1.

MATTER AND MEASUREMENTS

1.1 Matter
Chemistry is the study of matter and the changes it undergoes. Matter is anything
that occupies space and has mass. Matter includes things we can see and touch
(such as water, earth, and trees), as well as things we cannot (such as air and
atoms). Thus, everything in the universe has a “chemical” connection. Chemists
distinguish among several subcategories of matter based on composition and
properties. The classifications of matter include substances, mixtures, elements,
compounds, atoms and molecules.
1.1.1 Classifications of matter
The following figure summarizes how chemists classify matter.

First: Substances
A substance is a form of matter that has a definite (constant) composition and
distinct properties. Examples are water, ammonia, table sugar (sucrose), gold,
and oxygen. Substances differ from one another in composition and can be
identified by their appearance, smell, taste, and other properties. Substances
are either elements or compounds:

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 Elements: An element is a substance that cannot be separated into
simpler substances by chemical means. To date, 118 elements have been
positively identified. Most of them occur naturally on Earth. The others
have been created by scientists via nuclear processes.
Symbols of elements: Elements are given symbols that indicate their
names:
 Most of the symbols of elements comes from their English names
symbol of carbon is “C” and of oxygen is “O”. The symbols of some
elements are derived from their Latin names. For example, symbols of
gold, iron and sodium are “Au” from aurum, “Fe” from ferrum and
“Na” from natrium
 Symbols of elements are either one or two letters
 The first letter of a symbol is always capitalized, but any following
letters are not. For example, Co is the symbol for the element cobalt,
whereas CO is the formula for the carbon monoxide molecule
 The periodic table contains the names and symbols of all elements
 Compounds: A compound, is a substance composed of atoms of two or
more elements chemically united in fixed proportions. Hydrogen gas, for
example, burns in oxygen gas to form water, which has properties that are
distinctly different from those of the starting materials. Water is always
made up of two hydrogens and one oxygen regardless of where it comes
from Saudi Arabia, China, or Mars. Unlike mixtures, compounds can be
separated only by chemical means into their pure components.
Formulas of compounds: Compounds are given formulas that indicate
their names:
 Formula of a compound consists of the symbols of the elements that
constitutes the compound. For example, when carbon and oxygen react
with each other they, under certain conditions, form a compound that is
named “carbon monoxide” and given the formula “CO”. However,
different conditions they form a different compound that is named
“carbon dioxide” and given a different formula “CO2”
 The way compounds are named and their formulas are written depends
on rules that are well formulated
 Rules of naming compounds and writing their formula will be discussed
in the second chapter
Second: Mixtures
A mixture is a combination of two or more substances in which the substances
retain their distinct identities. Examples are air, soft drinks, milk, and cement.
Mixtures do not have constant composition. Therefore, samples of air
collected in different cities would probably differ in composition because of
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 differences in altitude, pollution, and so on. Mixtures are either homogeneous
or heterogeneous:
 Homogeneous mixture: A Homogeneous mixture is a mixture in which
the composition of the mixture is the same throughout (the composition is
uniform). Some familiar examples are air, soft drinks, milk, and cement
 Heterogeneous mixture: A Heterogeneous mixture is a mixture in which
the composition of the mixture is not the same throughout (the composition
is not uniform). Some familiar examples are the mixture of sand and iron
filing, both the sand grains and the iron filing remain separate.
Any mixture, whether homogeneous or heterogeneous, can be created and
then separated by physical means into pure components without changing the
identities of the components. Thus, sugar or salt can be recovered from a water
solution by evaporating the solution to dryness, and to separate the iron-sand
mixture, we can use a magnet to remove the iron from the sand.After
separation, the components of the mixture will have the same composition and
properties as they did before.

1.1.2 The three states of matter

All substances can exist in three states (solid, liquid and gas).As the following
figure shows, gases differ from liquids and solids in the distances between the
molecules:
 In a solid, molecules are held close together in an orderly fashion with
little freedom of motion.

3
  In a liquid, molecules are close together but are not held so rigidly in
position and can move past one another.
 In a gas, molecules are separated by distances that are large compared
with the size of the molecules.

The three states of matter can be interconverted without changing the

composition of the substance:
 Upon heating, a solid (for example, ice) melts to form a liquid (water). The
temperature at which this transition occurs is called the melting point of
the solid. Cooling a liquid will cause it to freeze into a solid.
 Upon heating, a liquid (for example, water) vaporize into a gas (vapor).
The temperature at which this transition occurs is called the boiling point
of the liquid. Cooling a gas will cause it to condense into a liquid.
1.1.3 Physical and chemical properties of matter
Substances differ by their physical properties and chemical composition.
 Physical properties of matter: Color, melting point, and boiling point are
physical properties. A physical property can be measured and observed
without changing the chemical composition or identity of a substance. For
example, we can measure the melting point of ice by heating a block of ice
and recording the temperature at which it melts to liquid water. Liquid
water differs from solid water, ice, only in appearance, not in composition,
so this is a physical change; we can freeze the water to recover the original
ice. Therefore, the melting point of a substance is a physical property.

4
 Similarly, when we say that helium gas is lighter than air, we are referring
to a physical property.
 Chemical properties of matter: The statement “Hydrogen gas burns in
oxygen gas to form water” describes a chemical property of hydrogen and
oxygen, because to observe this property we must carry out a chemical
change, in this case burning. After the chemical change, the original
chemical substance, the hydrogen and the oxygen, will have vanished, and
all that will be left is a different chemical substance which is water. We
cannot recover the hydrogen from the water by means of a physical
change, such as boiling or freezing. Also, when an egg is subjected to a
temperature of about 100°C, the yolk and the egg white undergo changes
that alter not only their physical appearance but their chemical makeup as
well. When eaten, the egg is changed again in our bodies by enzymes, and
this digestive action is a chemical change.
1.1.4 Categories of physical properties of matter
All physical properties of matter fall into one of two categories:
 Extensive properties: If the measured value of the physical property
depends on the amount of the matter then this property is an extensive
property. Mass of a matter, is an extensive property because its value
depends on the amount of matter, more matter means more mass. Values
of the same extensive property can be added together. For example:
a) The mass of two copper pieces is the sum of the masses of each piece.
b) The length of two adjacent tables is the sum of the lengths of each.
 Intensive properties: If the measured value of the physical property does
not depend on the amount of the matter then this property is an intensive
property. Values of the same extensive property cannot be added together.
For example:
a) Density of water filling a 100-cm3 glass is the same as the density of
water filling a 100-cm3 glass, and if we mix the contents of the two
glasses the density of the 1100 cm3 stays the same.
b) If we have the two previous glasses at the room temperature (25 °C)
then the temperature of each will be 25 °C, and if we mix the contents
of the two glasses the temperature of the 1100 cm3 stays at 25 °C and it
will not be 50 °C. Unlike mass, length, and volume, density,
temperature and other intensive properties are not additive.

1.2 SI Units
In 1960, the General Conference of Weights and Measures, the international
authority on units, proposed a revised metric system called the International

5
 System of Units (abbreviated SI, from the French S ystème I nternationale
d’Unites).
1.2.1 Base units
Physical quantities are two types, first is the base physical quantities that are
given seven base SI units, the second is the derived physical quantities that
are given derived SI units. The following table shows the seven base physical
quantities and their sven SI base units.

SI base unit
Base quantity
Name Symbol
length meter m
mass kilogram kg
time second s
electric current ampere A
Thermodynamic temperature kelvin K
amount of substance mole mol
luminous intensity candela cd

The SI units of length and mass are in decimal fashion.

The table blow shows the prefixes used for large quantities of these two
physical properties.

Prefixes describing the Large

Prefix (Symbol) Power Numeric Representation
24
yotta (Y) 10 1 septillion
21
zetta (Z) 10 1 sextillion
18
exa (E) 10 1 quintillion
15
peta (P) 10 1 quadrillion
12
tera (T) 10 1 trillion
9
giga (G) 10 1 billion
6
mega (M) 10 1 million
3
kilo (k) 10 1 thousand
0
no prefix 10 1 unit

The table blow shows the prefixes used for small quantities of these two
physical properties.

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 Prefixes describing the Small
Prefix (Symbol) Power Numeric Representation
0
no prefix 10 1 unit
-3
milli (m) 10 1 thousandth
-6
micro (µ) 10 1 millionth
-9
nano (n) 10 1 billionth
-12
pico (p) 10 1 trillionth
-15
femto (f) 10 1 quadrillionth
-18
atto (a) 10 1 quintillionth
-21
zepto (z) 10 1 sextillionth
-24
yocto (y) 10 1 septillionth

1.2.2 Derived units

Other than the seven base physical quantities all the rest of physical quantities
are derived from these seven quantities and their units are derived units. For
example, area is the product of a length multiplied by another length, thus area
is not a base but derived physical quantity and its unit is not a base unit a
derived unit.
1.2.3 Some important units
Below are some important physical quantities and their SI and non-SI Units.
First: Mass and weight
Although they are different quantities, the terms “mass” and “weight” are
often used interchangeably. Mass is a measure of the amount of matter in an
object but weight is the force that gravity exerts on the object. An apple with
a mass equals 180 g on the surface of the earth has the same mass anywhere
in the universe such as the surface of the moon. The mass of the apple is
constant and does not depend on its location. However, its weight on the
surface of the moon is only one-sixth that on the surface of the earth because
the force of gravity of the moon is one-sixth that of the earth. Chemists
determine masses with a balance. The SI unit of mass is the kilogram (kg). In
chemistry, however, the smaller gram (g) is more convenient:

1 kg = 1000 g = 1 × 103 g

Pound, abbreviated “lb”, is a non- SI Unit of mass that is used in few countries
of our world; it is

1 lb = 0.4536 kg = 453.6 g
1 kg = 1000 g = 2.2046 lb

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Second: Volume
The SI unit of volume is the cubic meter (m3). Generally, however, chemists
work with much smaller volumes, such as the cubic centimeter (cm3) and the
cubic decimeter (dm3):

1 cm3 = (1 × 10–2 m)3 = 1 × 10–6 m3

1 dm3 = (1 × 10–1 m)3 = 1 × 10–3 m3

Another common non-SI Unit of volume is the liter (L). A liter is the volume
occupied by one cubic decimeter. One liter of volume is equal to 1000
milliliters (mL):

1 L = 1 dm3= 1000 cm3 1000 mL

Even though the liter is not an SI unit, volumes are usually expressed in liters
and milliliters.
Third: Density
The equation for density is
mass
density =
volume
or
m
d=
V

Where d, m, and V denote density, mass, and volume, respectively. Because

density is an intensive property and does not depend on the quantity of mass
present, for a given substance the ratio of mass to volume always remains the
same; in other words, V increases as m does. The SI-derived unit for density
kg g
is the kilogram per cubic meter ( 3). Grams per cubic centimeter ( 3) and its
m cm
g
equivalent, grams per milliliter ( ), are commonly used for solid and liquid
mL
densities. Because gas densities are often very low, we express them in units
g
of grams per liter ( ):
L

kg g g
1000 =1 =1
m3 cm3 mL

The following table lists the densities of several substances.

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 g
Material Density ( )
cm3
Gold 19.3
Mercury 13.6
Lead 11.3
Silver 10.5
Iron 7.86
Aluminum 2.7
Rubber 1.1
Water 1.0
Cork 0.24
Air 0.0013

EXAMPLE 1.1
Gold is a precious metal that is chemically unreactive. It is used mainly in jewelry,
dentistry, and electronic devices. A piece of gold ingot with a mass of 301 g has a
volume of 15.6 cm3. Calculate the density of gold.
Solution
m 301 g g
d= = = 19.3 3
V 15.6 cm3 cm
Practice Exercise
A piece of platinum metal with a density of 21.5 g/cm3 has a volume of 4.49 cm3.
What is its mass?

EXAMPLE 1.2
The density of mercury, the only metal that is a liquid at room temperature, is 13.6
g
. Calculate the mass of 5.50 mL of the liquid.
cm3
Solution
5.50 mL = 5.50 cm3
g
m = d × V = 13.6 3 × 5.5 cm3 = 74.8 g
cm
Practice Exercise
The density of sulfuric acid solution in a certain car battery is 1.41 g/mL. Calculate
the mass of 242 mL of this solution.

Fourth: Temperature
Temperature is an arbitrary measure of the degree of hotness or coldness of
matter. There are three temperature scales are currently in use. Their units are
degrees Fahrenheit (°F), degrees Celsius (°C), and Kelvin (K):

9
 The Celsius scale, which is the most commonly used scale worldwide,
divides the range between the normal freezing point (0°C) and boiling
point (100°C) of water into 100 degrees, therefore it is sometimes called
“the centigrade scale”.
 The Fahrenheit scale, which is the least used scale worldwide but is used
in some countries like the United States and the United Kingdom but
outside their academic institutions and laboratories, defines the normal
freezing and boiling points of water to be exactly 32 °F and 212 °F,
respectively. We can use the following equations to convert between
degrees Celsius and degrees Fahrenheit:

5 °C
Temperature in °C = (Temperature in °F − 32 °F) × ( )
9 °F
9 °F
Temperature in °F = (Temperature in °C × ) + (32 °F)
5 °C

 The Kelvin scale (also called the absolute temperature scale) is the SI base
unit of temperature. By “absolute” we mean that the zero on the Kelvin
scale, denoted by 0 K, is the lowest temperature that can be attained
theoretically. The Kelvin scale defines the normal freezing and boiling
points of water to be exactly 273.15 K and 373 K, respectively. The Celsius
and the Kelvin scales have units of equal magnitude; that is, one degree
Celsius is equivalent to one Kelvin. To reach 0 K temperature in the
Celsius scale must be lowered down to – 273.15°C:

0 K= – 273.15°C = – 459.67 °F

We can use the following equations to convert between degrees Celsius

and Kelvin:

1K
Temperature in K = (Temperature in °C + 273.15 °C) × ( )
1 °C
1 °C
Temperature in °C = (Temperature in K − 273.15 K) × ( )
1K

And we can use the following equations to convert between degrees

Fahrenheit and Kelvin:

5K
Temperature in K = (Temperature in °F + 459.67 °F) ×
9 °F
9 °F
Temperature in °F = (Temperature in K × ) – (459.67 °F)
5K

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EXAMPLE 1.3
A) Mercury melting point is − 38.9 °C. How much is it in Kelvin and °F.
B) Normal human temperature is 98.6 °F. How much is it in Kelvin and °C?
C) Iron boiling point is 3135.35 K. How much is it in °C and °F.
Solution
1K
A) Temperature in K = (Temperature in °C + 273.15 °C) ×
1 °C
K
Temperature in K = (– 38.9 °C + 273.15 °C) = 234.3 K
°C
9 °F
Temperature in °F = ( × Temperature in °C) + 32 °F
5 °C
9 °F
Temperature in °F = ( × – 38.9 °C) + 32 °F = − 38.02 °F
5 °C
5K
B) Temperature in K = (Temperature in °F + 459.67 °F) ×
9 °F
5K
Temperature in K = (98.6 °F + 459.67 °F) × = 310.15 K
9 °F
5 °C
Temperature in °C = (Temperature in °F − 32 °F) × ( )
9 °F
5 °C
Temperature in °C = (98.6 °F − 32 °F) × ( ) = 37 °C
9 °F
1 °C
C) Temperature in °C = (Temperature in K − 273.15 K) × ( )
1K
1 °C
Temperature in °C = (3135.35 K − 273.15 K) × ( ) = 2862.20 °C
1K

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 9 °F
Temperature in °F = (Temperature in K × ) – (459.67 °F)
5K
9 °F
Temperature in °F = (3135.35 K × ) – (459.67 °F) = 5183.96 °F
5K
Practice Exercise
A) Convert – 38.83 °C, (the freezing point of mercury) to °F and to K.
B) Convert 346 °F, (the freezing point of nitrogen) to °C and to K.
C) Convert 77 K, (the boiling point of nitrogen) to °C and to °F.

Fifth: Pressure
Pressure is the force applied on unit area:

Fofce
Pressure =
Area
kg m
Force SI Unit ( 2 ) kg
Pressure SI Unit = = ( (ms 2 ) ) =
Area SI Unit m s2

kg
This unit “ ”, is called “Pascal” and abbreviated “Pa”:
m s2

kg
1 = 1 Pa
m s2

Pressure, as any other physical quantity, is measured by other units:

 The atmosphere unit, which is abbreviated “atm”:

1 atm = 101325 Pa

 The centimeter mercury unit, which is abbreviated “cmHg”:

1 cmHg = 1333.22 Pa

The millimeter mercury unit, which is abbreviated “mmHg” is one-tenth

the centimeter mercury unit:

1 mmHg = 0.1 cmHg = 133.322 Pa

This unit “mmHg”, is called “Torricelli” and abbreviated “Torr”:

1 Torr = 1 mmHg

 The pound per inch square unit, which is abbreviated “psi”:

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 1 psi = 6894.76 Pa

 The bar unit, which is symbolized as “bar”:

1 bar = 100000 Pa = 750.0617 mmHgm = 14.504 psi

From all of the above units of pressure, chemists mostly use the “Pa” unit, the
“atm” unit and the “mmHg” unit which is also called “Torr”.

EXAMPLE 1.4
A) It is found, in a cold day, that the atmospheric pressure in Riyadh is 743 mmHg.
How much this pressure in “atm” unit and in the SI Units?
B) If the pressure inside your car tire is 35 psi, how much is this pressure in the SI
Units and in bar unit?
C) A balloon full of air at a pressure equals to 0.35 atm. What would its pressure
be in “mmHg” unit and in the SI Units?
Solution
1 atm
A) Pressure in atm = Pressure in mmHg ×
760 mmHg
1 atm
Pressure in atm = 743 mmHg × = 0.978 atm
760 mmHg
133.322 Pa
Pressure in Pa = Pressure in mmHg ×
1 mmHg
133.322 Pa
Pressure in Pa = 743 mmHg × = 99058.2 Pa
1 mmHg
6894.76 Pa
B) Pressure in Pa = Pressure in psi ×
1 psi
6894.76 Pa
Pressure in Pa = 35 psi × = 241316.6 Pa
1 psi
1 bar
Pressure in bar = Pressure in psi ×
14.504 psi
1 bar
Pressure in Pa = 35 psi × = 2.41 bar
14.504 psi
760 mmHg
C) Pressure in mmHg = Pressure in atm ×
1 atm
760 mmHg
Pressure in Pa = 0.35 atm × = 266 mmHg
1 atm
Practice Exercise
A) It is found, in a hot day, that the atmospheric pressure in Riyadh is 737 mmHg.
How much is this pressure in “mmHg” and in “bar” units?
B) If the pressure inside a gaseous cylinder is 4.6 atm, how much is this pressure
in the SI Units in Torr.

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C) If the pressure outside an airplane at 40000 ft-altitude reads 0.18 bar. What
would this pressure be in “mmHg” unit and in the SI Unit of pressure

Sixth: Energy
Energy is usually defined as the ability to do work. It is manifested by the
forms it appears by or by the paths it transfers by. Work and heat are ways of
transferring energy from a system to another. Work is the easiest
manifestation of energy; it is defined the force causing a movement or
displacement. Therefore, mathematical equation of work is written as:

Work = force × distance

Accordingly, the SI Units of work is the SI Units of force times the the SI Unit
of distance:

kg m kg m2
The SI Units of work = ×m= =J
s2 s2

kg m2
This unit of work itself is the unit of energy. This SI Unit, , is named
s2
“Joule” and abbreviated as “J”. The unit “calorie”, abbreviated as “cal” is
another unit for energy:

kg m2
1 cal = 4.184 = 4.184 J
s2

It might be useful to mention that when the word “calorie” is written with
capital “C” as “Calorie” its value changes:

1 Cal = 1 kcal = 1000 cal = 4184 J

The Calorie” is mostly used in the fields of food, nutrients and physical
exercises. If there are 78 Calories in an average-mass apple (150 g), this is
equals to 78000 calorie or 18642 J. And a moderate-speed waking for one
kilometer burns 55 Calories that is equals to 55000 calorie or 230120 J.
Therefore, we should not confuse calorie with Calorie.
1.2.4 Dimensional analysis in solving problems
(Conversion factors)
Procedure we use to convert between units in solving chemistry problems is
called dimensional analysis (also called the factor-label method).

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Dimensional analysis is based on the relationship between different units that
express the same physical quantity. For example:
 Because 1 cal = 4.184 J we can covert one of them to the other using the
one of the following conversion factors::

1 cal 4.184 J
= 1 or =1
4.184 J 1 cal

 Because 1 atm = 101325 Pa we can covert one of them to the other using
the one of the following conversion factors::

1 atm 101325 Pa
= 1 or =1
101325 Pa 1 atm

 Because 1 in = 2.54 cm we can covert one of them to the other using the
one of the following conversion factors:

1 in 2.54 cm
= 1 or =1
2.54 cm 1 in

To apply dimensional analysis, we use the relationship

given quantity × conversion factor = desired quantity

The units of the quantity cancel as follows:

𝐝𝐞𝐬𝐢𝐫𝐞𝐝 𝐮𝐧𝐢𝐭
given unit × = desired unit
𝐠𝐢𝐯𝐞𝐧 𝐮𝐧𝐢𝐭

 To convert 12 inches to centimeters, we multiply the length by the

appropriate conversion factor:

2.54 cm
12 in × = 30.48 cm
1 in

 To convert 57.8 meters to centimeter, we multiply the length by the

appropriate conversion factor:
100 cm
57.8 m × = 5780 cm
1×m

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EXAMPLE 1.5
A person’s average daily intake of glucose (a form of sugar) is 0.0833 pound (lb).
What is this mass in milligrams (mg)? (1 lb = 453.6 g)
Solution
The sequence of conversions is
453.6 g 1000 mg
=1 =1
1 lb 1g

453.6 g 1000 mg
0.0833 lb × × = 3.78 × 104 mg
1 lb 1g
Practice Exercise
An aluminum foil has a mass of 1.07 kg. What is its mass in pounds?

EXAMPLE 1.6
An average adult has 5.2 L of blood. What is the volume of blood in m3?
Solution
1 m3
=1
1000 L

1 m3
5.2 L = 5.2 L × = 5.2 × 10–3 m3
1000 L
Practice Exercise
The volume of a room is 1.08 × 108 dm3. What is the volume in m3?

EXAMPLE 1.7
Liquid nitrogen is obtained from liquefied air and is used to prepare frozen goods and
in low-temperature research. The density of liquid nitrogen at its boiling point (– 196
°C or 77 K) is 0.808 g/cm3. Convert the density to units of kg/m3.
Solution
1000000 cm3 1 kg
=1 =1
1 m3 1000 g

g 1 kg 1000000 cm3
0.808 3
× × = 808 kg/m3
1 cm 1000 g 1 m3
Practice Exercise
The density of the lightest metal, lithium (Li), is 5.34 × 102 kg/m3. Convert the density
to g/cm3.

16
 2. ATOMS, MOLECULES AND IONS
2.1 Constituent of the atom
2.1.1 A brief historical background
The word “atom” came from the Greek word “atomos” which means
“indivisible”. It was chosen by Democritus about 2400 years ago. The theory
of Democritus is that atoms are indivisible, infinite in number, uncreated, and
eternal. Democritus attributed the properties of matter to the kind of its atoms.
Unfortunately, this brilliant vision of Democritus was overlooked because the
theory of the four elements (soil, water, air and fire) created by Empedocles
was adopted by the greatest Greek philosopher Aristotle. Although the theory
of Democritus survived among some Islsmic philosophers, the predomination
was in favor of the theory of Empedocles for nothing except that it was
adopted by Aristotle. Therefore, we can say that Aristotle adaptation of the
theory of the four elements is one of the disastrous event in the sciences of
nature. Now, our present understanding of the structure of matter began to
take shape in the early nineteenth century with Dalton’s atomic theory in
1808. Dalton resurrected Democritus's theory. Now, we know that all matter
is made of atoms, molecules, and ions. All of chemistry is concerned in one
way or another with these species.
2.1.2 The structure of the atom
After Dalton’s theory, a series of investigations that began in the 1850s and
extended into the twentieth century clearly demonstrated that atoms actually
possess internal structure; that is, they are made up of even smaller particles,
which are called subatomic particles. This led to the discovery of well-known
three such subatomic particles namely electrons, protons, and neutrons.
 The Electron: Electron was discovered by an English physicist, J. J.
Thomson in 1897. Electrons are negatively charged atomic particles.
Thomson determined the ratio of the electric charge its mass. In 1909, an
American physicist, R. Millikan measured the charge of an electron to be
1.6022 × 10–19 C which allows to determine that the mass of the electron
is 9.10 × 10–28 g.
 The Proton and the nucleus: Because atoms are neutral, an atom must
contain equal number of positive and negative charges. In 1904 Thomson
proposed that an atom could be thought of as a uniform, positive sphere
of matter in which electrons are embedded like raisins in a cake. This why
Thomson model is called the “plum-pudding model” for “plum-pudding”
is a kind of sweets originally offered in England at Christmas dinner. The

17
 following figures display Thompson’s model of the atom (left) and a
typical “plum-pudding” (right):

In 1909, the new Zealander physicist and chemist, Ernest Rutherford

discovered that the positive particles of the atom constitute the center of te
atom. These positive particles in the center of the atom are called the
“protons”. The number of protons of any atom equals the number of its
electrons and its electric charge equals that of the electron while its mass
equals about 1840 times the mass of the electron. The mass of the proton
is 1.67262 × 10–24 g. Thus, the mass of a nucleus constitutes most of the
mass of the entire atom. Regarding the volume of the space that an atom
1
occupies it is found that the nucleus occupies only about of the entire
1013
volume of the atom. Atomic dimensions are expressed in picometer (pm),
where 1 pm equals 1 × 10–12 m. A typical atomic radius is about 100 pm,
whereas the radius of an atomic nucleus is only about 5 × 10 –3 pm. If we
imagine that the size of the nucleus is the same as that of a ping pong ball,
then the first electron orbiting around it would be 666 m away.
 The neutron: In 1932, James Chadwick showed that atoms consist of a
third type of subatomic particles, which he named neutrons, because they
are electrically neutrals. The mass of the neutron is slightly greater than
that of protons. The following figure shows the location of the elementary
particles (protons, neutrons, and electrons) in an atom. The following
figure shows that electrons are as “clouds” around the nucleus.

18
 The table below shows their masses and charges.

Particle Mass (g) Electric Charge (C)

Electron 9.10938 × 10–28 – 1.6022 × 10–19
Proton 1.67262 × 10–24 + 1.6022 × 10–19
Neutron 1.67493 × 10–24 0

2.2 Symbols of elements

The following table shows the names and symbols of some of the more
common elements.

Chemists use symbols of one or two letters to represent the elements. The first
letter of a symbol is always capitalized, but any following letters are not. For
example, Co is the symbol for the element cobalt, whereas CO is the formula
for the carbon monoxide molecule. Most symbols are derived from the
English names of the elements but some are derived from their Latin names,
for example “Au” from aurum (gold), “Fe” from ferrum (iron) and “Na” from
natrium (sodium).

2.3 Atomic number, mass number and isotopes

2.3.1 The atomic number (Z): The atomic number is the number of protons in the
nucleus of each atom of an element. In a neutral atom the number of protons
is equal to the number of electrons, so the atomic number also indicates the

19
 number of electrons present in the atom. The chemical identity of an atom can
be determined solely from its atomic number. For example, The atomic
number of oxygen is 6; this means that each oxygen atom has 9 protons and 9
electrons, we can say with confidence that every atom in the universe that
contains 6 protons is definitely an oxygen atom.
2.3.2 The mass number (A): The mass number is the total number of neutrons and
protons in the nucleus of an atom of an element. Except for the hydrogen,
which has one proton and no neutrons, all atomic nuclei contain both protons
and neutrons. In general, the mass number is given by:

mass number = number of protons + number of neutrons

mass number = atomic number + number of neutrons

The number of neutrons in an atom is equal to the difference between the mass
number and the atomic number:

number of neutrons = (A – Z)

For example, if the mass number (A) of a particular boron atom is 12 and the
atomic number (Z) is 5 , then the number of neutrons is 7.
 The conventional way to denote the atomic number (Z) and the mass number
(A) of an atom of an element (X) is as follows:

mass number A
atomic numberZX
Hydrogen which has only one proton and no neutrons is written as:

1
1H
Uranium which has 92 protons and 143 neutrons is written as:

235
92U

20
2.3.3 Isotopes: Isotopes are atoms that have the same atomic number but different
mass numbers. Atoms of a given element do not all have the same mass. Most
elements have two or more isotopes. For example, there are three isotopes of
hydrogen:
 Hydrogen has one proton and no neutrons. This is written as 11H
 Deuterium has one proton and one neutron. This is written as 21H
 Tritium has one proton and two neutrons. This is written as 31H
Only hydrogen is given different names for each of its isotopes, but isotopes
of other elements are identified by their mass numbers. For example, the
isotopes of uranium are named “uranium-235” and “uranium-238”:
 Uranium-235 is written as 23592U
238
 Uranium-235 is written as 92U
The chemical properties of an element are determined by the protons and
electrons in its atoms; neutrons do not take part in chemical changes under
normal conditions. Therefore, isotopes of the same element have similar
chemistries and form the same types of compounds.

EXAMPLE 2.1
Give the number of protons, neutrons, and electrons in each of the following
species:
A) 20
11Na B) 22
11Na C) 178O D) 146C
Solution
A) number of protons = atomic number = 11
number of neutrons = mass number – number of protons
number of neutrons = 20 – 11 = 9
B) number of electrons = number of protons = 11
number of protons = atomic number = 11
number of neutrons = mass number – number of protons
number of neutrons = 22 – 11 = 11
C) number of protons = atomic number = 8
number of electrons = number of protons = 8
number of neutrons = mass number – number of protons
number of neutrons = 17 – 8 = 9
D) number of protons = atomic number = 6
number of electrons = number of protons = 6
number of neutrons = mass number – number of protons
number of neutrons = 14 – 6 = 8
Practice Exercise
How many protons, neutrons, and electrons are in the isotope of copper: 63
29Cu?

21
2.4 Atomic mass
The mass of an atom depends on the number of protons, and neutrons it
contains. Knowledge of an atom’s mass is important in laboratory work. But
atoms are extremely small particles. The smallest speck of dust that our
unaided eyes can detect contains as many as 1 × 1016 atoms. Clearly, we
cannot weigh a single atom, but it is possible to determine the mass of one
atom relative to another experimentally. The first step is to assign a value to
the mass of one atom of a given element so that it can be used as a standard.
By international agreement, atomic mass is the mass of the atom in atomic
mass units (amu). One atomic mass unit is defined as a mass exactly equal to
one-twelfth the mass of one carbon-12 atom which has six protons and six
neutrons. Setting the atomic mass of carbon-12 at 12 amu provides the
standard for measuring the atomic mass of the other elements. For example:
 Hydrogen atom is only 8.4% as massive as the carbon-12 atom. Thus, if
the mass of one carbon-12 atom is exactly 12 amu, the atomic mass of
hydrogen must be 0.084 × 12.00 amu or 1.008 amu.
 Similar calculations show that the atomic mass of oxygen is 15.999 amu
and that of iron is 55.845 amu.
2.4.1 The average atomic mass
When you look up the atomic mass of carbon in a table of elements, you will
find that its value is not 12.00 amu but 12.0111 amu. The reason for the
difference is that most naturally occurring elements (including carbon) have
more than one isotope. This means that when we measure the atomic mass of
an element, we must generally settle for the average mass of the naturally
occurring mixture of isotopes.

Average atomic mass = ∑percent of isotope × atomic mass of isotope

For example, carbon has many isotopes but only two are stable:
98.90% is carbon-12 (The atomic mass of carbon-12 = 12.0000 amu)
1.10% is carbon-13 (The atomic mass of carbon-13 = 13.0033 amu)
This means that, in nature, if we have in hand 1000 atom of carbon, we will
find 9890 atoms of carbon-12 and 110 atoms of carbon-13. Accordingly, the
mass of carbon atom, and any atom of any other element, should be averaged
as follows:

average atomic mass = aam

aam = ∑percent of isotope × atomic mass of isotope
aam of carbon = (0.9890) × (12.0000 amu) + (0.0110) × (13.0033 amu)
22
 aam of carbon = 12.011 amu

It is important to understand that when we say that the atomic mass of carbon
is 12.011 amu, we are referring to the average value.

EXAMPLE 2.2
The atomic masses of its two stable isotopes, 63 65
29Cu (69.09%) and 29Cu (30.91%),
are 62.93 amu and 64.9278 amu, respectively. Calculate the average atomic mass
of copper. The relative abundances are given in parentheses.
Solution
Average atomic mass = ∑percent of isotope × atomic mass of isotope
Average atomic mass = (0.6909) × (62.93 amu) + (0.3091) × (64.9278 amu)
Average atomic mass = 63.55 amu
Practice Exercise
The atomic masses of the two stable isotopes of boron, 105B (19.78%) and 115B
(80.22%), are 10.0129 amu and 11.0093 amu, respectively. Calculate the average
atomic mass of boron.

For simplicity, the word “average” is usually omitted when discussing the
atomic masses.
2.5 Quantum theory and electronic structure of atoms
After the discoveries of the 19th century, the theories and attempts to
understand the finite constituent of atoms were handcuffed by Handcuffed by
the disability of traditional physics. The new era in physics started in 1900
with a young German physicist named Max Planck who established the
quantum theory which turned physics upside down. Max Planck theory altered
our concept of nature forever and opened the door for a flurry of researches
and findings by Einstein, Bohr, de Broglie, Heisenberg, Schrodinger and so
many others. For electrons, quantum theory solved the puzzle of how
electrons present in atoms by the quantum numbers of each electron. The
quantum numbers act as identification number acts for us, for electrons,
quantum numbers act as thump print acts for us and for electrons, quantum
numbers act as home address acts for us. In any atom, no two electrons have
the same four quantum numbers.
2.5.1 Quantum numbers
1) Principal quantum number, n
 The principal quantum number (n) describes the size of the orbital.
 Orbitals for which n = 2 are larger than those for which n = 1, for
example.

23
  Because they have opposite electrical charges, electrons are attracted to
the nucleus of the atom.
 Energy must therefore be absorbed to excite an electron from an orbital
in which the electron is close to the nucleus (n = 1) into an orbital in
which it is further from the nucleus (n = 2).
 The principal quantum number therefore indirectly describes the energy
of an orbital.
 The allowed values of “n” are therefore 1, 2, 3, 4, 5, 6 and 7.
2) Angular quantum number, l
The angular quantum number (l) describes the shape of the orbital. Orbitals
have shapes that are described as:
 spherical (l = 0) and this is given the symbol “s”
 dumbbell (l = 1) and this is given the symbol “p”
 cloverleaf (l = 2) and this is given the symbol “d”
 cloverleaf (l = 3) and this is given the symbol “f”
3) Magnetic quantum number, 𝐦𝒍
The magnetic quantum number (m) describes the orientation of an orbital
in a magnetic field:
 There is only one way in which the orbital (l = 0) can be oriented in
space:
m𝑙 = 0
 There are three ways in which the orbital (l = 1) can be oriented in
space:
m𝑙 = – 1, m𝑙 = 0, m𝑙 = + 1
 There are five ways in which the orbital (l = 2) can be oriented in space:
m𝑙 = – 2, m𝑙 = – 1, m𝑙 = 0, m𝑙 = + 1, m𝑙 = + 1
 There are seven ways in which the orbital (l = 3) can be oriented in
space:
m𝑙 = – 3, m𝑙 = – 2, m𝑙 = – 1, m𝑙 = 0, m𝑙 = + 1, m𝑙 = + 2, m𝑙 = + 3
4) Spin quantum number, 𝐦𝐬
The spin quantum number (m) describes the direction of an electron spin
in its orbital. Spinning can be either clockwise or anticlockwise with no
third option:
1 1
ms = + or ms = –
2 2

The following table gives the four quantum numbers of each electron in any
orbital. It shows that, in any atom, no two electrons have the same four
quantum numbers.

24
n l 𝐦𝒍 𝐦𝐬
1
+
1 0 (s) 0 2
1
–
2
1
+
0 (s) 0 2
1
–
2
1
+
–1 2
1
–
2 2
1
+
1 (p) 0 2
1
–
2
1
+
+1 2
1
–
2
1
+
0 (s) 0 2
1
–
2
1
+
–1 2
1
–
2
1
+
1 (p) 0 2
1
–
2
1
+
+1 2
1
–
3 2
1
+
–2 2
1
–
2
1
+
–1 2
1
–
2 (d) 2
1
+
0 2
1
–
2
1
+
+1 2
1
–
2

25
 1
+
+2 2
1
–
2
1
+
0 (s) 0 2
1
–
2
1
+
–1 2
1
–
2
1
+
1 (p) 0 2
1
–
2
1
+
+1 2
1
–
2
1
+
–2 2
1
–
2
1
+
–1 2
1
–
4 2
1
+
2 (d) 0 2
1
–
2
1
+
+1 2
1
–
2
1
+
+2 2
1
–
2
1
+
–3 2
1
–
2
1
+
3 (f) –2 2
1
–
2
1
+
–1 2
1
–
2

26
 1
+
0 2
1
–
2
1
+
+1 2
1
–
2
1
+
+2 2
1
–
2
1
+
+3 2
1
–
2

2.5.3 Shapes of orbitals

The letters of subshells go in the order s, p, d and f:
 The “s” subshell has only one orbital.
 The “p” subshell has three orbitals that are equal in energy.
 The “d” subshell has five orbitals that are equal in energy.
 The “f” subshell has seven orbitals that are equal in energy.
Electron occupies all space it moves within. So, it is impossible to draw an
orbital. Although, in principle an electron can be found anywhere, we know
that during most of the time it is as close as possible to the nucleus. The shape
of the space which includes the electron most of its time, say 95% is as
follows:
1) Shape of the “s” Orbitals

The above figure shows the distribution of electron density in the hydrogen
1s orbital moving outward from the nucleus. The electron density
decreases as the distance from the nucleus increases. There is a 90 percent
probability of finding the electron within a sphere of radius 100 pm around
the nucleus. The following figure shows boundary surface diagrams for the

27
 1s, 2s, and 3s atomic orbitals. All s orbitals are spherical in shape but differ
in size, which increases as the principal quantum number increases.

:
2) Shape of the “p” Orbitals
It should be clear that the p orbitals start with the principal quantum
number n = 2. When l = 1, the magnetic quantum number m/ can have
values of − 1, 0 and + 1. Therefore, there are three p orbitals: px , py , and
pz as shown by the following figure.

These three p orbitals differ from one another only in orientation. The
boundary surface diagrams of p orbitals in the previous figure show that
each p orbital can be thought of as two lobes on opposite sides of the
nucleus. Like s orbitals, p orbitals increase in size from 2p to 3p to 4p
orbital and so on.
3) Shape of the “d” Orbitals
When / = 2, there are five d orbitals. The five d orbitals are 3dxy, 3dyz, 3dxz,
,3𝑑𝑥 2−𝑥 2 and 3𝑑𝑧 2 , these orbital are equal in energy and shown in the
following figure.

28
 4) Shape of the “f” Orbitals
The f orbitals are important in elements with atomic numbers greater than
57. In this general chemistry course, we are not concerned with elements
having greater than 57 electrons.
2.5.4 The rules of electronic distribution
1) The “Aufbau principle” = The “n + l” principle
 This first rule states that electrons occupy the lowest-energy subshell
before any other higher-energy subshell.
 Determining which subshell is lower or higher in energy is achieved by
the sum of the values of “n” and “l” as shown in the following table.

n l n+l
1 0 (s) 1
0 (s) 2
2
1 (p) 3
0 (s) 3
3 1 (p) 4
2 (d) 5
0 (s) 4
1 (p) 5
4
2 (d) 6
3 (f) 7

 The lowest sum is the lower energy.

 The above table shows that some higher-energy subshells are preceding
other subshells that are lower in energy. It also shows the presence of

29
 cases where some subshells are having the same value of summation.
In these cases, the lowest subshell is the one having the lowest value of
“n”. Accordingly, the above table is rearranged from left to wright as
follows:
1s 2s 2p 3s 3p 4s 3d 4p 4d 4f
 We know that any subshell has a certain number of orientations in the
magnetic field. These different orientations do not differ in energy.
Therefore, they are shown in the following manner:
 “s” subshell has only one orientation which is represented as:
s=0
𝐦𝒍 = 0
 “p” subshell has three orientations which are represented as:
p
𝐦𝒍 = − 1 𝐦𝒍 = 0 𝐦𝒍 = + 1
 “d” subshell has five orientations which are represented as:
d
𝐦𝒍 = − 3 𝐦𝒍 = − 2 𝐦𝒍 = − 1 𝐦𝒍 = 0 𝐦𝒍 = + 1 𝐦𝒍 = − 2 𝐦𝒍 = + 3

 “f” subshell has seven orientations which are represented as:

f
𝐦𝒍 = − 3 𝐦𝒍 = − 2 𝐦𝒍 = − 1 𝐦𝒍 = 0 𝐦𝒍 = + 1 𝐦𝒍 = − 2 𝐦𝒍 = + 3
2) The Pauli principle
 This second rule states that when an electron occupies an orbital it is
not possible for another electron to share it the same orbital unless it
spins in an opposite direction of the first electron.
 This rule means that, in the same atom, no two electrons can have the
same four quantum number (each electron has its own “address”).
3) The Hund’s rule’
 There is only one orientation in the magnetic field (orbital) in the “s”
subshell.
 There are three orientations in the magnetic field (orbitals) in the “p”
subshell.
 There are five orientations in the magnetic field (orbitals) in the “d”
subshell.
 There are seven orientations in the magnetic field (orbitals) in the “f”
subshell.
Hund’s rule states that when electrons occupy a subshell which has more
than one orientation in the magnetic field (i.e. more than one orbital, this

30
 is either p, d or f) they will not pair in the same orbital as long as other
orbitals are empty and the unpaired electrons spins in the same direction.
4) The rule of half-filled and fully-filled subshells
Half-filled and fully-filled subshells add more stability to electrons and
atoms. It is known that starting from the energy level where n = 4 and
higher, the difference in energy between subsequent subshells is so small.
Therefore, when two consecutive subshells are energetically close to each
other, they will seek to be half filled or fully filled even if this requires an
electron to be in the slightly-higher energy subshell rather than the slightly
lower energy subshell. The following configurations illustrates how
electrons distribute themselves within an atom. The table shows this
distribution for the first 36 elements in the periodic table of elements.
1
H
1s1
2
He (Note: its upper shell is full and its electron configuration is symbolized as [He])
1s 2
3
Li
1s 2 2s1
4
B2
1s 2 2s 2

5
B
1s 2 2s 2 2p1

6
C
1s 2 2s 2 2p2
7
N
1s 2 2s 2 2p3

8
O
1s 2 2s 2 2p4

9
F
1s 2 2s 2 2p5

10
Ne (Note: its upper shell is full and its electron configuration is symbolized as [Ne])
1s 2 2s 2 2p6

31
11
Na
1s 2 2s 2 2p6 3s1
12
Mg
1s 2 2s 2 2p6 3s2
13
Al
1s 2 2s 2 2p6 3s2 3p1

14
Si
1s 2 2s 2 2p6 3s2 3p2
15
P

1s 2 2s2 2p6 3s2 3p3

16
S
1s 2 2s 2 2p6 3s2 3p4

17
Cl
1s 2 2s 2 2p6 3s2 3p5

18
Ar (Note: its upper shell is full and its electron configuration is symbolized as [Ar])
1s 2 2s 2 2p6 3s2 3p6
19
K
1s 2 2s 2 2p6 3s2 3p6 4s1

20
Ca
1s 2 2s 2 2p6 3s2 3p6 4s2

21
Sc
1s 2 2s 2 2p6 3s2 3p6 4s2 3d1
22
Ti
1s 2 2s 2 2p6 3s2 3p6 4s2 3d2

23
V
1s 2 2s 2 2p6 3s2 3p6 4s2 3d3
24
Cr
1s 2 2s 2 2p6 3s2 3p6 4s1 3d5

25
Mn
1s 2 2s2 2p6 3s2 3p6 4s2 3d5

32
26
Fe
1s 2 2s 2 2p6 3s2 3p6 4s2 3d6

27
Co
1s 2 2s 2 2p6 3s2 3p6 4s2 3d7

28
Ni
1s 2 2s 2 2p6 3s2 3p6 4s2 3d8

29
Cu
1s 2 2s 2 2p6 3s2 3p6 4s1 3d10

30
Zn
1s 2 2s 2 2p6 3s2 3p6 4s2 3d10
31
Ga
1s 2 2s2 2p6 3s 2 3p6 4s 2 3d10 4p1
32
Ge
1s 2 2s2 2p6 3s 2 3p6 4s 2 3d10 4p2
33
As
1s 2 2s2 2p6 3s 2 3p6 4s 2 3d10 4p3
34
Se
1s 2 2s2 2p6 3s 2 3p6 4s 2 3d10 4p4
35
Br
1s 2 2s2 2p6 3s 2 3p6 4s 2 3d10 4p5
36
Kr (Note: its upper shell is full and its electron configuration is symbolized as [Kr])
1s 2 2s2 2p6 3s 2 3p6 4s2 3d10 4p6

As it appears from the above configurations, noble gases shells have the
maximum number of electrons it can accommodate. Any element comes after
a noble gas has the configuration of this noble gas as its core electrons plus
the extra electrons in the following shell.

33
Example 2.3
Give the four quantum numbers for each of the two electrons in a 6 s orbital.
Solution
Quantum number n l 𝐦𝒍 𝐦𝐬
1
First electron 6 0 0 +
2
1
Second electron 6 0 0 –
2
Practice exercise
Give the four quantum numbers for each of the six electrons in a 3p orbital of an
atom.

Example 2.4
A person gave the following four quantum numbers for each of the electrons in
the “p” subshell of the atom of 7N. Judge the answer.
Quantum number n l 𝐦𝒍 𝐦𝐬
1
First electron 3 0 0 +
2
1
Second electron 3 1 0 –
2
Third electron 3 1 –1 +1
Solution
 The “n” quantum numbers: they are correct for all the three electrons.
 “l” quantum numbers: they are correct for the second and the third electrons but
wrong for first electron because it is in the second subshell, p, which always
has l = 1.
 The “m𝑙 ” quantum numbers: according to Hund’s rule, all of the electrons must
be unpaired and their quantum numbers must be “– 1”, “0” and “+ 1”.
 The “m𝑠 ” quantum numbers: according to Pauli’s principle, “m𝑠 ” quantum
1 1
number can be either + or + and nothing else; and according to Hund’s rule,
2 2
1 1
they all of them must be either + or + .
2 2
Practice exercise
A person gave the four quantum numbers for each of the six electrons in the 3p
orbitals of an atm. Judge the answer.
Quantum number n l 𝐦𝒍 𝐦𝐬
1
First electron 3 1 –1 +
2
1
Second electron 3 1 –1 +
2
1
Third electron 3 0 0 –
2

34
 1
Fourth electron 3 0 0 –
2
1
Fifth electron 3 –1 +1 +
2
1
Sixth electron 4 –1 +1 +
2

2.5.4 Electron configurations of anions and cations

1) First: Anions
Anions are atoms having one or more than one electrons more than its
original electrons. Consider the following examples:
H: 1s1 H−: 1s2 or [He]
F: 1s2 2s2 2p5 F−: 1s2 2s2 2p6 or [Ne]
O: 1s2 2s2 2p4 O2−: 1s2 2s2 2p6 or [Ne]
N: 1s2 2s2 2p3 N3−: 1s2 2s2 2p5or [Ne]
All of these anions also have stable noble gas configurations. Notice that
F−, Na+, and Ne (and Al3+, O2−, and N3−) have the same electron
configuration. They are said to be isoelectronic because they have the
same number of electrons, and hence the same ground-state electron
configuration. Thus, H− and He are also isoelectronic.
2) Second: Cations
Cations are atoms having one or more than one electrons more than its
original electrons.
 Cations derived from elements that its upper subshell is “p”
Electrons of cations formed from atoms having “s” or “p” as its upper
subshell are removed from the upper subshell and its configuration can
be known easily. The electron configurations of some atoms and their
corresponding cations are as follows:
Na: [Ne]3s1 Na+: [Ne]
Ca: [Ar]4s2 Ca2+: [Ar]
Al: [Ne]3s2 3p1 Al3+: [Ne]
As it appears, all configuration becomes similar to the previous noble
gas configuration.
 Cations derived from elements that its upper subshell is “d”
Electrons of cations formed from atoms having “d” as its upper subshell
are removed from the upper subshell having the bigger principle
quantum number. The electron configurations of some atoms and their
corresponding cations are as follows:
Ti: [Ar]4s2 3d2 Ti2+: [Ar]3d2

35
 Fe: [Ar] 4s2 3d6 Fe3+: [Ar]3d5
Zn: [Ne]4s2 3d10 Zn2+: [Ne]3d10

Example 2.5
Write the electron configuration of the following:
A) 16S 2– B) 27Fe3+
Solution
A) 16S 2– has 18 electrons, (16 electrons + 2 electrons):
1s 2 2s 2 2p6 3s 2 3p6
B) 26Fe3+ has 23 electrons, (26 electrons – 3 electrons):
First: we write the electron configuration of the Fe atom:
1s 2 2s 2 2p6 3s 2 3p6 4s 2 3d7
Second: we identify which subshell is in the highest “n” quantum number to
find that it is 4s which has two electrons. These two electrons and a third
electron from the 3d electrons are removed to form Fe3+ cation having the
following electron configuration
1s 2 2s 2 2p6 3s 2 3p6 3d6
Practice exercise
Write the electron configuration of the following:
A) 15P 3– B) 31Ga3+

2.6 The periodic table of elements

The way electrons are distributed makes element so easy to be arranged
depending on the way the electrons of their atoms are distributed. Simply,
after knowing how electrons are distributed chemists became able to arrange
all elements in a systematic meaningful way called “the periodic table of
elements”.
2.6.1 Blocks, groups and periods
Blocks: The way electrons are distributed reveals that electrons in the highest
energy orbitals belong to a specified subshell, either “s”, “p”, “d”, or “f”. This
fact enables chemists to distribute elements into four blocks:
 s-block elements
 p-block elements
 d-block elements
 f-block elements
Groups: The way electrons are distributed reveals that number of electrons
in any subshell varies from an atom of an element to another atom of another
element. This fact enables chemists to distribute elements of each block into

36
a number of groups equals the maximum number of electrons for each
subshell:
 s-block elements are in two groups
 p-block elements are in six groups
 d-block elements are in ten groups
 f-block elements are in fourteen groups
The International Union of Pure and Applied Chemistry (IUPAC) has
recommended numbering the columns (groups) sequentially with Arabic
numerals 1 through 18. According to the type of subshell being filled, the
elements can be divided into four categories:

1) The representative elements:

The representative elements (also called main group elements) are the
elements in Groups 1A through 7A, all of which have incompletely filled
s or p subshells of the highest principal quantum number
2) The noble gases:
With the exception of helium, the noble gases (the Group 18 elements) all
have a completely filled p subshell. (The electron configurations are 1s2
for helium and ns2 np6 for the other noble gases, where n is the principal
quantum number for the outermost shell.)

37
 3) The transition elements (or transition metals):
The transition metals are ten groups the Groups from groups 3 to group 12.
These metals are sometimes referred to as the d -block transition elements.
4) The lanthanides and the actinides:
The lanthanides and actinides are sometimes called f -block transition
elements because they have incompletely filled f subshells.
Periods: The way electrons are distributed reveals that number of electrons
in any shell varies according to the shell principal quantum number, n. This
fact enables chemists to put elements that having the same highest principal
quantum number beside each other starting from left to right with the element
having only one electron at the far left and ending at the far right with the
element having the maximum number of electrons that can be accommodated
by the shell. This lead to arranging elements in seven rows called “periods”
designated as “period 1, “period 2”, “period 3”, …to “period 7”.

Example 2.6
For each of the four elements having the following atom numbers, determine the
block, the period, the group and the group name:
A) 9 B) 10 C) 12 D) 30
Solution
Answering the question requires writing the electron configuration of each:
A) 1s 2 2s 2 2p5
B) 1s 2 2s 2 2p6
C) 1s 2 2s 2 2p6 3s 2
D) 1s 2 2s 2 2p6 3s 2 3p6 4s 2 3d10
A B C D
Block p p p d
Period 2 2 3 4
Group 17 18 2 12
Group name Halogen Noble gases Alkali earth No group name
Practice exercise
For each of the four elements having the following atom numbers, determine the
block, the period, the group and the group name:
A) 8 B) 17 C) 19 D) 40

2.6.2 Periodic variation in physical properties

 Atomic radius
The atomic radius is one-half the distance between the two nuclei in two
adjacent metal atoms or in a diatomic molecule.

38
The figure above shows that:
 The atomic radius of elements decreases from left to wright because
number of electrons in the same shell increases from left to right making
stronger attractions and diminishing radius.
 The atomic radius of elements increases from up to down because the same
number of electrons is occupying a principal quantum number which its
distance from the nucleus increases from up to down.
 Atomic ionization energy

The atomic ionization energy is the energy needed to remove electrons

from the atom. If more than one electron is removed we will have “the first
ionization energy”, the “second ionization energy”, and so on. Ionization

39
 energy increases as the atomic radius decreases. Therefore, ionization
energy increases from right to left and from down to up.
 Atomic electron affinity

The electron affinity is the energy absorbed or released as a result of

attracting electron to an atom. The electron affinity increases as the atomic
radius decreases. Therefore, electron affinity increases from left to wright
and from down to up.

Example 2.7
A) Which is bigger in radius, the element 3X or the element 9Y? rationalize.
B) Which is higher in ionization energy, the element 19X or the element 34Y?
rationalize.
C) Which is higher in electron affinity, the element 12X or the element 38Y?
rationalize.
Solution
A) Answering the question requires writing the electron configuration of each:
3
X: 1s 2 2s1
9
Y: 1s 2 2s 2 2p5
Because their upper shell is the same (n = 2) and, in 3X, is occupied be less
number of electrons than in 9Y, then the bigger in radius is 9Y.
B) Answering the question requires writing the electron configuration of each:
19
X: 1s 2 2s 2 2p6 3s 2 3p6 4s1
34
Y: 1s 2 2s 2 2p6 3s 2 3p6 4s 2 3d6 4p4
Because their upper shell is the same (n = 4) and, in 19X, is occupied be less
number of electrons than 34Y, then the bigger in radius is 19 X. As a result,
ionizing 34Y is harder than ionizing 34Y making its ionization energy higher.

40
C) Answering the question requires writing the electron configuration of each:
12
X: 1s 2 2s 2 2p6 3s 2
38
Y: 1s 2 2s 2 2p6 3s 2 3p6 4s 2 3d10 4p6 5s 2
Because the upmost electrons of 12X are closer to nucleus than those of 38Y,
then the bigger in radius is 38Y. As a result, attracting an electron by 12X is
stronger than that by 38Y making its electron affinity higher than that of 12 X.
Practice exercise
A) Arrange the element 14X, 17Y and 35Z in decreasing ionization energy.
B) Arrange the element 11X, 12Y and 19Z in decreasing electron affinity.

2.7 Molecules and ions

Only the noble gases (group 18) of the periodic table (He, Ne, Ar, Kr, Xe, Rn,
and Og) exist as single atoms. This why they are called monatomic gases.
Most matter is composed of molecules or ions formed from atoms.
2.7.1 Molecules
A molecule is at least two atoms in a definite arrangement held together by
chemical bonds. Molecules are electrically neutral. A molecule may contain
atoms of the same element such as H2, O2 and O3, or atoms of two or more
elements bonded in a fixed ratio such as H2O, Na2SO4. Thus, a molecule is
not necessarily a compound made up of two or more elements. The hydrogen
molecule, H2, is called a diatomic molecule because it contains only two
atoms. Other elements that normally exist as diatomic molecules are N2, O2,
F2, Cl2, Br2 and I2. Of course, a diatomic molecule can contain atoms of
different elements. Examples are HCl, CO). The vast majority of molecules
contain more than two atoms and called polyatomic molecules. Examples of
polyatomic molecules are O3, H2O and Na3PO4.
2.7.2 Ions and ionic compounds
An ion is an atom or a group of atoms that has a positive or negative charge.
 Positive ions (Cations): Loss of electrons by an atom is the reason behind
the positive charges of cations. The number of positively charged protons
in the nucleus of an atom remains the same but negatively charged
electrons become less. For example, a sodium atom (Na) has 11 protons
and 11 electrons can lose an electron to become a sodium cation (Na+).
Other examples are in the table below.

Hydrogen H+ Chromium Cr 3+
Lithium Li+ Manganese(II) Mn2+
Sodium Na+ Iron(II) Fe2+
Potassium K+ Iron(III) Fe3+

41
 Cesium Cs + Cobalt(II) Co2+
Rubidium Rb+ Copper(I) Cu+
Magnesium Mg 2+ Copper(II) Cu2+
Calcium Ca2+ Zinc Zn2+
Strontium Sr 2+ Silver Ag +
Barium Ba2+ Cadmium Cd2+
Aluminum Al3+ Mercury(I) Hg 2+
2
Tin Sn2+ Mercury(II) Hg 2+
Lead(II) Pb2+ Ammonium NH4+

The above table shows that two or more atoms can combine to form cations
that has a net positive charge; these ions are classified as polyatomic
cations such as H3 O+ (hydronium), NH4+ (ammonium) and PH4+
phosphonium.
 Negative ions (Anions): Gain of electrons by an atom is the reason behind
the negative charges of anions. The number of positively charged protons
in the nucleus of an atom remains the same but negatively charged
electrons become more. The following table shows many positive ions. For
example, a chlorine atom (Cl) has 17 protons and 17 electrons can gain an
electron to become a chloride anion (Cl– ). Other examples are in the table
below.

Hydride H−
Nitride N 3−
Oxide O2−
Peroxide 𝑂22−
Sulfide S 2−
Fluoride F−
Chloride Cl−
Bromide Br −
Iodide I−
Hydroxide OH −
Cyanide CN −
Hydrogen
Carbonate CO3− carbonate HCO2−
3
(bicarbonate)
Hydrogen
Phosphate PO3− HPO2−
4 phosphate 4

42
 Nitrate NO−
3 Nitrite NO−2
Sulfite SO2−
3
Sulfate SO2−
4 Hydrogen sulfate
HSO−
(bisulfate) 4

Chlorate ClO3− Chlorite ClO2−

Chromate CrO2−
4 dichromate Cr2 O2−
7

The above table shows that two or more atoms can combine to form anions
that has a net negative charge; these ions are classified as polyatomic
anions such as OH– (hydroxide ion), CN– (cyanide ion) and NO–3 (nitrate).
 Ionic compounds: The chemical substances that are formed from positive
ions and negative ions are called ionic compounds. For example, sodium
chloride (NaCl), ordinary table salt, is an ionic compound because it is formed
from sodium cations, Na+, and chloride anions, Cl– . The positive ions (the
cations) in ionic compounds are metals such as sodium, calcium, iron…etc.
Also, there are some positive ions that are not metals such as those listed on a
previous table namely H3 O+ (hydronium), NH4+ (ammonium) and PH4+
phosphonium. On the other hand, the negative ions (the anions) are nonmetals
such as nitride, oxide and flouride…etc. Also, there are many negative ions
that are not nonmetals such as those listed on a previous table, examples are
3–
CO3− (carbonate), SO2–4 (sulfate) and PO4 (phosphate).
 Naming ionic compounds: The previous tables gives the names of many
cations and anions.
 For compounds formed from just two elements (binary compounds) and
for compounds formed from more than two elements, the name starts with
name of cation followed by the name of the anion. Examples are:
KBr is potassium bromide
ZnF2 is zinc fluoride
Al2O3 is aluminum oxide
LiOH is lithium hydroxide
Na3N is sodium nitride
KCN is potassium cyanide
Na3N is sodium nitride
Ca(CN)2 is calcium cyanide
Mg(OH)2 is magnesium hydroxide
 Cations of many transition metals can form more than one type of cation.
Iron can form two cations: Fe3+ and Fe2+. The old nomenclature system
assigns “-ic” and “-ous”:

43
  The ending “-ic” to the cation with more positive charges: Fe3+ is ferric
ion as in ferric chloride, FeCl3.
 The ending “-ous” to the cation with fewer positive charges: Fe2+ is
ferrous ion as in ferrous chloride, FeCl2.
The new nomenclature system done by the German chemist Stock, assigns
the Roman numeral:
“I” means one positive charge
“II” means two positive charges
“III” means three positive charges
“IV” means four positive charges
The following are examples:
FeCl2 is iron(II) chloride
FeCl3 is iron(III) chloride
MnO is manganese(II) oxide
Mn2O3 is manganese(III) oxide
MnO2 is manganese(IV) oxide

EXAMPLE 2.8
Name the following compounds:
A) Cu(NO3)2 B) KH2PO4 C) NH4ClO3
Solution
A) The nitrate anion (NO–3 ) has only one negative charge, so the copper cation must
have two positive charges: the compound copper(II) nitrate.
B) The cation is potassium ion and the anion is dihydrogen phosphate: the
compound is potassium dihydrogen phosphate.
A) The cation is ammonium ion and the anion is chlorate: the compound is
ammonium chlorate.
Practice Exercise
Name the following compounds:
A) PbO B) Li2SO3 C) Mn(SO4)2

EXAMPLE 2.9
Write chemical formulas for the following compounds:
A) mercury(I) nitrite B) cesium sulfide C) calcium phosphate
Solution
A) The mercury ion has one positive charge, but mercury(I) ion exists as diatomic
(that is, Hg 2+ –
2 ) and the anion is the nitrite ion (NO2 ): the formula is Hg2(NO2)2.
B) Sulfide ion has two negative charges, and cesium ion has one positive charge:
the formula is Cs2S.

44
C) The calcium ion has two positive charges (Ca2+), and phosphate ion is PO3–
4 : the
formula is Ca3(PO4)2.
Practice Exercise
Write formulas for the following ionic compounds:
A) rubidium sulfate B)) barium hydride C) aluminum carbonate

2.7.3 Molecules and molecular compounds

A molecule is an electrically neutral entity consisting of more than one atom.
Molecules are usually composed of nonmetallic elements. Molecular compounds
consisting of two different elements are binary compounds while those consisting of
three different elements are tertiary compounds.
 Naming binary molecular compounds: Binary molecular compounds are
named similarly as binary ionic compounds by placing the name of the first
element in the formula first, and the second element is named by adding -ide to
the root of the element name. Some examples are:
 “HCl” is hydrogen chloride
 “HBr” is hydrogen bromide
 “SiC” silicon carbide.
There are some cases where two elements form several different compounds (C
and O form CO and CO2); in such cases Greek prefixes are used to denote the
number of atoms of each element presents. The table below shows these Greek
prefixes.

Mono- Di- Tri- Tetra- Pent- Hexa- Hepta- Octa- Nona- Deca-
1 2 3 4 5 6 7 8 9 10

The following are some examples:

 “CO” is carbon monoxide and “CO2” is carbon dioxide
 “SO2” is sulfur dioxide and “SO3” is sulfur trioxide
 “NO2” is nitrogen dioxide and “N2O4” is dinitrogen tetroxide
The following guidelines are helpful in naming compounds with prefixes:
1. The prefix “mono-” may be omitted for the first element. This absence of a
prefix for the first element means that there is only one atom of that element
in the molecule:
For example, PCl3 is phosphorus trichloride not monophosphorus trichloride
2. For oxides, the ending “a” in the prefix is usually omitted. For example, N2O4
is dinitrogen tetroxide rather than dinitrogen tetraoxide.
3. Writing formulas for molecular compounds is usually straightforward. Thus,
the name “arsenic trifluoride” means that there are three “F” atoms and one

45
 “As” atom in each molecule, and the molecular formula is “AsF3”. Note that
the order of elements in the formula is the same as in its name.
4. Compounds containing hydrogen are named exceptionally. Many of them are
called by their common and nonsystematic names or by names that do not
indicate the number of hydrogen atoms. In some formulas, hydrogen is written
first not like other were it is written last. The following are some examples:
 B2H6 is diborane not diboron hexahydride
 CH4 is methane not carbon tetrahydride
 SiH4 is silane not silicon tetrahydride
 NH3 is ammonia not nitrogen triahydride
 PH3 is phosphine not phosphorus triahydride
 H2O is water not dihydrogen oxide
 H2S is hydrogen sulfide not dihydrogen sulfide

EXAMPLE 2.10
Name the following molecular compounds:
A) SiCl4 B) P4O10.
Solution
A) There are one silicon atom and four chlorine atoms: the compound is silicon
tetrachloride.
B) There are four phosphorus atoms and ten oxygen atoms: the compound is
tetraphosphorus decoxide.
Practice Exercise
Name the following molecular compounds:
A) NF3 b) Cl2O7

EXAMPLE 2.11
Write chemical formulas for the following molecular compounds:
A) carbon disulfide B) disilicon hexabromide
Solution
A) There are one carbon atom and two sulfur atoms: the formula is CS2.
B) There are two silicon atoms and six bromine atoms: the formula is Si2Br6.
Practice Exercise
Write chemical formulas for the following molecular compounds:
A) sulfur tetrafluoride B) dinitrogen pentoxide

2.7.2 Acids and bases

 Acids: An acid is a substance that has hydrogen atoms in its composition and
give them as ions, H+ when dissolved in water. Also, acids are defined as

46
 substances that increases hydrogen ions concentration of water, [H+], when
dissolved in it. When a hydrogen atom loses its electron all left is a proton.
Therefore, “H+” is also called “proton”. Acids are classified to two types:
 Naming binary acids: The following table gives the names anions which
ends with the suffix “-ide”:

Sulfide Fluoride Chloride Bromide Iodide Cyanide

S 2− F− Cl− Br − I− CN −

When one hydrogen ion (or more) is attached to any anion in the above
table, the molecular compound formed is named as follows:

Hydrogen Hydrogen Hydrogen Hydrogen Hydrogen Hydrogen

sulfide fluoride chloride bromide iodide cyanide
H2 S HF HCl HBr HI HCN

The aqueous solution of any one of these compounds is a binary acid and
it is named as the following table shows:

Hydrosulfuric Hydrochlori Hydrofluoric Hydrobromi Hydroiodic Hydrocyanic

acid c acid acid c acid acid acid
H2 S HF HCl HBr HI HCN

 Naming oxacids:
First: The names of oxoanions which ends with the suffix “-ate”:

Nitrate Carbonate Sulfate Phosphate Fluorate Chlorate Bromate Iodate

NO−3 CO2−
3 SO2−
4 PO3−
4 FO−
3 ClO−3 BrO−
3 IO−
3

When one hydrogen ion (or more) is attached to any anion listed in the
above table, the compound formed is an oxoacid named as follows:

Nitric Carbonic Sulfuric Phosphoric Fluoric Chloric Bromic Iodic

acid acid acid acid acid acid acid acid
HNO3 H2 CO3 H2 SO4 H3 PO4 HFO3 HClO3 HBrO3 HIO3

The last four acids are called “halic acids” because of the presence of
“halogen atoms”.

47
 All these acids in the table are called “the reference oxoacids” because
some other oxoacids are derived from them. This derivation comes from
adding or removing one or two oxygen atoms to the reference acid:
1. Addition of one “O” atom to a halic acid:
The addition of one “O” atom to a halic acid gives an acid called
“perhalic” acid. Thus, adding an “O” atom to (HFO3) changes chloric
acid to perfluoric acid (HFO4).
2. Removal of one “O” atom from the halic acid:
The removal of one “O” atom from the halic acid gives an acid called
“halous” acid. Thus, removing an “O” atom from (HFO3) changes
fluoric acid to fluorous acid (HFO2). There are other acids end with “-
ous”:
 Nitrous acid (HNO2 ) derived from nitric acid (HNO3 )
 Sulfurous acid (H2 SO3 ) derived from sulfuric acid (H2 SO3 )
 Phosphorous acid (H3 PO3 ) derived from phosphoric acid (H3 PO4 )
3. Removal of two “O” atoms from the “halic” acid:
The acid is called “hypohalous” acid. Thus, removing two O atoms
from (HFO3) changes fluoric acid to hypofluorous acid (HClO). There
are other acids end with “-ous”:
 Hyposulfurous acid (H2SO2) derived from sulfuric acid (H2SO4)
 Hypophosphorous acid (H3PO2) derived from phosphoric acid
(H3PO4).
Second: The names of oxoanions which ends with the suffix “-ite”:

Nitrite Sulfite Phosphite Fluorite Chlorite Bromite Iodite

NO−3 SO2−
4 PO2−
4 FO−3 ClO−
3 BrO−
3 IO−
3

When one hydrogen ion (or more) is attached to any anion listed in the
above table, the compound formed is an oxoacid named as follows:

Nitrous Sulfurous Phosphorous Fluorous Chlorous Bromous Iodous

acid acid acid acid acid acid acid
HNO3 H2 SO4 H3 PO4 HFO3 HClO3 HBrO3 HIO3

Third: Removal of hydrogen ions from some oxacids:

The names of anions in which one or more but not all the hydrogen
ions have been removed must indicate the number of remaining
hydrogen ions. For example:

48
  The removal of one hydrogen ion from phosphoric acid
(H3PO4) produces the ion H2PO–4 , the name of this ion is
dihydrogen phosphate.
 The removal of two hydrogen ion from phosphoric acid
(H3PO4) produces the ion HPO2– 4 , the name of this ion is
hydrogen phosphate.
Finally, the following table gives the names and formulas of the oxacids and
oxanions discussed above:

Oxacid Oxanion
Name Formula Name Formula
Nitric acid HNO3 Nitrate ion NO−3
Nitrous acid HNO2 Nitrite ion NO−2
Carbonic acid H2CO3 Carbonate ion CO2−
3
Sulfuric acid H2SO4 Sulfate ion SO42−

Sulfurous acid H2SO3 Sulfuite ion SO2−

3
Phosphoric acid H3PO4 Phosphate ion PO2−
4
Phosphorous acid H3PO3 Phosphite ion HPO2− 3
−
Perfloric acid HFO4 Perflorate ion FO4
Perchloric acid HClO4 Perchlorate ion ClO−4
Perbromic acid HBrO4 Perbromate ion BrO− 4
Periodic acid HIO4 Periodate ion IO−
4
Floric acid HFO3 Florate ion FO−3
Chloric acid HClO3 Chlorate ion ClO−3
Bromic acid HBrO3 Bromate ion BrO− 3
Iodic acid HIO3 Iodate ion IO−
3
Florous acid HFO2 Florite ion FO−2
Chlorous acid HClO2 Chlorite ion ClO−2
Bromous acid HBrO2 Bromite ion BrO− 2
Iodous acid HIO2 Iodite ion IO−
2
Hypoflorous acid HFO Hypoflorite ion FO−
Hypochlorous acid HClO Hypochlorite ion ClO−
Hypobromous acid HBrO Hypobromite ion BrO−
Hypoiodous acid HIO Hypoiodite ion IO−

EXAMPLE 2.12
Name the following oxoacid and oxoanion:
A) H3PO3 B) IO–4

49
Solution
A) The reference acid is phosphoric acid (H3PO4). Because H3PO3 has one
fewer O atom, it is phosphorous acid.
B) The reference acid is chloric acid (HIO3). Because the acid HIO4 has one
more O atom than our reference acid, it is called periodic acid and its
oxanion, IO–4 , is periodate ion.
Practice Exercise
Name the following oxoacid and oxoanion:
A) HBrO B) HSO–4 .

 Bases: A base is a substance that yields hydroxide ions (OH–) when dissolved
in water. Some examples are NaOH, KOH and Ba(OH)2. These compound are
named as ionic compounds are named. The name start with metal name snd
ends with the anion name which is hydroxide. Therefore, the names of the
previous three bases are sodium hydroxide, potassium hydroxide and barium
hydroxide respectively.
Ammonia (NH3) is a very famous base but it does not have OH– in its formula.
It is a molecular compound in its gaseous state or when it is a pure. When NH3
is dissolved in water, it reacts partially with water to yield NH4+ and OH– ions:

NH3 + H2O ⇌ NH4+ + OH–

Thus, its aqueous solution is properly classified as a base.

2.7.3 Hydrates
Hydrates are compounds that have a specific number of water molecules
attached to them. For example, in its normal state, each unit of copper(II) sulfate
has five water molecules associated with it. The systematic name for this
compound is copper(II) sulfate pentahydrate. Its formula is written as:

CuSO4·5H2O

The water molecules can be driven off by heating. When this occurs, the resulting
compound is CuSO4, which is named copper sulfate and sometimes called
anhydrous copper(II) sulfate. The word “anhydrous” means that the compound
no longer has water molecules associated with it. Some other hydrates are:
BaCl2·2H2O, LiCl·H2O, MgSO4·7H2O and Sr(NO3)2·4H2O. the names of the
previous hydrates are barium chloride dehydrate, lithium chloride monohydrate,
magnesium sulfate heptahydrate and strontium nitrate tetrahydrate
2.7.4 Familiar inorganic compounds

50
There are several compounds acquired their names since remote human history,
or have names that are so common among people worldwide and among
chemists. These compounds kept their common names. The following table gives
the formula and their common and systematic names.

51
 3. STOICHIOMETRY AND CHEMICAL EQUATIONS
3.1 Atomic mass unit, Avogadro’s number and the mole
3.1.1 Atomic mass unit
The unit used to express the mass of atoms, molecules and nuclear particles is
called the “atomic mass unit”, abbreviated “amu”; it is also called “Dalton”.
1
The atomic mass unit is the of mass which equals to the mass of a single
12
atom of carbon isotope 12C. As expected, its value is so small when compared
with the unit “gram”:

1 amu = 1.993 × 10–23 g

The atomic mass units (amu) provide a relative scale for the masses of the
elements. But because this mass is extremely small, no usable scale can be
devised to weigh the masses of atoms, molecules and nuclear particles.
3.1.2 Avogadro’s number
In any real situation, we deal with macroscopic samples containing enormous
numbers of atoms. Therefore, it is convenient to have a special unit to describe
a very large number of atoms. The idea of a unit to denote a particular number
of objects is not new. For examples of familiar units are: the pair = 2 items,
the dozen = 12 items. In 1811 a brilliant idea was provided by The Italian
scientist, Avogadro (1776 – 1856). The idea is that if we express the atomic
mass of an element in the unit of “gram” rather than in the unit of “amu” we
will have the same number of atoms regardless of the type of the element we
chose. Avogadro died before achieving his goal to determine this number.
However, the value was first determined in 1865 by the Austrian scientist
Josef Loschmidt. This number was named “Avogadro’s number” by the
French scientist Jean Perrin. In its present definition Avogadro’s number, NA,
is the number of carbon-12 atoms in 0.012 kg of carbon-12 isotope. Its
currently accepted value is
NA = 6.0221415 × 1023 = 6.022 × 1023
Thus, just as one dozen oranges contains 12 oranges, 1 mole of oranges
contains 6.022 × 1023 oranges. And as one dozen of hydrogen atoms contains
12 of H atoms, 1 mole of hydrogen atoms contains 6.022 × 1023 H atoms. The
enormity of Avogadro’s number is difficult to imagine. For example,
spreading 6.022 × 1023 oranges over the entire surface of Earth would produce
a layer of no less than 14 km into space!
3.1.3 The mole

52
 The mole (mol) is the amount of a substance that contains Avogadro’s number
of its particles (atoms, molecules, ions or any other particles). So, having one
mole of atoms, oranges or anything means having Avogadro’s number of
atoms, oranges or anything. We usually give the symbol “N” for the number
of particles we have. The value of “N” may equal Avogadro’s number, more
than Avogadro’s number or less than Avogadro’s number.
The mole is chosen as the SI unit for the “amount of substance”. The IUPAC
definition of the mole is that the mole is the amount of substance of a system
which contains as many elementary entities as there are atoms in 0.012
kilogram of carbon-12. When the mole is used, the elementary entities must
be specified and may be atoms, molecules, ions, electrons, other particles, or
specified groups of such particles.
3.1.3 The molar mass of an element
We have seen that 1 mole of carbon-12 atoms has a mass of exactly 12 g and
contains 6.022 × 1023 atoms. This mass (12 g) of carbon-12 is its molar mass
(M). Molar mass is defined as The mass (in grams or kilograms) of one mole
of units (such as atoms, molecules or ions) of a substance. Note that the
molar mass of carbon-12 (in grams) is numerically equal to its atomic mass in
amu. Likewise, the atomic mass of sodium is 22.99 amu and its molar mass is
22.99 g/mol, the atomic mass of phosphorus is 30.97 amu and its molar mass
is 30.97 g/mol and so on. Knowing the molar mass and Avogadro’s number,
we can calculate the mass of a single atom in grams. For example, we know
the molar mass of carbon-12 is 12.00 g and there are 6.022 × 1023 carbon-12
atoms in 1 mole of the substance; therefore, the mass of one carbon-12 atom
is calculated as follows:

12.00 g carbon−12 atoms

the mass of one carbon-12 atom = = 1.993 × 10–23 g
6.022 × 1023 carbon−12 atoms

It is very important to know the mathematical relations between “M”, “m”,

“n”, “N” and “NA”.
M = Molar mass of a substance in g/mole units (or kg/mole units)
m =Mass of a substance in g units (or kg units)
n = Number of moles of a substance
N = Number of particles (atoms, molecules or ions, …) of a substance
NA = Avogadro’s number
The relations between all of the above are:
m N m N
n= n= =
M NA M NA

53
 We can close this discussion saying that the above three equations ar so
important and are needed almost in all chemical calculations:

EXAMPLE 3.1
Helium (He) is a valuable gas used in industry, low-temperature research, deep-
sea diving tanks, and balloons. How many moles of He atoms are in 6.46 g of He?
Solution
m 6.46 g
n= = g = 1.61 mol
M 4.003
mol
Practice Exercise
How many moles of magnesium (Mg) are there in 87.3 g of Mg?

EXAMPLE 3.2
Zinc (Zn) is a silvery metal that is used in making brass (with copper) and in
plating iron to prevent corrosion. How many grams of Zn are in 0.356 mole of Zn?
Solution
m = n × M = 0.356 mole × 65.39 g/mol = 23.3 g
Practice Exercise
Calculate the number of grams of lead (Pb) in 12.4 moles of lead.

EXAMPLE 3.3
Sulfur (S) is a nonmetallic element that is present in coal. When coal is burned,
sulfur is converted to sulfur dioxide and eventually to sulfuric acid that gives rise
to the acid rain phenomenon. How many atoms are in 16.3 g of S?
Solution
m N
=
M NA

16.3 g N
g = atoms
32.07
mol
6.022 × 1023
mol

atoms
16.3 g × 6.022 × 1023
N= g
mol
= 3.06 × 1023 atoms
32.07
mol
Practice Exercise
Calculate the number of atoms in 0.551 g of potassium (K).

3.1.4 Molecular Mass and formula mass

Molecular mass

54
 We know that “H2O” is the formula water. Therefore, the mass of one mole
of water is the sum of the mass, in “amu” unit or in “g” unit, of two moles of
hydrogen atoms and one mole of oxygen atoms:

The molar mass of H2O = 2 × (atomic mass of H) + 1 × atomic mass of O

The molar mass of H2O = 2 × (1.008 amu) + 1 × (16.00 amu) = 18.016 amu
g g g
The molar mass of H2O = 2 × (1.008 ) + 1 × (16.00 ) = 18.016
mol mol mol

Now, because this molar mass of water is the mass of one mole of water and
because water consists of molecules, this mass is also called “the molecular
mass”

EXAMPLE 3.4
Calculate the molecular masses (in amu) of the following compounds:
A) Sulfur dioxide (SO2) B) Caffeine (C8H10N4O2).
Solution
A) MSO2 = 1 × 32.07 amu + 2 × 16.00 amu = 64.07 amu
B) MC8H10N4O2 = (8 × 12.01 amu) + (10 × 1.008 amu) + (4 × 14.01 amu) + 2 ×
16.00 amu = 194.20 amu
Practice Exercise
What is the molecular mass (in amu) of methanol (CH4O)?

From the above discussion we conclude that using the unit “amu” or the the
g
unit “ ” gives the same numerical value of the molar mass of the substance.
mol
Also, we conclude that the term “molar mass” applies for atomic, ionic and
molecular substances, whereas the term “molecular mass” applies only for
molecular substances

EXAMPLE 3.5
Methane (CH4) is the principal component of natural gas. How many moles of CH4
are present in 6.07 g of CH4?
Solution
m 6.07 g
n= = g g = 0.378 mol
M 1 × 12.01 + 4 × 1.008
mol mol
Practice Exercise
Calculate the number of moles of chloroform (CHCl3) in 198 g of CHCl3.

55
 The example below shows that a knowledge of the molar mass enables us to
calculate the numbers of moles of individual atoms in a given quantity of a
compound.

EXAMPLE 3.6
How many hydrogen atoms are present in 25.6 g of urea [(NH2)2CO], which is
used as a fertilizer, in animal feed, and in the manufacture of polymers? The molar
mass of urea is 60.06 g/mol.
Solution
m N
=
M NA
m × NA
N=
M
Nhydrogen atoms = 4 × Nurea molecules
atoms
m × NA 25.6 g × 6.022 × 1023
Nhydrogen atoms = 4 × =4× g
mol
= 1.03 × 1024 H atoms
M 60.06
mol
Practice Exercise
How many H atoms are in 72.5 g of isopropanol (rubbing alcohol), C3H8O?

Formula mass
Ionic compounds like NaCl and MgO are not consist of molecules. Therefore, for
them we do not use the term molecular mass but the term formula mass. The
formula unit of NaCl consists of one Na+ ion and one Cl– ion. Thus, the formula
mass of NaCl is the mass of one formula unit:

formula mass of NaCl = 22.99 amu + 35.45 amu = 58.44 amu

Note that its molar mass is 58.44 g/mol.

3.2 Percent composition of elements in compounds

Any compound is composed of two elements or more. The mass percent of
any element in the compound is called the “percent composition of the
element in a compound” and is obtained by dividing the mass of the element
in 1 mole of the compound by the molar mass of the compound and
multiplying by 100:

n × molar mass of element

percent composition of an element = × 100
molar mass of compound

Where “n” is the number of moles of the element in 1 mole of the compound.
For example, in 1 mole of hydrogen peroxide (H2O2) there are 2 moles of H
56
 atoms and 2 moles of O atoms. The molar masses of H2O2, H, and O are 34.02
g/mol, 1.008 g/mol, and 16.00 g/mol, respectively. Therefore, the percent
composition of H and O in H2O2 is calculated as follows:
g
2 × 1.008
percent composition of H = g
mol
× 100 = 5.926%
34.02
mol
g
2 × 16.00
percent composition of O = g
mol
× 100 = 94.06%
34.02
mol

EXAMPLE 3.7
Phosphoric acid (H3PO4) is a colorless, syrupy liquid used in detergents, fertilizers,
toothpastes, and in carbonated beverages for a “tangy” flavor. Calculate the
percent composition of H, P, and O in this compound.
Solution
The molar mass of H3PO4 is 97.99 g/mol
g
3 × 1.008
percent composition of H = g
mol
× 100 = 3.086%
97.99
mol
g
1 × 30.97
percent composition of P = g
mol
× 100 = 31.61%
97.99
mol
g
4 × 16.00
percent composition of O = g
mol
× 100 = 65.31%
97.99
mol
Practice Exercise
Calculate the percent composition by mass of each of the elements in sulfuric acid
(H2SO4).

3.3 Empirical and molecular formulas

3.3.1 Empirical formulas
The empirical formula of a compound is the formula which tells us the
numerical ratios of the elements in the formula. Usually we seek the ratios
that consists of the simplest (smallest) whole numbers. The procedure to
determine the empirical formula is as follows.
 First, from qualitative chemical analysis we know the elements of the
compound.
 Second, from quanitative chemical analysis, we know the mass (or the
mass percent) of each element present in a given mass of the compound.
 Third, we convert the masses to number of moles of each element.
 Forth, we obtain the mole ratio of elements to each other.
 Finally, we find the empirical formula of the compound.

EXAMPLE 3.8
57
Ascorbic acid is composed of 40.92 percent carbon (C), 4.58 percent hydrogen
(H), and 54.50 percent oxygen (O) by mass. Determine its empirical formula.
Solution
C : H : O
40.92 g 4.58 g 54.50 g
g : g : g
12.01 1.008 16.00
mol mol mol
3.407 : 4.54 : 3.406
3.407 4.54 3.406
: :
3.406 3.406 3.406
1 : 1.33 : 1
3 : 4 : 3
The result indicates that C, H and O are in the ratio 3:4:3 and the simplest
(smallest) empirical formula for ascorbic acid C3H4O3 is.
Practice Exercise
Determine the empirical formula of a compound having the following percent
composition by mass: K: 24.75%; Mn: 34.77%; O: 40.51%.

3.3.2 Molecular formulas

4 The molecular formula is that empirical formula with actual number of each
element in the compound, but the formula calculated from percent composition
by mass is the empirical formula because the subscripts in the formula are
always reduced to the smallest whole numbers. Any multiple of the simplest
(smallest) empirical formula is by itself an empirical formula but not the
simplest (smallest). The molecular formula is one of the many empirical
formulas. To know the molecular formula (the actual formula), we must know
the molar mass or the approximate molar mass of the compound in addition to
its empirical formula. The molar mass of a compound must be the molar mass
of the simplest (smallest) empirical formula or an integral multiple of it.

EXAMPLE 3.9
A sample of a compound contains 1.52 g of nitrogen (N) and 3.47 g of oxygen
(O). The molar mass of this compound is between 90 g and 95 g. Determine the
molecular formula and the accurate molar mass of the compound.
Solution
m
n=
M
1.52 g
nN = g = 0.108 mol
14.01
mol
3.47 g
nO = g = 0.217 mol
16.00
mol
N : O

58
 0.108 : 0.217
0.108 0.217
:
0.108 0.108
1 : 2
N2O is the simplest (smallest) empirical formula for compound.
Empirical formula molar mass = 1 × 14.01 + 2 × 16.00 = 46 g/mol
g
actual molar mass 90
: mol
g ≈2
emperical molar mass 46
mol
The actual molar mass is twice the empirical molar mass. This means that
molecular formula is 2 × NO2
The molecular formula is N2O4.
Practice Exercise
A sample of a compound consisting of boron (B) and hydrogen (H) contains 6.444
g of B and 1.803 g of H. The molar mass of the compound is about 30 g. What is
its molecular formula?

3.4 Chemical reactions and chemical equations

A chemical reaction is a process in which a substance (or substances) is
changed into one or more new substances. To communicate with one another
about chemical equations, chemists have devised a standard way to represent
what happens to atoms and molecules in a chemical reaction. This way is
called The chemical-reaction equations, or simply the chemical equations
the chemical equations use chemical symbols to show what happens during
a chemical reaction.
3.4.1 Writing chemical equations
The chemical equation consists of three parts. The first part is the most
important and the most to be forgotten or ignored.
 The first part is an arrow “”
 The second part is the reactants on the left side of the arrow an arrow “”
 The third part is the products on the right side of the arrow an arrow “”
The arrow is the speaker of the equation (The narrator). It tells us what and
how much we had at the beginning and what and how much we had at the end.
Consider what happens when hydrogen gas (H2) burns in oxygen (O2) of air
forming water (H2O).
This reaction is represented by the chemical equation as:
H2 + O2  H2O
The “plus” sign means “reacts with” and the arrow tells us the story as follows:
“water is produced on the expense of consuming hydrogen and oxygen. Thus,
this symbolic expression can be read as follows:
“Molecular hydrogen reacts with molecular oxygen to produce water”
59
If we carefully look at the equation, we can notice that it violates an important
law of nature which is the law of conservation of matter. However, this
violation can be simply prevented by ensuring that number of atoms of any
element on the right and on the left sides of the arrow are equal. This can be
done by balancing the equation. The balanced equation previous reaction is:
1
2H2 + O2  H2O
2

Usually, we prefer that equation is balanced in a way that gives whole

correct numbers without fractions. So, although the last equation is correctly
balanced, we prefer the following equation:

2H2 + O2  2H2O

2H2 + O2  2H2O

Two hydrogen one oxygen Two water

+ 
molecules molecules molecules

The figure tells us that this balanced chemical equation can be read in three
different ways:
1. “2 hydrogen molecules react with 1 oxygen molecule to form 2 water
molecules.”
2. “2 moles of hydrogen molecules react with 1 mole of oxygen molecules
to produce 2 moles of water molecules.”
3. “4.016 g of H2 react with 32.00 g of O2 to give 36.016 g of H2O.”
To provide additional information, chemists often indicate the physical states
of the reactants and products by using the letters g, l, and s to denote gas,
liquid, and solid, respectively. For example:

60
 2CO(g) + O2(g)  2CO2(g)
2HgO(s)  2Hg(l) + O2(g)

To represent what happens when the solid sodium chloride (NaCl) is added to
liquid water, we write:
H2 O
NaCl(s) → NaCl(aq)

where “aq” denotes the aqueous environment. (“aqua” means “water”).

Writing H2O above the arrow symbolizes the physical process of dissolving a
substance in water, although it is sometimes left out for simplicity.
Balancing chemical equations
You can balance a chemical equation by the following steps:
1) Identify all reactants and products and write their correct formulas on the
left side and right side of the equation, respectively.
2) Begin balancing the equation by trying different coefficients to make the
number of atoms of each element the same on both sides of the equation.
3) First, look for elements that appear only once on each side of the equation
with the same number of atoms on each side: The formulas containing
these elements must have the same coefficient. Therefore, there is no need
to adjust the coefficients of these elements at this point.
Next, look for elements that appear only once on each side of the equation
but in unequal numbers of atoms. Balance these elements.
Finally, balance elements that appear in two or more formulas on the same
side of the equation.
4. Check your balanced equation to be sure that you have the same total
number of each type of atoms on both sides of the equation arrow.
 Let’s consider the following specific example:

KClO3  KCl + O2

 We balance the O atoms:

2KClO3  KCl + 3O2

 We balance the K and Cl atoms:

2KClO3  2KCl + 3O2

61
  Let’s consider another example:

C2H6 + O2  CO2 + H2O

 We balance the C atoms:

C2H6 + O2  2CO2 + H2O

 We balance the H atoms:

C2H6 + O2  2CO2 + 3H2O

 We balance the O atoms:

7
C2H6 + O2  2CO2 + 3H2O
2

 We usually prefer the coefficients as whole numbers:

2C2H6 + 7O2  4CO2 + 6H2O

EXAMPLE 3.10
When aluminum metal is exposed to air, a protective layer of aluminum oxide
(Al2O3) forms on its surface. This layer prevents further reaction between
aluminum and oxygen, and it is the reason that aluminum beverage cans do not
corrode. [In the case of iron, the rust, or iron(III) oxide that forms is too porous to
protect the iron metal underneath, so rusting continues.] Write a balanced equation
for the formation of Al2O3.
Solution
 The unbalanced equation is:
Al + O2  Al2O3
 We see that there is one Al atom on the reactants side and there are two Al
atoms on the product side. We can balance the Al atoms by placing a coefficient
of 2 in front of Al on the reactants side:
2Al + O2  Al2O3
 There are two O atoms on the reactants side, and three O atoms on the product
3
side of the equation. We can balance the O atoms by placing a coefficient of
2
in front of O2 on the reactants side:
3
2Al + O2  Al2O3
2

62
 This is a balanced equation. However, equations are normally balanced with
the smallest set of whole number coefficients. Multiplying both sides of the
equation by 2 gives whole number coefficients:
4Al + 3O2  2Al2O3
Practice Exercise
Balance the equation representing the reaction between iron(III)oxide, Fe2O3, and
carbon monoxide (CO) to yield iron (Fe) and carbon dioxide (CO2).

3.5 Amounts of reactants and products in chemical reactions

Stoichiometry is the quantitative study of reactants and products in a
chemical reaction. Stoichiometry answers questions such as:
 “How much product will be formed as a result of the reaction of a specific
amount of a reactant?”
 “How much reactant must be used in a reaction to obtain a specific amount
of a product?”
To interpret a reaction quantitatively, we need to apply our knowledge of
molar masses and the mole concept.

Whether the units given for reactants (or products) are moles, grams, liters ,
or any other units, we use the “mole method” in which the “mole” is the unit
used to calculate the amount of reactants consumed or remained and the
amount of products formed in a reaction.

For example, industrially ammonia is synthesized from hydrogen and nitrogen

as follows:

N2(g) + 3H2(g)  2NH3(g)

The stoichiometric coefficients show that one mole of N2 reacts with three
moles of H2 to form two moles of NH3. The relative numbers of moles are the
same as the number of coefficients in the balanced chemical equation. The
way of representing this fact is usually done in tables like the following table:

N2(g) + 3H2(g)  2NH3(g)

Equation coefficient  1 3 2
Equation moles  1 mole 3 mol 1 mol

63
Let’s consider a case in which 6.0 moles of H2 react completely with N2 to
form NH3. To calculate the amount of NH3 produced in moles, we comply
with the equation coefficients:

N2(g) + 3H2(g)  2NH3(g)

Equation moles 3 2
Question moles 6 mol X

6.0 mol H2
X = 2 mol NH3 × = 4.0 mol NH3
3 mol H2

Now suppose 16.0 g of H2 reacted completely with N2 to form NH3, and we

need to know number of grams of NH3 formed. We do this calculation using
the “mole method”, we note that the link between H2 and NH3 is the mole
ratio from the balanced equation. So, we need to convert grams of H2 to moles
of H2, then to moles of NH3, and finally to grams of NH3:
m
n=
M
16 g
number of moles of H2 = g = 7.94 mol H2
2.016
mol

Then we construct our table

N2(g) + 3H2(g)  2NH3(g)

Equation moles 3 2
Question moles 7.94 mol X

7.94 mol H2
X = 2 mol NH3 × = 5.29 mol NH3
3 mol H2
m=n×M
g
mass of NH3 = 5.29 mol × 17.03 = 90.1 g NH3
mol

Similarly, we can calculate the mass in grams of N2 consumed.

The general approach for solving stoichiometry problems is as follows:
Write a balanced equation for the reaction.
1) Write a balanced equation for the reaction
2) Make sure that the amounts of the substances are in the unit of moles
3) Use the mole ratio from the balanced equation to calculate the number of
moles of the substance of interest
4) Convert the calculated moles of to any other unit you like
64
EXAMPLE 3.11
The food we eat is degraded in our bodies to provide energy. The degradation of
glucose (C6H12O6) to carbon dioxide (CO2) and water (H2O) is as follows:
C6H12O6 + 6O2  6CO2 + 6H2O
If 856 g of C6H12O6 is consumed what is the mass of CO2 produced?
Solution
m 856 g
Number of moles of C6H12O6 = = g = 4.750 mol C6H12O6
M 180.2
mol
C6H12O6 + 6O2  6CO2 + 6H2O
Equation moles 1 mole 6 mol
Question moles 4.750 mol X
X = number of moles of CO2 = 6 ×number of moles of C6H12O6
number of moles of CO2 = 6 × 4.750 mol = 28.50 mol CO2
g
mass of CO2 produced = n × M = 28.50 mol × 44.01 = 1.25 × 103 g CO2
mol
Practice Exercise
Methanol (CH3OH) burns in air according to the equation
2CH3OH + 3O2  2CO2 + 4H2O
If 209 g of methanol are a combusted, what is the mass of H2O produced?

EXAMPLE 3.12
A typical reaction of alkali metals with water is that between lithium and water:
2Li(s) + 2H2O(l)  2LiOH(aq) + H2(g)
How many grams of Li are needed to produce 9.89 g of H2?
Solution
m 9.89 g
Number of moles of H2 = = g = 5 mol H2
M 2 × 1.008
mol
2Li + 2H2O  2H2O + H2
Equation moles 2 mole 1 mol
Question moles X 5 mol
5 mol H2
X = number of moles of Li = 2 mol of Li × = 10 mol
1 mol H2
g
mass of Li needed = n × M = 10 mol × 6.941 = 69.41 g
mol
Practice Exercise
A key step in photochemical smog formation is followinghe reaction between
nitric oxide (NO) and oxygen to form nitrogen dioxide (NO2):
2NO(g) + O2(g)  2NO2(g)
How many grams of O2 are consumed to produce 2.21 g of NO2?

65
3.6 Limiting reactants (reagents)
Let’s imagine that some students visiting a friend got hungry and asked him
for something to eat. Also, Let’s imagine that he has nothing except a bag
containing 11 toast breads and 4 slices of cheese. To make a sandwich two
toasts and one cheese slice is needed. If we symbolize the toast as “Ts” and
the cheese as “Ch”, the formula of the sandwich will be “Ts2Ch”:

2Ts + Ch  Ts2Ch

We know that number “Ch” available is enough to produce only 4 “Ts 2Ch”
while some of the “Ts” will remain unreacted because it is present in access.
We say that “Ch” is the reactant which limits the amount of products because
it is the one which is consumed completely and we call it “the limiting
reactant”. At the same time, we say that “Ts” is the in access reactant because
some of it will be left over or will remain unreacted.
When a chemist carries out a reaction, the reactants are usually not present in
exact stoichiometric amounts as the balanced equation requires. This is
because the goal of a reaction is to produce the maximum quantity of a useful
compound from the starting materials, frequently a large excess of one
reactant is supplied to ensure that the more expensive reactant is completely
converted to the desired product. Consequently, some reactant will be left over
at the end of the reaction. In a reaction, the reactant consumed totally with no
left over is called the limiting reactant or the limiting reagent. It is called so
because the maximum amount of product formed is limited by its amount.
Once this reactant is used up, no more product can be formed. Any reactant
presents in a quantity greater than necessary to react with the quantity of the
limiting reactant is called excess reactant or excess reagent.
To determine which reactant is the limiting reactant we follow the steps below
for the industrial synthesis of methanol (CH3OH) from carbon monoxide and
hydrogen at high temperatures.
1) If not given, write the balanced chemical equation of the reaction.
CO(g) + 2H2(g)  CH3OH(aq)
2) If not given, calculate the number of moles of the initial quantities of the
reactants (CO and H2.)
Suppose we have 4 moles of CO and 6 moles of H2
3) Divide number of moles of each reactant by its coefficient in the chemical
equation.
𝟒
For CO: =4
𝟏
𝟔
For H2: =3
𝟐

66
 4) The reactant with the least quotient is the limiting reactant, the other is the
excess reactant. Therefore, in this reaction H2 is the limiting reactant, and
CO is the excess reactant.
5) After the limiting reagent has been identified, the rest of the problem can
be solved.

EXAMPLE 3.13
637.2 g of NH3 are treated with 1142 g of CO2 to produce urea (NH2)2CO:
2NH3 (g) + CO2(g)  (NH2)2CO(aq) + H2O(l)
A) Which of the two reactants is the limiting reagent?
B) Calculate the mass of (NH2)2CO formed
C) How much excess reagent (in grams) is left at the end of the reaction?
Solution
m 637.2 g
A) number of moles of NH3 = = g = 37.416 mol
M 17.03
mol
m 1142 g
number of moles of CO2 = = g = 25.943 mol
M 44.02
mol

2NH3 + CO2  (NH2)2CO + H2O

Equation moles 2 1
Question moles 37.416 25.943
Question moles
18.708 25.943
Equation moles
B) It is clear from the above that NH3 is the limiting reagent.
2NH3 + CO2  (NH2)2CO + H2O
Equation moles 2 mol 1mol
Question moles 37.416 mole X

37.416 mol × 1 mol

X = number of moles of (NH2)2CO = = 18.708 mol
2 mol
mass of (NH2)2CO = n × M = 18.708 mol × 60.06 g/mol = 1123.6 g
C)
2NH3 + CO2  (NH2)2CO + H2O
Equation moles 2 mol 1 mol
Question moles 37.416 mole Y
37.416 mol × 1 mol
Y = number of moles of CO2 reacted = = 18.708 mol
2 mol
number of moles of CO2 remains = 25.943 mol – 18.708 mol = 7.235 mol
mass of CO2 remains = n × M = 7.235 mol × 44.02 g/mol = 318.5 g
Practice Exercise

67
The reaction between aluminum and iron(III) oxide can generate temperatures
approaching 3000 °C and is used in welding metals:
2Al(g) + Fe2O3  Al2O3 + 2Fe
In one process, 124 g of Al are reacted with 601 g of Fe2O3. (a) Calculate the mass
(in grams) of Al2O3 formed. (b) How much of the excess reagent is left at the end of
the reaction?

3.7 Reaction yield (Yield percentage)

The amount of a product that should be produced as a result of a chemical
reactions can be calculated theoretically as explained in the previous two
section (section 3.5 and section 3.6). this amount of product calculated this
way is called “the theoretical yield” of the reaction. The theoretical yield is,
the amount of product that would result if all the limiting reagent reacted. Itis
the maximum obtainable yield, and cannot be known except by calculations
on the balanced equation.
The amount of a product that is produced in reality (not theoretically) as a
result of a chemical reactions is different from the theoretical yield which our
calculations give and is called “the actual yield”. For many reasons, the actual
yield is always less than the theoretical yield. Producing an amount of product
less than what it should be is not welcomed. As the amount of actual yield get
closer to the amount of the theoretical yield as we become more satisfied and
feel much successful.
Chemists have created a criterion that could be a measure of their efficiency
and success in production of chemicals. This criterion is called “the yield
percent”, or “the yield percentage”

actual yield
%yield = × 100
theoretical yield

EXAMPLE 3.14
In an industrial operation 3.54 × 107 g of TiCl4 reacted with 1.13 × 107 g of Mg:
TiCl4(g) + 2Mg(g)  Ti(s) + 2MgCl2(l)
A) Calculate the theoretical yield of Ti
B) Calculate the percent yield if 7.91 × 106 g of Ti are actually obtained
Solution
A) First we calculate the number of moles of reactants
m 3.54 × 107 g
number of moles of TiCl4 = = g = 1.87 × 105 mol
M 189.9
mol
m 7.91 × 106 g
number of moles of Mg = = g = 4.65 × 105 mol
M 24.31
mol

68
 Second we determine the limiting reactant
TiCl4 + 2Mg  Ti + 2MgCl2
Equation moles 1 mol 2 mol
5
Question moles 1.87 × 10 4.65 × 105
Question moles
1.87 × 105 2.35 × 105
Equation moles
It is clear from the last row that TiCl4 is the limiting reagent.
Finally, we calculate the theoretical yield of Ti
TiCl4 + 2Mg  Ti + 2MgCl2
Equation moles 1 mol 1 mol
5
Question moles 1.87 × 10 mole n
1.87 × 105 mol × 1 mol
Theoretical yield of Ti = = 1.87 × 105 mol
1 mol
m = n × M = 1.87 × 105 mol × 47.88 g/mol = 8.95 × 106 g
actual yield 7.91 × 106 g
B) %yield = × 100 = × 100 = 88.37%
theoretical yield 8.95 × 106 g
Practice Exercise
Industrially, vanadium metal, which is used in steel alloys, can be obtained by
reacting vanadium(V) oxide with calcium at high temperatures:
5Ca + V2O5  5CaO + 2V
In one process, 1.54 × 10 g of V2O5 react with 1.96 × 103 g of Ca. (a) Calculate the
3

theoretical yield of V. (b) Calculate the percent yield if 803 g of V are obtained.

3.8 Some kinds of chemical reactions

3.8.1 Combination reactions
A combination reaction is a reaction in which two or more substances react to
form one product. For example, magnesium metal burns in oxygen to produce
magnesium Oxide:

2Mg(s) + O2(g)  2MgO(g)

Other examples of combination reactions are:

C(s) + O2(g)  CO2(g)

N2(g) + 3H2 (g)  2NH3(g)
CaO(s) + H2O(L)  Ca(OH)2(s)
HCl(aq) + NaOH(aq)  NaCl(aq) + H2O(l)
CuO(s) + H2O(L)  Cu(OH)2(s)

69
3.8.2 Decomposition reactions
A decomposition reaction is a reaction in which one substance undergoes a
reaction to produce two or more other substances. For example, magnesium
oxide may decompose to produce magnesium metal and oxygen:

2MgO(g)  2Mg(s) + O2(g)

Other examples of decomposition reactions are:

CaCO3(s)  CaO(s) + CO2(g)

2NaN3(s)  2Na(s) + 3N2(g)
2KClO3(s)  2KCl(s) + 3O2(g)
PbCO3(s)  PbO(s) + CO2 (g)
Cu(OH)2(s)  CuO(s) + H2O(L)

The above examples clarify that decomposition reactions are the opposites of
combination reactions.
3.8.3 Combustion reactions
Combustion reactions is a reaction in which a substance (fuel) reacts (burns)
in oxygen O2 to produce either water or carbon dioxide or both.
First: The combustion reaction of hydrogen
The combustion reaction of hydrogen gas produces water:

H2(g) + 0.5O2(g)  H2O(l)

Second: The combustion reaction of carbon

The combustion reaction of solid carbon produces carbon dioxide:

C(s) + O2(g)  CO2(g)

Third: The combustion reaction of a substance containing hydrogen and

carbon:

CH4(g) + 2O2(g)  CO2(g) + 2H2O(l)

C3H8(g) + 5O2(g)  3CO2(g) + 4H2O(l)
C2H5OH(l) + 3O2(g)  2CO2(g) + 3H2O(l)
C6H12O6(g) + 6O2(g)  6CO2(g) + 6H2O(l)
C6H5NH2(l) + 7.75O2(g)  6CO2(g) + 3.5H2O(l) + 0.5N2(g)

70
Example 3.15
Write a balanced equation for:
a) The combination reaction between lithium metal and fluorine gas.
b) The decomposition reaction that occurs when solid barium carbonate (BaCO3) is
heated (two products form, a solid and a gas).
c) The combustion reaction benzene, C6H6(L).
Solution
a) Li(s) + 0.5F2(g)  LiF(s)
b) BaCO3(s)  BaO(s) + CO2(g)
c) C6H6(g) + 7.5O2(g)  6CO2(g) + 3H2O(g)
Practice Exercise
Write a balanced equation for:
a) The combination reaction between sodium, carbon and oxygen.
b) The electrical decomposition reaction of water.
c) The combustion reaction ethanol.

71
 4. GASES

4.1 Substances that exist as gases

We live at the bottom of an ocean of air whose composition by volume is
roughly 78 percent N2, 21 percent O2, and 1 percent of CO2 and other gases.
We will focus on the behavior of substances that exist as gases under normal
atmospheric conditions which are defined as 25 °C and 1 atm (atmosphere).
4.1.1 Elements that exist as gases
The figure below shows the elements that are gases under normal conditions.
 All the elements in Group 18, the noble gases, exist as monatomic gases:
He, Ne, Ar, Kr, Xe, Rn and Og.
 These elements of hydrogen, nitrogen, oxygen, fluorine, and chlorine exist
as diatomic molecules: H2, N2, O2, F2, and Cl2.
 Ozone is another form of oxygen that exist as tritomic molecules, O3.

4.1.2 Compounds that exist as gases

Poisonous compounds such as hydrogen sulfide (H2S) and hydrogen cyanide
(HCN) and many others such as CO, NO2, O3, and SO2 are gases under normal

72
 atmospheric conditions. The following is a list of the most famous gaseous
compounds.

Name Formula Name Formula

Hydrogen fluride HF Carbon monoxide CO
Hydrogen chloride HCl Carbon dioxide CO2
Hydrogen bromide HBr Nitrogen monoxide NO
Hydrogen iodide HI Nitrogen dioxide NO2
Hydrogen cyanide HCN Dinitrogen tetroxide N2O4
Hydrogen sulfide H2S Sulfur dioxide SO2
Ammonia NH3 Sulfur trioxide SO3

4.2 Four important properties in studying gases

The following table gives the four properties of gases that are so important to
know while studying or dealing with gases:

UNITS
PROPERTY SYMBOL
SI Units Non SI Units
Amount n Mole (mol) --------------
Temperature T Kelvin (K) --------------
Pressure P Pascal (Pa) atm
Volume V Cubic meter (m3 ) Liter (L)

4.3 Atmospheric pressure

4.3.1 Definition of atmospheric pressure
The pressure of the earth atmosphere is the effect of the force (weight) of the
Earth’s atmosphere on a specified area of the Earth’s surface. If we choose an
area on the surface of our Earth that equals 1 m2, there will be above it a
column of air extending all the way up to the far end of the Earth atmosphere.
The height of this column from sea level is about 90 km. Off course. The
height of this column from the sea level is more than from Everest peak (8850
m above sea level) and less than from the level of the dead sea (423 m below
sea level).
4.3.2 Definition of standard atmospheric pressure
The pressure of the atmosphere at sea level at 273 K is called “standard
atmospheric pressure”. Its value is 101,325 Pa which equals (1 atm or 760
mmHg). It is less than this value at areas above sea level and lower than this
value at areas below sea level.

73
4.4 Standard temperature and pressure (STP)
When studying gases, we encounter the term Standard Temperature and
Pressure (STP). STP means that temperature of the gas is 0 °C (273 K) and
pressure of the gas is101325 Pa (1 atm).

4.5 The gas laws

4.5.1 The ideal gas law (The relation between n, P, V and T of an ideal gas)
The mathematical relation between the gas quantity (n), pressure(P), volume
(V) and temperature (T) is given by a famous expression called “the ideal gas
law” or simply the gas law. The gas law is written as follow:

P×V=n×R×T
R is the gas constant.
P×V
=R
n×T

This means that:

P1 × V1 P2 × V2 P3 × V3
= = =…
n1 × T1 n2 × T2 n3 × T3

74
 If we have a gas with n = 1 mole, T = 273 K, P = 101325 Pa = 1 atm it will
occupy a volume (V) that equals 22.4 × 10–3 m3 = 22.4 L. We calculate the
value of R as follows:
1) Using the SI units:
101325 Pa × 22.4 × 10−3 m3 Pa m3
R= = 8.314 Pa
1 mol × 273 K mol K
Knowing here that:
Pascal unit × Cubic meter unit = Joule unit
The value of R is as follows:

𝐉
R = 8.314
𝐦𝐨𝐥 𝐊

2) Using the non SI units:

1 atm × 22.4 L atm L
R= = 0.0821
1 mol × 273 K mol K

𝐚𝐭𝐦 𝐋
R = 0.0821
𝐦𝐨𝐥 𝐊

The main conclusion here is that the numerical value of the gas constant,
R, depends on the units of the gas pressure and volume.
4.5.2 Special cases of the gas law
𝐏𝟏 × 𝐕𝟏 𝐏 ×𝐕
= 𝟐 𝟐
𝐧𝟏 × 𝐓𝟏 𝐧𝟐 × 𝐓𝟐
Case (1) The gas law at constant quantity and temperature
(Boyle’s law)
Boyle studied the relation between the gas pressure and volume when
its quantity and temperature are kept constant (n1 = n2 and T1 = T2 ):
P1 × V1 P ×V
= 2 2
n1 × T1 n2 × T2
P1 × V1 = P2 × V2
P × V = constant
He found that as pressure increases volume decreases:
1
P∝
V
The figures below show, in different ways, the relationship between the
gas P and V at constant n and T.

75
Case (2) The gas law at constant quantity and pressure
(Charles’s and Gay Lussac’s law)
Charles and Gay Lussac studied the relation between the gas T and V
when its n and P are kept constant (n1 = n2 and P1 = P2 ):
P1 × V1 P ×V
= 2 2
n1 × T1 n2 × T2
V1 V2
=
T1 T2
V
= constant
T
They found experimentally that as absolute temperature increases
volume directly increases:
V∝T
The figure below shows this relation and that the minimum temperature
that can be reached is – 273.16 °C which equals 0 K.

76
Case (3) The gas law at constant temperature and pressure
(Avogadro’s law)
Avogadro studied the relation between the gas n and V when its T and
P are kept constant (T1 = T2 and P1 = P2 ):
P1 × V1 P ×V
= 2 2
n1 × T1 n2 × T2
V1 V2
=
n1 n2
V
= constant
n
He found experimentally that as quantity increases volume increases:
V∝n
The figure below shows, the relation between the gas n and V at
constant T and P.

Case (4) the gas law at constant amount

(The cmbined gas law)
Sometimes only n is kept constant. In this case we find:

77
 P1 × V1 P2 × V2
=
T1 T2
P×V
= constant
T
If 1 mole of a gas is at STP its volume is called the molar volume at
STP which equals 22.41 L:
L atm
n×R×T 1.0 mol × 0.0821 × 273 K
V= = K mol
= 22.41 L
P 1.0 atm
Other cases
P1 P
= 2 (at constant n and V)
T1 T2
P1 P2
= (at constant T and V)
n1 n2
n1 × T1 = n2 × T2 (at constant P and V)
P1 × V1 P ×V
= 2 2 (at constant T)
n1 n2
P1 P2
= (at constant V)
n1 × T1 n2 × T2
V1 V2
= (at constant P)
n1 × T1 T2

EXAMPLE 4.1
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
5.43 L at 69.5 °C.
Solution
Because n, V and T are all known, we can use the ideal gas equation to calculate
P:
L atm
n×R×T 1.82 mol × 0.0821 × (69.5 °C + 273) K
P= = = 9.42 atm
K mol
V 5.43 L
Practice Exercise
Calculate the volume (in liters) occupied by 2.12 moles of nitric oxide (NO) at
6.54 atm and 76 °C.

EXAMPLE 4.2
Calculate the volume (in liters) occupied by 7.40 g of NH3 at STP.
Solution
m 7.4 g
n= = g = 0.435 mol
M 17.03
mol
L atm
n×R×T 0.435 mol × 0.0821 × 273 K
V= = = 9.75 L
K mol
P 1 atm
Practice Exercise
What is the volume (in liters) occupied by 49.8 g of HCl at STP?

78
EXAMPLE 4.3
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
balloon?
Solution
P1 × V1 = P2 × V2
1 atm × 0.55 L = 0.4 atm × V2
V2 = 1.4 L
Practice Exercise
A sample of chlorine gas occupies a volume of 946 mL at a pressure of 726 mmHg.
Calculate the pressure of the gas (in mmHg) if the volume is reduced at constant
temperature to 154 mL.

EXAMPLE 4.4
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 °C is heated to
85 °C at constant volume. Calculate its final pressure.
Solution
P1 P
= 2
T1 T2
1.2 atm P2
1K = 1K
(18 °C + 273 °C) × (85 °C +273 °C) ×
1 °C 1 °C
P2 = 1.48 atm
Practice Exercise
A sample of oxygen gas initially at 0.97 atm is heated from 21 °C to 268 °C at
constant volume. What is its final pressure?

EXAMPLE 4.5
A small bubble rises from the bottom of a lake, where the temperature and pressure
are 8 °C and 6.4 atm, to the water’s surface, where the temperature is 25 °C and
the pressure is 1.0 atm. Calculate the final volume of the bubble if its initial volume
was 2.1 mL.
Solution
P1 × V1 P ×V
= 2 2
n1 × T1 n2 × T2
6.4 atm × 2.1 mL 1 atm × V2
1K = 1K
(8 °C + 273 °C) × (25 °C + 273 °C) ×
1 °C 1 °C
6.4 atm × 2.1 L × 298 K
V2 =
281 K ×1 atm

79
V2 = 14.3 mL
Practice Exercise
A gas initially at 4.0 L, 1.2 atm, and 66 °C undergoes a change so that its final
volume and temperature are 1.7 L and 42 °C. What is its final pressure? Assume
the number of moles remains unchanged.

4.5.3 Calculations of the gas density and molar mass

From the gas law, P × V = n × R × T, and from the equation “m= n × M” we
can relate the gas density to its molar mass:
m m
P×V= ×R×T and P×M= ×R×T
M V
P×M=d×R×T

Unlike molecules in liquids and solids, gaseous molecules are separated by

distances that are large compared with their size. Consequently, the density of
gases is very and are expressed in grams per liter (g/L) rather than in grams
per milliliter (g/mL).

EXAMPLE 4.6
Calculate the density of carbon dioxide (CO2) in grams per liter (g/L) at 0.990 atm
and 55 °C.
Solution
P×M=d×R×T
0.99 atm × 44.1 g/mol = d × 0.0821 atm L/mol K × (55 °C + 273) K
d = 1.62 g/L
Practice Exercise
What is the density (in g/L) of uranium hexafluoride (UF6) at 779 mmHg and 62
°C?

EXAMPLE 4.7
A chemist has synthesized a greenish-yellow gaseous compound of chlorine and
oxygen and finds that its density is 7.71 g/L at 36 °C and 2.88 atm. Calculate the
molar mass of the compound.
Solution
To calculate gas molar mass, we need the density, temperature and pressure.
P×M=d×R×T
2.88 atm × M = 7.71 g/L × 0.0821 atm L/mol K × (36 °C + 273) K
M = 67.9 g/mol
Practice Exercise

80
The density of a gaseous organic compound is 3.38 g/L at 40 °C and 1.97 atm.
What is its molar mass?

EXAMPLE 4.8
Chemical analysis of a gaseous compound showed that it contained 33.0 percent
silicon (Si) and 67.0 percent fluorine (F) by mass. At 35 °C, 0.210 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
First, we find the empirical formula and its molar mass
Si : F
33 g 67 g
g : g
28.09 19
mol mol
1.17 mol : 3.53 mol
1.17 mol 3.53 mol
:
1.17 mol 1.17 mol
1 : 3
Therefore, the empirical formula is SiF3
Molar mass of the empirical formula SiF3 = 85.09 g/mol
Second, we find the actual molar mass (molar mass of molecular formula)
m
P×M= ×R×T
V
2.38 g
1.7 atm × M = × 0.0821 atm L/mol K × (35 °C + 273) K
0.21 L
M = 169 g/mol
Third, we divide actual molar mass by the empirical molar mass,
g
m 169
= mol
g = 1.99 = 2
V 85.09
mol
The molecular formula = 2 × The empirical formula = 2 × SiF3 = Si2F6
Practice Exercise
A gaseous compound is 78.14 percent boron (B) and 21.86 percent hydrogen (H).
At 27 °C, 74.3 mL of the gas exerted a pressure of 1.12 atm. If the mass of the gas
was 0.0934 g, what is its molecular formula?

4.6 Dalton’s law of partial pressures

MOLE FRACTION
Before we discuss this law, we need to know what does the term “mole
fraction” mean.
 When more than one substance (for example, two substances “A” and “B”)
are present together, and we know the number of moles of each “nA ” and
“nB ”, this means that we know the total number of moles “nTotal ”.

81
 Now, if we divide nA or nB by nTotal the quotient will have no unit.
 This quotient represent the mole fraction of each “XA ” and “XB ”.
 Therefore, we write:

𝐧𝐀 𝐧𝐁
𝐗𝐀 = and 𝐗 𝐁 =
𝐧𝐓𝐨𝐭𝐚𝐥 𝐧𝐓𝐨𝐭𝐚𝐥

In all 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 pressures, which states that the total pressure of a mixture of gases is
just the sum of the pressures that each gas would exert if it were present alone.
The figure below illustrates Dalton’s law. Consider a case in which two gases,
A and B, are in a container of volume V at temperature T as the figure blow
shows. According to the ideal gas equation, the pressure exerted by gas A and
by gas B are:

RT
PA = nA ×
V
RT
PB = nB ×
V

Because the two gases are mixed in the same container at the same
temperature, the total pressure PTotal is:

PTotal = PA + PB
RT
PTotal = (nA + nB ) ×
V
RT
PTotal = nTotal ×
V

82
 PA nA RT RT
= × = XA ×
PTotal nTotal V V
PA = XA × PTotal
PB n RT RT
= B × = XB ×
PTotal nTotal V V
PB = XB × PTotal

EXAMPLE 4.9
A mixture of 4.46 mol of neon gas, 0.74 mol of argon gas, and 2.15 mol of xenon
gas has a total pressure of 2.00 atm. What are the partial pressures of the gases?
Solution
number of moles of the substance
Mole fraction of a substance =
number of total moles of all substances
4.46 mol
XNe = = 0.607
4.46 mol + 0.74 mol + 2.15 mol
0.74 mol
XAr = = 0.1
4.46 mol + 0.74 mol + 2.15 mol
2.15 mol
XXe = = 0.29
4.46 mol + 0.74 mol + 2.15 mol
Pressure of any gas in the mixture = its mole fraction × total pressure
PNe = 0.607 × 2 atm = 1.21 atm
PAr = 0.1 × 2 atm = 0.2 atm
PXe = 0.29 × 2 atm = 0.586 atm
Practice Exercise
A sample of natural gas contains 8.24 moles of methane (CH4), 0.421 mole of
ethane (C2H6), and 0.116 mole of propane (C3H8). If the total pressure of the gases
is 1.37 atm, what are the partial pressures of the gases?

Collecting a gas over water

83
 Frequently, chemists need to collect gases over water.
For example, when chemists need O2(g) in their labs, they heat potassium
chlorate (KClO3):
2KClO3(s) → 2KCl(s) + 3O2(g)
The produced oxygen is allowed to escape through a hose immersed in water
and a flask is flipped over it as shown in the figure below.
Of course, oxygen will not be alone in the space above water surface; water
vapor too is occupying this space. (They become roomates).
The pressure above water is the pressure of both:

PTotal = Poxygen + Pwater vapor

EXAMPLE 4.10
Oxygen gas generated by the decomposition of potassium chlorate is collected
as shown in the previous figure. The volume of oxygen collected at 24°C and
atmospheric pressure of 762 mmHg is 128 mL. Calculate the mass (in grams)
of potassium chlorate consumed. The pressure of the water vapor at 297 K is
22.4 mmHg.
Solution
Poxygen = PTotal – Pwater vapor = 762 mmHg – 22.4 mmHg = 740 mmHg
1 atm 1L
P×V 740 mmHg × × 128 mL ×
760 mmHg 1000 mL
n= = atm L = 5.11 × 10−5 mol
R×T 0.0821 × 297 K
mol K
2KClO3  2KCl + 3O2
Equation moles  2 3
Question moles  X 5.11 × 10−5

5.11 × 10–5 mol

X = number of mol KClO3 = 2 mol × = 3.41 × 10−5 mol
3 mol
g
Mass of KClO3 = n × M = 3.41 × 10−5 mol × 123.427 = 4.21 × 10−5 g
mol
Practice Exercise
Hydrogen gas generated when calcium metal reacts with water is collected as
shown in the previous figure. The volume of gas collected at 30°C and
pressure of 988 mmHg is 641 mL. What is the mass (in grams) of the
hydrogen gas obtained? The pressure of water vapor at 30°C is 31.82 mmHg.

4.7 Gas stoichiometry

When the reactants and/or products are gases, we can use the relationships
between amounts (moles, n) and volume (V) to solve such problems. The
following examples show how the gas laws are used in these calculations.

84
Example 4.11
Calculate the volume of O2 (in liters) required for the complete combustion of
7.64 L of acetylene (C2H2) measured at the same temperature and pressure.
2C2H2 (g) + 5O2(g) → 4CO2(g) + 2H2O(l)
Solution
2C2H2 (g) + 5O2(g) → 4CO2(g) + 2H2O(l)
2L 5L
7.64 L Voxyg
5 L × 7.64 L
Voxyg = = 3.056 L
2L
Practice exercise
The equation of the reaction between nitric oxide and oxygen is:
2NO(g) + O2(g) → 2NO2(g)
If 9.0 L of NO reacted with excess O2 at STP, what is the volume of the NO2
produced?

Example 4.12
Assuming no change in temperature and pressure, calculate the volume of O2
(in liters) required for the complete combustion of 14.9 L of butane (C4H10):
2C4H10 (g) + 13O2(g) → 8CO2(g) + 10H2O(l)
Solution
2C4H10 (g) + 13O2(g) → 8CO2(g) + 10H2O(l)
2L 13 L
14.9 L Voxyg
13 L × 14.9 L
Voxyg = = 96.85 L
2L
Practice exercise
Sodium azide (NaN3) is used in some automobile air bags. The impact of a
collision triggers the decomposition of NaN3 as follows:
2NaN3(g) → 2Na(s) + 3N2(g)
The nitrogen gas produced quickly inflates the bag between the driver and the
windshield and dashboard. Calculate the volume of N2 generated at 80°C and
823 mmHg by the decomposition of 60.0 g of NaN3.

Example 4.13
The equation for the metabolic breakdown of glucose (C6H12O6) is the same
as the equation for the combustion of glucose in air:
C6H12O6(s) + 6O2(g) → 6CO2(g) + 6H2O(l)

85
 Calculate the volume of CO2 produced at 37 °C and 1.00 atm when 5.60 g of
glucose is used up in the reaction.
Solution
5.6 g
nCO2 = 6 × nC6 H12O6 = 6 × g = 0.1865 mol
180.156
mol
atm L
n×R×T 0.1865 mol × 0.0821 ×(37 + 273)K
V= = mol K
= 4.75 L
P 1 atm
Practice exercise
The combustion equation of methane is:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
If 15.0 moles of CH4 are reacted, calculate the volume of CO2 produced at
23.0 °C and 0.985 atm?

4.8 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. However, it becomes so clear to physicists and chemists
that this macroscopic and sensible behavior of gases is a reflection of the
behavior of its atomic and molecular microscopic behavior that opens the door
to a deeper understanding of properties such as expansion of gases on heating.
4.8.1 The five hypotheses of the theory
In the nineteenth century, a number of physicists, notably Ludwig Boltzmann
and James Clerk Maxwell, found that the physical properties of gases can be
explained in terms of the motion of individual molecules. This molecular
movement is a kinetic energy (KE). Maxwell, Boltzmann, and others
concluded a number of generalizations about gas behavior that have since
been known as the kinetic molecular theory of gases, or simply the kinetic
theory of gases. This theory is formulated as follows:
1) A gas is composed of molecules that are separated from each other by
distances far greater than their own dimensions. The molecules can be
considered to be “points”; that is, they possess mass but have negligible
volume.
2) Gas molecules exert neither attractive nor repulsive forces on one another.
3) Gas molecules are in constant motion in random directions.
4) Gas molecules frequently collide with one another and with the walls of
the container they occupy. Collisions are perfectly elastic (this means that
energy is transferred from one molecule to another as a result of a
collision). Nevertheless, the total energy of all the molecules in a system
remains the same.

86
 5) The average kinetic energy of the molecules is proportional to the
temperature of the gas in kelvins. Any two gases at the same temperature
will have the same average kinetic energy.
The average kinetic energy of a molecule with a mass equals “m” is given by
the following equation:
1
KE = m U 2
2

U is the speed of the molecule but U 2 is the mean square speed; the bar over
U2 means that it is the average of the square of the speeds of all the molecules
and is usually given the symbol Urms which means the root-mean-square
speed of all molecules. The value of Urms can be obtained using the following
equation:

3RT
Urms = √
M

Example 4.14
Calculate the root-mean-square speeds of helium atoms and nitrogen
m
molecules in at 25°C.
s
Solution
J
3RT 3 × 8.314 × 298 K m
Urms,He = √ =√ mol K
g 1 kg = 1362.6
MHe 4.003 × s
mol 1000 g

J
3RT 3 × 8.314 × 298 K m
Urms,N2 = √ =√ mol K
g 1 kg = 515.1
M N2 28.014 × s
mol 1000 g

Practice exercise
It is found that the value of Urms of an unknown gas is 1.5 times the value of
Urms of CO2(g) at the same temperature. Calculate the molar mass of the
unknown gas.

The kinetic molecular theory of gases presents another equation to be used for
the calculation of the kinetic energy of a specified quantity of the gas. If the
quantity of the gas is one mole, its kinetic energy is called “the molar kinetic
energy”, with “KE” as its symbol:

KE = 1.5 × R × T

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 This equation enables us to calculate the average kinetic energy of only one
molecules “ke” by dividing the equation by Avogadro’s number:

KE 1.5 × R × T
ke = = = 1.5 × k × T
NA NA
ke = 1.5 × k × T

where “k” is Boltzmann constant. Both equations of kinetic energy, either of

one mole or of only one molecule of the gas, indicate that the kinetic energy
of a specified quantity of the gas depends on nothing except the temperature.
This means it’s the same for all gases as long as their amounts and
temperatures are the same.
4.8.2 Application of kinetic theory to the gas laws
 Boyle’s Law: The pressure exerted by a gas results from the impact of its
molecules on the walls of the container. The number of collisions with the
walls per second is proportional to the number of molecules per unit
volume. Decreasing the volume of the gas increases its number per unit
volume and hence number of collisions. For this reason, the pressure of a
gas is inversely proportional to the volume it occupies.
 Charles’s Law: Because the average kinetic energy of gas molecules is
proportional to its absolute temperature, raising the temperature increases
the average kinetic energy. Consequently, increasing temperature
increases number of collisions and makes collisions stronger, thus the
pressure increases, and the volume of gas will expand until the gas pressure
is balanced by the constant external pressure.
 Avogadro’s Law: We have shown that the pressure of a gas is directly
proportional to both the amount and the temperature of the gas. In
Avogadro’s law temperature and pressure must be constant. If we increase
the amount of the gas the pressure will remain constant only if the volume
increase.
 Dalton’s Law of Partial Pressures: If molecules do not attract or repel
one another, then the pressure exerted by one type of molecule is
unaffected by the presence of another gas. Consequently, the total pressure
is given by the sum of individual gas pressures.
4.8.2 Distribution of molecular speeds
Maxwell investigated the molecular motion in more detail. If we have a large
number of molecules and we hold the temperature constant, the average
kinetic energy and the mean square speed will remain unchanged. How many
molecules are moving at a particular speed? To answer this question Maxwell

88
analyzed the behavior of gas molecules at different temperatures. The
following figure show typical Maxwell speed distribution curves for nitrogen
gas at three different temperatures.

At any given temperature, the peak of the curve represents the most probable
speed, that is, the speed of the largest number of molecules at the specified
temperature. Note that the most probable speed increases as temperature
increases (the peak shifts toward the right). Furthermore, the curve also begins
to flatten out with increasing temperature, indicating that larger numbers of
molecules are moving at greater speed. The following figure shows the speed
distributions of three gases at the same temperature.

89
 The difference in the curves can be explained by noting that lighter
molecules move faster, on average, than heavier ones.

4.9 Gas diffusion and effusion

4.9.1 Gas diffusion
Diffusion is the gradual mixing of molecules of one gas with molecules of
another by virtue of their kinetic properties. Despite the fact that molecular
speeds are very great, the diffusion process takes a relatively long time to
complete because diffusion of gases always happens gradually. For example,
when a bottle of concentrated ammonia solution is opened at one end of a
lab bench, it takes some time before a person at the other end of the bench
can smell it. The following figure shows that the reason is that a molecule
experiences numerous collisions while moving from one point “A” to point
“B”:

In 1832 the Scottish chemist Thomas Graham found that under the same
conditions of temperature and pressure, rates of diffusion for gases (r) are
inversely proportional to the square roots of their molar masses. This
statement, now known as Graham’s law of diffusion:

r1 M2
=√
r2 M1

4.9.2 Gas effusion

Gas effusion is the process by which a gas under pressure escapes from one
compartment of a container to another by passing through a small opening.
The following figure the effusion of a gas into a vacuum:
90
 Although effusion differs from diffusion in nature, the rate of effusion of a
gas has the same form as Graham’s law of diffusion. 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.

Example 4.15
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
r1 M2
=√
r2 M1
V1
V1 V2 Time1 M2
r1 = and r2 = but V1 = V2 therefore, V1 =√
Time1 Time2 M1
Time2
Time2 M2
=√
Time1 M1
4.73 min 159.808
=√
1.50 min M1
159.808
(3.153)2 =
M1
g
M1 = 16.07
mol

91
 g
This gas is methane, because methane molar mass is 16.04 , methane is
mol
flammable and is formed from carbon and hydrogen.
Practice exercise
A gas evolved from the fermentation of glucose is found to effuse through a
porous barrier in 15.0 min. Under the same temperature and pressure, it takes
12.0 min for an equal volume of N2 to effuse through the same barrier.
Calculate the molar mass of the gas and suggest what the gas might be.

4.10 Deviation from ideal behavior

The gas laws and the kinetic molecular theory assume that:
1) Attractive and repulsive forces between molecules of the gas are so small
and therefore can be ignore.
2) The volume occupied by the molecules of the gas is so small and therefore
ignored.
These two assumptions are in fact not true and cannot be accepted except
under strict conditions. When a gas obeys these strict conditions it is honored
as the “perfect gas” and rewarded with a law bearing its name “the perfect
gas law”:

P×V=n×R×T

The question now is: “Under what conditions will not real gases exhibit
PV
perfect behavior?” The following curves shows “ ” plotted against “P” for
RT
one mole of each of the four real gases and the ideal gas all at the same
temperature.

92
 PV
For the one mole of the ideal gas = 1 regardless of its pressure but for one
RT
PV
mole of any one of the real gases, = 1 only at zero or extremely small
RT
pressures and significant deviations occur as pressure increases. The
following is the interpretation to these observations:
Attractive forces operate among molecules at relatively short
distances. therefore, at low pressures the molecules in a gas are
far apart and they experience no attractive and repulsive forces.
But at high pressures, the molecules are much closer to one
another and intermolecular forces are significant enough to
affect the motion of the molecules, and the gas will not behave
perfectly. This nonperfect behavior can be observed much
significantly at lower temperature because cooling a gas
decreases the molecules’ average kinetic energy, which makes
molecules movement less freely.
To study real gases accurately, we need to modify the ideal gas equation to
take into account intermolecular forces and finite molecular volumes. this was
made by the Dutch physicist J. D. van der Waals in 1873. The following is his
logic:
1) The intermolecular attractions exerted between a molecule and its
neighbors tend to soften the collisions made by this molecule against the
wall which makes the gas pressure lowers than if it is ideal. Van der Waals
suggested that to correct the deviation, resulting from lowering the
pressure, a certain correction value must be added to the real pressure. This
n2
value he determined to be “a × ”. This means that the gas pressure must
V2
n2
be corrected to be (P + a × 2 ). “a” is constant for each gas, and it is related
V
to the strength of the forces between the molecules of the gas
2) Another correction concerns the volume occupied by the gas molecules. In
the perfect gas equation, “V” represents the volume of the container as a
free space that is occupied by nothing. However, each molecule does
occupy a finite, although small, volume, so the effective volume of the gas
is less than the volume of the container by a certain value. This value is
determined by van der Waals to be “n × b”. This means that the gas volume
must be corrected to be (V − n × b). “b” is constant for each gas, and it is
related to the volume occupied by the molecules of the gas.
3) From the previous two corrections the law of the real gas is written as:

n2
(P + a × ) × (V − n × b) = n × R × T
V2

93
 This equation is called the “van der Waals equation”, the “real gas
equation” and the “nonperfect gas equation”
4) From van der Waals equation it is so easy to understand that if the gas is a
perfect gas its values of the two constants “a” and “b” are zero.

Example 4.16
Given that 3.50 moles of NH3 occupy 5.20 L at 47° C, calculate the pressure
of the gas (in atm) using (A) the ideal gas equation and (B) the van der Waals
equation. (a = 4.17 atm L2/mol2, b = 0.0371 L/mol)
Solution
atm L
n×R×T 3.5 mol × 0.0821 × 320 K
A) P = = mol K
= 17.7 atm
V 5.2 L
n×R×T n2
B) P = ( ) – (a × )
V−n×b V2
atm L
3.5 mol × 0.0821 × 320 K atm L2 (3.5 mol)2
P=( mol K
L ) – (4.17 × ) = 16.2 atm
5.2 L − 3.5 mol × 0.0371 mol2 (5.2 L)2
mol
Practice exercise
At 27°C, 10.0 moles of a gas in a 1.50-L container exert a pressure of 130
atm. Is this an ideal gas?

94
 5. THEMOCHEMISTRY
5.1 System, state of the system and state function
5.1.1 System
A “system” is a part of the universe confined in a container and is the focus
of our interest. Everything outside the system is called the “surroundings”.
What separate the system from its surroundings is the “boundaries” of the
system.
5.1.1 State of the system
The “state of a system” is the values of all properties of the system such as
its composition, energy, temperature, pressure, and volume. Thus if we have
100 g of liquid water at 30 °C and 1.0 atm and someone are asked us “what
the state of this system”, then our correct answer will be “the state of the
system is that it is 100 g of water in its liquid state at 30 °C and 1.0 atm”.
5.1.3 State function of the System
The “State function of the System” is any property of the system that
indicates the state of the system and depend on its it such as its composition,
energy, temperature, pressure, and volume. Any property of the system
depends on its specified state not on the path which brought the system to this
specified state. We can change a gas state function, such as its volume, from
an initial value, Vi = 1 L to a final value, Vf = 3 L. If we manage to make the
amount and the temperature of the gas at the final state the same as it was at
the initial state, then the change in the volume can be achieved by changing
the pressure. This change in volume, ΔV = 2 L, will be the same regardless of
how we did this change, no matter how we arrive at the final state (for
example, the pressure of the gas can be increased then decreased, or it can be
increased then decreased then increased), the change in volume is always 2 L.
Thus, the volume of the gas is a state function.

5.2 PV-work and heat

5.2.1 PV-work
Work is many kinds, it includes mechanical work, electrical work, surface
work and many other types. Work is a way of transferring energy from a place
to another. It is not a property of the system. We can say that the temperature
of a substance is, for example, 25° C, but we cannot say that the work of the
system is, for example, 250 J.
We will concentrate only on the mechanical work of expansion and
compression of gases. The work done by or on the gas is given by the
following equation:

95
 w = – P × (Vf – Vi)
w = – P × ΔV

In the equation, the negative sign was intentionally placed. This is to make the
sign of work negative in cases of expansion (energy of the system decreases)
and positive in cases of compression (energy of the system increases).
Regarding units of the PV-work:
w = – P × ΔV
units of w = units of P × units of V
units of force
units of w = 2
× units of V
(units of area)
m
kg × 2
units of w = s
× m3
m2
units of w = kg m–1 s–2 × m3
units of w = Pascal × m3
units of w = kg m2 s–2 = J
As it appears, the product of pressure and volume equals the work done:
 If "P" is in "Pa" and "V" is in "m3", the unit of the work will be "J"
 If "P" is in "atm" and "V" is in "L" the unit of the work will be "atm L"
 1 atm L = 101.325 J
One way to illustrate this type of work is using a cylinder with its piston. The
figure below shows a gas in a cylinder fitted with a weightless, frictionless
movable piston at a certain temperature, pressure, and volume. It shows that
the gas expands by pushing the piston upward against a constant opposing
external atmospheric pressure, P.

96
 Because w = – P × (Vf – Vi), the work done by the gas: w = – P × (Vf – Vi)
has a negative quantity indicating that work done causes a decrease in the
energy of the gas. For gas expansion (work done on the system), ΔV < 0, so
(– PΔV) is a positive quantity indicating that work done causes an increase in
the energy of the gas.

EXAMPLE 5.1
A certain gas expands in volume from 2.0 L to 6.0 L at constant temperature.
Calculate the work done by the gas if it expands
A) against a vacuum. B) against a constant pressure of 1.2 atm.
Solution
A) w = – PΔV = – (0 × ΔV) = 0
Pa m3
B) w = – PΔV = – {1.2 atm × 101325 } × {(6 – 2) L } = – 4.86 × 10–2 J
atm 1000 L
Practice Exercise
A gas expands from 264 mL to 971 mL at constant temperature. Calculate the
work done by the gas if it expands against a constant pressure of 4.00 atm.

5.2.2 Heat
Like work, heat is not a state function. Heat is a way of transferring energy
from a place to another. It is not a property of the system. We can say that the
temperature of a substance is, for example, 25° C, but we cannot say that the
heat of the system is, for example, 250 J. For example, it takes 4184 J of
energy to raise the temperature of 100 g of water from 20°C to 30°C. This
energy can be gained in different ways such as:
A) Directly as heat energy from burner, without doing any work.
B) By doing work on the water without adding heat energy (for example, by
stirring the water with a magnetic stir bar).
C) By some combination of the procedures described in A and B.
The heat associated with a given process depends on how it is carried out.
Calculation of heat absorbed by a system requires understanding the effect of
how mass the substance is and how many degrees its temperature increases
on the amount of heat absorbed. This can be understood by knowing what
specific heat (s), heat capacity (C) and quantity of heat (q) mean.
First: specific heat (s)
The specific heat of a substance is the amount of heat required to raise the
temperature of only one gram of the substance by only one degree Celsius.
J
Its units are .
g °C

97
Second: heat capacity (C)
The heat capacity of a substance is the amount of heat required to raise the
temperature of any given mass, (m), of the substance by only one degree
J
Celsius. Its units are .
°C
The relationship between the heat capacity and specific heat of a substance is:

C=m×s

J
For example, the specific heat of water is 4.184 , and the heat capacity of
g °C
60.0 g of water is

J
C = 60.0 g × 4.184 J/g °C = 251
°C

The following table shows the specific heat of some common substances.

Third: quantity of heat (q)

The quantity of heat is the amount of heat required to raise the temperature
of any given mass, (m), of the substance by any Celsius degrees. Its unit is J.

98
 If we know s and m, then Δt we can calculate the amount q that has been
absorbed or released in a particular process. The equations for calculating the
quantity of heat is:

q = C × Δt = m × s × Δt

EXAMPLE 5.2
A 466-g sample of water is heated from 8.50 °C to 74.60 °C. Calculate the amount
J
of heat absorbed (in kilojoules) by the water. (sH2O = 4.184 )
g °C
Solution
J
q = m × s × Δt = 466 g × 4.184 × (74.60 °C – 8.50 °C) = 129000 J
g °C
kJ
q = 129000 J × 10–3 = 129 kJ
J
Practice Exercise
An iron bar (s = 0.45 J/g °C) of mass 869 g cools from 94°C to 5°C. Calculate the
heat released (in kilojoules) by the metal.

5.3 The first law of thermodynamics

The first law of thermodynamics, is based on the law of conservation of
energy. The law of conservation of energy states that energy can be converted
from one form to another, but cannot be created or destroyed. We can test the
validity of the first law by measuring the change in the internal energy of a
system between its initial state and its final state in a process. The change in
internal energy ΔE is given by the following equation:

ΔE = Ef – Ei

where Ei and Ef are the initial and the final internal energies of the system
respectively. Depending on the values of Ei and Ef, ΔE may be positive,
negative or zero. The internal energy of a system has two components: kinetic
energy and potential energy:
1) The kinetic energy component: The kinetic energy consists of various
types of molecular motion and the movement of electrons within
molecules.
2) Potential energy component: The Potential energy is determined by the
attractive interactions between electrons and nuclei and by repulsive
interactions between electrons and between nuclei in individual molecules,
as well as by interaction between molecules.

99
It is impossible to measure all these contributions accurately, so we cannot
calculate the total internal energy of a system with any certainty. Changes in
energy, on the other hand, can be determined experimentally. Consider the
following reaction

S(s) + O2(g)  SO2(g)

Our system is initially composed of S and O2 and finally composed of SO2.

We do not know the initial or the final internal energy, Ei and Ef, but the first
law of thermodynamic assures that the change in the internal energy, ΔE, of a
system is the sum of the heat exchange between the system and the
surroundings, q, and the work done on or by the system, w:

ΔE = q + w

The sign conventions for "q" and "w" are as follows:

q is positive for an endothermic process
q is negative for an exothermic process
w is positive for work done on the system by the surroundings
w is negative for work done by the system on the surroundings.
The table below summarizes the sign conventions

It is important to note that regardless of which procedure is taken, the change

in internal energy of the system, ΔE, depends on the sum of (q + w). In
summary, heat and work are not state functions because they are not properties
of a system. They manifest themselves only during a process (during a

100
 change). Thus, their values depend on the path of the process and vary
accordingly.

EXAMPLE 5.3
If the work done on a gas is 462 J and the heat released by the gas is 128 J, calculate
the change in the gas internal energy.
Solution
ΔE = q + w = (–128 J) + (+ 462 J) = + 334 J
Practice Exercise
A gas expands and does P - V work on the surroundings equal to 279 J. At the
same time, it absorbs 216 J of heat from the surroundings. What is the change in
energy of the system?

5.4 Enthalpy of reactions

The word enthalpy is originated from Greek. “en-” means “within” and
“thalpein” means “to heat”. Therefore, enthalpy means “heat content”. The
symbol for enthalpy is “H”.
 The heat absorbed or released by a system, at constant temperature, as
result of a change in the state of the system is called heat of reaction.
 The heat of the reaction at constant temperature is given a specified name
and symbol depending on whether it is also at constant volume or at
constant pressure:
 If it is at constant temperature and constant volume, it is named
“change in internal energy” and is given the symbol (ΔE).
 If it is at constant temperature and constant pressure, it is named
“change in enthalpy” and is given the symbol (ΔH).
Because most reactions are done at constant temperature and pressure, we
became more concerned about changes in enthalpy rather than changes in
internal energy. For any reaction of the type:

Reactants  products

Enthalpy of reaction, ΔH, is the change in enthalpy, and it is the difference

between the enthalpies “the heat content” of the products and the enthalpies
“the heat content” of the reactants:

ΔH = Hproducts – Hreactants

101
 There is no way to measure the absolute value of the enthalpy of a substance
(H). Fortunately, we do not need to know its value because what we care about
only is the increase or decrease (the change) in its value, (ΔH). The enthalpy
of reaction can be positive or negative, depending on the process.
 For an endothermic process (heat absorbed by the system from the
surroundings), ΔH is positive (that is, ΔH > 0).
 For an exothermic process (heat released by the system to the
surroundings), ΔH is negative (that is, ΔH < 0).

5.5 Thermochemical equations

At 0°C and a pressure of 1 atm, ice melts to form liquid water. Measurements
show that for every mole of solid water (ice) converted to liquid water under
these conditions, 6.01 kilojoules (kJ) of heat are absorbed by the system (ice).
Because the pressure is constant, the heat change is the enthalpy change, ΔH.
Furthermore, this is an endothermic process and ΔH is a positive. The
equation for this physical change is

H2O(s)  H2O(l) ΔH = 6.01 kJ

That is, when 1 mole of ice is converted to 1 mole of liquid water at constant
temperature and pressure, ice must have absorbed 6.01 kJ of heat.
As another example, consider the combustion of methane (CH4) at constant
temperature and pressure:

CH4(g) + 2O2(g)  CO2(g) + 2H2O(l). ΔH = – 2890.4 kJ

 when 1 mole of CH4 gas reacts with 2 moles of O2 gas to produce 1 mole
of CO2 and 2 moles of liquid H2O, 890.4 kJ of heat energy are released to
the surroundings.
 It is important to keep in mind that the ΔH value does not refer to a
particular reactant or product.
 Concerning ΔH for the previous reaction, all the following are true:
1. ΔH = – 2890.4 kJ/ mol CH4
2. ΔH = – 2890.4 kJ/ 2 mol O2
3. ΔH = – 2890.4 kJ/ mol CO2
4. ΔH = – 2890.4 kJ/ 2 mol CH2O
A thermochemical equation cannot be called so unless it satisfies the
following conditions:
1) The thermochemical equation must be balanced.

102
 2) In the thermochemical equation, the states of all substances must be
specified.
3) In the thermochemical equation, the value of ΔH must be written.
Thermochemical equations can be manipulated with as follows:
 Multiplying a thermochemical equation by a number or a fraction produces
a correct thermochemical equation as long as the value of ΔH is multiplied
by the same number.
 Reversing a thermochemical equation produces a correct thermochemical
equation as long as the sign of ΔH is changed to its opposite.
 Adding several thermochemical equations together produces a correct
thermochemical equation as long as all values of ΔH are added together.
(This is called Hess’s law).

EXAMPLE 5.4
Given the thermochemical equation
2SO2(g) + O2 (g)  2SO3(g) ΔH = –198.2 kJ
calculate the heat evolved when 87.9 g of SO2 (molar mass = 64.07 g/mol) is converted
to SO3.
Solution
87.9 g
Given moles of SO2 = g = 1.372 mol
64.07
mol

2SO2 + O2  2SO3 ΔH
Equation moles 2 mol − 198.2 kJ
Givnen moles 1.372 mol X
− 198.2 kJ × 1.372 mol SO2
X= = – 135.97 kJ
2 mol SO2
Practice Exercise
Calculate the heat evolved when 266 g of white phosphorus (P4) burns in air according
to the equation
P4(s) + 5O2(g)  P4O10(s) ΔH = – 3013 kJ/mol

5.6 Relationship between ΔH and ΔE

We know that:
ΔE = q + w and w = – P × ΔV
q = ΔH when “T” and “P” are constant
ΔE = ΔH – P × ΔV when “T” and “P” are constant
P×V=n×R×T
P × ΔV = R × T × Δng

103
 Therefore:

ΔE = ΔH – R × T × Δng

It is very important not to forget that the subscript “g” is to emphasize that
when calculating Δn only gases count:

Δng = ngases produced – ngases reacted

To understand the equation “ΔE = ΔH – R × T × Δng” let’s consider the

reaction between sodium metal and water at 1 atm and 298 K is:

2Na(s) + 2H2O(l)  2NaOH(aq) + H2(g) ΔH = – 367.5 kJ

This thermochemical equation says that when 2 moles of solid Na react with
2 moles of liquid water, 367.5 kJ of heat is released. The H2 gas produced
needs a space to occupy. Therefore, it pushes the air toward the atmosphere.
This means that some of the energy produced by the reaction as heat is used
to do work of pushing back a volume, ΔV, against atmospheric pressure, P.
To calculate the change in internal energy, we apply the previous equation:

ΔE = ΔH +w = ΔH – R × T × Δng
kJ
ΔE = (– 367.5 kJ) – (8.314 × 10–3 × 298 K × 1 mol) = – 369.98 kJ
mol K

EXAMPLE 5.5
Calculate ΔE for the following reaction at 1 atm and 25°C:
2CO(g) + O2(g)  2CO2(g) ΔH = – 566.0 kJ
Solution
ΔE = ΔH – R × T × Δng
Δng = (2 mol) – (3 mol) = – 1 mol
kJ
ΔE = (– 566.0 kJ) – (8.314 × 10–3 × 298 K × – 1 mol) = – 563.5 kJ
mol K
Practice Exercise
What is ΔE for the formation of 1 mole of CO at 1 atm and 258C?
1
C(graphite) + O2(g)  CO(g) ΔH = –110.5 kJ
2

104
5.6 Enthalpies of changes
5.6.1 Enthalpies of some physical changes
First: Main physical changes
1) Fusion (melting) and enthalpy of fusion
Freezing and enthalpy of freezing
Fusion is a physical process in which a substance changes from its solid
state to its liquid state. It is an endothermic process. The quantity of energy
required to fuse (melt) one mole of a solid substance is called “molar
enthalpy of fusion”, ΔHfus.
The following equations are examples of fusion:
Ar(s)  Ar(l) ΔH = 1.3 kJ
C6H6(s)  C6H6(l) ΔH = 10.9 kJ
CH3CH2OH(s)  CH3CH2OH(l) ΔH = 7.61 kJ
Hg(s)  Hg(l) ΔH = 23.4 kJ
H2O(s)  H2O(l) ΔH = 6.01 kJ
Freezing is simply the opposite of fusion.
2) Vaporization (evaporation) and enthalpy of vaporization
Condensation and enthalpy of condensation
Vaporization is a physical process in which a substance changes from its
liquid state to its gaseous state. It is an endothermic process. The quantity
of energy required to vaporize one mole of a liquid substance is called
“molar enthalpy of vaporization”, (ΔHvap).
The following equations are examples of vaporization:
Ar(l)  Ar(g) ΔH = 6.3 kJ
C6H6(l)  C6H6(g) ΔH = 31.0 kJ
CH3CH2OH(l)  CH3CH2OH(g) ΔH = 39.3 kJ
Hg(l)  Hg(g) ΔH = 59.0 kJ
H2O(l)  H2O(g) ΔH = 40.79 kJ
Condensation is simply the opposite of vaporization.
3) Sublimation and enthalpy of sublimation
Deposition and enthalpy of deposition
Sublimation is a physical process in which a substance changes directly
from its solid state to its gaseous state. It is an endothermic process. The
quantity of energy required to sublime one mole of a solid substance is
called “molar enthalpy of sublimation” (ΔHsub).
The following equations are examples of sublimation:
Ar(s)  Ar(g) ΔH = 7.6 kJ
C6H6(s)  C6H6(g) ΔH = 41.9 kJ
CH3CH2OH(s)  CH3CH2OH(g) ΔH = 46.91 kJ

105
 Hg(s)  Hg(g) ΔH = 82.4 kJ
H2O(s)  H2O(g) ΔH = 46.8 kJ
Deposition is simply the opposite of Sublimation.
Second: Relation between the main physical changes
A simple inspection and a quick glance to the three sets of thermochemical
equations given above should reveal that sublimation is the summation of
fusion and vaporization and ΔHsub = ΔHfus + ΔHvap.
5.6.1 Enthalpies of some chemical changes
1) Combustion reaction and enthalpy of combustion
A combustion reaction (also called burning) is the reaction in which a
substance reacts with oxygen (O2), usually with the release of heat and
light to produce a flame. The quantity of heat released as a result of
combusting one mole of a substance is called molar enthalpy of
combustion (ΔHcom).
The following equations are examples combustion reactions:
S(s) + O2(g)  SO2(g) ΔH = – 296.84 kJ
1
Mg(s) + O2(g)  MgO(g) ΔH = – 601.6 kJ
2
The most important combustion reactions are the combustion are:
 The combustion of hydrogen to produce H2O:
1
H2(g) + O2(g)  H2O(l) ΔH = – 285.8 kJ
2
 The combustion of carbon to produce CO2:
1
C(graphite) + O2(g)  CO2(g) ΔH = – 393.5 kJ
2
 The combustion of compounds containing both hydrogen and carbon
yield both H2O and CO2:
CH3CH2OH(l) + 5O2(g)  2CO2 + 3H2O(l) ΔH = – 1367 kJ
C3H8(g) + 5O2(g)  3CO2(g) + 4H2O(l) ΔH = – 2100 kJ
C6H12O6(s) + 6O2(g)  6CO2(g) + 6H2O(l) ΔH = – 22801 kJ
2) Formation reaction and standard enthalpy of formation
A formation reaction is the reaction in which one substance is produced
as a result of the reaction of its elements in their standard states. The
quantity of energy released or absorbed as a result of the formation of one
mole of a substance from the reaction between its elements in their
standard states is called standard molar enthalpy of formation (Δ𝐇𝐟° ).
From the definition of the formation reaction, it appears that if the
substance we have is an element in its standard state, it has no formation
reaction and therefore its standard enthalpy of formation equals zero.

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 When any element is in its standard state its Δ𝐇𝐟° = 0

The following reaction equations are examples formation reactions:

S(s) + O2(g)  SO2(g) ΔH = – 296.84 kJ

(Note: this reaction can also be called a combustion reaction)
1
Mg(s) + O2(g)  MgO(g) ΔH = – 601.6 kJ
2
(Note: this reaction can also be called a combustion reaction)
1
2C(graphite) + 3H2(g) + O2(g)  CH3CH2OH(l) ΔH = – 277.6 kJ
2
3C(graphite) + 4H2(g)  C3H8(g) ΔH = – 104.7 kJ
6C(graphite) + 6H2(g) + 3O2 C6H12O6(s) ΔH = – 1271 kJ

The standard enthalpies of formation are one of the most important tools
chemists use to determine the standard enthalpy of any physical or
°
chemical change, ΔHrxn . This can be accomplished simply by the
following equation:

° ° °
ΔHrxn = ΣΔHf,products – ΣΔHf,reactants

The equation says that the standard enthalpy of any change equals the sum
of the standard enthalpies of formation of products minus the sum of the
standard enthalpies of formation of reactants. For example, knowing that
the standard enthalpies of formation for gaseous carbon monoxide and
kJ kJ
gaseous carbon dioxide are – 110.5 and – 393.5 respectively
mol mol
enables us to calculate the standard oxidation of carbon monoxide to
carbon dioxide as follows:
1
CO(g) + O2(g)  CO2(g)
2
° ° °
ΔHrxn = ΣΔHf,products – ΣΔHf,reactants
° ° ° 1°
ΔHrxn = (Σ1 ×ΔHf,𝐶𝑂2
) – (Σ1 × ΔHf,CO + ΣΔHf,𝑂2
)
2
° kJ kJ 1
ΔHrxn = (Σ1 mol × – 393.5 ) – (Σ1 mol × – 110.5 + × 0)
mol mol 2
°
ΔHrxn = – 283 kJ

107
Standard enthalpies of formation are determined almost for all known substances
and are presented in thermodynamic tables found in references, textbooks and
internet sights. The following table gives some.

𝐤𝐉 𝐤𝐉
Compound Δ𝐇𝐟° ( ) Compound Δ𝐇𝐟° ( )
𝐦𝐨𝐥 𝐦𝐨𝐥
AgBr(s) – 99.5 C2H2(g) + 226.7
AgCl(s) – 127.0 C2H4(g) + 52.3
AgI(s) – 62.4 C2H6(g) – 84.7
Ag2O(s) – 30.6 C3H8(g) – 103.8
Ag2S(s) – 31.8 n– C4H10(g) – 124.7
Al2O3(s) – 1669.8 n– C5H12(l) – 173.1
BaCl2(s) – 860.1 C2H5OH(l) – 277.6
BaCO3(s) – 1218.8 CoO(s) – 239.3
BaO(s) – 558.1 Cr2O3(s) – 1128.4
BaSO4(s) – 1465.2 CuO(s) – 155.2
CaCl2(s) – 795.0 Cu2O(s) – 166.7
CaCO3 – 1207.0 CuS(s) – 48.5
CaO(s) – 635.5 CuSO4(s) – 769.9
Ca(OH)2(s) – 986.6 Fe2O3(s) – 822.2
CaSO4(s) – 1432.7 Fe3O4(s) – 1120.9
CCl4(l) – 139.5 HBr(g) – 36.2
CH4(g) – 74.8 HCl(g) – 92.3
CH3OH(l) – 238.6 HI(g) + 25.9
CO(g) – 110.5 HNO3(l) – 173.2
CO2(g) – 393.5 H2O(g) – 241.8
H2O(l) – 285.8 NH4Cl(s) – 315.4
H2O2(l) – 187.6 NH4NO3(s) – 365.1
H2S(g) – 20.1 NO(g) + 90.4
H2SO4(l) – 811.3 NO2(g) + 33.9
HgO(s) – 90.7 NiO(s) – 244.3
HgS(s) – 58.2 PbBr2(s) – 277.0
KBr(s) – 392.2 PbCl2(s) – 359.2
KCl(s) – 435.9 PbO(s) – 217.9
KClO3(s) – 391.4 PbO2(s) – 276.6
KF(s) – 562.6 Pb3O4(s) – 734.7
MgCl2(s) – 641.8 PCl3(g) – 306.4
MgCO3(s) – 1113 PCl5(g) – 398.9
MgO(s) – 601.8 SiO2(s) – 859.4
Mg(OH)2(s) – 924.7 SnCl2(s) – 349.8
MgSO4(s) – 1278.2 SnCl4(l) – 545.2
MnO(s) – 384.9 SnO(s) – 286.2
MnO2(s) – 519.7 SnO2(s) – 580.7
NaCl(s) – 411.0 SO2(g) – 296.1
NaF(s) – 569.0 So3(g) – 395.2
NaOH(s) – 426.7 ZnO(s) – 348.0
NH3(g) – 46.2 ZnS(s) – 202.9

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EXAMPLE 5.6
The thermite reaction involves aluminum and iron(III) oxide
2Al(s) + Fe2O3(s)  Al2O3(s) + 2Fe(l)
This reaction is highly exothermic and the liquid iron formed is used to weld metals.
Calculate the heat released in kilojoules per gram of Al reacted with Fe2O3.
° kJ ° kJ ° kJ
ΔHf,Al O
2 3 (s) = – 1669.8 , ΔH f,Fe(𝑙) = 12.40 / , ΔH f,Fe O
2 3 (s) = − 822.2 /
mol mol mol
Solution
° ° °
ΔHrxn = ΣΔHf,products – ΣΔHf,reactants
°
ΔHrxn = [ΔHf° (Al2O3) + 2ΔHf° (Fe)] – [2ΔHf° (Al) + ΔHf° (Fe2O3)]
°
ΔHrxn = [(– 1669.8 kJ/mol) + (2 mol × 12.40 kJ/mol)]
– [(2 mol × 0) + (– 822.2 kJ/mol)]
°
ΔHrxn = – 822.8 kJ/2 mol of Al reacted
Mass of Al reacted = n × M = 2 mol × 26.98 g/mol = 53.96 g
– 822.8 kJ per 53.96 g Al
X kJ per 1 g Al
– 822.8 kJ ×1 g
X= = – 15.25 kJ/g
53.96 g
Practice Exercise
Benzene (C6H6) burns in air to produce carbon dioxide gas and liquid water. Calculate
the heat released (in kilojoules) per gram of the compound reacted with oxygen.
° kJ ° kJ ° kJ
∆Hf,CO 3 (g) = − 393.5 , ∆Hf,H 3 O(𝑙) = − 285.8 , and ∆Hf,C H
6 6 (𝑙) = 49.04 .
mol mol mol

5.7 Hess’s law of heat summation

Germain Henri Hess (1802–1850) is a Swiss chemist. born in Switzerland but
spent most of his life in Russia. For formulating what is known as “Hess’s
law”, he is known as the father of thermochemistry Hess’s law can be stated
as follows: When reactants are converted to products, the change in enthalpy
is the same whether the reaction takes place in one step or in a series of steps.
Hess’s law is based on the fact that because H is a state function, ΔH depends
only on the initial and final state. The general rule in applying Hess’s law is
as follows:
1) to arrange a series of chemical equations in such a way that, when added
together, all species will cancel except for those that appear in the overall
desired reaction.
2) Multiply any reaction by the appropriate factor as needed. Do not forget to
multiply ΔH by the same factor.

109
 3) Reverse any reaction as needed. Do not forget to change the sign of the ΔH
to the opposing sign.
From the following equations:
°
C(graphite) + O2(g)  CO2(g) ΔHrxn = – 393.5 kJ
1 °
CO(g) + O2(g)  CO2(g) ΔHrxn = – 283.0 kJ
2

Our simple inspections suggest that the second equation should be reversed
then added to the first:
°
C(graphite) + O2(g)  CO2(g) ΔHrxn = – 393.5 kJ
1 °
CO2(g)  CO(g) + O2(g) ΔHrxn = + 283.0 kJ
2
1 °
C(graphite) + O2(g)  CO2(g) ΔHrxn = – 110.5 kJ
2

EXAMPLE 5.7
Calculate the standard enthalpy of formation of acetylene (C2H2) from its elements:
2C(graphite) + H2(g)  C2H2(g)
The equations for each step and the corresponding enthalpy changes are:
(a) C(graphite) + O2(g)  CO2(g) °
ΔHrxn = – 393.5 kJ/mol
1
(b) H2(g) + O2(g)  H2O(l) °
ΔHrxn = – 285.8 kJ/mol
2
(c) 2C2H2(g) + 5O2(g)  4CO2(g) + 2H2O(l) °
ΔHrxn = – 2598.8 kJ/mol
Solution
Careful look at the desired equation indicates that the first equation must be multiplied
1
by 2; and the third equation must be revered and multiplied by . So we will have
2
2C(graphite) + 2O2(g)  2CO2(g) °
ΔHrxn = – 787.0 kJ
1
H2(g) + O2(g)  H2O(l) °
ΔHrxn = – 285.8 kJ
2
2CO2(g) + H2O(l)  C2H2(g) + 2.5O2(g) °
ΔHrxn = + 1299.4 kJ
2C(graphite)  H2(g)  C2H2(g) °
ΔHrxn = + 226.6 kJ
Practice Exercise
Calculate the standard enthalpy of formation of carbon disulfide (CS2) from its
elements, given that:
C(graphite) + O2(g)  CO2(g) °
ΔHrxn = – 393.5 kJ
S(rhombic) + O2(g)  SO2(g) °
ΔHrxn = – 296.4 kJ
CS2(l) + 3O2(g)  CO2(g) + 2SO2(g) °
ΔHrxn = – 1073.6 kJ

110
 6. SOLUTIONS
6.1 Definition and types of solutions
A solution is a mixture of two or more components. One of the components
is called “solvent” the other (or the others) is (are) called “solute” (“solutes”):
Solvent + Solute = Solution
The table below gives some common types of solutions.

Our focus will be on liquid solutions:

 Solutions of gases in liquids
 Solutions of liquids in liquids
 Solutions of solids in liquids

6.2 Degrees of saturation of solutions

Chemists characterize solutions by their capacity to dissolve a solute.
Depending on the amount of solute dissolved we can differentiate between
three cases:
1) saturated solution: a solution is described as saturated when it contains
the maximum amount of a solute dissolved in the solvent at a specific
temperature.
2) unsaturated solution: a solution is described as supersaturated when it
contains less than its capacity to dissolve a solute.

111
 3) supersaturated solution: a solution is described as saturated when it
contains more than its capacity to dissolve a solute.

6.3 How solution is formed?

6.3.1 A Molecular view of the solution process
The intermolecular attractions between particles of a substance depends on its
state. Particles of gases has extremely weak intermolecular attractions or
none. But particles of liquid or a solid has considerable intermolecular
attractions that hold molecules together. Therefore, intermolecular attractions
have an important role in the formation of solutions of solids in liquids and of
liquids in liquids. When the liquid or the solid solute dissolves in the liquid
solvent particles of the solute disperse throughout the solvent and occupy
positions that are originally taken by solvent molecules. The ease with which
a solute particle replaces a solvent molecule depends on the relative strengths
of three types of interactions:
1) solvent-solvent interaction
2) solute-solute interaction
3) solvent-solute interaction
For simplicity and as figures below show, we can imagine the solution process
taking place in three distinct and simultaneous actions:
1) the separation of solvent molecules
2) the separation of solute molecules
3) the attraction between solvent and solute molecules.

The first and the second actions are endothermic because breaking attractive
forces requires energy (ΔH1 > 0 and ΔH2 > 0). The third action is exothermic

112
 because forming attractive forces releases energy (ΔH3 < 0). The enthalpy of
solution ΔHsoln is given by:

ΔHsoln = ΔH1 + ΔH2 + ΔH3

It is clear that there are three distinguished cases:

First case: If the solute-solvent attractions are stronger than the solvent-
solvent and the solute-solute attractions, the solution process
is exothermic (ΔHsoln > 0)
Second case: If the solute-solvent attractions are weaker than the solvent-
solvent and the solute-solute attractions, the solution process
is endothermic (ΔHsoln < 0).
Third case: If the solute-solvent attractions are equal to the solvent-
solvent and the solute-solute attractions, the solution process
is not endothermic or exothermic. In this case the solution is
described as an ideal solution.
6.3.2 The “like dissolve like” proverb
What does “Like dissolve like” mean? It means the following: “THE
SOLUTE CAN DISSOLVE IN THE SOLVENT IF THE
ATTRACTIVE FORCES BETWEEN ITS PARTICLES ARE LIKE
THOSE IN THE SOLVENT PARTICLES, BUT IF THEY ARE NOT,
THE SOLUTE CANNOT DISSOLVE IN THE SOLVENT”. This is
exactly what “Like dissolve like” means. Therefore, focusing on the
attractive forces of the solvent will be so helpful. Investigations revealed with
proven reliability that they are so many. So, we will not consider, at our level
here, except two types. The first is called “polar solvents” in which any ionic
or polar solute can dissolve but any nonionic or nonpolar solute cannot
dissolve. The second is called “nonpolar solvents” in which any nonionic or
nonpolar solute can dissolve but any ionic or polar solute cannot dissolve.
The following table gives some of the important polar and nonpolar solvents
that are widely used:

POLAR SOLVENTS NONPOLAR SOLVENTS

Water H2O Hexane CH3CH2CH2CH2CH2CH3
Formic acid HCO2H Benzene C6H6
Acetic acid CH3CO2H Toluene C6H5CH3
Methanol CH3OH 1,4-dioxene (CH3CH2O)2
Ethanol CH3CH2OH Chloroform CHCl3
n-butanol CH3CH2CH2CH2OH Diethyl ether (CH3CH2)2O

113
EXAMPLE 6.1
Knowing that:
A) Molecules of Br2, C6H6, CCl4, CH2O and CS2 are nonpolar
B) Molecules of H2O, CH2O and liquid NH3 are polar
C) KCl is an ionic compound
Predict the solubility in the following cases:
A) Bromine (Br2) in benzene (C6H6) and in water (H2O)
B) Potassium chloride (KCl) in (CCl4) and in liquid ammonia (NH3)
C) Formaldehyde (CH2O) in carbon disulfide (CS2) and in water (H2O)
Solution
A) Br2 is soluble C6H6 not in H2O
B) KCl is soluble in NH3 not in CCl4
C) CH2O is soluble in H2O not in CS2.
Practice Exercise
Knowing that I2 and CS2 are nonpolar and H2O is polar, Is iodine (I2) more
soluble in water or in carbon disulfide (CS2)?

6.4 The effect of temperature on solubility

6.4.1 Solid solubility and temperature
First, let’s carefully look and inspect the following figure:

The figure clearly shows that:

114
 1) Solubility of most ionic solid salts in water increases as temperature
increases
2) Solubility of a few ionic solid salts in water increases as temperature
decreases
3) Solubility of very rare solid salts in water is almost the same at all
temperatures
4) The solubility differs from a salt to another
5) The solubility for all salts can be determined and compared

EXAMPLE 6.2
Using the above curves answer the following questions:
1) At 40 °C, which is more soluble KCl or K2Cr2O7?
2) At 90 °C, which is more soluble KCl or K2Cr2O7?
Solution
1) At 40 °C, KCl is more soluble than K2Cr2O7
2) At 90 °C, K2Cr2O7 is more soluble than KCl
Practice Exercise
Using the curves of the solubility versus temperature,
1) At what temperature will the solubility of KCl equalizes that of KClO3?
2) At 47 °C, the solubility of KNO3 is 80 g/100 g of water. At what temperature
would the solubility of NaNO3 be the same?

6.4.2 Gas solubility and temperature

First, let’s carefully look and inspect the following figure:

115
 The figure clearly shows that:
1) In all cases and with no single exception, the solubility of any gas
decreases as temperature increases
2) The solubility differs from a gas to another
3) The solubility for all gases can be determined and compared

6.5 The effect of pressure on solubility

Due to the closeness between particles of solids and liquids, pressure has no
effect on the solubility of a liquid in a liquid or a solid in a liquid. However,
due to the spacing between particles of gases, pressure has a great effect on
the solubility of gases. Let’s look at the following figure:

The figure shows that as we increase the pressure of the gas above the liquid
it is forced to dissolve more. The quantitative relationship between gas
solubility and its pressure is given by Henry’s law, which states that the
solubility of a gas in a liquid is proportional to its pressure of over the
solution. It is presented by the following law:

c = kP

”c” is the molar concentration (the number of moles of gas in one liter of the
mol
solution, ( ).
L
“P” is the pressure (in atm) of the gas over the solution
“k” is a constant for each gas and is called Henry’s constant. Henry’s constant
mol
differs from a gas to another and its units are . Henry’s law can be
L × atm
understood qualitatively in terms of a theory called “the kinetic molecular
116
 theory of gases”. The amount of gas that will dissolve in the liquid depends
on how frequently the gas molecules collide with the liquid surface and
become trapped. We can understand this matter when we think about a bottle
of a refreshment drink:
1) The bottle is sealed at high pressure of CO2. This means that amount of
CO2 dissolved in these drinks is many times the amount dissolved under
normal atmospheric pressure.
2) When the cap of the bottle is removed the excess dissolved CO2 comes out
of solution, causing the effervescence, and the pressure in the bottle finally
falls to atmospheric pressure and the amount of CO2 remaining in the
beverage inside the bottle is then determined only by the normal
atmospheric partial pressure of CO2, 0.0003 atm.

EXAMPLE 6.3
mol
The solubility of nitrogen gas in water at 25 °C and 1 atm of N2 is 6.8 × 10–4 .
L
What is the molarity of nitrogen dissolved in water under atmospheric conditions?
The partial pressure of nitrogen gas in the atmosphere is 0.78 atm.
Solution
c=k×P
6.8 × 10–4 mol/L = k × 1 atm
mol
6.8 × 10–4
k= = 6.8 × 10–4 mol/L atm
L
1 atm
Therefore,
mol
c = 6.8 × 10–4 × 0.78 atm = 5.3 × 10–4 mol/L
L × atm
Practice Exercise
Calculate the molar concentration of oxygen in water at 25°C for a partial pressure
of 0.22 atm. The Henry’s constant for oxygen is 1.3 × 10–3 mol/L atm.

6.6 Concentrations of solutions

In any solution, the term “concentration” is used to compare the amount of
the solute with the amount of the solvent. The greater the amount of solute,
the more concentrated the solution is. Below we review four of the many ways
of expressing concentration. They are called: “mass percent”, “mole fraction”,
“molality”, and “molarity”. At the end we will see that knowing one of these
concentration units makes all other units able to be calculated.
6.6.1 Mass percent of solute (Solute%)
The mass percent of the solute in a solution (Solute%) is given by:

117
 𝐦𝐬𝐨𝐥𝐮𝐭𝐞
Solute% = × 𝟏𝟎𝟐
𝐭𝐨𝐭𝐚𝐥 𝐦𝐚𝐬𝐬 𝐨𝐟 𝐬𝐨𝐥𝐮𝐭𝐢𝐨𝐧

What does 25% C6H12O6 solution mean?

It means that:
1) The solute mass percent has no units
2) Water is the solvent and glucose is the solute
3) msolution = 100 g
4) msolute = 25 g
5) msolvent = 75 g
6) nsolvent, nsolute and ntotal can be calculated
7) Vsolution can be calculated if density of the solution (dsolution) is given

Example 6.4
A solution contains 131.4 g of glucose in 0.5 kg of water. Calculate glucose mass%.
Solution
mglucose
Glucose mass% = × 102
total mass of solution
131.4 g
Glucose mass% = g × 102 = 20.81%
131.4 g + 0.5 kg × 1000
kg
Practice Exercise
A solution contains 8.74 g NaNO3 in 75 g of water. Calculate the NaNO3 %.

6.6.1 Mole fraction (X)

Mole fraction of a component of a solution (Xcomponent) is given by:
𝐧𝐜𝐨𝐦𝐩𝐨𝐧𝐞𝐧𝐭 𝐧𝐜𝐨𝐦𝐩𝐨𝐧𝐞𝐧𝐭
Xcomponent = =
𝐭𝐨𝐭𝐚𝐥 𝐦𝐨𝐥𝐞𝐬 𝐨𝐟 𝐜𝐨𝐦𝐩𝐨𝐧𝐚𝐧𝐭𝐬 𝐧𝐭

In an aqueous solution, the mole fraction is 0.25 for C6H12O6, what does this
mean?
It means that:
1) The mole fraction has no units
2) Water is the solvent and glucose is the solute
3) nC6 H12O6 = 0.25 mol.
4) nsolvent = 0.75 mol.
5) mC6 H12O6 can be calculated.
6) msolvent can be calculated.
7) msolution can be calculated.
8) Vsolution can be calculated if density of the solution (dsolution) is given.

118
 Example 6.5
Calculate the mole fraction of 281 g of glucose (C6H12O6) in 450 mL aqueous
g
solution (dsolution = 0.998 ).
mL
solution
Mass = density × volume
g
Mass of solution = 0.998 × 450 mL = 449.1 g
mL
Mass of water = 449.1 g – 281 g = 168.1 g
mglucose 281 g
nglucose = = g = 1.56 mol
Mglucose 180
mol
mwater 168.1 g
nwater = = g = 9.34 mol
Mwater 18
mol
nt = nglucose + nwater = 1.56 mol + 9.34 mol = 10.9 mol
nglucose 1.56
Xglucose = = = 0.143
nt 10.9
Practice Exercise
A solution is made by dissolving 8.74 g sodium nitrate (NaNO3) in 75.0 g of water.
Calculate the mole fraction of sodium nitrate in the solution.

6.6.3 Molality (m)

Molality (m) expresses the concentration of a solution as the number of moles
of solute (nsolute) in one kilogram of the solvent (solv):
𝐧𝐬𝐨𝐥𝐮𝐭𝐞
Molality (m) =
𝐦𝐚𝐬𝐬𝐬𝐨𝐥𝐯 (𝐤𝐠)

What does 0.25 molal C6H12O6 solution mean?

It means that:
mol
1) The molality units are which is usually called “molal” which is
kg
abbreviated as “m”
2) Solvent is water and solute is glucose
3) nC6 H12O6 = 0.25 mol
4) msolvent = 1 kg = 1000 g
5) msolute can be calculated
6) nsolvent can be calculated
7) msolution can be calculated
8) Vsolution can be calculated if density of the solution (dsolution) is given.

Example 6.6

119
 A solution is made by dissolving 4.35 g glucose (C6H12O6) in 25.0 mL of water.
Calculate the molality of glucose in the solution. Water has a density of 1 g/mL.
Solution
g
msolvent = dsolvent × Vsolvent = 25 mL × 1 = 25 g = 0.025 kg
mL
4.35 g
g
nsolute 180 mol
molality = = mol
= 0.097 = 0.097 molal = 0.097 m
masssolv (kg) 0.025 kg kg
Practice Exercise
A solution is made by dissolving 8.74 g sodium nitrate (NaNO3) in 75.0 g of water.
Calculate the molality of sodium nitrate in the solution.

6.6.4 Molarity (M)

Molarity (M) expresses the concentration of a solution as the number of moles
of solute (nsolute) in one liter of the solution (solution):
𝐧𝐬𝐨𝐥𝐮𝐭𝐞
Molarity (M) =
𝐕𝐬𝐨𝐥𝐮𝐭𝐢𝐨𝐧 (𝐋)

What does 0.25 molar C6H12O6 solution mean?

It means that:
mol
1) The molality units are which is usually called “molar” which
kg
abbreviated as “M”
2) Solvent is water and solute is glucose
3) nC6 H12O6 = 0.25 mol
4) Vsolution = 1L = 1000 mL
5) msolute can be calculated
6) msolution can be calculated if density of the solution (dsolution) is given
7) msolvent can be calculated
8) nsolvent can be calculated

Example 6.7
Calculate the molarity of 19.6 g of glucose (C6H12O6) in 650 mL aqueous solution.
Solution
19.6 g
g
nsolute 180 mol
Molarity = = mol
650 mL = 0.168 = 0.168 molar = 0.168 M
Vsoln (L) mL
L
1000
L
Practice Exercise
Calculate the molarity of 8.74 g sodium nitrate (NaNO3) in 750 mL aqueous
solution.

120
 The dilution law
Solutions used routinely in the laboratory are often purchased or prepared in
a very concentrated form (called stock solutions). Solutions of lower
concentrations can then be prepared by adding water to the stock concentrated
solution, this process is called “dilution”. The main point to remember is that
when solvent is added to a solution, the number of moles of solute remains
unchanged:
The number of moles of solute remains the same
in the concentrated solution and in the in the diluted solution
𝐧𝐬𝐨𝐥𝐮𝐭𝐞,𝐜𝐨𝐧𝐜𝐞𝐧𝐭𝐫𝐚𝐭𝐞𝐝 𝐬𝐨𝐥𝐮𝐭𝐢𝐨𝐧 = 𝐧𝐬𝐨𝐥𝐮𝐭𝐞,𝐝𝐢𝐥𝐮𝐭𝐞𝐝 𝐬𝐨𝐥𝐮𝐭𝐢𝐨𝐧
Because:
𝐧𝐬𝐨𝐥𝐮𝐭𝐞,𝐜𝐨𝐧𝐜𝐞𝐧𝐭𝐫𝐚𝐭𝐞𝐝 𝐬𝐨𝐥𝐮𝐭𝐢𝐨𝐧 = 𝐧𝐬𝐨𝐥𝐮𝐭𝐞,𝐝𝐢𝐥𝐮𝐭𝐞𝐝 𝐬𝐨𝐥𝐮𝐭𝐢𝐨𝐧
The dilution law is:
Mconc × Vconc = Mdil × Vdil
Suppose we want to prepare 250 mL solution of CuSO4 with a concentration
of 0.1 M from a stock solution having a concentration of 1 M CuSO4:
𝐧𝐬𝐨𝐥𝐮𝐭𝐞,𝐝𝐢𝐥𝐮𝐭𝐞𝐝 𝐬𝐨𝐥𝐮𝐭𝐢𝐨𝐧 = 𝐧𝐬𝐨𝐥𝐮𝐭𝐞,𝐝𝐢𝐥𝐮𝐭𝐞𝐝 𝐬𝐨𝐥𝐮𝐭𝐢𝐨𝐧
Mconc × Vconc = Mdil × Vdil
1 × Vconc = 0.1 × 250
Vconc = 25 mL
The procedure is to take 25 mL from the 1 M CuSO4 stock solution and add
water to it until the volume becomes 250 mL. the resultant solution is 0.1
molar.

Example 6.8
How many milliliters of 3.0 M H2SO4 are needed to make 450 mL of 0.1 M H2SO4?
Solution
Mconc × Vconc = Mdil × Vdil
mol mol
3 × Vconc = 0.1 × 450 mL
L L
Vconc = 15 mL
Practice Exercise
Calculate the molarity of a sodium nitrate (NaNO3) solution which was prepared
by diluting 15 mL of a 5.5 mol/L NaNO3 stock solution to a volume equals to 150
mL.

121
Example 6.9
How many milliliters of water must be added to 60 mL of 18 M HCl to get a
solution that is 0.2 M?
Solution
Mconc × Vconc = Mdil × Vdil
18 M × 60 mL = 0.2 M × Vdil
Vdil = 5400 mL
Vdil = Vconc + Vwater
5400 mL = 60 mL + Vwater
Vwater = 5340 mL
Practice Exercise
mol
How many milliliters of water must be added to 15 mL of 5.5 NaNO3 stock
L
mol
solution to get a solution that is 0.15 ?
L

6.7 Interconversion between concentration’s units

The above discussion was an illustration to the main four types of
concentration units: solute mass%, mole fraction, molality and molarity. It
was mentioned that knowing any one of them enables us to determine the
other three. The following exercises shows how this can be done.

Example 6.10
An aqueous solution of hydrochloric acid contains 36% HCl by mass:
A) Calculate the mole fraction of HCl
B) Calculate the molality of HCl
Solution
m 36 g
A) nsolute = solute = g = 0.988 mol
Msolute 36.45
mol
msolvent = 100 g – 36 g = 64 g
m 64 g
nsolvent = solvent = g = 3.556 mol
Msolvent 18
mol
nsolute 0.988 mol
Xsolute = = = 0.217
nt (0.988 mol + 3.556 mol)
nsolute 0.988 mol
B) molality = = = 15.44 molal
masssolv (kg) 0.064 kg
Practice Exercise
Calculate the molality of a sodium nitrate (NaNO3) aqueous solution in which the
mass percent of NaNO3 is 43%.

122
 Example 6.11
A solution with a density of 0.876 g/mL contains 5 g of toluene (C7H8) dissolved in
225 g of benzene. Calculate the molality and molarity of the toluene solution.
Solution
m 5g
nsolute = solute = g = 0.054 mol
Msolute 92
mol
nsolute 0.054 mol
m= = = 0.34 molal
masssolv (kg) 0.225 kg
mson 5 g + 225 g
Vsoln = = g = 262.56 mL = 0.263 L
dsoln 0.876
mL
nsolute 0.054 mol
Molarity = = = 0.205 molar
Vsoln (L) 0.263 L
Practice Exercise
A solution with a density of 0.998 g/mL contains 281 g of glucose (C 6H12O6) and
168.1 g of water. Calculate the molality and molarity of the glucose solution.

Example 6.12
Calculate the glucose mass% in a 0.73 molal solution of glucose in water.
Solution
mglucose
Glucose% = × 102
total mass of solution
nglucose = 0.73 mol ,, mwater = 1 kg = 1000 g
mglucose = nglucopse × Mglucose = 0.73 × 180 = 131.4 g
msolution = mglucose + mwater = 131.4 + 1000 = 1131.4 g
131.4 g
Solute% = × 102 = 11.61%
1131.4 g
Practice Exercise
If the molality of a solution of urea (NH2CONH2) in water is 0.14 mol/kg, calculate
the mass percent of urea in the solution.

THE PROPERTIES OF A PURE LIQUID CHANGE

AFTER IT BECOMES NOT PURE
6.7 Vapor pressures, boiling points, and freezing points of pure liquids
6.7.1 Vapor pressures of pure liquids
The liquid molecules that evaporate become gaseous molecules and are called
“vapor” and exert a pressure called “vapor pressure”. The only liquid
molecules that can escape (free themselves) from its liquid state and become
gaseous (vapor) are those which are at the surface of the liquid and having the
highest energies and speeds. Any liquid molecule that does not have high
energy and speed will not vaporize even if it is at the surface of the liquid and
any liquid molecule that is not at the surface of the liquid will not vaporize

123
even if it has high energy and speed. Let’s look carefully to the following
figure:

The figure shows that before the evaporation process starts, the mercury levels
in the U-shaped manometer tube are equal. As soon as some molecules leave
the liquid, a vapor phase is established and its pressure is called the vapor
pressure. However, the process of evaporation does not continue indefinitely.
Eventually, the mercury levels stabilize and no further changes in pressure are
seen. As the concentration of molecules in the vapor phase increases, some
molecules start to condense from the gas phase to the liquid phase. Vapor
molecules differ in their energies and speeds. The only vapor molecules that
can condense back to liquid (trapped by the liquid molecules at the liquid
surface) are those which collide the surface of the liquid, and at the same time
having the lowest energies and speeds. Any vapor molecule that does not have
low energy and speed will not condense even if it collides the surface of the
liquid and any vapor molecule that does not collide the surface of the liquid
will not condense even if it has low energy and speed. As condensation rate
rises evaporation rate falls down until the two rates become equal. When the
two rates become equal, we say that a state of dynamic equilibrium is reached.
The vapor pressure measured when this dynamic equilibrium exists between
condensation and evaporation is called equilibrium vapor pressure. We often
use the simpler term “vapor pressure” when we talk about the equilibrium
vapor pressure of a liquid. It is important to note that the equilibrium vapor
pressure is the maximum vapor pressure of a liquid at a given temperature and
that it is constant at a constant temperature. Increasing temperature increases
not only the energy and speed of molecules but also increases the number of

124
 molecules having high energy and speed. Therefore, as temperature increases
vapor pressure increases. Vapor pressure of many liquids at different
temperatures are available in tables achieved by physicists and chemists.
6.7.2 Boiling points of pure liquids
As cleared out above, when liquid temperature increases its vapor pressure
increases. When the temperature increases the vapor pressure of the liquid will
equalize the external pressure at a certain temperature. At this certain
temperature the whole liquid molecules become in a situation of transition
from the liquid state to the gaseous state, and the surface of the liquid
disappears. This particular situation of evaporation at this certain temperature
is given a particular name. It is called boiling. And the temperature at which
this happens is called “the boiling point.” If the external pressure is the
standard pressure (1 atm) it is called “the standard boiling point”. For
example, the boiling point of water is 100 °C only if the pressure is 1 atm.
 If the external pressure is higher than standard pressure the boiling point
becomes higher than standard boiling point (for example, at 1.5 atm water
will boil at 110.5 °C).
 If the external pressure is lower than standard pressure the boiling point
becomes lower than standard boiling point (for example, at 0.4 atm water
will boil at 84 °C).
Off course, the value of this particular temperature differs from liquid to
liquid. The liquid which vaporizes easier has the lesser boiling point and vice
versa.
6.7.3 Freezing points of pure liquids
Decreasing the temperature of liquid molecules will decrease their energies
and speeds and consequently the attractive forces between them increase. At
a certain temperature, the liquid molecules start to be tightly bonded to their
neighboring molecules and cannot leave their positions. When this starts to
happen, we say: liquid freezes. We call the temperature at which the liquid
freezes “the freezing point.” If the pressure at which liquid freezes is 1 atm
this temperature is called “the standard freezing point”. For example, the
standard freezing point of water is 0 °C.
6.8 Vapor pressures of mixed liquids (Raoult’s law)
Here we do not have a pure liquid but two liquids. Suppose we have liquid
“A” and liquid “B”, and the number of moles we have are “nA and “nB ” and
the forces of attractions between the particles of both liquids are of the same
type. When both of them are pure, we will symbolize their vapor pressure as
PA° and PB° but when they are mixed together, we will symbolize their vapor
pressure in the mixture as PA and PB . If we mix the nA mole of A with nB mole

125
 of B, we will get a liquid solution with a known molar fraction of each, XA
and XB . The question now is: “what is the value of the vapor pressure of the
solution? (Psolution ). “Raoult” had proven that:
Psolution = PA + PB
°
(PA = × PA ) and (PB = XB × PB° )
Therefore, he proved that:
Psolution = (XA × PA° ) + (XB × PB° )
Because XA + XB =1, the last equation can be modified to be:
Psolution = XA × (PA° – PB° ) + PB°
OR
Psolution = XB ×(PB° – PA° ) + PA°
All of these previous equations are known as Raoult’s law. Raoult’s law is
applicable only if the forces of attractions between the particles of the mixed
liquids are of the same type. Any solution obeys Raoult’s law is called “ideal
solution”; if not it is called “nonideal solution”. Nonideal solution will not
be discussed at our level here.

Example 6.13
Calculate the vapor pressure of a solution of 252 g of pentane and 1400 g of heptane
at 20oC.
g °
(Mpentane = 72 and Ppentane = 420 mmHg)
mol
g °
(Mheptane = 100 and Pheptane = 36 mmHg)
mol
Solution
° °
Psolution = (Xpentane × Ppentane ) + (Xheptane × Pheptane )
mpentane 252 g
npentane = = g = 3.5 mol
Mpentane 72
mol
mheptane 1400 g
nheptane = = g = 14 mol
Mheptane 100
mol
npentane 3.5
Xpentane = = = 0.2
npentane + nheptane 3.5 + 14
Xpentane = 1 – Xpentane = 1 – 0.2 = 0.8
Psolution = (0.2 × 420 mmHg) + (0.8 × 36 mmHg) = 112.8 mmHg
Practice Exercise
Calculate the vapor pressure of a solution of 50 g of methanol and 50 g of ethanol at
20oC.
g °
(Mmethanol = 32 and Pmethanol = 94 mmHg)
mol
g °
(Methanol = 46 and Pethanol = 44 mmHg)
mol

126
6.9 The colligative properties of liquid solutions
(Vapor pressures, boiling points, and freezing points of nonpure liquids)

IN OUR DISCUSSION HERE,

THE SOLUTES ARE STRICTLY NONVOLATILE AND
NONELECTROLYTIC.

Colligative properties (or collective properties) are properties of the solution

that depend only on the number of solute particles and do not depend on their
nature. These properties are four:
1) Vapor pressure
2) Boiling point
3) Freezing point
4) Osmotic pressure
Suppose we have a known amount of a liquid solvent, and a known amount
of a nonvolatile and nonelectrolytic solute; and suppose we make a solution
of this solute in this solvent. Below, we will see what happens to the vapor
pressure, boiling point and freezing point of the liquid. Later on, we will
explain the osmotic pressure of the solution.
6.9.1 Vapor-pressure lowering
The vapor above the solution is the vapor of only the solvent. We can calculate
the molar fractions (Xsolvent and Xsolute). The question now is: “what is the
value of the vapor pressure of the solution (Psoln)?”. When the solvent was
°
pure its vapor pressure was Psolvent . However, the solvent molecules, after
dissolving solute particles, become attached to the solute particles. These
attachments hinder the evaporation of the solvent particles which in turn
makes the vapor pressure of the liquid lower than its value when it was pure
by an amount of ΔP which is called “vapor pressure lowering”. The value of
ΔP depends solely on the amount of the solute not on its nature. According to
Raoult’s law:
°
Psolvent = Xsolvent × Psolvent
Because the vapor pressure of the solution belongs only to the vapor pressure
of the solvent, Psolution is given as follows:
°
Psolution = Xsolvent × Psolvent
°
Psolution = (1 – Xsolute) × Psolvent
° °
Psolution = Psolvent – (Xsolute × Psolvent )
° °
Psolvent – Psolution = Xsolute × Psolvent
°
ΔP = Xsolute × Psolvent
127
 The presence of this kind of solutes makes the vapor pressure of the solution
less than that when the solvent is pure by a value equals to ΔP which depends
on the amount of the solute in the solution. This is why ΔP is considered a
colligative property.

EXAMPLE 6.14
Calculate the vapor pressure of a solution made by dissolving 218 g of glucose
(molar mass = 180.2 g/mol) in 460 mL of water at 30 °C. What is the vapor-
pressure lowering? The vapor pressure of pure water at 30 °C is 31.82 torr. Assume
the density of the solution is 1.00 g/mL.
Solution
460 g 218 g
nwater = g = 25.53 mol nglucose = g = 1.21 mol
18.016 180.15
mol mol
25.5 mol
Xwater = = 0.995
25.5 mol + 1.21 mol
°
Psolution = Xsolvent × Psolvent
Psolution = 0.995 × 31.82 mmHg = 30.4 mmHg
°
ΔP = Psolvent – Psolution = 31.82 mmHg – 30.4 mmHg = 1.42 mmHg
Practice Exercise
Calculate the vapor pressure and the vapor-pressure lowering at 35°C of a solution
°
of 82.4 g of urea in 212 mL of water. (Pwater = 42.2 mmHg).

6.9.2 Boiling point elevation

Boiling point (t b ) is the temperature at which the vapor pressure of the liquid
equalizes the external pressure. And the Standard boiling point (t °b ) is the
temperature at which the vapor pressure of the liquid equalizes the standard
external pressure (= 1 atm). As mentioned above, the vapor pressure of the
solution became less than that of the pure liquid. So, the vapor pressure of the
solution, at the temperature at which the pure liquid boils, will be less than
that needed for the solution to boil. So, we will find that the temperature at
which the vapor pressure of the solution equalizes the external pressure is
elevated by a certain value (ΔTb ).
7 The value of ΔTb is proportional to the solution molality (m):
ΔTb ∝ m
ΔTb = K b m
K b is the molal boiling-point elevation constant; its value differs from liquid
to another.
K ×n
ΔTb = b solute
msolvent (kg)

128
 If we prefer for masses as we usually are, using the gram unit rather than the
kilogram, then the conversion factor from kilogram unit to gram unit has to
be introduced in the equation:
°C msolute (kg)
Kb ( mol ) × kg °C kg 1000 g
kg
Msolute ( ) )× msolute (g) × (
Kb ( )
mol mol 1 kg
ΔTb (ºC) = = g
msolvent (kg) Msolute (mol) × msolvent (g)
Kb × msolute × 1000
ΔTb =
Msolute × msolvent
The last equation is used to determine “ΔTb ” but with its restriction that the
g
unit of “Msolute ” is “ ” and the unit of “msolvent ” is “g”.
mol

6.9.3 Freezing point depression

Freezing point is the temperature at which the liquid substance changes its
state to solid. Standard freezing point (t °f ) is the temperature at which the
liquid substance changes its state to solid at the standard external pressure
(= 1 atm). As mentioned before, at a particular low temperature, the liquid
molecules start to be tightly bonded to their neighboring molecules and cannot
leave their positions, and once this starts start happening, we say: liquid
freezes. But because the liquid we have here is not pure but contains a solute
that is nonvolatile, its molecules cannot bond tightly to each other at the same
temperature when the liquid is pure. Temperature of the solution must be
lowered by a certain value (ΔTf ) in order to freeze. The value of ΔTf is
proportional to the solution molality (m):
ΔTf ∝ m
ΔTf = K f m
K f is the molal freezing-point depression constant; its value differs from
liquid to another.
K ×n
ΔTf = f solute
msolvent (kg)
Again, if we prefer for masses as we usually are, using the gram unit rather
than the kilogram, then the conversion factor from kilogram unit to gram unit
has to be introduced in the equation:
°C msolute (kg)
Kf ( mol ) × kg °C kg g
kg
Msolute ( ) )× msolute (g) × 1000 ( )
Kf (
mol mol kg
ΔTf (ºC) = = g
msolvent (kg) Msolute (mol) × msolvent (g)
Kf × msolute × 1000
ΔTf =
Msolute × msolvent
And again, the last equation is used to determine “ΔTf ” but with its restriction
g
that the unit of “Msolute ” is “ ” and the unit of “msolvent ” is “g”.
mol

129
 The following table of some common liquids provides their;
1) standard boiling points (t °b )
2) molal boiling point elevation constant (K b )
3) standard freezing points (t °f )
4) molal boiling point elevation constant (K b )

EXAMPLE 6.15
Ethylene glycol, CH2(OH)CH2(OH), is an automobile antifreeze. It is water
soluble and nonvolatile. (Molar mass = 62.01 g/mol).
A) Calculate the boiling point and the freezing point of a solution made of 651 g
of this substance in 2505 g of water.
B) Would you keep this substance in your car radiator during the summer?
° °
Tfreezing,water = 0 °C and Tboiling,water = 100 °C
Kf,water = 1.86 °C/m and Kb,water = 0.52 °C/m
Solution
msolute 651 g
g
nsolute Msolute 62.01 mol
molality = = = mol
kg = 4.19
msolvent (kg) msolvent (kg) 2505 g × 10–3 kg
g
A) ΔTb = Kb m
ΔTb = 0.52 °C/m × 4.19 m = 2.2 °C
°
ΔTb = Tb,solution – Tb,water
2.2 °C = Tb,solution – 100 °C
Tb,solution = 102.2 °C

ΔTf = Kf m
ΔTf = 1.86 °C/m × 4.19 m = 7.8 °C
°
ΔTf = Tf,water – Tf,solution

130
 7.8 °C = 0 °C – Tf,solution
Tf,solution = – 7.8 °C
B) Because the solution will boil at 102.2 °C, it would be preferable to leave
the antifreeze in my car radiator in summer to prevent boiling.
Practice Exercise
Calculate the boiling and freezing points of a solution containing 478 g of ethylene
glycol (Molar mass = 62.01 g/mol) in 3202 g of water.
°
(Tboiling,water = 100 °C, Kb,water = 0.52 °C/m)
°
(Tfreezing,water = 0 °C, Kf,water = 1.86 °C/m)

EXAMPLE 6.16
A 7.85-g sample of an unknown compound is dissolved in 301 g of benzene. The
freezing point of the solution is 1.05 °C below that of pure benzene. Calculate the
molar mass of this compound.
Solution
ΔTf = 1.05 °C
°C kg g
Kf × msolute (g) × 1000
mol kg
ΔTf = g
Msolute (mol) × msolvent (g)
°C kg g
5.12 × 7.85 (g) × 1000 ( )
mol kg
1.05 °C =
Msolute × 301 (g)
g
Msolute = 127
mol
Practice Exercise
Calculate the boiling and freezing points of a solution containing 478 g of ethylene
glycol (Molar mass = 62.01 g/mol) in 3202 g of water.
°
(Tboiling,water = 100 °C, Kb,water = 0.52 °C/molal)
°
(Tfreezing,water = 0 °C, Kf,water = 1.86 °C/molal)

6.9.4 Vapor-Osmotic pressure

Semipermeable membranes?
 Old way to cool water is to put it in a pottery pot similar to the one shown in
the figure below.
 The walls of the pottery pots permit water inside the pot to pass through its
walls. This allows water to be in contact with the colder atmosphere outside
the pot. This way was one of the ancient technologies to cool drinking water.
these walls do not allow other substances such as ions of other materials to
pass through. It only allows water.

131
 Cells’ wall of the living creatures is depicted in the figure below.
 These walls allow the passage of water from outside to inside and vice versa
but not any other materials.
 Walls of the pottery pot and of the cells of living creatures are named
“semipermeable membranes”.
 Any semipermeable membrane allows the passage of solvent molecules but
blocks the passage of any solute molecules.
What is osmosis phenomenon?
Osmosis is the selective passage of solvent molecules through a porous
membrane or a wall from a dilute solution to a more concentrated one.
 First look and inspect the following figure.

 At the middle, there is a semipermeable membrane.

132
  Into each compartment a sugar solution is poured.
 The volume and temperature of the two sugar solutions are the same but their
concentrations are not.
 The pressure of water on the right side of the membrane is more than its
pressure on the left side.
 The amount of water passing through the membrane from right to left will be
more than that from left to right.
 The surface of the solution in the left side will rise up and that of the right side
will falls down.
 Eventually, equilibrium is reached, that is when amounts water passing
through both sides are the same.
 Once this happens the two pressures exerted on both sides of the membrane
become equal.
 The name of this pressure is osmotic pressure and its symbol is π.
 The osmotic pressure (π) of a solution is the pressure required to stop
osmosis.
 This osmotic pressure of the solution is calculated by the following equation:
π=M×R×T
M is the molarity of the solution and T is the temperature.
number of moles of solute
Molarity =
Volume of solution in liter
Therefore,
n
π= ×R×T
V
π×V=n×R×T

EXAMPLE 6.17
Calculate the molar concentration of an aqueous solution of sucrose (C12H22O11)
that has an osmotic pressure of 30.0 atm at 25 °C.
Solution
π 30 atm
M= = atm L = 1.23 mol/L
R×T 0.0821 × 298 K
mol K
Practice Exercise
What is the osmotic pressure (in atm) of a 0.884 M urea solution at 16 °C?

EXAMPLE 6.18
A I L of hemoglobin solution contains 35.0 g of hemoglobin. The osmotic pressure
is 10.0 mmHg at 25 °C, calculate the molar mass of hemoglobin.
Solution

133
 1 atm
π 10 mmHg ×
760 mmHg
M= = atm L = 5.38 × 10–4 mol/L
R×T 0.0821 × 298 K
mol K
nHb = M × V (L) = 5.38 × 10–4 mol/L × I L = 5.38 × 10–4 mol
m 35 g
MHb = Hb = –4
= 6.51 × 104 g/mol
nHb 5.38 × 10 mol
Practice Exercise
A 202-mL benzene solution containing 2.47 g of an organic polymer has an
osmotic pressure of 8.63 mmHg at 21 °C. Calculate the molar mass of the polymer.

134