CHAPTER 10

GASES

CONTENT
10.1 Characteristics of Gases
10.2 Pressure
10.3 The Gas Laws
10.4 The Ideal-Gas Equation
10.5 Further Applications of The Ideal Gas
Equation
10.6 Gas Mixture and Partial Pressures
10.7 Kinetic-Molecular Theory
10.8 Molecular Effusion and Diffusion
10.9 Real Gases: Deviations from Ideal
Behaviour
2

Learning Outcomes
Able to apply the Ideal Gas Law in
calculations involving gaseous system
Able to calculate partial and total
pressure in a mixture of gases (with or
without reaction)
Able to differentiate effusion and
diffusion
Able to apply kinetic molecular theory
in problem solving
3

Properties of gas
The properties of a gas depends upon four variables Pressure (P)
Is equal to force/unit area
Measured by a barometer
SI unit = Newtons/meter2 = 1 Pascal (Pa)
1 standard atmosphere = 101,325 Pa
1 atm = 760 mm Hg = 760 torr
Volume (V) of the gas = volume of the container
Temperature (T) measured in Kelvin
Number of moles (n)

Introduction to Pressure
Pressure Units
m
d
mass(m) acceleration 2 kg 2
Force F
kg
t

s
P=
= =
=
=
2
2
Area A
area(d )
m
m s2

1 Pascal (Pa)

= 1 kg/m.s2

1 Atmosphere (atm)
1 Bar

= 100 kPa

1 Atmosphere (atm)

= 1.013 bar

1 Atmosphere (atm)

= 14.7 psi

1 Atmosphere (atm)

= 760 mm Hg = 760 torr

1 torr

12/14/15

= 101,325 Pascals = 101.325 kPa

= 1 mm Hg = 133.3 Pa

Bonds
a HGFGJDF

Bonds
a HGFGJDF

Example 1
Convert 0.378 atm to: a) torr; b) pascal
(1atm = 760 torrs = 101325 Pa)

760 torr
0.357 atm
271 torr
1 atm
101325 Pa
0.357 atm
36173 Pa
1 atm
8

10.2.2 Pressure of Enclosed

Gases and Manometers
Closed-tube manometer
a measures pressure below atmospheric
pressure.
a difference in height of mercury level equals to
pressure of enclosed gas.

Open-tube manometer
a measures pressure near atmospheric pressure.
a difference in height of mercury level relates to
pressure of enclosed gas.
9

Bonds
a HGFGJDF

10

Example 2
A vessel connected to an open-end mercury
manometer is filled with gas to a pressure of
0.835 atm. The atmospheric pressure is 755
torr.
a) In which arm of the manometer will the
level of mercury be higher?
b) What is the height difference between the
2 arms of the manometer?
11

Example 2 (Answer)
a) Since the atmospheric pressure is greater
than the enclosed gas, the level attached to
the gas will be higher.
b)

0.835 atm 760 torr = 635 torr

1atm
P gas + Ph
= Patm
635 torr + Ph = 755
Ph = (755 - 635 ) torrs
= 120 torr = 120 mm Hg12

gas

Ideal Gases
Behave as described by the ideal gas equation; no real gas is
actually ideal
Within a few %, ideal gas equation describes most real gases at
room temperature and pressures of 1 atm or less
In real gases, particles attract each other reducing the pressure
Real gases behave more like ideal gases as pressure approaches
zero.

An equation relating the macroscopic variables that

describe some type of matter.
The ideal gas law is an equation of state for gases.
13

Bonds
Volume vs. 1/Pressure

1
V
P
P1 V1 = P2 V2
PV = k = constant
At Constant n,T
14

Boyle Law
A sample of gas has a volume of 54 ml at pressure 452
mmHg. What will the volume be if the pressure is
changed to 649 mmHg while the temperature is kept
constant?

Initial(1)
Final(2)

Vol/ ml Pressure/mmHg
54
452
?
649
P1V1

= P2V2

(452mmHg)(54ml) = (649mmHg)V2
V

= 37.6 ml

15

V T (abs.)
(n, P
constant)
V/T = k = constant
V1 /T1 = V2 T2

16

Bonds
a HGFGJDF

17

Example 3
A sample of gas has a volume of 364 ml at a
temperature of 25 C. What will the volume be if
the temperature is changed to 100.0 C while the
pressure is kept constant?
Initial(1)
Final (2)

Vol/ml
Temp/C Temp/K
364
25.0
25 + 273.15 = 298.15
?
100.0
100 + 273.15 =373.15

V1 V2

T1 T2
V1
V2 T2 455.6ml
T1

18

Vn

a Avogadros law: For a gas at constant

temperature and pressure, the volume of a
gas is directly proportional to the number
of moles of the gas.
a Note: This relationship is
obeyed closely by gases at
low pressure.

19

10.3.3 Avogadros Law: The

Quantity-Volume
Relationship
Avogadros hypothesis: Equal volume of
gases at the same temperature and pressure
contain equal numbers of molecules.
Ar
N2
H2
Volume

22.4L

22.4L

Pressure

1atm

1atm

Temperature

0 0C

0 0C

Mass of gas

39.95g

No. of molec.
1023

6.02 x 1023

22.4L
1atm
0 0C

28.01g

2.02g

6.02 x 1023

6.02 x
20

Example 4
Suppose we have a 12.2 L sample containing 0.5 mol oxygen
gas (O2) at a pressure of 1 atm. and a temperature of 25C. If
all this O2 were converted to ozone (O3) at the same
temperature and pressure, what would be the volume of
ozone? 3 O2(g)
2 O3
3 mol of O2 gives 2 mol of O3
0.5 mol of O2 = 0.5 mol O2 2 mol O3 = 0.33 mol O3

V1 V2

n1 n2

3 mol O2

V1
12.2 L
V2 n2
0.33 mol 8.05 L
n1
0.5 mol

21

The Ideal-Gas Equation

From Ideal-Gas Equation : PV = nRT
P1V1 P(2Vconstant
1)
n)
2

T1
T2
2)

V1 V2
(constant n & P)
T1 T2

3)

P1 (constant
P2
n & V)

T1 T2

4)

P1V1 (constant
P2V2
n & T)

22

Cont: The Ideal-Gas

Equation
The ideal-gas equation does not always
accurately describe real gases.The measured
volume,V for given P, n and T might differ from
the volume calculated from PV = nRT.
The standard conditions for gas behaviour
(where R is calculated based on 0 C and 1
atm) are not the same as the standard
conditions in thermodynamics (25C and 1
atm).

Note: Very small volume difference is noticed in

calculation involving real and ideal gas. 23

Determine volume of 1 mole gas x at STP.

Standard temperature and pressure
(STP):
P = 1atm n = 1 mol
R = 0.0821 L-atm/mol K
T(K) = T(C) + 273.15
= 0C + 273.15
= 273.15K

nRT
V
P
1.0 mol 0.0821 L.atm / K mol 273.15 K
V
1.0 atm
V 22.4 L
The volume occupied by 1 mol of ideal gas at STP, 22.4L is
known as the molar volume of an ideal gas at STP. 24

Example 5
What volume would be occupied by 100g of
oxygen (O2) at 18 C and 105 kNm-2?

n = 100 g
= 3.125 mol
T = 18 + 273
= 291 K

32
R = 8.31
nRTg/mol
V
Nm/K.mol
P

3.125mol 8.31Nm / mol.K 291K

V

105 10 Nm
3

V 0.0720m 3

25

Example 6
A metal cylinder holds 50.0 L of oxygen at
18.5 atm and 21C. What volume will the
gas occupy if the pressure is reduced to
1.00atm and temperature is maintained at
21C.
From PV = nRT
P 1V1 = P 2V2
When T, n are constant
V2 = P 1V1

P2

V2 = (18.5 atm) (50.0L) = 925 L

(1.00 atm)

26

Gas Density
Remember that the density of a gas is
the mass divided by the volume
Gas density is usually expressed a g/L
Molarity (M) =

m nM
PV
d=
andn =
V V
RT
PV M PM
d =

RT V RT
PM
d
RT

For a given pressure and temperature, the

molar concentration should be the same for any
gas

Two equal volumes of 2 different gases at the

same temperature and pressure will contain the
same # of molecules.
It doesnt matter if the gasses are the same or
different

The higher the molar mass, the

higher the density

Example 7
What is the density of CCl4 vapour at 714
torr and 125 oC?
Molar mass of CCl4, M = 12.0 + 4(35.5) =
154.0 g/mol
Pressure: 760 torr = 1 atm

714 torr : 714 torr 1 atm = 0.939 atm

760 torr

PM
0.939atm 154 g / mol
density, d

RT 0.0821L.atm / mol.K 398 K

28
density, d 4.43 g / L

Example 8
The industrial synthesis of nitric acid
involves the reaction of nitrogen dioxide gas
with water
3NO2 (g) + H2O (l)

2HNO3 (aq) + NO(g)

How many moles of nitric acid can be

prepared using 450 L of NO2 at a pressure of
5.00 atm and a temperature of 295 K?
29

Example 8 (Answer)
VNO2 = 450L, T = 295K,
3NO2 (g) + H2O (l)

P = 5.00 atm

2HNO3 (aq) + NO(g)

PV
5.00atm 450 L
n

RT 0.0821L.atm / mol.K 295 K

n 92.9mol
3 mol of NO2 will produce 2 mol of HNO3
92=.9mol
92.9 mol NO2 will produce
2mol
3mol
61.9mol

30

Exercise 10.3
1. A large flask is evacuated and found to weigh 134.567g. It is
then filled to a pressure of 735 torr at 310C with a gas of
unknown molar mass and then reweighed; its mass is 137.456g. The
flask is then filled with water and again weighted: its mass now
1067.9g. What is the molar mass of the unknown gas?
{use M=dRT/P, answer 79.7 g/mol}
(the density of water at 310C is 0.997g/cm3)

2. The density of a gas measured at 1.50 atm and 27C and

found to be 1.95 g/L. Calculate the molar mass of this gas.
{use M=dRT/P, answer 32.0 g/mol}

31

Daltons Law of Partial Pressures

The total pressure of a
mixture of gases is the sum
of the partial pressures of
its components
In gas mixtures each gas
acts independently of the
other gases present
Mathematically
P Total = P1 + P2 + P3 + ...

Mole Fractions
The best way to explain/understand the relationship between
total pressure and partial pressures is to look at the mole
fractions of each gas in a mixture
For a mixture of gases with components A, B and C, the mole
fraction (xA) is:
xA

nA
n A n B nC

Or

xA+ xB+ xC= 1

Each gas exerts a pressure that is the mole fraction of the gas
times the total pressure in the vessel
PA = xAP
Note that n

Example 9
Mixture of helium and oxygen are used in scuba diving tanks
to help prevent the bends. For particular dive, 46 L He at 25
C and 1.0 atm and 12 L O2 at 25 C and 1.0 atm were
pumped into a tank with a volume of 5.0 L. Calculate the
partial pressure of each gas and the total pressure in the tank
at 25 C.
PHe = 1.0 atm; VHe = 46 L ; R = 0.08206 L.atm/K.mol
THe= 25 +273 = 298K
P O2 = 1.0 atm ; V O2 = 25 L ; T O2 = 25 +273 = 298K

n = PV/RT

nHe
nO2

1.0atm 46 L

1.9mol

0.08206 L.atm / mol.K 298K

1.0atm 12 L

0.49mol
0.08206 L.atm / mol.K 298K
34

Example 9 (Answer)
Total tank volume, V = 5.0 L; T = 298 K
From P = nRT/V

1.9mol 0.08206 L.atm / mol.K 298K

PHe
9.3atm
5 .0 L

0.49mol 0.08206 L.atm / mol.K 298K

PO
2.4atm
5 .0 L
2

Total Pressure, Pt = PHe + PO2 = 9.3 + 2.4 = 11.7 atm

35

Mole Fractions and Partial

Pressure
a Mole fraction represented in terms of
pressure:
PV
X1

n1

nTOTAL

RT

P1 V
P2 V
P3 V
...
RT
RT
RT

P1 V

RT

V RT P P P ....
1

P1
P1

P1 P2 P3 .... PTOTAL

Xi

ni
nTOTAL

36

Pi
PTOTAL

Example 10
A 2.0 L tank containing oxygen at a pressure of 100 kPa is
connected to a 0.1 L tank containing helium at a pressure of
3.00 MPa and the gases are allowed to mix. What is the final
pressure assuming that the temperature is held constant?
From P1V1 = P2V2
He ; V1 = 0.1 L

V2 = 2.1 L

P1 = 3.00 MPa

P2 = ?

3000 kPa 0.1 L

P2
143 kPa
2.1 L
Pt PO2 PHe 95 143 238 kPa
37

Example 10 (Answer)
Volume of He increases from 0.1 L to 2.1 L
Volume of oxygen increases from 2.0 L to 2.1 L
Dalton: The total pressure is the sum of partial pressure.
O2 ; V1 = 2.0 L
V2 = 2.1 L
P1 = 100 kPa

P2 = ?

From P1V1 = P2V2

100kPa 2.0 L
P2
95kPa
2.1L
38

Exercise 2
1.

A gaseous mixture made from 6.00 g O2 and 9.00 g CH4 is placed in a 15.0 L
vessel at 00C. What is the partial pressure of each gas and what is the total

pressure in the vessel?

Note: use Pi = ni(RT/V ) {Answer: PO2=0.281 atm, PCH4=0.841 atm,Pt=1.122 atm}
2. A synthetic atmosphere composed of 1.5 mol percent CO 2, 18.0 mol percent O2
and 80.5 mol percent Ar.
a) Calculate the partial pressure of O2 in the mixture if the total pressure of the
atmosphere is to be 745 torr. {Ans.=134 torr}
b) If this atmosphere is to be held in a 120 L space at 295 K, how many moles
of O2 are needed? {use ni=Pi(V/RT), ans.=0.874 mol}

39

Kinetic-Molecular Theory of Gases

A simple model based on the actions of individual atoms
Gases consist of particles in constant motion
Pressure derived from bombardment with container
Kinetic energy described as Ek = mv2
Postulates of Kinetic Theory
Volume of particles is negligible
Particles are in constant motion
No inherent attractive or repulsive forces
The average kinetic energy of a collection of particles is
proportional to the temperature (K)
__

__

Ek T or Ek = c x T
(c is a constant that is the same for any gas)
40

Molecular Speeds:
Diffusion and Effusion
The root-mean-square (rms) molecular speed, u, is
a type of average molecular speed, equal to the
speed of a molecule having the average molecular
kinetic energy.
The square root of the previous equation gives:
Unit relationships
R
= 8.314 kgm2/s2/molK
T
= Temperature (K)
3RT
Mm = kg/mol (Molar Mass)
=

Mm

12/14/15

1 Joule = kgm2/s2
R
= 8.314 J/molK
(rms) = m/s
41

Cont: 10.8 Molecular

Effusion and Diffusion
a Consequences of the dependence of molecular
speeds on mass:
1. Effusion: the escape of gas molecules through a tiny hole
into an evacuated space.
2. Diffusion: the spread of one substance throughout a
space or throughout a second substance. E.g. molecules of a
perfume diffuse throughout
a room.

Effusion:

Diffusion

42

10.8.2 Diffusion and Mean

Free Path
a Diffusion (like effusion) is faster for light gas
molecules.
a Molecular collisions make diffusion more
complicated than effusion.
a Average distance of a gas molecule between
collisions is called mean free path.
a The higher the density of a gas, the smaller the
mean free path. The more molecules are in a
given volume, the shorter the average distance
traveled between collisions.
43

Grahams law of effusion: The rate of effusion of a gas is

inversely proportional to the square root of the mass of its
particle. Relative rates of effusion of two gases at the same
temperature and pressure are given by the inverse ratio of
the square roots of the masses of the gas particle:
Rate of effusion for gas 1
M 2

Rate of effusion for gas 2

M 1
M1 and M2 represents the molar masses of the gases.
Diffusion:
Distance traveled by gas 1
Distance traveled by gas 2

M
M

2
1

The same Grahams law is equally valid for effusion process also.

(SO)= 641gmSOol10kg=340.8m/s340.8=1

2
2
k
m

/
s
3
R
T
u
=M
.m
R
=
8
3
1
4
M
o
l
a
r
M
s
(
M
m
)
k
g
/
m
o
l
o
l
K
2
(C
H
m
4)=338.81.44k6g1kgmoCm
lHolK42/Ks102/k4sg229289o8KoK=681.m/s681.2

What is the ratio of the average speed of CH 4 (MW = 16 g/mol) molecules to that
of SO2 (MW = 64 g/mol) molecules at 298 K?
R = 8.314 J/(molK)

or 8.314 kgm2/s2/molK)

2 22

45

10.9 Real Gases: Deviations

from Ideal Behaviour
a Ideal gas- the molecules are assumed to occupy no space
and no attractions for one another.
a Real gas- Molecules have finite volumes and they attract one
another.
a At lower pressures (usually below 10 atm), the deviation from
ideal behaviour is negligible.

46

Cont: 10.9 Real Gases:

Deviations from Ideal
Behaviour

a Temperature determines how effective

attractive forces between gas molecules
are.
a At low temperature: gases deviate from
ideality: the average kinetic energy
decreases, intermolecular attractions
remain constant.
a At high temperature: gas molecules are far
apart, thus the finite volumes of the
47
molecules predominate.

v
d

48

Real Gases:
Deviations from Ideality

Real gases behave ideally at ordinary

temperatures and pressures.
At low temperatures and high pressures
real gases do not behave ideally.
The reasons for the deviations from
ideality are:
1. The molecules are very close to one
another, thus their volume is
important.
2. The molecular interactions also
become important.

J. van der Waals, 1837-1923,

Professor of Physics, Amsterdam.
Nobel Prize 1910.

Real Gases:
Deviations from Ideality
van der Waals equation accounts for the behavior of
real gases at low temperatures and high pressures.

n 2a
V nb nRT
P +
2
V

The van der Waals constants a and b take into account two things:
1. a accounts for intermolecular attraction
i. For nonpolar gases the attractive forces are London Forces
ii. For polar gases the attractive forces are dipole-dipole
attractions or hydrogen bonds.
2. b accounts for volume of gas molecules
At large volumes a and b are relatively small and van der Waals
equation reduces to ideal gas law at high temperatures and low.

Example 11
a. Calculate the pressure exerted by 84.0 g of ammonia, NH3, in a 5.00
L container at 200. oC using the ideal gas law.
b.Calculate the pressure exerted by 84.0 g of ammonia, NH3, in a 5.00
L container at 200. oC using the van der Waals equation. The van der
Waal's constants for ammonia are: a = 4.17 atm L2 mol-2 b =3.71x10-2 L
mol-1
Solution for part a,
PV = nRT
P = nRT/V n = 84.0g * 1mol/17 g T = 200 + 273
P = (4.94mol)(0.08206 L atm mol K )(473K)
(5 L)
P = 38.3 atm
-1

-1

Example 11 Solution part b

n 2a
V nb nRT
P +
2
V

nRT n 2 a
P
- 2
V - nb V
n = 84.0g * 1mol/17 g T = 200 + 273
P = (4.94mol)(0.08206 L atm mol-1 K-1)(473K)
5 L (4.94 mol*3.71E-2 L mol-1)

(4.94 mol)2*4.17 atm L2 mol-2

(5 L)2

P = 39.81 atm 4.07 atm = 35.74

P = 38.3 atm
7% error
Note that the units for a and b are different
a= atm.L2mol-2 b= Lmol-1

v
d

53

Example 12
A sample of KClO3 is partially decomposed, producing O2 gas
that is collected over water. The volume of gas collected is
0.250 l at 26C and 765 torr total pressure.
2KClO3(s)

2KCl (s) + 3O2 (g)

a) How many moles of O2 are collected?
b) How many grams of KClO3 were decomposed?
c) When dry, what volume would the collected O2 gas occupy at
the same temperature and pressure?
2KClO3(s) 2KCl (s) + 3O2 (g)
V total inside = 0.250L
Ttotal inside = 26C (273.15 + 26) = 299.15K
Ptotal inside = 765 torr

54

Example 12 (Answer)
a) PO2 = (765 - 25) torr. = 740 torr
PO2V
nO2
RT
740torr 1atm / 760torr 0.250 L
nO2
0.0821L.atm / mol.K 299.15K

nO2 9.9110 3 mol

b)

2KClO3(s) 2KCl (s) + 3O2 (g)

2 mols KClO3 3 mols of O2
Molar mass of KClO3 = 122.6 g/mol

gram KClO3

2molKClO3

3
molO
2

9.9110 3 molO2
0.811g

122.6 gKClO3

1
molKClO
3

55

Example 12 (Answer)
c) Use Boyles law:

V1 P1
V2
P2

V1= 0.250L ;
P2 = 765 torr.(assumed as water partial
by O2 )

pressure replaced

P1 = 740 torr (from O2 - water vapour)

V2 = (assumed dry O2 without water vapour)

0.250 L 740torr
V2
765torr
V2 0.242 L
56

END of CHAPTER 10

57