FOUNDATION CHEMISTRY CHM092

CHAPTER 4
STATE OF MATTER:
GAS
Contribution by:

Dr. Muhd Firdaus

Hairunnisa
 Topic
4.1 Introduction
4.2 Gas Laws
4.3 Ideal Gas Equation
4.4 Mixtures of Gases & Dalton’s Law of Partial
Pressures
4.5 Kinetic Molecular Theory of Gasses
4.6 Graham’s Law of Diffusion and Effusion
4.7 Real Gases: Deviations from Ideal
Behavior
4.8 Colligative Properties
4.9 Phase Diagrams
 Lesson Outcome
By the end of this chapter, students should be able to:
• Explain how to measure atmospheric pressure using a
barometer and gas pressure using a manometer (closed or
open tube).
• Convert between pressure units.
• Define Gas Laws (Boyle’s Law, Charles’ Law and Avogadro’s
Law) and solve quantitative problems using the respective laws.
• Explain Gas Laws (Boyle’s Law, Charles’ Law and Avogadro’s
Law) in terms of molecular theory.
• Explain the ideal gas law based on combination of the Boyle’s
Law, Charles’ Law and Avogadro’s Law and solve quantitative
problems using the ideal gas law.
• Define molar volume, standard temperature and pressure of an
ideal gas.
 Lesson Outcome
• Determine the molar mass, molar volume and density using
ideal gas law.
• Define Dalton’s Law of partial pressure.
• Calculate the partial pressure, mole fraction and total pressure
of a gas mixture using Dalton’s Law equation.
• Determine amount of gases collected over water using Dalton’s
Law of partial pressure.
• Explain the three postulates/assumptions applied in the kinetic
molecular theory.
• Define diffusion and effusion rate based on the kinetic molecular
theory.
• Solve quantitative problems using Graham’s Law.
• Explain why intermolecular forces between particles and
molecular volume cause a real gas to deviate from ideal behavior
at high pressure and low temperature.
• Use van der Waals equation to solve quantitative problems.
 Lesson Outcome
• Explain the vapour pressure of a pure solvent.
• Explain boiling point and freezing point of a solvent.
• Explain Roult’s Law.
• Explain the effect of solute on the partial pressure,
boiling point and freezing point of solvent.
• Solve quantitative problems using the respective
equations based on the Raoult’s Law.
• Differentiate segments in the heating curve for water
that ranges from below the melting point to above
the boiling point.
• Sketch and characterize the different phases in the
phase diagram of water.
 4.1 The states of matter
• Matter exists in three common states:
– solid
– liquid
– gas.
• The most stable state of a particular substance
can be changed by varying the temperature
and/or pressure.
 4.1 Describing gases
The atoms or
molecules of a gas
move freely to fill
The particles move whatever volume is
rapidly and collide available
constantly. •The particles widely
spaced
• Weak attractions
or repulsions
between them

The volume occupied by a

gas changes with changes
in:
Collisions of the
 pressure
particles cause changes
temperature
in the direction and velocity.
 amount of gas
 Gas Pressure
• Pressure (p):
– At any temperature above absolute zero,
atoms/molecules are always in motion.
– At the molecular level, atoms/molecules exert
forces through never-ending collisions with each
other and with the walls of their container.
– Pressure is the collective result of these collisions.
 Gas Pressure

Pressure = Force (N)

Area (m2)
(force = mass x acceleration)

Units of Pressure
1 pascal (Pa) = 1 N / m2
1 atm = 760 mmHg = 760 torr
1 atm = 101,325 Pa
 Gas Pressure

• The pressure of a gas depends on several factors

amount of gas present (n) in a given volume
volume of the container (V)
Temperature (T)
• The pressure of gas can be measure using:
 Barometer
 Manometer
 BAROMETER
-How it works??
Consist of glass tube that
filled with mercury (Hg)
The tube inverted in the dish
of mercury –some Hg will
flow out & some of them will
remain.
The weight of remaining Hg is
supported by the atm
pressure acting on the surface
of the Hg in the dish.
1 atm = 760 mmHg
 Manometer

A manometer measures the pressure of gases other

than atmosphere.

Closed-tube Open-tube
 Closed-end manometer

The Hg levels are equal A gas in the flask pushes the Hg

because both arms of the U level down in the left arm.
tube are evacuated. The difference in levels, Dh, equals
the gas pressure, Pgas.
 Open-end manometer

When Pgas is less than Patm, When Pgas is greater than Patm,
subtract Dh from Patm. add Dh to Patm.
Pgas < Patm Pgas > Patm
Pgas = Patm - Dh Pgas = Patm + Dh
 EXAMPLE 1
1) The pressure outside a jet plane flying at high altitude falls considerably below
standard atmospheric pressure. Therefore, the air inside the cabin must be
pressurized to protect the passengers.
What is the pressure in pascal (Pa) in the cabin if the barometer reading is 688
mmHg?

Strategy Because 1 atm = 760 mmHg = 101325 Pa, the following

conversion factor is needed to obtain the pressure in atmospheres
Solution The pressure in the cabin is given by

Pressure = 688 mmHg x 101325 Pa

760 mmHg
= 91729.52 Pa
 Checkpoint 1

The atmospheric pressure in Australia on a certain day was 730 mmHg. What was
the pressure in atm?

Ans:0.961 atm
 4.2 Gas Laws

The gas laws describe the physical behavior of

gases in terms of 4 variables:
– pressure (P)
– temperature (T)
– volume (V)
– amount (number of moles, n)

An ideal gas is a gas that exhibits linear

relationships among these variables.
No ideal gas actually exists, but most simple
gases behave nearly ideally at ordinary
temperatures and pressures.
 Boyle’s Law
At constant temperature, the volume occupied by a fixed amount of
gas is inversely proportional to the external pressure.

1
V or PV = constant
P

At fixed T and n,
P decreases as V increases
P increases as V decreases
Boyle’s Experiment, The Relationship Between The
Volume and Pressure of a Gas

 Boyle’s Law:
– Boyle investigated gases in a J-shaped tube.

- He determined that
volume was inversely
proportional to pressure:
pgasVgas = k
 P a 1/V
At constant temperature, the volume occupied by a
P x V = constant fixed amount of gas is inversely proportional to the
external pressure.
P1 x V1 = P2 x V2
Example 2 Applying the Volume-Pressure Relationship

PROBLEM: Boyle’s apprentice finds that the air trapped in a J tube

occupies 24.8 cm3 at 1.12 atm. By adding mercury to the
tube, he increases the pressure on the trapped air to 2.64
atm. Assuming constant temperature, what is the new
volume of air (in L)?

PLAN: The temperature and amount of gas are fixed, so this

problem involves a change in pressure and volume only.

V1 (cm3)
unit conversions

V1 (L)
multiply by P1/P2

V2 (L)
SOLUTION
P1 = 1.12 atm P2 = 2.64 atm
V1 = 24.8 cm3 V2 = unknown n and T are constant

24.8 cm3 x 1 mL x L
= 0.0248 L
1 cm3 103 mL

P1V1 P2V2
= P1V1 = P2V2
n1T1 n2T2

V2 = V1 x P1 = 0.0248 L x 1.12 atm = 0.0105 L

P2 2.46 atm
 Checkpoint 2

A gas occupying a volume of 725 mL at a pressure of

0.97 atmis allowed to expand at constant temperature
until its pressure reaches 0.541 atm. What is its final
volume?

Ans = 1.30 103 mL

 Boyle’s Law: A Molecular View
• Pressure is caused by the molecules striking the sides of the
container
• When you decrease the volume of the container with the
same number of molecules in the container, more molecules
will hit the wall at the same instant
• This results in increasing the pressure
Summary of Boyle’s Law
 Charles’s Law

At constant pressure, the volume occupied by a fixed

amount of gas is directly proportional to its absolute
(Kelvin) temperature.
V
VT = constant
T

At fixed P and n,
V decreases as T decreases
V increases as T increases
 Charles’s Law:
A Molecular View
 The pressure of gas inside and
outside the balloon are the same

 At high temperatures, the gas

molecules are moving faster, so they
hit the sides of the balloon harder –
causing the volume to become
larger

 At low temperatures, the gas

molecules are not moving as fast, so
they don’t hit the sides of the
balloon as hard – therefore the
volume is small
 Variation of Gas Volume with Temperature
at Constant Pressure

• If you plot volume vs.

temperature for any gas at
constant pressure, the points will
all fall on a straight line
• If the lines are extrapolated back
to a volume of “0,” they all show
the same temperature, −273.15
°C, called absolute zero

VαT
V = constant x T Temperature must be in Kelvin
T (K) = t (0C) + 273.15
V1/T1 = V2 /T2
29
 Applying the Volume-Temperature
Example 3 Relationship

PROBLEM: A tank of nitrogen occupies 35230 cm3 under a pressure of

1134 torr at 298 K. What is the volume in liters would it
occupy at 323 K if the pressure and amount of gas are keep
constant?
PLAN: The pressure and amount of gas are fixed, so this problem
involves a change in volume and temperature only.

V1 (cm3)
unit conversions

V1 (L)

V1 = V2 V2 = V1 x T2
T1 T2 T1
Solution

T1 = 298 K T2 = 323 K
V1 = 35230 cm3 V2 = unknown n and T are constant

35230 cm3 x 1 mL x L
= 35.23 L
1 cm3 103 mL

V1 V2
= P1V1 = P2V2
T1 T2

V2 = V1 x T2 = 35.23 L x 323 K
= 38.19 L
T1 298 K
 Checkpoint 3
A 36.4 L volume of methane gas is heated from 25C
to 88 C at constant pressure. What is the final
volume of the gas?

Ans: 44.1 L
Summary of Charles’s Law
 Avogadro’s Law

• Volume directly proportional to the number of gas molecules

V = constant x n
constant P and T
more gas molecules = larger volume
• Count number of gas molecules by moles
• Equal volumes of gases contain equal numbers of molecules
the gas doesn’t matter
 Avogadro’s Law
V a number of moles (n)
V = constant x n Constant temperature
Constant pressure
V1 = V2
n1 n2

35
Avogadro’s Law
 Applying the Volume-Amount
Example 4 Relationship
PROBLEM: A scale model of a blimp rises when it is filled with helium to
a volume of 55.0 dm3. When 1.10 mol of He is added to the
blimp, the volume is 26.2 dm3. How many more grams of He
must be added to make it rise? Assume constant T and P.

PLAN: The initial amount of helium (n1) is given, as well as the initial
volume (V1) and the volume needed to make it rise (V2). We
need to calculate n2 and hence the mass of He to be added.

n1 (mol) of He
multiply by V2 /V1
n2 (mol) of He
subtract n1
mol to be added
multiply by M
g to be added
SOLUTION

n1 = 1.10 mol n2 = unknown

V1 = 26.2 dm3 V2 = 55.0 dm3 T and P are constant

P1V1 P2V2 V1 V2
= =
n1T1 n2T2 n1 n2

n2 = n1 x V2 = 1.10 mol x 55.0 dm

3
= 2.31 mol He
V1 26.2 dm3

Additional amount of He needed = 2.31 mol – 1.10 mol = 1.21 mol He

4.003 g He
1.21 mol He x = 4.84 g He
1 mol He
 Checkpoint 4
Three balloons are filled with different amounts of an ideal gas.
One balloon is filled with 3 moles of the ideal gas, filling the
balloon to 30 L.

a) One balloon contains 2 moles of gas. What is the volume of the

balloon? Ans: 20 L
b) One balloon encloses a volume of 45 L. How many moles of
gas are in the balloon?
Ans: 4.5 moles
Summary of Avogadro’s Law

40
 Gas Laws - Ideal Gas Equation
Boyle’s law: P a 1 (at constant n and T)
V

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

Avogadro’s law: V a n (at constant P and T)

nT
Va
P
nT nT
V = constant x =R R is the gas constant
P P

PV = nRT
41
 4.3 Ideal Gas Equation
 The gas laws – the ideal gas equation:
o All four variables (p, V, T and n) can be related using a
single constant.
o This is known as the gas constant (R).
o In SI units, R = 8.314 J mol-1 K-1
o pV = nRT
o This is known as the ideal gas equation, because it
describes the behaviour of an ideal gas.
o T is in kelvin (T(K) = T (°C) + 273.15).
Gas Behavior at Standard Conditions

STP or standard temperature and pressure specifies

a pressure of 1 atm (760 torr) and a temperature of
0°C ( 273.15 K).

The standard molar volume is the volume of 1 mol of an

ideal gas at STP.
Standard molar volume = 22.4141 L or 22.4 L
Standard molar volume
 The conditions 0 0C and 1 atm are called standard
temperature and pressure (STP).

Experiments show that at STP, 1 mole of an ideal gas occupies

22.414 L.

PV = nRT
PV (1 atm)(22.414L)
R= =
nT (1 mol)(273.15 K)

R = 0.082057 L • atm / (mol • K)

45
 Example 5
If 32.05 grams of solid carbon dioxide evaporates, how many liters of CO2
gas will be formed at a temperature of 323 K and 1.19 atm of pressure?

PLAN: The mass of CO2 (g), the temperature (K) and pressure (atm)
are given. We need to calculate no.of moles of CO2 and then
using ideal gas equation, PV = nRT, we can find V.

Mass of CO2
divide by M
n (mol) of CO2

pV = nRT
V = nRT/p
SOLUTION
P = 1.19 atm n = mass/molar mass
T = 323 K = 32.05 g/ molar mass
V=?

pV = nRT
V = nRT/ p

Mol CO2 = 32.5 g/ 44 gmol-1

= 0.74

pV = nRT/ p
1.19 atm x V = 0.74 x (0.0821 atm L mol-1 K-1)(323 K)

V = nRT/ p
V = 26.8 L
 Checkpoint 5
A 1.00x 103 L steel storage tank contains 88.5 kg of
methane, CH4. If the temperature is 25 C, what is the
pressure inside the tank?

Ans: 135.1 atm

 Checkpoint 6

Sulfur hexafluoride (SF6) is

a colorless and odorless gas.

Due to its lack of chemical reactivity,

it is used as an insulator in electronic
equipment.

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.

Ans: 9.42 atm

 Checkpoint 7

Calculate the volume (in L) occupied by

7.40 g of NH3 at STP.

Ans: 9.74 L
 Density at Standard Conditions
• Density is the ratio of mass to volume
• Density of a gas is generally given in g/L
• The mass of 1 mole = molar mass
• The volume of 1 mole at STP = 22.4 L
 Gas Density
Substituting n into the ideal gas equation
n = mass / molar mass
=m/M
PV = nRT PV = m.R.T
M
Rearranging the equation:
M = m.R.T
V.P
Since density, d = mass/volume
PM
d = RT
 ALTERNATIVE FORMULA FOR
FINDING DENSITY OR MOLAR MASS

Density (d) Calculations

m PM m is the mass of the gas in g
d= =
V RT M is the molar mass of the gas

Molar Mass (M ) of a Gaseous Substance

dRT
M= d is the density of the gas in g/L
P

53
Example 6
Calculate the density of carbon
dioxide (CO2) in grams per liter (g/L)
at 0.990 atm and 55°C.
Strategy
We need to calculate gas density by using the equation.
Is sufficient information provided in the problem?
What temperature unit should be used?
Solution
To use Equation, we convert temperature to kelvins (T = 273 + 55 =
328 K) and use 44.01 g for the molar mass of CO2:
Alternatively, we can solve for the density by writing

Assuming that we have 1 mole of CO2, the mass is 44.01 g. The

volume of the gas can be obtained from the ideal gas equation

Therefore, the density of CO2 is given by

Comment ln units of grams per milliliter, the gas density is 1.62 ×

10−3 g/mL, which is a very small number. In comparison, the density
of water is 1.0 g/mL and that of gold is 19.3 g/cm3.
 Checkpoint 8

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 and determine its molecular formula.

Ans: 67.9 g/mol

Gas Stoichiometry
Example 7
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.

The reaction of calcium carbide (CaC2)

with water produces acetylene (C2H2), a
flammable gas.
Strategy Note that the temperature and pressure of O2 and
C2H2 are the same. Which gas law do we need to relate the
volume of the gases to the moles of gases?

Solution According to Avogadro’s law, at the same

temperature and pressure, the number of moles of gases are
directly related to their volumes. From the equation, we
have 5 mol O2 ≏ 2 mol C2H2; therefore, we can also write
5 L O2 ≏ 2 L C2H2. The volume of O2 that will react with 7.64 L
C2H2 is given by
Example 8
Sodium azide (NaN3) is used in some
automobile air bags. The impact of a
collision triggers the decomposition of
NaN3 as follows:

The nitrogen gas 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 An air bag can protect the
decomposition of 60.0 g of NaN3. driver in an automobile
collision.
Strategy From the balanced equation we see that
2 mol NaN3 ≏ 3 mol N2 so the conversion factor between NaN3
and N2 is

Because the mass of NaN3 is given, we can calculate the

number of moles of NaN3 and hence the number of moles of N2
produced.

Finally, we can calculate the volume of N2 using the ideal gas

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

so that

The volume of 1.38 moles of N2 can be obtained by using the

ideal gas equation:
Example 9
Aqueous lithium hydroxide solution is used to purify air in
spacecrafts and submarines because it absorbs carbon dioxide,
which is an end product of metabolism, according to the
equation

The pressure of carbon dioxide inside the cabin of a submarine

having a volume of 2.4 × 105 L is 7.9 × 10−3 atm at 312 K. A
solution of lithium hydroxide (LiOH) of negligible volume is
introduced into the cabin. Eventually the pressure of CO2 falls
to 1.2 × 10−4 atm. How many grams of lithium carbonate are
formed by this process?
Strategy How do we calculate the number of moles of CO2
reacted from the drop in CO2 pressure?

From the ideal gas equation we write

At constant T and V, the change in pressure of CO2, DP,

corresponds to the change in the number of moles of CO2, Dn.
Thus,

What is the conversion factor between CO2 and Li2CO3?

Solution The drop in CO2 pressure is
(7.9 × 10−3 atm) − (1.2 × 10−4 atm) or 7.8 × 10−3 atm
Therefore, the number of moles of CO2 reacted is given by

From the chemical equation we see that

≏
1 mol CO2 1 mol Li2CO3

so the amount of Li2CO3 formed is also 73 moles.

Then, with the molar mass of Li2CO3 (73.89 g), we calculate its mass:
 Checkpoint 9
(Past Year Oct 2012)
Potassium chlorate, KClO3, (Mw = 122.56
g/mol) decompose to give potassium chloride
and oxygen gas. (R= 0.0821 atm L mol-1 K-1)
i) Write balance equation for the reaction?

ii) What mass of KClO3, must be decomposed to

produce 126 L of oxygen gas at 133 °C and
666.8 torr? Ans: 270.7 g
 4.4 Dalton’s Law
The sum of the partial pressures of all
different gases in a mixture is equal to the
total pressure of the mixture.

P Total = PA + PB + PC + ..

PA = partial pressure of gas A

PB =partial pressure of gas B
PC = partial pressure of gas C
Dalton’s Law of Partial Pressures
V and T are constant

P1 P2 Ptotal = P1 + P2
68
Consider a case in which two gases, A and B, are in a
container of volume V.

nART nA is the number of moles of A

PA =
V
nBRT nB is the number of moles of B
PB =
V
nA nB
PT = PA + PB XA = XB =
nA + nB nA + nB

PA = XA PT PB = XB PT

mole fraction (Xi ) = ni

Pi = Xi PT (refer page 163) nT

69
Example 10
A mixture of gases contains 4.46 moles of neon (Ne), 0.74 mole of
argon (Ar), and 2.15 moles of xenon (Xe). Calculate the partial
pressures of the gases if the total pressure is 2.00 atm at a certain
temperature.

Strategy What is the relationship between the partial pressure of a

gas and the total gas pressure? How do we calculate the mole
fraction of a gas?

Solution According to Equation, the partial pressure of Ne (PNe) is

equal to the product of its mole fraction (XNe) and the total pressure
(PT)
Using Equation, we calculate the mole fraction of Ne as follows:

Therefore,

Similarly,

and

Check Make sure that the sum of the partial pressures is equal to the given
total pressure; that is,
(1.21 + 0.20 + 0.586) atm = 2.00 atm.
 Checkpoint 9
Exactly 8.00 g of O2 and 2.00 g of He was placed in a 5.00 L tank at 298 K.
Determine the total pressure of the mixture in atm, and find the partial pressures
and mole fractions of the two gases.

Answers
Total pressure = 3.67 atm
Mole fraction O2 = 0.33
Mole fraction He = 0.67
 Collecting a Gas over Water

2KClO3 (s) 2KCl (s) + 3O2 (g) PT = PO2 + PH2O

73
Vapor of Water and Temperature

74
Example 11
Oxygen gas generated by the decomposition of potassium chlorate is
collected.The volume of oxygen collected at 24°C and atmospheric
pressure of 762 mmHg is 128 mL. Calculate the mass (in grams) of
oxygen gas obtained.
The pressure of the water vapor at 24°C is 22.4 mmHg.

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

Solution From Dalton’s law of partial pressures we know that

Therefore,

From the ideal gas equation we write

where m and are the mass of O2 collected and the molar mass of
O2, respectively.
Rearranging the equation we obtain

Check The density of the oxygen gas is (0.164 g/0.128 L), or 1.28 g/L,
which is a reasonable value for gases under atmospheric conditions
 Checkpoint 10
(Past year March 2011)
A sample of Zn metal reacts completely with excess hydrochloric
acid:
Zn (s) + 2HCl (aq)  ZnCl2 (aq) + H2 (g)
The hydrogen gas is collected over water at 25  C. The volume of
the gas is 7.80 L and the pressure is 0.980 atm. Calculate the mass of
Zn metal consumed in the reaction.
(vapour pressure of water at 25 C = 23.88 mmHg).

Ans: 19.8 g
 Chemistry in Action : Scuba Diving and the Gas
Laws
Boyle's Law Depth (ft) Pressure (atm)

P V 0 1

33 2

66 3

•As a diver descends, the water pressure around him

increases, causing air in his scuba equipment and body to
occupy a smaller volume (compress).
•As he ascends, water pressure decreases, so Boyle's Law
states that the air in his gear and body expand to occupy a
greater volume.
78
 4.5 KINETIC
MOLECULAR THEORY
OF GASES

79
 Postulates of the Kinetic-Molecular Theory
(pg. 167)
Postulate 1 (*) : Gases are composed of molecules whose size is negligible compared
with the average distance between them. (No particle volume)

Postulate 2 (*) : Molecules move randomly in straight lines in all directions and at
various speeds.

Postulate 3 (*) : The forces of attraction or repulsion between two molecules

(intermolecular forces) in a gas are very weak or negligible, except when they collide.
(No attractive and repulsive forces)

Postulate 4 : When molecules collide with one another, the collisions are elastic.

Postulate 5 : The average kinetic energy of a molecule is proportional to the absolute

temperature.
 Relationship of KMT to the gas laws
• Compressibility of Gases
Gas can be compressed as it does not have volume
(assumption 1)
• Boyle’s Law
P a collision rate with wall of gas container
Collision rate a number density
Number density a 1/V
P a 1/V
• Charles’s Law
P a collision rate with wall of gas container
Collision rate a average kinetic energy of gas molecules
Average kinetic energy a T
PaT 81
 Relationship of KMT to the gas laws
• Avogadro’s Law
P a collision rate with wall of gas container
Collision rate a number density
Number density a n
Pan

• Dalton’s Law of Partial Pressures

Molecules do not attract or repel one another
P exerted by one type of molecule is unaffected by the
presence of another gas
Ptotal = SPi 82
Molecular
speed
 Molecular Velocities
• All the gas molecules in a sample can travel at different speeds.
• The distribution of speeds follows a statistical pattern, the “average
velocity” of the molecules.
• The method of average velocity is called the root-mean-square
method, where the rms average velocity, urms, is a type of average
molecular speed, equal to the speed of a molecule having the
average molecular
kinetic energy.

• As the absolute temperature increases, the

average velocity increases
– the distribution function “spreads out,”
resulting in more molecules with faster
speeds
 Temperature and Molecular Velocities

• KEavg = ½NAmu2
– NA is Avogadro’s number
• KEavg = 1.5RT
– R is the gas constant in energy units, 8.314 J/mol∙K
• 1 J = 1 kg∙m2/s2
• Equating and solving we get
– NA∙mass = molar mass in kg/mol

• As temperature increases, the average velocity increases

Root-mean-square speeds

urms =  3RT
Mm

Where;
R = 8.314 J/K · mol
T = Temperature (K)
Mm = Molar mass (kg/mol)
MAXWELL SPEED DISTRIBUTION CURVES
urms =  3RT
Mm
The distribution of speeds
of three different gases
at the same temperature
Lighter molecules are moving faster

The distribution of speeds

for nitrogen gas molecules
at three different temperatures
More molecules are moving faster at
higher temperature

87
Example 12
Calculate the root-mean-square speeds of helium atoms and nitrogen
molecules in m/s at 25°C.

Strategy To calculate the root-mean-square speed we need

M
Equation 3RT
urms =
What units should we use for R and so that urms will be expressed
in m/s?

Solution
To calculate urms, the units of R should be 8.314 J/K · mol and,
because 1 J = 1 kg m2/s2, the molar mass must be in kg/mol.

The molar mass of He is 4.003 g/mol, or 4.003 × 10−3 kg/mol.

 Using the conversion factor
1 J = 1 kg m2/s2 we get

Check
The procedure is the same for Because He is a lighter gas, we
N2, the molar mass of which is expect it to move faster, on average,
28.02 g/mol, or 2.802 × 10−2 than N2. A quick way to check the
kg/mol so that we write answers is to note that the ratio of the
two urms values (1.36 × 103/515 ≈ 2.6)
should be equal to the square root of
the ratios of the molar masses of N2 to
He, that is,
4.6 GRAHAM’S LAW OF
DIFFUSION & EFFUSION
90
 4.6 Diffusion and Effusion
• The process of a collection of molecules spreading out from
high concentration to low concentration is called diffusion.
• The process by which a collection of molecules escapes
through a small hole into a vacuum is called effusion.
• The rates of diffusion and effusion of a gas are both related to
its rms average velocity.
• For gases at the same temperature, this means that the rate
of gas movement is inversely proportional to the square root
of its molar mass.
 Graham’s Law of Effusion
Description: the rate of effusion of gas molecules from a particular
hole is inversely proportional to the square root of molecular weight of
the gas at constant temperature and pressure.

• For two different gases at the same temperature, the ratio of their rates of
effusion is given by the following equation:
Gas diffusion is the gradual mixing of molecules (molecules
spreading out) of one gas with molecules of another by virtue of
their kinetic properties.


r1 M2
=
r2 M1

molecular path
NH4Cl

NH3 is lighter,
diffuses faster.
Solid NH4Cl appears
at HCl bottle first.
NH3 HCl
17 g/mol 36 g/mol
93
Gas effusion is the process by which gas under pressure
escapes from one compartment of a container to another by
passing through a small opening.


r1 t2 M2
= =
r2 t1 M1

94
Example 12
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.
Gas effusion. Gas molecules
move from a high-pressure
Calculate the molar mass of the region (left) to a low-pressure
one through a pinhole.
unknown gas, and suggest what
this gas might be.
Strategy
The rate of diffusion is the number of molecules passing through a porous
barrier in a given time.
The longer the time it takes, the slower is the rate.
Therefore, the rate is inversely proportional to the time required for diffusion.
Equation can be written as r1/r2 = t2/t1 = , where t1 and t2 are the
times for effusion for gases 1 and 2, respectively.

Solution From the molar mass of Br2, we write


r1
=
t2
=
M2
r2 t1 M1

Where is the molar mass of the unknown gas. Solving for we obtain

Because the molar mass of carbon is 12.01 g and that of hydrogen is 1.008
g, the gas is methane (CH4).
Example 13 Applying Graham’s Law of Effusion

PROBLEM: A mixture of helium (He) and methane (CH4) is placed in an

effusion apparatus. Calculate the ratio of their effusion rates.

PLAN: The effusion rate is inversely proportional √M for each gas, so

we find the molar mass for each substance using its formula and
take the square root. The ratio of the effusion rates is the
inverse of the ratio of these square roots.

SOLUTION: M of CH4 = 16.04 g/mol M of He = 4.003 g/mol

rate

rate
He

CH4
= √ 4.003
16.04
= 2.002
 Checkpoint 11
(Past year March 2011)
A sample of unknown gas effuses in 11.1 min.
An equal volume of H2 in same apparatus under
same conditions effuses in 2.42 min. What is the
molar mass of unknown gas?

Ans: 42.077 g/mol

 4.7 REAL GASES:
DEVIATIONS FROM
IDEAL BEHAVIOR

99
 Real gases
• The ideal gas model makes two assumptions:
– A gas has negligible forces between its constituent atoms or
molecules
– Gas atoms or molecules have negligible volumes
• Neither of these assumptions is true for a real gas
• At sufficiently high pressure and low temperature, all gases can
be liquefied.
 Real gases
• the PV/RT ratio for a real gas is
generally lower than ideal for
“low” pressures – meaning the
most important factor is the
intermolecular attractions
• the PV/RT ratio for a real gas is
generally higher than ideal for
“high” pressures – meaning the
most important factor is the
molecular volume

(1 atm = 1.013 x 105 Pa)

 Real gases
• The ideal gas model can
still be used to discuss
the properties of real
gases, as long as
conditions do not
become too extreme.

• Cl2, He and N2 are nearly

ideal at room
temperature at
pressures below 10×105
Pa.
(1 atm = 1.013 x 105 Pa)
 Real gases
• The van der Waals equation:
– A modified ideal gas equation that accounts for attractive forces
and molecular volumes.

– Adds two correction terms to the ideal gas equation.

– Each correction term includes a constant that has a specific value

for every gas.
 Real gases

• The first correction term a relates to

the strength of the attractive
intermolecular forces.
• The second correction term b
relates to the mass of the gaseous
atoms/molecule (molecular
volume).
 Checkpoint 10
Think!

• Based on their respective

van der Waals constant, is
Ar or CO2 expected to
behave more nearly like
an ideal gas at high
pressure? Explain
 Real gases
• To describe real gas behaviour more
accurately, the pressure, P, and the volume, V,
in the ideal gas equation need to be adjusted
in order to account for the
• intermolecular forces and
• significant molecular volume
 The Effect Of Intermolecular
Attractions
• At normal pressures, the free volume between gas molecules are so large that
attractions between molecules are negligible, and the gas behaves nearly
ideally.
• At higher pressures (external), when the intermolecular distance decreases,
molecules tend to attract one another.
• As nearby molecules attract those approaching the container wall, reduces
their force of impact on the wall, thus, results in decreased gas pressure.
 The Effect Of Intermolecular
Attractions
•At very low temperature, the molecules move very
slowly. This allows the molecules to be close to each
other for a longer time to exert an attractive force to
one another.
•These intermolecular forces between molecules
especially those hitting the container wall lowers the
gas pressure.
Pgas < Pideal
 The Effect Of Molecular Volume

• At normal pressures, the space between molecules (free

volume) is enormous (very large) compared with the volume
of the molecules themselves (molecular volume).
• Therefore, the free volume is approximately equal to the
container volume. Vreal Videal
• As the applied pressure increases, free volume decreases, the
molecular volume makes up a greater proportion of the
container volume.
• At very high pressures, the free volume becomes significantly
less than the container volume.
The Effect Of Molecular Volume
 Example 13
If 1.000 mol of an ideal gas were confined to 22.41 L at 0.0 °C, it would exert a pressure
of 1.000 atm. Use the van der Waals equation and given the constants for Cl2 to estimate
the pressure exerted by 1.000 mol of Cl2(g) in 22.41 L at 0.0 °C.

Solution

Van der Waals constants Cl2 for a = 6.49

L2.atm/mol2 and b = 0.0562 L/mol
 Checkpoint 11

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

Ans: 17.7 atm

(b)the van der Waals equation.

Ans: 16.2 atm

 Summary
• Real gas deviates from Ideal gas behaviour at high
pressure and low temperature.
• Intermolecular forces are partially responsible for the
fact that real gases do not exactly obey the ideal gas
laws.
• The van der Waals equation for a real gas makes
corrections for the volume of the gas molecules and
for the attractive force between them.
4.8 COLLIGATIVE
PROPERTIES OF
THE SOLUTIONS

114
 Colligative properties
• Solutions prepared from nonvolatile solutes differ significantly
in particular properties from pure solvent. These properties
are called colligative properties.
• Nonvolatile solutes:
– Solutes that can’t evaporate from solution.
• Colligative properties depend on number of solute particles in
solution rather than chemical identities.
• There are four colligative properties to consider:
– Vapor pressure lowering (Raoult’s Law)
– Boiling point elevation
– Freezing point depression
– Osmotic pressure (not in syllabus)
 Liquids
- Vapour pressure of a Solution
• Vapour pressure:
– The distribution of molecular energies guarantees
that some of the molecules in any liquid have
enough kinetic energy to overcome the
intermolecular forces that confine the liquid.
– Whenever a liquid has an exposed surface, some
of its molecules will escape into the vapour phase.
 Liquids
• Vapour pressure:
– The number of molecules of a liquid that have enough energy
to escape into the vapour phase depends on:
• the strength of intermolecular forces
• the temperature.
 Liquids
• Vapour pressure:
– Vapour pressure is the pressure at which dynamic
equilibrium is achieved in a closed container.
 Boiling Point and Normal Boiling
Point
• A liquid boils at the temperature where the
vapour pressure of the liquid equals to the
external pressure or the prevailing atmospheric
pressure.
• Normal boiling point (Tb) – The boiling point of
the liquid at 1 atm, that is, the temperature at
which the vapour pressure of the liquid is equal
to an external pressure of 1 atm.
Boiling Point and Normal Boiling
Point
 Melting Point and Normal Melting
Point
• The temperature at which the liquid and solid phases of a
substance coexist in equilibrium at a specific pressure OR it is the
temperature at which the solid and liquid states have the same
vapour pressure.
• Normal melting point or freezing point (Tf): The temperature at
which the solid and the liquid have the same vapour pressure
under conditions when the pressure on the sample is 1 atm.
E.g. the normal melting point or freezing point of ice is 0oC.
 Introduction to solutions
and solubility

• Solution:
– homogeneous mixture of two or more pure
substance
– may be gaseous, liquid or solid.
• Solvent:
– liquid of a liquid solution.
 Introduction to solutions
and solubility
• Solute:
– dissolved substance in liquid solution.
• Solubility:
– maximum amount of solute that dissolves
completely in a given amount of solvent at a
particular temperature, T.
 IDEAL SOLUTION
• An ideal or perfect solution obey Raoult’s law over a wide
range of concentrations. The measured vapour pressure can
be predicted by the Raoult’s law.
• The components in an ideal solution must be structurally
similar (i.e. having similar shapes
• The molecules of both the solute and the solvent in the
solution will have the same tendency to vaporize as they are
in the their respective pure liquid state
 Vapor Pressure Lowering
• Raoult’s law:
– Raoult’s law describes the relationship between vapour
pressure, mole fraction and vapour pressure of pure
component:

Where;
PA : the vapour pressure or the partial pressure of component
A above a solution
PoA: the product of the vapour pressure of the pure component
A
XA : the mole fraction of A in the solution
 Raoult’s Law

Solution

Non-volatile Volatile
solute solute

A solution with non-volatile solute : the vapour pressure

above the solution is due to the partial pressure of the
solvent only.
 Vapor Pressure Lowering
a) When a nonvolatile solute is added to a volatile solvent,
i) The non-volatile solute has no tendency to escape from
the solution into the vapour phase.
ii) It reduces the number of solvent molecules per unit
volume at the surface, thus lowers the escaping
tendency of the solvent molecules to the space above the
liquid, thus, lowers the vapour pressure of the solvent.
b) To calculate the depressed vapour pressure of a solution
i) The total vapour pressure of the solution will be equal to the
partial pressure, PA , of the solvent A as the non-volatile solute does
not contribution to the vapour pressure .
 ii) Apply Raoult’s law for ideal solution.

c) The vapour pressure lowering (PoA - PA = ΔP )

depends on the mole fraction of the solute, the more solute present
the greater is the lowering.
 Example 14

Calculate the vapor pressure of water in a solution prepared

by mixing 99.5 g of C12H22O11 with 300.0 mL of H2O

Given: 99.5 g C12H22O11, 300.0 mL H2O

P°H2O = 23.8 torr, 1mol C12H22O11 = 342.30g, 1mol H2O = 18.02g

PH2O ?

g C12H22O11 mol C12H22O11

cH2O PH2O
mL H2O g H2 O mol H2O
Solution:
Checkpoint 12

Calculate the total vapor pressure of a solution made by dissolving

25.0 g of glucose (C6H12O6) in 215 g of water at 50 oC.
(mmC6H12O6=180.2 g/mol, mmH2O = 18.02 g/mol vapor pressure of
H2O @ 50 oC = 92.5 torr)

Ans: 91.4 torr

 Raoult’s Law
A solution with volatile solute:
• Solutions containing more than one
volatile component: Both the solute (B)
and solvent (A) contribute to the total
vapour pressure of the solution (Ptotal) .
– For component A

– For component B
 Summary: Vapour Pressure
Lowering
2 formulas can be used to calculate vapor-pressure
lowering, ∆P :
1. PA= xAP0A
∆P = P0A - PA

2. ∆P = xBP0A
 Example 15

Calculate the total vapor pressure of an ideal solution made by mixing

0.500 mol of ether (C4H10O) with 0.250 mol of ethanol (C2H6O) at 20°C

Given: 0.500 mol C4H10O, Pºether=440 torr, 0.250 mol C2H6O, Pºethanol = 44.6
torr Ptotal?

Conceptual
mol C4H10O
Plan:

c P
mol C2H6O
 Solution
Solution:
 EXAMPLE 16
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 vapour-pressure
lowering?
Strategy We need Raoult’s law to determine the vapor pressure of a
solution. Note that glucose is a nonvolatile solute.

Solution The vapor pressure of a solution (P1) is

First we calculate the number of moles of glucose and water in the solution:
The mole fraction of water, X1, is given by

we find the vapor pressure of water at 30°C to be 31.82 mmHg.

Therefore, the vapor pressure of the glucose solution is

P1 = 0.955  31.82 mmHg

= 30.4 mmHg

Finally, the vapor-pressure lowering (DP) is (31.82 − 30.4) mmHg , or 1.4

mmHg.
 Alternative answer:
ΔP = xBPoA
xB = n2
n1 + n2
= 1.21 mol = 0.0453 mol
25.5mol + 1.21 mol
ΔP = 0.0453 mol x 31.82mmHg
= 1.4 mmHg
Checkpoint 13

Ans: 0.46 torr

 Checkpoint 14

Calculate the total vapor pressure of a solution prepared by mixing

3.95 g of CS2 with 2.43 g of C3H6O. Both components are volatile.

Ans: 443 torr

 Boiling Point Elevation
a) When a nonvolatile solute is added to a volatile solvent
i) The vapour pressure of the solvent is lowered. Thus, the solution
must be heated to a higher temperature than the boiling point of the
pure solvent to reach the external vapour pressure of 1 atm in order for
boiling to occur.
ii) This means that the presence of a nonvolatile solute elevates the
boiling point of the solvent.
 Boiling Point Elevation

b)To calculate the elevated boiling point of a

solution
The magnitude of the elevation, ΔTb , depends on
the concentration of the solute and is given by the
expression.
(Bpsolution – Bpsolvent) = ΔTb = Kbmsolute

Kb : boiling point elevation constant of the solvent.

Unit = oC kgmol-1.
msolute : molality = mol of solute/mass of solvent.
Unit = mol kg-1
Boiling Point Elevation
DTb = Tb – T b 0

T b0 is the boiling point of

the pure solvent
T b is the boiling point of
the solution

Tb > T b0 DTb > 0

DTb = Kb m
m is the molality of the solution

Kb is the molal boiling-point

elevation constant (0C/m)
for a given solvent

145
 Example
Calculate 18point of a solution made by dissolving
the boiling
1.00 g of glycerin, C3H8O3, in 54.0 g of water
Given: 1.00 g C3H8O3, 54.0 g H2O
Find: Tb, sol’n, °C
Conceptual g C3H8O3, kg H2O m DTb
Plan:
m = mol/kg, DTb = mKb, Kb for H2O = 0.512 °C/m,
Relationships:
BPH2O = 100.0 °C, 1 mol C3H8O3 = 92.09 g
Solve:
 Freezing Point Depression
a) When a nonvolatile solute is added to a solvent e.g. water
i) The resulting solution will not freeze at 0 oC (freezing point of ice)
because the water in the solution has a lower vapour pressure than
that of pure ice.
ii) As the temperature decreases below 0 oC, the vapour pressure of
the ice decreases more rapidly than that of the liquid water.
iii) As cooling continues, the vapour pressure of the ice and the liquid
water will eventually become equal. The temperature at which this
occurs is the new freezing point of the solution and is below 0 oC .
Hence the freezing point has been depressed.
 Freezing Point Depression
b) To calculate the depressed freezing point of a
solution
The expression for the depression of freezing
point, ΔTf , is given by
ΔTf = Kf msolute
Kf :- the molal freezing point constant ;
msolute :- molality of the solution
Freezing-Point Depression

DTf = T f – Tf
0

T f0 is the freezing point of

the pure solvent
T f is the freezing point of
the solution
T 0f > Tf DTf > 0

DTf = Kf m
m is the molality of the solution

Kf is the molal freezing-point

depression constant (0C/m)
for a given solvent
Values of Kf And Kb
 Example 19

Ethylene glycol (EG), CH2(OH)CH2(OH), is a common automobile

antifreeze. It is water soluble and fairly nonvolatile (b.p. 197°C).
Calculate the freezing point of a solution containing 651 g of this
substance in 2505 g of water.

Would you keep this substance in your car radiator during the
summer? The molar mass of ethylene glycol is 62.01 g.
• Strategy This question asks for the depression in freezing
point of the solution.

• The information given enables us to calculate the molality of

the solution and we refer to Table 12.2 for the Kf of water.

• Solution To solve for the molality of the solution, we need to

know the number of moles of EG and the mass of the solvent
in kilograms.
We find the molar mass of EG, and convert the mass of the
solvent to 2.505 kg, and calculate the molality as follows:
Because pure water freezes at 0°C, the solution will freeze at
(0 − 7.79)°C or -7.79°C.
We can calculate boiling-point elevation in the same way as
follows:

Because the solution will boil at (100 + 2.2)°C, or 102.2°C, it

would be preferable to leave the antifreeze in your car
radiator in summer to prevent the solution from boiling.
 Checkpoint 15

1. How many grams of ethylene glycol, C2H6O2, must be added to 1.0 kg H2O to
give a solution that boils at 105 °C?
Ans: 610 g
2. Calculate the freezing point depression of a solution that contains 5.15 g
of benzene (C6H6) dissolved in 50.0 g of CCl4. (Kf for CCl4= 30°C/m)
Ans: 39.6°C

3. A 7.85-g sample of a compound with the empirical formula C5H4 is

dissolved in 301 g of benzene. The freezing point of the solution is
1.05°C below that of pure benzene. What are the molar mass and
molecular formula of this compound?
Ans:127 g/mol; C10H8

155
Summary
• Vapour pressure is the pressure at which
the number of molecules escaping into the
vapour phase matches the number re-
entering.
• Colligative properties are dependent on the
number of solute particles.
• Raoult’s law shows that the pressure above
a solution is proportional to the mole
fraction of the solvent.
• Each component in an ideal solution obeys
Raoult’s law.
4.9 PHASE
DIAGRAMS

157
 The Structure and Properties of Water

The unique macroscopic behavior of water that emerges from its atomic and
molecular properties
 The Unique Nature of Water

• great solvent properties due to polarity

and hydrogen bonding ability
• exceptional high specific heat capacity
• high surface tension and capillarity
• density differences of liquid and solid
states
 H-bonding ability of water
hydrogen bond donor

hydrogen bond acceptor

Each H2O molecule can form four H bonds to other molecules, resulting
in a tetrahedral arrangement.
The hexagonal structure of ice

• Ice has an open structure due to H bonding.

Ice is therefore less dense than liquid water.
3-D Structure of Water
Water is a Unique
Substance
Maximum Density
40C
Density of Water

Ice is less dense than water

162
 Phase Transitions
• The three main phases of matter
are gas, liquid and solid.
• A phase change is the transition of
a substance from one phase to
another.
• Phase changes depend on
temperature, pressure, and the
magnitudes of bonding and
intermolecular forces.
Phase Transitions
 Phase Transitions

• Heating water at constant atmospheric

pressure:
 Phase Diagrams

• A phase diagram summarizes the conditions

at which a substance exists as a solid, liquid,
or gas.
• A convenient way of representing the phases
of a substance as a function of temperature
and pressure:
 Triple point
 Critical point
 Phase equilibrium lines
 Phase Diagrams
Triple point
• The point on a phase diagram representing the
temperature and pressure at which three phases
of a substance coexist in equilibrium.

Critical point
• The point where system is at its critical pressure
and temp
 Phase Diagrams

Critical pressure (Pc)

• the minimum pressure that must be applied to bring
about liquefaction at the critical temperature
• vapor pressure at critical temp.
Critical temperature (Tc)
• the temperature above which the gas cannot be made
to liquefy, no matter how great the applied pressure
• Temp. where substance must always be gas, no matter
what pressure.
 PHASE DIAGRAMS

Supercritical fluids
– Form upon compression of gases at high temperature
or heating a liquid to very high temperature at high
pressure.
– A supercritical fluid has certain properties of both
liquids and gases.
– At the critical temperature or critical pressure the
densities in the gas phase and liquid phase become
equal and no phase boundary can be observed.
 Phase diagrams (P vs T):
- It summarised the phase behaviour of a substance
Phase diagrams - water:

A NEGATIVE SLOPE of solid-

liquid boundary line:
The molar volume of ice is
greater than that of liquid
water hence water is denser
than ice.
An increase in pressure
favors the liquid phase.
Phase diagrams - carbon dioxide:

A POSITIVE SLOPE of solid-liquid

boundary line:
Almost all other substances have
the positive slope of solid-liquid
boundary line.
 The Dry Ice (CO2 (s) )
• It is very useful as a
refrigerant
• It looks like ice and does
not melt
• Sublimation process occur
when solid CO2 is heated
to -78 °C at 1 atm.
At 1 atm
CO2 (s) CO2 (g)
Example 20

Describe any changes in

the phase present when
water is
a) Kept at 0oC while the
pressure is increased from
that at point 1 to that at
point 5
b) Kept at 1.00 atm while
the temperature is
increased from that at
point 6 to that at point 9
Answer:

a) At point 1, H2O exist as a vapor. At point 2 a solid-

vapor equilibrium. At point 3 all H2O change into a
solid. At point 4 solid-liquid equilibrium. At point 5 is
a liquid phase

b)At point 6, H2O exist as a solid. At point 4 is solid-

liquid equilibrium. At point 7 is a liquid. At point 8 is a
liquid-gas equilibrium. At point 9 is a gas phase.
 Checkpoint 16

What phase exists at the point labeled a,b and c?

P (atm)

a
1 b

10 20 30 40 50 60 70 80 90
T (°C)
 Checkpoint 17

Shown below is a phase diagram for compound

Y. At 25°C and 1 atm Y will exist as a ________:

P (atm)

1 a b c

10 20 30 40 50 60 70 80 90
T (°C)
 Checkpoint 18

Based on the phase diagram shown below, which of the following statements are correct?
I. Sublimation occurs at a point in the transformation that occurs along a straight line from point
A to point F.
II. C and E represent points where the gas and liquid phases are in equilibrium.
III. Hvap can be measured at point B.
IV. Molecules at point D have a greater average kinetic energy than those at point F.
V. The temperature at point E is called the critical temperature of the compound.

a) II, V d) II, IV, V

b) I, III, IV e) I, II, IV
c) I, II, III
Summary
• A phase change occurs when a
substance undergoes a transition from
one phase to another and required
energy to be either supplied or
removed.
• Temperatures and pressures at which
equilibria can exist between phases are
shown in a phase diagram.
• Supercritical fluids contain properties of
both liquids and solids.