faster , on average , than N2+A quick
way to check the answers is to note that the ratio of the two urms values (1.36 x 103/515 ≈2.6 )
should be equal to the square root of the ratios of the molar masses of N2 to he , that is
√28/4 ≈ 2.6

Practice Exercise : Calculate the root –mean-square speed of molecular chlorine in m/s at
20℃.
 The calculation in previous example has an interesting relationship to the compositions of Earth,s
atmosphere . Unlike Jupiter , Earth does not have appreciable amounts of hydrgen or heluim in
its atmosphere . Why is this the case ? a smaller planet than jupiter , Earth has a weaker
gravitational attraction for these lighter molecules A fairly straightforward calculation shows that
to escape Earth.s Gravitational field , a molecular must possess an escape velocity equal to or
greater than 1.1 x 104 m/s because the average speed of helium is considerably greater than of
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

molecular nitrogen or molecular oxygen more heluim atoms escape Earth,s atmosphere . On the

other hand , Jupiter with a mass about 320 times greater than that of Earth,atmosphere into
outer space . Consequently , only a trace amount of helium is present in our atmosphere . On the
other hand , Jupiter , with s mass about 320 times greater than of Earth, retains both heavy and
light gases in its atmosphere .

Gas Diffusion and Effusion

We will now discuss two phenomena based on gaseous motion .

2022/2023 2022/2023 2022/2023

Gas Diffusion

A direct demonstration of gaseous random motion is provided by diffusion , the gradual mixing
of molecules of one gas with molecules of another by virtue of their kinetic properties .Deapite
the fact that molecular speeds are very great , the diffusion process takes a relatively long time
to complete . for example , when a bottle of concentrated ammonia solurio is opened at one end
of a lab bench , it takes some time bfore a person at the other end of the bench can smell it . the
reason is that a molecule experiences numerous collisions while moving from one end of the
bench to the other , as shown in figure thus, diffusion of gases always happens gradually ,
and 30504101603434
not instantly as molecular speeds seem to suggest . furthermore ,30504101603434
30504101603434 because the root –mean-
square speed of a light gas is greater than that of a heavier gas ( see Example ) a lighter gas
will diffuse through a certain apace more quickly than will a heavier gas figure illustrates
gaseous diffusion.

In 1832 the scottish chenmist thomas Graham found that under the same conditions of
temperature and pressure, rates of diffusion for gases are inversely proportional to the square
roots of their molar masses . this statement , now known as Graham ,s law of diffusion , is
expressed mathematically as
 are there
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

figure(13) The path traveled by a single gas molecule each change direction represents a collision
with another molecule
2022/2023 2022/2023 2022/2023
the Kinetic molecular theory of gases

30504101603434 30504101603434 30504101603434

Gas Effusion:

whereas diffusion is a process by which one gas gradually mixes with another , effusion in the
process by which a gas under pressure escapes from one compartment a container to another by
passing through a small opening .Figure shows the effusion of a gas into a vacum . Although
 effusion differs from diffusion in nature , the rate of effusion of a gas has the same form as
Graham,s law of diffusion , see the following equation:
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

A helium –filled rubber balloon deflates faster than an air filled one because

the rate of effusion through the pores of the rubber is faster for the lighter helium atoms than for
the air molecules .Industrially , gas effusion is used to separate uranium isotopes in the forms of
gaseous 235 UF6 and 238 UF6.By subjecting the gases to many stages of effusion , scinentists were
able to obtain highly enriched 235 U isotope, which was used in the construction of atomic bombs
during world War II. example shows as application of graham,s law.

2022/2023 2022/2023 2022/2023

Example( 15 ):

A flammable gas made up only of carbon and hydrogen is found to effuse through a porous
barrier in 1.50 min . Under the same conditions of temperature and pressure , it takes an equal
volume of bromine vapor 4.73 min to effuse through the same barrier .

calculate the molar mass of the unknown gas , and suggest what this gas might be.

Solution:

from the molar mass or Br2 , we write

30504101603434 30504101603434 30504101603434

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Deviation from ideal Behavior:

The gas laws and the kinetic molecular theory assume that molecules in the gaseous stste
do not exert any force , either attractive or repulsive , on one another . the other assumtion is
that the volume of molecules is negligibly small compared with that of the container A gas that
satisfies these two conditions is said to exhibit ideal behavior.

Although we can assume that real gases behave like an ideal gas , we cannot expect them to do
so under all conditions . for example , without intermolecular forces, gases could not condense to
2022/2023 2022/2023 2022/2023
form liquids . The important question is : Under what conditions willgases most likely exhibit
nonideal behavior ?

figure (15) shows PV⁄ RT plotted against P for three real gases and an ideal gas at a given
temperature .This graph provides a test of ideal gas behavior. According to the ideal gas
equation ( for 1 mole of gas ) PV⁄ RT equals 1 , regardless of the actual gas pressure . ( when n
= 1, PV= nRT becomes PV= RT, or PV⁄ RT= 1.) for real gases this is true only at moderately low
pressures ( ≤ 5 atm ) : significant deviations occur as pressure increases . Attractive forces
operate omong molecules at relatively short distances at atmospheric pressure , the molecules in
a gas are far apart and the attractive forces
30504101603434
are negligible . At high pressures
30504101603434
, the density of the
30504101603434

gas increases : the molecules are much closer to one another . intermolecular forces can then be
significant enough to affect the motion of the molecules , and the gas will not behave ideally .
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Another way to observe the nonideal behavior of gases is to lower the temperature .
Cooling a gas decreaes the molecules's average Kinetic , which in a sense deprives molecules
of the drive they need to break from their mutual attraction .

To study real gases accurately ,then we need to modify the ideal gas equation,thaking into
account intermolecular forces and finite molecular volumes , Such an analysis was first made by
the Dutch physicist J.D. van der Waals +in 1873 . Besides being mathematically simple . van der
Waals, treatment provides us with an interpretation of real gas behavior at the molecular level.
2022/2023 2022/2023 2022/2023
Consider the approach of a particular molecule toward the wall of a container ( figure 16 )
. The intermolecular attractions exerted by its neighbors tend to soften the impact made by this
molecule against the wall. The overall effect is a lower gas pressure than we would expect for an
ideal gas . Van der Waals suggested that the pressure exerted by an ideal gas , Pideal, is related to
the experimentally measured pressure Preal, by the equation

𝑎𝑛2
Pideal = P real +
𝑉2

observed correction
pressure term
30504101603434 30504101603434 30504101603434

Where:

a is a constant and n and V are the number of moles and volume of the container , respectively .
the correction term for pressure ( an2⁄ v2 ) can be understood as follows . the intermolecular
interaction that gives rise to nonideal behavior depends on how frequently any two molecules
 approach each other closely . the frequency of such “ encounters “ increases with the square of
the number of molecules per unit volume ( n2⁄ v2 ) because the probabitity of finding each of the
two molecules in a particular region is proportional to n ⁄ v . Thus a is just a proportion ality
constant .

another correction concerns the volume occupied by the gas molecules . In the ideal gas
equation , V represents the volume of the container .
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

However , each molecule does occupy ( V-nb) , where n is the number of moles of the gas
and b is a constant the term nb represent the volume occupied by n moles of the gas.

Having taken into account the corrections for pressure and volume , we can rewrite the ideal gas
equation as follows:

2022/2023 2022/2023 2022/2023

The previous equation relating P,VTand n for a nonideal gas , is known as the Van der Waals
equation .

The Van der Waals constants a and b are selected to give the best possible agreement
between equation and observed of a particular gas .

table (3) lists the values of a and b for a number

of gases . The value of a indcates how strongly

molecules of a given type of gas attract one another

30504101603434 30504101603434 30504101603434

we see that heluim atoms have the weakest

attraction for one another , because heluim has the

smallest a value . there is also rough correlation

between molecular size and b generally , the larger

the molecule ( or atom) the greater b is , but the

relationship between b and molecular ( or atomic)

 size is not a simple one.

Example (16) compares the pressure of a gas

calculated using the ideal gas equatio and the van

der Waals equation

Table (3):Van der waals constants

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Example(16 ):

Given that 3.5 moles of NH3 occupy 5.20 L at 47℃ , calculate the pressure of the gas ( in atm )
using :

(a) The ideal gas equation

( b) The Van der Waals equation .

Solution:
2022/2023 2022/2023 2022/2023
( a) Using the ideal gas equation we have the following data:

V = 5.20 L

T= (47+273) = 320 oK

N=3.50 mol

R= 0.0821 L.atm/K . mol

𝑛𝑅𝑇
P= 𝑉

3.5 (0.082)(320)
P= = 17.7 atm
5.20
30504101603434 30504101603434 30504101603434

( b)Using the Van der Waals equation .

From table (3) :

a= 4.17 atm.L2/mol2
 b=0.0371 L/mol

𝑎𝑛2 4.17∗3.5∗3.5
= =1.89 atm
𝑉2 5.20∗5.20

𝑎𝑛2
= 1.89 atm
𝑉2

nb=0.130L
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

finally, substituting these values in the Van der Waals equation,we have

( P + 1.89) (5.2 – 3.5*0.130) = 3.5*0.082*320

P = 16.2 atm

check based on your understanding of nonideal gas behavior , is it reasonable that the pressure
calculated using the van der Waals equation should be smaller than using the ideal gas equation
? why ?

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Liquefaction of Gases - Critical Temperature And Pressure :

Two important properties of gases are important in developing methods for their
liquefaction: critical temperature and critical pressure. The critical temperature of a gas is the
temperature at or above which no amount of pressure, however great, will cause the gas to
liquefy. The minimum pressure required to liquefy the gas at the critical temperature is called the
critical pressure.

For example, the critical temperature for carbon dioxide is 304 K (87.8°F [31°C]). That
means that no amount of pressure applied to a sample of carbon dioxide gas at or above 304 oK
(87.8°F [31°C]) will cause the gas to liquefy. At or below that temperature, however, the gas can
be liquefied provided sufficient pressure is applied. The corresponding critical pressure for carbon
dioxide at 304K (87.8°F [31°C]) is 72.9 atmospheres.
30504101603434 30504101603434 In other words, 30504101603434
the application of a
pressure of 72.9 atmospheres of pressure on a sample of carbon dioxide gas at 304K (87.8°F
[31°C]) will cause the gas to liquefy.

Differences in critical temperatures among gases means that some gases are easier to
liquify than are others. The critical temperature of carbon dioxide is high enough so that it can be
liquified relatively easily at or near room temperature. By comparison, the critical temperature
of nitrogen gas is 126K (-232.6°F [-147°C]) and that of helium is 5.3K (-449.9°F [-267.7°C]).
Liquefying gases such as nitrogen and helium obviously present much greater difficulties than
does the liquefaction of carbon dioxide.
 Andrews and Thomson worked in Belfast on the liquefaction of gases during the 1860s and
early 1870s but much of their work was, for several reasons, not published until many years after
it was done, and then only in part. Their surviving notebooks and letters show that their results
anticipate some of the better-known and more systematic work of the Dutch school of Van der
Waals and Kamerlingh Onnes in the 1890s.

The Liquefaction of Gases :

Thomas Andrews was a scientist whose experimental skills were evidently comparable to
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

those of the illustrious James Joule . Ten years of care and devotion went into Andrews ' study
of the liquefaction of carbon dioxide ( called carbonic acid in his day ) , the essential results of
which are contained in this diagram taken from his 1869 paper .

It is a pressure – volume diagram Upon which are drawn isothermal carbon dioxide
curves for temperatures ranging from 13.1oC to 48.1oC pressure ranging from 50 to 100
atmospheres. Isothermal air curves are included in the upper left quadrant to illustrate the
degree of deviation of the carbon dioxide curves from the rectangular hyperbola associated with
ideal gas behavior.

The lowest isothermal curve (13.1°C) shows that at a pressure of around 47 atmospheres,
condensation occurs. The compressed gas separates into two distinct coexistent portions – vapor
and liquid – along a line of constant pressure

2022/2023 2022/2023 2022/2023

30504101603434 30504101603434 30504101603434

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

With further compression driving the conversion to the liquid form until finally the whole is
converted to liquid , at which point compressibility becomes markedly reduced.

In the next isothermal curve (21.5 oC) , where condensation takes place at a pressure of

about 60 atmospheres, gas and liquid are 30504101603434

30504101603434 closer still in density, the liquid occupying nearly a third
30504101603434

of the volume of the gas. As James Clerk Maxwell put it in Theory of Heat ,"The exceedingly
dense gas is approaching in its properties to the exceedingly light liquid ".

These properties eventually coincide at the isopycnic point (the point of inflexion on the
critical isotherm, marked X in the figure below) Corresponding to the critical pressure of 72.8
atmospheres and a critical temperature of 31 oC . isopycnic means ‘of equal density’.
 The isopycnic point (sometimes called the critical point) is where the densities of vapor
and liquid coincide; this occurs under the conditions of critical temperature Tc and critical
pressure pc. Above the critical temperature, isothermals do not show any discontinuity; it is not
possible to detect the point at which a liquid becomes a gas or vice versa. If liquid carbon
dioxide, represented by point Z in the figure below, is heated at constant pressure until its
temperature reaches 48°C, its condition at different temperatures will be represented by the line
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

ZY. At Z the substance concerned is a liquid; at Y it is a gas. The change has taken place
smoothly and continuously, representing continuity of state .

2022/2023 2022/2023 2022/2023

Figure ( 12 ):shows the relation between the pressure and the volume for carbon dioxide at different temperature.

30504101603434 30504101603434 30504101603434

Practce Exercise
 1. A pressure that will support a column of Hg to a height of 256 mm would support a column
of water to what height? The density of mercury is 13.6 g/cm3; the density of water is 1.00
g/cm3.

A. 348 cm B. 1.00  102 ft C. 18.8 mm D. 33.8 ft E. 76.0 cm

2. Which of the following is/are characteristic(s) of gases?

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

A. High compressibility
B. Relatively large distances between molecules
C. Formation of homogeneous mixtures regardless of the nature of gases
D. High compressibility AND relatively large distances between molecules
E. High compressibility, relatively large distances between molecules AND formation of
homogeneous mixtures regardless of the nature of gases

3. A sample of a gas occupies 1.40  103 mL at 25C and 760 mmHg. What volume will it
occupy at the same temperature and 380 mmHg?

A. 2,800 mL B. 2,100 mL C. 1,400 mL D. 1,050 mL E. 700 mL

4. A sample of nitrogen gas has a volume of 32.4 L at 20C. The gas is heated to 220ºC at
constant pressure. What is the final volume of nitrogen?
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A. 2.94 L B. 19.3 L C. 31.4 L D. 54.5 L E. 356 L

5. If 30.0 L of oxygen are cooled from 200ºC to 1C at constant pressure, what is the new
volume of oxygen?

A. 0.150 L B. 17.4 L C. 23.0 L D. 51.8 L E. 6.00  103 L

6. A sample of N2 gas occupies 2.40 L at 20C. If the gas is in a container that can contract or
expand at constant pressure, at what temperature will the N2 occupy 4.80 L?

A. 10C B. 40C C. 146C D. 313 E. 685C

7. The gas pressure in an aerosol can is 1.8 atm at 25C. If the gas is an ideal gas, what
pressure would develop in the can if it were
30504101603434
heated to 475C?
30504101603434 30504101603434

A. 0.095 atm B. 0.717 atm C. 3.26 atm D. 4.52 atm E. 34.2 atm

8. If the pressure of a gas sample is quadrupled and the absolute temperature is doubled, by
what factor does the volume of the sample change?
A.8 B. 2 C. ½ D. ¼ E. 1/8
 9. If the pressure on a gas sample is tripled and the absolute temperature is quadrupled, by
what factor will the volume of the sample change?

A. 12 B. 4/3 C. ¾ D. 1/3 E. 4

10. A small bubble rises from the bottom of a lake, where the temperature and pressure are 4C
and 3.0 atm, to the water's surface, where the temperature is 25C and the pressure is 0.95 atm.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Calculate the final volume of the bubble if its initial volume was 2.1 mL.

A. 0.72 mL B. 6.2 mL C. 41.4 mL D. 22.4 mL E. 7.1 mL

11. The temperature of an ideal gas in a 5.00 L container originally at 1 atm pressure and 25C is
lowered to 220 K. Calculate the new pressure of the gas.

A. 1.0 atm B. 1.35 atm C. 8.8 atm D. 0.738 atm E. 0.114 atm

12. 0.820 mole of hydrogen gas has a volume of 2.00 L at a certain temperature and pressure.
What is the volume of 0.125 mol of this gas at the same temperature and pressure?

A. 0.0512 L B. 0.250 L C. 0.305 L D. 4.01 L E. 19.5 L

13. At what temperature will a fixed amount of gas with a volume of 175 L at 15C and 760
mmHg2022/2023
occupy a volume of 198 L at a pressure of 640 mm Hg?
2022/2023 2022/2023

A. 274C B. 214C C. 114C D. 1C E. -59C

14. At what temperature will a fixed mass of gas with a volume of 125 L at 15C and 750 mmHg
occupy a volume of 101 L at a pressure of 645 mm Hg?

A. -73C B. 10.4C C. 2C D. 34C E. 200C

15. Calculate the volume occupied by 35.2 g of methane gas (CH4) at 25C and 1.0 atm.
R = 0.0821 L • atm/K•mol.
A. 0.0186 L B. 4.5 L C. 11.2 L D. 49.2 L E. 53.7 L

16. Calculate the volume occupied by 25.2 g of CO2 at 0.84 atm and 25C.
30504101603434 30504101603434 30504101603434
A. 0.060 L B. 1.34 L C. 16.9 L D. 24.2 L E. 734 L
 17. A gas evolved during the fermentation of sugar was collected at 22.5C and 702 mmHg. After
purification its volume was found to be 25.0 L. How many moles of gas were collected?

A. 0.95 mol B. 1.05 mol C. 12.5 mol D. 22.4 mol E. 724 mol

18. How many molecules of N2 gas can be present in a 2.5 L flask at 50C and 650 mmHg?

A. 2.1  10-23 molecules B. 4.9  1022 molecules

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

C. 3.1  1023 molecules D. 3.6  1025 molecules E. 0.081 molecules

19. Calculate the mass, in grams, of 2.74 L of CO gas measured at 33C and 945 mmHg.

A. 0.263 g B. 2.46 g C. 3.80 g D. 35.2 g E. 206 g

20. 0.500 mole of ammonia (NH3) occupies a 1.2 L flask at 150C. Calculate the pressure of the
ammonia inside the flask.

A. 6.91  10-2 atm B. 5.13 atm C. 12.2 atm D. 14.5 atm E. 22.4 a

21. Gases are sold in large cylinders for laboratory use. What pressure, in atmospheres, will be
exerted by 2,500 g of oxygen gas (O2) when stored at 22C in a 40.0 L cylinder?

A. 3.55 atm B. 1,510 atm C. 47.3 atm D. 7.56  104 atm E. 10.2 atm

22. Calculate
2022/2023 the number of kilograms of helium needed to inflate a balloon
2022/2023 to a volume of
2022/2023

100,000 L at an atmospheric pressure of 250 mmHg and a temperature of -35C.

A. 1.68 kg B. 3.36 kg C. 5.21 kg D. 6.74 kg E. 5120 kg

23. Calculate the density, in g/L, of CO2 gas at 27C and 0.50 atm pressure.

A. 0.89 g/L B. 1.12 g/L C. 9.93 g/L D. 46.0 g/L E.2.17 kg/L

24. Calculate the density of CO2(g) at 100C and 10.0 atm pressure.

A. 1.44 g/L B. 134 g/L C. 44.0 g/L D. 53.6 g/L E. 14.4 g/L

25. Calculate the density of Br2(g) at 59.0C and 1.00 atm pressure.

A. 27.2 g/L
30504101603434
B. 5.83 g/L C. 769 g/L
30504101603434
D. 22.4 g/L E. 3.45 g/L
30504101603434

26. Calculate the density, in g/L, of SF6 gas at 27C and 0.500 atm pressure.

A. 3.38  10-3 g/L B. 2.96 g/L C. 22.4 g/L D. 32.9 g/L E. 3.38 kg/L

27. Calculate the density, in g/L, of chlorine (Cl2) gas at STP.

A. 2.13  10-2 g/L B.46.9 g/L C. 1.58 g/L D. 3.16 g/L E. 0.316 kg/L
 28. Calculate the density of Ar(g) at -11C and 675 mmHg.

A. 1.52 g/L B. 1.65 g/L C. -39.3 g/L D. 39.95 g/L E. 1254 g/L

29. Which of the following gases will have the greatest density at the same specified temperature
and pressure?

A. H2 B. CClF3 C. CO2 D. C2H6 E. CF4

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

30. Which one of the following gases is "lighter-than-air"?

A. Cl2 B. SO2 C. P D. NO2 E. Ne

31. Two moles of chlorine gas at 20.0C are heated to 350C while the volume is kept constant.
The density of the gas

A. increases. B. decreases. C. remains the same.

D. Not enough information is given to correctly answer the question.

32. Determine the molar mass of chloroform gas if a sample weighing 0.389 g is collected in a
flask with a volume of 102 cm3 at 97C. The pressure of the chloroform is 728 mmHg.

A. 187 g/mol B. 121 g/mol C.112 g/mol D.31.6 g/mol E.8.28  10-3 g/mol

33. What is the molar mass of Freon-11 gas2022/2023

2022/2023 if its density is 6.13 g/L at STP?
2022/2023

A. 0.274 g/mol B. 3.64 g/mol C. 78.2 g/mol D.137 g/mol E.365 g/mol

34. Determine the molar mass of Freon-11 gas if a sample weighing 0.597 g occupies 100. cm3
at 95C, and 1,000. mmHg.

A. 0.19 g/mol B. 35.3 g/mol C. 70.9 g/mol D. 137 g/mol E.384 g/mol

35. 1.018 g of Freon-113 gas is trapped in a 145 mL container at 760. mmHg and 50.0C. What
is the molar mass of Freon-113?

A. 21.7 g/mol B. 28.8 g/mol C. 46.1 g/mol D.186 g/mol E.245 g/mol

36. 30504101603434
A 0.271 g sample of an unknown vapor occupies 294 mL at 140C30504101603434
30504101603434
and 847 mmHg. The
empirical formula of the compound is CH2. What is the molecular formula of the compound?

A. CH2 B. C2H4 C.C3H6 D. C4H E. C6H12

37. A gaseous compound is 30.4% nitrogen and 69.6% oxygen by mass. A 5.25-g sample of the
gas occupies a volume of 1.00 L and exerts a pressure of 1.26 atm at -4.0C. Which of the
following is its molecular formula?

A. NO B. NO2 C. N3O6 D. N2O4 E. N2O5

 38. A mixture of three gases has a total pressure of 1,380 mmHg at 298 K. The mixture is
analyzed and is found to contain 1.27 mol CO2, 3.04 mol CO, and 1.50 mol Ar. What is the partial
pressure of Ar?

A. 0.258 atm B. 301 mmHg C.356 mmHg D.5,345 mmHg E. 8,020 mmHg

39. A sample of hydrogen gas was collected over water at 21C and 685 mmHg. The volume of
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

the container was 7.80 L. Calculate the mass of H2(g) collected. (Vapor pressure of water = 18.6
mmHg at 21C.)

A. 0.283 g B. 0.572 g C. 0.589 g D. 7.14 g E. 435 g

40. A sample of carbon monoxide gas was collected in a 2.0 L flask by displacing water at 28C
and 810 mmHg. Calculate the number of CO molecules in the flask. The vapor pressure of water
at 28C is 28.3 mmHg.

A. 5.0  1022 B. 5.2  1022 C. 3.8  1023 D. 5.4  1023 E. 3.8  1025

41. Air contains 78% N2, 21% O2, and 1% Ar, by volume. What is the density of air at 1,000. torr
and -10C?

A. 1.0 g/L B. 6.1 g/L C. 1.3 g/L D.1.8 g/L E. 0.56 g/L
2022/2023 2022/2023 2022/2023
42. What volume of oxygen gas at 320 K and 680 torr will react completely with 2.50 L of NO gas
at the same temperature and pressure? 2NO(g) + O2(g) → 2NO2(g)

A. 1.25 L B. 2.50 L C. 3.00 L D. 1.00 L E. 5.00 L

43. What volume of CO2 gas at 645 torr and 800 K could be produced by the reaction of 45 g of
CaCO3 according to the equation? CaCO3(s) → CaO(s) + CO2(g)

A. 0.449 L B. 22.4 L C. 25.0 L D. 34.8 L E. 45.7 mL

44. How many liters of chlorine gas at 25C and 0.950 atm can be produced by the reaction of
12.0 g of MnO2? MnO2(s) + 4HCl(aq) → MnCl2(aq) + 2H2O(l) + Cl2(g)

A.
30504101603434 5.36  10-3 L B. 0.138 L C. 0.282 L
30504101603434 D. 3.09 L30504101603434
E.3.55 L

45. How many liters of chlorine gas at 200C and 0.500 atm can be produced by the reaction of
12.0 g of MnO2 with HCl as follows? MnO2(s) + 4HCl(aq) → MnCl2(aq) + 2H2O(l) +
Cl2(g) A. 10.7 L B. 3.09 L C. 4.53 L D. 0.138 L E. 0.093 L
 46. How many liters of chlorine gas at 650 mmHg and 25C can be produced by the reaction of
2.00 L of 2.50 M HCl solution with excess MnO2? MnO2(s) + 4HCl(aq) → MnCl2(aq) + 2H2O(l)
+ Cl2(g)

A. 1.25 L B. 24.2 L C. 35.7 L D. 88.6 L E. 143 L

47. Chlorine gas can be prepared in the laboratory by the reaction of solid manganese dioxide
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

with hydrochloric acid. (The other reaction products are aqueous manganese chloride and water.)
How much MnO2 should be added to excess HCl to obtain 275 mL of chlorine gas at 5.0C and
650 mmHg?
A. 1.18  10-4 g B. 0.896 g C. 1.22 g D. 49.8 g E. 8,440 g

48. How many liters of oxygen gas at 153C and 0.820 atm can be produced by the
decomposition of 22.4 g of solid KClO3? (The other decomposition product is solid potassium
chloride.)

A. 3.0 L B. 0.085 L C. 4.20 L D. 7.79 L E. 11.7 L

49. When active metals such as magnesium are immersed in acid solution, hydrogen gas is
evolved. Calculate the volume of H2(g) at 30.1C and 0.85 atm that can be formed when 275 mL
of 0.725 M HCl solution reacts with excess Mg to give hydrogen gas and aqueous magnesium
chloride.
2022/2023 2022/2023 2022/2023

A. 3.4  10-3 L B. 2.2 L C. 2.9 D. 5.8 L E. 11.7 L

50. Calculate the volume of H2(g) at 273 K and 2.00 atm that will be formed when 275 mL of
0.725 M HCl solution reacts with excess Mg to give hydrogen gas and aqueous magnesium
chloride.

A. 0.56 L B. 1.12 L C. 2.23 L D. 4.47 L E. 3.54 L

51. What mass of KClO3 must be decomposed to produce 126 L of oxygen gas at 133C
and 0.880 atm? (The other reaction product is solid KCl.)
A. 24.6 g B. 70.8 g C. 272 g D. 408 g E. 612 g

Which statement is false?

52. 30504101603434 30504101603434 30504101603434

A. The average kinetic energies of molecules from samples of different "ideal" gases is the same
at the same temperature.
B. The molecules of an ideal gas are relatively far apart.
C. All molecules of an ideal gas have the same kinetic energy at constant temperature.
D. Molecules of a gas undergo many collisions with each other and the container walls.
E. Molecules of greater mass have a lower average speed than those of less mass at the
same temperature.
 53. Complete this sentence: The molecules of different samples of an ideal gas have the same
average kinetic energies, at the same ________.

A. pressure B. temperature C. volume D. density

54. If equal masses of O2(g) and HBr(g) are in separate containers of equal volume and
temperature, which one of the following statements is true?
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

A. The pressure in the O2 container is greater than that in the HBr container.
B. There are more HBr molecules than O2 molecules.
C. The average velocity of the O2 molecules is less than that of the HBr molecules.
D. The average kinetic energy of HBr molecules is greater than that of O2 molecules.
E. The pressures of both gases are the same.

55. Which gas has molecules with the greatest average molecular speed at 25C?

A. CH4 B. Kr C. N2 D. CO2 E. Ar

56. Which of the following gas molecules have the highest average kinetic energy at 25C?

A. H2 B. O2 C. N2 D. Cl2

2022/2023 E. All the gases have the same average kinetic energy.
2022/2023 2022/2023

57. Deviations from the ideal gas law are greater at

A. low temperatures and low pressures.

B. low temperatures and high pressures.
C. high temperatures and high pressures.
D. high temperatures and low pressures.

58. For a substance that remains a gas under the conditions listed, deviation from the ideal gas
law would be most pronounced at

A. 100C and 2.0 atm. B.0C and 2.0 atm. C. -100C and 2.0 atm.
D. -100C and 4.0 atm. E. 100C and 4.0 atm.
30504101603434 30504101603434 30504101603434
A. 59. What is the pressure of the gas trapped in the apparatus shown below when the
atmospheric pressure is 720 mmHg?
A. 12 mmHg
B. 708 mmHg
C. 720 mmHg
D. 732 mmHg
E. 760 mmHg
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

60. Determine the pressure of the gas trapped in the apparatus shown below when the
atmospheric pressure is 695 mmHg.

2022/2023 2022/2023 2022/2023

A. 45 mmHg
B. 650 mmHg
C. 695 mmHg
D. 740 mmHg
E. 760 mmHg

30504101603434 30504101603434 30504101603434

61. 10.0 g of gaseous ammonia and 6.50 g of oxygen gas are introduced into a previously
evacuated 5.50 L vessel. If the ammonia and oxygen then react to yield NO gas and water vapor,
what is the final gas pressure inside the vessel at 23ºC?

A. 1.79 atm B. 6.48 atm C. 3.50 atm D. 0.285 atm E. 3.67 atm
 62. 5.00 g of hydrogen gas and 50.0 g of oxygen gas are introduced into an otherwise empty
9.00 L steel cylinder, and the hydrogen is ignited by an electric spark. If the reaction product is
gaseous water and the temperature of the cylinder is maintained at 35ºC, what is the final gas
pressure inside the cylinder?

A. 7.86 atm B. 18.3 atm C. 2.58 atm D.6.96 atm E. 0.92 atm

63. 9.45 g of liquid hexane (C6H14) is introduced into a 10.0 L vessel containing 13.15 atm of
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

oxygen gas at 21ºC and ignited, yielding carbon dioxide and water. If the vessel is then cooled to
-10ºC, what will be the gas pressure inside the vessel?

A. 3.09 atm B. 13.15 atm C. 1.42 atm D. 10.9 atm E. 12.6 atm

64. 10.0 g of gaseous ammonia and 6.50 g of oxygen gas are introduced into a previously
evacuated 5.50 L vessel. If the ammonia and oxygen then react to yield NO gas and water vapor,
what is the final density of the gas mixture inside the vessel at 23ºC?

A. 1.68 g/L B. 3.00 g/L C. 1.32 g/L D. 2.20 g/L E. 16.5 g/L

65. A method of removing CO2 from a spacecraft is to allow the CO2 to react with sodium
hydroxide. (The products of the reaction are sodium carbonate and water.) What volume of
carbon dioxide at 25C and 749 mmHg can be removed per kilogram of sodium hydroxide that
reacts?
A.2022/2023
301 L B. 284 L C. 276 L 2022/2023
D. 310 L E. 620 2022/2023

66. A spacecraft is filled with 0.500 atm of N2 and 0.500 atm of O2. Suppose a micrometeor
strikes this spacecraft and puts a very small hole in its side. Under these circumstances,

A. O2 is lost from the craft 6.9% faster than N2 is lost.

B. O2 is lost from the craft 14% faster than N2 is lost.
C. N2 is lost from the craft 6.9% faster than O2 is lost.
D. N2 is lost from the craft 14% faster than O2 is lost.
E. N2 and O2 are lost from the craft at the same rate.

67. A spacecraft is filled with 0.500 atm of O2 and 0.500 atm of He. If there is a very small hole
in the side of this craft such that gas is lost slowly into outer space,

A. He is lost 2.8 times faster than O2 is lost.

30504101603434 30504101603434 30504101603434

B. He is lost 8 times faster than O2 is lost.

C. He is lost twice as fast as O2 is lost.
D. O2 is lost 2.8 times faster than He is lost.
E. O2 is lost 8 times faster than He is lost.
 68. 1.000 atm of dry nitrogen, placed in a container having a pinhole opening in its side, leaks
from the container 3.54 times faster than does 1.000 atm of an unknown gas placed in this same
apparatus. Which of the following species could be the unknown gas?

A. NH3 B. C4H10 C. SF6 D. UF6 E. Rn

69. 1.000 atm of oxygen gas, placed in a container having a pinhole opening in its side,
leaks from the container 2.14 times faster than does 1.000 atm of an unknown gas placed in this
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

same apparatus. Which of the following species could be the unknown gas?
A. Cl B. SF6 C. Kr D. UF6 E. Xe

70. Samples of the following volatile liquids are opened simultaneously at one end of a room. If
you are standing at the opposite end of this room, which species would you smell first?
[Assume that your nose is equally sensitive to all these species.]

A. ethyl acetate (CH3COOC2H5)

B. camphor (C10H16O)
C. diethyl ether (C2H5OC2H5)
D. naphthalene (C10H8)
E. pentanethiol (C5H11SH)

71. A sample of mercury(II) oxide is placed in a 5.00 L evacuated container and heated until it
decomposes entirely to mercury metal and oxygen gas. After the container is cooled to 25C, the
pressure of the gas inside is 1.73 atm. What mass of mercury(II) oxide was originally placed into
2022/2023 2022/2023 2022/2023

the container?

A. 913 g B. 76.6 g C. 1.51 g D. 45.6 g E. 153 g

72. The mole fraction of oxygen molecules in dry air is 0.2095. What volume of dry air at 1.00
atm and 25C is required for burning 1.00 L of hexane (C6H14, density = 0.660 g/mL) completely,
yielding carbon dioxide and water?

A. 187 L B. 712 L C. 1780 L D. 894 L E. 8490 L

73. The mole fraction of oxygen molecules in dry air is 0.2095. What volume of dry air at
1.00 atm and 25C is required for burning 1.00 L of octane (C8H18, density = 0.7025 g/mL)
completely, yielding carbon dioxide and water?
30504101603434 30504101603434 30504101603434
A. 718 L B. 367 L C. 8980 L D. 1880 L E.150 L

74. A block of dry ice (solid CO2, density = 1.56 g/mL) of dimensions 25.0 cm  25.0 cm 
25.0 cm is left to sublime (i.e., to pass from the solid phase to the gas phase) in a closed
chamber of dimensions 4.00 m  5.00 m  3.00 m. The partial pressure of carbon dioxide in this
chamber at 25C will be

A. 171 mmHg. B.107 mmHg. C.0.225 mmHg. D.0.171 mmHg. E.14.4 mmHg.
 75. A 2.50-L flask contains a mixture of methane (CH4) and propane (C3H8) at a pressure of 1.45
atm and 20C. When this gas mixture is then burned in excess oxygen, 8.60 g of carbon dioxide
is formed. (The other product is water.) What is the mole fraction of methane in the original gas
mixture?

A. 0.34 B. 1.00 C. 0.66 D. 0.85 E. 0.15

76. What is the definition of "gas"?

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

77. What is standard temperature and standard pressure?

78. What is the significance of the magnitude of the van der Waals "a" constant?

79. Liquid oxygen boils at -183C. What is this temperature in kelvins?

80. How many grams of N2O, nitrous oxide, are contained in 500. mL of the
gas at STP?
81. Calculate the density of N2O gas, in grams per liter, at 110C and 12 atm.
82. Calculate the molar mass of a gaseous substance if 0.125 g of the gas occupies
93.3 mL at STP.

83. What is the density, in molecules per cubic centimeter, of N2 gas at 25C and 650 mmHg?

84. An2022/2023
aerosol can with a volume of 0.50 L has a bursting point of 2.6 atm.
2022/2023 If the can
2022/2023

contains 1.0 g CO2 and is heated to 400C, will it burst?

85. Phosgene, a gas used in World War I, consists of 12.41% C, 16.17% O, and 71.69% Cl. 1.00
L of this gas at STP has a mass of 4.42 g. What is the molecular formula of phosgene?

86. The van der Waals equation is a modification of the ideal gas equation. For what two facts
does this equation account?

87. On a spring morning (20C) you fill your tires to a pressure of 2.25 atmospheres. As you ride
along, the tire heats up to 45C from the friction on the road. What is the pressure in your tires
now?
88. A gas-filled balloon with a volume of 12.5 L at 0.90 atm and 21C is allowed to rise to the
stratosphere where the temperature is -5C and the pressure is 1.0 millibar. What is the final
volume of the balloon? 1.000 atm = 1.01330504101603434
30504101603434
bar. 30504101603434

89. What volume of H2 is formed at STP when 6.0 g of Al is treated with excess NaOH?
2NaOH + 2Al + 6H2O → 2NaAl(OH)4 + 3H2(g)
 90. What is V in the table below?
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

91. What is P in the table below?

92. What is T in the table below?

93. What is P in the table below?

2022/2023 2022/2023 2022/2023

94. Today is a beautiful day for a picnic in the mountains, so we seal our peanut butter sandwich
in a plastic sandwich bag at the base of the mountain. The approximate volume of the sandwich
bag not occupied by the sandwich is 200. mL. The pressure at the base of the mountain is 1.0
atm. If the pressure at the top of the mountain is 0.8 atm, what is the final volume of gas in our
sandwich bag?

95. What is Boyle's law?

30504101603434 30504101603434 30504101603434
96. Give five examples of elements that occur as gases at room temperature and pressure?

97. Give five examples of compounds that exist as gases at room temperature and pressure. 98.
Change 75C to K.
99. What is Charles' law? What effect does the relationship described in Charles' law have on a
balloon that is left in the sun?
 100. A balloon is blown up in the morning (23C) to a volume of 1.00 liter. If this balloon is
left in a hot car with the windows left up and the car warms up to 35C, what will be the final
volume of the balloon?
101. At constant pressure, the density of a gas depends on temperature. Does the density
increase or decrease as the temperature increases?
102. In a weather forecast on a Seattle radio station the barometric pressure was reported
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

to be 29.4 inches. What is the pressure in SI units? (1 inch = 25.4 mm, 1 atm = 760 m103. At
STP, 1 mole of gas has a molar volume of 22.4 L. What is the density of oxygen at STP?
104. What is Gay-Lussac's Law? How will this affect the pressure in our car tires?
105. Ammonium nitrite undergoes decomposition to produce only gases as shown below.

NH4NO2(s) → N2(g) + 2H2O(g)

How many liters of gas will be produced by the decomposition of 32.0 g of NH 4NO2 at 525C and
1.5 atm?

106. There is a power plant in Portland, Oregon that is very concerned about global
warming. This plant takes all of its exhaust gases from its boilers and recycles the CO 2 using the
Solvay process to make sodium hydrogen carbonate. The reaction is shown below.

+ H2O(l) + CO2(g) + NaCl(aq) → NaHCO

NH3(g)2022/2023 3(aq) + NH4Cl(aq)
2022/2023 2022/2023

How many liters each of NH3 and CO2 (both at STP) are needed to make 3.00 kg of sodium
bicarbonate?

107. Baking powder is made up of sodium hydrogen carbonate and calcium hydrogen
phosphate. When baking powder is wet, these components react to produce carbon dioxide. The
equation for this reaction is given below.
NaHCO3(aq) + CaHPO4(aq) → NaCaPO4(aq) + CO2(g) + H2O(l)
How many liters of carbon dioxide can be formed at room temperature from 4.00 g of NaHCO3
and excess CaHPO4?

108.30504101603434
Packaged cake mixes usually contain baking powder, a mixture
30504101603434
of sodium hydrogen
30504101603434

carbonate and calcium hydrogen phosphate that react to produce carbon dioxide gas when they
come into contact with water. Many such mixes have special instructions for use at high altitudes.
Why?
 109. Many automobiles produce about 5 grams of NO for each mile they are driven. How
many liters of NO gas at STP would be produced on a 100-mile trip?
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

110. A particular coal sample contains 2.32% S. When the coal is burned, the sulfur is
converted to SO2 (g). What volume of SO2 (g), measured at 25C and 749 mmHg, is produced by
burning 2.0  106 lb of this coal? (1 lb = 454 g)

111.At standard temperature and pressure, a given sample of water vapor occupies a volume of
2.80 L. How many moles of water vapor are present?

112.At standard temperature and pressure, a given sample of water vapor occupies a volume of
2.80 L. What is the weight of the water?

113.At standard temperature and pressure, a given sample of water vapor occupies a volume of
2.80 L. How many hydrogen atoms are present in the container?

114.Gasoline
2022/2023 (which can be considered to be octane, C8H18) burns in oxygen
2022/2023 2022/2023to produce carbon

dioxide and water. What volume of oxygen at STP is necessary to react with 1.0 gal of gasoline?
(The density of gasoline is 0.81 g/mL. 1 gal = 3.78 L)

115.Gasoline (which can be considered to be octane, C8H18) burns in oxygen to produce carbon
dioxide and water. What volume of carbon dioxide at STP is generated as a result of the
combustion of 1.0 gal of gasoline? (The density of gasoline is 0.81 g/mL. 1 gal = 3.78 L)

30504101603434 30504101603434 30504101603434

 UG_31186536@f-eng.tanta.edu.eg UG_31186536@f-eng.tanta.edu.eg UG_31186536@f-eng.tanta.edu.eg
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Thermo
dyanmic
2022/2023 2022/2023 2022/2023

Chapter 2

30504101603434
Thermodynamic
30504101603434 30504101603434

Thermodynamic can be defined as science of energy

The name thermodynamic stems from Greek words thermo means (heat)

and dynamic means (power)….

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Thermodynamic includes all aspects of energy and energy

transformations…

Law of conservation of energy

Energy can change from one form to another but the total amount of energy
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

remains constant,

i.e. the energy cannot be created or destroyed…

Notes of dimensions and units:-

Any physical quantity can be characterized by Dimensions……

The arbitrary magnitudes assigned to the dimensions are called units..

2022/2023 2022/2023 2022/2023

Types of Dimensions:-

1- Primary dimensions ( fundamentals dimension)

mass, time, temperature,…….

2- Secondary Dimensions ( derived dimensions ):

𝑚
, energy , volume
𝑠

Systems
30504101603434 30504101603434 30504101603434

1-Metric System :( SI- International System)

Mass k.g

Length m

Time s

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2-English system (United States Customary System)

Mass 1bm (pound mass)

Length Ft

Time s
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Relation between 1bm & kg

1bm= 0.4539 kg

Relation between ft & m

• 1ft= .3048m

• Force = (mass) (acceleration)

𝑠𝑝𝑒𝑒𝑑
• acceleration =
𝑡𝑖𝑚𝑒

𝒅
• speed =
2022/2023 𝒕 2022/2023 2022/2023

• F= ma
𝒎
• Kg . = N SI system
𝒔𝟐

𝒇𝒕
• bm. = bf English system
𝒔𝟐

Unit of force SI (kg.m⁄ s2) =N (Newton)

English system 32.174 (1bm.ft⁄ s2)

30504101603434 30504101603434 30504101603434

1N=1kg.m⁄s2 =1bf (pound-force)

1bf =32.174 1bm.ft
⁄s2

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Definition of Newton: -It is defined as the force required to accelerate

a mass of 1 kg at a rate of 1 m/s2

Definition of pound – force:- It is defined as the force required to

accelerate a mass of 32.174 1bm at a rate of 1 Ft./s2….

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Mass & weight

W = mg

It is the gravitational force applied to a body ….

Specific weight (W):-

Ⱳ =𝝆 𝒈

2022/2023 2022/2023 2022/2023

The weight of unit volume of a substance called specific weight

Where

Ⱳ = specific weight ….

𝝆 = density…

G = gravitational force (acceleration gravity)

30504101603434 30504101603434 30504101603434

Gravitational force (g) SI system g = 9.807 m/s2

English system g = 32.174 Ft /s2

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Work :-

It defines as force times distance ….

It is a form of energy ….
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Unit of Work = (N.m)

1 N.m = 1J

SI System (N.m = J kJ

Work

English system (Btu)

2022/2023 2022/2023 2022/2023

(British Thermal Unit)

Example (1) :-

A tank filled with oil whose density is 𝜌 = 850 𝑘𝑔/𝑚 3, If the

volume of the tank is V= 2m3

30504101603434 30504101603434 30504101603434

Determine the amount of the mass in the tank?

Solution:

• 𝜌 = 850 𝑘𝑔/𝑚 3

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• V= 2m3
𝑚
• ∴𝜌 = 𝑣
𝑚
• 850 = 2

• m = 850 ( 2)

• = 1700 kg
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Example(2) :-

What is the force required to accelerate a mass of 30 kg at a

rate of 15 m/s2 ?

Solution:-

Force = mass (acceleration)

2022/2023 2022/2023 2022/2023

F=ma

F= 30 kg .15m/s2

= 30 x 15 kg. m/s = 450 k.g .m/s2 = 450 N

Example(3) :-

What is the force required to

30504101603434 accelerate a mass of 30504101603434
30504101603434 60 1bm at a

rate of 45 ft /s2 ?

Solution:

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Force = mass x acceleration

F= ma

F= 60 1bm x 45 Ft /s2
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

= 60 x 45 1bm. Ft /s2 = 2700*32 1bf

Example(4) :-

Determine the mass and the weight of the air contained in a room

whose dimensions are 6mx6mx8m. Assume the density of the air

is 1.16 kg/m3

Solution
2022/2023 2022/2023 2022/2023

𝑚
𝜌 =
𝑣

The volume of the room = volume of the air

= 6m x 6m x 8m

= 288 m3

30504101603434 30504101603434 30504101603434

𝑚
𝜌 =
𝑣
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎𝑖𝑟
1.16 kg/m3 =
288𝑚 3

The mass of the air = 1.16 x 288 = 334.1 kg

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Weight = mass x gravitational acceleration

W= m g

W= 334 . 1 kg x 9.807 m/s2 =3277 kg . m/s2 =3277 N

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Example( 5 ) :-

Determine the mass and the weight of the air contained in the

room whose dimensions are 15 ft x 20 ft x 20 ft. Assume the

density of the air is 0.0724 lbm / ft 3

Solution

The volume of the room = the volume of the air

2022/2023 2022/2023 2022/2023

= 15 ft x 20 ft x 20 ft = 6000 ft3

𝑚
∴𝜌 =
𝑣
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎𝑖𝑟
0.0724 lbm / ft 3 =
6000𝑚 3

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎𝑖𝑟 = 0.0724 lbm . ft /s3 x 6000 ft3 = 434.4 1bm

30504101603434 30504101603434 30504101603434

2
Weight = 434 x 32.174 lbm . ft/s

W = 434.4 x 32.174 lbf = 13976. 38 lbf

System :- ( thermodynamic system)

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It Is defined as a quantity of matter or a region of space chosen for study…..

Surrounding:-

The mass or a region outside the system….

Boundary:-

The real or imaginary surface that separates the system from its
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

surrounding…..

Surrounding

System

Boundary

2022/2023 2022/2023 2022/2023

Types of system:-

1- closed system :-( control mass)

No mass can enter or leave the system but energy can cross the boundary

in the form of heat or work.

2- Isolated system:-

30504101603434 30504101603434 30504101603434

It is a special case of the closed system.

No mass can enter or leave the system and the energy cannot cross the

boundary …

3- Open system:-

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Both mass and energy can cross the boundary…

Forms of energy:

Energy exits in numerous forms of energy such as:-

• Potential energy
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

• Kinetic energy

• Chemical energy

• Thermal energy

• Nuclear energy

• Electrical energy

• Magnetic energy

• Mechanical energy

2022/2023 2022/2023 2022/2023

Their sum form total energy

Energy can be divided into two groups :-

1- Macroscopic forms of energy

2- Microscopic forms of energy

1-The macroscopic forms of energy:-

All forms
30504101603434 of energy outside the system ….
30504101603434 30504101603434

2-The microscopic forms of energy

Are those related to the structure of the molecules and the degree of

molecule activity …

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Internal energy ( U ) :

All the sum of the microscopic of energy called internal energy ….

Kinetic energy :- ( K.E)

The energy that a system possesses as a result of its motion …

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

𝒎𝒗𝟐
K.E =
𝟐

Where :-

K.E: kinetic energy

υ : velocity of the system….

m: mass

Potential Energy :( P.E)

2022/2023 2022/2023 2022/2023

The energy that the system possesses as a result of its elevation

in a gravitational field

P.E = m g z

Where:-

P.E : potential energy

m: mass
30504101603434 30504101603434 30504101603434

g: gravitational acceleration

Z: the elevation of the center of gravity of the system

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Total energy = Internal energy+ kinetic energy + Potential

energy

∆ E = ∆U + ∆K.E + ∆P .E

𝑚𝜐2
∆ E = ∆U + + mgz
2
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Temperature scales :-

Temperature scales

In SI system Celsius scale ( 0c )

In English system Fahrenheit scale ( 0F )

Thermodynamic scales:-

2022/2023 2022/2023 2022/2023

In SI system Kelvin scale (0K)

In English system Rankin scale (0R)

Temperature scales :-

The relation between Kelvin scale and Celsius scale

T ( K ) = T ( 0C ) + 273

The relation between Rankin30504101603434

30504101603434
scale and Fahrenheit scale
30504101603434

T ( 0R ) = T ( 0F ) + 460

The Temperature scales in two unit system are related by :-

T ( 0F ) = 1.8 T (0C) + 32

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T (0 R ) = 1.8 T ( K)

The Temperature differences ∆T on both scales is the same

∆T (0C ) = ∆ T ( K )

∆T ( 0F ) = ∆ T ( 0R )
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Example ( 6) :-
During the heating process the temperature of the system was 100C Express

this temperature in K 0R , 0F ?

Solution:- T ( K ) = T ( 0C ) + 273

= 10+273 = 283 K
2022/2023 2022/2023 2022/2023

T (0 R ) = 1.8 T ( K)

= 1.8 (283) = 509.4 0R

T ( 0F ) = 1.8 T (10) + 32

= 1.8 + 32 = 50 0F

--------------------------------------------------------------------
30504101603434 30504101603434 30504101603434

---------------------

• Ordinary temperature scales:

In SI system → Celsius scale (o C )

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In English system → Fahrenheit scale ( 0F )

• Absolute temperature scales :

In SI system → Kelvin scale ( K )

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

In English system → Rankin scale ( 0R )

Example (7) :-

The deep body temperature of a healthy person is 37 o C. What is it in Kelvin

?

Solution:

T ( 0 k ) = T ( 0C ) + 273

T ( 0 k ) = 37 + 273 = 310 K

Example (8) :-
2022/2023 2022/2023 2022/2023

Consider a system whose temperature 180C. Express this temperature in

0
R. K. 0F ?

Solution:-

T (K) = T ( 0C ) + 273

= 18 + 273 = 291 K

T (0 R ) = 1.8 T( K)
30504101603434 30504101603434 30504101603434

= 1.8 (291)= 523.8 0R

T ( 0F ) = 1.8 T (0C) + 32 = 1.8 (18) + 32 = 64.40F

Example (9) :-

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The temperature of a system rises by 300C during a heating process.

Express this rise in Temperature in Kelvin?

Solution:-

∆T (0C ) = 𝟑𝟎℃

∴ ∆𝑻(℃) = ∆𝑻(𝑲)
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

∴ ∆𝑻(𝑲) = 𝟑𝟎 𝑲

Example (10) :-

The temperature of the system drops by 270F during a cooling process.

Express this drop in temperature in 0R?

Solution:-

∆T ( 0F ) = 𝟐𝟕 ( 0F )

. : ∆T ( 0F ) = ∆ T ( 0R )
2022/2023 2022/2023 2022/2023

∴ ∆ T ( 0R ) = 270 R

First law of thermodynamic (law of conservation of energy)

There are three forms of the first law of thermodynamic :

1- The energy can’t be created or destroyed but it can transfer from one

form to another ….

2- The
30504101603434 total amount of energy 30504101603434
of the system and the surrounding
30504101603434 are

constant

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3- During the interaction between the system and the surrounding the

amount of energy gained by the system must be exactly equal to the amount

of energy lost the surrounding .

Units of heat:-

Calory: -
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

The amount of heat required to rise the temperature 1 gram of distilled

water 1℃ from14.5 ℃ to 15.5 ℃

Btu: -

The amount of heat required to rise the temperature of 1lbm of distilled

water 10F

Specific heat (s):

The amount of heat required to rise the temperature of 1 gm of matter 1°𝐶

2022/2023 2022/2023 2022/2023

Heat capacity (C) :-

the amount of heat required to rise the temperature of all the body 10C

C= S m

Where:-

C: heat capacity

m: the mass of the body

30504101603434 30504101603434 30504101603434

S: specific heat

Molar heat capacity (Cm)

The amount of heat required to rise the temperature of 1 gmole of matter

10C

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Molar heat capacity at constant volume (Cv):-

The amount of heat required to rise the temperature of 1 gmole of matter

10C at constant volume

Molar heat capacity at constant pressure (Cp):-

The amount of heat required to rise the temperature of 1 gmole of matter

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

10C at constant pressure

Work (W):-

The mechanical work is the result of force (F) multiply by the distance (l)

that the force is transferred.

W=FxL

Work: - it is the energy transfer associated with force acting through

distance

2022/2023 2022/2023 2022/2023

This definition suitable in mechanical field but not in the chemical field so

it must change the force and the distance by volume and pressure

30504101603434 30504101603434 30504101603434

Consider

The gas enclosed in the piston cylinder .

During chemical change the piston allowed to transfer the distance (L)

under pressure (P) the area of the piston (A)

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Pressure = force per unit area

𝑬
∴ P= 𝑨

∴ W = F x L = force x distance

F= P A

W=P AxL
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

V= AL

∴ W= P ∆ V

Where :-

W: work

∆V : change in volume

P : pressure
𝒘
W = ∫𝟎 𝒅𝒘

2022/2023 𝒗𝟐 2022/2023 2022/2023

W= ∫𝒗𝟏 𝒑𝒅𝒗 general formula

Example (11):-

A rigid tank contains air at 500 Kpa and 150 o C . As a result of heat

transfer to the surrounding the temperature and the pressure inside the

tank drop to 65 o C and 400Kpa respectively . Determine the boundary work

done during this process ?

30504101603434 30504101603434 30504101603434

Solution:
𝒗𝟐
W= ∫𝒗𝟏 𝒑𝒅𝒗

We have a rigid tank

The volume of the tank is constant

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𝑽𝟐
∫𝑽𝟏 𝒅𝒗 =0
𝒗𝟐
W= ∫𝒗𝟏 𝒑𝒅𝒗 = 0.0

Example (12):-

A friction less piston – cylinder device contain 0.1 lbm of water vapor at 20

psia and 320 ℉ heat is now added to the system

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

unit the temperature reaches 400℉ If the piston is not attached to the shaft

and its pressure was constant. determine the work done by the system

during this process

where:-`

1Btu = 5.404 psia ft3

𝑝𝑠𝑖𝑎 𝑓𝑡 3
R = .5956 1𝑏𝑚 𝑅

Solution :

2022/2023 2 2 2022/2023 2022/2023

W =∫1 𝑝𝑑𝑣 = 𝑝 ∫1 𝑑𝑣
W = p ( V2 – V1 )
PV = mR T
to calculate V1 :
𝑝𝑠𝑖𝑎 𝑓𝑡 3
20 psia (V1) = 0.1 1bm x 0.5956 (320 + 460) R
1𝑏𝑚 𝑅
0.1 𝑥 0.5956 𝑥 780
V1 = = 2.32 ft3
20

To calculate V2:-
P V2 = m R T2
𝑝𝑠𝑖𝑎 𝐹𝑡 3
20 psia(V2) = 0.1 1bm (0 .5956) (400+ 460) OR
30504101603434 1𝑏𝑚 𝑅
30504101603434 30504101603434
0.1 𝑥 0.5956 𝑥 860
V2= =2.56 ft3
20

The work done by the system:-

W = P (V2 – V1)
W = 20 psia (2.56 – 2.32) ft3
= 20 x .24 = 4.80 psia .ft3

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𝑩𝒕𝒖
= 4.8 psia ft3 x𝟓.𝟒𝟎𝟒 𝒑𝒔𝒊𝒂 𝑭𝒕 = 0.89 Btu
𝟑

Example (13):-

A piston cylinder device initially contains 0.4 m3 of air at 100 K pa and 80 0C

. The Air is now compressed to 0.1 m3 in such away that the temperature
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

inside the cylinder remains constant. Determine the work done during the

process?

Solution:-

𝟐
W =∫𝟏 𝒑𝒅𝒗
P1V1 = n RT=C

𝐶
P=𝑉

2𝑐 2 𝑑𝑣
W=∫1 dv = C ∫1 = C[𝐼𝑛𝑣]
𝑣 𝑣
2022/2023 2022/2023 2022/2023
𝑣 𝑣
=C [In v2 – In v1] = C In 𝑉2 = P1V1 In𝑉2
1 1

0.1
W = 100 (0.4) In 0.4 = -55.45 K pa.m3
-------------------------------------------------------------------------------
----
* Thermo dynamic can be defined as science of energy

*First law of thermo dynamics

30504101603434 30504101603434 30504101603434

*The energy can not be destroyed or created but it can change from one

form to another but the total amount of energy remains constant.

The first law of thermodynamics:

Or the conservation of energy:-

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Net energy transfer to (or from) the system as heat and work) = [net

increase (or decrease) in the total energy of the system]

Q±W= ∆E

Q :- net heat transfer across system boundaries

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Q = ∑ 𝑸𝒊𝒏 − ∑ 𝑸𝒐𝒖𝒕

W: - net work done in all forms

W= ( ∑ 𝑊𝑜𝑢𝑡 − ∑ 𝑊𝑖𝑛 )

∆ E = ∆ U + ∆ K.E + ∆ P .E

Where:

∆E : net change in total energy of the system = E2-E1

2022/2023 2022/2023 2022/2023

∆ E = ∆ U + ∆ K.E + ∆ P .E

∆ E = net change in total energy of the system

∆ U = net change in the internal energy of the system (U2 –U 1)

∆ K.E = net change in kinetic energy of the system

∆ K.E = ( K.E )2 - ( K.E )1

30504101603434 30504101603434 30504101603434
∆ P. E = net change in the potential energy of the system

∆ P. E = ( P. E)2 − (P. E)1

• U 2 : final internal energy

• U1 : initial internal energy
• (K.E)2 : final kinetic energy

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• (K.E)1 : initial kinetic energy

• (P.E ) 2 : final potential energy
• (P.E ) 1 : 𝜑.initial potential energy

Example (14) :-

A rigid tank contains a hot fluid that is cooled while being stirred by a paddle
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

wheel. The initial internal energy of the fluid is 800 K J during the cooling

process, the fluid losses 500K J of heat, and the paddle wheel does 100 kJ of

work on the fluid. Determine the final internal energy of the fluid. Neglect the

energy stored in the paddle wheel….

Solution :-

U1 = 800K J

Q = -500K J
2022/2023 2022/2023 2022/2023
W = +100 K J

∆E=Q±W

∆E=Q+W

∆ E = -500K J + 100K J = -400K J

∆ E = ∆ U + ∆ (K.E) + ∆ (P .E)

∆ E = (U2 – U1)

The energy stored in the paddle wheel is

30504101603434
neglected
30504101603434 30504101603434

∆ (K.E) + ∆ (P.E) = 0.0

∆ E =∆U = (U2 – U1)
-400 K J = U2 – 800
U2 = 800 – 400
U2 = 400 KG = final internal energy

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Net Change total energy = ∆ E = Q – W

Change in internal energy ∆ U = Q - W

Heat work
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

• Net heart transfer at constant Volume (q v):-

∆ E= q – w

∆ E= ∆U + ∆K.E + ∆ P.E

∆U = q - W (1)

𝟐
Where W = work =∫𝟏 𝒑𝒅𝒗

IF
2022/2023 2022/2023 2022/2023

V= constant
∴ dv =0.0
𝑊 = 0.0
Sub. in eqn (1) :.
∴∆u = qv

Net change ( Net heat transfer

in internal energy

at constant volume

∆U= U2
30504101603434 – U1 30504101603434 30504101603434

∆U depended on initial state and final state

∴ ∆𝑢 = 𝑞 v

qV depends on initial state and final state

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Prove that the net heat transfer at constant volume depends on the initial

state and final state??

Net heat transfer at constant pressure qp ) :-

∆ E= q –W

Where: - ∆ u the net change in the internal energy

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

q=heat transfer

W= work

q= ∆ U + W

∴ ∆𝑈 = U2 –U1 + w (1)

∴ q = U 2 – U1
2
𝑊 = ∫ 𝑝𝑑𝑣
1

At constant pressure
2022/2023 2022/2023 2022/2023
2
W =𝑃 ∫1 𝑑𝑣 = P(V2- V1) (2)

From eq: (2) sub. in eq (1):-

qp = U2 -U1 + P(V2- V1)

=U2 - U1 + PV2 - PV 1 = (U2 +PV2) – PV1 - U1

qp = (U2 + PV2) = (PV1-U1)

H= U + PV = enthalpy
30504101603434 30504101603434 30504101603434

H2 = U2 + PV2

H1 = U1 + PVv1

∴qp= H 2 – H1

qp = ∆ H

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{Net heart transfer at constant} = {net change in the enthalpy}

∆ H = H 2 – H1

∴∆ H depends on the initial state and final state

… qp = ∆ H

∴qp depends on the initial state and final state at constant pressure
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

The relation between q v and q p(net heat transfer at constant volume and

Net heat transfer at constant pressure) :-

H=U+PV

Where:-

H = enthalpy

U = internal energy

P= pressure

V2022/2023
= volume 2022/2023 2022/2023

∆ H = ∆ u + ∆ (PV)

∆H+qp at const pressure

∆ H = q p = ∆ u + ∆ (p v)

qp = ∆u + p ∆v + v∆ p

p constant
30504101603434 30504101603434 30504101603434

q p = ∆ u + p∆ v

q p = ∆u + w

∆ 𝑢 =Qvat const volume

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∴q p = 𝒒 v+w

qpis larger than q by work (w) , because at constant volume the system

can’t do work on the surrounding and the surrounding can’t do work on the

system …

∴ at constant volume the increase in heat transfer go to increase the

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

internal energy …. At constant pressure the increase in heat Transfer go

(1) to do work

(2) To increase the internal energy

CP (molar heat capacity at constant pressure) :-

The amount of heat required to rise the temperature 1 g mole of Mather 1

℃ at constant pressure ….

Cv (molar heat capacity at constant volume) :-

2022/2023 2022/2023 2022/2023
The amount of heat required to rise the temperature 1 g mole of Mather 1

℃ at constant volume….

--------------------------------------------------------------------------------

----------

Relation between molar heat capacity at constant pressure and molar

heat capacity at constant volume (Cp and Cv):-

Cp = Cv + w
30504101603434 30504101603434 30504101603434

where :-

Cp : molar heat capacity at constant pressure …

Cv : molar heat capacity at constant volume….

W : work

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2
W = ∫1 𝑝𝑑𝑣

at constant pressure

w= p∆ v

Cp = Cv + p∆V ----- (1)

… Pv = n RT
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

From the definition of Cp and Cv

n=1

PV = RT

∆ PV = ∆ (RT)

P∆ V + V∆ P = R ∆ T + T ∆ R

P = constant

P∆ V = R∆ T

2022/2023 2022/2023 2022/2023

∆ T = 1 ( from the definition of Cp and Cv )

P∆ V = R

From eqn. (2) in (1) Cp = Cv + R

In ideal gases there is a difference between Cp and Cv …..

In solids and liquids there is no difference between Cp and Cv … Cp = Cv

because the change in volume at constant pressure is very small and can

be neglected….
30504101603434 30504101603434 30504101603434

For ideal gases

1- Cp and Cv are constant

2- they depend on the type of the gas

3- they don’t depend on the temperature

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For real; gases:-

1- Cp and Cv depend on the temperature

2- C p = ∝ +𝛽 𝑇 + 𝛾T 2

where :

∝ , 𝜷 , 𝜹 are constants there are thermodynamic tables

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

give the values of ∝ , 𝛃 , 𝛄 for different gases

if the molecule of the ideal gas

if the molecule of the ideal gas contain two a atom such as (H2.O2,….)
𝟕
Cp = 𝟒 R
𝟓
Cv = 𝟐 R

If the molecule of the ideal gas contains one atom such as (He, Ne….)
𝟓
Cp = 𝟐 R
2022/2023 𝟑 2022/2023 2022/2023
Cv = 𝟐 R

The ratio between molar heat capacity at constant pressure (Cp) and

molar heat capacity at constant volume (Cv)

𝒄𝒑
𝜸=
𝒄𝑽

The value of depends on the number of atoms in the molecule

1) if the molecule contain two atoms :

𝟕
𝒄𝒑 𝑹 𝟕
30504101603434 𝜸=𝒄 = 𝟐 =
30504101603434
𝟓 = 1.4 30504101603434
𝑽 𝑹 𝟓
𝟐

2) if the molecular contains one atom:-

𝟓
𝒄𝒑 𝑹 𝟓
𝜸=𝒄 = 𝟐
𝟑 = = 1.67
𝑽 𝑹 𝟑
𝟐

Determination of heat transfer at constant pressure qp for ideal gases:-

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𝑻
q p= ∫𝑻 𝟐 𝒅𝑻= ∆H
𝟏

for ideal gases Cp = constant

𝑻
qp = ∆ H = Cp∫𝑻 𝟐 𝒅𝑻
𝟏

= Cp [ 𝑻]𝑻𝟐
𝑻𝟏 = 𝑪𝒑 [𝑻𝟏 − 𝑻𝟐 ]

q p = ∆ H = Cp ∆T
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

where :

qp : net heat transfer at constant pressure

∆ H = net change in the enthalpy

Cp= molar heat capacity at constant pressure

∆T = ( T2 –T1) = net change in temperature

Determination of heat transfer at constant volume qv for ideal gases qv

2022/2023 𝑻 2022/2023 2022/2023
= ∫𝑻 𝟐 𝑪𝒗𝒅 𝑻 = ∆ 𝒖
𝟏

For ideal gases Cv = constant

𝑻
qv = ∆ U = Cv∫𝑻 𝟐 𝒅 𝑻
𝟏

=Cv [ 𝑻]𝑻𝟐
𝑻𝟏 = 𝑪𝒗 [𝑻𝟏 − 𝑻𝟐 ]

q v = ∆ U = Cv ∆T

where:

q :-net heat transfer at constant volume

30504101603434 30504101603434 30504101603434

∆ U = net change in the internal energy

CV = molar heat capacity at constant volume

∆T = ( T2 –T1) = net change in temperature

Determination of heat transfer at constant pressure qp for real gases :-

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𝑇
qP= ∫𝑇 2 𝐶𝑝𝑑 𝑇 = ∆ 𝐻 (1)
1

for real gases

𝐶𝑝 =∝ +𝛽 𝑇 + 𝛾T 2 (2)

From eqn.(2) sub. in eqn. (1):-

𝑇
qp= ∆ 𝐻 ∫𝑇 2(∝ +𝛽 𝑇 + 𝛾T 2)𝑑𝑇
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

𝑇 𝑇 𝑇
=∫𝑇 2 ∝ 𝑑𝑇 + 2
∫𝑇1 𝛽 𝑇 𝑑𝑇 + ∫𝑇 2 𝛾 T 2 𝑑𝑇
1 1

∝ , 𝛽 and 𝛿 are constant

𝑇 𝑇 𝑇
qp =∆ 𝐻 =∝ ∫𝑇 2 𝑑𝑇 + 𝛽 ∫𝑇 2 𝑇 𝑑𝑇 + 𝛾 ∫𝑇 2 T 2 𝑑𝑇
1 1 1

𝑇 𝛽 𝑇 𝛾 𝑇
=∝ [𝑇] 𝑇21 + [ T 2 ] 𝑇21 + [ T 3 ]𝑇21
2 3
𝛽 𝛾
qp =∆ 𝐻 =∝( T2 –T1)+ 2 [ T22-T12] + 3 [ T23-T13]

Determination of heat transfer at constant volume qV for real gases

2022/2023 2022/2023 2022/2023
𝑻𝟐
qv = ∫𝑻𝟏 𝐂𝐯 𝒅 𝑻 = ∆ 𝑼------------- (1)

Cp = Cv + R
Cv = Cp –R ------ (1)
Cp = ∝ +𝜷 𝑻 + 𝜹T 2 _________ (2)
From eqn.(2) sub. in eqn. (1):-

𝐶𝑣 =∝ +𝛽 𝑇 + 𝛾T 2 - R -------------- (3)

From eqn.(3) sub. in eqn. (1 ):-

30504101603434 𝑇 30504101603434 30504101603434
qv= ∫𝑇 2{(∝ −𝑅) + 𝛽 𝑇 + 𝛾 T 2}𝑑𝑇 = ∆ 𝑈
1

𝑇 𝑇 𝑇
=∫𝑇 2(∝ −𝑅) 𝑑𝑇 + 2
∫𝑇1 𝛽 𝑇 𝑑𝑇 + ∫𝑇 2 𝛾 T 2 𝑑𝑇
1 1

∝ , 𝛽 and 𝛿 are constant

𝑇 𝑇 𝑇
qv =∆ 𝐻 = (∝ −𝑅) ∫𝑇 2 𝑑𝑇 + 𝛽 ∫𝑇 2 𝑇 𝑑𝑇 + 𝛾 ∫𝑇 2 T 2 𝑑𝑇
1 1 1

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𝑇 𝛽 𝑇 𝛾 𝑇
= (∝ −𝑅)[𝑇] 𝑇21 + [ T 2 ] 𝑇21 + [ T 3 ] 𝑇21
2 3
𝛽 𝛾
qv =∆ 𝑈 = (∝ −𝑅)( T2 –T1)+ 2 [ T22-T12] + 3 [ T23-T13]

Application of first law of thermodynamics on system consists of ideal

gas:-

This application means that determination of:-

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

1- The amount of work (w)

2- Net change in heat transfer (q)

3- Net change of internal energy (∆ u)

4- Net change of enthalpy (∆ H)

A) Application of first law of thermodynamics in case of expansion of ideal

gas at constant temperature:-

T= constant

2022/2023
U∝ T 2022/2023 2022/2023

∴ ∆ 𝑇 = 0.0
∴ ∆ 𝑈 = 0. 𝟎
from first law of thermodynamics:-
∆U=q−w
q=w
2
W = ∫1 𝑝𝑑𝑣
𝑉
q= W = ∫𝑉 2 𝑝𝑑𝑣---------- (1)
1

the gas is deal

𝑛𝑇𝑅
P v= n RT
30504101603434 P= --------(2)
30504101603434 30504101603434
𝑉

From eqn. (2) sub. in (1)

𝑉 𝑛𝑅𝑇
q = W= ∫𝑣 2 𝑑𝑣
1 𝑉
𝑉 𝑑𝑣
= 𝑛 𝑅𝑇 ∫𝑣 2
1 𝑉
𝒗
q=w =n RT [ 𝐼𝑛𝑣 ]𝒗𝟐𝟏
= nRT [ I n v2 – Inv1]

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𝑣
q = W = n R T In(𝑣2 )-------(3)
1

T= constant
𝑃1V1 = 𝑃2V2
𝑉2 𝑃
=𝑃1 - ------- (4)
𝑉1 2

From eqn. (4) sub. (3)

P
q= w = nRT In (p1 )
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

H= U + PV
∆H=∆ U +∆ PV -------(5)
∆ PV =𝑃2V2 - P1V1
𝑃2V2= P1V1
∆ PV = 0.0
∆ H = ∆ U + ∆ (PV)
∆ H = ∆U = 0.0

Example(15) :-
2022/2023 2022/2023 2022/2023

35 liter of H2 gas produced by the reaction between acid and

metal at 1 atmospheric pressure calculate the work done by

the gas against surrounding :

1- in L.atm

2- in colory

30504101603434
3- in Joule 30504101603434 30504101603434

4- in Erg

solution :-

𝜌 = 1 𝑎𝑡𝑚
∆ v = 35 liter
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W = 𝜌 ∆𝑉 → 𝑊 = 1 × 35 = 35 𝐿. 𝑎𝑡𝑚
𝑐𝑎𝑙 𝐿.𝑎𝑡𝑚
2 = R = 0.082
𝑔 𝑚𝑜𝑙𝑒 °𝐾 𝑔𝑚𝑜𝑙𝑒 °𝐾
𝑐𝑎𝑙
2 𝑔𝑚𝑒𝑙𝑒0𝑘
W= 35 L.atm x 𝑙.𝑎𝑡𝑚
0.082
𝑔𝑚𝑒𝑙.0𝑘

70
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

W= cal = 853.65 cal

0,082

1 cal = 4,182 Joule

4,182 𝐽𝑜𝑢𝑙𝑒
W= 847 cal x
1 𝑐𝑎𝑙

=3569.86 Joule

1 Joule = 107 erg

107 erg
w=3569.86 Joule x
1 𝐽𝑜𝑢𝑙𝑒

w= 3569.86 x107 erg

2022/2023 2022/2023 2022/2023

Example ( 16) :-

Calculate the amount of heat transfer in erg must be given for 1

mole of ideal gas expands at constant temperature 25 ℃ from

initial pressure 1 atm. to final pressure 0.25 atm?

Solution:
30504101603434 30504101603434 30504101603434

q=??
1 mole
p1 = 1 atm
T= 25℃ + 2273 = 298 °𝑘
𝒗𝟐
q= w= nR T In 𝒗𝟏

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or
𝒑
q = w = n R T In𝒑𝟏
𝟐

1
q = 1(2) (289) In 0.25 = 826.23 cal

1cal = 4.182 Joule

1 Joule = 107 erg
4.182 𝐽𝑜𝑢𝑙𝑒
q = 826.23 cal x
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

1 𝑐𝑎𝑙
107 erg
= 3455.299 J x 1J

= 3.455 x 1010 erg

Example (17) :-

Calculate the work done when 1mole of sulpher dioxide SO2at

constant temperature 27℃ expands from initial pressure 1 atm to

final pressure 10 atm

2022/2023 2022/2023 2022/2023

1) If SO2 acts as ideal gas

2) If SO2 acts as real gas ….

Show the work increases or decreases??

solution :-

w =?
n= 1mole
30504101603434 30504101603434 30504101603434
T = 27℃ + 273 = 300 °𝑘
P1 =1 atmp2 = 10 atm
1…
𝒑𝟏
W = Nr T In
𝒑𝟐

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1
W= 1 (2) 300 In
10

= -1381.55 cal
3- If SO2 acts as a real gas , the work will decrease because the

amount of heat transfer part of it go to resist the attraction force

and the rest do work….

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Example (18 ) :-

Calculate the amount of heat transfer in Calory required to

increase the volume of matter 1 cm3 against pressure 1 atm at

constant temp ?

Solution;-

Q= ?
2022/2023 2022/2023 2022/2023

∆ V = 1Cm3
P=1 atm
W = P∆
U∝ 𝑇
∆ T = 0.0
∆ U =0.0
∆U = q –W
∴ 𝒒 = 𝒘 = 𝑷∆ 𝒗
𝑞 = 𝑃∆ 𝑣 = 1 atm .1cm3
30504101603434 30504101603434 30504101603434
1L = 1000 cm 3
q= 1 atm. cm3
1𝐿
q= 1 atm. cm3 x 1000 𝑐𝑚3

q =0.001 atm .L
𝑐𝑎𝑙 𝐿.𝑎𝑡𝑚
2 𝑔𝑚𝑜𝑙𝑒 °𝑘 = 0.082 𝑔𝑚𝑜𝑙𝑒 °𝑘

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𝑐𝑎𝑙
2 𝑔𝑚𝑜𝑙𝑒 °𝑘
q = 0.001 L. atm x 0.082 𝑙.𝑎𝑡𝑚
𝑔𝑜𝑚𝑙𝑒 °𝑘

q = 0.024 cal

Example (19)

Calculate the work done when 1 mole of ideal gas expands from
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

initial volume 10 L to final volume 20 L at 25 ℃ in erg ??

Solution:-

W = ??
n= 1mole
V1 = 10 L
V2 = 20 L
T = 25 ℃ + 273 = 298 °𝐾
𝒗
W= nR T In 𝒗𝟐
𝟏

20
W= 1 (2) ( 298 ) In 10
2022/2023 2022/2023 2022/2023
4.182 𝑗𝑜𝑢𝑙𝑒 107 𝑒𝑟𝑔
=2x 298 In 2 cal x × 1 𝐽𝑜𝑢𝑙𝑒
1 𝑐𝑎𝑙
10
= 1.73 x 10 erg
1 cal = 4.182 joule
1 joule = 10 7 erg

Example (20) :-

Find the mathematical equation which used to Calculate the work

done by 1 mole of real gas that obey Vander vall equation when
30504101603434 30504101603434 30504101603434
expands at constant temperature from volume V1 to final volume V2?

Solution:
𝒂
(V2- n b ) (P + V2 ) = n R T

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Where:-

a and b are constant

𝒂 𝐧𝐑𝐓
( P+ 𝒗 ) = 𝒗−𝒏𝒃
𝟐

𝒏𝑹𝑻 𝒂
P=[ - ]
𝒗−𝒂𝒃 𝒗𝟐
𝒗𝟐
∴𝒘 = ∫ 𝑷𝒅𝒗
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

𝒗𝟏
𝒗 𝒏𝑹𝑻 𝒂
∴ 𝑾 = ∫𝒗 𝟐 [ 𝒗−𝒏𝒃 − ]dv
𝟏 𝒗𝟐
𝒗𝟐 𝒏𝑹 𝑻 𝒂 𝒗𝟐 𝒂
W= ∫𝒗𝟏 - ∫ dv
𝑽−𝒏𝒃 𝒗𝟐 𝒗 𝟏 𝒗𝟐
𝒗 𝒅𝒗 𝒗
∴ 𝑾 = 𝒏 𝑹 𝑻 ∫𝒗 𝟐 𝒗−𝒏𝒃- a ∫𝒗𝟏 𝒗 −𝟐 𝒅 𝒗
𝟐
𝟏

𝒗 𝒗−𝟏
W= 𝒏𝑹𝑻 [𝑰𝒏 (𝒗 − 𝒃)] ∫𝒗 𝟐 − 𝒂 [ −𝟏 ]
𝟏

(𝒗𝟐−𝒏𝒃 ) 𝟏 𝟏
𝑾 = 𝒏𝑹𝑻 [𝒍𝒏 +𝒂 [ − ] ]
(𝒗𝟏−𝒏𝒃 ) 𝒗𝟐 𝒗𝟐 +
𝒗𝟐−𝒏𝒃 𝟏 𝟏
𝑾 = 𝒏𝑹𝑻 𝑰𝒏 ( )+ 𝒂 [ − ]
𝒗𝟏 − 𝒏𝒃 𝒗𝟐 𝒗𝟏

2022/2023 2022/2023 2022/2023

Example (21) :-

find the work done by 1 mole of chlorine when expands at constant

temperature 50℃ from volume 1 L to final volume 50 L :-

1) if the chlorine acts as ideal gas

2) if the chlorine acts as real gas

a= 6.493
30504101603434 b= 0.05 30504101603434 30504101603434

solution:-

1) if CL2 acts as ideal gas :-

𝑣
W= nR T In 𝑣2
1

50
W= 1 (0.082) (50 + 273) In 1

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W=103.61 atm.L
2) if cl2 acts as real gas :-
𝒗 𝟏 𝟏
3) 𝑾 = 𝒏𝑹𝑻 𝑰𝒏 (𝒗 𝟐−𝒏𝒃 ) + 𝒂 [𝒗 − 𝒗 ]
−𝒏𝒃 𝟏 𝟐 𝟏

50−1(0.056) 1 1
W= 1 (0.082) ( 50+273) In[ 1−1 (0.056) ]+ 6.493 [50 − 1]

W =98.747 atm.L

Adiabatic Expansion or contraction of ident gas :

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

isolated = a didactic + Q X

SYSTEM

-Q X

Adiabatic changes mean that:-

It is the process in which the system does not gain or loss heat

. It is isolated system
2022/2023 2022/2023 2022/2023

Some definitions:-

1) reservoir :- any body that can supply or absorb finite amount

of heat without any change in temperature :-

2) heat engine: it I a special device that converts the heat into

work

3) Thermal Efficiency
30504101603434 30504101603434 30504101603434

Thermal
𝑵𝒆𝒕 𝑾𝒐𝒓𝒌 𝑶𝒖𝒕𝒑𝒖𝒕
Efficiency=
𝑵𝒆𝒕 𝒉𝒆𝒂𝒕 𝒊𝒏𝒑𝒖𝒕

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𝑾𝒏𝒆𝒕 ,𝒐𝒖𝒕
M th =
𝑸𝒊𝒏

Wnet, out = Qin – Qout

Where:
Mth, thermal efficiency
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Wnet, out: net work out

Qin: heat input

Qout: heat output

Example (22):

Heat is transferred to a heat engine from a furnace at a rate 80 kJ /

hr. if the rate waste heat rejection to a near river is 50 kJ /hr

Determine the net work output and the thermal efficiency for
2022/2023 2022/2023 2022/2023

the heat engine?

solution :-

80 K J / hr = Q in Q out = 50 k J / hr
heat engine

Wnet, out = Qin – Qout

W net,out
30504101603434= 80-50= 30 kJ /hr 30504101603434 30504101603434

𝑾𝒏𝒆𝒕 ,𝒐𝒖𝒕 𝟑𝟎
M th = =
𝑸𝒊𝒏 𝟖𝟎

M th = 0.375 = 37.5%

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Second law of Thermodynamic

Kelvin –Planck Clausius

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Statement Statement

Related to related to

Heat engine refrigerator

pump

Kelvin – Planck statement of second law of thermodynamic:

It is impossible for any device that operates on a cycle to receive

heat
2022/2023from a single reservoir and2022/2023
produce net amount net amount of
2022/2023

work

(No heat engine can have thermal efficiency 100%)

Clausius statement for the second law of thermodynamic:-

It is impossible to construct advice that operates an a cycle and

produces no effect other than the transfer of heat from a lower

30504101603434 30504101603434 30504101603434
temperature Body to a higher temperature Body without doing a

work.

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Wnet out

heat
Q in Q out
Engin
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

work

law high
refrigerato
temp. Temp
Q in r or Q out
heat past Body
body

Q in ≠ 𝐐𝒐𝒖𝒕

2022/2023 2022/2023 2022/2023

Third law of thermodynamic :-

As the system approaches absolute zero all the processes cease

and the entropy of the system approaches a minimum value this the

minimum value entropy is not necessarily zero although it is zero for

a perfect crystal ……
30504101603434 30504101603434 30504101603434
Heat engines:

It is special device which converts the heat into work require to use.

The heat engines can be characterize by the following :-

1) They receive heat from a high temperature source

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2) They convert part of this heat to work

3) They reject the remaining waste heat to low temperature sink

4) They operate on cycle

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Example of Heat Engines is Carnet Cycle:

Determination of efficiency

The heat engine used in Carnot cycle consists of cylinder with

piston and containing ideal gas Ideal gas

Cylinder piston

2022/2023 2022/2023 2022/2023

30504101603434 30504101603434 30504101603434

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The Carnot Cycle

No heat engine can be more efficient than a reversible heat engine working
between the same temperature limits.

Sadi Carnot (1824) showed that the most efficient possible cycle is one in
which all the heat supplied is supplied at one fixed temperature, and all
the heat rejected is rejected at a lower fixed temperature.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

The cycle therefore consists of two isothermal processes joined by two

adiabatic processes. Since all the processes are reversible, then the
adiabatic processes in the cycle are also isentropic. This is shown below on
a T-s diagram.

2022/2023 2022/2023 2022/2023

30504101603434 30504101603434 30504101603434

𝑞2
∆ s1 =
𝑇2

∆ s2 = 0.0
−𝑞1
∆ s3 =
𝑇1

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∆ s4 = 0.0
∆ stotal = 0.0 = ∆ s1 +∆ s2 +∆ s3+∆ s4
𝑞2 −𝑞1
0.0 = + 0.0 + + 0.0
𝑇2 𝑇1
𝒒𝟐 𝒒𝟏
0.0 = -
𝑻𝟐 𝑻𝟏
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

𝒒𝟏 𝒒𝟐
=
𝑻𝟏 𝑻𝟐
1) 𝒒𝟏 𝑻𝟏
=
𝒒𝟏 𝑻𝟐

𝒒𝟏 𝑻
= 𝑻𝒍
𝒒𝟏 𝑯

TH : - temperature of the high temperature reservoir

TL :- temperature of the law temperature reservoir

𝑾𝒏𝒆𝒕 ,𝒐𝒖𝒕
Thermal efficiency = Mth = 𝑸𝒊𝒏
𝒒𝟐− 𝒒𝟏
Mth =
2022/2023 2022/2023 2022/2023
𝒒𝟐
𝒒 𝒒𝟏
Mth =𝒒𝟐 -
𝟐 𝒒𝟐
𝒒𝟏
= 1-𝒒 (2)
𝟐

𝑻𝟏 𝑻 𝑻𝟏
Mth = 1 - = 𝑻𝟐 -
𝑻𝟐 𝟐 𝑻𝟐
𝑻𝟐 − 𝑻𝟏
Mth= 𝑻𝟐

𝑻 𝑯 − 𝑻𝑳
Mth=
𝑻𝑯

30504101603434 30504101603434 30504101603434

Carnot Cycle Composed of four reversible processes two iso thermal

process and two adiabatic process

1) reversible isothermal expansion :-

The ideal gas expand and absorbs heat ( q2) at constant temperature ( T2 ) .
the change in entropy ∆ S1

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𝒒𝟐
∆ S1 =
𝑻𝟐

2) reversible adiabatic expansion :-

The temperature drops from T2 to 𝑇1 the ideal gas expands in an adiabatic
process
Q 2 = 0.0 , ∆ S2 = 0.0
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

3) reversible isothermal compression:-

The ideal gas compressed and reject heat ( -q1) at constant temperature ( T1
) . the change in entropy ∆ S3
−𝒒𝟏
∆ S3 =
𝑻𝟏

4) reversible adiabatic compression :-

The temperature rises up from T1 to 𝑇2 and the ideal gas compressed in an adiabatic
process
∴ Q 4 = 0.0
, ∆ S4 = 0.0
2022/2023 2022/2023 2022/2023
Example (23)

Compare between the efficiency of two heat engine one of them used water

and the other used mercury , where the temperature of high temperature

reservoir is the boiling point of them at atmospheric pressure ( B.pt of H2o =

100℃ and B.pt of Hg = 357℃ ) and the law temperature resrvor 25 ℃ in bath

of them ?

Solution :-
30504101603434 30504101603434 30504101603434

𝑇2 = 100℃ 𝑇2 = 357℃
Heat engine Heat engine

Water Hg
𝑇1 = 25 ℃ 𝑇1 = 25℃

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𝑻 𝟐 − 𝑻𝟏
Mth =
𝑻𝟐
( 𝟏𝟎𝟎+𝟐𝟕𝟑 )−(𝟐𝟓+𝟐𝟕𝟑 )
MH2o = ( 𝟏𝟎𝟎+𝟐𝟕𝟑)
= 0.201= 20.1 %
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

( 𝟑𝟓𝟕+𝟐𝟕𝟑 )–(𝟐𝟓−𝟐𝟕𝟑 ) 𝟔𝟑𝟎−𝟐𝟒𝟖

MHg = ( 𝟑𝟓𝟕+𝟐𝟕𝟑)
=
𝟔𝟑𝟎

=0.527= 52.7 %
MH2o < MHg

Practice Exercise

1. Which of these species has the highest entropy (S) at 25C?

A. CH3OH(l) B. CO(g) C. MgCO3(s) D. H2O(l) E. Ni(s)

2. Which of these species has the highest

2022/2023
entropy (S) at 25C?
2022/2023 2022/2023
A. CO(g) B. CH4(g) C. NaCl(s) D. H2O(l) E. Fe(s)

3. Arrange these compounds in order of increasing standard molar entropy at

25C: C3H8(g), C2H4(g), ZnS(s), and H2O(l).
A. ZnS(s) < H2O(l) < C3H8(g) < C2H4(g)
B. C2H4(g) < H2O(l) < C3H8(g) < NaCl(s)
C. ZnS(s) < C3H8(g) < C2H4(g) < H2O(l)
D. C3H8(g) < C2H4(g) < H2O(l) < ZnS(s)
E. ZnS(s) < H2O(l) < C2H4(g) < C3H8(g)

4. Arrange the following substances in the order of increasing entropy at

25C.
30504101603434 30504101603434 30504101603434

A. SiF4(g) < SiH4(g) < NaF(s) < HF(g) < Al(s)

B. HF(g) < Al(s) < NaF(s) < SiF4(g) < SiH4(g)
C. Al(s) < NaF(s) < HF(g) < SiH4(g) < SiF4(g)
D. Al(s) < HF(g) < NaF(s) < SiF4(g) < SiH4(g)
E. NaF(s) < Al(s) < HF(g) < SiF4(g) < SiH4(g)

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5. Which response includes all the following processes that are accompanied
by an increase in entropy?

A. 1, 2, 3, 4 B. 1, 2 C. 2, 3, 4 D. 3, 4 E. 1, 4

6. Which response includes all of the following processes that are

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

accompanied by an increase in entropy?

A. 1, 2 B. 1, 3 C. 3, 4 D. 3 E. 2, 4

7. Without reference to a table, arrange these reactions according to

increasing S.

A. 1 < 3 < 2 B. 2 < 3 < 1 C. 2 < 1 < 3

D. 3 < 2 < 1
2022/2023 E. 3 < 1 < 2022/2023
2 2022/2023

8. Arrange these reactions according to increasing S.

A. 1 < 2 < 3 B. 2 < 3 < 1 C. 3 < 2 < 1

D. 2 < 1 < 3 E. 1 < 3 < 2

9. Determine S for the reaction SO3(g) + H2O(l) → H2SO4(l).

30504101603434 30504101603434 30504101603434

A. 169.2 J/K·mol B. 1343.2 J/K·mol C. -169.2 J/K·mol

D. -29.4 J/K·mol E. 29.4 J/K·mol

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10. Calculate S for the reaction SO2(s) + NO2(g) → SO3(g) + NO(g).

A. 53.6 J/K·mol B. -53.6 J/K·mol C. -22.2 J/K·mol

D. 474.8 J/K·mol E. -474.8 J/K·mol
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

30504101603434 30504101603434 30504101603434

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11. Calculate S at 25C for the reduction of PbO(s), 2PbO(s) + C(s) →
2Pb(s) + CO2(g) given these absolute entropies:

A. +198.8 J/K·mol B. +488.0 J/K·mol C. +353.6 J/K·mol

D. -203.3 J/K·mol E. +203.3 J/K·mol
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

12. HI has a normal boiling point of -35.4C, and its Hvap is 21.16 kJ/mol.
Calculate the molar entropy of vaporization (Svap).
A. 598 J/K·mol B. 68.6 J/K·mol C. 75.2 J/K·mol
D. 0.068 J/K·mol E. 89.0 J/K·mol

13. The entropy change on vaporization (Svap) of a compound or element is :

A. always negative. B. always positive
.C. sometimes positive and sometimes negativ

14. A negative sign for G indicates that, at constant T and P,

A. the reaction is exothermic.
B. the reaction is endothermic.
C. the reaction is fast.
2022/2023 2022/2023 2022/2023
D. the reaction is spontaneous.
E. S must be > 0

15. Calculate G for the reaction 3NO2(g) + H2O(l) → 2HNO3(l) + NO(g).

A. 8.7 kJ/mol B. 192 kJ/mol C. -414 kJ/mol

D. -192 kJ/mol E. -155 kJ/mol

30504101603434 30504101603434 30504101603434

16. Ozone (O3) in the atmosphere can react with nitric oxide (NO):
O3(g) + NO(g) → NO2(g) + O2(g).
Calculate the G for this reaction at 25C. (H = -199 kJ/mol, S = -4.1
J/K·mol)
A. 1020 kJ/mol B. -1.22  103 kJ/mol
C. 2.00  103 kJ/mol D. -1.42  103 kJ/mol E. -198 kJ/mol

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17. Sodium carbonate can be made by heating sodium bicarbonate:

2NaHCO3(s) → Na2CO3(s) + CO2(g) + H2O(g)
Given that H = 128.9 kJ/mol and G = 33.1 kJ/mol at 25C, above what
minimum temperature will the reaction become spontaneous under standard
state conditions?
A. 0.4 K B. 3.9 K C. 321 K D. 401 K E. 525 K

18. The element oxygen was prepared by Joseph Priestley in 1774 by heating
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

mercury(II) oxide: HgO(s) → Hg(l) + (1/2)O2(g), H = 90.84 kJ/mol.

Estimate the temperature at which this reaction will become spontaneous
under standard state conditions.

A. 108 K B. 430 K C. 620 K D. 775 K E. 840 K

19. For the reaction H2(g) + S(s) → H2S(g), H = -20.2 kJ/mol and S =
+43.1 J/K·mol. Which of these statements is true?
A. The reaction is only spontaneous at low temperatures.
B. The reaction is spontaneous at all temperatures.
C. G becomes less favorable as temperature increases.
D. The reaction is spontaneous only at high temperatures.
E. The reaction is at equilibrium at 25
2022/2023
C under standard conditions
2022/2023 2022/2023

20. The normal freezing point of ammonia is -78C. Predict the signs of H,
S, and G for ammonia when it freezes at -80C and 1 atm: NH3(l) → NH3(s)

A. A
30504101603434 B. B C. C D. D E. E
30504101603434 30504101603434

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22. At 1500C the equilibrium constant for the reaction

CO(g) + 2H2(g) CH3OH(g) has the value Kp = 1.4  10-7. Calculate G
for this reaction at 1500C.
A. 105 kJ/mol B. 1.07 kJ/mol C. -233 kJ/mol
D. -105 kJ/mol E. 233 kJ/mol

23. Calculate Kp at 298 K for the reaction SO2(g) + NO2(g) → SO3(g) +

NO(g).
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

A. 6.99  10-7 B. 5.71  10-8 C. 14.2 D. 475 E. 1.42  106

24. The equilibrium constant at 427C for the reaction N2(g) +

3H2(g) 2NH3(g) is Kp = 9.4  10-5. Calculate the value of G for the
reaction under these conditions.
A. -33 kJ/mol B. -54 kJ/mol
C. 54 kJ/mol D. 33 kJ/mol E. 1.3 J/mol
2022/2023 2022/2023 2022/2023

25. Determine the equilibrium constant Kp at 25C for the reaction N2(g) +
3H2(g) 2NH3(g)
( (NH3(g)) = -16.6 kJ/mol)
A. 1.52  10-6 B. 6.60  105
C. 8.28  10-2 D. 2.60 E. 13.4

26. Calculate the equilibrium constant for the decomposition of water,

2H2O(l) 2H2(g) + O2(g) at 25C, given that (H2O(l)) = -237.2
kJ/mol.
A. 0.83 B. 6.3  10-84
C. 2.5  10-42 D. 1.6  1083 E. 4.7  105
30504101603434 30504101603434 30504101603434

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27. Nitrosyl chloride (NOCl) decomposes at elevated temperatures according

to the equation 2NOCl(g) 2NO(g) + Cl2(g). Calculate Kp for this reaction
at 227C.
(For this reaction H = 81.2 kJ/mol, S = 128 J/K·mol)
A. 1.59  10-2 B. 2.10  10-7
C. 62.8 D. 4.90  106 E. 3.20  109

28. The equilibrium constant for the reaction AgBr(s) Ag+(aq) + Br- (aq)
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

is the solubility product constant, Ksp = 7.7  10-13 at 25C. Calculate G for
the reaction when [Ag+] = 1.0  10-2 M and [Br-] = 1.0  10-3 M. Is the
reaction spontaneous or nonspontaneous at these concentrations?
A. G = 69.1 kJ/mol, nonspontaneous
B. G = -69.1 kJ/mol, spontaneous
C. G = 97.5 kJ/mol, spontaneous
D. G = 40.6 kJ/mol, nonspontaneous
E. G = -97.5 kJ/mol, nonspontaneous

29. For the reaction 2C(graphite) + H2(g) → C2H2(g), G= +209.2 kJ/mol at
25C. If P(H2) = 100. atm, and P(C2H2) = 0.10 atm, calculate G for this
reaction.
A. +207.8 kJ/mol B. +226.3 kJ/mol
C. +192.1 kJ/mol
2022/2023 D. +17.3 kJ/mol
2022/2023 E. -16.9 kJ/mol
2022/2023

30. Determine the equilibrium constant (Kp) at 25C for the reaction CO(g) +
H2O(g) CO2(g) + H2(g). G = -28.5 kJ/mol.
A. 2.9  10 -60 B. 1.0  10-4
C. 1.2 D. 1.0  105 E. 3.4  1059

31. Kw for the auto-ionization of water, H2O(l) → H+(aq) + OH- (aq), is 1.0 
10-14. What are the signs (+/-) of S and H for the reaction at 25C?
A. S = (+) and H = (+) B. S = (+) and H = (-)
C. S = (-) and H = (+) D. S = (-) and H = (-)

32. A spontaneous endothermic reaction

30504101603434
always
30504101603434 30504101603434

A. causes the surroundings to get colder.

B. bursts into flame.
C. requires a spark to initiate it.
D. releases heat to the surroundings.

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33. The reaction rates of many spontaneous reactions are actually very slow.
Which of these statements is the best explanation for this observation?
A. Kp for the reaction is less than one.
B. The activation energy of the reaction is large.
C. G for the reaction is positive.
D. Such reactions are endothermic.
E. The entropy change is negative.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

34. The solubility product constant at 25C for AgI(s) in water has the value
8.3  10-17. Calculate Grxn at 25C for the process AgI(s) Ag+(aq) + I-
(aq) where [Ag+] = 9.1  10-9 and [I-] = 9.1  10-9.
A. +4.4 kJ/mol B. +91.7 kJ/mol
C. 0.0 kJ/mol D. -91.7 kJ/mol E. -4.4 kJ/mol

35. Calculate G for the combustion of ethanol vapor, C2H5OH(g), at 750C
in oxygen to form carbon dioxide and water vapor. The following data is valid
at 25C:

A. -1407 kJ/mol B. -2151 kJ/mol

2022/2023 2022/2023 2022/2023

C. -1307 kJ/mol D. -4486 kJ/mol E. -1377 kJ/mol

36. Find the temperature at which the reaction N2O4(g) 2NO2(g) will be
in equilibrium when both gases are present at partial pressures of 1.00 atm.

A. 300C B. 28C C. 55C D. 32C E. 562C

37. Predict the normal boiling point of triethylborane (C6H15B) using the
following data:
30504101603434 30504101603434 30504101603434

A. 92C B. -21C C. 21C D. 365C E. 256C

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38. A sample of solid naphthalene is introduced into an evacuated flask. Use

the data below to calculate the equilibrium vapor pressure of naphthalene
(C10H8) in the flask at 35C.

A. 890. mmHg B. 0.21 mmHg

C. 696 mmHg D. 0.086 mmHg E. 833 mmHg
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

39. The standard free energy of formation of gaseous hydrogen iodide is

1.30 kJ/mol at 25C. Find Kp for the reaction H2(g) + I2(s) 2HI(g) at this
temperature.
A. 7.0 B. 7100 C. 1.0 D. 2.4 E. 2.9

40. Find the temperature at which Kp = 4.00 for the reaction

N2O4(g) 2NO2(g).
[Given: at 25C, for NO2(g), = 33.85 kJ/mol, S = 240.46 J/mol·K; for
N2O4(g), = 9.66 kJ/mol, S = 304.3 J/mol·K; assume that H and S
are independent of temperature.]
A. 197C B. 56C C. 36C D. 79C E. 476C

41. Find
2022/2023 the temperature at which K2022/2023
p = 42.0 for the reaction H2(g) +
2022/2023

I2(g) 2HI(g).
[Given: at 25C, for H2(g), = 0, S = 131.0 J/mol·K; for I2(g), =
62.26 kJ/mol, S = 260.6 J/mol·K; for HI(g), = 25.9 kJ/mol, S = 206.3
J/mol·K; assume that H and S are independent of temperature.]
A. 1040 K B. 168 K C. 539 K D. 1400 K E. 34,200 K

42. For the reaction HCONH2(g) NH3(g) + CO(g), Kc = 4.84 at 400 K. If

H for this reaction is 29 kJ/mol, find Kc at 500 K.
A. 5.8 B. 0.17 C. 27 D. 0.88 E. 10.3

43. In the gas phase, formic acid forms a dimer,

2HCOOH(g)
30504101603434
(HCOOH)2(g). For this reaction, H = -60.130504101603434
30504101603434
kJ/mol and
G = -13.9 kJ/mol at 25C. Find the equilibrium constant (Kp) for this
reaction at 75C.
A. 8960 B. 273 C. 0.120 D. 8.33 E. 1.12  10-4

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44. In the gas phase, methyl isocyanate (CH3NC) isomerizes to acetonitrile

(CH3CN),
H3C-NC (g) H3C-CN (g)
with H = -89.5 kJ/mol and G = - 73.8 kJ/mol at 25C. Find the
equilibrium constant for this reaction at 100C.
A. 1.68  10-10 B. 5.96  109
C. 2.16  1010 D. 4.63  10-11 E. 8.64  1012
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

45. Which species will have the greatest absolute entropy at 25C?
A. Ne(g) B. C2H2(g) C. H2O(l) D. C2H5OH(l) E. C4H10(g)

46. Which species will have the lowest absolute entropy at 25C?
A. C2H5OH(l) B. C2H2(g)
C. C3H8(g) D. C3H7OH(l) E. C2H6(g)

47. For the reaction CuS(s) + H2(g) H2S(g) + Cu(s),

(CuS) = -53.6 kJ/mol
(H2S) = -33.6 kJ/mol
(CuS) = -53.1 kJ/mol
(H2S) = - 20.6 kJ/mol
Will this reaction proceed spontaneously at 298 K and 1 atm pressure?
2022/2023 2022/2023 2022/2023

48. For the reaction CuS(s) + H2(g) H2S(g) + Cu(s),

(CuS) = -53.6 kJ/mol
(H2S) = -33.6 kJ/mol
(CuS) = -53.1 kJ/mol
(H2S) = - 20.6 kJ/mol
Calculate the value of the equilibrium constant (Kp) for this reaction at 298 K.

49. For the reaction CuS(s) + H2(g) H2S(g) + Cu(s),

(CuS) = -53.6 kJ/mol
(H2S) = -33.6 kJ/mol
30504101603434 (CuS) = -53.1 kJ/mol 30504101603434 30504101603434
(H2S) = -20.6 kJ/mol
Calculate G at 798 K and 1 atm pressure (assume S and H do not
change with temperature).

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50. For the reaction CuS(s) + H2(g) H2S(g) + Cu(s),

(CuS) = -53.6 kJ/mol
(H2S) = -33.6 kJ/mol
(CuS) = -53.1 kJ/mol
(H2S) = -20.6 kJ/mol
Calculate the value of the equilibrium constant (Kp) at 798 K and 1 atm
pressure.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

51. For the reaction SbCl5(g) SbCl3(g) + Cl2(g),

(SbCl5) = -334.34 kJ/mol
(SbCl3) = -301.25 kJ/mol
(SbCl5) = -394.34 kJ/mol
(SbCl3) = -313.80 kJ/mol
Will this reaction proceed spontaneously at 298 K and 1 atm pressure?

52. For the reaction SbCl5(g) SbCl3(g) + Cl2(g),

(SbCl5) = -334.34 kJ/mol
(SbCl3) = -301.25 kJ/mol
(SbCl5) = -394.34 kJ/mol
2022/2023 (SbCl3) = -313.80 kJ/mol 2022/2023 2022/2023

Calculate the value of the equilibrium constant (Kp) for this reaction at 298
K.

53. For the reaction SbCl5(g) SbCl3(g) + Cl2(g),

(SbCl5) = -334.34 kJ/mol
(SbCl3) = -301.25 kJ/mol
(SbCl5) = -394.34 kJ/mol
(SbCl3) = -313.80 kJ/mol
Calculate G at 800 K and 1 atm pressure (assume S and H do not
change with temperature).
30504101603434 30504101603434 30504101603434

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54. For the reaction SbCl5(g) SbCl3(g) + Cl2(g),

(SbCl5) = -334.34 kJ/mol
(SbCl3) = -301.25 kJ/mol
(SbCl5) = -394.34 kJ/mol
(SbCl3) = -313.80 kJ/mol
Calculate the value of the equilibrium constant (Kp) at 800 K and 1 atm
pressure.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

55. Assuming S and H do not vary with temperature, at what
temperature will the reaction shown below become spontaneous?

C(s) + H2O(g) → H2(g) + CO(s) (S = 133.6 J/K·mol; H = 131.3

kJ/mol)

56. Rubidium has a heat of vaporization of 69.0 kJ/mol at its boiling pt

(686C). Calculate S for this process, Rb(l) → Rb(g), at 1 atm and 686C.
57. The free energy of formation of nitric oxide, NO, at 1000 K (roughly the
temperature in an automobile engine during ignition) is about 78 kJ/mol.
Calculate the equilibrium constant Kp for the reaction N2(g) +
O2(g)
2022/2023
2NO(g) at this temperature.
2022/2023 2022/2023

58. Predict the sign of S for the reaction O2(g) → 2O(g).

59. Predict the sign of S for the process N2(g, 10 atm) → N2(g, 1atm).

60. Predict the sign of S for the reaction 6CO2(g) + 6H2O(g) → C6H12O6(g)
+ 6O2(g).

61. What is the free energy change for the reaction SiO2(s) + Pb(s) →
PbO2(s) + Si(s)?
30504101603434 30504101603434 30504101603434
(PbO2) = -217 kJ/mol
(SiO2) = -856 kJ/mol

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62. Is the reaction SiO2(s) + Pb(s) → PbO2(s) + Si(s) spontaneous?

(PbO2) = -217 kJ/mol
(SiO2) = -856 kJ/mol
63. For a certain reaction, G = 87 kJ/mol, H = 100 kJ/mol at STP. At
what temperature, in K, is the reaction in equilibrium, assuming that S and
H are temperature-independent?

64. The heat of vaporization of water is 2.27 kJ/g. What is Svap per mole at
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

the normal boiling point?

65. Calculate the free energy of formation of NaBr(s) given the following
information:

NaBr(s) → Na(s) + (1/2)Br2(l), G = 349 kJ/mol

66. The following reaction is nonspontaneous at 25C:

Cu2O(s) → 2Cu(s) + (1/2)O2(g), G = 141 kJ/mol

If S = 75.8 J/K·mol, what is the lowest temperature at which the reaction
will be spontaneous?
2022/2023 2022/2023 2022/2023

67. For the reaction 3H2(g) + N2(g) 2NH3(g), Kc = 9.0 at 350C.

Calculate Kp.
68. For the reaction 3H2(g) + N2(g) 2NH3(g), Kc = 9.0 at 350C.
Calculate G at 350C.

69. For the reaction 3H2(g) + N2(g) 2NH3(g), Kc = 9.0 at 350C. In

what direction does this reaction proceed at 350C under standard state
conditions?

70. For the reaction 3H2(g) + N2(g)30504101603434

30504101603434
2NH3(g), Kc = 9.0 at 30504101603434
350C. What is
the value of G at this temperature when 1.0 mol NH3, 5.0 mol N2, and 5.0
mol H2 are mixed in a 2.5 L reactor?

71. For the reaction 3H2(g) + N2(g) 2NH3(g), Kc = 9.0 at 350C. In what
direction does the reaction proceed when 1.0 mol NH3, 5.0 mol N2, and 5.0
mol H2 are mixed in a 2.5 L reactor?

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72. Consider the reaction CO(g) + 2H2(g) CH3OH(l) at 25C.

(CO) = -137.3 kJ/mol
(CH3OH) = -166.3 kJ/mol
(CO) = -110.5 kJ/mol
(CH3OH) = -238.7 kJ/mol
S (CO) = 197.9 J/K·mol
S (CH3OH) = 126.8 J/K·mol
Calculate G at 25C.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

73. Consider the reaction CO(g) + 2H2(g) CH3OH(l) at 25C.

(CO) = -137.3 kJ/mol
(CH3OH) = -166.3 kJ/mol
(CO) = -110.5 kJ/mol
(CH3OH) = -238.7 kJ/mol
S (CO) = 197.9 J/K·mol
S (CH3OH) = 126.8 J/K·mol
Calculate value of the equilibrium constant (Kp) for this reaction at 25C.

74. Consider the reaction CO(g) + 2H2(g) CH3OH(l) at 25C.

(CO) = -137.3 kJ/mol
2022/2023 (CH3OH) = -166.3 kJ/mol2022/2023 2022/2023

(CO) = -110.5 kJ/mol

(CH3OH) = -238.7 kJ/mol
S (CO) = 197.9 J/K·mol
S (CH3OH) = 126.8 J/K·mol
Calculate S(H2(g)).

75. For the reaction H2O2(g) → H2O(g) + (1/2)O2(g), H = -106 kJ/mol and
S = 58 J/K·mol at 25C. Calculate G for this reaction at this temperature.

76. For the reaction H2O2(g) → H2O(g) + (1/2)O2(g), H = -106 kJ/mol and
S = 58 J/K·mol at 25C. Is H2O2(g) stable with respect to dissociation into
water vapor and oxygen gas at 25C?
30504101603434 30504101603434 30504101603434

77. How does the entropy change when a solid is melted?

78. How does the entropy change when a liquid is vaporized?

79. How does the entropy change when a molecular solid is dissolved in
water?

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80. How does the entropy change when a gas is liquified?

81. Choose the substance with the higher entropy per mole at a given
temperature: O2(g) at 5 atm or O2(g) at 0.5 atm.

82. Choose the substance with the higher entropy per mole at a given
temperature: Br2(l) or Br2(g).
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

83. Choose the substance with the higher entropy per mole at a given
temperature: 1 mole of N2(g) in a 22.4 L container or 1 mole of N2(g) in a
2.24 L container.

84. Choose the substance with the higher entropy per mole at a given
temperature: CO2(g) or CO2(aq).

85. Hvap for ethanol is 38.7 kJ/mol at its boiling point (78C). What is Ssurr
when 1.00 mole of ethanol is boiled?

86. Given the following data, calculate the boiling point of HCOOH (formic
acid).
2022/2023 2022/2023 2022/2023

87. At 700 K, the equilibrium constant for the reaction CO(g) +

H2O(g) CO2(g) + H2(g) is 5.10. What is G for this reaction at this
temperature?

88. For a given substance the entropy

30504101603434
always increases in the 30504101603434
30504101603434
following
order:
S (gas) < S (liq) < S (solid).
True False

89. The entropy change S for the reaction NH4Cl(s) → NH3(g) + HCl(g) will
be negative.
True False

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Fertilizers
2022/2023 2022/2023 2022/2023

Chapter 3
30504101603434 30504101603434 30504101603434

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Definition of Fertilizers:
 A fertilizer or fertiliser (in British English) is any material of natural
or synthetic origin which is applied to soils to supply one or more plant
nutrients essential to the growth of plants.

 Fertilizers enhance the growth of plants.

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Fertilizer production

1. UREA

Urea (NH2CONH2) or carbamide is an organic compound has two —NH2

groups joined by a carbonyl (C=O) functional group.

Raw materials

1- NH3
2- CO2
2022/2023 2022/2023 2022/2023

Reaction

30504101603434 30504101603434 30504101603434

1.1 Urea Processes

Once – Through

Partial recycle

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Total recycle (All new plants)

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Partial Recycle Process

Part of the off – gas is recycled back to the reactor.

The
2022/2023amount of ammonia is reduced to 15% to that of once through
2022/2023 2022/2023 that
must be used in other processes.

Investment cost is somewhat lower than the total recycle process,

30504101603434 30504101603434 30504101603434

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Total Recycle Processes

All unconverted NH3 and CO2is recycled back to the reactor (99%
conversion).

No nitrogen co-product is necessary.

Most flexible urea process as it depends only NH3 and CO2 supply.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Most expensive in investment and operating cost.

Classification of Total recycle Processes

Reactor outlet contains UREA, NH3, CO2, H2O, and CARBAMATE which
must be decomposed before recycle.

2022/2023 2022/2023 2022/2023

Three major design considerations:

• to separate the urea from other constituents,

• to recover excess NH3 and
• decompose the carbamate for recycle.

30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

30504101603434 30504101603434 30504101603434

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Urea is always made in an ammonia plant because it produces CO2 as by

product, which can be used directly without further treatment.

Two reactions are involved in the manufacture of urea.

- First ammonium carbonate is formed under pressure by highly

exothermic reaction between carbon dioxide and ammonia
- Second the endothermic decomposition reaction.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Unconverted carbon dioxide and ammonia, along with undecomposed

carbamate, must be recovered and reused.

The synthesis is further complicated by the formation of a dimer called

biuret, NH2CONHCONH2.H2O which must be kept low because it
adversely affects the growth of some plants.

Granulation

Granular urea has gained importance since it minimize air pollution

granules has higher strength larger sizes and is more compatible with
other granular fertilizers.

2. PHOSPHOROUS

Elemental
2022/2023 phosphorus exists in two major forms
2022/2023 2022/2023

White phosphorus

Red phosphorus,

PHOSPHATE ROCK

Phosphate rock is a natural mineral found in the form of sedimentary rocks

containing various amounts of calcium phosphates.

Purification

Calcium
30504101603434 phosphate is obtained 30504101603434
after removal of various impurities present
30504101603434

in phosphate rock.

The up grading of ore and removal of impurities is carried out by

Floatation of phosphate rock.

Clays , quartz and silicates , carbonates , phosphates bearing iron and

aluminum are the common impurities which are associated with phosphate
rock.

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Froth floatation is a widely used technique in the phosphate industry.

Froth floatation is generally employed with siliceous ores.

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

In the floatation of phosphate ores, apatite particles are generally directly

transferred to the froth fraction (direct floatation) by using anionic
collectors such as fatty acids.

The
2022/2023 anionic collectors selectively 2022/2023
attach themselves to the phosphate
2022/2023
particles, render them hydrophobic and lift them to the surface by the
froth and air bubbles formed.

The mineral bearing froth may simply overflow the cells or paddles or may
be skimmed off.

Quartz and other silicates are removed from the bottom of the floatation
cells.

A second stage of floatation may be required to remove silica from the

phosphate-rich float by cationic collectors (usually amines), when silica is
floated and the phosphate particles settle to the underflow.

Several treatments have been proposed,

30504101603434 30504101603434
including floatation, calcination,
30504101603434

acid washing, magnetic separation and heavy media separation for the
removal of free carbonates from the phosphates

2.1 YELLOW PHOSPHORUS

Raw materials

Calcium phosphate, Sand, Coke

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Reaction

2Ca3(PO4)2 + 10C + 6SiO2 ‫→ــ‬ CaSiO3 + P4 + 10CO

Rock phosphate is crushed as fine powder,

Complete transformation to phosphorous pentoxide (P2O5) and finally

element phosphorous is possible.

The powdered rock phosphate is mixed with sand and coke powder in
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

the required proportion and charged into electric furnace having

electrodes at bottom.

The base of furnace is heated with carbon blocks as the temperature

increases due to electrical heating.

Reaction of rock phosphate with sand starts at about 11500C resulting

into calcium silicate and P2O5.

Further increasing the temperature to 15000C carbon particle reacted

with P2O5 there by phosphorous and carbon monoxide formed which is
collected from top outlet.

Residual calcium silicate settles down at bottom in form of slag which

is taken out time to time from the outlet provided at bottom of the
furnace.
2022/2023 2022/2023 2022/2023

Product gases which is mixture of phosphorous and carbon monoxide

is cooled in a water cooler thereby phosphorous solidify and carbon
monoxide gas is separated.

Purification of phosphorous is carried out by melting it and treating

with chromic acid (mixture of K2Cr2O7 and H2SO4).

The carbon and silicon impurities are removed due to oxidation.

Pure phosphorous which is pale yellow colour is washed with water

before it is casted into sticks.
30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Recovery of the products

The fumes emerging from the furnace are first freed from any mineral
and other fine reagents.
2022/2023 2022/2023 2022/2023

The remaining gases consist of phosphorous, CO and SiF4, are sent to a

bottom of tower in which water is sprayed from two different heights.

Care should be taken that temperature should not drop below 600C.

The phosphorous condenses out but does not solidify, is collected

under water which reacts with the SiF4 gas, converting into metasilicic and
fluorosilicic acids.

The
30504101603434 fluorinated components 30504101603434
are subsequently recovered 30504101603434
from the
solution.

CO which is completely freed from phosphorous and fluorine compounds is

then cooled, dried and subsequently used as a fuel.

The slags consisting of CaSiO3, which are produced in the furnace and
subsequently discharged from outlet provided at base of furnace, are good
additives for cements,

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Air-port runway construction and antiskid conglomerates.

The liquid phosphorous, after decolouration with activated carbon is

filtered and solidify to yellow phosphorous. It is stored under water.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2-2. RED PHOSPHORUS

2022/2023 Raw material,2022/2023

Yellow phosphorous 2022/2023

Batch process

Yellow phosphorous obtain from earlier process is taken into iron pot
provided with safety outlet and thermometer jackets.

Conversion of yellow phosphorous to red phosphorous is exothermic

reaction and strict maintenance of temperature in range 2400C to 2500C in
required as conversion do not take place below 2400C and above 2500C
accident chances are there.

After complete conversion product is washed with NaOH solution as

yellow phosphorous is soluble but red phosphorous is not soluble in NaOH
30504101603434 30504101603434 30504101603434
Continuous process

In the process liquid white phosphorous is maintained at boiling point

for 5-6hrs to achieve 35 to 50% conversion.

The product is taken into screw conveyer in which unreacted

phosphorous vaporizes which is recrystallize and recycled.

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The red phosphorous is of high purity and therefore doesn't require

further purification.

3. SUPERPHOSPHATE

Superphosphate, Ca(H2PO4)2, phosphate and concentrated sulfuric acid.

Equal amounts of the two ingredients are thoroughly mixed, dried and
cured. The hardened mass is either ground or granulated.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

The monocalcium phosphate of single superphosphate dissolves in the

soil moisture and the roots absorb phosphoric acid in that form.

Raw Materials

Calcium phosphate , Sulfuric acid , Water

2022/2023 2022/2023 2022/2023

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

3.1 The manufacture of superphosphate involves following steps

a)
2022/2023 Preparation of phosphate rock
2022/2023 2022/2023

Phosphate rock is finely ground.

Grinding of phosphate rock to fine powder has following advantages

1- Increase the rate of reaction

2- Less sulfuric acid is needed
3- The increase in the ratio of CaO:P2O5 raises the consumption of
sulfuric acid per unit of P2O5 and decreases the grade.
4- Silica has no adverse effect and higher chloride content in the
phosphate rock is acceptable.

b) Mixing with acid

30504101603434 30504101603434 30504101603434

A finely ground phosphate rock is mixed with sulfuric acid in a cone mixer.

The commercial concentrated sulfuric acid (77 to 98 %) is diluted to

around 68 to 75% before reacting with the rock.

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c) Curing and drying of the original slurry by completion of the

reactions

The fluid material from the cone mixer goes to a den where it solidifies
owing to a continued reaction and crystallization of monocalcium
phosphate.

The superphosphate is removed from the den after 0.5 to 4 hours.

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

It is still at temperature of about 100°C and plastic in nature.

d) Excavation, milling, and bagging of the finished product

The product from the den is sent to storage piles for final curing of 2 to
6 weeks.

During curing, the free acid, moisture and the unreacted rock content
decreases, whereas the available water-soluble phosphorus content
increases.

The cured product is crushed in a hammer mill or cage mill to a size of

about 6 mesh.

e) Granulation

2022/2023When granular superphosphate is required, the product is granulated

2022/2023 2022/2023
before or after curing.

Granulation before curing is advantageous as it requires less steam or

water.

After granulation, the product is dried in a direct contact drier and

screened.

Super phosphate is manufactured by

1. Batch process

2. Continuous process
30504101603434 30504101603434 30504101603434
1. Batch - den process

Rock phosphate and sulfuric acid in correct quantities are added to a

pan mixer of 1 to 2 tons capacity.

After mixing for 2 minutes, the fluid slurry is discharged into a box den
which has 10 to 40 ton capacity.

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When the den is filled completely after 1 hour, it is moved slowly to a

mechanical cutter which removes thin slices of product to the conveyor.

Some plants have two dens, which are used alternatively. This set up
gives a production rate of 40 tons per hour.

2. Continuous-den process:

Ground phosphate rock is fed by a weigh feeder into a double-conical

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

mixer, where it is thoroughly mixed with metered quantities of sulfuric

acid.

The acid and water are fed into the cone mixer to provide the
necessary mixing with the phosphate rock.

The sulfuric acid is dilute with water in the cone.

The heat of dilution of the sulfuric acid serves to maintain proper

reaction temperature, and excess heat is dissipated by evaporation of
extra water added.

The fresh superphosphate is discharged from the cone mixer into a pug
mill, where additional mixing takes place and the reaction starts.

From the pug mill the superphosphate drops onto the den conveyor, which
has a very low travel speed to allow
2022/2023
about 1hr for solidifying before
2022/2023 2022/2023

reaching the cutter.

The conveyers den is enclosed so that fumes do not escape into the
working area.

These fumes are scrubbed will water sprays to remove acid and
fluoride before being exhausted to the atmosphere.

Scrubber water is neutralized by passing through the limestone bed.

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

4. AMMONIUM PHOSPHATE

Ammonium phosphate ((NH4)3PO4) also known as ammonium

orthophosphate is the salt of ammonia and phosphoric acid.
2022/2023 2022/2023 2022/2023

It consists of ammonium cations and phosphate anion.

It is water soluble and the aqueous solution on boiling losses ammonia.

Raw Materials

Ammonia, Phosphoric acid

Reactions

30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

The two principal steps are

a) Neutralizationm b) Granulation

a) Neutralization

Quantities of phosphoric acid and ammonia in the neutralization step

are different form mono ammonium
2022/2023 phosphate (MAP) and diammonium
2022/2023 2022/2023

phosphate (DAP).

Phosphoric and ammonia are added to the first of three continuous

mixed reactors, anhydrous ammonia is added beneath the slurry level in
the first neutralizer in an amount equivalent to 80% neutralization.

Further ammonia is added in the 2nd and 3rd tanks to obtain

conversion to the diammonium salt if a higher nitrogen containing fertilizer
is needed.

The exothermic reaction heats the slurry nearly to the boiling point
(130°C).
30504101603434 30504101603434 30504101603434
Unreacted and excess NH3 vapor is collected from the top of each tank
and recharged below the liquid level for reducing NH3 losses (less than
3%).

The hot slurry containing about 16 to 20% water is pumped into the
granulator, where more ammonia is added to increase the molar ratio to
approximately 2.0.

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b) Granulation

Slurry from the third neutralized is mixed with KCl and absorbed in a
bed of dry recycle fertilizer moving through a rotating drum granulator.

This provides a tumbling action to coal recycle material with a slurry

film.

A rotary adiabatic drier reduces the moisture to less than 1%, with 10
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

minute contact time with air initially at 1500C.

Dried product is separated into three fractions on a double deck screen.

Nitrophosphate Fertilizers

The Mixed-Acid Process for preparation of Nitrophosphates

Phosphate Rock Digestion and Ammoniation

The first step of the process is the digestion of phosphate rock with
nitric acid, which results in a solution of phosphoric acid and calcium
nitrate (first reactor).

Ca(PO4)2 + 6HNO3 → 3Ca(NO3)2 + 2H3PO4 + 22.25 kcal

In the second reactor the overflow from the first reactor is ammoniated,
2022/2023 2022/2023 2022/2023
and scrubber liquor is added.

Reactions.

HNO3 + NH3 → NH4NO3 + 22.27 kcal

H3PO4 + 2NH3 → (NH4)2 HPO4 + 33.52 kcal

2H3PO4 + Ca(NO3)2 + 4NH3 →CaHPO4 + (NH4)2 HPO4 + 2NH4NO3

+ 66.67 kcal

The third reactor provides for final Ammoniation of overflow from the
second reactor.

Phosphoric
30504101603434 and sulfuric acids are added and the KCl dissolved
30504101603434 (when NPK
30504101603434

is produced).

If sulfuric acid is introduced, the sulfate ions induce the precipitation of

calcium sulfate

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following the reaction:

Ca(NO3)2 + H2SO4 → 2HNO3 + CaSO4 + 9.37 kcal

This calcium sulfate can be removed by filtration, but generally it is left in

the slurry

After neutralization other components, e.g., ammonium phosphates,

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

superphosphates, ammonium sulfate and compounds containing

potassium and magnesium, may be added.

Most of these materials may also be added before or during neutralization,

but if the raw material contains chloride, the pH-value of the slurry should
be 5-6 to avoid development of hydrogen chloride.

Granulation and Drying

The slurry in the buffer tank typically contains about 10% of water and
the temperature is about 140°C.

Granulation and drying occur simultaneously in a combined granulator-

dryer called a Spherodizer®.

2022/2023 Screening,
Crushing, and Recycle Handling Product sized 2-4
2022/2023 mm is
2022/2023
separated from the granulator discharge by screens.

The oversize material is crushed and recycled with undersize to the

granulator.

Nutrient recovery From Gas Streams

A multistage scrubbing system captures fumes from the reactors and any
dust that escapes the cyclones.

The nutrient content of the scrubber liquor increases as it moves counter

currently through the reactor gas scrubbing

system
30504101603434 to the granulator exhaust gas scrubber.
30504101603434 30504101603434

Three main macronutrients in the fertilizers :

• Nitrogen (N)
• Phosphorus (P)
• Potassium (K)

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Fertilizers are classified in many ways.

1- They are classified according to whether they provide a single nutrient

(say, N, P, or K),

as "straight fertilizers.“

Or "Multinutrient fertilizers" (or "complex fertilizers") provide two or more

nutrients, for example N and P.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2- Fertilizers are also sometimes classified as inorganic or organic.

Inorganic are sometimes called synthetic fertilizers since various chemical

treatments are required for their manufacture

Example(1):

Calculate the weight of pure H2SO4 And phosphate ore required to

produce 1000kg from H3PO4 and calculate the weight of gypsum
produced ,Assuming that the phosphate ore is 100% tri-calcium
phosphate?

(P=31 , Ca=40 ,S=32 )

Solution:
2022/2023 2022/2023 2022/2023
Ca3(PO4)2+3H2SO4+6H2O=2H3PO4+ 3CaSO4.2H2O

310 3X98 2X98 3X172

X Y 1000 Z

X= weight of phosphate ore = (1000*310)/(2*98)=1582.6kg

Ca3(PO4)2+3H2SO4+6H2O=2H3PO4+ 3CaSO4.2H2O

310 3X98 2X98 3X172

X Y 1000 Z

X= weight of phosphate ore = (1000*310)/(2*98)=1582.6kg

30504101603434 30504101603434 30504101603434

Y= weight of H2SO4= (1000* 3*98)/(2*98)=1500 kg

Z= weight of gypsum = (1000*3*172)/(2*98)=2630 kg

Practice Exercise

Repeat the previous example , If The purity of the phosphate ore

70% tri-calcium phosphate and 30% inert substances ?
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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Cement
2022/2023
Chapter 4 2022/2023 2022/2023

30504101603434 30504101603434 30504101603434

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Cement
HISTORICAL BACKGROUND

The term cement is commonly used to refer to powdered materials which

develop strong adhesive qualities when combined with water.

These materials are more properly known as hydraulic cements.

Gypsum plaster, common lime, hydraulic limes, natural pozzolana, and
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Portland cements are the more common hydraulic cements, with Portland
.cement being the most important in construction

Cement was first invented by the Egyptians. Cement was later

reinvented by the Greeks and the Babylonians who made their mortar out of
lime. Later, the Romans produced cement from pozzolana, an ash found in all
.of the volcanic areas of Italy, by mixing the ash with lime

Cement is a fine grayish powder which, when mixed with water, forms
a thick paste. When this paste is mixed with sand and gravel and allowed to
.dry it is called concrete

About ninety-nine percent of all cement used today is Portland cement.

The name Portland cement is not a brand name. This name was given to the
cement by Joseph Aspdin of Leeds, England who obtained a patent for his
product in 1824.
2022/2023 2022/2023 2022/2023

The concrete made from the cement resembled the color of the
natural limestone quarried on the Isle of Portland in the English Channel. The
balance of cement used today consists of masonry cement, which is fifty
.percent Portland cement and fifty percent ground lime rock

The first cement manufactured in the United States was produced in 1871
.by David Saylor of Coplay, Pennsylvania

:There are two types of raw materials which are combined to make cement

Lime-containing materials, such as limestone, marble, oyster shells, marl,

.chalk, etc
30504101603434 30504101603434 30504101603434

Clay and clay-like materials, such as shale, slag from blast furnaces, bauxite,
.iron ore, silica, sand, etc

It takes approximately 3,400 lbs. of raw materials to make one ton (2,000
lbs.) of Portland cement. The mixture of materials is finely ground in a raw
mill. The resultant raw mix is burned in a rotary kiln at temperatures around
4482 degrees Celsius to form clinker. The clinker nodules are then ground

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with about 3 % gypsum to produce cement with a fineness typically of less

than 90 micrometers

Defination of cement :

A cement is a binder, a substance used in construction that sets and

hardens and can bind other materials together.

The most important types of cement are used as a component in the

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

production of mortar in masonry, and of concrete- which is a combination of

cement and an aggregate to form a strong building material .

Raw materials used in the manufacture of cement:

1-Lime Stone is consider as a source of CaO

% of Ferric oxide , Silicon oxide & Aluminum oxide must be not

excide (4%)

% of MgO must be not excide 3.2%

2-Clay which is a source of Al2O3 & SiO2 and its composition is hydrous
Aluminum Silicate
2022/2023 2022/2023 2022/2023
Al2O3 . SiO2 . 2H2O

3- Other material which added to adjust the composition of the mixture such
as Sand which is added to reach % SiO2 =22% in the Cement

Iron pyrites added as a source of Iron Oxides

and Bauxite as a source of Aluminum oxides

4- Gypsum added in (2-3%) , it grind with clinker to adjust the time of

hardening of the cement

30504101603434 30504101603434 30504101603434

PRODUCTION PROCESSES:

:The production of cement takes place with several steps

• Quarrying of limestone and shale

• Dredging the ocean floor for shells
• Digging for clay and marl

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• Grinding
• Blending of components
• Fine grinding
• Burning
• Finish grinding
• Packaging and/or shipping
• Quarrying, Dredging, and Digging

Quarrying of limestone and shale is accomplished by using explosives

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

to blast the rocks from the ground. After blasting, huge power shovels are
used to load dump trucks or small railroad cars for transportation to the
.cement plant, which is usually nearby

The ocean floor is dredged to obtain the shells, while clay and marl are
dug out of the ground with power shovels. All of the raw materials are
.transported to the plant

Grinding

After the raw materials have been transported to the plant, the limestone and
shale which have been blasted out of the quarry must be crushed into smaller
pieces. Some of the pieces, when blasted out, are quite large. The pieces are
then dumped into primary crushers which reduce them to the size of a
softball. The pieces are carried by conveyors
2022/2023 2022/2023 to secondary crushers which
2022/2023
crush the rocks into fragments usually no larger than 3/4 inch across.

Blending

After the rock is crushed, plant chemists analyze the rock and raw materials
to determine their mineral content. The chemists also determine the
proportions of each raw material to utilize in order to obtain a uniform cement
product. The various raw materials are then mixed in proper proportions and
.prepared for fine grinding

Fine Grinding

When the raw materials have been blended, they must be ground into a fine
:powder. This may be done by one30504101603434
30504101603434
of two methods 30504101603434

Wet process, or Dry process

The wet process of fine grinding is the older process, having been used
in Europe prior to the manufacture of cement in the United States. This
process is used more often when clay and marl, which are very moist, are
included in the composition of the cement. In the wet process, the blended
raw materials are moved into ball or tube mills which are cylindrical rotating
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drums which contain steel balls. These steel balls grind the raw materials into
smaller fragments of up to 200 of an inch. As the grinding is done, water is
added until a slurry (thin mud) forms, and the slurry is stored in open tanks
where additional mixing is done. Some of the water may be removed from the
slurry before it is burned, or the slurry may be sent to the kiln as is and the
.water evaporated during the burning

The dry process of fine grinding is accomplished with a similar set of

ball or tube mills; however, water is not added during the grinding. The dry
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

materials are stored in silos where additional mixing and blending may be
.done

Burning

Burning the blended materials is the key in the process of making

cement. The wet or dry mix is fed into the kiln, which is one of the largest
pieces of moving machinery in the industry. It is generally twelve feet or more
in diameter and 500 feet or more in length, made of steel and lined with
firebrick. It revolves on large roller bearings and is gradually slanted with the
.intake end higher than the output end

As the kiln revolves, the materials roll and slide downward for
approximately four hours. In the burning zone, where the heat can reach
3,000 degrees Fahrenheit, the materials
2022/2023 become incandescent and
2022/2023 change in
2022/2023
color from purple to violet to orange. Here, the gases are driven from the raw
materials, which actually change the properties of the raw materials. What
emerges is “clinker” which is round, marble-sized, glass-hard balls which are
harder than the quarried rock. The clinker is then fed into a cooler where it is
.cooled for storage

Finish Grinding

The cooled clinker is mixed with a small amount of gypsum, which will
help regulate the setting time when the cement is mixed with other materials
and becomes concrete. Here again there are primary and secondary grinders.
The primary grinders leave the clinker , ground to the fineness of sand, and
the secondary grinders leave the clinker
30504101603434 ground to the fineness30504101603434
30504101603434 of flour, which
.is the final product ready for marketing

Packaging/Shipping

The final product is shipped either in bulk (ships, barges, tanker trucks,
railroad cars, etc.) or in strong paper bags which are filled by machine. In the
United States, one bag of Portland cement contains 94 pounds of cement,

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and a “barrel” weighs four times that amount, or 376 pounds. In Canada, one
.bag weighs 87 1/2 pounds and a “barrel” weighs 350 pounds

. Masonry cement bags contain only seventy pounds of cement

When cement is shipped, the shipping documents may include “sack

weights.” This must be verified by the auditor since only the cement is
.taxable. “Sack weights” must be excluded
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

FLOW CHARTS OF MANUFACTURING PROCESS

The following pages contain flowcharts of the manufacturing process of

Portland cement. The first chart represents the process in approximately
ninety percent of the plants currently in operation.

The second chart represents the process being used in approximately ten
percent of the plants currently in operations. However, the second process is
the one being adopted for virtually all new cement plants

2022/2023 2022/2023 2022/2023

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

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Typical Manufacturing Processing Flow Chart

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

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Methods of the Production of Cement :

There are two methods for production of cement .:

1-dry method

2-wet method

the two methods are differs in the ratio of the percentage of water to the
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

other materials.

The choose of the suitable method for the production depends on:

1-type and quality of the raw materials

2-the availability of the fuel.

Manufacture of Cement :

Production of cement depends on :

It takes approximately 3,400 lbs. of raw materials to make one ton (2,000 lbs.)
of Portland cement. The mixture of materials is finely ground in a ball mill.
The resultant raw mix is burned in a rotary kiln at temperatures around 4482
2022/2023 2022/2023 2022/2023

degrees Celsius to form clinker.

The clinker are then ground with about 3 % gypsum to produce cement with
a fineness typically of less than 90 micrometers.
The type of cement depends on the smoothness
The chemical activity of it is directly proportional with the surface area

1-What is the purpose of adding Gypsum in the production of

cement :
30504101603434 30504101603434 30504101603434
 Gypsum is a mineral and is hydrated calcium sulfate in chemical form. It
added in (2-3%)
 Gypsum plays a very important role in controlling the rate of hardening
of the cement. , make the cement hardening slowly
 Cement free from gypsum takes few minutes for hardening

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Effect of increasing the percentage of gypsum in cement?

Weakens the strength of the cement .

2-Effect of ferric oxide
 Its percentage is at least 3%
 It helps in burning , it lowers the temperature of burning inside the
furnace
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

 If its percentage increases , it will react with calcium forming compounds

do not have a properties of hardening
3- Effect of Calcium (lime):
 If the amount of calcium increases too much, The cement damaged and
exposed to cracking
 If the amount of calcium decreases too much , the strength of cement
decreases .
4- Effect of Aluminum oxide:

 If the amount of Al2O3 increases , the burning of cement will occur at

2022/2023 high temperature and the produced

2022/2023 cement will be fast –hardening
2022/2023 .
 If the amount of Al2O3 decreases , the hardening of the produced
cement will be very slow.

5-Effect of Silica:

If the amount of Silica (SiO2 ) increases than the required amount,

1- the strength of cement decreases and

2-the hardening of the produced cement will be very slow.

30504101603434 30504101603434 30504101603434

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Composition of Clinker:

1- Tricalcium Silicate (C3S)

(3CaO . SiO2) 25-50%

2-Dicalcium Silicate (C2S)

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

(2CaO . SiO2) 21-45%

3-Tricalcium Aluminate (C3A)

(3CaO . Al2O3) 5-11 %

4- Tetra calcium Aluminumo ferrite (C4AF)

(3CaO . SiO2) 9 -11%

5- Calcium oxide unreacted

2022/2023 2022/2023 2022/2023

6- Magnesium oxide unreacted

Reactions inside the rotary kiln (furnace) :

1-All Ferric oxide react with Al2O3 and CaO to form C4AF

2-The remaining Al2O3 react with CaO To form C3A

3- part of CaO react with SiO2 forming C2S

4- the remaining CaO react with C2S forming C3S

30504101603434 30504101603434 30504101603434

5- If any part of CaO remains , it will be CaO unreacted

6- MgO will be Unreacted

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Responsibilities:

1- The compound which is responsible for the hardening of the cement is

C3A

2- The compound which is responsible for Primary strength of Cement is C3S

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

3- The compounds which are responsible for final strength of Cement is C2S
& C3S

Hydraulic modulus=( Wt Of CaO/(Wt of SiO2 +Fe2O3 + Al2O3 ))

= 2.2 -1.8

Silica Modulus =( Wt Of SiO2/(Wt of Fe2O3+Al2O3))

=2.5-

Alumina modulus =( Wt Of Al2O3/Wt of Fe2O3)

2022/2023 2022/2023 2022/2023

=1-5

Example (1):

The Chemical Composition of a sample of cement are as the following:

( loss 0.81% , SO3 2.37% , MgO 0.79% , Fe2O3 3.11% , Al2O3 4.74% ,
SiO2 23.44% , CaO 64.74%) Calculate the weight % of the following
compounds :

30504101603434 30504101603434 30504101603434

1- the compound which responsible for the hardening of the cement

2- the compound which responsible for sea water and salt resistant

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Solution:

the compound which responsible for sea water and salt resistant is
C4AF

 4CaO. Al2O3. Fe2O3 = 4CaO + Al2O3 +Fe2O3

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

485 224 102 159

y X 3.11

% C4AF = y = 3.11*485/159 = 9.49=the weight % of the compound which

responsible for sea water and salt resistant

X= weight of Al2O3 = 3.11*102/159 =2

The remaining Al2O3= 4.74 – 2=2.74

the compound which responsible for the hardening of the cement

:C3A
2022/2023 2022/2023 2022/2023

3CaO. Al2O3 = 3CaO + Al2O3

270 168 102

Z 2.74

% C3A =Z = 2.74 *270 /102 = 7.25 % = the weight % of the compound

which responsible for the hardening of the cement

Example(2):
30504101603434 30504101603434 30504101603434

The Chemical Composition of a sample of cement are as the following:

( loss 3.7% , MgO 0.8 % , Fe2O3 3.1% , Al2O3 4.5% , SiO2 23.4% , CaO
64.5%) Calculate the weight % of the following compounds :

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1- the compound which responsible for the hardening of the cement

2- the compound which responsible for sea water and salt resistant

3-hydraulic modulus

4- Silica modulus
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

5- Alumina modulus

Solution:

the compound which responsible for sea water and salt resistant is
C4AF

4CaO. Al2O3. Fe2O3= 4CaO + Al2O3 + Fe2O3

485 224 102 159

X 3.1
2022/2023 2022/2023 2022/2023

% C4AF = 3.1*485/159 = 9.46 = the compound which responsible for sea

water and salt resistant

X= weight of Al2O3 = 3.1*102/159 =1.99

The remaining Al2O3= 4.5 – 1.99=2.51

the compound which responsible for the hardening of the cement :

C3A
30504101603434 30504101603434 30504101603434
3CaO.Al2O3 = 3CaO + Al2O3

270 168 102

x 2.51

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% C3A = 2.51 *270 /102 = 6.64 = the compound which responsible for
hardening of the cement

Hydraulic modulus=( Wt Of CaO/(Wt of SiO2+Fe2O3+Al2O3))

= ( 64.5/(23.4+3.1+4.5)) =64.5/31=2.081
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Silica Modulus =( Wt Of SiO2/(Wt of Fe2O3+Al2O3))

=( 23.4/(3.1+4.5))=23.4/7.6=3.079

Alumina modulus = ( Wt Of Al2O3/Wt of Fe2O3)

=4.5/3.1= 1.45

TYPES OF CEMENT:

The following are the types of cement that are in practice:

1-Ordinary
2022/2023 Portland Cement (OPC).
2022/2023 2022/2023

2- Rapid Hardening Portland Cement (RHPC)

3- High Alumina Cement

4-White cement

5- Blast Furnace Slag Cement

6-Sea water Cement

30504101603434 30504101603434 30504101603434
7- Low Heat Cement

1-Ordinary Portland Cement.

This cement used in the Concrete structures (ordinary – reinforced –

Prestressed )

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• It is used in bricks , roads , Airports and in the pipes and blocks )

• It is the most common one .
• It is widely used.

It is the most common type of cement in general use around the world,
used as a basic ingredient of concrete, mortar, stucco, and most non-
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

specialty grout. It was developed from other types of hydraulic lime in

England in the mid 19th century and usually originates from limestone.

It is a fine powder produced by heating materials in a kiln to form

what is called clinker, grinding the clinker, and adding small amounts of other
materials. Several types of Portland cement are available, with the most
common being called ordinary Portland cement (OPC) which is grey in color,
but a white Portland cement is also available.

Portland cement is caustic, so it can cause chemical burns. The

powder can cause irritation or, with severe exposure, lung cancer and can
contain some hazardous components such as crystalline silica and
2022/2023 2022/2023 2022/2023
hexavalent chromium. Environmental concerns are the high energy
consumption required to mine, manufacture, and transport the cement and
the related air pollution, including the release of greenhouse
gases (e.g., carbon dioxide), dioxin, NOx, SO2, and particulates.

The low cost and widespread availability of the limestone, shales, and
other naturally occurring materials used in Portland cement make it one of the
lowest-cost materials widely used over the last century throughout the world.
Concrete produced from Portland cement is one of the most versatile
construction materials available in the world.
30504101603434 30504101603434 30504101603434

2-Rapid Hardening Portland Cement (RHPC) :

1-It is similar to OPC but with higher tri-calcium silicate (C3S) content and
finer grinding.

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2-It gains strength more quickly than OPC, though the final strength is
only slightly higher.

3-It is also called as High-Early Strength Portland Cement.

4-The one-day strength of this cement is equal to the three-day strength

of OPC with the same water-cement ratio.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

3- High Alumina Cement:

1- It is produced from the burning from the lime stone and Bauxite as a
source of Aluminum oxides

2- The percentage of Aluminum oxide is 35-41%

3- The one-day strength of this cement is equal to the 28days strength of

OPC with the same water-cement ratio.

4- Resist sea water and acids

2022/2023 2022/2023 2022/2023

1- produce high temperature .

2- used in coating the muffle furnaces.

4-White Portland cement :

White Portland cement or white ordinary Portland cement (WOPC) is

similar to ordinary, grey Portland cement in all respects except for its high
degree of whiteness.

Obtaining this colour requires some modification to the method of

manufacture;
30504101603434 because of this, it is 30504101603434
somewhat more expensive than the grey
30504101603434

product. The main requirement is to have low iron content which should be
less than 0.5% expressed as Fe2O3 for white cement and less than 0.9% for
off-white cement.

It helps to have the iron oxide as ferrous oxide (FeO) which is obtained
via slight reducing conditions i.e. operating with zero excess oxygen at the

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kiln exit. This gives the clinker and cement a green tinge. Other metals such
as Cr, Mn, Ti, etc. in trace content can also give color tinges, so for a project
it is best to use cement from a single source.

 This cement is made from raw materials containing very little Iron
Oxide and Manganese Oxide.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

 These oxides influence whiteness of white Portland cement.

 It produced from China clay , together with chalk or limestone.
 t is used in combination with white aggregates to produce
white concrete for decorative work
 White Portland cement is also used in combination with inorganic
pigments (10%) to produce brightly colored concretes and mortars .

5-Blast Furnace Slag Cement:

• Portland Blast Furnace Slag Cement is particularly suitable for rivers,

ports, roads and tunnels.
•
2022/2023 It contains high percentage of2022/2023
CaO , SiO2 , Al2O3 2022/2023

• It produced by mixing OPC with blast furnace slag .

• If blast furnace slag contain :
• SiO2>CaO It Called Acidic Slag
• SiO2<CaO It Called basic Slag which is the favorite one in the
production of this type of cement

6-Sea water Cement:

• It produced by mixing lime stone with sand and Iron pyrites ,then
30504101603434
grinding and produced clinker
30504101603434 30504101603434

• Clinker is grinding with gypsum to produce Sea water cement

• It resist the sea water ,
• It used in the concrete structure which exposed to sea water &
barrier waves.

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3- Low Heat Cement:

• It dose not produce high amount of heat during setting and hardening
• It is used in mass construction works
• It is highly resistance against rupture
• Disadvantage:
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

1-its compressive strength is lower than the ordinary cement

2-It can not be used in cold weather because it will retard the setting
time than in the ordinary weather.

Green cement

Green cement is a cementation material that meets or exceeds the

functional performance capabilities of ordinary Portland cement by
incorporating and optimizing recycled materials, thereby reducing
consumption of natural raw materials, water, and energy, resulting in a more
sustainable construction material.
2022/2023 2022/2023 2022/2023

New manufacturing processes for producing green cement are being

researched with the goal to reduce, or even eliminate, the production and
release of damaging pollutants and greenhouse gasses, particularly CO2.

Growing environmental concerns and increasing cost of fuels of fossil

origin have resulted in many countries in sharp reduction of the resources
needed to produce cement and effluents (dust and exhaust gases)

Peter Trimble, a design student at the University of Edinburgh has

proposed 'DUPE' based on Sporosarcina pasteurii, a bacterium with binding
30504101603434 30504101603434 30504101603434
qualities which, when mixed with sand and urine produces a concrete said to
be 70% as strong as conventional materials.

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Electrochemistry
2022/2023
Chapter 5 2022/2023 2022/2023

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Electrochemistry
It is the branch of physical chemistry that studies the relationship
between electricity, as a measurable and quantitative phenomenon, and
identifiable chemical change, with either electricity considered an outcome of
a particular chemical change or vice-versa.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

These reactions involve electric charges moving between electrodes

and an electrolyte (or ionic species in a solution). Thus electrochemistry deals
with the interaction between electrical energy and chemical change.

When a chemical reaction is caused by an externally supplied current,

as in electrolysis, or if an electric current is produced by a spontaneous
chemical reaction as in a battery, it is called
an electrochemical reaction. Chemical reactions where electrons are
transferred directly between molecules and/or atoms are called oxidation-
reduction or (redox) reactions. In general, electrochemistry describes the
overall reactions when individual redox reactions are separate but connected
by an
2022/2023 external electric circuit and an 2022/2023
intervening electrolyte. 2022/2023

Electrochemical Reactions

In electrochemical reactions, electrons are transferred from one species to

another.

Electrochemical cells consist of two electrodes:1- an anode (the electrode at

which the oxidation reaction occurs) and 2- a cathode (the electrode at which
the reduction reaction occurs).

Oxidation and reduction (Redox)

30504101603434
The term "redox" stands for reduction-oxidation. It refers to
30504101603434 30504101603434

electrochemical processes involving electron transfer to or from

a molecule or ion changing itsoxidation state. This reaction can occur through
the application of an external voltage or through the release of chemical
energy. Oxidation and reduction describe the change of oxidation state that
takes place in the atoms, ions or molecules involved in an electrochemical

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reaction. Formally, oxidation state is the hypotheticalcharge that an atom

would have if all bonds to atoms of different elements were 100% ionic. An
atom or ion that gives up an electron to another atom or ion has its oxidation
state increase, and the recipient of the negatively charged electron has its
oxidation state decrease.

For example, when atomic sodium reacts with atomic chlorine,

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

sodium donates one electron and attains an oxidation state of +1. Chlorine
accepts the electron and its oxidation state is reduced to −1. The sign of the
oxidation state (positive/negative) actually corresponds to the value of each
ion's electronic charge. The attraction of the differently charged sodium and
chlorine ions is the reason they then form an ionic bond.

The loss of electrons from an atom or molecule is called oxidation, and

the gain of electrons is reduction. This can be easily remembered through the
use of mnemonic devices. Two of the most popular are "OIL RIG" (Oxidation
Is Loss, Reduction Is Gain) and "LEO" the lion says "GER" (Lose Electrons:
Oxidation, Gain Electrons: Reduction). Oxidation and reduction always occur
2022/2023 2022/2023 2022/2023
in a paired fashion such that one species is oxidized when another is reduced.
For cases where electrons are shared (covalent bonds) between atoms with
large differences in electronegativity, the electron is assigned to the atom
with the largest electronegativity in determining the oxidation state.

The atom or molecule which loses electrons is known as the reducing agent,
or reductant, and the substance which accepts the electrons is called
the oxidizing agent, or oxidant. Thus, the oxidizing agent is always being
reduced in a reaction; the reducing agent is always being oxidized. Oxygen is
a common
30504101603434 oxidizing agent, but not30504101603434
the only one. Despite the name, an
30504101603434

oxidation reaction does not necessarily need to involve oxygen. In fact,

a fire can be fed by an oxidant other than oxygen; fluorine fires are often
unquenchable, as fluorine is an even stronger oxidant (it has a
higher electronegativity and thus accepts electrons even better) than oxygen.

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For reactions involving oxygen, the gain of oxygen implies the oxidation of the
atom or molecule to which the oxygen is added (and the oxygen is reduced).
In organic compounds, such as butane or ethanol, the loss of hydrogen
implies oxidation of the molecule from which it is lost (and the hydrogen is
reduced). This follows because the hydrogen donates its electron in covalent
bonds with non-metals but it takes the electron along when it is lost.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Conversely, loss of oxygen or gain of hydrogen implies reduction.

Electromotive Force (e.m.f)

• The potential difference between the potential of the anode and

potential of the cathode in a cell is called the electromotive force
(e.m.f).

• It is also called the cell potential, and is designated Ecell.

Standard Reduction Potentials

Reduction potentials for many electrodes have been measured and tabulated

2022/2023 2022/2023 2022/2023

30504101603434 30504101603434 30504101603434

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Reduction
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

30504101603434 30504101603434 30504101603434

• The strongest oxidizers have the most positive reduction potentials.

The strongest reducers have the most negative reduction potentials

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

• The greater the difference between the two standard reduction potential
of the electrodes , the greater the voltage of the cell.

2022/2023 2022/2023 2022/2023

30504101603434 30504101603434 30504101603434

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Standard Hydrogen Electrode

• Their values are referenced to a standard hydrogen electrode (SHE).

• By definition, the reduction potential for hydrogen is 0 V:

2 H+ (aq, 1M) + 2 e− ⎯⎯→ H2 (g, 1 atm)

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

Galvanic cells (also called Voltaic cells)

Electrochemical cell

An electrochemical cell is a device that produces an electric current from

energy released by a spontaneous redox reaction. This kind of cell includes
the Galvanic cell or Voltaic cell, named after Luigi Galvani and Alessandro
Volta, both scientists who conducted
30504101603434
several experiments on chemical
30504101603434 30504101603434

reactions and electric current during the late 18th century.

Electrochemical cells have two conductive electrodes (the anode and the
cathode). The anode is defined as the electrode where oxidation occurs and
the cathodes the electrode where the reduction takes place. Electrodes can be
made from any sufficiently conductive materials, such as metals,

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semiconductors, graphite, and even conductive polymers. In between these

electrodes is the electrolyte, which contains ions that can freely move.

The galvanic cell uses two different metal electrodes, each in an

electrolyte where the positively charged ions are the oxidized form of the
electrode metal. One electrode will undergo oxidation (the anode) and the
other will undergo reduction (the cathode). The metal of the anode will
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

oxidize, going from an oxidation state of 0 (in the solid form) to a positive
oxidation state and become an ion. At the cathode, the metal ion in solution
will accept one or more electrons from the cathode and the ion's oxidation
state is reduced to 0. This forms a solid metal that electrodeposits on the
cathode. The two electrodes must be electrically connected to each other,
allowing for a flow of electrons that leave the metal of the anode and flow
through this connection to the ions at the surface of the cathode. This flow of
electrons is an electric current that can be used to do work, such as turn a
motor or power a light.

A galvanic cell whose electrodes are zinc and copper submerged

2022/2023 2022/2023 2022/2023
in zinc sulfate and copper sulfate, respectively, is known as a Daniell cell.

• use spontaneous chemical reactions to generate electrical energy in

the form of an electrical current  ΔG < 0

-
e

Anode Salt Bridge Cathode

-
30504101603434 30504101603434 30504101603434
+

Electrolyte, e.g. Electrolyte, e.g.

ZnSO CuSO

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Most batteries are made from Voltaic cells!

• Made up of two half cells

• Oxidation (loss of electrons) occurs at the negative anode

• Reduction (gain of electrons) occurs at the postive cathode

• Salt bridge acts to complete the circuit by joining the two half cells
together
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

• For the example above, the reactions occurring are:

• Anode: Zn(s) → Zn2+(aq) + 2e-

• Cathode: Cu2+(aq) + 2e- → Cu(s)

• The shorthand notation for this cell is

• Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s

Cell potentials
• The cell potential, E, is a measure of how well a cell reaction can push
and pull electrons through a circuit
• The electrical energy generated by the spontaneous reaction
• proportional to the cell potential.
2022/2023 2022/2023 2022/2023
• The standard cell potential (the cell potential measured when all the
species are in their standard states) is given by:
• Ecell = E°cathode - E°anode

Voltaic Cell:

30504101603434 30504101603434 30504101603434

• A typical cell looks like this.

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• The oxidation occurs at the anode.

• The reduction occurs at the cathode.

Electromotive Force (emf)

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

• Water only spontaneously flows one way in a waterfall.

• Likewise, electrons only spontaneously flow one way in a redox

reaction—from higher to lower potential energy.
2022/2023 2022/2023 2022/2023
Example( 1)

Which of the following statements relating to electrochemistry

are correct ?

(i) Oxidation involves the loss of electrons

(ii) Reduction involves the gain of electrons

(iii) Galvanic cells use electricity to produce chemicals

(iv) The anode in a Galvanic cell is positive

(v) Oxidation always occurs at the cathode

30504101603434 30504101603434 30504101603434

Answer: (i) and (ii)

Standard electrode potential

To allow prediction of the cell potential, tabulations of standard electrode

potential are available. Such tabulations are referenced to the standard

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hydrogen electrode (SHE). The standard hydrogen electrode undergoes the

reaction

2 H+(aq) + 2 e− → H2

which is shown as reduction but, in fact, the SHE can act as either the
anode or the cathode, depending on the relative oxidation/reduction
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

potential of the other electrode/electrolyte combination. The term

standard in SHE requires a supply of hydrogen gas bubbled through the
electrolyte at a pressure of 1 atm and an acidic electrolyte with H+ activity
equal to 1 (usually assumed to be [H+] = 1 mol/liter).

The SHE electrode can be connected to any other electrode by a salt

bridge to form a cell. If the second electrode is also at standard
conditions, then the measured cell potential is called the standard
electrode potential for the electrode. The standard electrode potential for
the SHE is zero, by definition. The polarity of the standard electrode
potential provides information about the relative reduction potential of the
electrode
2022/2023 compared to the SHE. If the electrode has a positive
2022/2023 potential
2022/2023

with respect to the SHE, then that means it is a strongly reducing

electrode which forces the SHE to be the anode (an example is Cu in
aqueous CuSO4with a standard electrode potential of 0.337 V).
Conversely, if the measured potential is negative, the electrode is more
oxidizing than the SHE (such as Zn in ZnSO4where the standard electrode
potential is −0.76 V).

Example ( 2 ):

The standard potential of

30504101603434
the Ag+/Ag electrode is30504101603434
30504101603434
+0.80 V and
the standard potential of the cell Fe(s)|Fe2+(aq)||Ag+(aq)|Ag(s)
is +1.24 V. What is the standard potential of the Fe2+/Fe
electrode?

Half reactions Fe → Fe2+ + 2e- Anodic reaction

Ag+ + e- → Ag Cathodic reaction

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E˚cell = Ecathode - Eanode

Eanode = Ecathode - E˚cell

Eanode = 0.80 V – 1.24 V

Eanode = -0.44 V
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

1)Oxidation reactions :

It is the reactions which produce electrons (loss electron or more )

The General form of the oxidation reaction is :

M —› M+z + Ze

Where Z express the valancy of the metal :

K —› K+ + e

Cu —› Cu++ + 2e

Al —› Al +++ + 3e

2) Reduction reactions:
2022/2023 2022/2023 2022/2023
It is the reactions which gain one electron ( or more )

The General form of the reduction reaction is :

M+z + Ze —› M

Where Z express the valancy of the metal :

K+ + e —› K

Cu++ + 2e —› Cu

Al +++ + 3e —› Al

30504101603434 30504101603434 30504101603434

Types of the electrodes :

There are three types of the electrode :

1) First Type :

It consists of metallic rode immersed in solution of its salt such as :

cupper rode immersed in cupper sulphate solution :

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General form : M/M++

e.g. Zn/Zn++ , Cu/Cu++ , Al/ Al+++

It can be used as the anode in the electrolytic cell :

Zn —› Zn++ + 2 e

Cu —› Cu++ + 2e
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Al —› Al +++ + 3e

But in case of using it as the cathode :

Zn++ + e —› Zn

Cu++ + 2e —› Cu

Al +++ + 3e —› Al

2) Second Type :

It consists of metallic rode coated with slightly soluble salt and

immersed in solution salt shared with the slightly soluble salt in
the negative ion .

2022/2023
The general form of the electrode
2022/2023
: 2022/2023

M /MX(s) / X-

Ag / Ag Cl(s) / H Cl

It can be used as the anode in the electrolytic cell :

Ag —› Ag+ + e

Ag+ + Cl- —› Ag Cl (s)

--------------------------------

Ag + Cl- —› Ag Cl (s) + e
30504101603434 30504101603434 30504101603434
But in case of using it as the cathode :

Ag+ + e —› Ag

Ag Cl (s) —› Ag+ + Cl-

--------------------------------

Ag Cl (s) + e —› Ag + Cl-

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3) Third Type :
It is known as oxidation reduction electrode (Redox electrode) , It
consists of rode of noble metals ( gold or platinum ) do not
corrosive , this rode immersed in solution contain oxidation
reduction salts .
e.g.
(Pt) M+n , M+m
(Pt) Fe++ , Fe+++
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

(Pt) Sn+2 , Sn +4

It can be used as the anode in the electrolytic cell :

Sn+2 —› Sn+4 + 2e

Also ,It can be used as the cathode in the electrolytic cell :

Sn+4 + 2e —› Sn+2

Standard Cell Potentials

The cell potential at standard conditions can be found through this

equation:
2022/2023
Ecell = Ered (cathode) − Ered (anode)
2022/2023 2022/2023

Because cell potential is based on the potential energy per unit of

charge, it is an intensive property.

Cell Potentials

For the oxidation in this cell

Ered = −0.76 V

• For the reduction,

• Ered = +0.34 V
30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Cell Potentials

Ecell = Ered (cathode) − Ered (anode)

= +0.34 V − (−0.76 V)
2022/2023 2022/2023 2022/2023

= +1.10 V

Free Energy Change

G for a redox reaction can be found by using the equation

G = −nFE

where:

n : is the number of moles of electrons transferred, and

F : is a constant, the Faraday.

30504101603434 30504101603434 30504101603434

1 F = 96,485 C/mol = 96,485 J/V-mol

E: potential difference

Free Energy
Under standard conditions,

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G = −nF E°cell

Where :

E°cell is the standard cell potential

Relationship between Gibbs Free Energy and Equilibrium

constant:

ΔG° = - RT lnK
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

ΔG for a reaction depends on the concentration by:

ΔG = ΔG° + RT ln Q

where : Q = [product]

[reactant]

But ΔG = -n F Ecell and

ΔG° = - n F E°cell

-nFEcell = -nFE°cell + RT ln Q

Dividing across by nF gives :

2022/2023
Ecell = E°cell – (RT/ nF) ln Q
2022/2023 2022/2023

Nernst Equation

Nernst equation:

𝑅𝑇
𝐸 = 𝐸𝑂 − ln 𝑄
𝑛𝐹

or, using base-10 logarithms,

2.303 𝑅𝑇
𝐸 = 𝐸𝑂 − ln 𝑄Q
log
𝑛𝐹
30504101603434 30504101603434 2.303 𝑅𝑇 30504101603434
At room temperature (25C = 25+273 = 298 K), = 0.0592 V
𝐹

Thus the equation becomes

0.0592
𝐸 = 𝐸𝑂 − ln 𝑄 Q
log
𝑛

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Example (3):

If the standard cell potential at 298 K is 1.10 V for the following

reaction Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s), then what is the
change in Gibbs Free Energy?

ΔG° = -n F E°cell

Half reactions: Zn → Zn2+ + 2e-

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Cu2+ + 2e- → Cu

n = no of moles of electrons = 2

F = Faradays constant = 96,500 C/mol

E°cell = 1.10 V = 1.10 J/C

ΔG° = - (2) (96500 C/mol) (1.10 J/C)

= - 212300 J/mol

= - 212.3 kJ/mol

Example(4):
2022/2023 2022/2023 2022/2023

The equilibrium constant for the reaction

Ni(s) + Hg2Cl2(s) → 2Hg(l) + 2Cl-(aq) + Ni2+(aq)
is 1.8 × 1019 at 298K. What is the value of the standard cell
potential E°cell for this reaction?

ΔG° = -RT ln K

= - (8.314 J K-1 mol-1) (298 K) ln (1.8 × 1019)

= - 109847.8 J mol-1

= - 1.098 × 105 J mol-1

ΔG° = -n F E°cell
30504101603434 30504101603434 30504101603434

E°cell = -ΔG°

nF

= -(-1.098 × 105 J mol-1) = 0.57 J/C = 0.57 V

(2 mol) (96500 C)

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Example ( 5 ):

Write the type of electrode then write the reaction & Nernest
equation for the following electrode :

1) Ag |Ag 2+ ,

2) Zn |Zn++ ,

3) Al / Al+++
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Solution:

1) Ag |Ag +
First type electrode its general form M|M +z

The electrode reaction :

Ag —› Ag+ + e

Nernest equation:
𝑹𝑻 [𝑷𝒓𝒐𝒅𝒖𝒄𝒕]
e=eo - ln [𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏]
𝒁𝑭

2022/2023 𝑹𝑻 [𝐀𝐠+]
e=eo - ln
2022/2023 2022/2023
𝒁𝑭 [𝐀𝐠 ]

where : Z=1 & [Ag] =1

𝑹𝑻 [𝐀𝐠+]
e=eo - ln
𝑭 𝟏

2) Zn |Zn 2+
First type electrode its general form M|M +z

The electrode reaction :

Zn —› Zn ++ + 2 e

Nernest equation:
30504101603434 30504101603434 30504101603434

𝑹𝑻 [𝐙𝐧+]
e=eo - ln
𝒁𝑭 [𝐙𝐧 ]

where Z=2 & [Zn] =1

𝑹𝑻 [𝐙𝐧+𝟐]
e=eo - ln
𝟐𝑭 𝟏

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3) Al |Al +3
First type electrode its general form M|M +z

The electrode reaction :

Al —› Al++ + + 3 e

Nernest equation:
𝑹𝑻 [𝐀𝐥+𝟑]
e=eo - ln
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

𝒁𝑭 [𝐀𝐥 ]

where Z=3 & [Al] =1

𝑹𝑻 [𝐀𝐥+𝟑]
e=eo - ln
𝟐𝑭 𝟏

Example ( 6 ):

Write the type of electrode then write the reaction & Nernest
equation for the following electrode :

1) Ag / Ag Cl(s) / H Cl

2) Pb / PbCl2(s) / KCl

Solution:
2022/2023 2022/2023 2022/2023
1) Ag / Ag Cl(s) / H Cl

The type of this electrode is from the second type .

It is reaction :

It can be used as the anode in the electrolytic cell :

Ag —› Ag+ + e

Ag+ + Cl- —› Ag Cl (s)

--------------------------------

Ag + Cl
30504101603434
- —› Ag Cl (s) + e over all
30504101603434 cell reaction 30504101603434

Nernest equation:
𝑹𝑻 [𝑷𝒓𝒐𝒅𝒖𝒄𝒕]
e=eo - ln [𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏]
𝒁𝑭

𝑹𝑻 [𝐀𝐠 𝐂𝐥]
e=eo - ln [𝐀𝐠 ][𝐂𝐥−]
𝒁𝑭

where : Z=1 , [AgCl] = 1 & [Ag] =1

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𝑹𝑻 [𝐂𝐥−]
e=eo - ln
𝑭 𝟏

2) Pb / PbCl2(s) / KCl

The type of this electrode is from the second type .

It is reaction :

It can be used as anode or cathode in the electrolytic cell

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

In case of using it as anode :

Pb —› Pb++ + 2 e

Pb++ +2 Cl- —› Pb Cl2 (s)

--------------------------------

Pb + 2Cl- —› Pb Cl2(s) + 2e over all cell reaction

Nernest equation:
𝑹𝑻 [𝑷𝒓𝒐𝒅𝒖𝒄𝒕]
e=eo - ln [𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏]
𝒁𝑭

2022/2023 𝑹𝑻
2022/2023[𝐏𝐛 𝐂𝐥𝟐] 2022/2023
e=eo - ln [𝐏𝐛 ][𝐂𝐥−]𝟐
𝒁𝑭

where : Z=1 , [PbCl2] = 1 & [Pb] =1

𝑹𝑻 [𝐂𝐥−]𝟐
e=eo - ln
𝟐𝑭 𝟏

Example ( 7 ):

Write the type of electrode then write the reaction & Nernest
equation for the following electrode :

1) (Pt) Fe++ , Fe+++

2) (Pt) Sn+2 , Sn +4
30504101603434 30504101603434 30504101603434

1) (Pt) Fe++ , Fe+++

The type of the electrode is redox electrode (third type)

The electrode reaction :

It can be used as cathode and as anode in the electrolytic cell :

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Fe+2 <—> Fe +3 + 2e

Nernest equation:
𝑹𝑻 [𝑷𝒓𝒐𝒅𝒖𝒄𝒕]
e=eo - ln [𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏]
𝒁𝑭

𝑹𝑻 [𝐅𝐞+𝟑]
e=eo - ln [𝐅𝐞+𝟐 ]
𝒁𝑭

where : Z=1
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2) (Pt) Sn+2 , Sn +4
The type of the electrode is redox electrode (third type)

The electrode reaction :

It can be used as cathode and as anode in the electrolytic cell :

Sn+2 <—> Sn +4 + 2e

Nernest equation:
𝑹𝑻 [𝑷𝒓𝒐𝒅𝒖𝒄𝒕]
e=eo - ln [𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏]
𝒁𝑭

2022/2023 2022/2023 2022/2023

𝑹𝑻 [𝐒𝐧+𝟒]
e=eo - ln [𝐒𝐧+𝟐 ]
𝒁𝑭

where : Z=2

Example ( 8 ):

Write the type of hydrogen electrode then write the reaction &
Nernest equation for it .

(Pt) H2 , H+
The type of the electrode is from the first type
30504101603434 30504101603434 30504101603434
The electrode reaction :

It can be used as cathode and as anode in the electrolytic cell :

H2 <—> 2H+ + 2e

Nernest equation:

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𝑹𝑻 [𝑷𝒓𝒐𝒅𝒖𝒄𝒕]
e=eo - ln
𝒁𝑭 [𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏]

𝑹𝑻 [𝐇+]𝟐
e=eo - ln
𝒁𝑭 𝑷𝑯𝟐

where : Z=2 , P H2 =1
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Example ( 9 ):

Write the type of Quinhydrone electrode then write its

reaction & apply Nernest equation for it .

The type of the electrode is from the first type

The electrode reaction :

It can be used as cathode and as anode in the electrolytic cell :

QH2 <—> Q + 2H+ + 2e

Nernest equation:
𝑹𝑻 [𝑷𝒓𝒐𝒅𝒖𝒄𝒕]
e=eo -
2022/2023 ln [𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏] 2022/2023 2022/2023
𝒁𝑭

𝑹𝑻 [𝑸][𝐇+]𝟐
e=eo - ln
𝒁𝑭 [𝑸𝑯𝟐]

where : Z=2 , [Q]=QUINONE =1

[QH2 ] =Quinhydrone = 1

Example ( 10 ):

Write the type of Oxygen electrode then write the reaction &
Nernest equation for it .
30504101603434 30504101603434 30504101603434

(Pt) OH- /O2

The type of the electrode is from the first type

The electrode reaction :

It can be used as cathode or as anode in the electrolytic cell :

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4OH- <—> O2 + 2H2 O + 4e

Nernest equation:
𝑹𝑻 [𝑷𝒓𝒐𝒅𝒖𝒄𝒕]
e=eo - ln
𝒁𝑭 [𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏]

𝑹𝑻 [𝑷𝑶𝟐][𝐇𝟐𝐎]𝟐
e=eo - ln
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

𝒁𝑭 [𝟒𝑶𝑯−]𝟒

where : Z=4 , P O2 =1 , [H2 O]=1

Example ( 11 ): For the following cell:

Cd(s)|Cd2+(0.01M)||Ag+(0.01M)|Ag(s)

Find the following:

1-Write the over all cell reaction

2-calculate the e.m.f. of the cell , if you know that:

Eo oxi Ag/Ag+ =0.8 volt , Eo oxi Cd/Cd+ =0.403 volt

1- Write the over all cell reaction:

2022/2023 2022/2023 2022/2023
Half reactions Cd → Cd2+ + 2e- Anodic reaction

2 Ag+ +2 e- → 2Ag Cathodic reaction

-----------------------------------

Overall cell reaction 2Ag+ + Cd → Cd2+ + 2Ag

2- The e.m.f. of the cell:

Nernest equation:
𝑹𝑻 [𝑷𝒓𝒐𝒅𝒖𝒄𝒕]
e=eo - ln [𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏]
𝒁𝑭

30504101603434 30504101603434 30504101603434

𝑹𝑻 [𝑪𝒅++][𝐀𝐠]𝟐
e=eo - ln [𝑪𝒅][𝑨𝒈+]𝟐
𝒁𝑭

Z=2 , [Ag]=1 , [Cd] =1

E˚cell = Ecathode ,red. + Eanode ,Oxi

E˚cell = Eo(Cd/Cd++) + E˚(Ag+/Ag)

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Eo cell =- 0.40 + 0.80= 0.4 V

Eo cell = 0.4 V
𝑹𝑻 [𝟎.𝟎𝟏] 𝟎.𝟎𝟓𝟗 [𝟎.𝟎𝟏]
e=eo - ln [𝟎.𝟎𝟏]𝟐 = e=0.4 – log [𝟎.𝟎𝟏]𝟐 = 0.0332 volt
𝒁𝑭 𝟐

Exercise :

1- For the following cell:

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Ag(s)|AgBr(0.34M) / AgBr (0.34M) || Fe+++(0.1M)|Fe++(0.02M) (Pt)

Find the following:

1-Draw the cell .

2- Write the over all cell reaction

3-calculate the e.m.f. of the cell , if you know that:

Eo oxi Ag/AgBr =-0.0713 volt ,

Eo red Fe+++,Fe ++ =- 0.77 volt

2022/2023 2022/2023 2022/2023

30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Corrosion of
metals and
protection of
metals against
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Corrosion

Chapter 6
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Corrosion of metals and protection of metals against

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Corrosion

Corrosion is :

• A natural phenomenon that occurs over time.

• An electrochemical reaction (on metals)

• Happens at different rates with different metals and

in different environments
Definition of corrosion

 Corrosion is defined as the deterioration of a material, usually a metal,

because of a reaction with its 2022/2023
2022/2023
environment. 2022/2023

 Corrosion is:

A natural phenomenon that occurs over time.

30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Importance of corrosion
2022/2023 2022/2023 2022/2023

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Corrosion is a big industrial problem since it causes enormous financial losses

to industry through the following:

1-Plant shut down as a result of equipment failure.

2-Cost of the replacing the failed equipment with a new one.

3-Cost of protecting the plant against corrosion.

4-Loss of product which becomes contaminated with corrosion products .

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

5-Decrease the efficiency of the equipments owing to the deposition of

corrosion products on the surface of this equipments.

6-Loss of life e.g. boiler explosion and failure of the plant.

Classification of Corrosion

1-Chemical corrosion

Which defined as It takes place due to direct attack by acids or alkalis.

2-Electrochemical Corrosion (indirect attack)due

to the formation of Galvanic cell

2022/2023 2022/2023 2022/2023

How to predict the tendency of metal to dissolve in acids?

• according to the position in the e.m.s

• The metal lying above H2 in the e.m.s dissolve in acids(Known as active
metals because it is easy to convert from atoms into ions i.e. easy to loss
their electrons.
• -the higher the position of the metal the higher its dissolution tendency
• -Metals below H2 in the e.m.s do not dissolve in acids (known by Nobel
metals)because it is difficult to loss their electrons and convert into ions

• Na
30504101603434 30504101603434 30504101603434
• Mg
• Al
• Fe
• Zn ( active metals)
• Ni
• Sn
• Pb

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• Hydrogen ………………………………………………
• Cu
• Ag( )Nobel metal(
• Au
• Pt

Factors Influence Corrosion:

The important factors which may influence the corrosion process are:
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

a) Nature of the metal, nature of the environment and the corrosion products.

b) Temperature.

c) Concentration of electrolyte.

d) Electrode potential.

f) Aeration.

g) Agitation.

h) pH of the electrolyte.

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Corrosion Electrochemical:

 It takes place due to the formation of Galvanic cell (dissimilar metal cell
,
Oxygen concentration cells , Stress corrosion cells,….)

1-Dissimilar metal corrosion cells

• These cells are set up when two different metals become in

contact in the presence of an electrolyte

• The less Nobel metals acts as the anode and the more Nobel
30504101603434metals acts as the cathode where H2 evaluation takes
30504101603434 place.
30504101603434

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Fe Cu
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Fe / electrolyte / Cu

Anodic reaction (-ve):

Fe ----> Fe+2 + 2e

Cathodic reaction (+ve)

0.5 O2+H2O+2e --> 2OH-

Fe ion
2022/2023 combine with OH ion to form Ferrous hydroxide which
2022/2023 oxidize
2022/2023

to ferric oxide known as rust.

Examples from practice on the occurrence of corrosion by dissimilar

metal corrosion cells

1-Steel tank contain steel shaft and cupper impeller

Fe / electrolyte / Cu

Anodic reaction (-ve):

Fe ----> Fe+2 + 2e
30504101603434 30504101603434 30504101603434

Cathodic reaction (+ve)

0.5 O2+H2O+2e --> 2OH-

Fe ion combine with OH ion to form Ferrous hydroxide which oxidize to ferric
oxide known as rust.

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

2-Tank from steel with solderSn-Pb alloy:

30504101603434 30504101603434 30504101603434

3-Tank from steel with cupper pipe and Aluminum Tape:

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

• The first dissimilar metal corrosion cell formed between the cupper pipe and the
Iron Tank

Fe / electrolyte / Cu

Anodic reaction (-ve):

Fe ----> Fe+2 + 2e

2022/2023 2022/2023 2022/2023

Cathodic reaction (+ve)

0.5 O2+H2O+2e --> 2OH-

Fe ion combine with OH ion to form Ferrous hydroxide which oxidize to ferric
oxide known as rust.

• The second dissimilar metal corrosion cell formed between the cupper pipe and
the Aluminum Tape

Al / electrolyte / Cu

Anodic reaction (-ve):

Al ---->
30504101603434 Al+3 + 3e 30504101603434 30504101603434

Cathodic reaction (+ve)

0.5 O2+H2O+2e --> 2OH-

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2-Differential aeration (oxygenation)cells:

• This type of corrosion cells takes place whenever there is a

difference in the dissolved O2 conc. at metal surface :

This cell written in the form:

Fe(O2poor area) /electrolyte/ Fe(O2rich area)

Fe(O2poor area) Anodic reaction (-ve):

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Fe ----> Fe+2 + 2e

Fe(O2rich area) Cathodic reaction (+ve)

0.5 O2+H2O+2e --> 2OH-

Fe ion combine with OH ion to form Ferrous hydroxide which oxidize to ferric
oxide known as rust.

To illustrate the differential aeration cell are set up as following :

 If the dissolved O2 is removed from one compartment by passing a

steam of N2 bubbles and the galvanometer is detected the presence of
potential difference between the O2 rich compartment and the O2 poor
compartment .
2022/2023 2022/2023 2022/2023

30504101603434 30504101603434 30504101603434

Example from practice on the occurrence of corrosion by Differential

aeration (oxygenation)cells

1- Corrosion of a steel surface at the center of a drop of rain or dew.

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The center of the dew is O2 poor area(anode)where the center of the dew
are subjected to corrosion This cell written in the form:

Fe(O2poor area) /electrolyte/ Fe(O2rich area)

Fe(O2poor area) Anodic reaction (-ve):

Fe ----> Fe+2 + 2e

Fe(O2rich area) Cathodic reaction (+ve)

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

0.5 O2+H2O+2e --> 2OH-

Fe ion combine with OH ion to form Ferrous hydroxide which oxidize to ferric
oxide known as rust.

2022/2023 2022/2023 2022/2023

2- Water steel storage Tank filled with water:

• Differential aeration (oxygenation) cells are formed on the surface of the

tank near the surface of the water
• This cell written in the form:
• Fe(O2poor area) /electrolyte/ Fe(O2rich area)
• Fe(O2poor area) Anodic reaction (-ve):
Fe ----> Fe+2 + 2e
• Fe(O2rich area) Cathodic reaction (+ve):
0.5 O2+H2O+2e --> 2OH-
30504101603434 30504101603434 30504101603434
• Fe ion combine with OH- ion to form Ferrous hydroxide which oxidize to
ferric oxide known as rust.

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O2rich area
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

O2poor area

Tank filled with water

3-Corrosion of buried (underground) steel pipe line passing through

soils of different porosity:

 Differential aeration cell are formed between the high porosity sand
soil (O2 rich area) and the low permeability clay soil (O2 poor area)

Fe(O2poor area) /electrolyte/ Fe(O2rich area)

Fe(O2poor area) Anodic reaction (-ve):

Fe ----> Fe+2 + 2e
2022/2023 2022/2023 2022/2023

Fe(O2rich area) Cathodic reaction (+ve) :

0.5 O2+H2O+2e --> 2OH-

Fe ion combine with OH ion to form Ferrous hydroxide which oxidize to ferric
oxide known as rust.

30504101603434 30504101603434 30504101603434

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Surface of the soil

---------------------------------------------------------
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Steel pipe in

high porosity sand

soil (O2 rich area) Steel pipe in

the low permeability

clay soil (O2 poor area)

3- Differential strain cell:

• This type of corrosion cells takes place when there is a

difference in the degree of stain between two locations on the
metallic structure .the strained part act as anode and the
2022/2023 2022/2023 2022/2023
unstrained part acts as a cathode .

fabrication or welding

unstrained part strained part

30504101603434 30504101603434 30504101603434

Fe(stained area) /electrolyte/ Fe(unstained area)

Fe(stained area) Anodic reaction (-ve):

Fe ----> Fe+2 + 2e

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Fe(unstained area) Cathodic reaction (+ve)

0.5 O2+H2O+2e --> 2OH-

Fe ion combine with OH ion to form Ferrous hydroxide which oxidize to ferric
oxide known as rust.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

4-Pitting corrosion:

Certain conditions, such as low concentrations of oxygen or high

2022/2023 2022/2023 2022/2023
concentrations of species such as chloride which complete asanions, can
interfere with a given alloy's ability to re-form a passivating film. In the worst
case, almost all of the surface will remain protected, but tiny local fluctuations
will degrade the oxide film in a few critical points. Corrosion at these points
will be greatly amplified, and can cause corrosion pits of several types,
depending upon conditions.

While the corrosion pits only nucleate under fairly extreme

circumstances, they can continue to grow even when conditions return to
normal, since the interior of a pit is naturally deprived of oxygen and locally
30504101603434 30504101603434 30504101603434
the pH decreases to very low values and the corrosion rate increases due to
an autocatalytic process. In extreme cases, the sharp tips of extremely long
and narrow corrosion pits can cause stress concentration to the point that
otherwise tough alloys can shatter; a thin film pierced by an invisibly small
hole can hide a thumb sized pit from view.

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These problems are especially dangerous because they are difficult to

detect before a part or structure fails. Pitting remains among the most
common and damaging forms of corrosion in passivated alloys , but it can be
prevented by control of the alloy's environment.

Pitting results when a small hole, or cavity, forms in the metal, usually
as a result of de-passivation of a small area. This area becomes anodic, while
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

part of the remaining metal becomes Cathodic, producing a localized galvanic

reaction.

The deterioration of this small area penetrates the metal and can lead to
failure. This form of corrosion is often difficult to detect due to the fact that it
is usually relatively small and may be covered and hidden by corrosion-
produced compounds.

5-Crevice corrosion:

2022/2023 2022/2023 2022/2023

Corrosion in the crevice between the tube and tube sheet (both made of type
316 stainless steel) of a heat exchanger in a seawater desalination plant.[4]
30504101603434 30504101603434 30504101603434

Crevice corrosion is a localized form of corrosion occurring in confined

spaces (crevices), to which the access of the working fluid from the
environment is limited. Formation of a differential aeration cell leads to
corrosion inside the crevices. Examples of crevices are gaps and contact areas

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between parts, under gaskets or seals, inside cracks and seams, spaces filled
with deposits and under sludge piles.

Crevice corrosion is influenced by the crevice type (metal-metal, metal-

nonmetal), crevice geometry (size, surface finish), and metallurgical and
environmental factors. The susceptibility to crevice corrosion can be evaluated
with ASTM standard procedures. A critical crevice corrosion temperature is
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

commonly used to rank a material's resistance to crevice corrosion.

6-High-temperature corrosion (Sulfidation):

High-temperature corrosion is chemical deterioration of a material

(typically a metal) as a result of heating.

This non-galvanic form of corrosion can occur when a metal is subjected

to a hot atmosphere containing oxygen, sulfur, or other compounds capable
of oxidizing (or assisting the oxidation of) the material concerned. For
example, materials used in aerospace, power generation and even in car
2022/2023 2022/2023 2022/2023
engines have to resist sustained periods at high temperature in which they
may be exposed to an atmosphere containing potentially highly corrosive
products of combustion.

The products of high-temperature corrosion can potentially be turned to

the advantage of the engineer. The formation of oxides on stainless steels, for
example, can provide a protective layer preventing further atmospheric
attack, allowing for a material to be used for sustained periods at both room
and high temperatures in hostile conditions. Such high-temperature corrosion
products, in the form of compacted30504101603434
30504101603434
oxide layer glazes, prevent30504101603434
or reduce
wear during high-temperature sliding contact of metallic (or metallic and
ceramic) surfaces.

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7-Microbial corrosion:

Microbial corrosion, or commonly known as microbiologically influenced

corrosion (MIC), is a corrosion caused or promoted by microorganisms,
usually chemoautotrophs. It can apply to both metallic and non-metallic
materials, in the presence or absence of oxygen.

Sulfate-reducing bacteria are active in the absence of oxygen

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

(anaerobic); they produce hydrogen sulfide, causing sulfide stress cracking. In

the presence of oxygen (aerobic), some bacteria may directly oxidize iron to
iron oxides and hydroxides, other bacteria oxidize sulfur and produce sulfuric
acid causing biogenic sulfide corrosion. Concentration cells can form in the
deposits of corrosion products, leading to localized corrosion.

Corrosion removal (Rust removal)

Often it is possible to chemically remove the products of corrosion. For

example, phosphoric acid in the form of naval jelly is often applied to ferrous
tools or
2022/2023 surfaces to remove rust. Corrosion
2022/2023 removal should not be confused
2022/2023

with Electropolishing, which removes some layers of the underlying metal to

make a smooth surface. For example, phosphoric acid may also be used to
electropolish copper but it does this by removing copper, not the products of
copper corrosion.

Resistance to corrosion:

Some metals are more intrinsically resistant to corrosion than others (for
some examples, see galvanic series). There are various ways of protecting
metals from corrosion (oxidation) including painting, hot dip galvanizing, and
30504101603434 30504101603434 30504101603434
combinations of these.

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Intrinsic chemistry
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Gold nuggets do not naturally corrode, even on a geological time scale.

The materials most resistant to corrosion are those for which corrosion
is thermodynamically unfavorable. Any corrosion products
of gold or platinum tend to decompose spontaneously into pure metal, which
is why these elements can be found in metallic form on Earth and have long
been valued. More common "base" metals can only be protected by more
temporary means.

Some metals have naturally slow2022/2023

2022/2023
reaction kinetics, even though their
2022/2023

corrosion is thermodynamically favorable. These include such metals

as zinc, magnesium, and cadmium. While corrosion of these metals is
continuous and ongoing, it happens at an acceptably slow rate. An extreme
example is graphite, which releases large amounts of energy upon oxidation,
but has such slow kinetics that it is effectively immune to electrochemical
corrosion under normal conditions.

Passivation

Passivation
30504101603434 refers to the spontaneous formation of an ultrathin
30504101603434 film of
30504101603434

corrosion products, known as a passive film, on the metal's surface that act as
a barrier to further oxidation. The chemical composition and microstructure of
a passive film are different from the underlying metal. Typical passive film
thickness on aluminum, stainless steels, and alloys is within 10 nanometers.
The passive film is different from oxide layers that are formed upon heating

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and are in the micrometer thickness range – the passive film recovers if
removed or damaged whereas the oxide layer does not. Passivation in natural
environments such as air, water and soil at moderate pH is seen in such
materials as aluminum, stainless steel, titanium, and silicon

Pitting corrosion:
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Certain conditions, such as low concentrations of oxygen or high

concentrations of species such as chloride which complete as anions, can
interfere with a given alloy's ability to re-form a passivating film. In the worst
case, almost all of the surface will remain protected, but tiny local fluctuations
will degrade the oxide film in a few critical
2022/2023 2022/2023
points. Corrosion at these points
2022/2023

will be greatly amplified, and can cause corrosion pits of several types,
depending upon conditions.

While the corrosion pits only nucleate under fairly extreme

circumstances, they can continue to grow even when conditions return to
normal, since the interior of a pit is naturally deprived of oxygen and locally
the pH decreases to very low values and the corrosion rate increases due to
an autocatalytic process. In extreme cases, the sharp tips of extremely long
and narrow corrosion pits can cause stress concentration to the point that
otherwise
30504101603434 tough alloys can shatter;30504101603434
a thin film pierced by an invisibly small
30504101603434

hole can hide a thumb sized pit from view.

These problems are especially dangerous because they are difficult to

detect before a part or structure fails. Pitting remains among the most
common and damaging forms of corrosion in passivated alloys , but it can be
prevented by control of the alloy's environment.

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Pitting results when a small hole, or cavity, forms in the metal, usually
as a result of de-passivation of a small area. This area becomes anodic, while
part of the remaining metal becomes Cathodic, producing a localized galvanic
reaction.

The deterioration of this small area penetrates the metal and can lead to
failure. This form of corrosion is often difficult to detect due to the fact that it
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

is usually relatively small and may be covered and hidden by corrosion-

produced compounds.

Methods of protecting metals against corrosion:

 I-Coating:

1- Inorganic coating

• _enamel (glassy layer)

• -Cement coating
• -Oxidation
• -Organic coating
•
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-Temporary Coating (coating with lubricating oil or Vaseline
2022/2023
which
2022/2023

removed easily by an organic solvent )

2- metallic coating

1- coating with more Nobel metal)must be free from cracks or pores )

like Cu.

2- Coating with less Nobel metal like Zn

II-Inhibitors:

They are Chemical substances added to the corrosive solution in a small

amount (e.g.0.1%) they classified according their mechanism of action
into:
30504101603434 30504101603434 30504101603434

1- Cathodic inhibitors:
they are substance that interfere with the Cathodic reaction of the
corrosion cell ,they include the following :

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i-substances such as ZnSO4 that react with the catholically formed OH

ions to form insoluble Zn(OH)2 which deposit on the cathode and isolate
them from the corrosion cell.

ii- Oxygen scavengers such as hydrazine (N2H4) these substances

eliminates O2 from the corrosive solution

2-Anodic inhibitors:
 they are substance that interfere with the anodic reaction of the
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

corrosion cell ,they include the following :

i-substances such as Na2CO3 that react with the anodically
formed Fe ions to form insoluble iron carbonate which deposit on the
anode and isolate it from the corrosive medium.
ii-Passivators, these are oxidizing agents such as Na2CrO4 which
leads to the formation of an oxide film on the steel which protect the
structure against corrosion.

3- Adsorption inhibitors:
 These are organic substances containing polar group such as NH2
through which adsorption of the organic compound takes place on the
metal with the formation of a continuous film on the metal surface
which isolate the metal from the corrosive solution.
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4-Cathodic Protection
 Cathodic protection of underground steel pipeline (externally
using less Nobel galvanic anode (galvanic cell ) Zn or Mg rod

Surface of the soil

---------------------------------------------------------

30504101603434 30504101603434 30504101603434

Steel pipeline
cathode
Zn or Mg rod

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Battery

Surface of the soil

---------------------------------------------------------
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Steel pipeline

cathode

scrap iron anode

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 Cathodic protection of an underground pipeline (externally) using
impressed current (electrolytic cell)

Practice Exercise

1-How to judge the ability of different metals to corrosion

:According to their position in the electromotive series ?

30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Corrosion of
Steel
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Reinforcement in
Concrete
Chapter 7
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Corrosion of Steel Reinforcement in Concrete

• One of the principal causes of concrete deterioration

• The damage is especially large in the structures exposed to marine

environment , contaminated ground water, or deicing chemicals.

• 1991 report Federal Highway Administration

(FHWA) in U. S. reported that 134,00 (23% of the total) bridges required

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

immediate repair and 226,000 (39% of the total) were also deficient. The
total repair cost was estimated at $ 90 billion dollars.

CRACKING OF CONCRETE Heat of hydration

• Alkali-aggregate reactivity

• Carbonation

• Sulfate attack

• Acid and chemicals

• Reinforcement corrosion

Corrosion of Steel Reinforcement in Concrete

2022/2023 2022/2023 2022/2023

• It is an electrochemical process :
the following conditions are required to occur the electrochemical cell:

• 1- Electrolyte ( solution inside the concrete)

• 2- Electronic conductor (steel bars)

• 3- Parts around the steel bar where the oxidation reaction occurs ( loss
of electrons- anodic parts).

• 4- Parts around the steel bar where the reduction reaction occurs (
gain of electrons- Cathodic parts).

• The
30504101603434 conditions 1 & 2 are available in the concrete in all cases
30504101603434 but 3 & 4
30504101603434

are Determinants of corrosion .

3 & 4 are available in one of the following cases :

1- presence two different metals in the concrete (due to any reasons).

2-presence of metallic impurities in the steel bar .( may be the steel bar
impure)

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3- presence of the differential strain parts in the steel bars ( the strained parts
act as anode to the other unstrained parts ).

• 4- Presence of differential aeration oxygenation cells due to the

difference in the porosity of the concrete ( the oxygen poor parts act
as anode while the oxygen rich parts act as cathode )

• This reason is the most common one which causing Corrosion of Steel
Reinforcement in Concrete .
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

• 5- Presence of differential temperature cells in the concrete ( the

highest temperature parts act as anode while the coldest parts act as
cathode ).

• 6- Presence of differential concentration cells in the concrete ( the

parts of the steel bar exposed to solution of low concentration act as
anode).

2022/2023 2022/2023 2022/2023

30504101603434 30504101603434 30504101603434

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Electrochemical Process of Steel Corrosion

Anodic and Cathodic Reactions

Anode: Fe ----->2e- + Fe2+

(metallic iron)
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Cathode: (½) O2 + H2O + 2e- ---> 2(OH)-

air water

2022/2023 2022/2023 2022/2023

Damage the Concrete

REINFORCEMENT CORROSION

• Corrosion of reinforcement steel takes place when the passive

layer damages.
30504101603434 30504101603434 30504101603434

• Passive layer is a layer of iron oxides and hydroxides .

How is the passive layer formed on the reinforcement steel ?

1-Layer of the iron oxides and hydroxides formed on the

reinforcement steel as a result of exposing it to the atmospheric
oxygen.

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2- Compounds of hydrated calcium ferrite are formed on the

reinforcement steel as a result of penetration of the fluid from the
wet concrete to the surface of the steel.

3-Around the reinforcement steel , there is an amount of the

unreacted ferric hydroxide and calcium hydroxide

• These oxides rise the pH inside the concrete around the steel
to be (pH=13)
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

The factors affecting decreasing the pH of the solution inside the

concrete?

1- presence of some acidic impurities in the concrete which

lead to decreasing the pH less than 11.5.

2-Increasing the permeability of the concrete which allow to

the carbon dioxide from air and chloride from solution to
penetrate to the steel and decrease the pH.

• carbon dioxide (from air) react with calcium hydroxide (from

water) to form insoluble white calcium carbonate Which coat
the concrete ( forming carbonation process) which leads to
decreasing the strength of the concrete
2022/2023 2022/2023 2022/2023
Chloride Limits

• ACI 318 (0.1 – 0.15%; water soluble)

• ACI 224 (0.2%; acid soluble)

• BS 8110 (0.4%; total)

Oxidation State vs. Increase of Volume

30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

CARBONATION

• Ca(OH)2 + CO2 → CaCO3 + H2O

• Reduction in pH (up to 8.5)

2022/2023 2022/2023 2022/2023

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

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Control of Corrosion

• Permeability of concrete( ‫ )الخرسانة الصماء‬is the key to

control the various processes involved in the phenomena.

1-Concrete mixture parameters to ensure low permeability,

e.g.,(w/c) low water-cement ratio, adequate cement content, control
of aggregate size and grading.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2- Using suitable concrete cover

-- ACI Building Code 318 specifies minimum concrete cover of 50

mm for walls and slabs, and 63 mm for other members is
recommended.

– Current practice for coastal structures in the North Sea

requires a minimum 50 mm of cover on conventional
reinforcement,

and 70 mm on prestressing steel.

– other agencies requires 75 mm minimum concrete

cover.

3-Waterproof membranes
2022/2023 2022/2023 2022/2023
– (‫(استخدام وسائل عزل مناسبة لخفض تغلغل الرطوبة واالكسجين‬: are
used when they are protected from physical damage by asphaltic
concrete wearing surfaces; therefore, the surface life of the
asphaltic concrete is about 15 years.

4- Overlay of watertight concrete: 37.5 to 63 mm thick, provides a

more durable protection to the penetration of fluids into reinforced
or prestressed concrete members.

5- Protective coatings for reinforcing steel are of two types:

– anodic coatings (e.g., zinc-coated steel) very limited use

30504101603434
due to concern regarding the long-term durability.
30504101603434 30504101603434

– and barrier coatings (e.g., epoxy-coated steel), long-

time performance of epoxy-coated rebars is still under
investigation in many countries.

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Epoxy-coated Steel

6- Cathodic protection techniques carried out either by:

– Supplying externally a current flow in the opposite

direction

2022/2023 – or by using sacrificial anodes.

2022/2023 2022/2023

• Due to its complex and high cost the system is finding limited
applications.

30504101603434 30504101603434 30504101603434

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Chemical
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Equilibrium
Chapter 8

2022/2023 2022/2023 2022/2023

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What is a Chemical Equilibrium?

A+B C+D

• The concentrations of all reactants &products remain constant with

time at the equilibrium.
• Any chemical reactions carried out in a closed vessel will reach
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Equilibrium.

Types of chemical reactions:

1- Complete (irreversible) reactions:

The reaction takes place instantaneously or at once,

these reactions occurs in one direction

Examples: NaCl +AgNO3 NaNO3 + AgCl (white ppt)

Mg+ H2 SO4 MgSO4+ H2

2022/2023 2022/2023 2022/2023

2-Incomplete (reversible) reactions:

The reactions occur in both directions, forward and backward, so both

reactant and products are always found in solution and can combine again.

Examples:

CH3COOH + C2H5OH = CH3COOC2H5 + H2O

Acetic acid ethyl alcohol ethyl methyl ester

30504101603434 30504101603434 30504101603434

Factors affecting the rate of chemical reaction:

The rate of chemical reaction is defined as the amount of the reacting

substances (in moles) transformed per second into resultants.

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Factors influence the rate of chemical reaction are:

1) Temperature

2) Catalyst

3) Concentration ( pressure in case of gases)

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

1. Temperature :
The rate of the reaction increases with increasing the
temperature .
The rate of the reaction doubled when the temperature increases
10 C .
2.Catalyst
Catalyst is a substance, which increases the velocity of the
reaction without Affecting on the composition or quantity.
3.Concentration
Increasing the concentration of substance; increases the
chances of collision of its molecules with those of other reacting
substances and increases the speed of reaction.
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1. Reversible Reaction
A+B C+D

 The velocity of a chemical reaction at constant temperature is

proportional to the product of the active masses (concentration)of the
reacting substance .

 Where : the concentration used in moles/litre

V α [A] * [B]

V = K *[A] *[B]

 K
30504101603434 is the velocity constant 30504101603434 30504101603434

 given temperature.

If the reaction 2A+ B 2C

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V= K [A]2 *[B] at constant temp.

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

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At Equilibrium

V1=V2

k1[A][B]=k2[C][D]

30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Le’ Chatelier's principle or "The Equilibrium Law",:

When any system at equilibrium is subjected to change

in concentration, temperature, volume, or pressure, then the system readjusts
itself to (partially) counteract the effect
2022/2023 of the applied change and
2022/2023 a new
2022/2023
equilibrium is

Established.

• If a change occurs in one of the factors controlling the equilibrium,

the equilibrium becomes displaced in such a direction to minimize the
effect of the change imposed.

• Three ways can affect the outcome of the equilibrium:

❖ Changing concentrations by adding or removing products or reactants

to the reaction vessel.

❖ •
30504101603434 Changing partial pressure 30504101603434
of gaseous reactants and products.
30504101603434

❖ • Changing the temperature.

Effect of change in concentration

 Changing the concentration of a chemical will shift the equilibrium to

the side that would reduce that change in concentration.

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 This can be illustrated by the following equation:

 CO + 2 H2 ⇌ CH3OH

 Suppose we were to increase the concentration of CO in the system.

Using Le Chatelier's principle, we can predict that the amount of methanol will
increase, decreasing the total change in CO.

Example:
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

For Reaction A+ B C +D

• Increase in [A] will force the reaction to move to the right

• Increase in [B] will force the reaction to move to the right

• Increase in [C] will force the reaction to move to the Left

• Increase in [D] will force the reaction to move to the Left

Effect of change in pressure:

 Changes in pressure are attributable to changes in volume.

 Considering the reaction of nitrogen

2022/2023 2022/2023
gas with hydrogen gas to form
2022/2023

ammonia:

 N2 + 3 H2 ⇌ 2 NH3 ΔH = -92kJ mol−1

 4 moles ⇌ 2 moles

 If we increase the pressure ,the reaction will goes to decrease the

pressure by decreasing the number of molecules .

 Effect of temperature on equilibrium reactions:

• The effect of a change of temperature on a reaction will

depend on whether the reaction is exothermic or
30504101603434
endothermic. 30504101603434 30504101603434

• In exothermic reactions:

increasing temperature will force the reaction to go

to the backward direction.

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• In endothermic reactions:

increasing temperature will force the reaction to go

to the forward direction.

Note: Chemical equilibrium occurs only in reversible reaction

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

when the rate of forward

reaction is equal to the rate of backward where the
concentration of reactants and
products remains unchanged at the same temperature and
pressure.

Application to industrial process:

1) Synthesis of ammonia: [ Exothermic]

N2 (g) + 3H2 (g) → 2NH3 + 24000 Cal

(4 moles ) (2 moles)
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❖ (+) sign because it is an exothermic reaction

❖ Increasing pressure favors forward reaction

❖ The reaction is exothermic so temperature must decrease.

(by decreasing the Temp., the velocity of the reaction will decrease as the
collision between molecules will decrease and longer time will be needed, so it
need a catalyst )

❖ For gases reactions , the reaction is slow so a catalyst such as: [ iron
oxide + chromium] is used.

❖ pressure used = 200- 300 atm, optimum Temperature =550 – 600 ºC

30504101603434 30504101603434 30504101603434
(not high &not low)

2)Synthesis of nitric oxide :[Endothermic ]

N2(g) + O2(g) 2NO(g) - 43000 Cal

(2 moles) ( 2moles)

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❖ (-)sign because it is an endothermic reaction

❖ The pressure has no effect ( moles of product=moles of reactants)

❖ Increasing the temperature favors endothermic reaction.

(By increasing the temperature the velocity of the reaction will increase as the
collision between molecules will increase and shorter time will be needed )

❖ We can not use catalyst at high temperature.

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

1) Synthesis of sulpher trioxide: [Exothermic ]

2SO2+O2 2SO3+22600 cal

(3moles) (2 moles)

❖ (+)sign because it is an exothermic reaction

❖ Increasing pressure favors forward reaction .

❖ increasing the temperature favors back reaction

❖ Excess oxygen as a catalyst from the air favors the forward reaction.
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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Example(2):
The reaction for the formation of nitrosyl chloride:
2022/2023 2022/2023 2022/2023
2NO(g)+Cl 2 (g) = 2NOCl(g)
was studied at 25 ºC. The pressures at equilibrium were:
P N O C l =1.2 atm.
P N O =5*10 - 2 atm.
PCl2 =3*10 - 1 atm.
Calculate the value of K p at 25 ºC.
Answer:
K p = (P N O C l ) 2 / P C l 2 *(P N O ) 2
= (1.2) 2 / [(3*10 - 1 ) * ( 5*10 - 2 ) 2 ]=1.9*10 3
30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Ionic
Equilibrium
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Chapter 9
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Ionic Equilibrium

Ionization: a process in which unionized molecules are changed into

ions.

Types of electrolytes:

Strong electrolytes
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

complete ionization

All Salts, strong acids & strong bases

+ -
HCl H +Cl
+ -
NaOH Na +OH
+ -
Na Cl Na + Cl
No equilibrium take places ,so no equilibrium
constant

2022/2023 2022/2023 2022/2023

Weak electrolytes

partial ionization

Weak acids and weak bases

- +
CH3 COOH CH3 COO + H

+ -
NH4OH
30504101603434 NH4 + 30504101603434
OH 30504101603434

The reaction stop when reached equilibrium(IONIC

Equilibrium ), so it has equilibrium constant (K)

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Ostwald Law(1888):

• Described the relation between the extent of ionization (α)

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

and concentration (C) mole/ liter for solutions.

• Weak electrolyte dissociates in water to ions .

2022/2023 2022/2023 2022/2023

Where :

[A+], [B-] : concentrations of the ions produced

[AB] :the undissociated form at equilibrium state.

K : ionization or dissociation constant

Suppose :

V = volume
30504101603434 30504101603434 30504101603434
Concentration = number of moles/ volume (L

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In case of very weak electrolyte

α = very small value and can be neglected

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Where : C =1/V

Determination of (α) Experimentally:

• Determine the value of( Ʌ v ) : equivalent conductance with different

weak electrolyte concentrations and calculated K in each case.

• K was always constant and independent of the dilution only in case of

weak electrolytes.
2022/2023 2022/2023 2022/2023
• Determine the value of(Ʌ o )= equivalent conductance at infinite
dilution.

If λv↑ + α↑ ---------> λ v + α

α= Ʌ v /Ʌo

30504101603434 30504101603434 30504101603434

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Example(1)
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

•
2022/2023 Concentration of hydrogen2022/2023
ion: 2022/2023

The acid can be considered very weak

[α ‹‹‹‹ 1]

30504101603434 30504101603434 30504101603434

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The Ionic Product of Water

• Water is very slightly ionized

( Very weak electrolyte)

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

H2O is very weak electrolyte

[H2O] = constant value

[H2O]*K=constant value

[H2O]*K=KW= ion product of water

[H+] * [OH-]= KW= 10-14 at constant temperature

2022/2023 2022/2023 2022/2023

For example:

at samples of H2O:
30504101603434 30504101603434 30504101603434
1- When [H+] = 10-5> 10-7 (acidic solution)

2-When [H+] = 10-9< 10-7 ( alkaline solution)

3- When [OH-] =10-11<10-7 (acidic solution)

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The Hydrogen Ion Exponent:( pH)

• pH is defined as the negative exponent of 10 which gives the

hydrogen ion concentration , pH= - log 10[H+]

• pOH = - log [OH-]

• [H+][OH-] = Kw =10-14
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

• -log [H+]-log[OH-]=-log10-14

• pH +pOH =14

2022/2023 2022/2023 2022/2023

Example (2):

What is the pH value of:

• Pure water.

• HCl (0.01 mole/L).

• NaOH (0.001 mole/L).

30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Example (3):

The ionization constant of acetic acid at 25 0C is 1.82x10-5.

Calculate the pH of 0.1 mole/ L acid.

2022/2023 2022/2023 2022/2023

Another method of calculating [H+]: According to Ostwald’s dilution

30504101603434 30504101603434 30504101603434

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pH= -log [H+]= 2.87

Common Ion Effect

• The ionization of a weak electrolyte is diminished by the

addition of a strong electrolyte, which lead to a common ion,
acetic acid is largely suppressed by the addition of either
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

sodium acetate or hydrochloric acid(strong electrolyte).

• Cs : the concentration of the strong electrolyte(completely

ionized), moles/liter

• C : the original concentration of the weak electrolyte

( including both dissociated and un dissociated molecules)

• α- : the degree of ionization in the presence of the strong

2022/2023
electrolyte 2022/2023 2022/2023

30504101603434 30504101603434 30504101603434

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Example (4):

The equivalent conductance of acetic acid at infinite dilution is 387

cm3 atm-1 mole-1 at the same temperature but at the dilution of 1
mole in 1000 liters, the equivalent conductance is 55cm3 atm-1 mole-
1. Find the percentage ionization of 0.1 mole/L acetic acid solution.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

Example (5):

If the pH value of 0.1 mole/L acetic acid is 2.872,

calculate the ionization constant of the acid.

Answer

C=0.1

pH= 2.872
30504101603434 30504101603434 30504101603434
K=?

pH= -log [H+]

2.872 = -log [H+]

[H+]= 1.353x10-3

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CH3COOH CH3COO- + H+
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Assignment :

What is the [H]+ conc. of 0.01 N of acetic acid ?

• If 1.64 gm Na-acetate is dissolved in 1 L of 0.01 N of acetic

acid , what will be the[H]+ conc.?

Ka=1.8*10-5,

M.wt of Na-acetate =82

2022/2023 2022/2023 2022/2023

30504101603434 30504101603434 30504101603434

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Material
Balance
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Chapter 10
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30504101603434 30504101603434 30504101603434

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Material Balance
A mass balance, also called a material balance, is an application of conservation
of mass to the analysis of physical systems. By accounting for material entering and
leaving a system, mass flows can be identified which might have been unknown, or
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

difficult to measure without this technique.

The exact conservation law used in the analysis of the system depends on the
context of the problem, but all revolve around mass conservation, i.e. that matter cannot
disappear or be created spontaneously.

Therefore, mass balances are used widely in engineering and environmental

analyses. For example, mass balance theory is used to design chemical reactors, to
analyze alternative processes to produce chemicals, as well as to
model pollution dispersion and other processes of physical systems.

Closely related and complementary analysis techniques include the population

balance,
2022/2023 energy balance and the somewhat
2022/2023more complex entropy balance.
2022/2023 These

techniques are required for thorough design and analysis of systems such as
the refrigeration cycle.

In environmental monitoring the term budget calculations is used to describe mass

balance equations where they are used to evaluate the monitoring data (comparing input
and output, etc.) In biology the dynamic energy budget theory for metabolic
organization makes explicit use of mass and energy balances.

The General Balance Equation Suppose propane is a component of both the input and
output streams of a continuous process unit shown below, these flow rates of the input
30504101603434 30504101603434 30504101603434
and output are measured and found to be different. Figure (1)

Process unit

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Figure (1) the industrial process

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

If there are no leaks and the measurements are correct, then the other possibilities that
can account for this difference are that propane is either being generated, consumed, or
accumulated within the unit. A balance (or inventory) on a material in a system (a single
process unit, a collection of units, or an entire process) may be written in the following
general way:
Material Balance

➢ A mass balance, also called a material balance, is an application of law

of conservation of mass .
➢ The matter cannot disappear or be created spontaneously.
➢ The law of conservation of mass states that for any system closed to all
transfers of matter the mass of the system must remain constant over time,
2022/2023 2022/2023 2022/2023
➢ i.e. the mass cannot change quantity if it is not added or removed.
➢ The general form for a mass balance is The mass that enters a system must, by
conservation of mass, either leave the system or accumulate within the
system .
The General Balance Equation :

𝑰𝒏𝒑𝒖𝒕 = 𝑶𝒖𝒕𝒑𝒖𝒕
Mathematically the mass balance for a system without a chemical reaction is as
follows:

30504101603434 𝑰𝒏𝒑𝒖𝒕 = 𝑶𝒖𝒕𝒑𝒖𝒕 + 𝑨𝒄𝒄𝒖𝒎𝒖𝒍𝒂𝒕𝒊𝒐𝒏

30504101603434 30504101603434

Example (1):
Wet air contain 20%
s moisture wanted to be dried to air contain 2%moisture by
passing the air through drying process contain Silica gel used to dry air .the weight of
silica gel is 2 Kg.calculate the percentage of moisture in the Silica gel after drying 100
Kg of wet air.

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Solution:
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

The General Balance Equation:

𝑰𝒏𝒑𝒖𝒕 = 𝑶𝒖𝒕𝒑𝒖𝒕

100 = 𝑤𝑎𝑡𝑒𝑟 𝑖𝑛 𝑠𝑖𝑙𝑖𝑐𝑎 𝑔𝑒𝑙 (𝑊) + 𝑃

100 = 𝑊 + 𝑃 → 1
Air balance :

𝑰𝒏𝒑𝒖𝒕 = 𝑶𝒖𝒕𝒑𝒖𝒕
80 98
100 × = ×𝑃
100 100
2022/2023 𝑃= 82 𝐾𝑔
2022/2023 2022/2023

Substitute in equation (1):

100 = 𝑊 + 𝑃

𝑊 = 100 − 82 = 18 𝐾𝑔

Amount of water absorbed in Silica gel = 18 Kg

Percentage of water absorbed in Silica gel :

𝑤𝑎𝑡𝑒𝑟
%𝑊 = × 100%
𝑤𝑎𝑡𝑒𝑟 + 𝑆𝑖𝑙𝑖𝑐𝑎 𝑔𝑒𝑙

30504101603434
18 30504101603434 30504101603434
%𝑊 = × 100 = 0.9 × 100 = 90%
18 + 2

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Example (2):
A paste of pulp and paper contains 90% water by mass enters to the dryer , where 100
Kg of the water evaporated from the original paste ,the composition of the pulp
produced from the dryer 20% Water . calculate The weight of the original paste entered
to the dryer in Kilogram.

Solution:
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

The General Balance Equation:

𝑰𝒏𝒑𝒖𝒕 = 𝑶𝒖𝒕𝒑𝒖𝒕

𝐹 =𝑊+𝑃
2022/2023 2022/2023 2022/2023
𝐹 = 100 + 𝑃 → 1
pulp balance :

𝑰𝒏𝒑𝒖𝒕 = 𝑶𝒖𝒕𝒑𝒖𝒕
1 80
×𝐹 = ×𝑃 →2
100 100
Substitute in equation (2) by equation (1):

1 80
× (100 + 𝑃) = ×𝑃 →2
30504101603434 100 100
30504101603434 30504101603434

1 1 80
× 100 + ×𝑃= ×𝑃
100 100 100
1 = 𝑃 + 80𝑃 = 81𝑃
81
𝑃= = 81 𝐾𝑔
1

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Substitute in equation (1):

𝐹 = 100 + 81 = 181 𝐾𝑔
The weight of the original paste entered to the dryer in Kilogram.= 181 Kg

Example (3):
Wet paste entered to dryer (1) with a rate 400 Kg/hr , contain 95% by weight Water and
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

leave this dryer with 25% water to go to another dryer (2) , and leave it with 2% water.
Calculate the percentage of the evaporated water from every dryer to the actual amount
of the water present in the original paste enters to the dryer (1) .

Solution:

2022/2023 2022/2023 2022/2023

The General Balance Equation on the first dryers :

𝑰𝒏𝒑𝒖𝒕 = 𝑶𝒖𝒕𝒑𝒖𝒕

𝐹 = 𝑊1 + 𝑃1

400 = 𝑊1 + 𝑃1 → 1
pulp balance on the first dryer :

𝑰𝒏𝒑𝒖𝒕 = 𝑶𝒖𝒕𝒑𝒖𝒕
5 75
×𝐹 = × 𝑃1
30504101603434
100 30504101603434
100 30504101603434

5 75
× 400 = × 𝑃1
100 100
5 × 400 = 75 × 𝑃1
5 × 400
𝑃1 = = 27 𝐾𝑔
75

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Substitute in equation (1):

400 = 𝑊1 + 27

𝑊1 = 400 − 27 = 373 𝐾𝑔
Percentage of evaporated water from first dryer to the actual amount of the water
present in the original paste enters to the dryer (1) = % W1

𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑒𝑣𝑎𝑝𝑜𝑟𝑎𝑡𝑒𝑑 𝑓𝑟𝑜𝑚 𝑓𝑖𝑟𝑠𝑡 𝑑𝑟𝑦𝑒𝑟

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

𝑊1 = × 100%
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑒𝑛𝑡𝑒𝑟𝑒𝑑 𝑓𝑖𝑟𝑠𝑡 𝑑𝑟𝑦𝑒𝑟

95
Amount of water entered to the first dryer = × 400 = 380 𝐾𝑔
100
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑒𝑣𝑎𝑝𝑜𝑟𝑎𝑡𝑒𝑑 𝑓𝑟𝑜𝑚 𝑓𝑖𝑟𝑠𝑡 𝑑𝑟𝑦𝑒𝑟
𝑊1 = × 100%
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑒𝑛𝑡𝑒𝑟𝑒𝑑 𝑓𝑖𝑟𝑠𝑡 𝑑𝑟𝑦𝑒𝑟

373
𝑊1 = × 100% = 98%
380

The General Balance Equation on the second dryers :

𝑰𝒏𝒑𝒖𝒕 = 𝑶𝒖𝒕𝒑𝒖𝒕
2022/2023 2022/2023 2022/2023

𝑃1 = 𝑊2 + 𝑃2

27 = 𝑊2 + 𝑃2 → 2
pulp balance on the first dryer :

𝑰𝒏𝒑𝒖𝒕 = 𝑶𝒖𝒕𝒑𝒖𝒕
25 98
× 𝑃1 = × 𝑃2
100 100
25 98
× 27 = × 𝑃2
100 100
30504101603434 30504101603434 30504101603434

25 × 27 = 98 × 𝑃2
25 × 27
𝑃2 = = 7 𝐾𝑔
98
Substitute in equation (2):

27 = 𝑊2 + 7

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𝑊2 = 27 − 7 = 20 𝐾𝑔
Percentage of evaporated water from second dryer to the actual amount of the water
present in the original paste enters to the dryer (1) = % W2

𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑒𝑣𝑎𝑝𝑜𝑟𝑎𝑡𝑒𝑑 𝑓𝑟𝑜𝑚 𝑠𝑒𝑐𝑜𝑛𝑑 𝑑𝑟𝑦𝑒𝑟

𝑊2 = × 100%
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑒𝑛𝑡𝑒𝑟𝑒𝑑 𝑓𝑖𝑟𝑠𝑡 𝑑𝑟𝑦𝑒𝑟

95
Amount of water entered to the first dryer = × 400 = 380 𝐾𝑔
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

100
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑒𝑣𝑎𝑝𝑜𝑟𝑎𝑡𝑒𝑑 𝑓𝑟𝑜𝑚 𝑠𝑒𝑐𝑜𝑛𝑑 𝑑𝑟𝑦𝑒𝑟
𝑊2 = × 100%
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑒𝑛𝑡𝑒𝑟𝑒𝑑 𝑓𝑖𝑟𝑠𝑡 𝑑𝑟𝑦𝑒𝑟

20
𝑊2 = × 100% = 6%
380

Example (4):
Mixed acid used in the production of Dyes, its composition is: (75% H2SO4 , 15%
HNO3 , 10%H2O ) and as a result of the reaction , the composition of the mixed acid
changed To : (65% H2SO4 , 10% HNO3 , 25%H2O ) .The concentration of this mixed
acid return to its original value by adding concentrated sulfuric acid 98% H2SO4 and
concentrated nitric acid 90% HNO3.Calculate the weight of the mixed acid , the
concentrated sulfuric acid and concentrated nitric acid needed to produce 1 ton from
the mixed acid suitable for the production
2022/2023 of dyes.
2022/2023 2022/2023

Solution:

The General Balance Equation on the Mixer :

30504101603434 30504101603434 30504101603434
𝑰𝒏𝒑𝒖𝒕 = 𝑶𝒖𝒕𝒑𝒖𝒕

𝐹+𝑁+𝑆 =𝑃

𝐹+𝑁+𝑆 =1 →1
Sulfuric balance :

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𝑰𝒏𝒑𝒖𝒕 = 𝑶𝒖𝒕𝒑𝒖𝒕
65 98 75
×𝐹+ ×𝑆= ×𝑃 →2
100 100 100
100 75 98
𝐹= ×( ×𝑃− × 𝑆)
65 100 100
75 98
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

𝐹=( 𝑃 − 𝑆) =
65 65
75 98 75 98
𝐹=( × 1 − 𝑆) = ( − 𝑆) → 3
65 65 65 65
Nitric balance :

𝑰𝒏𝒑𝒖𝒕 = 𝑶𝒖𝒕𝒑𝒖𝒕
10 90 15
×𝐹+ ×𝑁 = ×𝑃
100 100 100
10 90 15
×𝐹+ ×𝑁 = ×1
100 100 100
100 15 10
2022/2023 𝑁= ( 2022/2023
− × 𝐹) 2022/2023
90 100 100
15 10
𝑁= − ×𝐹 →4
90 90
Substitute in equation (1) by equation (3 & 4)

𝐹+𝑁+𝑆 =1 →1
75 98 15 10
( − 𝑆) + − ×𝐹+𝑆 =1
65 65 90 90
75 98 15 10 75 98
( − 𝑆) + − × ( − 𝑆) + 𝑆 = 1
30504101603434 65 65 90 30504101603434
90 65 65 30504101603434

10 75 98 15
(1 − ) ( − 𝑆) + +𝑆 =1
90 65 65 90
80 75 98 15
( − 𝑆) + 𝑆 = 1 −
90 65 65 90

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75 98 75 90
( − 𝑆) + 𝑆 = ×
65 65 90 80
75 98 75
− 𝑆+𝑆 =
65 65 80
98 75 75
− 𝑆+𝑆 = −
65 80 65
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

−0.5𝑆 = −0.21
−0.21
∴𝑆=
−0.5
∴ 𝑆 = 0.42 𝑡𝑜𝑛
Substitute in equation (3)

75 98 75 98
𝐹=( × 1 − 𝑆) = ( − 𝑆) → 3
65 65 65 65
75 98 75 98
𝐹=( − 𝑆) = ( − × 0.42) = 0.50 𝑡𝑜𝑛
65 65 65 65
Substitute in equation (4)
2022/2023 2022/2023 2022/2023

15 10
𝑁= − ×𝐹 →4
90 90
15 10
𝑁= − × 0.50 = 0.05 𝑡𝑜𝑛
90 90
The weight of the mixed acid , the concentrated sulpheric acid and concentrated nitric
acid needed to produce 1 ton from the mixed acid suitable for the production of dyes
are:

the weight of the mixed acid = F = 0.42 ton

the concentrated sulfuric acid = S =0.5 ton

30504101603434 30504101603434 30504101603434
The concentrated nitric acid = N = 0.05 ton

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Example (5):
• A paste of pulp and paper contains 71% water by mass enters to the
dryer , where 60% of the water removed from the paste :

o calculate :
o the composition of the pulp produced from the dryer.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2. weight of the removed water per Kilogram of the original paste

entered to the dryer.

Solution: W

F 60%water P

paste of pulp x% water

71% water (1-x)%pulp

29% pulp

• Assume 1 Kg of the original past

F = 1 Kg
2022/2023 2022/2023 2022/2023

• The General Balance Equation :

o Input = Output

F=W+P

1=W+P

W= 0.6 (0.71 ) F = 0.6( 0.71) (1)=0.426 Kg =weight of the

removed water

F=W + P

30504101603434
1 = 0.426 + P 30504101603434 30504101603434

P = 1- 0.426 = 0.574 Kg

Material balance on water :

0.71 (1) = w + P(x)

0.71 = 0.426 + 0.574 (x )

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0.284 = 0.574 (x)

X =0.49

Material balance on pulp :

0.29 F = 0.0 + P(1-x)

0.29 (1) = 0.574 +0.574 (1-x)

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

o the composition of the pulp produced from the dryer.

% water = 0.49

% pulp = 1-x = 1- 0.49 =0.51

weight of the removed water per Kilogram of the original paste entered
to the dryer = W

=0.426 Kg

Example (6):
 A paste of pulp and paper contains 80% water by mass enters to the
dryer , where 100 Kg of the water evaporated from the original paste
the composition of the pulp produced from the dryer 40% Water .
2022/2023 2022/2023 2022/2023
calculate :

The weight of the original paste entered to the dryer in Kilogram.

Solution: W =100Kg

F P

paste of pulp 40% water

80% water 60%pulp

20% pulp

• The
30504101603434 General Balance Equation :
30504101603434 30504101603434

o Input = Output

F=W+P

F = 100 + P (1)

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Material balance on water :

0.80 (F) = W + P(0.4)

0.8 F = 100 + 0.4 P (2)

Substitute from equation(1) in equation (2)

0.8 (100 + P ) = 100 + 0.4 P

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

80 + 0.8 P = 100 + 0.4 P

0.4 P = 20

P = 20/ 0.4 =50 Kg

F=100 + P =100 + 50 = 150 Kg

The weight of the original paste entered to the dryer in Kilogram.

= 150 Kg

Example (7):
 Wet paste entered to dryer (1)2022/2023
2022/2023
with a rate 200 Kg/hr , contain 92% by
2022/2023
weight Water and leave this dryer with 19% water to go to another
dryer (2) , and leave it with 2% water :

Calculate:

% of the evaporated water from every dryer to the actual amount of the
water present in the original paste enters to the dryer (1) .

Solution: W1 w2

F=200Kg/hr P1 P2

paste of pulp 19%

30504101603434
water
30504101603434
2% 30504101603434
water 92%
water 81%

8%solid solid 98% solid

• The General Balance Equation :

Input = Output

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OVER ALL MATERIAL BLANCE ON DRYER (1):

F = W1 + P1

200 = w1 + P1

W1= 200 – P1 (1)

Material balance on water ON DRYER 1 :

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

0.92 (F) = W1 + P1(0.19)

0.92(200) = W1 + 0.19 P1 (2)

Substitute from equation(1) in equation (2)

184 = ( 200 – P1 ) + 0.19 P1

200 -184 = 0.81 P1

16 = 0.81 P1

P1 = 19.75 Kg

W1 = 200 – 19.75 =180.25 Kg

% of the evaporated water from dryer (1) to the actual amount of the
2022/2023
water present in the original paste enters to the dryer (1) 2022/2023
2022/2023
= 180.25 /
184 = 0.9796 = 97.96 %

The actual amount of water entered to dryer 1 =200(0.92)=184 Kg

OVER ALL MATERIAL BALANCE ON DRYER (2):

P1 = W2 + P2

19.75 = w2 + P2

W2= 19.75 – P2 (3)

30504101603434 30504101603434 30504101603434
Material balance on water ON DRYER 2 :

0.19 (19.75) = W2 + P2(0.02) (4)

SUBSTIUTE FROM EQUATION 3 IN EQUATION 4

0.19(19.75) =( 19.75- P2) + 0.02 P2

15.9975 = 0.98 P2

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P2 = 16.32 Kg

W2 = 19.75 – 16.32 =3.43 Kg

% of the evaporated water from dryer (2) to the actual amount of the
water present in the original paste enters to the dryer (1) = 3.43/ 184
= 0.0186 = 1.86 %
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Example (8):
 18.63% H2SO4 used in the production of Hydrogen gas by the
electrolysis , the concentration of the acid decreased to 12.3% .

 200 Liter of 77.7% of H2SO4 added to the acid of 12.3% to increase

the concentration of H2SO4 to 18.63%.

 Calculate the amount of the acid which will be entered to the cell of
the electrolysis.

Solution: W =200 L

F 77.7%H2SO4 p

2022/2023 2022/2023 81.37% water

2022/2023

12.3% H2SO4 18.63 %H2SO4

87.7 % water

• The General Balance Equation :

Input = Output

Overall mass balance:

F+W=P

F +200 = P
30504101603434 30504101603434 30504101603434
F = P -200 (1)

Material balance on H2SO4 :

0.123 (F) +0.777(200) =P(0.1863)

0.123 F +155.4 = 0.1863 P (2)

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Substitute from equation(1) in equation (2)

0.123 ( P-200 ) + 155.4 = 0.1863 P

155.4 - 24.6 = 0.1863 P -0.123P

0.0633 P = 130.8

P = 2066.35 Liter
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

F = P - 200 = 2066.35 - 200 = 1866.35 L

 The amount of the acid which will be entered to the cell of the
electrolysis.

= 1866.35 L

Example (9):
 Mixed acid used in the production of Dyes, its composition is: (65%
H2SO4 , 20% HNO3 , 15%H2O ) and as a result of the reaction , the
composition of the mixed acid changed To : (60% H2SO4 , 10% HNO3
2022/2023 2022/2023 2022/2023
, 30%H2O ) .The concentration of this mixed acid return to its original
value by adding concentrated sulpheric acid 96% H2SO4 and
concentrated nitric acid 90% HNO3.

 Calculate the weight of the mixed acid , the concentrated sulpheric acid
and concentrated nitric acid needed to produce 1 ton from the mixed
acid suitable for the production of dyes.

Solution: S N

F 96%H2SO4 90 %HNO3 p = 1000Kg

15 % water
30504101603434 30504101603434 30504101603434
60 % H2SO4 65 %H2SO4

10% HNO3 20%HNO3

30 % water

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• The General Balance Equation :

Input = Output

Overall mass balance:

F+S+N=P

F + S + N = 1000 (1)
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Material balance on H2SO4 :

0.60 (F) +0.96(S) =P(0.65)

0.60 F +0.96 S = 0.65 (1000) (2)

Material balance on HNO3 :

0.10 (F) +0.90(N) =P(0.20)

0.10 F + 0.90 N = 0.20 (1000) (3)

By solving equation (1) ,equation (2) & equation (3)

Substitute from equation(1) in equation (2)

P=
2022/2023 2022/2023 2022/2023
N=

S=

F=

 The weight of the mixed acid , the concentrated sulpheric acid and
concentrated nitric acid needed to produce 1 ton from the mixed acid
suitable for the production of dyes are:

the weight of the mixed acid = F =

the concentrated sulpheric acid = S =

30504101603434 30504101603434 30504101603434
The concentrated nitric acid = N =

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Example (5)
A mixture containing 50% benzene (B) and toluene (T) by mass is fed to a distillation
column by a rate 10000 Kg/hr. An overhead stream of 95wt% B is produced, and 96%
of the Toluene leaves in the bottom stream. The rate of the vapor leaved
leavingfrom the top
of the distillation column was 8000 kg/hr. determine the returned ratio from the
condenser.
Solution:
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

The General Balance Equation:

𝑰𝒏𝒑𝒖𝒕 = 𝑶𝒖𝒕𝒑𝒖𝒕
Overall mass balance:

𝐹 =𝐷+𝑊

10000 = 𝐷 + 𝑊

𝑊 = 10000 − 𝐷 → 1
30504101603434 30504101603434 30504101603434

Material balance on benzene (B):

50 95 4
× 10000 = 𝐷+ 𝑊→2
100 100 100
Substitute from equation (1) in equation (2) and solving we obtain:

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50 95 4
× 10000 = 𝐷+ 𝑊
100 100 100
50 × 10000 = 95𝐷 + 4(10000 − 𝐷 )

50 × 10000 = 95𝐷 + 4 × 10000 − 4 × 𝐷

50 × 10000 − 4 × 10000 = 95𝐷 − 4𝐷

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

460000 = 91𝐷
460000
𝐷= = 5054.9𝐾𝑔 ≅ 5055𝐾𝑔
91
Substitute in equation (1)

𝑊 = 10000 − 5055 = 4945𝐾𝑔

For the condenser:

2022/2023 2022/2023 2022/2023

The General Balance Equation:

𝑰𝒏𝒑𝒖𝒕 = 𝑶𝒖𝒕𝒑𝒖𝒕
Overall mass balance:

𝑉 =𝐷+𝐿

8000 = 5055 + 𝐿

𝐿 = 8000 − 5055 = 2945 𝐾𝑔

30504101603434 30504101603434 30504101603434
𝐿 2945
The returned ratio (R) = % = % = 0.58
𝐷 5055

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

Practice Exercise
1- Solve in details then choose the correct
answer
30504101603434 30504101603434 30504101603434
1- A mixture containing 80% benzene (B) and toluene (T) by mass is fed to a
distillation column. An overhead stream of 96wt% B is produced, and 94% of
the Toluene leaves in the bottom stream. The rate of bottom stream is 4000
Kg/hr. The rate of the vapor leaved from the top of the distillation column
10000 Kg /hr . Assuming basis is one hour
The amount of distillate leave the condenser to be final product = ……….Kg
a) 4000 b) 22500 c)10000 d) 18500
2- In the question (1) the amount of Benzene in the distillate = ……….Kg

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a) 18500 b) 4500 c)17760 d) 740

3- In the question (1) the amount of Toluene in the distillate = ……….Kg
a) 18500 b) 4500 c)17760 d) 740
4- In the question (1) the amount of the feed to distillation column = ……….Kg
a) 19000 b) 4000 c)22500 d) 10000
5- In the question (1) the amount of Benzene in the feed = ……….Kg
a) 19000 b) 10000 c) 4500 d) 18000
6- In the question (1) the amount of Toluene in the feed = ……….Kg
a) 19000 b) 10000 c) 4500 d) 18400
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

7- In the question (1) the amount of liquid leave the condenser = ……….Kg
a) 10000 b) 19000 c) 8500 d) 18240
8- In the question (1) the returned ratio (R) =……………%
a) 0 b) 90 c) 46 d) 100

2- A mixture containing 70% benzene (B) and 30% toluene (T) by mass is fed
to a distillation column. An overhead stream of 98 wt% B is produced, and
95% of the Toluene leaves in the bottom stream. The rate of the upper
steam was 100 kg. Determine :

1-The feed to the distillation column

2- The rate of the bottom steam.

3- the amount of the vapor enters

2022/2023
to the condenser (If the 2022/2023
2022/2023
returned
ratio =L/D=2.5)

3- A mixture containing 50% benzene (B) and toluene (T) by mass is fed to a
distillation column by a rate 10000 Kg/hr. An overhead stream of 95wt% B is
produced, and 96% of the Toluene leaves in the bottom stream. The rate of
the vapor leaved from the top of the distillation column was 8000 kg/hr.
Determine :

The returned ratio from the condenser .

30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

Combustion
30504101603434
Chapter 11
30504101603434 30504101603434

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Combustion

Combustion Reaction Definition

A combustion reaction is a type of chemical reaction where

a compound and an oxidant is reacted to produce heat and a new product.
The general form of a combustion reaction is the reaction between a
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

hydrocarbon and oxygen to yield carbon dioxide and water:

hydrocarbon + O2 → CO2 + H2O
In addition to heat, it's also common (although not necessary) for a
combustion reaction to release light and produce a flame. In order for a
combustion reaction to begin, the activation energy for the reaction must be
overcome. Often, combustion reactions are started with a match or other
flame, which provides heat to initiate the reaction. Once combustion starts,
enough heat may be produced to sustain it until it runs out of either fuel or
oxygen.

2022/2023 2022/2023 2022/2023

Combustion Reaction Examples

Examples of combustion reactions include:

2 H2 + O2 → 2H2O + heat
CH4 + 2 O2 → CO2 + 2 H2O + heat
Other examples include lighting a match or a burning campfire.

Fuels.

Substances
30504101603434 or materials which 30504101603434
undergo combustion are called fuels. The
30504101603434

most common examples are natural gas, propane, kerosene, diesel, petrol,
charcoal, coal, wood, etc.

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Liquid fuels:

Combustion of a liquid fuel in an oxidizing atmosphere actually happens

in the gas phase. It is the vapor that burns, not the liquid. Therefore, a liquid
will normally catch fire only above a certain temperature: its flash point. The
flash point of a liquid fuel is the lowest temperature at which it can form an
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

ignitable mix with air. It is the minimum temperature at which there is

enough evaporated fuel in the air to start combustion.

Solid fuels:

The act of combustion consists of three relatively distinct but

overlapping phases:

1. Preheating phase, when the unburned fuel is heated up to its flash

point and then fire point. Flammable gases start being evolved in a
process similar to dry distillation.
2022/2023 2022/2023 2022/2023

2. Distillation phase or gaseous phase, when the mix of evolved

flammable gases with oxygen is ignited. Energy is produced in the form
of heat and light. Flames are often visible. Heat transfer from the
combustion to the solid maintains the evolution of flammable vapours.

3. Charcoal phase or solid phase, when the output of flammable gases

30504101603434 30504101603434 30504101603434
from the material is too low for persistent presence of flame and
the charred fuel does not burn rapidly and just glows and later
only smoulders.

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

A general scheme of polymer combustion

What is Combustion?
• Combustion takes place when fuel, most commonly a fossil fuel, reacts
with the oxygen in air to produce heat.

• The heat created by the burning of a fossil fuel is used in the operation
of equipment
2022/2023
such as boilers, furnaces, kilns, and engines.
2022/2023 2022/2023

• CO2 (carbon dioxide) and H20 (water) are created as byproducts of the
exothermic reaction.
• CH4 + 2O2 → CO2 + 2H2O + Heat
• C + O2 → CO2 + Heat
• 2H2 + O2 → 2H2O + Heat

Complete Combustion:
• All carbon converted to carbon oxide , all hydrogen
converted to water and all sulfur converted to sulfur dioxide
30504101603434 30504101603434 30504101603434
C+ O 2 → CO 2
2H 2 + O 2 → 2H 2 O
S+ O 2 → SO 2

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Incomplete Combustion:
• Incomplete combustion , all carbon converted to carbon monoxide , all
hydrogen converted to water and all sulfur converted to sulfur dioxide

C+0.5 O2 → CO

2H2 + O2 → 2 H2O

S+ O2 → SO2
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Types of combustion reactions

in complete combustion
complete combustion
all carbon converted to carbon
all carbon converted to carbon monoxide , all hydrogen converted
dioxide , all hydrogen converted to to water and all sulfur converted to
water and all sulfur converted to sulfur dioxide
sulfur dioxide
C+0.5 O2 → CO
2022/2023 C+ O2 → CO2 2022/2023 2022/2023
2H2 + O2 → 2H2O
2H2 + O2 → 2H2O
S+ O2 → SO2
S+ O2 → SO2

Atmospheric air consists of:

Atmospheric air consists of :

• 21% O2 & 79% N2 by volume

• 23% O2 & 77% N2 by weight

30504101603434 30504101603434 30504101603434

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air
by volume by weight
21% O2 & 79% N2 23% O2 & 77% N2
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Notes :
➢ Theoretical amount of oxygen needed for burn the fuel should be calculated
from the combustion equation assuming that the combustion is complete
combustion and fuel burned with efficiency 100%
➢ Theoretical amount of air needed for burn the fuel should be calculated from
Theoretical amount of oxygen
➢ Actual amount of oxygen needed for burn the fuel should be calculated from the
combustion equation assuming that the combustion is complete combustion and
fuel burned with efficiency not 100% (for example 80%)
➢ Actual amount of air needed for burn the fuel should be calculated from Actual
amount of oxygen
➢ Excess air is calculated from the equation :
➢ Excess oxygen = Theoretical oxygen
2022/2023 – Actual oxygen
2022/2023 2022/2023

Combustion Products:
Combustion products are the substances or compounds that result from a
chemical reaction known as combustion. Combustion is a chemical process in
which a fuel (such as a hydrocarbon) reacts with an oxidizing agent (usually
oxygen) to produce heat, light, and various chemical byproducts. The specific
combustion products produced depend on the type of fuel, the combustion
conditions, and the presence of impurities.

30504101603434 30504101603434 30504101603434

Common combustion products include:

1-Carbon Dioxide (CO2): In complete combustion, carbon in the fuel

combines with oxygen to produce carbon dioxide. CO2 is a greenhouse
gas and a major contributor to global warming.

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1- Water Vapor (H2O): Water vapor is also produced during combustion,

especially when hydrogen is present in the fuel.

2- Carbon Monoxide (CO): In incomplete combustion, where there is

insufficient oxygen, carbon monoxide is produced. CO is a toxic gas
and a health hazard.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

3- Nitrogen Oxides (NOx): High-temperature combustion processes can

lead to the formation of nitrogen oxides, such as nitrogen dioxide
(NO2) and nitric oxide (NO). NOx is a major air pollutant.

4- Sulfur Dioxide (SO2): If the fuel contains sulfur compounds,

combustion can produce sulfur dioxide, which contributes to acid rain
and air pollution.

5- Particulate Matter (PM): Small particles or soot can be produced during

combustion, especially in the case of solid fuels. PM can have adverse
2022/2023
health effects and contribute to air pollution.
2022/2023 2022/2023

6- Unburned Hydrocarbons: Incomplete combustion can lead to the

release of unburned hydrocarbons, which are a component of smog.

7- Ash and Residues: Solid fuels, such as wood or coal, leave behind ash
and residues after combustion.

The exact composition of combustion products can vary widely depending on

the combustion process, the type of fuel, and the presence of air pollutants
control technologies. Understanding
30504101603434 and managing combustion30504101603434
30504101603434 products is
essential for addressing environmental and health concerns associated with
combustion processes, such as those in vehicles, power plants, and industrial
facilities.

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Example (1):
If the composition of the coal is:

element C H2 O2 S N2 H2O ash

Percentage % by 80% 6% 5% 1% 1% 2% 5%
weight
Calculate the theoretical amount of the air required to burn one kilogram from this coal,
then calculate the weight of the combustion products.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Solution:
1. Carbon combustion :
𝐶 + 𝑂2 → 𝐶𝑂2
12 32 → 44
0.80 𝑥1

0.80 × 32
𝑥1 = weight of the 𝑂2 needed to burn the carbon = = 2.13𝐾𝑔
12

2. Hydrogen combustion :
1
𝐻2 + 𝑂 → 𝐻2 𝑂
2 2
1
1×2 × 32 → 18
2022/2023 2
2022/2023 2022/2023
0.06 𝑥2

0.06 × 16
𝑥2 = weight of the 𝑂2 needed to burn the hydrogen =
2
= 0.48 𝐾𝑔

3. Sulfur combustion :

𝑆 + 𝑂2 → 𝑆𝑂2
32 32 → 64
0.01 𝑥3 64

0.01 × 32
30504101603434 𝑥3 = weight of the 𝑂2 needed to burn the sulfur =
30504101603434 = 0.01 𝐾𝑔
30504101603434
32
∴ The totalWeight of the 𝑂2 needed from air = Weight of O2 needed to burn the fuel –
weight of the O2 presence in the fuel

∴ The totalWeight of the 𝑂2 needed from air = ( 𝑥1 + 𝑥2 + 𝑥3 ) − 0.05 =

= (2.13 + 0.32 + 0.01) − 0.05

= 2.41kg

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100 𝐾𝑔 𝐴𝑖𝑟 → 23 𝐾𝑔 𝑂2
𝑋 𝐾𝑔 𝐴𝑖𝑟 → 2.41 𝐾𝑔 𝑂2
2.41 × 100
∴ 𝑇ℎ𝑒 𝑡𝑜𝑡𝑎𝑙 𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑛𝑒𝑒𝑑𝑒𝑑 𝑎𝑖𝑟 (𝑋) = = 10.5 𝐾𝑔
23
Combustion products:

1. nitrogen:
Nitrogen: = Weight of nitrogen from air + Weight of nitrogen in the coal
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Weight of nitrogen from air = 10.5-2.41=8.1 kg

Weight of nitrogen in the coal =0.01kg

∴ The total Weight of N2 in the combustion products =8.1+0.01=8.11 kg

2. carbon dioxide:
𝐶 + 𝑂2 → 𝐶𝑂2
12 32 → 44
0.80 𝑥1 𝑦1

0.80 × 44
𝑦1 = weight of the 𝐶𝑂2 obtained = = 3.0 𝐾𝑔
12

3. Water:
1
2022/2023 𝐻22022/2023
+ 𝑂2 → 𝐻2 𝑂 2022/2023
2
1
1×2 × 32 → 18
2
0.06 𝑥2 𝑦2

0.06 × 18
𝑦2 = weight of the water = = 0.54 𝐾𝑔
2
water = Weight of water from combustion + Weight of water in the coal

Weight of water from combustion = 0.54 kg

Weight of water in the coal =0.02kg

∴ The total Weight of water in the combustion products =0.54+0.02=0. 56 kg

30504101603434 30504101603434 30504101603434
4. Sulfur dioxide :
𝑆 + 𝑂2 → 𝑆𝑂2
32 32 → 64
0.01 𝑥3 𝑦3

0.01 × 64
𝑦3 = weight of the sulfur dioxide formed = = 0.02 𝐾𝑔
32

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∴ The total Weight of the combustion products

= 𝐶𝑂2 + 𝐻2 O + 𝑆𝑂2 + 𝑁2 + Ash

= 3.0 +8.11 + 0.56 +0.02+0.05= 11.74 Kg

Example (2):

Calculate the least amount of the air needed to burn 20 Kg from butane C4H10
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

(complete combustion)

Solution :
13
𝐶4 𝐻10 + 𝑂 − − − −→ 4𝐶𝑂2 + 5𝐻2 𝑂
2 2
13
58 × 32 − −−→ 4 × 44 5 × 18
2
20 𝑥 − −−→ 4 × 44 5 × 18

20 × 13 × 32
X = the weight of the oxygen needed to burnnbutane = = 71.7
2 × 58
≈ 72 Kg

2022/2023
100 𝐾𝑔 𝐴𝑖𝑟 → 23 𝐾𝑔 𝑂2
2022/2023 2022/2023
𝑋 𝐾𝑔 𝐴𝑖𝑟 → 72 𝐾𝑔 𝑂2
72 × 100
∴ 𝑇ℎ𝑒 𝑡𝑜𝑡𝑎𝑙 𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑛𝑒𝑒𝑑𝑒𝑑 𝑎𝑖𝑟 (𝑋) = = 313 𝐾𝑔
23

Example (3):
Calculate the weight of air needed to burn one hundred kilogram of liquid fuel (82 %
Carbon , 13% Hydrogen , 5% sulfur ) Complete combustion.

Solution :
13
𝐶4 𝐻10 + 𝑂 − − − −→ 4𝐶𝑂2 + 5𝐻2 𝑂
2 2
30504101603434 30504101603434 30504101603434
13
12 × 4 + 10 × 1 × 32 −
2
→ 4 × 44 5 × 18

58 208 −→ 176 90

100 𝑥 − −−→ 176 90

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100 × 208
X = the weight of the oxygen needed to burn fuel = = 358.8
58
≈ 359 Kg

100 𝐾𝑔 𝐴𝑖𝑟 → 23 𝐾𝑔 𝑂2
𝑋 𝐾𝑔 𝐴𝑖𝑟 → 359 𝐾𝑔 𝑂2
359 × 100
∴ 𝑇ℎ𝑒 𝑡𝑜𝑡𝑎𝑙 𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑛𝑒𝑒𝑑𝑒𝑑 𝑎𝑖𝑟 (𝑋) = = 1561𝐾𝑔
23
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Example (4):
Gaseous Fuel used in a furnace Its Composition is C5H12. Calculate the weight of the
air (actual and theoretical )needed to burn 100 kilogram from that fuel (complete
combustion) Assuming that the percentage of the combustion 90% .Calculate the
composition of the wet combustion product by volume and by weight.

Solution:
𝐶5 𝐻12 + 8𝑂2 − − − −→ 5𝐶𝑂2 + 6𝐻2 𝑂
12 × 5 + 12 × 1 8 × 32 −→ 5 × 44 6 × 18

72 256 −→ 220 108

100 𝑥 − −−→ 220 108

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100 × 256
X = the weight of the oxygen needed to burn fuel = = 355.6
72
≈ 356 Kg

100 𝐾𝑔 𝐴𝑖𝑟 → 23 𝐾𝑔 𝑂2
𝑋 𝐾𝑔 𝐴𝑖𝑟 → 356 𝐾𝑔 𝑂2
356 × 100
∴ 𝑇ℎ𝑒 𝑡𝑜𝑡𝑎𝑙 𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑛𝑒𝑒𝑑𝑒𝑑 𝑎𝑖𝑟 (𝑋) = = 1547.8 ≈ 1548 𝐾𝑔
23
This is the amount of theoretical air needed to burn 100 Kg of fuel complete
combustion.

The actual amount of air needed to burn100 Kg of fuel complete combustion

30504101603434with efficiency (90%) 30504101603434 30504101603434

𝐶5 𝐻12 + 8𝑂2 − − − −→ 5𝐶𝑂2 + 6𝐻2 𝑂

12 × 5 + 12 × 1 8 × 32 −→ 5 × 44 6 × 18

72 256 −→ 220 108

90
100 × 𝑥 − −−→ 220 108
100

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100 × 256 × 90
X = the weight of the oxygen needed to burn fuel = = 320 Kg
72 × 100
100 𝐾𝑔 𝐴𝑖𝑟 → 23 𝐾𝑔 𝑂2
𝑋 𝐾𝑔 𝐴𝑖𝑟 → 320 𝐾𝑔 𝑂2
320 × 100
∴ 𝑇ℎ𝑒 𝑡𝑜𝑡𝑎𝑙 𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑛𝑒𝑒𝑑𝑒𝑑 𝑎𝑖𝑟 (𝑋) = = 1391.3𝐾𝑔
23
≈ 1392 𝐾𝑔
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

The weight of combustion products :

We have the following as combustion products :

➢ Un burned fuel
➢ Excess oxygen }Becausethecombustionisincomplete
➢ Nitrogen
➢ Carbon dioxide
➢ Water vapor
10
Weight of un burned fuel = × 𝑡𝑜𝑡𝑎𝑙 𝑤𝑒𝑖𝑔𝑡ℎ 𝑜𝑓 𝑓𝑢𝑒𝑙
100
10
Weight of un burned fuel = × 100 = 10 𝐾𝑔
100
Wight of excess oxygen :

2022/2023 the excess weight of the oxygen =2022/2023

thioratical wieght of oxygen − 2022/2023
Acual weigh of Oxygen =

the excess weight of the oxygen = 356 − 320 = 36 Kg

weight of Nitrogen from air :

100 𝐾𝑔 𝐴𝑖𝑟 → 77 𝐾𝑔 𝑁2
1548 𝐾𝑔 𝐴𝑖𝑟 → 𝑋 𝐾𝑔 𝑁2
77 × 1548
∴ 𝑇ℎ𝑒 𝑡𝑜𝑡𝑎𝑙 𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑁𝑖𝑡𝑟𝑜𝑔𝑒𝑛 𝑓𝑟𝑜𝑚 𝑎𝑖𝑟 (𝑋) = = 1191.9𝐾𝑔
100
≈ 1192 𝐾𝑔

weight of Carbon dioxide :

30504101603434
𝐶5 𝐻12 + 8𝑂230504101603434
− − − −→ 5𝐶𝑂2 + 6𝐻2 𝑂30504101603434
12 × 5 + 12 × 1 8 × 32 −→ 5 × 44 6 × 18
= = = =
72 256 −→ 220 108

90
100 × 𝑥 − −−→ 𝑦1 𝑦2
100

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220 × 100 × 90
𝒚𝟏 = weight of the 𝐶𝑂2 fromed = = 275𝐾𝑔
100 × 72
weight of water vapor formed

108 × 100 × 90
𝒚𝟐 = weight of the water vapor fromed = = 135𝐾𝑔
100 × 72

Substance Mass % Molecular Number of moles(moles) % moles

(Kg) Mass weight (Kg)
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

1 Un burned 10 0.1% 72 7.2 10%

fuel
2 Nitrogen 1192 72% 28 42.6 57.5%
3 Excess 36 2.9% 32 1.125 1.5%
oxygen
4 Carbon 275 17% 44 6.25 8%
dioxide
5 Water vapor 135 8% 18 17 23%
6 Sum 1648 100% - 74.175 100%

Example(5):
If the composition of the coal is :
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•

C=82% , H2=4% , O2= 5% ,S=1% ,N2=1% , H2O = 2% , ash

=5%

Calculate the theoretical amount of the air required to burn one

kilogram from this coal , Then calculate the weight of the
combustion products?

Answer:

C + O2 = CO2

12 32
30504101603434 30504101603434 30504101603434

0.82 x

X= weight of the O2 needed to burn the carbon =

0.82*32/12=2.187 Kg

H2 + ½ O2 = H2O

2 16

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0.04 x2

X2= weight of the O2 needed to burn the hydrogen = 0.04*16

/2=0.32 Kg

S + O2 = SO2

32 32

0.01 X3
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

X3= weight of the O2 needed to burn the sulfur

= 0.01*32/32=0.01 Kg

Weight of the O2 needed from air =

Weight of O2 needed to burn the fuel –weight of the O2 presence in

the fuel

= (2.187+0.32+0.01)-0.05 = 2.467kg

Weight of the needed air= 2.467*100/23

=10.72 Kg

Combustion products :
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• 1- nitrogen

• Weight of nitrogen from air =

• 10.72-2.47=8.253 kg

• Weight of nitrogen in the coal =0.01kg

• Weight of N2 in the combustion products

=8.253+0.01=8.263 kg

• 2- carbon dioxide:
30504101603434 30504101603434 30504101603434
C + O2 = CO2

12 44

0.82 y

y= weight of the CO2 in the combustion products = 0.82*44/12=3.0

Kg

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• 3- Water vapour :

H2 + ½ O2 = H2O

2 18

0.04 y2

y2= weight of the H2O produced= 0.04*18 =0.38Kg

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

4- Sulfur dioxide :

S + O2 = SO2

32 64

0.01 y3

y3= weight of the SO2= 0.01*64/32=0.02 Kg

• Weight of the combustion products=

= CO2 + N2 +H2O +SO2 + Ash

= 3.0 +8.263 + (0.38 +0.02)+0.02+0.05

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= 11.733Kg

• Example(6):
-------------

• Calculate the least amount of the air needed to burn 29 Kg

from butane C4H10 (complete combustion) ?

Answer:

C4H10 + (13/2) O2 -----> 4CO2 + 5H2O

30504101603434 30504101603434 30504101603434
58 (13/2)32

29 x

X = The weight of the oxygen needed to burn 29 Kg of

butane= (29*13*32)/(2*58)

= 104 Kg

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The weight of the air = (104*100)/23

=452Kg

Example (7):

Gaseous Fuel used in a furnace Its Composition is C4H10 .

Calculate the weight of the air needed to burn one kilogram
from that fuel (complete combustion) Assuming that the
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

percentage of the combustion 80% .Calculate the composition

of the dry combustion product by volume and by weight ?

Solution :

The com bustion reaction of the fuel is :

𝟏𝟑
C4H10 + 𝟐
O2 = 4CO2 + 5 H2O

The composition of the combustion product by volume :

Assume that 1 mole of butane:

𝟏𝟑
C4H10 + O2 = 4CO2 + 5 H2O
𝟐

1 6.5 4 5
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0.8

compound No. of moles %

CO2 0.8x
4
= 3.2 10.98
1

C4H10 0.2 0.69

O2 0.2x 6.5 = 1.3 4.46

30504101603434 30504101603434 30504101603434

N2 6.5 x
79
= 24.45 83.87
21

Sum. =29.15

% by volume :

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80 3.2
CO2 =4x = 3.2 x 100 = 10.98
100 29.15

1 𝑥 20
C4H10 = = 0.2 0.69
100

13 20
O2 = x =1.3 4.46
2 100

13 79 24.46 83.87
N2 = 2 x =
21 29.15 100
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

The composition of the dry combustion products by weight :

compounds No. of moles molecular weight % by weight

Mass

CO2 3.2 x 44= 140.8 16.03

C4H10 0.2 x 58 = 11.6 1.32

O2 1.3 x 32 = 41.6 4.73

N2 24.45 x 28 = 684.6 77.92

total 878.6 100

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Practice Excercises
1- Gaseous Fuel used in a furnace Its Composition is C5H12. Calculate the
weight of the air (actual and theoretical )needed to burn one kilogram from
that fuel (complete combustion) Assuming that the percentage of the
combustion 80% .Calculate the composition of the wet combustion product by
volume and by weight.

30504101603434 30504101603434 30504101603434

2- Gaseous Fuel used in a furnace Its Composition is :

60% C2H6

40% C3H8

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Calculate the weight of the air needed to burn one kilogram from that fuel
(complete combustion) Assuming that the percentage of the combustion 90% for
ethane and 80% for Propane .Calculate the composition of the combustion product?
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

30504101603434 30504101603434 30504101603434

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Water Treatment
Techniques
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Chapter 12

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WATER TREATEMENT TECHNIQUES

Three-quarters of the surface of the earth is covered with water. While this
is an impressive statistic, it is pale beside the spectacular Photographs that have
come to us from outer space. They reveal a beautiful blue planet bathed in
water, partly hidden by a veil of vapor.
30504101603434 30504101603434 30504101603434
Life came into being in this water. As living things became more complex
and specialized, they left the sea for the land, taking water with them as the
major part of their bodies. On the Planet Earth, water is life.
The proper study of water is the water molecule." The formula for water—
H2O—by itself tells us only its composition and molecular weight. It does
nothing to explain the remarkable properties that result from its unique

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molecular arrangement (see Figure 1). Two hydrogen atoms are located 105°
apart, adjacent to the oxygen atom, so that the molecule is asymmetrical,
positively charged on the hydrogen side and negatively charged on the oxygen
side. For this reason, water is said to be dipolar. This causes the molecules to
agglomerate, the hydrogen of one molecule attracting the oxygen of a
neighboring molecule.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

The linking of molecules resulting from this attractive force is called

hydrogen bonding, One of the consequences of hydrogen bonding is that
molecules of H2O cannot leave the surface of a body of water as readily as they
could without this intermolecular attraction. The energy required to rupture the
hydrogen bond and liberate a molecule of H2O to form vapor is much greater
than for other common chemical compounds. Because of this fact, the water
vapor—steam—has a high energy content and is an effective medium for
transferring energy in industrial plant operations, buildings, and homes.

Water also releases more heat upon freezing than do other compounds.
Furthermore, for each incremental change in temperature, water absorbs or
2022/2023 2022/2023 2022/2023
releases more heat—i.e., has great heat capacity—than many substances, so it
is an effective heat transfer medium.
The freezing of water is unusual compared to other liquids. Hydrogen bonding
produces a crystal arrangement that causes ice to expand beyond its original
liquid volume so that its density is less than that of the liquid and the ice floats.
If this were not the case, lakes would freeze from the bottom up, and
life as we know it could not exist.
Table 1.1 compares the boiling point and other heat properties of water
with similar molecules, such as hydrogen sulfide, and with dissimilar
30504101603434 30504101603434 30504101603434
compounds that are liquid at room temperature.
Because of the unusual structure of the water molecule, it is present in
the natural environment in all three states of matter, solid as ice, liquid as
water, and gas as vapor. It is the only chemical compound having this unusual
character.

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In addition to its unusual heat properties, water has physical properties

quite different from other liquids. Its high surface tension is easily
demonstrated by the experiment of "floating" a needle on the surface of water
in a glass (Figure 2).
This high surface tension, due to hydrogen bonding, also causes water to
rise in a capillary tube (Figure 1.3). This capillarity is partly responsible for the
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

system of circulation developed by living plants through their roots and tissue
systems.

2022/2023 2022/2023 2022/2023

30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Water is often called the universal solvent. Water molecules in contact with
a crystal orient themselves to neutralize the attractive forces between the ions
in the crystal structure. The liberated ions are then hydrated by these water
2022/2023 2022/2023 2022/2023
molecules as shown in Figure 1.4, preventing them from recombining and
recrystalizing.
This solvency and hydration effect is shown quantitatively by water's relatively
high dielectric constant.

30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Water ionizes so very slightly, producing only 107 moles of hydrogen and 107
moles of hydroxyl ions per liter, that it is an insulator—it cannot conduct
electrical current. As salts or other ionizing materials dissolve in water, electrical
conductivity develops. The conductivity of naturally occurring waters provides
a measure of their dissolved mineral content Another important phenomenon
occurring in water solutions related to dissolved matter (solutes), rather than
to water (solvent), is osmotic pressure.
2022/2023 2022/2023 2022/2023

If two aqueous solutions are separated by a membrane, water will pass

from the more dilute into the more concentrated one. This important process
controls the performance of all living cells. It explains the effectiveness of food
preservation by salting; the salt creates a strong solution, disrupting the cells
of organisms that might cause food spoilage, as the water inside their bodies
leaves in an attempt to dilute the external salt solution.
In specially designed membrane cells, the osmotic flow of water across
the membrane can be reversed by applying a sufficiently high pressure to the
more concentrated
30504101603434 solution. This process of "reverse osmosis" is30504101603434
30504101603434 a practical one
for desalination of water.
Finally, viscosity is another property of water affecting its treatment and
use. It is a measure of internal friction—the friction of one layer of molecules
moving across another. As water temperature rises, this internal friction
decreases.

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Because of the temperature effect, dissolved salts and gases can diffuse
more rapidly through warmer water, chemical treatment is hastened, and the
physical processes of sedimentation and degasification proceed faster.

WATER CHEMISTRY AND INTERPRETATION OF WATER ANALYSES

1. ALKALINITY AND ACIDITY
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Probably the most fundamental concept in the approach to understanding

water chemistry is the acidity-alkalinity relationship. The first step in grasping
this is an understanding of the dissociation of the water molecule itself into
hydrogen ions and hydroxyl ions, according to equation:
H2O= H+ + OH- (1)
K = [H+] [OH-] = 10-14
(For the sake of simplicity, this book will use the hydrogen ion, H+, while
recognizing that it actually exists in a hydrated form, the hydronium ion—
H3O+.)

THE pH NOTATION
2022/2023 2022/2023 2022/2023
Since the dissociation constant is so very small, 1014, at neutrality where
there are the same number of hydrogen and hydroxyl ions there are only 10 7
moles/l of each. This is equal to only 104 moles/L, corresponding to an actual
concentration of only 0.0001 mg/L H+ ion, equivalent to 0.005 mg/L as CaCO3.
Because we are dealing with such small numbers in the dissociation of
water into its ions, it is more convenient to substitute an expression involving
the power of 10. This expression is defined as pH, in which the relationship is:
PH = -log[H+]
The dissociation constant, K, changes with temperature, and this must
30504101603434 30504101603434 30504101603434
be taken into account in interpreting data involving H+ and OH- ions. For
example, many water treatment operations are carried out at high
temperatures, and samples from the system are usually cooled prior to analysis.
The H+ and OH- concentrations measured on the cooled sample, even
though different from those in the hot system, are usually used for control
purposes. But a physical chemist needing to know the conditions prevailing in

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the hot system must use the dissociation constant for the temperature in that
system.

The hydrogen ion concentration can be measured with a pH meter. It can

also be titrated (see glossary) when the concentration becomes large enough
to detectable by chemical analysis. Since pH is a logarithmic function, the
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

hydrogen ion concentration increases by a factor of 10 for each unit of pH

reduction.

When the pH drops below approximately 5, the hydrogen ion begins to

reach milligrams per liter levels, concentrated enough to be determined by
titration, using the correct organic dye indicator.
The chemical indicator originally selected by the water chemist for this
purpose was methyl orange, changing color at pH 4.2 to 4.4. The color change
of this indicator was so subtle—orange on the alkaline side to salmon pink on
the acid side—that researchers looked for a substitute to give a more
pronounced color change.
2022/2023 2022/2023 2022/2023

The one they developed produces a blue color on the alkaline side and
red on the acid side, with gray at the endpoint. Even though this special
indicator has replaced methyl orange, the water chemist still defines alkalinity
as methyl orange alkalinity ("M" alkalinity) which exists above the approximate
pH range of 4.2 to 4.4. M acidity is strong mineral acidity that exists below this
pH range. An approximate relationship between pH value and mineral acidity.

As the pH of a water solution is increased and exceeds about 9.6 to

30504101603434 30504101603434 30504101603434
9.8, a measurable concentration of hydroxyl ions begins to appear. The
hydroxyl alkalinity (caustic or OH alkalinity) can be determined either by using
a pH meter (or the equivalent in a colorimetric comparator) or by titration.
The relationship between hydroxyl alkalinity and pH is shown in Table 4.4.

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

An understanding of these concepts is necessary to put these acidity-

alkalinity relationships into perspective. To the theoretical chemist, a pH of 7 is
considered neutral; to the water chemist, a pH of 7 in itself means very little.
He must also know how much total alkalinity and how much free or combined
CO2 may be present.
For the water chemist, then, the dividing point between acidity and
alkalinity is not pH 7.0, but rather the2022/2023
2022/2023
M alkalinity endpoint, corresponding
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to a
pH of approximately 4.4.
The water chemist is also concerned with P alkalinity (phenolphthalein
alkalinity), which exists when the pH is over a range of 8.2 to 8.4, corresponding
to the change in phenolphthalein indicator from a colorless condition below 8.2
to pink or red above 8.4. In most natural water supplies, the pH is less than
8.2, so there is no P alkalinity.
Very few natural waters have a pH below about 5.0, so it is seldom that
strong mineral acids are found in fresh water. The pH range between the M
endpoint and the P endpoint defines the alkaline range in which bicarbonate
30504101603434 30504101603434 30504101603434
alkalinity exists and weak acids may be present, the most prominent of which
is carbonic acid—carbon dioxide in solution.

THE IMPORTANCE OF CO2

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The atmosphere is a mixture of gases containing about 79% N2 and 21%

O2 by volume. However, it also includes 0.04% CO2, extremely important to
the balance of life on the planet.
Carbon dioxide is produced by the combustion of fuel. Even before human
activities made a significant contribution to the CO2 content of the atmosphere,
the respiration of animal life—which is also a fuel consuming process—
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

introduced CO2 into the air. Plants containing chlorophyll utilize carbon dioxide
in building cellular material such as carbohydrates. This reaction is called
photosynthesis because photons of energy from the sun are needed for the
reaction.

The chlorophyll catalyzes the reaction between water and CO2. Since the
solubility of CO2 in water is less than 2000 mg/L at ambient air temperatures in
a CO2-saturated atmosphere, at the normal atmospheric level of 0.04% CO2
less than 1 mg/L CO2 dissolves in 2022/2023
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rainwater. However, once the rainwater
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penetrates the mantle of soil, it is exposed to CO2 gas levels a hundredfold

greater than in the atmosphere, created by the respiration of soil organisms as
they convert organic food into its products of combustion. Well waters, then,
which have percolated through this CO2-rich zone may contain from 10 to
several 100 mg/L dissolved CO2.

When CO2 dissolves in water, it reacts with water to form carbonic acid,
which dissociates into the hydrogen ion and the bicarbonate ion according to
the reaction:
30504101603434 30504101603434 30504101603434

If distilled water is completely saturated with CO2, approximately 1600

mg/L dissolves in the water, and the pH is decreased to approximately 4. The
equivalent amount of a strong acid like H2SO4 would decrease the pH to about
2.5, illustrating the weak character of carbonic acid.

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THE SOURCE OF ALKALINITY

The alkalinity of most natural water supplies is caused by dissolved
bicarbonate (HCO3-) salts. The following equations show how water containing
CO2 from the atmosphere and from respiration of soil organisms dissolves
magnesium and calcium from a common mineral, dolomite (CaCO3 • MgCO3),
to produce hardness and alkalinity in ground water:
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

In the pH range of 4.4 to 8.2, there remains a balance between excess CO 2

and bicarbonate ions which is measured by pH value.

This shows that a water containing 1 mg/L CO2 and 10 mg/L alkalinity has
the same pH as one containing 10 mg/L CO 2 and 100 mg/L alkalinity. In the
first case, the addition of 1 mg/L CO2 would produce a large change in pH,
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whereas in the second case, the same 1 mg/L CO2 addition would not produce
a noticeable change. The alkalinity moderates or buffers the pH change, and
alkalinity is known as a buffer.

Water attacks and dissolves many other minerals from the lithosphere in
addition to dolomite.
shows the distribution of the elements in the earth's crust. The three most
prominent are present in the form of oxides, SiO2, Al2O3,and Fe2O3, which are
only very slightly soluble in water.
CO3-2 /HCO3-
30504101603434
DISTRIBUTION 30504101603434 30504101603434

Most natural waters contain bicarbonate alkalinity and are at a pH less than
about 8.2 to 8.4. Above this pH, CO2 ceases to exist in measurable quantities
and the carbonate ion begins to make itself known. The equilibrium reaction is
as follows:

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Many lime-treated waters have a pH above the phenolphthalein

endpoint—that is, they contain P alkalinity. In the range of pH 8.2 to 9.6, the
bicarbonate and carbonate ions exist together in the absence of measurable
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

carbon dioxide or hydroxyl ions.

The distribution between the carbonate and bicarbonate ions can also be
calculated after measuring P and M alkalinities according to the following
equations.
CO3-- = 2 X P
HCO3- = M - CO3 = M - 2P

The distribution of all forms of CO3--

As the pH increases above 9.6, the hydroxyl alkalinity becomes measurable.

EFFECTS OF IMPURITIES
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If magnesium is precipitated with calcium carbonate, the residual calcium
in solution may be increased. The inclusion of other impurities, also been shown
to increase the solubility of calcium carbonate. It would seem, then, that
empirical data from a variety of plants should be used cautiously in estimating
what to expect in a given situation; if the calculation involves lime treatment of
an unknown water supply and the contamination levels are not fully denned,
there is no substitute for an actual bench test to determine the response of that
water to lime treatment.
Magnesium solubility is as difficult to predict with accuracy as calcium
30504101603434 30504101603434 30504101603434
solubility, and for the same general reasons. The solubility of magnesium
hydroxide is reported to be in the range of 30 to 40 mg/L at 770F (250C).
Because of the difference in solubility product relationship:

KCa = [Ca2+] X [CO32-] KMg = [Mg2+] X [OH-]2

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Magnesium concentration is affected more by changes in hydroxyl

concentration than calcium is by changes in carbonate concentration. Any
increase in carbonate produces a corresponding decrease in calcium, but an
increase in hydroxyl concentration affects the magnesium concentration in a
squared relationship. Thus a doubling of OH- will cause Mg2+ to drop to one-
fourth its original value.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

When water is softened with lime—in the pH range of 9.5 to 10.5—

magnesiumprecipitates as the hydroxide and the precipitate is positively
charged. In the same pH range, CaCO3 precipitate is negatively charged.
Furthermore, silica in the system is usually present as a strong, negatively
charged colloid. Sodium aluminate may be introduced in the system as a strong
anionic complex. All of this may account for the coprecipitation of magnesium
with calcium, the strong adsorption of silica on Mg(OH)2 precipitate, and the
low residual magnesium often achieved by the treatment of water with sodium
aluminate in addition to lime.
DISSOLVED GASES
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Carbon dioxide, for example, dissolves to form carbonic acid, which ionizes
to produce H+ and HCO3- ions. Other ionizing gases include sulfur dioxide,
hydrogen sulfide, and hydrocyanic acid, which form weak acids when dissolved
in water. Because of this effect, the addition of a strong acid to water containing
these gases will force the equilibrium to the left, essentially eliminating the
ionized portion so that all of the gas is in molecular form and free to escape
from the water as gas molecules. For example, with CO2:

30504101603434 30504101603434 30504101603434

On the other end of the scale is ammonia, which dissolves and ionizes to
forma weak base according to the equation: There are other gases that dissolve
in water, but do not ionize. Among these are oxygen, nitrogen, and methane.
The most prominent of these in its effect on water systems is oxygen. This

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corrosion, however, is usually caused by dissolved oxygen which is free to

attack the bare metal surface when it is wetted by a water which cannot form
a protective calcium carbonate film or scale.

MINERALS AND CONDUCTANCE

An important consideration in water chemistry is electrical conductivity. The
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

higher the mineral content of the water, the higher its conductivity. This has
several important consequences. First, the higher the conductivity, the more
freely can electrical current flow through the water, and the more rapid is the
corrosion rate if other conditions favor corrosion. Second, the higher the
conductivity, the less completely ionized are the minerals dissolved in the water,
as the ions are packed more closely together and collide more frequently. This
decreases the activity coefficient, or freedom, increasing the solubility of CaCO3
and other slightly soluble materials. As a result, CaCO3 is more soluble in
seawater than in resh water under equal conditions of pH, alkalinity, and
temperature. There are many factors involved in the corrosion process, of which
pH, conductivity ,temperature, and dissolved oxygen are usually foremost.
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Other important factors in the corrosion mechanism include the presence of
dissimilar metals in the system, with the more anodic becoming corroded, and
dissimilarities in them etallurgical structure of a single metal in the system.
SOLIDMATTER
Solid matter occurs in most waters as suspended solids and colloidal matter.
The concentration of suspended solids is determined by filtration, the collected
solids on the filter membrane being dried and weighed. Those suspended solids
which are large and heavy are called settleable solids, and these may be
determined volume tricallyin a settling cone as a simple control test or weighed.
30504101603434 30504101603434 30504101603434
The solids remaining with supernatant water above the settled matter are
fine and called turbidity.
Turbidity in water is measured by the effect of the fine suspended particles on
a light beam. Light-interference analytical methods are classified as
nephelometric, and one system of turbidity measurement uses nephelometric
turbidity units (NTU). The original nephelometric method used a standardized

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candle, providing results in Jackson turbidity units (JTU), named for the man
whod eveloped the standard candle. Turbidity standards prepared with
formazin forcomparator tube determinations have given rise to a third turbidity
unit, the FTU.
The JTU is measured with a transmitted light beam, while the NTU is measured
by light scattering, so there is no comparison between the two units that applies
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

to all waters. In the case of turbidity standards prepared from 325 mesh
diatomaceous earth, a reading of 100 NTU is equivalent to about 40 JTU.
Colloidal matter in water is sometimes beneficial and sometimes harmful.
Beneficial colloids are those that provide a dispersant effect by acting as
protective colloids. In a suspension of clay or silt in water, the smallest particles
usually carrya negative charge. If these negative charges are neutralized, the
particles are coagulated; however, if additional negative charges are introduced
into the system deliberately, sedimentation may be prevented. Sodium silicate
probably works in
this way; so too do some kinds of organic materials in water, such as lignins
and tannins, which occur in highly colored water sources. Silica in itself can be
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troublesome ,forming a very hard scale when it deposits on heat transfer
surfaces.

ORGANICS IN WATER
While tannin and lignin are generally present as colloidal suspensions in
water, many organic compounds are actually soluble in water. There is an
astounding variety of organic compounds in water, put there both by nature
and humankind.

30504101603434 30504101603434 30504101603434

It is unusual for a water analysis to show all of this organic matter broken
down by individual molecular constituents, because of the great variety. If the
analyst should know what may be present [for example, polychlorinated
biphenyls(PCBs), or total trihalomethane (TTHM)], it can be found. it is not at
all unusual to find an increase in one test, such as BOD, with a concurrent
decrease in another test, such as TOC.

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

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30504101603434 30504101603434 30504101603434

CLASS 1—PRIMARY CONSTITUENTS
This category includes dissolved solids generally exceeding 5 mg/L, and
often several orders of magnitude above this level, Bicarbonate (HCO3—
Molecular Weight 61), The bicarbonate ion is the principal alkaline constituent
of almost all water supplies.

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It is generally found in the range of 5 to 500 mg/L, as CaCO3. Its

introduction into the water by the dissolving action of bacterially produced CO2
on carbonate- containing minerals has been explained elsewhere. Normal
activities of the human population also introduce alkaline materials into water,
evidenced by a typical increase of alkalinity of sewage plant effluent of 100 to
150 mg/L above the alkalinity of the municipal water supply. Much of this is
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

due to the alkalinity of industrial and domestic detergents.

Alkalinity in drinking water supplies seldom exceeds 300 mg/L. The control
of alkalinity is important in many industrial applications because of its
significancein the calcium carbonate stability index. Alkalinity control is
important in both concentrated boiler water and cooling water in evaporative
cooling systems. Calcium is the major component of hardness in water and
usually is in the range of 5 to 500 mg/L, as CaCO3, (2 to 200 mg/L as Ca).
It is present in many minerals, principally limestone and gypsum. Limestone
deposits are often the residue of the
Fossils of tiny aquatic organisms, such as polyps, that have taken calcium from
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the seawater in which they lived, and used it for their skeletons. This is but one
of many cycles in nature whereby some component of the environment is
continually withdrawn by living things and eventually returned directly or
indirectly.

Calcium removed from water in softening operations is later returned to

the environment, often to the watershed, by way of a precipitate or a brine
which is the by-product of the softening reaction. Calcium is a major factor in
determining stability index. Calcium reduction is often required in treating
30504101603434 30504101603434 30504101603434
cooling tower makeup. Complete removal is required for many industrial
operations, particularly for boiler makeup, textile finishing operations, and
cleaning and rinsing in metal finishing operations.

Hardness
What is Hardness?

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Hardness of water is a measure of its capacity to precipitate soap and is

caused mainly by the presence of divalent cations of calcium (Ca +2) and
magnesium (Mg+2). Other multivalent cations also cause water hardness such
as Fe+3, Sr+2, Zn+2, Mn+2.

Types of Hardness
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

1. Total Hardness (TH)

Hardness caused by calcium ions and magnesium ions. Calcium and
magnesium are normally the only significant minerals that cause hardness, so
it is generally assumed that:

Total Harness (TH) = Ca+2 hardness + Mg+2 hardness

Carbonate Hardness (CH):

Carbonate hardness is caused primarily by the bicarbonate salts of calcium
and magnesium, which are calcium bicarbonate, Ca(HCO3)2, and magnesium
bicarbonate Mg(HCO3)2. Calcium and magnesium combined with carbonate
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(CO3) also contribute to carbonate hardness.

Non-Carbonate Hardness (NCH):

Non-carbonate hardness is a measure of calcium and magnesium salts
other than carbonate and bicarbonate salts.
These salts ate calcium sulfate (CaSO4), calcium chloride (CaCl2),
magnesium sulfate (MgSO4), and magnesium chloride (MgCl2). Therefore, non-
carbonate hardness is hardness exceeding carbonate hardness.
If the total hardness (TH) is greater than alkalinity (ALK), then:
30504101603434 30504101603434 30504101603434
Carbonate Hardness (CH) = alkalinity (ALK)

Non-carbonate Hardness(NCH)=total hardness –carbonate hardness

(CH)

If the total hardness (TH) is less than alkalinity (ALK),

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then:
Carbonate Hardness (CH) = total hardness (TH)
Non-carbonate Hardness (NCH) = 0

Example(1):
A sample of water has 210 mg/l alkalinity, 330 mg/l total hardness and
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

290 mg/l calcium hardness. Find out the following?

a) Magnesium hardness
b) Carbonate hardness
c) Non-carbonate hardness.
Solution:
a) Mg hardness = TH – Ca hardness = 330-290 = 40 mg/l
Since TH is greater than Alk
b) Carbonate hardness = ALK = 210 mg/l
c) Non-Carbonate hardness = TH – CH = 330-210 = 120 mg/l

Water Hardness
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Public tolerance of hardness varies, however, a level ranging from 60 to 120
mg/l as CaCO3 is generally acceptable.
Disadvantages of hardness

1. excessive soap consumption during laundering

2. scale-formation in hot water heaters and pipes.

Hardness
30504101603434 Ranges 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

CALCULATING CALCIUM HARDNESS AS CaCO3

The hardness (in mg/L as CaCO3) for any given metallic ion is calculated
using Equation the following equation.

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Example (2)
A water sample has calcium content of 51 mg/L. What is this calcium
hardness expressed as CaCO3?

30504101603434 30504101603434 30504101603434

Example (3)

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The calcium content of a water sample is 26 mg/L. What is this calcium

hardness expressed as CaCO3?
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

CALCULATING MAGNESIUM HARDNESS AS CaCO3:

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Example(4):
A sample of water contains 24 mg/L magnesium. Express this
magnesium hardness as CaCO3.
Solution
Referring to Equation 21.2:

30504101603434 30504101603434 30504101603434

Example(5):

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The magnesium content of a water sample is 16 mg/L. Express this

magnesium hardness as CaCO3.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

CALCULATING TOTAL HARDNESS

Calcium and magnesium ions are the primary cause of hardness in
water. To find total hardness,
we simply add the concentrations of calcium and magnesium ions,
expressed in terms of calcium
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carbonate (CaCO3):

Example(6 ):

30504101603434 30504101603434 30504101603434

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Example(7):
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

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CALCULATING CARBONATE AND NONCARBONATE HARDNESS

As mentioned,
30504101603434 total hardness is comprised of calcium and magnesium
30504101603434 30504101603434

hardness. Once total hardness has been calculated, it is sometimes used to

determine another expression hardness — carbonate and non carbonate.
When hardness is numerically greater than the sum of carbonate and
carbonate alkalinity, that amount of hardness equivalent to the total alkalinity

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(both in units of mg CaCO3/L) is referred to as the carbonate hardness; the

amount of hardness in excess of this is the noncarbonated hardness.
When the hardness is numerically equal to or less than the sum of
carbonate and noncarbonate alkalinity, all hardness is carbonate hardness,
and noncarbonate hardness is absent.
Again, the total hardness is comprised or carbonate hardness and
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

noncarbonate hardness:

Total hardness = carbonate hardness + noncarbonate hardness

When the alkalinity (as CaCO3) is greater than the total hardness, all the
hardness is carbonate hardness:
Total hardness (mg/L) as CaCO3 = carbonate hardness (mg/L) as CaCO3
Total hardness mg L as CaCO3 carbonate hardness mg L as CaCO3
noncarbonate hardness mg L as CaCO3

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30504101603434 30504101603434 30504101603434

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Example(8):
A water sample contains 110 mg/L alkalinity as CaCO3 and 105 mg/L
total hardness as CaCO3.
What is the carbonate and noncarbonate hardness of the sample?
Solution
Because the alkalinity is greater than the total hardness, all the hardness is
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

carbonate hardness:
Total hardness (mg/L) as CaCO3 = Carbonate hardness (mg/L) as CaCO3
105 mg/L as CaCO3 = Carbonate hardness
No noncarbonate hardness is present in this water.
Example(9):
The alkalinity of a water sample is 80 mg/L as CaCO3. If the total hardness of
the water sample is 112 mg/L as CaCO3, what is the carbonate and
noncarbonate hardness (in mg/L as CaCO3)?
Solution
Alkalinity is less than total hardness; therefore, both carbonate and
noncarbonate hardness will be present in the hardness of the sample.
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CALCULATION FOR REMOVAL OF NONCARBONATE HARDNESS

Soda ash is used for precipitation and removal of noncarbonate
hardness. To calculate the soda ash dosage required, we use, in
combination, Equations.
30504101603434 30504101603434 30504101603434

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Example(10)
A water sample has a total hardness of 250 mg/L as CaCO3 and a total
alkalinity of 180 mg/L. What soda ash dosage will be required to remove
the noncarbonate hardness (in mg/L)?
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Solution
Calculate the noncarbonate hardness using Equation

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ALKALINITY DETERMINATION
Alkalinity measures the acid-neutralizing capacity of a water sample. It is
an aggregate property of the water sample and can be interpreted in terms of
specific substances only when a complete chemical composition of the sample
is also performed. The alkalinity of surface waters is primarily due to the
carbonate, bicarbonate, and hydroxide content and is often interpreted in
terms of the concentrations of these constituents.
The higher the alkalinity, the greater the capacity of the water to
neutralize acids; conversely, the lower
30504101603434
the alkalinity, the less the
30504101603434
neutralizing
30504101603434

capacity. To detect the different types of alkalinity, the water is tested for
phenolphthalein and total alkalinity, using Equations

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Example(11):
A 100-mL water sample is tested for phenolphthalein alkalinity. If 1.3-mL
titrant is used to pH 8.3and the sulfuric acid solution has a normality of 0.02
N, what is the phenolphthalein alkalinity of the water?
Solution
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Referring to Equation:

Example(12):
A 100-mL sample of water is tested for alkalinity. The normality of the
30504101603434 30504101603434 30504101603434
sulfuric acid used for titrating is 0.02 N. If 0 mL is used to pH 8.3, and 7.6 ml
titrant is used to pH 4.5, what is the phenolphthalein and total alkalinity of the
sample?
Solution

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

DETERMINING BICARBONATE, CARBONATE, AND

HYDROXIDE KALINITY
Interpretation of phenolphthalein and total alkalinity test results (assuming
all of the alkalinity found is due to carbonate, bicarbonate, or hydroxide) can
be made .

Example(13):
A water sample is tested for phenolphthalein and total alkalinity. If the
phenolphthalein alkalinity is 10 mg/L as CaCO3 and the total alkalinity is 52
2022/2023 2022/2023 2022/2023
mg/L as CaCO3, what are the bicarbonate, carbonate, and hydroxide
alkalinities of the water?

30504101603434 30504101603434 30504101603434

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Solution
Based on titration test results, phenolphthalein alkalinity (10 mg/L) is less
than half of the total alkalinity (52 mg/L ÷ 2 = 26 mg/L; see Table 21.1);
therefore, each type of alkalinity is calculated as follows:
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Example(14):
Results of alkalinity titrations on a water sample are as follows:
Sample was 100 ml
- 1.4 ml titrant was used to pH 8.3
- 2.4 ml total titrant was used to pH 2022/2023
2022/2023
4.5 2022/2023

- Acid normality was 0.02 N H2SO4

What is the phenolphthalein, total bicarbonate, carbonate and hydroxide
alkalinity?
Solution :

30504101603434 30504101603434 30504101603434

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Problems Caused By Hardness

1. Excessive soap is needed for washing (i.e. soap will not lather). Some
modern detergents work less efficiently because anions (also known as
surfactants) which are meant to hold dirt particles in suspension react with
Ca2+ and Mg2+ instead.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2. Soap based on animal fats can react with Ca2+ and Mg2+ forming a
precipitation that can ruin cloths and irritate skin.

3. Some foods, particular dried beans and peas, become tough and rubbery
when cooked in hard water. Calcium ions cause cross-linking to occur
between certain molecules within the beans, the subsequent structure
prevents water entering and the bean remains hard.

4. Scale can clog pipes and fittings. Also heating elements can become 90%
less efficient with a 25mm coating of CaCO3.

Water Softening
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There are three basic ways to soften water:

1. Force insoluble substances, such as CaCO3 and Mg(OH)2, to precipitate

before water enters the system.

2. Remove the Ca2+ and Mg2+ ions from the water.

3. Prevent the Ca2+ ions from CaCO3 by complexing them.
Notes:

1. Temporary hardness also called Carbonate hardness ( CH) –caused by

Calcium and Magnesium carbonates
30504101603434
and bicarbonates --removed
30504101603434
by
30504101603434

• Boiling and
• Addition of lime.
2. Permanent hardness (NCH) Due to Sulphates, Chlorides and Nitrates of
Calcium & Magnesium Removed by
• Lime –Soda process,

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• Base exchange, Zeolite or Ion exchange process

• Demineralisation or Deionisation process,
• Revese Osmosis.
Lime & Soda help in removing entire hardness, both CH and NCH

Water softening → Removal of hardness to satisfy the requirements

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Temporary hardness of water [carbonate hardness]→ Due to the

presence of carbonate and bicarbonate of calcium and magnesium CaCO₃,
dissolves in water containing CO₂ and exists in the form of bicarbonates in
natural water
- Removal → By boiling
Calcium bicarbonate Calcium carbonate

Ca (HCO₃)₂ + Heat ------> CaCO₃ + CO₂ +H₂O

The magnesium carbonate (MgCO₃) is fairly dissolved in water and cannot

be removed by boiling, but can be removed by adding lime →
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Soluble Hydrated lime Insoluble.
↑↑↑↑
MgCO₃ +Ca (OH) ₂----> Mg (OH) ₂ + CaCO₃ ↓

Similarly Magnesium bicarbonate → Calcium bicarbonate Magnesium

hydroxide↓

Permanent hardness[Bicarbonate hardness] → due to presence of

sulphate, chlorides, and nitrates of calcium and magnesium.Ca⁺⁺, Mg⁺⁺, Fe⁺⁺,
30504101603434 30504101603434 30504101603434
Mn⁺⁺ etc. also contribute hardness to the water

Methods of removal of hardness:

1. Lime soda process

2. Base-exchange process/zeolite process

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3. Demineralization.

Lime Softening
Chemical precipitation is one of the more common methods used to soften
water. Chemicals normally used are lime (calcium hydroxide, Ca(OH)2) and
soda ash (sodium carbonate, Na2CO3). Lime is used to remove chemicals that
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

cause carbonate hardness. Soda ash is used to remove chemicals that cause
non-carbonate hardness.

When lime and soda ash are added, hardness-causing minerals form
nearly insoluble precipitates. Calcium hardness is precipitated as calcium
carbonate (CaCO3). Magnesium hardness is precipitated as magnesium
hydroxide (Mg(OH)2). These precipitates are then removed by conventional
processes of coagulation/flocculation, sedimentation, and filtration.

Because precipitates are very slightly soluble, some hardness remains in

the water--usually about 50 to 85 mg/l
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(as CaCO3). This hardness2022/2023
2022/2023
level is
desirable to prevent corrosion problems associated with water being too soft
and having little or no hardness.

LIME ADDITION

30504101603434 30504101603434 30504101603434

CO2 does not contribute to the hardness, but it reacts with the lime, and
therefore uses up some lime before the lime can start removing the hardness.

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LIME AND SODA ASH ADDITION

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

LIME DOSAGE CALCULATION FOR REMOVAL OF CARBONATE

HARDNESS
The lime–soda ash water-softening process uses lime, Ca(OH)2, and
soda ash, Na2CO3, to precipitate hardness from solution. Carbonate hardness
(calcium and magnesium bicarbonates) is complexed by lime.
Noncarbonate hardness (calcium and2022/2023
2022/2023
magnesium sulfates or chlorides)
2022/2023

requires the addition of soda ash for precipitation. The molecular weights of
various chemicals and compounds used in lime–soda as softening calculations
are as follow:

30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

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30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

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30504101603434 30504101603434 30504101603434

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Example(15):
A water sample has a carbon dioxide content of 4 mg/L as CO2, total
alkalinity of 130 mg/L as CaCO3, and magnesium content of 26 mg/L as
Mg2+. Approximately how much quicklime (CaO × 90% purity) will be
required for softening? (Assume 15% excess lime.)
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

30504101603434 30504101603434 30504101603434

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Example(16):
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

CALCULATION FOR REMOVAL OF NONCARBONATE HARDNESS

Soda ash is used for precipitation and removal of noncarbonate
hardness. To calculate the soda ash dosage required, we use, in
combination, Equations.
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Ion Exchange Softening

30504101603434 30504101603434 30504101603434
Ion-exchange is used extensively in small water systems and
individual homes. Ion-exchange resin, (zeolite) exchanges one ion from
the water being treated for another ion that is in the resin (sodium is one
component of softening salt, with chlorine being the other). Zeolite resin
exchanges sodium for calcium and magnesium. The following chemical

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reactions show the exchange process, where X represents zeolite, the

exchange material.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

These reactions represent cation exchange, the exchange of positive ions.

To replenish the sodium ions used, units need to be regenerated with
material containing high amounts of sodium, normally salt brine.
Example(17):
If water contains 10 grains per gallon of hardness, how many gallons of
water would the resin remove? The tank holds 500 cubic feet of resin with
capability of removing 45,000 grains per gallon per cubic foot.

2022/2023 2022/2023 2022/2023

ION EXCHANGE CAPACITY

An ion exchange softener is a common alternative to the use of lime
and
30504101603434 soda ash for softening water. Natural water sources contain
30504101603434 dissolved
30504101603434

minerals that dissociate in water to form charged particles called ions.

Of main concern are the positively charged ions of calcium, magnesium,
and sodium; bicarbonate, sulfate, and chloride are the normal negatively
charged ions of concern. An ion exchange medium, called resin is a
material that exchanges a hardness-causing ion for another one that does

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not cause hardness, holds the new ion temporarily, and then releases it
when a regenerating solution is poured over the resin.
The removal capacity of an exchange resin is generally reported
as grains (gr) of hardness removal per cubic foot (ft3) of resin. To
calculate the removal capacity of the softener, we use:
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Exchange capacity (grains) = Removal capacity (grains/cu ft) ×

media volume (cu ft)

Example(18):
The hardness removal capacity of an exchange resin is 24,000
grains/cu ft. If the softener contains a total of 70 cu ft of resin, what is the
total exchange capacity (in grains) of the softener?
Solution
Exchange capacity (grains) = 22,000 grains/cu ft × 70 cu ft
= 1,540,000 grains

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Example(19):
An ion-exchange water softener has a diameter of 7 ft. The depth of resin
is 5 ft. If the resin has a removal capacity of 22-kilograins/cu ft, what is
the total exchange capacity of the softener (in grains)?
Solution
Before the exchange capacity of a softener can be calculated, the cu ft
resin volume must be known:

30504101603434 30504101603434 30504101603434

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WATER TREATMENT CAPACITY

To calculate when the resin must be regenerated (based on volume of
water treated), we must know the exchange capacity of the softener and
the hardness of the water:
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Example(20):
An ion-exchange softener has an exchange capacity of 2,455,000
grains. If the hardness of the water to be treated is 18.6 grains/gallon,
how many gallons of water can be treated before regeneration of the resin
is required?
Solution
Referring to Equation

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Water treatment
Objectives of water treatment
- The principal objective of water treatment is to provide potable
water that is chemically and biologically safe for human consumption.
It should also be free from unpleasant tastes and odors.
- Water treatment aims at producing water that satisfies a set of
drinking water quality standards at a reasonable price to the consumers.
-
30504101603434 Removal of solids in water. Solids maybe suspended,30504101603434
30504101603434 dissolved or
colloidal. Some of the dissolved solids should stay in water at healthy
concentrations.

Water classification by source

- Ground- vs. Surface Water

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1. COAGULATION
Colloidal species encountered in raw water and wastewater include clay,
silica, iron and other heavy metals, color, and organic solids such as the
debris of dead organisms. Colloids may also be produced in precipitation
processes such as lime softening. Oil in wastewater is frequently colloidal.
Among the wide variety of colloidal materials in water, there is a broad
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

distribution of particle sizes.

Colloids always require coagulation to achievean effective size and
settling rate; but even larger particles, which are not truly colloidal and would
settle if given enough time, may require coagulation to form larger, faster
settling floe. When insufficient settling time is available in a treatment plant to
remove suspended solids, coagulation and flocculation may cause them to
grow in size and settle rapidly enough to overcome the physical limitation of
the plant design.
Colloids are categorized as hydrophobic (water hating) or hydrophilic
(water loving). Hydrophobic colloids do not react with water; most natural
clays are hydrophobic. Hydrophilic colloids react with water; the organics
2022/2023 2022/2023 2022/2023
causing color are hydrophilic. Of importance in water treatment, the
hydrophiloc colloids may chemically react with the coagulant used in the
treatment process. So hydrophilic colloids require more coagulant than
hydrophobic, which do not chemically react with the coagulant.

High intensity mixing, which distributes the coagulant and promotes

rapid collisions, is most effective. The frequency and number of particle
collisions are also important in coagulation. In a low turbidity water, the
addition of solids such as clay or the recycle of previously settled solids may
30504101603434 30504101603434 30504101603434
be required to increase the number of particle collisions.

2. FLOCCULATION
The floe formed by the agglomeration of several colloids may not be large
enough to settle or dewater at the desired rate. A flocculant gathers together
floe particles in a net, bridging from one surface to another and binding the

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individual particles into large agglomerates Alum, iron salts, and high
molecular weight polymers are common flocculants.
Flocculation is promoted by slow mixing, which brings the floes gently
together; too high a mixing velocity tears them apart, and they seldom re-
form to their optimum size and strength. Flocculation not only increases the
size of floe particles, but it also affects the physical nature of the floe. Sludge
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

and slurries, when flocculated, dewater at faster rates on sand beds and in
mechanical dewatering equipment because of the less gelatinous structure of
the floc.

COAGULA TION AND FLOCCULA TION CHEMICALS:

Historically, metal coagulants (alum and iron salts) have been most
widely used in water clarification. These products function both as coagulants
and flocculants.
When added to water, they form positively charged species in the typical pH
range for clarification, about 6-7. This hydrolysis reaction produces insoluble
gelatinous aluminum or ferric hydroxide.
2022/2023 2022/2023 2022/2023

A12(SO4)3 + 6H2O — 2Al(OH)3 + 3H2SO4 (1)

FeCl3 + 3H2O - Fe(OH)3 + 3 HCl (2)
Note that the by-products are hydroxide precipitates and mineral acids;
the latter react with alkalinity in the water, reducing pH and producing a
second byproduct,CO2. Sometimes the gaseous CO2 by-product interferes with
the coagulation process by coming out of solution, adsorbing on the hydrous
precipitate, and causing floe flotation rather than settling.
Poly aluminum chloride, a product in wide use in Japan, avoids the
30504101603434 30504101603434 30504101603434
problem of alkalinity reduction. When the material hydrolyzes, the floc formed
incorporates the chloride ion into the floe structure so it is not available to
produce acid, reduce alkalinity, and form by-product CO2. Even if there are
no suspended solids in the water initially, the metal coagulants form floes
which enmesh the destabilized colloids. However, the voluminous sludge

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produced by the addition of metal coagulants create disposal problems

because they are usually difficult to dewater.

This is why alum and iron salts are not often used to improve efficiency
of centrifuges, filter presses, and other dewatering devices.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Metal coagulants are particularly sensitive to pH and alkalinity. If pH is

not in the proper range, clarification is poor, and iron or aluminum may be
solubilized and cause problems to the water user. The lower the coagulant
dosage, them ore sensitive the floe is to pH changes.

SOLIDS/LIQUIDS SEPARATION
1. Screening
Straining includes such conventional devices as bar screens traveling
trash screens remove relatively large floating and suspended debris).
2. Sedimentation
Sedimentation is the removal of suspended solids from water by
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gravitational settling. The settling rate of particles is affected by their size,
shape, and density as well as by the liquid they are settling through. As a
particle settles, it accelerates until Filtration
3. Filtration
Granular Media Filtration. Granular media filtration is generally applicable
for removal of suspended solids in the 5 to 50 mg/L range where an effluent
of less than 1 JTU (Jackson turbidity unit) is required. Sand filters have been
used form any years as a final polishing step in municipal and industrial water
plants where the clarifier effluent contains 5 to 20 mg/L of suspended solids.
30504101603434 30504101603434 30504101603434

4. Adsorption: is dependent on the physical characteristics of the suspended

solids and the filter media. It is a function of filter media grain size and
such floe properties as size, shear strength, and adhesiveness. Adsorption
is also affected by the chemical characteristics of the suspended solids, the
water, and the filter media.

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WATER DISINFECTION BY CHLORINE

- Disinfection requirements
Disinfection reduces pathogenic microorganisms in water to levels
designated safe by public health standards. This prevents the transmission
of disease. An effective disinfection system kills or neutralizes all pathogens
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

in the water. It is automatic, simply maintained, safe, and inexpensive. An

ideal system treats all the water and provides residual (long term)
disinfection. Chemicals should be easily stored and not make the water
foul-tasting.

Testing water for biological quality The biological quality of drinking

water is determined by tests for total coliform (which includes E. coli and
fecal coliforms). These organisms are found in the intestinal tract of warm-
blooded animals and in soil. Fecal coliforms and E. coli only come from
human and animal fecal waste. The presence of coliform in water indicates
pathogenic contamination,
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Chlorine treatment Chlorine readily combines with chemicals dissolved
in water, microorganisms, small animals, plant material, tastes, odors, and
colors. These components "use up" chlorine and comprise the chlorine
demand of the treatment system. It is important to add sufficient chlorine
to the water to meet the chlorine demand and provide residual disinfection.
The chlorine that does not combine with other components in the water is
free (residual) chlorine, and the breakpoint is the point at which free
chlorine is available for continuous disinfection.
An ideal system supplies free chlorine at a concentration of 0.3-0.5
30504101603434 30504101603434 30504101603434
mg/l. Simple test kits, most commonly the DPD colorimetric test kit (so
called because diethyl phenylene diamine produces the color reaction), are
available for testing breakpoint and chlorine residual in private systems.
The kit must test free chlorine, not total chlorine.

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Contact time with microorganisms The contact (retention) time in

chlorination is that period between introduction of the disinfectant and
when the water is used. A long interaction between chlorine and the
microorganisms results in an effective disinfection process. Contact time
varies with chlorine concentration, the type of pathogens present, pH, and
temperature of the water.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

The calculation procedure is given below. Contact time must increase

under conditions of low water temperature or high pH (alkalinity).
Complete mixing of chlorine and water is necessary, and often a holding
tank is needed to achieve appropriate contact time. In a private well
system, the minimum-size holding tank is determined by multiplying the
capacity of the pump by 10. For example, a 5-gallons-perminute (gpm)
pump requires a 50-gallon holding tank.
Pressure tanks are not recommended for this purpose since they
usually have a combined inlet/ outlet and all the water does not pass
through the tank. An alternative to the holding tank is a long length of
coiled pipe to increase contact between water and chlorine. Scaling and
2022/2023 2022/2023 2022/2023
sediment build-up inside the pipe make this method inferior to the holding
tank.

Chlorination levels If a system does not allow adequate contact time

with normal dosages of chlorine, super chlorination followed by
dechlorination (chlorine removal) may be necessary. Super chlorination
provides a chlorine residual of 3.0-5.0 mg/l, 10 times the recommended
minimum breakpoint chlorine concentration. Retention time for super
chlorination is approximately 5 minutes. Activated carbon filtration removes
30504101603434 30504101603434 30504101603434
the high chlorine residual (see: Fact Sheet 3: "Activated Carbon Treatment
of Drinking Water")

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WATER TREATEMENT TECHNIQUES

Three-quarters of the surface of the earth is covered with water. While this
is an impressive statistic, it is pale beside the spectacular Photographs that
have come to us from outer space. They reveal a beautiful blue planet bathed
in water, partly hidden by a veil of vapor.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Life came into being in this water. As living things became more
complex and specialized, they left the sea for the land, taking water with
them as the major part of their bodies. On the Planet Earth, water is life.
The proper study of water is the water molecule." The formula for water—
H2O—by itself tells us only its composition and molecular weight. It does
nothing to explain the remarkable properties that result from its unique
molecular arrangement (see Figure 1). Two hydrogen atoms are located 105°
apart, adjacent to the oxygen atom, so that the molecule is asymmetrical,
positively charged on the hydrogen side and negatively charged on the
oxygen side. For this reason, water is said to be dipolar. This causes the
molecules to agglomerate, the hydrogen of one molecule attracting the
2022/2023 2022/2023 2022/2023
oxygen of a neighboring molecule.
The linking of molecules resulting from this attractive force is called
hydrogen bonding, One of the consequences of hydrogen bonding is that
molecules of H2O cannot leave the surface of a body of water as readily as
they could without this intermolecular attraction. The energy required to
rupture the hydrogen bond and liberate a molecule of H2O to form vapor is
much greater than for other common chemical compounds. Because of this
fact, the water vapor—steam—has a high energy content and is an effective
medium for transferring energy in industrial plant operations, buildings, and
30504101603434 30504101603434 30504101603434
homes.

Water also releases more heat upon freezing than do other compounds.
Furthermore, for each incremental change in temperature, water absorbs or
releases more heat—i.e., has great heat capacity—than many substances, so
it is an effective heat transfer medium.

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The freezing of water is unusual compared to other liquids. Hydrogen bonding

produces a crystal arrangement that causes ice to expand beyond its original
liquid volume so that its density is less than that of the liquid and the ice
floats.
If this were not the case, lakes would freeze from the bottom up, and
life as we know it could not exist.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Table 1.1 compares the boiling point and other heat properties of water
with similar molecules, such as hydrogen sulfide, and with dissimilar
compounds that are liquid at room temperature.
Because of the unusual structure of the water molecule, it is present in
the natural environment in all three states of matter, solid as ice, liquid as
water, and gas as vapor. It is the only chemical compound having this
unusual character.

In addition to its unusual heat properties, water has physical properties

quite different from other liquids. Its high surface tension is easily
demonstrated by the experiment of "floating" a needle on the surface of
2022/2023 2022/2023 2022/2023
water in a glass (Figure 2).
This high surface tension, due to hydrogen bonding, also causes water to
rise in a capillary tube (Figure 1.3). This capillarity is partly responsible for the
system of circulation developed by living plants through their roots and tissue
systems.

30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

Water is often called the universal solvent. Water molecules in contact

with a crystal orient themselves to neutralize the attractive forces between
the ions in the crystal structure. The liberated ions are then hydrated by these
water molecules as shown in Figure 1.4, preventing them from recombining
and recrystalizing.
This solvency
30504101603434 and hydration effect 30504101603434
is shown quantitatively by water's relatively
30504101603434

high dielectric constant.

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 UG_31186536@f-eng.tanta.edu.eg UG_31186536@f-eng.tanta.edu.eg UG_31186536@f-eng.tanta.edu.eg
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Water ionizes so very slightly, producing only 107 moles of hydrogen

and 107 moles of hydroxyl ions per liter, that it is an insulator—it cannot
conduct electrical current. As salts or other ionizing materials dissolve in
water, electrical conductivity develops. The conductivity of naturally occurring
waters provides a measure of their dissolved mineral content Another
important phenomenon occurring in water solutions related to dissolved
matter (solutes), rather than to water (solvent), is osmotic pressure.
2022/2023 2022/2023 2022/2023

If two aqueous solutions are separated by a membrane, water will pass

from the more dilute into the more concentrated one. This important process
controls the performance of all living cells. It explains the effectiveness of
food preservation by salting; the salt creates a strong solution, disrupting the
cells of organisms that might cause food spoilage, as the water inside their
bodies leaves in an attempt to dilute the external salt solution.
In specially designed membrane cells, the osmotic flow of water across
the membrane can be reversed by applying a sufficiently high pressure to the
more concentrated
30504101603434 solution. This process of "reverse osmosis" 30504101603434
30504101603434 is a practical
one for desalination of water.
Finally, viscosity is another property of water affecting its treatment and
use. It is a measure of internal friction—the friction of one layer of molecules
moving across another. As water temperature rises, this internal friction
decreases.

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Because of the temperature effect, dissolved salts and gases can diffuse
more rapidly through warmer water, chemical treatment is hastened, and the
physical processes of sedimentation and degasification proceed faster.

WATER CHEMISTRY AND INTERPRETATION OF WATER ANALYSES

2. ALKALINITY AND ACIDITY
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Probably the most fundamental concept in the approach to

understanding water chemistry is the acidity-alkalinity relationship. The first
step in grasping this is an understanding of the dissociation of the water
molecule itself into hydrogen ions and hydroxyl ions, according to equation:
H2O= H+ + OH- (1)
K = [H+] [OH-] = 10-14
(For the sake of simplicity, this book will use the hydrogen ion, H+,
while recognizing that it actually exists in a hydrated form, the hydronium ion
—H3O+.)

THE pH NOTATION
2022/2023 2022/2023 2022/2023
Since the dissociation constant is so very small, 1014, at neutrality where
there are the same number of hydrogen and hydroxyl ions there are only 107
moles/l of each. This is equal to only 104 moles/L, corresponding to an actual
concentration of only 0.0001 mg/L H+ ion, equivalent to 0.005 mg/L as
CaCO3.
Because we are dealing with such small numbers in the dissociation of
water into its ions, it is more convenient to substitute an expression involving
the power of 10. This expression is defined as pH, in which the relationship is:
pH = -log[H+]
30504101603434 30504101603434 30504101603434
The dissociation constant, K, changes with temperature, and this must
be taken into account in interpreting data involving H+ and OH- ions. For
example, many water treatment operations are carried out at high
temperatures, and samples from the system are usually cooled prior to
analysis.

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The H+ and OH- concentrations measured on the cooled sample, even

though different from those in the hot system, are usually used for control
purposes. But a physical chemist needing to know the conditions prevailing in
the hot system must use the dissociation constant for the temperature in that
system.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

The hydrogen ion concentration can be measured with a pH meter. It

can also be titrated (see glossary) when the concentration becomes large
enough to detectable by chemical analysis. Since pH is a logarithmic function,
the hydrogen ion concentration increases by a factor of 10 for each unit of pH
reduction.

When the pH drops below approximately 5, the hydrogen ion begins

to reach milligrams per liter levels, concentrated enough to be determined by
titration, using the correct organic dye indicator.
The chemical indicator originally selected by the water chemist for this
purpose was methyl orange, changing color at pH 4.2 to 4.4. The color
2022/2023 2022/2023 2022/2023
change of this indicator was so subtle—orange on the alkaline side to salmon
pink on the acid side—that researchers looked for a substitute to give a more
pronounced color change.

The one they developed produces a blue color on the alkaline side and
red on the acid side, with gray at the endpoint. Even though this special
indicator has replaced methyl orange, the water chemist still defines alkalinity
as methyl orange alkalinity ("M" alkalinity) which exists above the
approximate pH range of 4.2 to 4.4. M acidity is strong mineral acidity that
30504101603434 30504101603434 30504101603434
exists below this pH range. An approximate relationship between pH value
and mineral acidity.

As the pH of a water solution is increased and exceeds about 9.6 to

9.8 a measurable concentration of hydroxyl ions begins to appear. The

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hydroxyl alkalinity (caustic or OH alkalinity) can be determined either by using

a pH meter (or the equivalent in a colorimetric comparator) or by titration.
The relationship between hydroxyl alkalinity and pH is shown in Table 4.4.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

An understanding of these concepts is necessary to put these acidity-

alkalinity relationships into perspective. To the theoretical chemist, a pH of 7
is considered neutral; to the water chemist, a pH of 7 in itself means very
little.
2022/2023 He must also know how much 2022/2023
total alkalinity and how much2022/2023
free or
combined CO2 may be present.
For the water chemist, then, the dividing point between acidity and
alkalinity is not pH 7.0, but rather the M alkalinity endpoint, corresponding to
a pH of approximately 4.4.
The water chemist is also concerned with P alkalinity (phenolphthalein
alkalinity), which exists when the pH is over a range of 8.2 to 8.4,
corresponding to the change in phenolphthalein indicator from a colorless
condition below 8.2 to pink or red above 8.4. In most natural water supplies,
the pH is
30504101603434 less than 8.2, so there is 30504101603434
no P alkalinity. 30504101603434

Very few natural waters have a pH below about 5.0, so it is seldom that
strong mineral acids are found in fresh water. The pH range between the M
endpoint and the P endpoint defines the alkaline range in which bicarbonate
alkalinity exists and weak acids may be present, the most prominent of which
is carbonic acid—carbon dioxide in solution.

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THE IMPORTANCE OF CO2

The atmosphere is a mixture of gases containing about 79% N2 and 21%
O2 by volume. However, it also includes 0.04% CO2, extremely important to
the balance of life on the planet.
Carbon dioxide is produced by the combustion of fuel. Even before
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

human activities made a significant contribution to the CO2 content of the

atmosphere, the respiration of animal life—which is also a fuel consuming
process—introduced CO2 into the air. Plants containing chlorophyll utilize
carbon dioxide in building cellular material such as carbohydrates. This
reaction is called
photosynthesis because photons of energy from the sun are needed for the
reaction.

2022/2023 2022/2023 2022/2023

The chlorophyll catalyzes the reaction between water and CO2. Since the
solubility of CO2 in water is less than 2000 mg/L at ambient air temperatures
in a CO2-saturated atmosphere, at the normal atmospheric level of 0.04% CO2
less than 1 mg/L CO2 dissolves in rainwater. However, once the rainwater
penetrates the mantle of soil, it is exposed to CO2 gas levels a hundredfold
greater than in the atmosphere, created by the respiration of soil organisms
as they convert organic food into its products of combustion. Well waters,
then, which have percolated through this CO2-rich zone may contain from 10
30504101603434 30504101603434 30504101603434
to several 100 mg/L dissolved CO2.

When CO2 dissolves in water, it reacts with water to form carbonic acid,
which dissociates into the hydrogen ion and the bicarbonate ion according to
the reaction:

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If distilled water is completely saturated with CO2, approximately 1600

mg/L dissolves in the water, and the pH is decreased to approximately 4. The
equivalent amount of a strong acid like H2SO4 would decrease the pH to
about 2.5, illustrating the weak character of carbonic acid.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

THE SOURCE OF ALKALINITY

The alkalinity of most natural water supplies is caused by dissolved
bicarbonate (HCO3-) salts. The following equations show how water
containing CO2 from the atmosphere and from respiration of soil organisms
dissolves magnesium and calcium from a common mineral, dolomite (CaCO3 •
MgCO3), to produce hardness and alkalinity in ground water:

2022/2023 2022/2023 2022/2023

In the pH range of 4.4 to 8.2, there remains a balance between excess CO2
and bicarbonate ions which is measured by pH value.

This shows that a water containing 1 mg/L CO2 and 10 mg/L alkalinity
has the same pH as one containing 10 mg/L CO2 and 100 mg/L alkalinity. In
the first case, the addition of 1 mg/L CO2 would produce a large change in
pH, whereas in the second case, the same 1 mg/L CO2 addition would not
produce a noticeable change. The alkalinity moderates or buffers the pH
change, and alkalinity is known as a buffer.
30504101603434 30504101603434 30504101603434

Water attacks and dissolves many other minerals from the lithosphere in
addition to dolomite.
shows the distribution of the elements in the earth's crust. The three most
prominent are present in the form of oxides, SiO2, Al2O3,and Fe2O3, which are
only very slightly soluble in water.

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CO3-2 /HCO3- DISTRIBUTION

Most natural waters contain bicarbonate alkalinity and are at a pH less
than about 8.2 to 8.4. Above this pH, CO2 ceases to exist in measurable
quantities and the carbonate ion begins to make itself known. The equilibrium
reaction is as follows:
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Many lime-treated waters have a pH above the phenolphthalein

endpoint—that is, they contain P alkalinity. In the range of pH 8.2 to 9.6, the
bicarbonate and carbonate ions exist together in the absence of measurable
carbon dioxide or hydroxyl ions.
The distribution between the carbonate and bicarbonate ions can also be
calculated after measuring P and M alkalinities according to the following
equations.

CO3 = 2 X P
2022/2023
HCO3 = M 2022/2023
- CO3 = M - 2P 2022/2023

The distribution of all forms of CO2--

As the pH increases above 9.6, the hydroxyl alkalinity becomes measurable.

EFFECTS OF IMPURITIES
If magnesium is precipitated with calcium carbonate, the residual
calcium in solution may be increased. The inclusion of other impurities, also
been shown to increase the solubility of calcium carbonate. It would seem,
then, that
30504101603434 empirical data from a variety of plants should be used
30504101603434 cautiously in
30504101603434

estimating what to expect in a given situation; if the calculation involves lime

treatment of an unknown water supply and the contamination levels are not
fully denned, there is no substitute for an actual bench test to determine the
response of that water to lime treatment.

335
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Magnesium solubility is as difficult to predict with accuracy as calcium

solubility, and for the same general reasons. The solubility of magnesium
hydroxide is reported to be in the range of 30 to 40 mg/L at 770F (250C).
Because of the difference in solubility product relationship:

KCa = [Ca2+] X [CO32-] KMg = [Mg2+] X [OH-]2

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Magnesium concentration is affected more by changes in hydroxyl

concentration than calcium is by changes in carbonate concentration. Any
increase in carbonate produces a corresponding decrease in calcium, but an
increase in hydroxyl concentration affects the magnesium concentration in a
squared relationship. Thus a doubling of OH- will cause Mg2+ to drop to one-
fourth its original value.

When water is softened with lime—in the pH range of 9.5 to 10.5—

magnesiumprecipitates as the hydroxide and the precipitate is positively
charged. In the same pH range, CaCO3 precipitate is negatively charged.
2022/2023 2022/2023 2022/2023
Furthermore, silica in the system is usually present as a strong, negatively
charged colloid. Sodium aluminate may be introduced in the system as a
strong anionic complex. All of this may account for the coprecipitation of
magnesium with calcium, the strong adsorption of silica on Mg(OH)2
precipitate, and the low residual magnesium often achieved by the treatment
of water with sodium aluminate in addition to lime.

DISSOLVED GASES
Carbon dioxide, for example, dissolves to form carbonic acid, which
30504101603434 30504101603434 30504101603434
ionizes to produce H+ and HCO3- ions. Other ionizing gases include sulfur
dioxide, hydrogen sulfide, and hydrocyanic acid, which form weak acids when
dissolved in water. Because of this effect, the addition of a strong acid to
water containing these gases will force the equilibrium to the left, essentially
eliminating the ionized portion so that all of the gas is in molecular form and
free to escape from the water as gas molecules. For example, with CO2:

336
 UG_31186536@f-eng.tanta.edu.eg UG_31186536@f-eng.tanta.edu.eg UG_31186536@f-eng.tanta.edu.eg

On the other end of the scale is ammonia, which dissolves and ionizes to
form a weak base according to the equation: There are other gases that
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

dissolve in water, but do not ionize. Among these are oxygen, nitrogen, and
methane. The most prominent of these in its effect on water systems is
oxygen. This corrosion, however, is usually caused by dissolved oxygen which
is free to attack the bare metal surface when it is wetted by a water which
cannot form a protective calcium carbonate film or scale.

MINERALS AND CONDUCTANCE

An important consideration in water chemistry is electrical conductivity.
The higher the mineral content of the water, the higher its conductivity. This
has several important consequences. First, the higher the conductivity, the
more
2022/2023 freely can electrical current flow through the water, and the2022/2023
2022/2023 more rapid
is the corrosion rate if other conditions favor corrosion. Second, the higher
the conductivity, the less completely ionized are the minerals dissolved in the
water, as the ions are packed more closely together and collide more
frequently. This decreases the activity coefficient, or freedom, increasing the
solubility of CaCO3 and other slightly soluble materials. As a result, CaCO3 is
more soluble in seawater than in resh water under equal conditions of pH,
alkalinity, and temperature. There are many factors involved in the corrosion
process, of which pH, conductivity ,temperature, and dissolved oxygen are
usually foremost.
30504101603434 30504101603434 30504101603434
Other important factors in the corrosion mechanism include the presence of
dissimilar metals in the system, with the more anodic becoming corroded, and
dissimilarities in them etallurgical structure of a single metal in the system.
SOLIDMATTER
Solid matter occurs in most waters as suspended solids and colloidal
matter. The concentration of suspended solids is determined by filtration, the

337
 UG_31186536@f-eng.tanta.edu.eg UG_31186536@f-eng.tanta.edu.eg UG_31186536@f-eng.tanta.edu.eg

collected solids on the filter membrane being dried and weighed. Those
suspended solids which are large and heavy are called settleable solids, and
these may be determined volume tricallyin a settling cone as a simple control
test or weighed.
The solids remaining with supernatant water above the settled matter are
fine and called turbidity.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Turbidity in water is measured by the effect of the fine suspended particles on

a light beam. Light-interference analytical methods are classified as
nephelometric, and one system of turbidity measurement uses nephelometric
turbidity units (NTU). The original nephelometric method used a standardized
candle, providing results in Jackson turbidity units (JTU), named for the man
who developed the standard candle. Turbidity standards prepared with
formazin forcomparator tube determinations have given rise to a third
turbidity unit, the FTU.
The JTU is measured with a transmitted light beam, while the NTU is
measured by light scattering, so there is no comparison between the two
units that applies to all waters. In the case of turbidity standards prepared
2022/2023 2022/2023 2022/2023
from 325 mesh diatomaceous earth, a reading of 100 NTU is equivalent to
about 40 JTU.
Colloidal matter in water is sometimes beneficial and sometimes harmful.
Beneficial colloids are those that provide a dispersant effect by acting as
protective colloids. In a suspension of clay or silt in water, the smallest
particles usually carrya negative charge. If these negative charges are
neutralized, the particles are coagulated; however, if additional negative
charges are introduced into the system deliberately, sedimentation may be
prevented. Sodium silicate probably works in
30504101603434 30504101603434 30504101603434
this way; so too do some kinds of organic materials in water, such as lignins
and tannins, which occur in highly colored water sources. Silica in itself can be
troublesome ,forming a very hard scale when it deposits on heat transfer
surfaces.

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ORGANICS IN WATER
While tannin and lignin are generally present as colloidal suspensions in
water, many organic compounds are actually soluble in water. There is an
astounding variety of organic compounds in water, put there both by nature
and humankind.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

It is unusual for a water analysis to show all of this organic matter broken
down by individual molecular constituents, because of the great variety. If the
analyst should know what may be present [for example, polychlorinated
biphenyls(PCBs), or total trihalomethane (TTHM)], it can be found. it is not at
all unusual to find an increase in one test, such as BOD, with a concurrent
decrease in another test, such as TOC.

2022/2023 2022/2023 2022/2023

30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

CLASS 1—PRIMARY CONSTITUENTS

30504101603434 30504101603434 30504101603434
This category includes dissolved solids generally exceeding 5 mg/L, and
often several orders of magnitude above this level, Bicarbonate (HCO3—
Molecular Weight 61), The bicarbonate ion is the principal alkaline constituent
of almost all water supplies.

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It is generally found in the range of 5 to 500 mg/L, as CaCO3. Its

introduction into the water by the dissolving action of bacterially produced
CO2 on carbonate- containing minerals has been explained elsewhere. Normal
activities of the human population also introduce alkaline materials into water,
evidenced by a typical increase of alkalinity of sewage plant effluent of 100 to
150 mg/L above the alkalinity of the municipal water supply. Much of this is
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

due to the alkalinity of industrial and domestic detergents.

Alkalinity in drinking water supplies seldom exceeds 300 mg/L. The

control of alkalinity is important in many industrial applications because of its
signification the calcium carbonate stability index. Alkalinity control is
important in both concentrated boiler water and cooling water in evaporative
cooling systems. Calcium is the major component of hardness in water and
usually is in the range of 5 to 500 mg/L, as CaCO3, (2 to 200 mg/L as Ca).
It is present in many minerals, principally limestone and gypsum. Limestone
deposits are often the residue of the
Fossils of tiny aquatic organisms, such as polyps, that have taken calcium
2022/2023 2022/2023 2022/2023
from the seawater in which they lived, and used it for their skeletons. This is
but one of many cycles in nature whereby some component of the
environment is continually withdrawn by living things and eventually returned
directly or indirectly.

Calcium removed from water in softening operations is later returned to

the environment, often to the watershed, by way of a precipitate or a brine
which is the by-product of the softening reaction. Calcium is a major factor in
determining stability index. Calcium reduction is often required in treating
30504101603434 30504101603434 30504101603434
cooling tower makeup. Complete removal is required for many industrial
operations, particularly for boiler makeup, textile finishing operations, and
cleaning and rinsing in metal finishing operations.

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Hardness
What is Hardness?
Hardness of water is a measure of its capacity to precipitate soap and
is caused mainly by the presence of divalent cations of calcium (Ca+2) and
magnesium (Mg+2). Other multivalent cations also cause water hardness such
as Fe+3, Sr+2, Zn+2, Mn+2.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Types of Hardness
2. Total Hardness (TH)
Hardness caused by calcium ions and magnesium ions. Calcium and
magnesium are normally the only significant minerals that cause hardness, so
it is generally assumed that:

Total Harness (TH) = Ca+2 hardness + Mg+2 hardness

Carbonate Hardness (CH):

Carbonate hardness is caused primarily by the bicarbonate salts of
2022/2023 2022/2023 2022/2023
calcium and magnesium, which are calcium bicarbonate, Ca(HCO3)2, and
magnesium bicarbonate Mg(HCO3)2. Calcium and magnesium combined with
carbonate (CO3) also contribute to carbonate hardness.

Non-Carbonate Hardness (NCH):

Non-carbonate hardness is a measure of calcium and magnesium salts
other than carbonate and bicarbonate salts.
These salts ate calcium sulfate (CaSO4), calcium chloride (CaCl2),
magnesium sulfate (MgSO4), and magnesium chloride (MgCl2). Therefore,
30504101603434 30504101603434 30504101603434
non-carbonate hardness is hardness exceeding carbonate hardness.
If the total hardness (TH) is greater than alkalinity (ALK), then:
Carbonate Hardness (CH) = alkalinity (ALK)
Non-carbonate Hardness(NCH)=total hardness –carbonate hardness
(CH)

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If the total hardness (TH) is less than alkalinity (ALK),

then:
Carbonate Hardness (CH) = total hardness (TH)
Non-carbonate Hardness (NCH) = 0

Example(1):
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

A sample of water has 210 mg/l alkalinity, 330 mg/l total hardness and
290 mg/l calcium hardness. Find out the following?
a) Magnesium hardness
b) Carbonate hardness
c) Non-carbonate hardness.

Solution:
a) Mg hardness = TH – Ca hardness = 330-290 = 40 mg/l
Since TH is greater than Alk
b) Carbonate hardness = ALK = 210 mg/l
c) Non-Carbonate hardness = TH – CH = 330-210 = 120 mg/l
2022/2023 2022/2023 2022/2023

Water Hardness
Public tolerance of hardness varies, however, a level ranging from 60 to
120 mg/l as CaCO3 is generally acceptable.
Disadvantages of hardness

3. excessive soap consumption during laundering

4. scale-formation in hot water heaters and pipes.

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Hardness Ranges
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

CALCULATING CALCIUM HARDNESS AS CaCO3

The hardness (in mg/L as CaCO3) for any given metallic ion is calculated
using Equation the following equation.

2022/2023 2022/2023 2022/2023

Example (2)
A water sample has calcium content of 51 mg/L. What is this calcium
hardness expressed as CaCO3?

30504101603434 30504101603434 30504101603434

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Example (3)
The calcium content of a water sample is 26 mg/L. What is this calcium
hardness expressed as CaCO3?
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

CALCULATING MAGNESIUM HARDNESS AS CaCO3:

2022/2023 2022/2023 2022/2023

Example(4):
A sample of water contains 24 mg/L magnesium. Express this
magnesium hardness as CaCO3.

Solution
Referring to Equation 21.2:
30504101603434 30504101603434 30504101603434

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Example(5):
The magnesium content of a water sample is 16 mg/L. Express this
magnesium hardness as CaCO3.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

CALCULATING
2022/2023 TOTAL HARDNESS
2022/2023 2022/2023

Calcium and magnesium ions are the primary cause of hardness in

water. To find total hardness,
we simply add the concentrations of calcium and magnesium ions,
expressed in terms of calcium
carbonate (CaCO3):

30504101603434 30504101603434 30504101603434

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Example(6 ):
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Example(7):

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

CALCULATING CARBONATE AND NONCARBONATE HARDNESS

As mentioned, total hardness is comprised of calcium and magnesium
hardness. Once total hardness has been calculated, it is sometimes used to
determine another expression hardness — carbonate and non carbonate.
2022/2023 2022/2023 2022/2023
When hardness is numerically greater than the sum of carbonate and
carbonate alkalinity, that amount of hardness equivalent to the total alkalinity
(both in units of mg CaCO3/L) is referred to as the carbonate hardness; the
amount of hardness in excess of this is the noncarbonated hardness.
When the hardness is numerically equal to or less than the sum of
carbonate and noncarbonate alkalinity, all hardness is carbonate hardness,
and noncarbonate hardness is absent.
Again, the total hardness is comprised or carbonate hardness and

noncarbonate hardness:
30504101603434 30504101603434 30504101603434

Total hardness = carbonate hardness + noncarbonate hardness

When the alkalinity (as CaCO3) is greater than the total hardness, all the
hardness is carbonate hardness:

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Total hardness (mg/L) as CaCO3 = carbonate hardness (mg/L) as CaCO3

Total hardness mg L as CaCO3 carbonate hardness mg L as CaCO3
noncarbonate hardness mg L as CaCO3
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

Example(8):
A water sample contains 110 mg/L alkalinity as CaCO3 and 105 mg/L
total hardness as CaCO3.
What is the carbonate and noncarbonate hardness of the sample?
Solution
Because the alkalinity is greater than the total hardness, all the hardness is
carbonate hardness:
Total hardness
30504101603434 (mg/L) as CaCO3 =30504101603434
Carbonate hardness (mg/L)30504101603434
as CaCO3
105 mg/L as CaCO3 = Carbonate hardness
No noncarbonate hardness is present in this water.

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Example(9):
The alkalinity of a water sample is 80 mg/L as CaCO3. If the total hardness of
the water sample is 112 mg/L as CaCO3, what is the carbonate and
noncarbonate hardness (in mg/L as CaCO3)?
Solution
Alkalinity is less than total hardness; therefore, both carbonate and
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

noncarbonate hardness will be present in the hardness of the sample.

CALCULATION FOR REMOVAL OF NONCARBONATE HARDNESS

Soda ash is used for precipitation and removal of noncarbonate
hardness. To calculate the soda ash dosage required, we use, in
combination, Equations.
2022/2023 2022/2023 2022/2023

30504101603434 30504101603434 30504101603434

Example(10)
A water sample has a total hardness of 250 mg/L as CaCO3 and a total
alkalinity of 180 mg/L. What soda ash dosage will be required to remove
the noncarbonate hardness (in mg/L)?
Solution

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Calculate the noncarbonate hardness using Equation

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

ALKALINITY DETERMINATION
Alkalinity measures the acid-neutralizing capacity of a water sample. It is
an aggregate property of the water sample and can be interpreted in terms of
specific substances only when a complete chemical composition of the sample
is also performed. The alkalinity of surface waters is primarily due to the
carbonate, bicarbonate, and hydroxide content and is often interpreted in
terms
2022/2023 of the concentrations of these 2022/2023
constituents. 2022/2023

The higher the alkalinity, the greater the capacity of the water to
neutralize acids; conversely, the lower the alkalinity, the less the neutralizing
capacity. To detect the different types of alkalinity, the water is tested for
phenolphthalein and total alkalinity, using Equations

30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Example(11):
A 100-mL water sample is tested for phenolphthalein alkalinity. If 1.3-mL
titrant is used to pH 8.3and the sulfuric acid solution has a normality of 0.02
N, what is the phenolphthalein alkalinity of the water?

Solution
Referring to Equation:

2022/2023 2022/2023 2022/2023

Example(12):
A 100-mL sample of water is tested for alkalinity. The normality of the
sulfuric acid used for titrating is 0.02 N. If 0 mL is used to pH 8.3, and 7.6 ml
titrant is used to pH 4.5, what is the phenolphthalein and total alkalinity of the
sample?
30504101603434 30504101603434 30504101603434

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Solution
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

DETERMINING BICARBONATE, CARBONATE, AND HYDROXIDE

KALINITY
Interpretation of phenolphthalein and total alkalinity test results (assuming
all of the alkalinity found is due to carbonate, bicarbonate, or hydroxide) can
be made .

Example(13):
A water sample is tested for phenolphthalein and total alkalinity. If the
phenolphthalein
2022/2023 alkalinity is 10 mg/L2022/2023
as CaCO3 and the total alkalinity is 52
2022/2023

mg/L as CaCO3, what are the bicarbonate, carbonate, and hydroxide

alkalinities of the water?

30504101603434 30504101603434 30504101603434

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Solution
Based on titration test results, phenolphthalein alkalinity (10 mg/L) is less
than half of the total alkalinity (52 mg/L ÷ 2 = 26 mg/L; see Table 21.1);
therefore, each type of alkalinity is calculated as follows:
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Example(14):
2022/2023 2022/2023 2022/2023
Results of alkalinity titrations on a water sample are as follows:
Sample was 100 ml
- 1.4 ml titrant was used to pH 8.3
- 2.4 ml total titrant was used to pH 4.5
- Acid normality was 0.02 N H2SO4
What is the phenolphthalein, total bicarbonate, carbonate and hydroxide
alkalinity?

30504101603434 30504101603434 30504101603434

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Solution :
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

30504101603434 30504101603434 30504101603434

Problems Caused By Hardness

1- Excessive soap is needed for washing (i.e. soap will not lather). Some
modern detergents work less efficiently because anions (also known as

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surfactants) which are meant to hold dirt particles in suspension react

with Ca2+ and Mg2+ instead.
2- Soap based on animal fats can react with Ca2+ and Mg2+ forming a
precipitation that can ruin cloths and irritate skin.
3- Some foods, particular dried beans and peas, become tough and
rubbery when cooked in hard water. Calcium ions cause cross-linking
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

to occur between certain molecules within the beans, the subsequent

structure prevents water entering and the bean remains hard.
4- Scale can clog pipes and fittings. Also heating elements can become
90% less efficient with a 25mm coating of CaCO3.

Water Softening
There are three basic ways to soften water:
1- Force insoluble substances, such as CaCO3 and Mg(OH)2, to
precipitate before water enters the system.
2- Remove the Ca2+ and Mg2+ ions from the water.
3- Prevent the Ca2+ ions from CaCO3 by complexing them.
2022/2023 2022/2023 2022/2023

Notes:

1- Temporary hardness also called Carbonate hardness ( CH) –caused by

Calcium and Magnesium carbonates and bicarbonates --removed by
• Boiling and
• Addition of lime.
2- Permanent hardness (NCH) Due to Sulphates, Chlorides and Nitrates of
Calcium & Magnesium Removed by
• Lime –Soda process,
• Base exchange, Zeolite or Ion exchange process
30504101603434 30504101603434 30504101603434

• Demineralisation or Deionisation process,

• Revese Osmosis.
Lime & Soda help in removing entire hardness, both CH and NCH

Water softening → Removal of hardness to satisfy the requirements

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Temporary hardness of water [carbonate hardness]→ Due to the

presence of carbonate and bicarbonate of calcium and magnesium CaCO₃,
dissolves in water containing CO₂ and exists in the form of bicarbonates in
natural water
- Removal → By boiling
Calcium bicarbonate Calcium carbonate
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Ca (HCO₃)₂ + Heat ------> CaCO₃ + CO₂ +H₂O

The magnesium carbonate (MgCO₃) is fairly dissolved in water and cannot

be removed by boiling, but can be removed by adding lime →
Soluble Hydrated lime Insoluble.
↑↑↑↑
MgCO₃ +Ca (OH) ₂----> Mg (OH) ₂ + CaCO₃ ↓

Similarly Magnesium bicarbonate → Calcium bicarbonate Magnesium

hydroxide↓
2022/2023 2022/2023 2022/2023

Permanent hardness[Bicarbonate hardness] → due to presence of

sulphate, chlorides, and nitrates of calcium and magnesium.Ca⁺⁺, Mg⁺⁺, Fe⁺⁺,
Mn⁺⁺ etc. also contribute hardness to the water

Methods of removal of hardness:

1- Lime soda process
2- Base-exchange process/zeolite process
3- Demineralization.
30504101603434 30504101603434 30504101603434

Lime Softening
Chemical precipitation is one of the more common methods used to soften
water. Chemicals normally used are lime (calcium hydroxide, Ca(OH)2) and
soda ash (sodium carbonate, Na2CO3). Lime is used to remove chemicals that

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cause carbonate hardness. Soda ash is used to remove chemicals that cause
non-carbonate hardness.

When lime and soda ash are added, hardness-causing minerals form
nearly insoluble precipitates. Calcium hardness is precipitated as calcium
carbonate (CaCO3). Magnesium hardness is precipitated as magnesium
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

hydroxide (Mg(OH)2). These precipitates are then removed by conventional

processes of coagulation/flocculation, sedimentation, and filtration.

Because precipitates are very slightly soluble, some hardness remains in

the water--usually about 50 to 85 mg/l (as CaCO3). This hardness level is
desirable to prevent corrosion problems associated with water being too soft
and having little or no hardness.

LIME ADDITION

2022/2023 2022/2023 2022/2023

CO2 does not contribute to the hardness, but it reacts with the lime, and
therefore uses up some lime before the lime can start removing the hardness.

LIME AND SODA ASH ADDITION

30504101603434 30504101603434 30504101603434

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LIME DOSAGE CALCULATION FOR REMOVAL OF CARBONATE

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

HARDNESS
The lime–soda ash water-softening process uses lime, Ca(OH)2, and
soda ash, Na2CO3, to precipitate hardness from solution. Carbonate hardness
(calcium and magnesium bicarbonates) is complexed by lime.
Noncarbonate hardness (calcium and magnesium sulfates or chlorides)
requires the addition of soda ash for precipitation. The molecular weights of
various chemicals and compounds used in lime–soda as softening calculations
are as follow:

2022/2023 2022/2023 2022/2023

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Example(15):
A water sample has a carbon dioxide content of 4 mg/L as CO2, total
alkalinity of 130 mg/L as CaCO3, and magnesium content of 26 mg/L as
Mg2+. Approximately how much quicklime (CaO × 90% purity) will be
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required for softening? (Assume 15% excess lime.)

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

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Example(16):
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

CALCULATION FOR REMOVAL OF NONCARBONATE HARDNESS

Soda ash is used for precipitation and removal of noncarbonate
hardness. To calculate the soda ash dosage required, we use, in
combination, Equations.
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Ion Exchange Softening

Ion-exchange is used extensively in small water systems and
individual homes. Ion-exchange resin, (zeolite) exchanges one ion from
the water being treated for another ion that is in the resin (sodium is one

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component of softening salt, with chlorine being the other). Zeolite resin
exchanges sodium for calcium and magnesium. The following chemical
reactions show the exchange process, where X represents zeolite, the
exchange material.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

These reactions represent cation exchange, the exchange of positive ions.

To replenish the sodium ions used, units need to be regenerated with
material containing high amounts of sodium, normally salt brine.

Example(17):
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If water contains 10 grains per gallon of hardness, how many gallons of

water would the resin remove? The tank holds 500 cubic feet of resin with
capability of removing 45,000 grains per gallon per cubic foot.

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ION EXCHANGE CAPACITY

An ion exchange softener is a common alternative to the use of lime
and soda ash for softening water. Natural water sources contain dissolved
minerals that dissociate in water to form charged particles called ions.

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Of main concern are the positively charged ions of calcium, magnesium,

and sodium; bicarbonate, sulfate, and chloride are the normal negatively
charged ions of concern. An ion exchange medium, called resin is a
material that exchanges a hardness-causing ion for another one that does
not cause hardness, holds the new ion temporarily, and then releases it
when a regenerating solution is poured over the resin.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

The removal capacity of an exchange resin is generally reported

as grains (gr) of hardness removal per cubic foot (ft3) of resin. To
calculate the removal capacity of the softener, we use:

Exchange capacity (grains) = Removal capacity (grains/cu ft) ×

media volume (cu ft)

Example(18):
The hardness removal capacity of an exchange resin is 24,000
grains/cu ft. If the softener contains a total of 70 cu ft of resin, what is the
total exchange capacity (in grains) of the softener?
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Solution
Exchange capacity (grains) = 22,000 grains/cu ft × 70 cu ft
= 1,540,000 grains

Example(19):
An ion-exchange water softener has a diameter of 7 ft. The depth of resin
is 5 ft. If the resin has a removal capacity of 22-kilograins/cu ft, what is
the total exchange capacity of the softener (in grains)?
Solution
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Before the exchange capacity of a softener can be calculated, the cu ft
resin volume must be known:

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

WATER TREATMENT CAPACITY

To calculate when the resin must be regenerated (based on volume of
water treated), we must know the exchange capacity of the softener and
the hardness of the water:

Example(20):

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An ion-exchange softener has2022/2023
an exchange capacity of 2,455,000
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grains. If the hardness of the water to be treated is 18.6 grains/gallon,

how many gallons of water can be treated before regeneration of the resin
is required?
Solution
Referring to Equation

Water treatment
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Objectives of water treatment
- The principal objective of water treatment is to provide potable
water that is chemically and biologically safe for human consumption.
It should also be free from unpleasant tastes and odors.
- Water treatment aims at producing water that satisfies a set of
drinking water quality standards at a reasonable price to the consumers.

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- Removal of solids in water. Solids maybe suspended, dissolved or

colloidal. Some of the dissolved solids should stay in water at healthy
concentrations.

Water classification by source

- Ground- vs. Surface Water
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

3. COAGULATION
Colloidal species encountered in raw water and wastewater include clay,
silica, iron and other heavy metals, color, and organic solids such as the
debris of dead organisms. Colloids may also be produced in precipitation
processes such as lime softening. Oil in wastewater is frequently colloidal.
Among the wide variety of colloidal materials in water, there is a broad
distribution of particle sizes.
Colloids always require coagulation to achievean effective size and
settling rate; but even larger particles, which are not truly colloidal and would
settle if given enough time, may require coagulation to form larger, faster
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settling floe. When insufficient settling time is available in a treatment plant to
remove suspended solids, coagulation and flocculation may cause them to
grow in size and settle rapidly enough to overcome the physical limitation of
the plant design.
Colloids are categorized as hydrophobic (water hating) or hydrophilic
(water loving). Hydrophobic colloids do not react with water; most natural
clays are hydrophobic. Hydrophilic colloids react with water; the organics
causing color are hydrophilic. Of importance in water treatment, the
hydrophiloc colloids may chemically react with the coagulant used in the
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treatment process. So hydrophilic colloids require more coagulant than
hydrophobic, which do not chemically react with the coagulant.

High intensity mixing, which distributes the coagulant and promotes

rapid collisions, is most effective. The frequency and number of particle
collisions are also important in coagulation. In a low turbidity water, the

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addition of solids such as clay or the recycle of previously settled solids may
be required to increase the number of particle collisions.
4. FLOCCULATION
The floe formed by the agglomeration of several colloids may not be large
enough to settle or dewater at the desired rate. A flocculant gathers together
floe particles in a net, bridging from one surface to another and binding the
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

individual particles into large agglomerates Alum, iron salts, and high
molecular weight polymers are common flocculants.
Flocculation is promoted by slow mixing, which brings the floes gently
together; too high a mixing velocity tears them apart, and they seldom re-
form to their optimum size and strength. Flocculation not only increases the
size of floe particles, but it also affects the physical nature of the floe. Sludge
and slurries, when flocculated, dewater at faster rates on sand beds and in
mechanical dewatering equipment because of the less gelatinous structure of
the floc.

COAGULA TION AND FLOCCULA TION CHEMICALS:

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Historically, metal coagulants (alum and iron salts) have been most
widely used in water clarification. These products function both as coagulants
and flocculants.
When added to water, they form positively charged species in the typical pH
range for clarification, about 6-7. This hydrolysis reaction produces insoluble
gelatinous aluminum or ferric hydroxide.
Al2(SO4)3 + 6H2O — 2Al(OH)3 + 3H2SO4 (1)
FeCl3 + 3H2O - Fe(OH)3 + 3 HCl (2)
Note that the by-products are hydroxide precipitates and mineral acids;
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the latter react with alkalinity in the water, reducing pH and producing a
second byproduct,CO2. Sometimes the gaseous CO2 by-product interferes with
the coagulation process by coming out of solution, adsorbing on the hydrous
precipitate, and causing floe flotation rather than settling.
Poly aluminum chloride, a product in wide use in Japan, avoids the
problem of alkalinity reduction. When the material hydrolyzes, the floc formed

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incorporates the chloride ion into the floe structure so it is not available to
produce acid, reduce alkalinity, and form by-product CO2. Even if there are
no suspended solids in the water initially, the metal coagulants form floes
which enmesh the destabilized colloids. However, the voluminous sludge
produced by the addition of metal coagulants create disposal problems
because they are usually difficult to dewater.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

This is why alum and iron salts are not often used to improve efficiency
of centrifuges, filter presses, and other dewatering devices.

Metal coagulants are particularly sensitive to pH and alkalinity. If pH is

not in the proper range, clarification is poor, and iron or aluminum may be
solubilized and cause problems to the water user. The lower the coagulant
dosage, them ore sensitive the floe is to pH changes.

SOLIDS/LIQUIDS SEPARATION
a. Screening
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Straining includes such conventional devices as bar screens traveling
trash screens remove relatively large floating and suspended debris).
b. Sedimentation
Sedimentation is the removal of suspended solids from water by
gravitational settling. The settling rate of particles is affected by their size,
shape, and density as well as by the liquid they are settling through. As a
particle settles, it accelerates until Filtration
4- Filtration
Granular Media Filtration. Granular media filtration is generally applicable
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for removal of suspended solids in the 5 to 50 mg/L range where an effluent
of less than 1 JTU (Jackson turbidity unit) is required. Sand filters have been
used form any years as a final polishing step in municipal and industrial water
plants where the clarifier effluent contains 5 to 20 mg/L of suspended solids.

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5- Adsorption: is dependent on the physical characteristics of the suspended

solids and the filter media. It is a function of filter media grain size and
such floe properties as size, shear strength, and adhesiveness. Adsorption
is also affected by the chemical characteristics of the suspended solids, the
water, and the filter media.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

WATER DISINFECTION BY CHLORINE

- Disinfection requirements
Disinfection reduces pathogenic microorganisms in water to levels
designated safe by public health standards. This prevents the transmission
of disease. An effective disinfection system kills or neutralizes all pathogens
in the water. It is automatic, simply maintained, safe, and inexpensive. An
ideal system treats all the water and provides residual (long term)
disinfection. Chemicals should be easily stored and not make the water
foul-tasting.

Testing water for biological quality The biological quality of drinking

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water is determined by tests for total coliform (which includes E. coli and
fecal coliforms). These organisms are found in the intestinal tract of warm-
blooded animals and in soil. Fecal coliforms and E. coli only come from
human and animal fecal waste. The presence of coliform in water indicates
pathogenic contamination,
Chlorine treatment Chlorine readily combines with chemicals dissolved
in water, microorganisms, small animals, plant material, tastes, odors, and
colors. These components "use up" chlorine and comprise the chlorine
demand of the treatment system. It is important to add sufficient chlorine
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to the water to meet the chlorine demand and provide residual disinfection.
The chlorine that does not combine with other components in the water is
free (residual) chlorine, and the breakpoint is the point at which free
chlorine is available for continuous disinfection.
An ideal system supplies free chlorine at a concentration of 0.3-0.5
mg/l. Simple test kits, most commonly the DPD colorimetric test kit (so

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called because diethyl phenylene diamine produces the color reaction), are
available for testing breakpoint and chlorine residual in private systems.
The kit must test free chlorine, not total chlorine.

Contact time with microorganisms The contact (retention) time in

chlorination is that period between introduction of the disinfectant and
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

when the water is used. A long interaction between chlorine and the
microorganisms results in an effective disinfection process. Contact time
varies with chlorine concentration, the type of pathogens present, pH, and
temperature of the water.
The calculation procedure is given below. Contact time must increase
under conditions of low water temperature or high pH (alkalinity).
Complete mixing of chlorine and water is necessary, and often a holding
tank is needed to achieve appropriate contact time. In a private well
system, the minimum-size holding tank is determined by multiplying the
capacity of the pump by 10. For example, a 5-gallons-perminute (gpm)
pump requires a 50-gallon holding tank.
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Pressure tanks are not recommended for this purpose since they
usually have a combined inlet/ outlet and all the water does not pass
through the tank. An alternative to the holding tank is a long length of
coiled pipe to increase contact between water and chlorine. Scaling and
sediment build-up inside the pipe make this method inferior to the holding
tank.

Chlorination levels If a system does not allow adequate contact time

with normal dosages of chlorine, super chlorination followed by
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dechlorination (chlorine removal) may be necessary. Super chlorination
provides a chlorine residual of 3.0-5.0 mg/l, 10 times the recommended
minimum breakpoint chlorine concentration. Retention time for super
chlorination is approximately 5 minutes. Activated carbon filtration removes
the high chlorine residual (see: Fact Sheet 3: "Activated Carbon Treatment
of Drinking Water")

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Engineering
Nanotechnology
Chapter 13
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Nanoparticle
Nano definitions:
1. Nanoparticles are particles between 1 and 100 nanometers (nm) in size with a
surrounding interfacial layer. The interfacial layer is an integral part of
nanoscale matter, fundamentally affecting all of its properties.
2. a particle is defined as a small object that behaves as a whole unit with respect
to its transport and properties.
3. Particle of any shape with dimensions in the 1 × 10−9 and 1 × 10−7 m range.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

4. The two dimensions Tubes and fibers with below 100 nm .

5. a nano-object with all three external dimensions in the nanoscale, whose longest
and shortest axes do not differ significantly.

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Figure (1) gold nao particles solution

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Figure (2) gold nano particles

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Figure (3) Silica Nano particles solution

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Figure (4)TEM (a, b, and c) images of prepared mesoporous silica nanoparticles with
mean outer diameter: (a) 20nm, (b) 45nm, and (c) 80nm. SEM (d) image
corresponding to (b). The insets are a high magnification of mesoporous silica
particle.
Difference between nanoparticles and colloid:
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Colloid:
is a mixture which has solid particles dispersed in a liquid medium. the particles with
size range from nanometers (10−9 m) to micrometers (10−6 m).
Colloids can contain particles too large to be nanoparticles.
Nanoparticles smaller than colloidal .
history of nanomaterial

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the history of nanomaterial utilization is ancient, and human beings used these materials
a long time ago for various applications.
The Lycurgus Cup is another fascinating example from the past. It is a dichroic cup
produced by the Romans in the 4th century A.D. It resembles jade in direct light,
whereas it shows a translucent ruby color in the case of transmitted light. It shows color
variations depending on the incident light. These color variations appear due to the
presence of nanoparticles of Ag and Au
Classification of nanoparticles due to the particle size:
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

➢ Ultrafine particles are the same as nanoparticles and between 1 and 100 nm in
size.
➢ fine particles are sized between 100 and 2,500 nm.
➢ coarse particles cover a range between 2,500 and 10,000 nm.
Properties of nano :
materials behave very differently compared to larger scales and it is still very difficult
to predict the physical and chemical properties of particles of such a very small size.
The principal parameters of nanoparticles are their shape, size, surface characteristics
and inner structure.
1. Nanomaterials may have a significantly lower melting point or phase
transition temperature and appreciably reduced lattice constants, due to a
huge fraction of surface atoms in the total amount of atoms.

2.
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which are one or two orders of magnitude higher than that of single
crystals in the bulk form. The enhancement in mechanical strength is
simply due to the reduced probability of defects.

3. Optical properties of nanomaterials can be significantly different from bulk

crystals. For example, the optical absorption peak of a semiconductor
nanoparticle shifts to a short wavelength, due to an increased band gap.
The color of metallic nanoparticles may change with their sizes due to
surface plasmon resonance.

4. Electrical conductivity decreases with a reduced dimension due to

increased surface scattering. However, electrical conductivity of
nanomaterials could also be enhanced
30504101603434
appreciably, due to the 30504101603434
30504101603434
better
ordering in microstructure, e.g. in polymeric fibrils.

5. High surface to volume ratio.

6. Low percolation threshold.

7. Increasing hardness to wear resistance with decrasing the grain size.

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8. Increasing resistivity withdecreasing the grain size.

Synthesis of nano :
Two main approaches are used for the synthesis of nanomaterials:
1. Top-down approaches
2. bottom-down approaches
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

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Figure (5a)

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Figures (5a,5b) synthesis of nanomaterials

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Top-down approaches
In top-down approaches, bulk materials are divided to produce nanostructured
materials.
The “top-down” approach, which involves the breaking down of large pieces of material
to generate the required nanostructures from them.
top-down approaches include :
➢ mechanical milling.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

➢ laser ablation.
➢ Etching.
➢ Sputtering.
➢ electro-explosion.

Mechanical milling:
Done using ball mill.
Ball milling is a grinding method that grinds particles into extremely fine powders.
Ball milling is a mechanical process and thus all the structural and chemical changes
are produced by mechanical energy.
Advantages :
1. is a cost effective method for producing materials at the nanoscale from bulk
materials.
2022/2023 2022/2023 2022/2023

2. an effective method for producing blends of different phases.

3. helpful in the production of nanocomposites.
4. . Nano powders of 2 to 20 nm in size can be produced. The size of Nano
powder also depends upon the speed of the rotation of the balls.
Disadvantages;

1. As the process is not so sophisticated, therefore the shape of the nanomaterial

is irregular.
2. There may be contaminants inserted from ball and milling additives.
3. This method produces crystal defects.

Used for producing Nano materials such as:

1. oxide- and carbide-strengthened aluminum alloys.
2. wear-resistant spray coatings. 30504101603434
30504101603434 30504101603434
3. aluminum/nickel/magnesium/copper-based nanoalloys.

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

Figure (6) ball mill

Electrospinning:
➢ Electrospinning is one of the simplest top-down methods for the development
of nanostructured.
➢ used to produce nanofibers from a wide variety of materials, typically polymers
➢ The electrospinning process is a vital method to synthesize nanofibrous
30504101603434scaffolds, that uses high voltage to create an electric field between
30504101603434 a droplet of
30504101603434
the polymer solution at the tip of a needle and a collector plate.
Advantages :
➢ High resolution (nanoscale)
➢ Excellent cell to cell interaction
➢ Homogenous cell to cell strut

Disadvantages :
➢ Using toxic solutions.

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➢ Inhomogeneous cell distribution.

➢ Sometimes low mechanical properties of the products.
➢ Low cell density control ability.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Figure (7) Electrospinning

2022/2023 2022/2023 2022/2023

Figure (7) Electrospinning types

Lithography:
It is a process used to create patterns on a nanoscale, which helps in the fabrication of
nanodevices and systems.
Lithography refers to the fabrication of one- and two-dimensional structures in which
at least one of the lateral dimensions is in the nanometer range.
30504101603434 30504101603434 30504101603434
Lithography is a useful tool for developing nanoarchitectures using a focused beam of
light or electrons.

Lithography can be divided into two main types:

• masked lithography
• maskless lithography

masked lithography:

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In masked nanolithography, nanopatterns are transferred over a large surface area using
a specific mask or template.
Masked lithography includes photolithography nanoimprint lithography and soft
lithography.
Maskless lithography:
In maskless lithography, arbitrary nanopattern writing is carried out without the
involvement of a mask.
Masked lithography less includes scanning probe lithography, focused ion beam
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

lithography and electron beam lithography.

2022/2023 2022/2023 2022/2023

Figure(8) Schematic of optical lithography.

Sputtering:
Sputtering is a process used to produce nanomaterials via bombarding solid surfaces
with high-energy.
particles such as plasma or gas. Sputtering is an effective method for producing thin
films of nanomaterials.
Sputter deposition is a physical vapor deposition (PVD) method of thin film deposition
30504101603434 30504101603434 30504101603434
by the phenomenon of sputtering.
Sputtering is a process through which microscopic particles of a target material get
ejected from its surface after the bombardment of energetic ions of gas or gaseous
plasma. Momentum exchange between atoms and ions of the element causes sputtering.
Sputtering is a technique to deposit thin films of different materials onto a surface.
Materials such as metals, plastics, and ceramics are deposited on the surface through
different processes.

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

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Figure(8) Sputtering
30504101603434 30504101603434 30504101603434

The arc discharge method:

The arc discharge method is useful for the generation of various nanostructured
materials.
In arc discharge synthesis, the source material is vaporized through an arc discharge
between electrodes followed by condensation, nucleation, and growth of nanoparticles.
It is more known for producing carbon-based materials, such as fullerenes, carbon nano
horns (CNHs), carbon nanotubes, few-layer graphene (FLG), metal or metal oxide ,and
amorphous spherical carbon nanoparticles

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

2022/2023 2022/2023 2022/2023

Figure(9) The arc discharge method

Advantages :
➢ Simplicity
➢ low-cost procedures .
➢ avoiding the multistep purification.
Disadvantages :

➢ Arc discharge process has scale up limitations .

➢ sometimes requires the addition of
30504101603434
a small amount of metal catalysts,
30504101603434
which increases
30504101603434
the yield of nanotubes. So the resulting products contain some catalyst particles
Laser ablation:
Laser ablation synthesis involves nanoparticle generation using a powerful laser beam
that hits
the target material.
Laser ablation is a method for fabricating various kinds of nanoparticles including
semiconductor quantum dots, carbon nanotubes, nanowires, and core shell

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nanoparticles. In this method, nanoparticles are generated by nucleation and growth of

laser-vaporized species in a background gas.
Advantages :

➢ The extremely rapid quenching of vapor is advantageous in producing high

purity nanoparticles in the quantum size range (< 10 nm).
➢ allows control over material properties using process parameters including
laser tuning and multi-target precursors.
➢ provides high production rates.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

➢ good particle size control.

➢ good mono dispersity.
Disadvantages :
lack of precision due to the shot-to-shot variation in laser power and its nonlinear
effect on the ablation process. To overcome these several different normalization
techniques have been investigated.

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30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Figure(10) Laser ablation

Bottom-up approaches:

The “bottom-up” approach, which implies assembling

single atoms and molecules into larger nanostructures.
2022/2023 2022/2023 2022/2023
It is included :

➢ Chemical vapor deposition.

➢ Solvothermal and hydrothermal methods.
➢ The sol–gel method.
➢ Soft and hard templating methods.
➢ Reverse micelle methods.

Chemical vapor deposition (CVD):

Chemical vapor deposition methods have great significance in the generation of
carbon-based nanomaterials.
Chemical Vapor Deposition (CVD) is a process in which the substrate is exposed to
one or more volatile precursors, which30504101603434
30504101603434
react and/or decompose on the30504101603434
substrate surface
to produce the desired thin film deposit.
Chemical vapor deposition (CVD) is parent to a family of processes whereby a solid
material is deposited from a vapor by a chemical reaction occurring on or in the vicinity
of a normally heated substrate surface. The resulting solid material is in the form of
a thin film, powder, or single crystal. By varying experimental conditions, including
substrate material, substrate temperature, and composition of the reaction gas mixture,
total pressure gas flows, etc., materials with a wide range of physical, tribological, and
chemical properties can be grown.

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Advantages :
➢ high capacity to create pure thin films or nanoparticles.
➢ high manufacturing yield.
➢ simplicity in scaling up.
Disadvantages :
➢ the lack of precursors that are highly volatile, nontoxic and nonpyrophoric.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

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Figure(11) Chemical vapor deposition

Solvothermal and hydrothermal methods.
The hydrothermal process is one of the most well-known and extensively used methods
30504101603434 30504101603434 30504101603434
used to produce nanostructured materials.
In the hydrothermal method, nanostructured materials are attained through a
heterogeneous reaction carried out in an aqueous medium at high pressure and
temperature around the critical point in a sealed vessel.
What are the advantages of solvothermal process?
The main advantage of this method is that almost any material can be dissolved in the
solvent by increasing the temperature and pressure to its critical point.
Advantages :

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➢ No use of catalysts and that it occurs under extremely low heating, indicating
low energy demand.
Disadvantages :
➢ using of the toxic solvent like CCl4
➢ need expensive autoclaves.
➢ the impossibility of observing the crystal as it grows if a steel tube is used.to
overcame this There are autoclaves made out of thick walled glass, which can
be used up to 300 °C and 10 bar.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Figure (12) Solvothermal and hydrothermal methods

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30504101603434 30504101603434 30504101603434

Figure (13) a) hydrothermal and (b) solvothermal synthesis of ZnO/GO

The sol–gel method:
The sol–gel method is a wet chemical technique that is extensively used for the
development of nanomaterials. This method is used for the development of various
kinds of high-quality metal-oxide-based nanomaterials.

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This method is called a sol–gel method as during the synthesis of the metal-oxide
nanoparticles, the liquid precursor is transformed to a sol, and the sol is ultimately
converted into a network structure that is called a gel.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Figure (14) Different routes of the sol-gel processing.

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30504101603434 30504101603434 30504101603434

Figure (15) The sol–gel synthesis steps.

Advantages :
➢ Considering from the Simplest way to produce nanomaterial
➢ Homogeneity method.
➢ Low cost .
➢ Reliability and reproducibility.
➢ Controllability.

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➢ Films are easily anchored on the substrate bearing the complicated shapes and
large surface area .
➢ Suitable for deposition on other substrates lie stainless steel, steel plate
,aluminum plates, Silica/glass rushing rings, glass wool.
➢ Easy to perform in the laboratory
➢ Possibility of obtaining special products such as powders, films or coatings,
microspheres, fibers.
➢ Obtaining new solids with improved properties;
➢ High purity and homogeneity of the materials obtained;
➢ Saving energy during the process;
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Disadvantages :
➢ high costs for the fabrication .
➢ high energy requirements.
➢ high temperature, and pressure requirements.
➢ decreased stability.
➢ altered physicochemical features.
➢ Longe period for deposition .
➢ Not possible to attach thick layer of nano particles on the substrate .

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Figure (16) Sketch of the Synthesis of ZnO thin film by sol-gel method.

30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Figure (17) The schematic illustrating the fabrication process of undoped and Cr-
doped TiO2 Nano powders and gas sensors is shown.
Soft and hard templating methods:
Soft and hard template methods are extensively used to produce nonporous materials.
The soft template method is a simple conventional method for the generation of
nanostructured materials.
The hard-templating synthetic route, 2022/2023
2022/2023 also known as “Nano casting,” is another
2022/2023

straightforward technique to obtain mesoporous structures.

The difference between the soft method and hard method:
The main difference of soft and hard template methods is the template. The soft
templates are typically in fluid-like and non-rigid materials i.e surfactant and hard
templates are typically solid-state materials with specific morphology and structure.

30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Figure (18) Soft and hard templating methods

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30504101603434 30504101603434 30504101603434

Figure (19) Soft and hard templating

Reverse micelle methods:
The reverse micelle method is also a useful technique for producing nanomaterials with
the desired shapes and sizes. An oil-in-water emulsion results in normal micelles, in
which hydrophobic tails are aimed towards a core that has trapped oil droplets within
it.

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Reverse micelles are used for the selective separation and purification of biomolecules,
and for the synthesis of nanoparticles. Reverse micelles are nanometer-size droplets of
aqueous phase, stabilized by surfactants in an organic phase.
Reverse micelles are amphiphilic polymers consisting of a hydrophilic core shielded
by a hydrophobic shell. This formulation approach provides enhanced solubility and
stability of the peptide drug that is encapsulated into the core along with a greater
degree of permeability through biological membranes
Advantages :
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

➢ Different shapes might help target drug-delivery applications.

Disadvantages :
➢ the poor solubility of small-sized micelles.
➢ poor loading capacity.
➢ poor physical stability in vivo.

2022/2023 2022/2023 2022/2023

Figure (20) reverse micelle method

30504101603434 30504101603434 30504101603434

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Figure (21) a) Schematic showing the synthetic steps of the GA-MNPs. (b)
Synthesis of L-MNPs through the nonionic reverse micelle method.
Characterization of Nanoparticles :
There are two types of characterization :
➢ Physical characteristics
➢ Chemical characteristics.
Physical characteristics:
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1. particle size analysis and morphology:

using electron microscopy scanning electron microscope(SEM)and
Transmission electron microscopy (TEM).
2. Particle size determination:
Using light scattering techniques or disc sentrifugations.
3. Nanoparticle interactions to know formulation development :
Using Zeta potential measurements.
4. Viscosity .
5. Solubility .
6. Surface area and porosity measurements:
Using Brunner-Emmett-Teller theory(BET) is used to measure the surface area
of solid or porous materials through using equations .
7. crystalline morphology:
30504101603434 30504101603434 30504101603434

using X-Ray diffraction

Chemical characteristics:
1. knowing the functional groups :
using Fourier Transform Infrared Radiation Spectroscopy(FTIR).
2. Organic component analysis:
Using liquid chromatography – Mass Spectroscopy.
3. Purity and amounts of impurities.

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4. Surface chemistry and surface analysis.

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Figure (21) Nanomaterials with various morphologies.

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

Solutions
Chapter 14
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 ‫‪UG_31186536@f-eng.tanta.edu.eg‬‬ ‫‪UG_31186536@f-eng.tanta.edu.eg‬‬ ‫‪UG_31186536@f-eng.tanta.edu.eg‬‬

‫المحاليل ‪Solutions‬‬
‫المحاليل هي مخاليط متجانسة ‪homogeneous mixtures‬يمكن ان تختلف نسب مكوناتها وبذلك تختلف عن‬
‫المركب الكيميائي ‪.‬‬

‫ويمكن تقسيم المحاليل الي األنواع اآلتية‪:‬‬

‫غازات في غازات ‪ :‬مثل الهواء الجوي ‪.‬‬ ‫•‬

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫غازات في سوائل ‪ :‬مثل المياه الغازية ‪.‬‬ ‫•‬

‫غازات في مواد صلبة ‪ :‬مثل مسحوق الفحم في كمامات الغازات السامة ‪.‬‬ ‫•‬
‫سوائل في سوائل ‪ :‬مثل مخلوط الماء والكحول ‪.‬‬ ‫•‬
‫مواد صلبة في سوائل ‪ :‬مثل محاليل األمالح ‪.‬‬ ‫•‬
‫مواد صلبة في مواد صلبة‪ :‬مثل السبائك المختلفة ‪.‬‬ ‫•‬
‫ويتكون المحلول من مذيب ومذاب فالمادة الموجودة بكمية أكبر تعرف بالمذيب في حين المادة الموجودة بكمية أقل‬
‫تعرف بالمذاب‪.‬‬

‫ويوجد نوع أخر من المحاليل وهو محلول الصلب في الصلب مثل المحلول الناتج من الشب البوتاسيومي أو الشب‬
‫األمونيومي أو مثل المحلول الناتج من ذوبان كبريتات البوتاسيوم في كبريتات األمونيوم ‪.‬‬

‫المقصود بالذوبانية ‪:‬‬

‫إذا كان المحلول ال يزال ممكنة أن يذيب زيادة من مذاب عند نفس درجة الحرارة فإنه يعرف بالمحلول الغير مشبع‬
‫درجة الحرارة فإنه يعرف بالمحلول المشبع ومن الممكن‬
‫‪2022/2023‬‬
‫‪2022/2023‬أن يذيب زيادة من مذاب عند نفس‬
‫‪2022/2023‬‬
‫‪.‬وعندما ال يمكنه‬
‫الحصول علي محاليل فوق مشبعة أي محاليل تحتوى علي زيادة من المذاب الذائب أكثر مما يمكن إذابته عند درجة‬
‫حرارة معينة ‪.‬‬

‫تركيز المحاليل (طرق التعبير عن تركيز المحاليل ) ‪:‬‬

‫يعرف تركيز المحلول بأنه الكميات أو األحجام النسبية لمكونات المحلول ‪.‬‬

‫ويعبر عن تركيز المحلول بالطرق األتية ‪:‬‬

‫‪ .1‬طريقة وزن الحجم ‪:‬‬

‫يعبر عن التركيز بداللة وحدات كتلة إلي واحدات الحجوم ‪:‬‬

‫• جم ‪ /‬لتر (‪ :)C‬عبارة عن كتلة المادة المذابة بالجرام في لتر من المحلول ‪ .‬مثل كلوريد الصوديوم تركيزه‬
‫‪30504101603434‬من الماء وبعد الذوبان يكمل الماء حتي يصل الحجم‬
‫‪30504101603434‬‬
‫لتر حيث يتم إذابة ‪ 5‬جم من الملح في كمية‬ ‫‪ 5‬جرام ‪/‬‬
‫‪30504101603434‬‬
‫الكلي إلي لتر ‪.‬‬
‫• الموالرية (‪ : )Molarity‬عدد الجرامات الجزيئيية للمذاب الموجودة في واحد لتر من المحلول‬

‫عدد الجرامات فيللمذاب لتر محلول‬

‫=𝑚‬
‫الوزن الجزيئي للمادة المذابة‬

‫‪(NaCl)= 2 m‬يعني أن لدينا ‪ 2‬جرام جزيئيي من كلوريد الصوديوم المذابة في لتر من المحلول‪.‬‬

‫‪398‬‬
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‫مثال ‪:‬‬

‫ما وزن نترات الفضة الصلبة الالزمة لتحضير محلول حجمه ‪ 500‬سم ‪3‬وتركيزه )‪(m = 1.5‬‬

‫الحل ‪:‬‬

‫‪Given AgNO3 v=500 cm3‬‬ ‫‪C= 1.5 m‬‬

‫عدد الجرامات فيللمذاب لتر محلول‬

‫=𝑚‬
‫الوزن الجزيئي للمادة المذابة‬
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫الوزن الجزيئيي لنترات الفضة (‪170 = )16*3( + 14 + 108 = )AgNO3‬‬

‫عدد الجرامات فيللمذاب لتر محلول‬

‫‪= 1.5‬‬
‫‪170‬‬

‫عدد الجرامات المذابة في لتر محلول = ‪ 255 =170 * 1.5‬جرام‬

‫لدينا ‪ 255‬جرام من نترات الفضة مذابة في لتر ( ‪ 1000‬سم ‪ ) 3‬من المحلول‬

‫‪255 g‬‬ ‫‪1000 cm3‬‬

‫‪Xg‬‬ ‫‪500 cm3‬‬

‫‪255 Х 500‬‬
‫=𝑋‬
‫‪1000‬‬

‫كمية نترات الفضة المذابة في ‪ 500‬سم ‪ 3‬من المحلول = (‪ 127.5 = 1000 / ) 500 * 255‬جرام‬
‫‪2022/2023‬‬ ‫‪2022/2023‬‬ ‫‪2022/2023‬‬
‫العيارية ( ‪ : )Normality‬عدد األوزان المكافئة من المادة المذابة في لتر من المحلول ‪.‬‬ ‫•‬
‫عدد الجرامات فيللمذاب لتر محلول‬
‫العيارية (‪= )Normality‬‬
‫الوزن المكافئ‬

‫الوزن الجزيئي‬
‫الوزن المكافئ =‬
‫التكافؤ‬

‫‪(Nacl) =2 N‬معناها أن لدينا ‪ 2‬جرام مكافئ من كلوريد الصوديوم مذابة في لتر من المحلول ‪.‬‬

‫مثال (‪: )1‬‬

‫إحسب عيارية المحلول الذي يحتوي علي ‪ 26.5‬جرام من كربونات الصوديوم ‪.‬‬

‫الحل ‪:‬‬
‫‪30504101603434‬‬ ‫‪30504101603434‬‬ ‫‪30504101603434‬‬
‫عدد الجرامات فيللمذاب لتر محلول‬
‫العيارية ( ‪= )Normality‬‬
‫الوزن المكافئ‬

‫الوزن الجزيئي‬
‫الوزن المكافئ =‬
‫التكافؤ‬

‫الوزن الجزيئيي لكربونات الصوديوم (‪106 = )16*3( + 12 + )23*2( = )Na2CO3‬‬

‫الوزن الجزيئي‬
‫الوزن المكافئ =‬
‫التكافؤ‬

‫‪399‬‬
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‫‪106‬‬
‫= ‪53‬‬ ‫الوزن المكافئ =‬
‫‪2‬‬

‫عدد الجرامات فيللمذاب لتر محلول‬

‫العيارية ( ‪= )Normality‬‬
‫الوزن المكافئ‬

‫‪26.5‬‬
‫‪N 0.05‬‬ ‫=‬ ‫العيارية ( ‪= )Normality‬‬
‫‪53‬‬

‫مثال (‪: )2‬‬

‫إذا أراد تحضير محلول صوديوم هيدروكسيد (‪(NaOH = 2 N‬إحسب كم جرام من هيدروكسيد الصوديوم‬
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫يجب إذابتها في ‪ 1‬لتر ؟‬

‫الحل ‪:‬‬

‫عدد الجرامات فيللمذاب لتر محلول‬

‫العيارية ( ‪= )Normality‬‬
‫الوزن المكافئ‬

‫الوزن الجزيئي‬
‫الوزن المكافئ =‬
‫التكافؤ‬

‫االوزن الجزيئيي لصوديوم هيدروكسيد (‪40 = 16 + 1 + 23 = )(NaOH‬‬

‫‪40‬‬
‫= ‪40‬‬ ‫الوزن المكافئ =‬
‫‪1‬‬

‫عدد الجرامات فيللمذاب لتر محلول‬

‫العيارية ( ‪= )Normality‬‬
‫الوزن المكافئ‬

‫‪2022/2023‬‬ ‫‪2022/2023‬‬ ‫‪2022/2023‬عدد الجرامات فيللمذاب لتر محلول‬

‫العيارية ( ‪= )2N‬‬
‫‪40‬‬

‫عدد الجرامات المذابة في لتر من المحلول = ‪ 80 = 40 *2‬جرام‬

‫‪ .2‬طريقة وزن الوزن ‪:‬‬

‫عدد الجرامات المذابة من المذاب‬
‫النسبة المئوية بالوزن = ‪ 100‬محلولجرام " الجرامات كلها" × ‪100‬‬ ‫•‬

‫‪NaCl =5 %‬كل ‪ 100‬جرام من المحلول يحتوي علي ‪ 5‬جرام كلوريد الصوديوم‬

‫‪ 100‬محلول = مادة مذابة ‪ +‬المذيب‬

‫وزن الماء ( المذيب ) = ‪ 95= 5-100‬جرام‬

‫مثال ‪:‬‬
‫‪30504101603434‬‬ ‫‪30504101603434‬‬ ‫‪30504101603434‬‬

‫إحسب النسبة المئوية بالوزن التي تنتج عند إذابة ‪ 10‬جرام سكر في ‪ 40‬جرام ماء ‪.‬‬

‫الحل ‪:‬‬

‫وزن المحلول ( سكر ‪ +‬ماء ) = ‪ 50 = 40 + 10‬جرام محلول‬

‫محلول به ‪ 10‬جرام سكر مذابة في ‪ 50‬جرام محلول‬

‫)‪Sugar g (10g‬‬ ‫‪50 g solution‬‬

‫‪400‬‬
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‫‪Xg‬‬ ‫‪100 g‬‬

‫‪100 Х10‬‬
‫=𝑋‬
‫‪50‬‬

‫وزن السكر المذاب في ‪ 100‬جرام محلول = (‪% 20 = 50 / )10*100‬‬

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫إذن تركيز المحلول ‪% 20‬‬

‫المواللية (‪ : )Molality M‬عدد الجرامات الجزيئيية المذابة من المادة في ‪ 1000‬جرام (‪ 1‬كيلو جرام‬ ‫•‬
‫) من المذيب ‪.‬‬
‫عدد الجرامات المذابة في ‪ 1000‬جرام مذيب‬
‫المواللية (‪= )Molality M‬‬
‫الوزن الجزيئي‬

‫إذا كان لدينا محلول من كلوريد الصوديوم تركيزه = ‪M 2.5‬معني ذلك أنه إذا كان لدينا ‪ 1000‬جرام من المذيب‬
‫الماء فإنه مذاب فيهم ‪ 2.5‬مول ( جرام جزيئي ) من كلوريد الصوديوم ‪.‬‬

‫مثال ‪:‬‬

‫إذا كان لدينا محلول من كلوريد الصوديوم يبلغ تركيزه ‪ 2‬موالل (‪ )2M‬إحسب تركيزه الموالري علما بأن‬
‫‪3‬‬
‫كثافة المحلول هي ‪ 1.28‬جرام ‪ /‬سم‬
‫‪2022/2023‬‬ ‫‪2022/2023‬‬ ‫‪2022/2023‬‬

‫الحل ‪:‬‬

‫عدد الجرامات المذابة في ‪ 1000‬جرام مذيب‬

‫المواللية (‪= )Molality M‬‬
‫الوزن الجزيئي‬

‫‪ 2‬موالل = يعني أن لدينا ‪ 2‬جرام جزيئي من كلوريد الصوديوم المذابة في ‪ 1000‬جرام ماء‬

‫الوزن الجزيئيي لكلوريد الصوديوم (‪58.5 = 35.5+ 23 = )NaCl‬‬

‫الوزن‬
‫عدد الموالت (‪= )n‬‬
‫الوزن الجزيئي لكلوريد الصوديوم‬

‫الوزن‬
‫‪=2‬‬
‫‪58.5‬‬

‫‪30504101603434‬‬
‫‪ 11730504101603434‬جرام من كلوريد الصوديوم‬
‫‪30504101603434‬‬
‫الوزن = ‪= 58.5 *2‬‬

‫الموالرية هي عدد الجرامات الجزيئيية للمذاب الموجودة في واحد لتر من المحلول‬

‫وزن المحلول = وزن المذاب ( كلوريد الصودبوم ) ‪ +‬وزن المذيب (الماء )‬

‫وزن المحلول = ‪ 1117 = 100 + 117‬جرام محلول‬

‫وزن المحلول‬
‫حجم المحلول =‬
‫كثافة المحلول‬

‫‪401‬‬
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‫‪1117‬‬
‫= ‪ 872‬سم‪ 3‬من المحلول‬ ‫حجم المحلول =‬
‫‪1.28‬‬

‫‪ 872‬سم‪ 3‬من المحلول‬ ‫‪2‬مول ( جرام جزيئي)‬

‫‪ 1000‬سم‪ 3‬من المحلول‬ ‫‪X‬مول(جرام جزيئي)‬

‫عدد الموالت من كلوريد الصوديوم المذابة في لتر من المحلول = (‪ 2.29 = 872 / )1000*2‬مول‬
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫الكسر المولي ( الكسر الجزبئي ) ‪:‬‬ ‫•‬

‫هي النسبة المئوية بين عدد الجرامات الجزيئية ألحد مكونات المحلول مقسومة علي العدد الكلي للجرامات الجزيئية للمحلول‬
‫‪.‬‬

‫فإذا كان لدينا محلول مكون من مادة أ ‪ ,‬ب ‪ ,‬ج وكانت عدد الجرامات الجزيئية للمادة األولي أ هي (‪ )nA‬و عدد‬
‫الجرامات الجزيئية للمادة الثانية ب هي (‪ )nB‬و عدد الجرامات الجزيئية للمادة الثالثة ج هي (‪ )nC‬فإن ‪:‬‬
‫‪nA‬‬
‫‪nA +nB +nC‬‬
‫الكسر المولي للمادة األولي (‪= : )nA‬‬

‫‪nB‬‬
‫الكسر المولي للمادة الثانية (‪= : )nB‬‬
‫‪nA +nB +nC‬‬

‫‪nC‬‬
‫الكسر المولي للمادة الثالثة (‪= : )nC‬‬
‫‪nA +nB +nC‬‬

‫مثال ‪:‬‬
‫‪2022/2023‬‬ ‫‪2022/2023‬‬ ‫‪2022/2023‬‬
‫إحسب الكسر الجزيئي لجزيئات حامض الهيدروكلوريك (‪ )HCl‬في محلول مائي من حمض الهيدروكلوريك‬
‫تركيزه ‪ 10‬مولل (‪. )10 M‬‬

‫الحل ‪:‬‬

‫عدد الجرامات المذابة في ‪ 1000‬جرام مذيب‬

‫المواللية (‪= )Molality M‬‬
‫الوزن الجزيئي‬

‫لدينا ‪ 10‬مول ( جرام جزيئي ) من حامض الهيدروكلوريك المذابة في ‪ 1000‬جرام ماء‬

‫عدد موالت الحامض‬

‫الكسر الجزيئي للحامض =‬
‫عدد الموالت الكلي للمحلول‬

‫عدد موالت الحامض = ‪ 10‬مول‬

‫‪30504101603434‬‬ ‫‪18‬‬
‫‪30504101603434‬‬ ‫‪=1*2+ 16 = )H2O(30504101603434‬‬
‫الوزن الجزيئيي للماء‬

‫وزن الماء‬
‫=‬ ‫عدد موالت الماء =‬
‫الوزن الجزيئي للماء‬

‫‪1000‬‬
‫= ‪55.56‬‬ ‫عدد موالت الماء =‬
‫‪18‬‬

‫‪10‬‬
‫= ‪15‬‬ ‫‪55.56+10‬‬
‫الكسر الجزيئي للحامض =‬

‫‪402‬‬
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‫محاليل الغازات في الغازات‬

‫وهذه المحاليل يحكمها قانون دالتون للضغوط الجزئية ‪.‬‬

‫محاليل الغازات في السوائل ‪:‬‬

‫يذوب الغاز في السائل ‪ ,‬ونتحكم درجة الذوبان طبيعة كل من السائل والغاز ‪ ,‬وكذلك درجة الحرارة و ضغط‬
‫الغاز ‪ .‬بعض الغازات قابليتها للذوبان في الماء كبيرة ‪ ,‬وهي الغازات التي تتفاعل كيميائيا مع الماء مثل غاز‬
‫النشادر‪ NH3‬و كلوريد الهيدروجين ‪ HCl‬و ثاني اكسيد الكبريت‪ SO2‬وغيرها ‪ .‬وهناك غازات أخرى ذوبانها‬
‫في الماء ضعيف مثل غازات األكسجين والنيتروجين واأليدروجين وغيرهما ‪.‬‬
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫قانون هنري لذوبان الغازات في السوائل ‪Henery,s low‬‬

‫"عند ثبوت درجة الحرارة ‪ ,‬يتناسب وزن الغاز الذائب في حجم معين من المذيب السائل ‪ liquid solvent‬مع‬
‫ضغط الغاز فوق السائل "‬
‫𝑚‬
‫𝑝𝛼𝑚‬ ‫𝑝𝐾 = 𝑚 𝑟𝑜‬ ‫𝑟𝑜‬ ‫𝐾=‬
‫𝑝‬

‫حيث ‪:‬‬

‫‪ : m‬وزن الغاز السائل في وحدة الحجوم من السائل‬

‫‪ :P‬ضغط الغاز فوق السائل‪.‬‬

‫‪ :K‬ثابت التناسب ‪.‬‬

‫‪2022/2023‬‬ ‫‪2022/2023‬المذيب ‪ .‬أي في حالة المحاليل المخففة جدا ‪.‬‬

‫صحيح في حالة الغازات شحيحة الذوبان في‬ ‫وقانون هنرى‬
‫‪2022/2023‬‬

‫العوامل المؤثرة علي عملية الذوبان ‪:‬‬

‫طبيعة المذيب والمذاب ‪:‬‬

‫تتأثر ذوبانية غاز في سائل بطبيعة كال من الغاز (المذاب) والسائل (المذيب ) فمثال يذوب الميثان بمدي طفيف في‬
‫الماء ولكنه يذوب بقدر كبير في الهيدروكربونات حيث انه يتشابه معه كيميائيا إلي حد ما ‪.‬ال يمكن إعتبار التشابه‬
‫الكيميائي مبدأ مسلما به للحكم علي ذوبانية الغازات في السوائل فبالرغم من إختالف الخواص الكيميائية لإلستيلين‬
‫إختالفا تاما عن خواص الماء إال أنه يذوب في الماء بدرجة كبيرة ‪.‬‬

‫تأثير درجة الحرارة علي الذوبانية ‪:‬‬

‫أوال‪ :‬تأثير درجة الحرارة علي ذوبانية الغازات في السوائل ‪ :‬تبدي معظم الغازات تناقصا لذوبانيتها مع الماء كلما‬
‫إزدادت درجة الحرارة ويكون ذلك صحيحا مهما كان نوع المذيب المستعمل ‪.‬‬
‫‪30504101603434‬‬ ‫‪30504101603434‬‬ ‫‪30504101603434‬‬

‫أما بالنسبة لغاز موجود في تالمس مع محلوله المشبع عند درجة حرارة معينة يعبر عنه باإلتزان التالي ‪:‬‬

‫غاز في الطور الغازي غاز في المحلول المشبع‬

‫غاز في مذيب‬ ‫غاز في الطور الغازي‬

‫فإن اإلتزان يزاح نحو اليمين (نحو تكوين الغاز في الطور الغازي ) وذلك عند زيادة درجة الحرارة أي يصبح‬
‫الغاز أقل قابلية للذوبان ‪.‬‬
‫ةدعاقل اقبط‬
‫‪.‬هييليتاشول‬
‫‪403‬‬
 ‫‪UG_31186536@f-eng.tanta.edu.eg‬‬ ‫‪UG_31186536@f-eng.tanta.edu.eg‬‬ ‫‪UG_31186536@f-eng.tanta.edu.eg‬‬

‫هناك أمثلة قليلة معروفة تذداد فيها ذوبانية الغاز مع زيادة درجة الحرارة مثل ذوبانية الغازات النبيلة في المذيبات‬
‫الهيدروكربونية وبصفة خاصة في مدي درجات الحرارة من ‪ °288‬كلفن إلي ‪ ° 303‬كلفن ‪.‬‬

‫ثانيا ‪ :‬تأثير درجة الحرارة في محاليل المواد الصلبة في السوائل ‪:‬‬

‫تزداد ذوبانية المواد الصلبة في المذيبات المختلفة بزيادة درجة الحرارة فالشكل الموضح (منحني ذوبانية المواد‬
‫الصلبة في الماء ) يوضح أن ذوبانية المواد الصلبة مثل ( كلوريد الصوديوم – ونترات البوتاسيوم ونترات األمونيوم‬
‫) تزداد بزيادة درجة الحرارة بنسب مختلفة ماعدا بالنسبة لكبريتات الصوديوم فنجد أن ذوبانية كبريتات الصوديوم‬
‫المائية تزداد بزيادة درجة الحرارة حتي ‪ °32‬م ثم يتحول المركب من كبريتات الصوديوم المائية إلي كبريتات‬
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫الصوديوم الالمائية وذلك عند ‪ ° 32‬م وعند إذن تقل الذوبانية بزيادة درجة الحرارة ‪.‬‬

‫ويمكن تمثيل اإلتزان العام الذي ينشأ بين محلول مشبع في وجود مذاب صلب بالمعادلة التالية‬

‫مادة صلبة محلول مشبع ( مذاب إلي مذيب)‬

‫من اليمين إلي اليسار‬

‫فإذا أصبح الصلب أكثر قابلية للذوبان مع إرتفاع درجة الحرارة فإم اإلتزان يتحرك من اليميت إلي اليسار طبقا‬
‫لمبدأ لوشاتليه ويمكننا القول أن عملية الذوبان الصلب في محلول مشبع هي عملية ماصة للحرارة ‪.‬‬

‫‪2022/2023‬‬ ‫‪2022/2023‬‬ ‫‪2022/2023‬‬

‫شكل (‪ )1‬منحني ذوبانية مواد صلبة في الماء‬

‫تأثير الضغط علي ذوبانية غاز في سائل ‪:‬‬

‫عند درجة حرارة ثابتة ينشأ اإلتزان التالي بين محلول غاز مشبع والغاز الموجود فوقه في الطور الغازي‬
‫‪30504101603434‬‬ ‫‪30504101603434‬‬ ‫‪30504101603434‬‬

‫غاز في الطور الغازيمحلول مشبع (غاز في سائل )‬

‫نفرض أن الضغط قد أزيد علي هذا النظام ‪ :‬زيادة الضغط سوف يكون لها تأثير علي الغاز المالمس للمحلول‬
‫المشبع وسوف يؤد ي إلي إزاجة اإلتزان في اإلتجاه الذي يؤدي إلي إنقاص ذلك الضغط ويمكن أن ينقص الضغط‬
‫بزيادة كمية الغاز الذائب أي أن الغاز يصبح أكثر قابلية للذوبان في المذيب إذا أزيد الضغط الواقع عليه وعلي ذلك‬
‫يمكن التعبير عن حالة اإلتزان عن طريق ثابت اإلتزان (‪)k‬‬

‫‪404‬‬
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‫تركيز الغاز‬
‫ثابت إلتزان (‪= )k‬‬
‫تركيز الغاز في المحلول المشبع‬

‫ويمكن التعبير عن تركيز الغاز في الطور الغازي بمعرفة ضغطه (‪ )p‬بينما يعبر عن تركيز الغاز في المحلول‬
‫(‪ )C‬وهي كتلة الغاز المذاب في وحدة الحجوم من مذيب لمحلول مشبع‬
‫𝑝‬
‫=𝑘‬
‫𝑚‬

‫𝑝 = 𝑘𝑚‬
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫𝑝‬
‫=𝑚‬
‫𝑘‬

‫حيث ‪:‬‬

‫‪ :P‬هو ضغط الغاز الموجود في حالة اتزان مع الطور السائل‬

‫‪ :m‬كتلة الغاز الذائبة في حجم معلوم من المذيب‬

‫ويعرف هذا القانون بقانون هنري وينص علي ‪ :‬كتلة الغاز الذائب في حجم معلوم من المذيب عند درجة حرارة‬
‫معينة يتناسب تناسبا طرديا مع ضغط الغاز الموجود في حالة إتزان مع الطور السائل ‪.‬‬

‫محاليل الغازات في السوائل ‪:‬‬

‫الغازات ضعيفة الذوبانية تطيع قانون هنري إلي حد كبير بشرط أال يكون الضغط عاليا جدا و أال تكون درجة‬
‫الحرارة منخفضة جدا أي عند الظروف التي تدعم حيودا بسيطا عن الغاز المثالي ‪.‬‬

‫تطيع قانون‬
‫‪2022/2023‬‬ ‫األمونيا وكلوريد الهيدروجين في الماء ) ال‬ ‫‪2022/2023‬لتنتج أنواع جديدة في المحلول مثل (‬
‫‪2022/2023‬‬ ‫الغازات التي تتأين‬
‫هنري ‪.‬‬

‫الغازات التي تطيع قانون هنري وهي في الحالة النقية سوف تستمر في طاعته عندما يكون في خليط غازي وفي‬
‫هذه الحالة يمكن تطبيق قانون هنري علي كل غاز علي حدي‬
‫‪𝑝1‬‬
‫= ‪𝑥1‬‬
‫‪𝑘1‬‬
‫‪𝑝2‬‬
‫= ‪𝑥2‬‬
‫‪𝑘2‬‬

‫أي أن الصورة الجديدة لقانون هنري تصبح ‪:‬‬

‫𝑝‬
‫= 𝑥‬
‫‪30504101603434‬‬
‫𝑘‬
‫‪30504101603434‬‬ ‫‪30504101603434‬‬

‫حيث ‪:‬‬

‫‪ :x‬هو الكسر المولي ( الكسر الجزيئي ) للغاز‬

‫‪ :P‬هو الضغط الجزيئي للغاز في الخليط‬

‫‪ : k‬هو ثابت اإلتزان‬

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‫ويمكن القول بأن ذوبانية كل غاز في خليط لعدة غازات يتناسب تناسبا طرديا مع الضغط الجزيئ للغاز ‪ .‬ومن‬
‫الطبيعي أن تختلف قيمة من غاز إلي أخر ‪.‬‬

‫مثال ‪ :‬إحسب ذوبانية األكسجين (تركيز األكسجين مواللية ) بإستخام قانون هنري في الماء عند درجة حرارة‬
‫‪ °25‬م وضغط غاز جزيئ ‪ 190‬مم زئبق علما بأن ثابت اإلتزان = ‪ 3.03 × 107‬مم زئبق‬

‫الحل ‪:‬‬

‫عدد موالت األكسجين‬

‫عدد الموالت الكلي) عدد موالت األكسجين‪+‬عدد موالت الماء(‬
‫الكسر المولي لألكسجين =‬
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫ملحوظة عدد موالت األكسجين قليلة جدا في المحلول فتهمل بالنسبة لعدد موالت الماء ليصبح عدد موالت‬
‫المحلول الكلي هو نفسه عدد موالت الماء (تهمل في المقام )‬

‫نفرض أن عدد موالت األكسجين مذابة في ‪ 1000‬جرام مذيب (ماء )‬

‫‪𝑛𝑂2‬‬ ‫‪𝑛𝑂2‬‬ ‫‪𝑛𝑂2‬‬

‫=𝑥‬ ‫=‬ ‫=‬
‫𝑙𝑎𝑡𝑜𝑡𝑛‬ ‫𝑂 ‪𝑛𝐻2 𝑂 + 𝑛𝑂2 𝑛𝐻2‬‬

‫‪190‬‬ ‫‪𝑛𝑂2‬‬
‫‪7‬‬
‫‪= 1000‬‬
‫‪3.03 × 10‬‬
‫‪18‬‬

‫𝑒𝑙𝑜𝑚 ‪𝑛𝑂2 = 3.2 × 10−4‬‬

‫جرام‬
‫‪2022/2023‬‬ ‫‪2022/2023‬مذيب هي ‪3.2 × 10−4‬أي أن لدينا مول‬
‫الجراماتالجزيئية من المذابة في ‪ 1000‬جرام‬ ‫الموالية ‪ :‬عدد‬
‫‪2022/2023‬‬
‫جزيئ من األكسجين تذوب في ‪ 1000‬جرام ماء‬

‫عدد الجرامات المذابة في ‪ 1000‬جرام مذيب‬

‫= ‪3.2 × 10−4‬‬ ‫المواللية (‪( )Molality M‬التركيز)=‬
‫الوزن الجزيئي‬

‫الغازات في المواد الصلبة ‪:‬‬

‫يمكن للمادة الصلبة أن تأخذ الغازات علي أشكال مختلفة ‪:‬‬

‫يحدث إتحاد كيميائى كما في حالة ثاني أكسيد الكربون و اكسيد الكالسيوم ‪.‬‬

‫‪𝐶𝑎𝑂 + 𝐶𝑂2 → 𝐶𝑎𝐶𝑂3‬‬

‫قد يذوب الغاز في المادة الصلبة ويعطي مخلوطا متجانسا كما في حالة األيدروجين ومعدن البالديوم ‪.‬‬

‫لتميزها عن‬
‫‪30504101603434‬‬ ‫‪30504101603434‬الظاهرة اإلدمصاص ‪adsorption‬‬
‫علي سطح المادة الصلبة وتسمي تلك‬ ‫يبقي الغاز ملتصقا‬
‫‪30504101603434‬‬

‫اإلمتصاص ‪ absorption‬حيث يكون التوزيع متساويا تقريبا‪.‬‬

‫وهذه الظاهرة قد تكون إدمصاصا طبيعيا ‪physical adsorption‬وقد تكون إدمصاصا كيميائيا ‪chemical‬‬
‫‪ adsorption‬وهذه الظاهرة تفسر عمل الكثير من المواد المساعدة في التفاعالت الغازية ‪(contact catalysts‬‬
‫)‪.‬‬

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‫ةجرد تداز املك زاغلا ةلاسإ ةيلباق تداز املك‬

‫صاصمدالاهي ‪:‬‬
‫العوامل المؤثرة علي اإلدمصاص‬

‫طبيعة الغاز ‪ :‬يكون اإلدمصاص أكبر ما يمكن في حالة الغازات األكثر قابلية لإلسالة ‪.‬‬ ‫•‬
‫طبيعة المادة الصلبة ‪ :‬يزيد اإلدمصاص علي المادة الصلبة كلما زادت مساحتها حيث أن مساحة السطح‬ ‫•‬
‫المعرض للغاز تكون كبيرة ‪ .‬فمثال يستعمل مسحوق الفحم المنشط ‪ activated charcoal‬في كمامات‬
‫الغازات ‪ ,‬كما أنه يستعمل صناعيا لفصل الغازات القابلة لإلسالة عن غيرها عن طريق االدمصاص ‪.‬‬
‫درجة الحرارة ‪ :‬إرتفاع درجة الحرارة يقلل من االدمصاص حيث أن اإلدمصاص يكون عادة طارد‬ ‫•‬
‫للحرارة ‪ .‬وحسب قاعدة لوشاتيليه يزيد التبريد من الإلدمصاص و إرتفاع درجة الحرارة يطرد الغاز‬
‫الموجود علي المادة الصلبة ‪.‬‬
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫الضغط ‪ :‬عند درجة الحرارة الثابتة نجد أن وزن الغاز الموجود المدمص ‪ adsorbed‬بواسطة وزن معين‬ ‫•‬
‫من المادة الصلبة يزيد بزيادة ضغط الغاز ‪ ,‬ولكنه ال يتناسب طرديا معه بل تمثل الزيادة بالمعادلة ‪:‬‬
‫𝑥‬
‫𝑛𝑃𝐾 =‬
‫𝑚‬

‫حيث ‪:‬‬

‫‪ : x‬هو وزن الغاز ‪.‬‬

‫‪ : m‬وزن المادة الصلبة‬

‫‪ : P‬ضغط الغاز‪.‬‬

‫‪ : K, n‬ثابتان يتوقفان علي درجة الحرارة ونوع الغاز والمادة الصلبة‪ ,‬وتتراوح قيمة ‪n‬بينصفر و واحد صحيح‪.‬‬

‫‪2022/2023‬‬ ‫‪2022/2023‬‬ ‫السوائل ‪:‬‬ ‫السوائل في‬

‫‪2022/2023‬‬

‫عند رج سائلين مع بعضهما تحدث حالة من ثالثة ‪:‬‬

‫يمتزج السائالن تمام االمتزاج ‪completely miscible liquids‬‬ ‫•‬

‫ال يمتزج السائالن ‪completely immiscible liquids‬‬ ‫•‬
‫يمتزج السائالن إمتزاجا محدودا‪partially miscible liquids‬‬ ‫•‬

‫اوال‪ :‬محاليل السوائل في السوائل تامة االمتزاج ‪:‬‬

‫يعرف السلوك المثالي لسائلين بأنه الذي ال ينتج عنه أي تغير في قوي التجاذب بين جزيئيات أيا من السائلين عند‬
‫إضافة أحدهما إلي اآلخر وفي هذه الحالة فإن كل سائل يكون له ضغط بخارى جزئي يتناسب مع الكسر الجزئي‬
‫للسائل ‪.‬‬

‫في خليط السائلين حسب قانون راؤول للسوائل المثالية ‪:‬‬

‫‪30504101603434‬‬ ‫‪30504101603434‬‬ ‫‪30504101603434‬‬

‫‪407‬‬
 ‫‪UG_31186536@f-eng.tanta.edu.eg‬‬ ‫‪UG_31186536@f-eng.tanta.edu.eg‬‬ ‫‪UG_31186536@f-eng.tanta.edu.eg‬‬
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫شكل (‪ )2‬قانون رؤول للسوائل المثالية‬

‫𝐴𝑁 𝐴𝑃 = 𝐴~𝑃‬

‫𝐵𝑁 𝐵𝑃 = 𝐵 ~𝑃‬

‫حيث ‪:‬‬

‫‪: PA, PB‬ضغطي بخاري السائلين ‪A, B‬في الحالة النقية‪.‬‬

‫𝐵 ~ 𝑃 ‪ : 𝑃~𝐴 ,‬الضغوط الجزيئيية للسائلين‪ A,B‬في الخليط ‪.‬‬

‫‪2022/2023‬‬ ‫الخليط‪.‬‬
‫‪2022/2023‬‬ ‫‪2022/2023‬الجزيئيية للسائلين‪ A, B‬في‬
‫‪: NA, NB‬الكسور‬

‫والضغط الكلي للخليط يساوي مجموع الضغوط الجزيئيية‬

‫𝐵 ~𝑃 ‪𝑃 = 𝑃~𝐴 +‬‬

‫حيث ‪:‬‬

‫في الرسم الموضح و الذي يبين العالقة بين ضغط البخار والتركيب لخليط سائلين تاما االمتزاج نجد أنه عند أي‬
‫‪ : x‬تركيب‬

‫الضغطالجزئي لبخار السائل ‪A‬يساوي ‪xm‬‬

‫الضغط الجزئي لبخار السائل ‪B‬يساوي ‪xn‬‬

‫‪30504101603434‬‬ ‫‪30504101603434‬‬ ‫‪: 30504101603434‬‬

‫والضغط الكلي للخليط‬

‫𝑋𝑂 = 𝑛𝑥 ‪𝑃 = 𝑃~𝐴 + 𝑃~ 𝐵 = 𝑥𝑚 +‬‬

‫نالحظ في حالة الس وائل المثالية فان خطي الضغوط الجزيئيية للسائلين يكونان خطوطا مستقيمة تصل بين ضغط‬
‫بخار أحد السائبين النقين والتركيب ‪ %100‬من المكون األخر كما أن الضغط الكلي للخليط عند أي تركيب يقع‬
‫علي الخط المستقيم الواصل بين ضغطي بخاري السائلين النقيين ‪.‬‬

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‫عادة ينحرف خليط سائلين تاما اإلمتزاج عن الحالة المثالية وتوجد ‪ 3‬حاالت كما في الرسم‬
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫شكل (‪ )3‬األشكال المختلفة للحيود عن قانون رؤول للسوائل المثالية‬

‫في الحالة األولي يحدث إنحراف صغير جدا ويظل الضغط الكلي للخليط أي المحلول محصورا بين ضغطي‬
‫بخاري السائلين ‪A , B‬النقيين ‪ .‬أما في الحالة الثانية فإن قوي التجاذب بين السائلين تتغير نتيجة اآلضافة وتكون‬
‫أكبر منها بين جزيئيلت ‪A‬و بعضها أو بين جزيئيات ‪B‬و بعضها و بذلك تقل الضغوط الجزيئيية وتتقوس خطوط‬
‫الضغوط الجزيئيية والضغط الكلي إلي أسفل ‪.‬‬

‫عنها بين‬
‫‪2022/2023‬‬ ‫ينتج عنه صغر قوى التجاذب بين الجزيئيات‬ ‫‪2022/2023‬ن إضافة السائلين ‪A ,B‬إلي بعضهما‬
‫‪2022/2023‬‬ ‫وفي الحالة الثالثة فإ‬
‫جزيئيات ‪A‬وبعضها أو بين جزيئيات ‪B‬وبعضها وبذلك يزيد ضغط البخار الجزئي للسائلين وتتقوس خطوط‬
‫الضغوط الجزيئيية والضغط الكلي إلي أعلي ‪ .‬ويستفاد من ذلك في تقطير محاليل السوائل تامة اإلمتزاج ‪.‬‬

‫الحيود الموجب عن قانون راؤولت ‪:‬‬

‫نجد أن هناك بعض المحاليل غير المثالية للسوائل تاما اإلمتزاج تظهر حيودا موجبا عن قانون راؤولت حيث نجد‬
‫أن التجاذب من النوع (‪ )A-B‬يكون أقل منه بالنسبة للنوعين (‪ )B-B( / )A-A‬ويحدث زيادة في الحجم وإمتصاص‬
‫للحرارة ونتيجة لهذا النوع من التجاذب في المحاليل فأن قابلية جزيئات ‪ A‬للهرب من المحلول سوف تكون أكبر‬
‫من قابليتها في السائل النقي ‪ A‬وتكون قابلية جزيئات (‪ )B‬للهرب من المحلول أكبر من قابليتها للهرب من السائل‬
‫النقي(‪ . ) B‬وتكون الضغوط الجزيئية لكل مادة من المادتين أكبر مماهو متوقع من قانون راؤولت وبالتالي يبدي‬
‫المحلول حيودا موجبا عن قانون راؤولت ‪.‬‬

‫هناك حيود موجب بسيط عن قانون راؤولت كما هو الحال في حالة خليط من رابع كلوريد الكربون والهبتين أو‬
‫حيود موجب كبير مثل حالة خليط من الكحول اإليثيلي‬
‫‪30504101603434‬‬ ‫‪30504101603434‬الكربون والسيكلوهكسان وهناك أيضا‬
‫‪30504101603434‬‬ ‫خليط من رابع كلوريد‬
‫والكلوروفورم ‪.‬‬

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫شكل (‪ )4‬الحيود الموجب عن قانون رؤول للسوائل المثالية‬

‫الحيود السالب عن قانون راؤولت ‪:‬‬

‫يكون خليط السوائل الثنائية التي تبدي مثل هذا الحيود نجد أن جزيئات (‪ )A‬وجزيئات (‪ )B‬التجاذب بينهما يكون‬
‫أكبر من متوسط التجاذب مابين جزيئات (‪ )A‬أو جزيئات (‪ )B‬كما يحدث عند خلطهما نقص في الحجم وإنبعاث‬
‫حرارة و سوف تكون قابلية جزيئلت كل مادة سواء (‪ )A‬أو (‪ )B‬للهرب من المحلول أقل من قابليتها بالنسبة للسوائل‬
‫سوف يكون أقل مما هو متوقع من قانون راؤولت ويحدث‬
‫‪2022/2023‬‬ ‫فإن الضغط البخاري الجزيئي لكل مادة‬
‫‪2022/2023‬‬ ‫النقية وعلي ذلك‬
‫‪2022/2023‬‬
‫نقص في الحجم ‪.‬ويظهر النظام حيودا سالبا عن قانون راؤولت ‪.‬‬

‫وتبدي محاليل الماء والميثانول حيودا سالبا بسيطا عن قانون راؤولت أما خليط الكلوروفورم و األسيتون أو خليط‬
‫النيتريك والماء فإنهما يبديان حيودا سالبا كبيرا عن قانون راؤولت ‪.‬‬

‫‪30504101603434‬‬ ‫‪30504101603434‬‬ ‫‪30504101603434‬‬

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫شكل (‪ )5‬الحيود السالب عن قانون رؤول للسوائل المثالية‬

‫مثال‪ :‬إذا كان لدينا محلول يتكون من ‪ 6‬جرام جزيئي من البنزين و ‪ 4‬جرام جزيئي من الطولوين وكان ضغط‬
‫بخار المشبع للبنزين النقي هو ‪ 80‬مم زئبق وللطولوين النقي ‪ 50‬مم زئبق عند نفس درجة الحرارة ‪.‬فأحسب الضغط‬
‫البخاري الجزئي لكل من البنزين والطولوين ‪.‬‬

‫الحل ‪ :‬من قانون راؤولت‬

‫‪𝑃°𝐴 = 𝑃° 𝑏𝑒𝑛𝑧𝑒𝑛𝑒 = 80 𝑚𝑚𝐻𝑔,‬‬ ‫𝑔𝐻𝑚𝑚 ‪𝑃° 𝐵 = 𝑃° 𝑡𝑜𝑙𝑢𝑛𝑒 = 50‬‬

‫‪2022/2023‬‬ ‫𝐴𝑋 × 𝐴‪𝑃°‬‬

‫‪𝑃𝐴 =2022/2023‬‬ ‫‪2022/2023‬‬

‫𝐴𝑛‬ ‫𝐴𝑛‬ ‫‪6‬‬

‫= 𝐴𝑋‬ ‫=‬ ‫=‬ ‫‪= 0.6‬‬
‫𝑙𝑎𝑡𝑜𝑡𝑛‬ ‫𝐵𝑛 ‪𝑛𝐴 +‬‬ ‫‪6+4‬‬

‫𝑔𝐻𝑚𝑚 ‪𝑃𝐴 = 80 × 0.6 = 48‬‬

‫𝐵𝑋 × 𝐵 ‪𝑃𝐵 = 𝑃°‬‬

‫𝐵𝑛‬ ‫𝐵𝑛‬ ‫‪4‬‬

‫= 𝐵𝑋‬ ‫=‬ ‫=‬ ‫‪= 0.4‬‬
‫𝑙𝑎𝑡𝑜𝑡𝑛‬ ‫𝐵𝑛 ‪𝑛𝐴 +‬‬ ‫‪6+4‬‬

‫𝑔𝐻𝑚𝑚 ‪𝑃𝐵 = 50 × 0.4 = 20‬‬

‫الضغط البخاري الكلي = الضغط البخاري الجزئي للبنزين ‪ +‬الضغط البخاري الجزئي للطولوين‬
‫‪30504101603434‬‬ ‫زئبق‬
‫‪30504101603434‬‬ ‫‪ 68 = 20 + 48 = 30504101603434‬مم‬
‫الضغط البخاري الكلي‬

‫ثالثا ‪ :‬السوائل محدودة اإلمتزاج ‪:‬‬

‫إذا أضافت سائل مثل اإليثير إالي الماء قطرة قطرة مع التقليب فإن اإليثير يذوب في الماء إلي حد معين فإن أضفنا‬
‫المزيد من اإليثير بعد ذلك فإنه ال يذوب وتتكون طبقتين من السوائل محدودة اإلمتزاج الطبقة السفلي عبارة عن‬
‫ماء مشبع باإليثير والطبقة العليا إيثير مشبع بالماء فهما محدودي اإلمتزاج ‪.‬‬

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‫وتتوقف درجة ذوبان السوائل محدودة اإلمتزاج علي ‪:‬درجة الحرارة وتوجد منها ‪ 3‬حاالت ‪:‬‬

‫محاليل لها درجة حرارة حرجة عظمى ‪:‬‬ ‫•‬

‫مثال (خليط الفينول والماء ) حيث أنه عند أي درجة حرارة يتواجد عندنا طبقتين محدودي اإلمتزاج من الماء‬
‫المشبع بالفينول والفينول المشبع بالماء ويتغير تركيب هاتين الطبقتين بزيادة درجة الحرارة و تزداد ذوبانية كال‬
‫من الماء والفينول في بعضهما بزيادة درجة الحرارة إلي أن تصل إلي درجة حرارة معينة تعرف بالدرجة الحرجة‬
‫العظمي (‪ °65.9‬م) بعدها يصبح الفينول والماء تاما اإلمتزاج ‪.‬‬
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫‪2022/2023‬‬ ‫‪2022/2023‬‬ ‫‪2022/2023‬‬

‫شكل (‪ )5‬الفينولمعالماء‬

‫محاليل لها درجة حرارة حرجة صغري ‪:‬‬ ‫•‬

‫مثال (خليط من ثالثي اإلثيل أمين مع الماء ) حيث أن درجة ذوبان كل من السائلين تزداد إنخفاض درجة الحرارة‬
‫حيث توجد درجة حرارة حرجة صغري (‪ ° 18.5‬م ) فإذا وصل الخليط لهذه الدرجة أو أقل منها فإنهما يمتزجان‬
‫تماما ويتكون محلول تام اإلمتزاج من الماء و ثالثي اإلثيل أمين أما في درجات الحرارة المرتفعة (أكبر من ‪18.5‬‬
‫‪ °‬م ) فإنه يكون لدينا طبقتين من ماء مشبع في ثالثي اإلثيل أمين و ثالثي اإلثيل أمين مشبع بالماء ‪.‬‬

‫‪30504101603434‬‬ ‫‪30504101603434‬‬ ‫‪30504101603434‬‬

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‫شكل (‪)6‬ثالثياإلثيألمينمعالماء‬

‫محاليل لها درجة حرارة عظمي و درجة حرارة صغري ‪:‬‬ ‫•‬
‫مثال (خليط النيكوتين و الماء ) حيث أن رفع درجات الحرارة و كذلك ضغطهما يزيد من ذوبانية كال من السائلين‬
‫في األخر وعلي ذلك تكون هناك درجة حرارة حرجة عظمي (‪ ° 208‬م) بعدها يتحول الخليط إلي طبقة واحدة من‬
‫محلول تام اإلمتزاج من النيكوتين في الماء ‪ .‬وأيضا لدينا درجة درجة حرارة حرجة صغرى (‪ °60.8‬م ) تحت‬
‫هذه الدرجة يكون لدينا طبقة واحدة من محلول تام اإلمتزاج من النيكوتين في الماء ‪ .‬والمساحة المحاطة بالمنحني‬
‫تحتوي علي سوائل محدودة اإلمتزاج طبقتين من النيكوتين المشبع بالماء والماء المشبع بالنيكوتين ‪.‬‬
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫‪2022/2023‬‬ ‫‪2022/2023‬‬ ‫‪2022/2023‬‬

‫شكل (‪)7‬النيكوتينمعالماء‬

‫ثالثا ‪ :‬سوائل عديمة اإلمتزاج ‪:‬‬

‫مثل (الماء والزيت ) و (الماء والنيتروبنزين ) حيث أنه عند خلط الماء والزيت تتكون طبقتين منفصلتين ال يذوبان‬
‫في بعضهما وكل منهما ال يؤثر علي األخر لذلك فإن الضغط البخاري الكلي للخليط يساوي مجموع الضغط البخاري‬
‫المشبع للسائلين النقيين‬

‫𝐵 ‪𝑃𝑡𝑜𝑡𝑎𝑙 = 𝑝° 𝐴 + 𝑝°‬‬

‫حيث ‪:‬‬

‫‪ : P‬الضغط البخاري الكلي للخليط‬

‫𝐴 ‪ : 𝑝°‬ضغط البخار المشبع للسائل النقي (‪)A‬‬
‫‪30504101603434‬‬ ‫‪30504101603434‬‬ ‫‪30504101603434‬‬
‫𝐵 ‪ : 𝑝°‬ضغط البخار المشبع للسائل النقي (‪)B‬‬

‫وال يتأثر الضغط الكلي بنسبة كال من السائلين في الخليط و يكون الضغط البخاري الكلي للخليط أكبر من الضغط‬
‫البخاري للسائل النقي (‪ )A‬والضغط البخاري للسائل النقي (‪ )B‬كما هو موضح بالرسم (العالقة بين التركيب‬
‫والضغط البخاري )‬

‫وعند رسم العالقة بين درجة الحرارة كمحور ص والتركيب كمحور س نجد أن درجة غليان الخليط (‪ )A-B‬تكون‬
‫أقل من درجة غليان (‪ )A‬النقي ودرجة غليان (‪ )B‬النقي ‪.‬‬

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‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫شكل (‪)8‬العالقة بين التركيب والضغط البخاري‬

‫التقطير التجزيئي للسوائل عديمة اإلمتزاج ‪:‬‬

‫‪2022/2023‬‬ ‫‪2022/2023‬‬ ‫‪2022/2023‬‬

‫شكل (‪ )9‬التقطيرالتجزيئيللسوائلعديمةاإلمتزاج‬

‫بما أن نقطة الغليان هي درجة الحرارة التي يصبح عندها الضغط البخاري مساويا للضغط الخارجي (الضغط‬
‫الجوي ) ولذلك فإن خليطا من سائلين عديمي اإلمتزاج سوف يغلي عند درجة حرارة أدني من درجة غليان السائل‬
‫النقي (‪ )A‬والسائل النقي (‪ )B‬وذلك فإن الضغط البخاري الكلي للخليط قد دخل إلي قيمة مساوية للضغط الجوي‬
‫الظاهرة في فصل وتنقية المواد العضوية التي ال تمتزج‬
‫‪30504101603434‬‬
‫‪ 30504101603434‬غليان كال من السائلين وتستغل هذه‬
‫‪30504101603434‬‬
‫عند قيمة أقل من درجة‬
‫بالماء ولها درجة غليان عاليا فمثل هذه المواد لو قطرت تقطير عادي تتحلل أو تحترق فإذا خلطنا النيتروبنزين‬
‫الذي يغلي عند ‪ °210‬م مع الماء الذي يغلي عند ‪ ° 100‬م ف‘نه عند عمل تقطير تجزيئي للخليط المكون من الماء‬
‫والنيتروبنزين فإن الخليط يغلي عند درجة حرارة أقل من ‪ ° 100‬م عند نفس الضغط الجوي العادي وبمجرد أن‬
‫يتبخر أحد المكونين (الماء ) سوف ترتفع درجة الغليان مباشرة إلي تلك الخاصة بالمادة األقل تطايرا ةوهي‬
‫النيتروبنزين وبذلك يمكن فصل الماء عن النيتروبنزين حيث أنه يتم تجميع الماء الذي يتبخر أوال في دورق تجميعي‬
‫وعندما ترتفع درجة غليان الخليط إلي درجة غليان النيتروبنزين نحصل علي المكون األخر ‪.‬‬

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‫قانون التوزيع ‪:‬‬

‫الضغط البخاري للمادة)𝑨( النقية‬ ‫عدد موالت المادة𝐴‬

‫=‬
‫الضغط البخاري للمادة)𝐵( النقية‬ ‫عدد موالت المادة𝐵‬

‫𝐴‪𝑝°‬‬ ‫𝐴𝑛‬
‫‪°‬‬
‫=‬
‫𝐵𝑝‬ ‫𝐵𝑛‬

‫الوزن‬
‫عدد الموالت (‪= )n‬‬
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫الوزن الجزيئي‬

‫𝐴𝑊‬
‫= 𝐴𝑛‬
‫𝐴𝑡𝑤 ‪𝑚.‬‬
‫𝐵𝑊‬
‫= 𝐵𝑛‬
‫𝐵𝑡𝑤 ‪𝑚.‬‬

‫مثال ‪:‬عند تقطير هيدروكربون (‪ )A‬مع بخار الماء (‪ )B‬عند درجة حرارة ‪ °95‬م و ضغط خارجي مقداره ‪740‬‬
‫مم زئبق ‪ .‬وكان الضغط البخاري للماء النقي عند هذه الدرجة هي ‪ 634‬مم زئبق أحتوي التقطير علي ‪ %55‬من‬
‫وزنه هيدروكربون ‪ .‬إحسب الوزن الجزيئي للهيدروكربون ‪.‬‬

‫الحل ‪:‬‬

‫𝑔𝐻𝑚𝑚‪𝑝° 𝐴 = 634 𝑚𝑚𝐻𝑔 𝑃𝑡𝑜𝑡𝑎𝑙 = 740‬‬

‫‪2022/2023‬‬ ‫𝐵 ‪= 𝑝° 𝐴 + 𝑝°‬‬
‫‪𝑃𝑡𝑜𝑡𝑎𝑙 2022/2023‬‬ ‫‪2022/2023‬‬

‫‪740 = 𝑝° 𝐴 + 634‬‬

‫𝑔𝐻𝑚𝑚 ‪𝑝° 𝐴 = 106‬‬

‫ومن قانون التوزيع ‪:‬‬

‫𝐴 ‪𝑝°‬‬ ‫𝐴𝑛‬
‫‪°‬‬
‫=‬
‫𝐵𝑝‬ ‫𝐵𝑛‬

‫𝐴𝑊‬
‫= 𝐴𝑛‬
‫𝐴𝑡𝑤 ‪𝑚.‬‬

‫إذا فرضنا انه لدينا ‪ 100‬جرام من الخليط كوزن فإنه يكون لدينا ‪ 55‬جرام هيدروكربون و ‪ 45‬جرام من ماء‬
‫‪30504101603434‬‬ ‫‪30504101603434‬‬ ‫‪30504101603434‬‬
‫ليكون المجموع الكلي لألوزان يساوي ‪ 100‬جرام‬
‫‪55‬‬
‫= 𝐴𝑛‬
‫𝐴𝑡𝑤 ‪𝑚.‬‬

‫‪45‬‬
‫= 𝐵𝑛‬ ‫𝑒𝑙𝑜𝑚‪= 2.2‬‬
‫‪18‬‬

‫‪415‬‬
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‫𝐴 ‪𝑝°‬‬ ‫𝐴𝑛‬
‫= ‪∴ °‬‬
‫𝐵𝑝‬ ‫𝐵𝑛‬

‫‪55‬‬
‫‪106‬‬ ‫𝐴𝑡𝑤‪𝑚.‬‬
‫=‬
‫‪634‬‬ ‫‪2.2‬‬

‫‪𝑚. 𝑤𝑡𝐴 = 127‬‬

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫تقطير مخلوط سائلين تاما االمتزاج ‪:‬‬

‫في حالة عندما يكون الضغط الكلي لخليط سائلين تاما اإلمتزاج يقع بين ضغطي بخاري السائلين النقيين (الحالة‬
‫األولي ) فان العالقة بين تركيب الخليط و درجة الحرارة تكون كما بالرسم حيث يوجد خطان بيانيان أحدهما يمثل‬
‫البخار و األخر يمثل السائل ألنه عند نفس درجة الحرارة يختلف تركيب السائل عن البخار الذي ينتج منه حيث أن‬
‫البخار يحتوي علي نسبة أكبر من السائل األقل غليانا (األكثر تطايرا ) و بتكرار عمليات التقطير وجمع البخار ثم‬
‫التقطير ثانية يمكن فصل السائلين ‪A ,B‬عن بعضهما ‪.‬‬

‫‪2022/2023‬‬ ‫‪2022/2023‬‬ ‫‪2022/2023‬‬

‫شكل (‪ )10‬العالقة بين التركيب ودرجة الحرارة للسوائل تاما اإلمتزاج‬

‫مثال ذلك عملية التقطير التجزيئيي للبترول في أبراج التقطير التجزئي حيث يسخن البترول الخام وهو عبارة عن‬
‫خليط من األيدروكربونات إلي درجة الغليان فيتكون بخار به نسبة أكبر من السائل األكثر تطايرا ويتكثف هذا البخلر‬
‫في برج التقطير متحوال إلي سائل يقابل أبخرة ساخنة من أسفل فيغلي ليعطي بخار به نسبة أكبر من المركب األكثر‬
‫‪30504101603434‬األيدروكربونية الخفيفة يليها الجازولين فالكيروسين‬
‫‪30504101603434‬‬ ‫‪30504101603434‬هذه العمليات ينتج من أعلي البرج المواد‬
‫تطايرا و هكذا بتكرار‬
‫فالسوالر ويتبقي المازوت و المواد األسفلتية في أجهزة التقطير ‪.‬‬

‫المواد الصلبة في السوائل ‪:‬‬

‫بعض المواد الصلبة شحيحة الذوبان في الماء ‪Sparingly soluble‬وبعضها سريع الذوبان في الماء ‪readily‬‬
‫‪ soluble‬وتتعين درجة الذوبان في المحلول ‪ solubility‬عند درجة حرارة معينة ‪ ,‬بأن تذاب المادة في الماء‬
‫بالت حريك عند درجة الحرارة الثابتة حتي ال يذيب السائل أكثر مما به ‪ ,‬ويبقي جزء من المادة الصلبة بدون ذوبان‬

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‫‪ .‬ويكون المحلول عندئذ محلوال مشبعا ‪ saturated solution‬وبتحليل حجم معين من المحلول المشبع يمكن تعيين‬
‫درجة الذوبان ويعبر عنها بالجرام من المادة المذابة ‪ solute‬في ‪ 100‬جرام من المادة المذيبة ‪.solvent‬‬

‫وتقل درجة الذوبان بإنخفاض درجة الحرارة إذا كان المحلول المبرد مشبعا فأما أن تنفصل الزيادة من المادة المذابة‬
‫عن درجة الذوبان الجديدة ‪ ,‬أو يصبح المحلول فوق المشبع ‪ super saturated‬وهذه حالة غير ثابتة ‪.‬‬

‫فيكفي عندئذ أن يرج المحلول أو يقلب أو تسقط فيه ذرة صغيرة من المادة الصلبة فتنفصل الزيادة الذائبة في المحلول‬
‫و يتحول إلي محلول مشبع من جديد والشكل يمثل درجة الذوبان لمادة صلبة في مذيب سائل كالماء مثال ‪.‬‬

‫ويالحظ أن درجة الذوبان تزيد بارتفاع درجة الحرارة‪.‬‬

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫‪2022/2023‬‬ ‫‪2022/2023‬‬ ‫‪2022/2023‬‬

‫شكل (‪ )11‬العالقة بين درجة الحرارة ودرجة الذوبان للمواد الصلبة في السوائل‬

‫والمحلول ‪ A‬هو محلول غير مشبع وبتبريده تقل درجة الذوبان في حين أن تركيز الحلول ثابت ‪ ,‬أي أن المحلول‬
‫يقترب تدريجيا من درجة التشبع ويصبح مشبعا عند النقطة ‪B‬ودرجة الحرارة ‪t2‬‬

‫وإذا إ ستمر التبريد تحت ظروف تسمح بتكوين محلول فوق مشبع فان تركيز المحلول فوق المشبع يصبح ‪c‬عند‬
‫درجة الحرارة ‪ t1‬وإذا قلب المحلول ليعود إلي الحالة الثابتة ‪ stable state‬فإن الزيادة من المادة الصلبة تنفصل ‪,‬‬
‫ويصبح تركيز المحلول ممثال بالنقطة‪ , D‬حيث أنها درجة الذوبان عند نفس درجة الحرارة ‪ ,‬ولو حدث التبريد بعد‬
‫النقطة‪ B‬تحت ظروف تمنع تكون الحالة غير الثابتة فإن المادة الصلبة تنفصل تدريجيا ويقل تركيز المحلول ويكون‬
‫مشبعا طول الوقت ‪ .‬أي أن التركيز يتبع خط الذوبان من‪ B‬الي‪., D‬‬

‫وعلي ذلك يمكن التلخيص بأن أي نقطة علي الخط البياني تمثل محلوال مشبعا عند درجة حرارة معينة ‪ .‬و أي نقطة‬
‫أفل الخط الباني تمثل محلوال غير مشبع أما أعلي الخط الباني فتكون جميع المحاليل في حالة غير ثابتة أي تكون‬
‫‪30504101603434‬‬ ‫‪30504101603434‬‬ ‫‪30504101603434‬‬
‫فوق مشبعة ويمكنها أن تفقد بسهولة جزءا من المادة الصلبة وتصبح محاليال مشبعة ‪.‬‬

‫محاليل المواد الصلبة في السوائل ‪:‬‬

‫مثل كلوريد الصوديوم في الماء أو محلول السكر في الماء فعند إذابة كلوريد الصوديوم في الماء يتكون لدينا محلول‬
‫ويستمر الذوبان إلي حد معين ال يستطيع بعده المذيب أن يتقبل مزيدا من المذاب حيث يكون لدينا محلول مشبع و‬
‫تتوقف درجة الذوبان علي قابلية ذوبان المذاب في المذيب و درجة الحرارة ‪.‬‬

‫الخواص العامة لمحاليل صلب في سائل ‪:‬‬

‫‪417‬‬
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‫الضغط البخاري للمحلول يكون أقل من الضغط البخاري للسائل النقي عند نفس درجة الحرارة ‪.‬‬ ‫•‬
‫درجة غليان المحلول تكون أكبر من درجة غليان السائل النقي عند نفس الضغط ‪.‬‬ ‫•‬
‫درجة تجمد المحلول تكون أقل من درجة تجمد السائل النقي عند نفس الضغط ‪.‬‬ ‫•‬
‫يكتسب المحلول خاصية جديدة هي الضغط األسموزي‬ ‫•‬
‫أوال ‪ :‬اإلنخفاض في الضغط البخاري ‪:‬‬

‫عند ذوبان مادة صلبة في سائل فإن الضغط البخاري للسائل ينخفض أي أن الضغط البخاري للمحلول يكون أقل‬
‫من الضغط البخاري للسائل النقي عند نفس درجة الحرارة ‪.‬‬
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫لدينا محلول صلب في سائل ‪:‬‬

‫𝑙𝑥 𝑙 ‪𝑃𝑡𝑜𝑡𝑎𝑙 = 𝑃𝑠 + 𝑃𝑙 = 𝑃° 𝑠 𝑥𝑠 + 𝑃°‬‬

‫حيث ‪:‬‬

‫𝑙𝑎𝑡𝑜𝑡𝑃 ‪ :‬الضغط البخاري الكلي‬

‫𝑠𝑃‪ :‬الضغط الجزئي للصلب‬

‫𝑙𝑃‪ :‬الضغط الجزئي للسائل‬

‫𝑠 ‪ :𝑃°‬ضغط البخار للمادة الصلبة النقية ( الغير متطايرة )= صفر‬

‫𝑠𝑥‪ :‬الكسر الجزئي للمادة الصلبة‬

‫𝑙 ‪ :𝑃°‬ضغط البخار للمادة السائلة النقية‬

‫‪2022/2023‬‬ ‫‪2022/2023‬‬ ‫‪2022/2023‬‬
‫𝑙𝑥‪ :‬الكسر الجزئي للمادة السائلة‬

‫𝑙𝑥 𝑙 ‪∴ 𝑃𝑡𝑜𝑡𝑎𝑙 = 𝑃°‬‬

‫اإلنخفاض في ضغط بخار السائل يتناسب تناسبا طرديا مع الكسر الجزيئي للمذاب وقد وجد أنه بالنسبة للمحاليل‬
‫المخففة للمواد الغير إلكتروليتية ( محلول مثالي ) فإن اإلنخفاض في الضغط البخاري لسائل ال يعتمد علي نوعية‬
‫المذاب لكنه يعتمد علي الكسر الجزيئي وهذا يعني أنه لو أذبنا نفس العدد من الجرامات الجزيئية من مواد غير‬
‫إلكتروليتية مختلفة مثل ( كلوريد الصوديوم وكلوريد البوتاسيوم ) في كميات متساوية من سائل ما فإن الضغط‬
‫البخاري للسائل ينخفض بنفس القدر في كل الحاالت ‪.‬‬

‫ثانيا ‪ :‬اإلرتفاع في درجة الحرارة ‪:‬‬

‫بما أن درجة غليان السائل هي درجة الحرارة التي يكون عندها الضغط البخاري للمحلول مساويا للضغط الجوي‬
‫النقي (المذيب ) وذلك ألن الضغط البخاري للمحلول‬
‫‪30504101603434‬‬ ‫المحلول تكون أعلي من درجة غليان السائل‬
‫‪30504101603434‬‬ ‫فإن درجة غليان‬
‫‪30504101603434‬‬
‫يكون أقل من الضغط البخاري للسائل النقي ‪ .‬وعلي ذلك فإن اإلرتفاع في درجة الغليان يعتمد علي الكسر الجزيئي‬
‫للمذاب و ال يعتمد علي نوعية المذاب أي أنه إذا أذبنا نفس العدد من الجرامات الجزيئية من مواد غير إلكتروليتية‬
‫مختلفة في كميات متساوية من سائل فإن درجة الغليان ترتفع بنفس القدر ‪.‬‬

‫يعرف اإلرتفاع الجزئي في درجة الغليان بأنه اإلرتفاع في درجة الغليان الذي ينتج عند ذوبان واحد جرام جزيئي‬
‫من مادة غير إلكتروليتية (مذاب ) في ‪ 1000‬جرام من المذيب ويرمز له بالرمز (‪)KB‬‬

‫𝐵𝐾‪ :‬اإلرتفاع الجزئي في درجة الغليان‬

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‫𝐵𝑇 ∆ ‪:‬اإلرتفاع في درجة الغليان (‪ 1‬جرام جزيئي من المذاب في ‪ 1000‬جرام من المذيب )‬

‫𝑠𝑛 𝐵𝐾 = 𝐵𝑇 ∆‬

‫𝑠𝑊‬
‫= 𝑠𝑛‬
‫𝑠𝑡𝑤 ‪𝑚.‬‬

‫إذا أذبنا (‪ )n‬جرام جزيئي من المادة الصلبة في (‪ )WL‬جرام من المذيب فإن المعادلة تصبح‬
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫𝑠𝑊‬ ‫‪1000‬‬
‫× 𝐵𝐾 = 𝑠𝑛 𝐵𝐾 = 𝐵𝑇 ∆‬ ‫×‬
‫𝑠𝑡𝑤 ‪𝑚.‬‬ ‫𝑙𝑊‬

‫حيث ‪:‬‬

‫𝐵𝑇 ∆ ‪ :‬اإلرتفاع في درجة الغليان‬

‫𝐵𝐾‪ :‬اإلرتفاع الجزئي في درجة الغليان‬

‫𝑠𝑊‪ :‬وزن المذاب الصلب‬

‫𝑠𝑡𝑤 ‪ :𝑚.‬الوزن الجزيئي للمادة الصلبة‬

‫𝑙𝑊‪ :‬وزن المذيب‬

‫ومن المعادلة يتضح لنا أنه يمكن تعيين الوزن الجزيئي لمادة غير إلكتروليتية صلبة و ذلك بقياس اإلرتفاع في‬
‫درجة الغليان ‪.‬‬
‫‪2022/2023‬‬ ‫‪2022/2023‬‬ ‫‪2022/2023‬‬
‫ثالثا‪ :‬اإلنخفاض في درجة التجمد ‪:‬‬

‫من المعروف أن درجة التجمد هي ‪ :‬درجة الحرارة التي يتساوي عندها الضغط البخاري للمادة في الحالة السائلة‬
‫مع الضغط البخاري للمادة في الحالة الصلبة ‪.‬‬

‫عند إذابة مادة لبة في سائل لتكوين محلول من الصلب في السائل فإن درجة تجمد المحلول تكون أقل من درجة‬
‫تجمد السائل النقي عند نفس الضغط ‪.‬‬

‫وقد وجد أن (‪ )Kf‬اإلنخفاض الجزئي في درجة التجمد وهو مقدار األنخفاض في درجة التجمد الناتج عن إذابة‬
‫واحد جرام جزيئي من مادة غير إلكتروليتية (مذاب صلب ) في ‪ 1000‬جرام من المذيب ‪.‬‬

‫𝑠𝑊‬ ‫‪1000‬‬
‫× 𝑓𝐾 = 𝑠𝑛 𝑓𝐾 = 𝑓𝑇 ∆‬ ‫×‬
‫𝑠𝑡𝑤 ‪𝑚.‬‬ ‫𝑙𝑊‬
‫‪30504101603434‬‬ ‫‪30504101603434‬‬ ‫‪30504101603434‬‬
‫حيث ‪:‬‬

‫𝑓𝑇 ∆ اإلنخفاض في درجة التجمد‬

‫𝑓𝐾 ااإلنخفاض الجزئي في درجة التجمد‬

‫𝑠𝑊 وزن المذاب الصلب‬

‫𝑠𝑡𝑤 ‪ 𝑚.‬الوزن الجزيئي للمادة الصلبة‬

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‫𝑙𝑊 وزن المذيب‬

‫ومن المعادلة يتضح لنا أنه يمكن تعيين الوزن الجزيئي لمادة غير إلكتروليتية صلبة و ذلك بقياس اإلنخفاض في‬
‫درجة التجمد ‪.‬‬

‫مثال ‪:‬‬

‫إحسب كال من درجة الغليان ودرجة التجمد لمحلول يحتوي علي ‪ 2.85‬جرام من السكر مذابة في ‪ 25‬جرام من‬
‫الماء علما بأن اإلرتفاع الجزئي للماء هو ‪ ° 0.513‬م واإلنخفاض الجزئي له هو ‪ ° 1.86‬م والوزن الجزيئي‬
‫للسكر هو ‪. 342‬‬
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫الحل ‪:‬‬

‫𝑔 ‪𝐾𝑓 = 1.86℃𝐾𝐵 = 0.513℃ 𝑊𝑠 = 2.85 𝑔𝑚. 𝑤𝑡𝑠 = 342 𝑊𝑙 = 25‬‬

‫𝑠𝑊‬ ‫‪1000‬‬
‫× 𝐵𝐾 = 𝑠𝑛 𝐵𝐾 = 𝐵𝑇 ∆‬ ‫×‬
‫𝑠𝑡𝑤 ‪𝑚.‬‬ ‫𝑙𝑊‬

‫‪2.85‬‬ ‫‪1000‬‬
‫× ‪∆ 𝑇𝐵 = 0.513‬‬ ‫×‬
‫‪342‬‬ ‫‪25‬‬

‫℃‪∆ 𝑇𝐵 = 0.171‬‬

‫الغليان‬
‫‪2022/2023‬‬ ‫النقي المذيب ( الماء ) ‪ +‬اإلرتفاع في درجة‬ ‫‪2022/2023‬غليان المحلول = درجة غليان السائل‬
‫‪2022/2023‬‬ ‫ويكون بذلك درجة‬

‫درجة غليان المحلول = ‪ ° 100.171 = 0.171 + 100‬م‬

‫𝑠𝑊‬ ‫‪1000‬‬
‫× 𝑓𝐾 = 𝑠𝑛 𝑓𝐾 = 𝑓𝑇 ∆‬ ‫×‬
‫𝑠𝑡𝑤 ‪𝑚.‬‬ ‫𝑙𝑊‬

‫‪2.85‬‬ ‫‪1000‬‬
‫× ‪∆ 𝑇𝑓 = 𝐾𝑓 𝑛𝑠 = 1.86‬‬ ‫×‬
‫‪342‬‬ ‫‪25‬‬

‫℃‪∆ 𝑇𝑓 = 0.620‬‬

‫ويكون بذلك درجة تجمد المحلول = درجة تجمد السائل النقي المذيب ( الماء ) ‪ -‬اإلنخفاض في درجة التجمد‬

‫درجة تجمد المحلول = ‪ ° 0.620- = 0.620 - 0‬م‬

‫مثال ‪ :‬محلول يتكون من ‪ 0.3005‬جرام من اليوريا مذابة في ‪ 20‬جرام ماء درجة تجمده تساوي (‪ °0.465-‬م)‬
‫‪30504101603434‬‬ ‫‪30504101603434‬‬ ‫‪30504101603434‬‬
‫إحسب الوزن الجزيئي لليوريا علما بأن اإلنخفاض الجزئي للماء في درجة التجمد هو ‪ ° 1.86‬م و أن درجة تجمد‬
‫الماء هي صفر ‪ °‬م ‪.‬‬

‫الحل ‪:‬‬

‫𝑔 ‪𝐾𝑓 = 1.86℃𝑊𝑠 = 0.3005 𝑔 𝑚. 𝑤𝑡𝑠 =? 𝑊𝑙 = 20‬‬

‫درجة تجمد المحلول = درجة تجمد السائل النقي المذيب ( الماء ) ‪ -‬اإلنخفاض في درجة التجمد‬

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‫‪ - 0 = 0.465-‬اإلنخفاض في درجة التجمد‬

‫اإلنخفاض في درجة التجمد = ‪ ° 0.465‬م‬

‫𝑠𝑊‬ ‫‪1000‬‬
‫× 𝑓𝐾 = 𝑠𝑛 𝑓𝐾 = 𝑓𝑇 ∆‬ ‫×‬
‫𝑠𝑡𝑤 ‪𝑚.‬‬ ‫𝑙𝑊‬

‫‪0.3005‬‬ ‫‪1000‬‬
‫× ‪0.465 = 𝐾𝑓 𝑛𝑠 = 1.86‬‬ ‫×‬
‫𝑠𝑡𝑤 ‪𝑚.‬‬ ‫‪20‬‬

‫‪𝑚. 𝑤𝑡𝑠 = 60.1‬‬

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫رابعا ‪:‬الضغط األسموزي ‪:‬‬

‫هناك تشابه بين سلوك الغازات والمحاليل من حيث قدرتها علي اإلنتشار فإذا وضعنا بلورة من برمنجنات البوتاسيوم‬
‫في قاع إناء و أضفنا إليه كمية من الماء بحرص نجد أنه بعد فترة أن المحلول يتلون باللون البنفسجي ويصبح‬
‫متجانس ويرجع ذلك إلي إنتشار المادة المذابة و اإلنتشار هنا يشابه أنتشار الغازات حيث يحدث نتيجة إلنتشار‬
‫جزيئات المذاب أو جزيئات المذيب أو كالهما فجزيئات المذاب تنتقل من الجزء األكثر تركيزا إلي الجزء األقل‬
‫تركيزا وجزيئات المذيب تنتقل من الجزء األكثر تركيزا إلي الجزء اإلقل تركيزا ‪.‬‬

‫وكما أن للغازات ضغط فإن المحاليل لها ضغط من نوع آخر يعرف بالضغط األسموزي ويمكن توضيحه‬
‫بالتجربة األتية ‪:‬‬

‫يتكون الجهاز اوآل كما بالشكل من إسطوانة مصنوعة من مادة مسامية نتصلة بأنبوبة زجاجية رفيعة و طويلة‬
‫(أنبوبة شعرية ) ‪.‬تبلل هذه اإلسطوانة من الخارج بمحلول كبريتات النحاس ثم تبلل بمحلول حديدوسيانيد البوتاسيوم‬
‫فيترسب في مسامها حديدوسيانيد النحاس وتصبح اإلسطوانة بمثابة غشاء شبه منفذ ‪ .‬تمأل اإلسطوانة بمحلول مثل‬
‫السكرثم تغمر في إناء به ماء وبعد فترة من الزمن نالحظ إرتفاع مستوى المحلول في األنبوبة الشعرية ويرجع ذلك‬
‫‪2022/2023‬‬ ‫‪2022/2023‬‬ ‫‪2022/2023‬‬
‫إلي إنتشار جزيئات الماء خالل الغشاء شبه المنفذ ويترتب علي ذلك إرتفاع المحلول في األنبوبة الشعرية ‪.‬نتيجة‬
‫ألن الضغط الواقع علي جدار اإلسطوانة الداخلي أكبر من الضغط الواقع علي جدار اإلسطوانة الخارجي هذا‬
‫الضغط الناشئ يتساوي عندما يتوقف إرتفاع السائل في األنبوبة الشعرية ‪.‬‬

‫‪30504101603434‬‬ ‫‪30504101603434‬‬ ‫‪30504101603434‬‬

‫شكل (‪ )12‬تجربة الضغط األسموزي‬

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‫تعريف الضغط األسموزي ‪ :‬أنه القوة المسببة لإلنتشار الغشائي وهي تساوي الفرق بين مستوي المحلول في األنبوبة‬
‫ومستوي الماء خارجها ‪.‬‬

‫القانون الذي يحدد الضغط األسموزي ‪:‬‬

‫لقد وجد فانت هوف أن الضغط األسموزي لمحلول مادة غير إلكتروليتية مخففة يتناسب تناسبا طرديا مع التركيز‬
‫الجزئي للمحلول وكذلك مع درجة الحرارة المطلقة ‪.‬‬

‫𝐶∝𝑃‬
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫𝑇∝𝑃‬

‫𝑇𝐶 ∝ 𝑃 ∴‬

‫𝑇𝐶𝑅 = 𝑃 ∴‬
‫𝑛‬
‫=𝐶‬
‫𝑣‬
‫𝑛‬
‫𝑇 𝑅=𝑃∴‬
‫𝑣‬
‫𝑇𝑛𝑅 = 𝑣𝑃 ∴‬

‫حيث ‪:‬‬

‫𝑃‪ :‬الضغط األسموزي‬

‫‪2022/2023‬‬ ‫‪2022/2023‬‬ ‫‪2022/2023‬‬
‫𝐶‪ :‬التركيز الجزئي للمحلول‬

‫𝑇‪ :‬درجة الحرارة المطلقة ( بالكلفن )‬

‫𝑅‪ :‬الثابت العام للغازات وقيمته تساوي ‪ 0.082‬لتر‪ .‬ض‪.‬ج ‪ /‬مول ‪.‬كلفن‬

‫𝑛‪:‬عدد الموالت‬

‫𝑣‪:‬الحجم‬

‫وعلي ذلك يمكن القول أن قانون آفوجادرو للغازت بنطبق علي المحاليل المخففة فإذا أذيب واحد جرام جزيئي من‬
‫مادة غير الكتروليتية في ‪ 22.4‬لتر من مذيب في الضغط األسموزي من المحلول الناتج يساوي واحد جو عند درجة‬
‫الصفر المئوي ‪.‬‬

‫‪30504101603434‬‬ ‫‪30504101603434‬‬
‫‪30504101603434‬في المواد الصلبة ‪:‬‬
‫محاليل المواد الصلبة‬

‫يوجد نوعان من محاليل المواد الصلبة في المواد الصلبة ‪ ,‬النوع األول ينتج عند التبلور من المحاليل المائية بالنسبة‬
‫لألمالح المتشابهة في تركيبها الكيميائي مثل أمالح الشبة حيث تعطي من محلولها المشترك بلورات مختلطة‬
‫متجانسة والنوع الثاني ينتج عن التابلور من المصهور كما في حالة السبائك ‪.‬‬

‫وقد وجد أن أفضل طريقة لدراسة هذه األنظمة هو عم طريق عمل منجنيات أطوار المادة في حالة االتزان والتي‬
‫تمثل العالقة بين تركيب السبيكة ودرجة الحرارة و ما يحدث نتيجة عمليات التسخين والتبريد من تغير في حاالت‬
‫أو أطوار السبيكة المختلفة وتنتج هذه المنحنيات من دراسة منحنيات التبريد (العالقة بين الزمن و درجة الحرارة )‬

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‫لسبائك ذات تركيب ثابت عند تبريدها من حالة المصهور إلي الحالة الصلبة ومنحنيات اإلتزان أو منحنيات األطوار‬
‫تعتبر في الواقع تعبير بالرسم عن قاعدة تسمي قاعدة الطور أو قاعدة وجوه المادة والتي تنص علي ‪:‬‬

‫‪𝐹 =𝐶−𝑃+2‬‬

‫حيث ‪:‬‬

‫‪ F :‬عدد درجات التغير التي يجب تثبيتها حتي نحدد حالة اإلتزان مثل الضغط‪ ,‬التركيز والحرارة ‪.‬‬

‫‪ :C‬عدد مكونات النظام (إثنين في حالة السبائك الثنائية )‬

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫‪ :P‬عدد األطوار أو األوجه وهو الجزء المتجانس من المادة‬

‫وعندما تجرى التجارب االزمة لرسم هذه المنحنيات تحت الضغط الجوي العادي فان الضغط يكون ثابتا وهو أحد‬
‫المتغيرات وتصبح القاعدة في هذه الحالة ‪:‬‬

‫‪𝐹 =𝐶−𝑃+1‬‬

‫وكتطبيق لهذه القاعدة في األنظمة الثنائية (‪ )C=2‬نجد أن ‪:‬‬

‫‪𝑃=1‬‬ ‫‪∴ 𝐹 = 2−1+1 = 2‬‬

‫‪𝑃=2‬‬ ‫‪∴ 𝐹 = 2−2+1 = 1‬‬

‫‪𝑃=3‬‬ ‫‪∴ 𝐹 = 2−3+1 = 0‬‬

‫‪2022/2023‬‬
‫األطوار ‪:‬‬ ‫‪2022/2023‬أنه يوجد أنواع أساسية من منحنيات‬
‫‪2022/2023‬‬
‫وقد بينت التجارب‬

‫النوع األول ‪ :‬يمتزج المكونان تماما في حالة المصهور ويكونان عديما االمتزاج في الحالة الصلبة ‪.‬‬ ‫•‬
‫النوع الثاني ‪ :‬حيث يمتزج المكونان امتزاجا تاما في حالتي الصلب والمصهور ويكونان مايعرف‬ ‫•‬
‫بالمحلول الصلب ‪.Solid Solution‬‬
‫النوع الثالث ‪ :‬حيث يتفاعل المكونان لتكوين مركب كيميائي ‪.‬‬ ‫•‬
‫النوع الرابع ‪ :‬حيث ال يوجد إمتزاج بين المكونين في حالتي الصلب ‪ ,‬و المصهور ونادرا ما يوجد هذا‬ ‫•‬
‫النوع من السبائك المعدنية ‪.‬‬
‫أوال ‪ :‬المكونان تاما اإلمتزاج في حالة المصهور وعديما االمتزاج في الحالة الصلبة ‪:‬‬

‫‪30504101603434‬‬ ‫‪30504101603434‬‬ ‫‪30504101603434‬‬

‫‪423‬‬
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‫شكل (‪ )13‬منحني األطوار والتبريد للمواد الصلبة في حالة تمام اإلمتزاج في الحالة السائلة وعديما اإلمتزاج‬
‫في الحالة الصلبة‬

‫مثال لهذا النوع نظام الخارصين والكادميوم ‪.‬‬

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫شكل (‪ )14‬منحني األطوار‬

‫‪2022/2023‬ليعطي مادة صلبة‪ A‬النقي ويتغير تركيب المصهور‬

‫‪2022/2023‬‬
‫‪x 2022/2023‬من الحالة ‪ M‬يبدأ في التبلور عند ‪g‬‬
‫بتبريد مصهور مثل‬
‫في اتجاه‪ E‬حيث يتجمد المصهور ‪.‬‬

‫تطبيق قاعدة الطور ‪:‬‬

‫عند ‪ M :‬يوجد المكونان ‪A ,B‬أي أن ‪C=2‬‬

‫ويوجد طور واحد وهو حالة المصهور ألنه يوجد امتزاج تام في حالة المصهور ‪P=1‬‬

‫‪∴𝐹 =𝐶−𝑃+1‬‬

‫‪∴𝐹 =2−1+1=2‬‬

‫أي أنه يوجد درجتان للتغير وهما التركيب ودرجة الحرارة حيث يمكن تغير كال منهما مع اإلحتفاظ بحالة‬
‫المصهور ‪.‬‬
‫‪30504101603434‬‬ ‫‪30504101603434‬‬ ‫‪30504101603434‬‬
‫‪C=2‬‬ ‫عند ‪ N :‬المكونات ثابتة في كل الحاالت‬

‫ويوجد طورانفي حالة اتزان وهما المصهور وصلب‪ A‬النقي‪P=2‬‬

‫‪∴𝐹 =𝐶−𝑃+1‬‬

‫‪∴𝐹 =2−2+1=1‬‬

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‫أي أنه يوجد درجة واحدة للتغير وهي درجة الحرارة التي بتغيرها (خالل عملية التبريد) يتحدد تركيب المصهور‬
‫علي الخط‪ gE‬حتي تظل حالتي المصهور وصلب‪ A‬في حالة إتزان ‪.‬‬

‫عند ‪E :‬‬

‫يبدأ إنفصال صلب ‪ B‬النقي بالضافة الي الصلب‪ A‬وبالتاي يوجد ‪ 3‬أطوار وهي صلب‪ A‬وصلب‪ ( B‬عديما‬
‫اإلمتزاج) و المصهور ‪.‬‬

‫‪∴𝐹 =𝐶−𝑃+1‬‬
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫‪∴𝐹 =2−3+1=0‬‬

‫أي أنه يوجد صفرا من درجات التغير وبالتالي تثبت درجة الحرارة حتي ينتهي تجمد السبيكة وهو ما يظهر كخط‬
‫أفقي في منحني التبريد ‪.‬‬

‫النقطة ‪ F‬تمثل درجة حرارة ثابتة وتركيبا ثابتا وتسمي نقطة ‪ eutectic‬وتمثل أقل درجة انصهار في هذا النظام‬
‫وعندها فإن سرعة التبريد تساوي صفرا حيث يتجمد ما تبقي من المصهور ‪.‬‬

‫نالحظ أن التركيب ‪E‬اليمثل مركبا كيميائيا وإن كان يمثل تركيب ثابت ودرجة انصهار ثابتة ألنه يظهر تحت‬
‫الميكرسكوب غير متجانس (بلورات ‪ A,B‬عديما اإلمتزاج في الحالة الصلبة )‬

‫للتركيب ‪ X‬عند النقطة‪ N‬يوجد طوران ‪:‬‬

‫مصهور تركيبه ‪ O‬وصلب‪ A‬النقي ‪ .‬وتكون النسبة بينهما كالنسبة العكسية ‪:‬‬

‫𝑑𝑖𝑢𝑞𝑖𝐿‬ ‫𝐹𝑁 𝑂‬
‫= =‬
‫𝑑𝑖𝑙𝑜𝑆‬ ‫𝑂𝑁 𝐴‬
‫‪2022/2023‬‬ ‫‪2022/2023‬‬ ‫‪2022/2023‬‬

‫ثانيا ‪ :‬المكونان تاما اإلمتزاج في حالتي الصلب و المصهور‪:‬‬

‫‪30504101603434‬‬ ‫‪30504101603434‬‬ ‫‪30504101603434‬‬

‫شكل (‪ )15‬منحني األطوار والتبريد للمواد الصلبة في حالة تمام اإلمتزاج في الحالة السائلة و الحالة الصلبة‬

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‫مثال لهذا النوع نظام النحاس والنيكل ‪.‬‬

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫شكل (‪ )16‬منحني األطوار‬

‫خط الصلب يمثل تغير درجة اإلنصهار مع التركيب ‪ ,‬وخط المصهور يمثل تغير تركيب المصهور الموجود في‬
‫حالة إتزان مع الصلب ‪.‬‬

‫بتبريد مصهور‪ X‬من حالة المصهور يعطي عند النقطة‪ N‬بلورات تركيبها‪ M‬يقع علي خط الصلب و يتغير تركيب‬
‫‪2022/2023‬‬ ‫‪2022/2023‬‬ ‫‪2022/2023‬‬
‫المصهور في اإلتجاه من‪ N‬الي‪ Z‬بينما يتغير تركيب البلورات المنفصلة في اإلتجاه من‪M‬إلي‪. D‬‬

‫عند النقطة‪ N‬يبدأ إنفصال المحلول الصلب من المصهور و ينتهي التجمد عند النقطة‪ O‬وبينهما تقل سرعة التبريد‬
‫حتي ينتهي التجمد ثم تعود إلي سرعتها األولي ‪.‬‬

‫بتطبيق قاعدة الطور ‪:‬‬

‫عند النقطة ‪N :‬‬

‫يوجد مكونان ‪C=2‬وطور واحد هو المصهور ( إمتزاج كامل في حالة المصهور ) ‪P=1‬‬

‫‪∴𝐹 =𝐶−𝑃+1‬‬

‫‪∴𝐹 =2−1+1=2‬‬
‫‪30504101603434‬‬ ‫‪30504101603434‬‬ ‫‪30504101603434‬‬

‫أي أنه يوجد درجتان للتغير وهما التركيب و درجة الحرارة ‪.‬‬

‫عند النقطة ‪D :‬‬

‫يوجد مكونان ‪C=2‬‬

‫وطور واحد هو الحالة الصلبة (إمتزاج كامل في الحالة الصلبة ) ‪P=1‬‬

‫‪426‬‬
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‫‪∴𝐹 =𝐶−𝑃+1‬‬

‫‪∴𝐹 =2−1+1=2‬‬

‫ولكن عند أي نقطة داخل الشكل بين خطي الصلب والمصهور مثال النقطة يوجد مكونان ‪C=2‬‬

‫ويوجد طوران مصهور يقع تركيبه علي خط المصهور مثل ومحلول صلب يقع تركيبه علي خط الصلب مثل‬

‫‪∴𝐹 =𝐶−𝑃+1‬‬

‫‪∴𝐹 =2−2+1=1‬‬
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫أي أنه يوجد متغير واحد هو درجة الحرارة عند تغيرها يتحدد تركيب كال من المصهور والصلب علي خطي‬
‫المصهور والصلب علي الترتيب المقابلين لدرجة حرارة معينة وذلك حتي يظل الصلب والمصهور موجودان في‬
‫حالة إتزان ‪.‬‬

‫وتكون نسبة المصهور إلي المحلول الصلب عند النقطة ‪ O‬كالنسبة العكسية ‪.‬‬
‫𝑑𝑖𝑢𝑞𝑖𝐿‬ ‫𝑌𝑂‬
‫=‬
‫𝑑𝑖𝑙𝑜𝑆‬ ‫𝑍𝑂‬

‫ثالثا ‪ :‬المكونان يتفاعالن لتكوين مركب كيميائي ‪:‬‬

‫‪2022/2023‬‬ ‫‪2022/2023‬‬ ‫‪2022/2023‬‬

‫‪30504101603434‬‬ ‫‪30504101603434‬‬ ‫‪30504101603434‬‬

‫شكل (‪ )17‬منحني األطوار‬

‫مثال لذلك نظام الماغنسيوم والخارصين ونالحظ في هذا النظام أن المركب يقسم النظامين الي نظامين قد يكونا من‬
‫أيا من األنواع السابقة وفي هذة الحالة يوجد نقطتان ‪. eutectic‬‬

‫باإلضافة إلي الثالث حاالت السابقة يوجد أنظمة أخري كما يوجد أنواع عديدة من النظام الثالث أهمها عندما يوجد‬
‫إمتزاج جزئي في الحالة الصلبة وهذه سوف يقابلها الطالب فيما بعد في دراسة علم الفلزات ‪.‬‬

‫‪427‬‬
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‫أمثلة محلولة ‪:‬‬

‫مثال (‪: )1‬‬

‫فلزان أ درجة إنصهاره ‪ ° 710‬م ‪ ,‬ب درجة إنصهاره ‪ ° 820‬م ‪ ,‬يمتزجان تماما في حالة المصهور وعديما‬
‫اإلمتزاج في الحالة الصلبة ‪ ,‬يكونان خليط ‪eutectic‬عند درجة حرارة ‪ ° 630‬م يحتوي علي ‪ %65‬أ ‪ .‬المطلوب‬
‫‪:‬‬

‫ارسم منحني األطوار في حالة االتزان لهذا النظام ‪.‬‬

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫أوجد األتي لسبيكة تحتوي علي ‪ %70‬أ ‪:‬‬

‫درجة بداية التجمد ودرجة نهاية التجمد ‪.‬‬ ‫•‬

‫رسم منحني التبريد لهذه السبيكة ‪.‬‬ ‫•‬
‫ايجاد التركيب الكيميائي ونسب األطوار عند درجة حرارة ‪ ° 575‬م ‪.‬‬ ‫•‬
‫تطبيق قاعدة الطور عند درجة حرارة ‪ ° 675‬م ‪.‬‬ ‫•‬

‫‪2022/2023‬‬ ‫‪2022/2023‬‬ ‫‪2022/2023‬‬

‫الحل ‪:‬‬

‫درجة بداية التجمد = ‪ ° 735‬م‬

‫‪30504101603434‬‬ ‫‪30504101603434‬‬
‫‪ ° 63030504101603434‬م‬
‫درجة نهاية التجمد =‬

‫من الرسم ‪ :‬السبيكة ‪ %70‬ب عند درجة حرارة ‪ ° 675‬م (تمثله النقطة ‪ )c‬يوجد طوران ‪:‬‬

‫مصهور تمثله النقطة‪ D‬يحتوي علي ‪ %50‬ب وصلب ب النقي تمثله النقطة‪ F‬والنسبة بينهما كالنسبة العكسية‬

‫نسبة المصهور 𝐷‬ ‫‪𝐶𝐹 3‬‬

‫=‬ ‫=‬
‫صلب ب النقي‬ ‫‪𝐷𝐶 2‬‬

‫‪428‬‬
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‫بتطبيق قاعدة أطوار المادة عند ‪ ° 675‬م ‪:‬‬

‫‪C=2‬‬ ‫‪,‬‬ ‫‪P=2‬‬

‫‪∴𝐹 =𝐶−𝑃+1‬‬

‫‪∴𝐹 =2−2+1=1‬‬

‫مثال (‪: )2‬‬

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫‪ ° 1‬م ‪ ,‬تاما اإلمتزاج في حالتي الصلب و المصهور‬

‫معدنان أ درجة إنصهاره ‪ ° 850‬م ‪ ,‬ب درجة إنصهاره ‪250‬‬
‫‪ ,‬وتبدأ السبيكة المحتوية علي ‪ %95‬أ في التجمد عند درجة حرارة ‪ ° 900‬م وتنفصل منها مادة صلبة تحتوي علي‬
‫‪" %26‬ب" في حين تبدأ السبيكة المحتوية علي ‪ %45‬أ في التجمد عند درجة حرارة ‪ °1215‬م وتنفصل منها مادة‬
‫صلبة تحتوي علي ‪" %97‬ب"‪ .‬المطلوب ‪:‬‬

‫إرسم منحني األطوار في حالة اإلتزان لهذا النظام ‪.‬‬ ‫•‬

‫أوجد األتي لسبيكة تحتوي علي ‪ %55‬أ ‪:‬‬ ‫•‬
‫درجة بداية التجمد ودرجة نهاية التجمد ‪.‬‬ ‫•‬
‫رسم منحني التبريد لهذه السبيكة ‪.‬‬ ‫•‬
‫إيجاد التركيب الكيميائي ونسب األطوار وتطبيق قاعدة األطوار علي هذه السبيكة عند درجة حرارة ‪ °1100‬م‬ ‫•‬
‫‪.‬‬

‫‪2022/2023‬‬ ‫‪2022/2023‬‬ ‫‪2022/2023‬‬

‫‪30504101603434‬‬ ‫‪30504101603434‬‬ ‫‪30504101603434‬‬

‫الحل ‪:‬‬

‫درجة بداية التجمد = ‪ °1150‬م‬

‫درجة نهاية التجمد = ‪ °980‬م‬

‫‪429‬‬
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‫من الرسم ‪ :‬السبيكة ‪ %55‬أ (‪ %45‬ب ) عند درجة حرارة ‪ °1100‬م (تمثله النقطة‪ ) c‬يوجد طوران ‪:‬‬

‫محلول صلب يقع علي خط الصلب تمثله النقطة‪ F‬ويحتوي علي ‪%30‬أ ‪ ,‬مصهور يقع علي خط المصهور و تمثله‬
‫النقطة ‪ D‬ويحتوي علي ‪%37‬ب ‪ .‬والنسبة بينهما كالنسبة العكسية‬

‫نسبة الصلب ‪F‬‬ ‫‪𝐷𝐶 63 − 55‬‬

‫=‬ ‫=‬
‫المصهور𝐷‬ ‫‪𝐶𝐹 55 − 30‬‬

‫بتطبيق قاعدة أطوار المادة عند ‪ °1100‬م ‪:‬‬

‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫يوجد طوران صلب‪ , F‬ومصهور‪ ,D‬يوجد مكونان ايضا ‪:‬‬

‫‪C=2‬‬ ‫‪,‬‬ ‫‪P=2‬‬

‫‪∴𝐹 =𝐶−𝑃+1‬‬

‫‪∴𝐹 =2−2+1=1‬‬

‫مثال (‪: )3‬‬

‫فلزان أ درجة إنصهاره ‪ ° 1400‬م ‪ ,‬ب درجة إنصهاره ‪ ° 1800‬م ‪ ,‬يتفاعالن لتكوين مركب كيميائي أ‪2‬ب‪ 3‬يحتوي‬
‫علي ‪ %50‬أ عند درجة حرارة ‪ ° 1600‬م ‪ ,‬الفلز أ والمركب أ‪2‬ب‪ 3‬تاما اإلمتزاج في حالة المصهور وعديما‬
‫اإلمتزاج في الحالة الصلبة ‪ ,‬يكونان خليط ‪eutectic‬عند درجة حرارة ‪ ° 1100‬م يحتوي علي ‪ %15‬ب ‪ .‬كما أن‬
‫الفلز ب والمركب أ‪2‬ب‪3‬تاما اإلمتزاج أيضا في حالة المصهور وعديما اإلمتزاج في الحالة الصلبة ‪ ,‬يكونان خليط‬
‫‪eutectic‬عند درجة حرارة ‪ ° 700‬م يحتوي علي ‪ %20‬أ ‪ .‬المطلوب ‪:‬‬

‫‪2022/2023‬‬ ‫‪.2022/2023‬‬
‫منحني األطوار في حالة االتزان لهذا النظام‬ ‫إرسم‬
‫‪2022/2023‬‬ ‫•‬
‫أوجد األتي لسبيكة تحتوي علي ‪ %50‬ب ‪:‬‬ ‫•‬
‫درجة بداية التجمد ودرجة نهاية التجمد ‪.‬‬ ‫•‬
‫رسم منحني التبريد لهذه السبيكة ‪.‬‬ ‫•‬
‫إيجاد نسب األوجه الموجودة عند درجة حرارة ‪ °600‬م ‪.‬‬ ‫•‬
‫الحل ‪:‬‬

‫‪30504101603434‬‬ ‫‪30504101603434‬‬ ‫‪30504101603434‬‬

‫‪430‬‬
 ‫‪UG_31186536@f-eng.tanta.edu.eg‬‬ ‫‪UG_31186536@f-eng.tanta.edu.eg‬‬ ‫‪UG_31186536@f-eng.tanta.edu.eg‬‬
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

‫‪2022/2023‬‬ ‫‪2022/2023‬‬ ‫‪2022/2023‬‬

‫درجة بداية التجمد = ‪ ° 1600‬م‬

‫درجة نهاية التجمد = ‪ ° 1600‬م‬

‫عند درجة حرارة ‪° 600‬م يوجد وجه واحد وهو المركب أ‪2‬ب‪ 3‬الصلب ونسبته ‪%100‬‬

‫‪C=1‬‬ ‫‪,‬‬ ‫‪P=1‬‬

‫‪∴𝐹 =𝐶−𝑃+1‬‬

‫‪∴𝐹 =1−1+1=1‬‬

‫‪30504101603434‬‬ ‫‪30504101603434‬‬ ‫‪30504101603434‬‬

‫‪431‬‬
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References
1-Bastawissi, A. E., "Engineering Chemistry," El-Turky Press, Tanta,
Egypt, 2006.

2-Rashed, I. G., "Engineering Chemistry," El-Mansoura Press, El-

Mansoura, Egypt, 2006.
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

3-Zayed, M. A. and El-Sherbeeny, M. "Engineering Chemistry," Shebin-

Elkom Press, Shebin-Elkom, Egypt, 2006

4-Jain, P. C., " Engineering Chemistry," Dhanpat Rai of Sons, Delhi,

1982.

5-Shereve, R. N. and Brink, J. A., "Chemical Process Industries, 6th

ed., McGraw-Hill Inc., 1985.

6-Chigier, N., "Energy, Combustion and Environment," McGraw -Hill

Inc., 1981.

7-A.H. Mahvi, J. Nouri, Omrani and F. Golami , Application Of Platanus

Orientalis Leaves in removal of cadmium from aqueous solutions, Word

2022/2023 2022/2023 2022/2023

Applied Sci. J.,2,1,40-44(2007)

8-Siva Sanker ," Engineering Chemistry " 1st ed., McGraw Hill (2008 )

9- Dr. M. R. SenaPati "Advanced Engineering Chemistry", Laxmi

Publications(P)LTD , 2nd., ed. (2006)

10- K. Eric (1992). Nanosystems: Molecular Machinery, Manufacturing, and

Computation. New York: John Wiley & Sons. ISBN 0-471-57547-X.

30504101603434 30504101603434 30504101603434

432
 UG_31186536@f-eng.tanta.edu.eg UG_31186536@f-eng.tanta.edu.eg UG_31186536@f-eng.tanta.edu.eg

Contents

No. of Title Of the Chapter pages

chapter
‫ﻋﺒﺪﺍﻟﺮﺣﻤﻦ ﻣﺤﻤﺪ ﻋﺎﺻﻢ ﺑﺴﻴﻮﻧﻲ ﻣﺤﻤﻮﺩ‬

1 Gases 2

2 Thermodynamic 67

3 Fertilizer 123

4 Cement 145

5 Electrochemistry 170

6 Corrosion 197

7 Corrosion of Steel Reinforcement 224

2022/2023 in concrete 2022/2023 2022/2023

8 Chemical Equilibrium 236

9 Ionic Equilibrium 247

10 Material balance 259

11 Combustion 271

12 Water treatment and Technology 283

13
30504101603434 Engineering30504101603434
Nanotechnology 306
30504101603434

14 Solutions 340

References 368

433