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H2 Chemistry Notes

H2 Chemistry (9729)
Lecture Notes 5
The Gaseous State
Assessment Objectives:
Candidates should be able to:
(a) state the basic assumptions of the kinetic theory as applied to an ideal gas
(b) explain qualitatively in terms of intermolecular forces and molecular size:
(i) the conditions necessary for a gas to approach ideal behaviour
(ii) the limitations of ideality at very high pressures and very low temperatures
(c) state and use the general gas equation pV = nRT in calculations, including the determination of Mr
(d) Use Dalton’s Law to determine the partial pressure of gases in a mixture.

Lecture Outline
1. Kinetic Theory of Matter
2. The Gas Laws
3. Mixture of Gases (Partial Pressures)
4. Real and Ideal Gases
5. Deviation from Ideal Gas Behaviours

Recommended Materials:
1) Cann, Peter and Hughes, Peter, Chapter 4.13 & 4.14, Chemistry for advanced level, 2002 (540 CAN)
2) Silberberg, Martin S., Chapter 5 & 12.1, Chemistry: The Molecular Nature of Matter and Change, 3 rd
ed., 2003 (540 SIL)
3) Advanced Study Guide Chemistry by C S Toh, published by Step-by-Step International Pte. Ltd.

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1. Introduction:
a. Definitions and Physical Properties of Gases
Gases are made up of particles that are separated by large distances (due to weak intermolecular
forces between the particles) and these particles are constantly moving around.

These constant movements in a container result in constant

collisions with the walls of the container, giving rise to the
phenomenon known as the “pressure” of the gas.
The gas particles are constantly moving as they possess kinetic
energy (K.E.). The amount of K.E. depends on the temperature of the gas.

In summary, the gaseous state is characterized by the following physical properties:

- Gases do not have a fixed shape and volume, i.e. gases assume the volumes and shapes of
their containers.
- Gases are highly compressible and gas volume changes greatly with pressure.
- Gases exert pressure equally in all directions.
- Gases mix evenly and completely when confined to the same container.
- Gases have much lower densities than solids or liquids.
- Gases are poor heat conductors, i.e. good insulators.

b. Kinetic Theory of Matter

The Kinetic Theory describes the particles in solids, liquids and gases and the movement of these particles.
Some of the characteristics that distinguish these three states of matters are:

Property Solids Liquids Gases

Takes the shape of the
Takes the shape and
Shape and Volume Fixed container,
volume of the container
fixed volume
Forces between
Strong Less strong Weak
particles
Arrangement of
Orderly manner Not in orderly manner Random arrangement
particles

Close but not as close as

Packing of particles Close Far apart
solids
High; packed closely, Low; far apart, high
Density High
the volume is very small volume
Compressibility Nil Almost Nil High
Boiling / Melting
High Moderate to high Low
point
Movement of Vibrate and rotate about Vibrate, rotate and move Vibrate, rotate and
particles fixed position anywhere but at a lower move anywhere within
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speed as compared to
the container
gases
More than solids but less
Energy Little High
than gases
Yes due to particles
Depends on the depth of
Pressure Negligible bouncing off the walls of
the liquid
the container

Changes of States

sublimation

melting vaporisation
Solid Liquid Gas
freezing condensation

deposition

Note:
- Vapour pressure of a liquid is the pressure exerted by those molecules that escape from the
liquid to form a separate vapour phase above the liquid.
- Saturated vapour pressure is the maximum vapour pressure that is exerted by a vapour when
it is in dynamic equilibrium with its liquid (in a closed container).
- Boiling: A liquid boils when its saturated vapour pressure equals the external pressure. When
external pressure decreases, the boiling point also decreases.
E.g. H2O boils at 100ºC at 1 atm (101kPa) but boils at 93ºC at 80 kPa.

2. Gas Laws
The physical behaviour of a sample of gas can be described completely by four measurable
macroscopic properties:
SI Units
p = pressure exerted by the gas Pa
V = volume occupied by the
m3
gas
T = temperature of the gas K
n = amount of the gas mol

2.1 Avogadro’s Law

At a constant temperature and constant pressure, the volume of a gas, V, is directly
proportional to the number of moles of the gas, n.
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Vn
V
= constant
n
V1 V2
=
n 1 n2

2.2 Boyle’s Law

At a constant temperature, the volume of a given mass of gas, V, is inversely proportional to
the pressure, p.

1
p V
pV = Constant
 p1V1 = p2V2

Additional Information:

A diver's body can be affected by Boyle's law. As the diver goes deeper into the sea, water pressure
increases and this causes the volume of the compressible body areas (which contain air spaces such as,
air canals, lungs, sinuses nasal passages and hollow organs) to decrease. As a result, the diver would
suffer the consequences as explained by Boyle's law in them. This way, it is very important that divers
foresee the problems which their bodies might have to face.
2.3 Charles’ Law
At a constant pressure, the volume of a given mass of gas, V, is directly proportional to its
absolute temperature, T.

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VT
V
= constant
T
V1 V2
=
T1 T2

2.4 Gay-Lussac’s Law

At a constant volume, the pressure of the gas, P, is directly proportional to its absolute
temperature, T

pT
P
= constant
T
p1 p2
=
T1 T2

2.5 The Ideal Gas Equation / The General Gas Law

From Avogadro’s Law, V  n
1
From Boyle’s Law, p  V
From Charles’ Law, V  T
From Gay-Lussac’s Law, p  T
Combining Avogadro’s Law, Boyle’s Law, Charles’ Law, and Gay-Lussac’s Law
nT
V p

For 1 mole of gas, constant R is designated as molar gas constant, R.

R is also known as universal gas constant.

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pV
=constant =R
nT

These expressions can be combined to form one single equation for the behaviour of gases: The
Ideal Gas Equation. It gives the relationship between the volume of a given mass of gas and the prevailing
conditions (temperature, pressure and the number of moles).

Ideal Gas Equation / General Gas Equation

pV =nRT

Where R: Universal Gas Constant (Molar gas constant)

Value of R depends on units of P, V, n and T
P Pressure Pa or Nm-2 atm
V Volume m3 dm3
n No. of moles mol mol
T Temperature K K
R Universal Gas 8.31 J K-1 mol-1 atm dm3 mol-1 K-1 0.0821
Constant (S.I. units)

Determination of molar gas constant, R

1 atm = 760 mmHg = 101000 Pa

Useful conversions:
(approximately)
1 dm3 = 1000 cm3 = 10-3 m3

1 mol of gas occupies 22.4 dm3 at s.t.p, i.e., 0oC and

101000 Pa or Nm-2
V = 22.4 dm3 = 0.0224 m3

To derive R, the exact value of 101325 Pa is used:

pV = nRT
pV
R = nT
(101325 ×0 . 0224 )
= (1×273 )
= 8.31 Nm K-1 mol-1
= 8.31 J K-1 mol-1

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The ideal gas equation can also be used to find the molar mass (M) or the density () of the gas.

m m
n= ρ=
Given that M and V ,

pV =nRT
m
pV = RT
M
mRT ρ RT
M= =
pV p
Mp
ρ=
RT

Exercise 1
1. Calculate the pressure exerted by 0.05 mol of gas at 25oC and having a volume of 500 cm3.
Solution:
pV =nRT
p×500×10−6 =0 . 05×8. 31×298
0 . 05×8 .31×298
p=
500×10−6
=247638 Pa = 2. 48 × 10 5 Pa

2. A sample of a gas exerts a pressure of 82.5 kPa in a 300 cm3 container at 25oC. What pressure
would the same gas sample exert in a 500 cm3 container at 50oC?
Solution:
p1 V 1 p 2 V 2
=
T1 T2
82 .5×300 p 2 ×500
=
298 (273+50 )
p 2 =82 . 5×300×323 =53 . 7 kPa
298×500

3. Which of the following diagrams correctly describes the behaviour of a fixed mass of an ideal gas? [T
is measured in K] J86 & N91

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A B C D E

P P PV V
PV

constant T constant V constant T constant T constant P

V T P V T

Ans: E

4. Which graph is correct for a given mass of an ideal gas at constant pressure?
J2000
A B C D
V V V V

T/ºC T/ºC T/ºC T/ºC

Ans: C

For each of the questions below, one or more of the three numbered statements 1 to 3 may be correct.
The responses A to D should be selected on the basis of

A B C D
1, 2 and 3 are 1 and 2 only are 2 and 3 only are 1 only is correct
correct correct correct
5. Which of the following equations apply to an ideal gas?
(p = pressure, V = volume, m = mass, M = molar mass,  = density,
c = concentration, R = gas constant, T = temperature) J91
ρ RT cRT
1 p= M 2 pV = MRT 3 pV = M
Ans: D

6. The Gas Laws can be summarised in the ideal gas equation, pV = nRT, where each symbol has its
usual meaning. Which of the following statements are correct? N92

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1 One mole of any ideal gas occupies the same volume under the same conditions of temperature
and pressure.
2 The density of an ideal gas at constant pressure is inversely proportional to temperature.
3 The volume of a given mass of an ideal gas is doubled if its temperature is
raised from 250C to 50OC at constant pressure.
Ans: B

3. Mixture of Gases
3.1 Partial Pressure
The pressure of gas is due to the particles bouncing off the walls of the container after hitting onto
them. For a mixture of gases which do not react with each other, each gas exerts its own pressure
(independent of the other gases) - known as its partial pressure. The partial pressure of each gas
is the pressure it would exert if it alone occupied the same volume.

3.2 Dalton's Law of Partial Pressure

At constant temperature, for gases which do not react chemically, the total pressure of a mixture of
gases in a given volume is equal to the sum of the partial pressures of the constituent gases.

pT = pA + pB + pC + ….

3.3 Mole Fraction, Partial Pressure and Total Pressure

Assuming a mixture of gas A and gas B contained in a volume, V, at temperature, T,
n A RT
Partial pressure of gas A: pA = V
nB RT
Partial pressure of gas B: pB = V

Total pressure, pT = pA + pB
n A RT nB RT
= V + V
( n A + n B ) RT
= V

n A RT ( n A + n B ) RT
pA / pT = V / V

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n A RT V
= V x (n A + n B ) RT
nA
=
n A + nB
= χA , where χA is the mole fraction of gas A.
Hence partial pressure of a particular gas is the product of the mole fraction of the gas and the
total pressure of the mixture.

pA = χApT
nA
= n + n pT
A B

Exercise 2
7. A 2.0 dm3 flask contained 0.2 mol of nitrogen and 0.4 mol of oxygen at 400K.
Calculate:
(a) the partial pressure of nitrogen
(b) the partial pressure of oxygen
(c) the total pressure in the flask.
Solution: PV = nRT
a) pN2 = (0.2 x 8.31 x 400) / 2 x 10-3 = 332400 Pa
b) pO2 = (0.4 x 8.31 x 400) / 2 x 10-3 = 664800 Pa
c) pT = pN2 + pO2 = 332400 + 664800 = 997200 Pa = 9.97 X 105 Pa
8. A gas mixture consists of 0.4 mol of N2, 0.6 mol of O2 and 0.2 mol of Ar at a total pressure of 300
kPa. Calculate the partial pressure of each gas in the mixture.
Solution: pN2 = χN2pT = 0.4 / (0.4 + 0.6 + 0.2) x 300 = 100 kPa
pO2 = 0.6 / 1.2 x 300 = 150 kPa
pAr = 0.2 / 1.2 x 300 = 50 kPa

9. A 2 dm3 flask containing a gas N at a pressure of 7 atm was connected to another flask containing a
gas M with a volume of 3 dm3 at a pressure of 4 atm. What is the final pressure, assuming that the 2
gases do not react and temperature was constant throughout?
Solution: For gas N, For gas M,
pbeforeVbefore = pafterVafter pbeforeVbefore = pafterVafter
7 x 2 = pN (5) 4 x 3 = PM (5)
pN = 2.8 atm pM = 2.4 atm
pT = pN + pM = 2.8 + 2.4 = 5.2 atm

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Alternative solution:
(Pm,1)(Vm,1) + (Pn,1)(Vn,1) = (Pm,2)(Vm,2) + (Pn,2)(Vn,2)
(Vm,2) and (Vn,2) are the same  Same final total volume  (Vm,2) + (Vn,2) = Vt
Applying Dalton’s Law for mixture of gases that do not react with each other,
(Pm,2) + (Pn,2) = Pt
(4)(3) + (7)(2) = Pt Vt
Vt = 5 dm3
Pt = 5.2 atm

4. Real and Ideal Gases

The Kinetic Theory of Gases is a mathematical model that is used to study the behaviour of gases. It is an
attempt to explain the macroscopic properties (e.g. p, V, T, n) of a gas in terms of its molecular behaviour.

In reality, an ideal gas does not exist; it is a hypothetical gas that allows us to gain a better understanding
of real gases by simplifying their complexities so that behaviour of gases can be more easily understood.
The kinetic theory therefore takes into account various assumptions as applied to an ideal gas.

4.1 Features of an Ideal Gas (Assumptions of the Kinetic Theory applied to Ideal Gases)
- The volume of each gas particle is negligible compared to the total volume occupied by the
gas.
- There are negligible forces of attraction between particles.
- When the particles collide, the collision is perfectly elastic, i.e., the particles bounce apart
after they collide with no loss of kinetic energy and particles do not stick together after
collision.
- The gas particles are in constant random motion.
- The average kinetic energy of the particles is proportional to the absolute temperature.

4.2 Features of a Real Gas

- The particles have a certain volume, i.e., the volume of particles is not completely negligible in
comparison to the total volume of the gas.
- There are forces of attraction between particles, though they are usually very weak.
- When the particles collide, the collision is not elastic, i.e., there is loss of kinetic energy and
the particles stick together after collision.

5. Deviation from Ideal Gas Behaviours

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An ideal gas (one which obeys the ideal gas equation) is hypothetical in nature. All real gases do
not obey the ideal gas equation. Deviations from the ideal gas behaviour can be observed by

pV
plotting nRT versus p. An ideal gas will have a constant value of 1 since pV = nRT = constant.

Real gases deviate most from ideal gas behaviour at high pressure and low temperature (not far
from the boiling point).

Deviation from ideality is due to:

1) Forces of attraction between gas particles becoming more significant.
2) Volume occupied by each gas particle becoming more significant.

5.1 Factors affecting forces of attraction

Fig 1: Graph of pV/RT vs p (atm) for 1 mol of nitrogen gas at 3 different temperatures
- Temperature: At low temperatures, the kinetic energy of the gas particles decreases and the
particles move closer to one another. This causes the attractive forces between the particles
to become more significant. Hence at lower temperatures, there will be greater deviation.
(Fig 1)

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- Pressure

Increase
in
pressure

low pressure high

pressure
When pressure of the gas increases, the gas particles are closer together and the attractive forces
between the particles becomes more significant. Hence at higher pressures, there will be
greater deviation. (Fig 1)

- Type of molecule / size of molecule:

Fig 2: Graph of pV/RT vs p (atm) for 1 mol of several gases at 300 K

Referring to Fig 2, all four gases are non-polar molecules. CO 2 deviates the most from ideal gas
because it has the greatest number of electrons and hence, the strongest induced dipole-induced
dipole interactions.

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Likewise, a polar molecule would deviate more than a non-polar molecule of similar Mr due the
additional permanent dipole-permanent dipole interactions (and hydrogen bonding, if applicable).

Exercise 3
10. Which of the following gases shows the greatest deviation from ideality?
A Ammonia C Methane
B Ethene D Nitrogen Ans: A

Give a reason for your choice.

Comparing the strength of intermolecular forces of attraction, ammonia will show the greatest deviation
from ideality because ammonia has hydrogen bonding between molecules. Hydrogen bonding is stronger
than induced dipole-induced dipole attractions which exist in ethene, methane and nitrogen.

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