CHE 205 (PHYSICAL CHEMISTRY I)

KINETIC THEORY OF GASES

Gas is one of the fundamental states of mater. Pure substances can exist mainly in three different forms;
solid, liquid and gas. The parameters required to describe the state of a gas are pressure (p), volume (V),
temperature (T) and number of moles (n). These parameters are known as state variables.

Between about 1850 and 1880, James Clerk Maxwell (1831–1879), Rudolf Clausius (1822–1888), Ludwig
Boltzmann (1844 –1906), and others developed the kinetic theory of gases. The kinetic-molecular theory
is the model that accounts for macroscopic gas behaviour at the level of individual particles (atoms or
molecules). They based the theory on the idea that all gases behave similarly as far as particle motion is
concerned. Using kinetic gas theory, it is possible to derive or explain the experimental behaviour of
gases. It is important to note that:

1. Gases are mostly empty space. The total volume of the gas molecules is negligibly small compared with
that of the container to which they are confined.
2. Gas molecules are in constant chaotic motion. They gas molecules collide frequently with one another
and with the walls of the container. This behaviour makes their velocities to constantly change.
3. Gas molecules flow freely and have relatively low densities.
4. Collisions of gas molecules are elastic. The colliding molecules exchange energy but do not lose any
energy through friction. Thus, their total kinetic energy is constant. There are no attractive forces that
would tend to make molecules stick to one another or to the container walls.
5. Gas pressure is caused by collisions of molecules with the walls of the container. As a result, pressure
increases with the energy and frequency of the collisions.
6. Gas volume changes significantly with pressure and temperature. Gases are compressible.
7. Gases mix in any proportions to form solutions; liquids and solids generally do not. For instance, Air
is a solution of 18 gases.

Distribution of Molecular Velocities

At any time, the distribution of velocities is influenced by molar mass (M) and temperature (T).

As shown in Figure 2A, gases with low molecular mass will have their molecules moving at higher speeds.
As presented in Figure 2A. For gases with a high molecular mass, the average speed is low and the
distribution of speeds is less broad.

At a low temperature, most molecules of gases move with a speed close to the most probable value, but
at a high temperature, there is a broad spread of velocities. Each particle has a molecular speed (c); most
are moving near the most probable speed, but some are much faster and others much slower. The curve
(Figure 2B) flattens and spread at higher temperatures; and the most probable speed (the peak of each
curve) increases as the temperature increases.

The increase in most probable speed occurs because the average kinetic energy (e) of the molecules,
which is related to the most probable speed (cmp), is proportional to the absolute temperature (T). That
is e  T or e = c T , where c is a constant that is the same for any gas.
1
Generally, at a high temperature value, gases tend to have high average velocities and broad distribution
of velocities, that is, more molecules of the gases will possess high speeds and a few molecules will possess
low speeds.

Figure 1: Maxwell-Boltzmann distribution of velocities

A B

Figure 2: Effect of molecular mass (A) and temperature (B) on distribution of velocities

For fractions of molecules that have velocities in the range of c + dc is proportional to width of the range
f(c)dc, where f(c) is the distribution of speeds or velocities.

2
 3

 M  2 2 − MC 2

f (c ) = 4   c e 2 RT
dc (1)
 2 RT 

Equation 1 is known as Maxwell-Boltzmann distribution of speeds. In Equation 1, M = molecular mass

of the gas; T = temperature in Kelvin (K); c = root mean square velocity (m s–1); R = gas constant (8.314 J
mol–1 K–1);  = 227 ; and dc = change in velocity.

It implies that from Equation 1 that:

2
− MC
(i) The presence of decaying exponential function ( e 2 RT
) implies that small fraction of molecules
has very high speed. The values of e − x becomes smaller whenever x2 is large (i.e. when c is large).
2
MC 2 − MC
(ii) The 2RT part of the e 2 RT
in the exponent is large when M is large. This signifies that the
exponential factor will tend towards zero when M is large. Therefore, large molecules will not be
able to possess very high speeds.
MC 2
(iii) The factor 2RT is small when T is high. Therefore, a great fraction of the molecules will possess
high speeds at high temperature values.
2
2 − MC
(iv) The value of tends c e 2 RT
towards zero as c goes to zero. Therefore, the fraction of the molecules
with very low speed will be very small.
3

 M 2
(v) The 4   factor ensures that a zero (0) will be obtained when fractions over the entire
 2 RT 
range of speeds are added up.

Average and Root Mean Square Velocities

If n represents the molecules of a gas having individual velocities c1, c2, c3, ………, ci, then

c1 + c2 + c3 + ...... + ci 1 N
C= =  ci (2)
N N i =1

8RT
Similarly, C = (3)
M

In Equations 2 and 3, C represents the average velocity of the gas (m s–1) and M is the molar mass (kg
mol–1).

It is known that pV = 13 nN Amc 2 (4)

pV = nRT (5)
3
 3RT
Combining Equations 4 and 5 gives c = (6)
mN A

But M = mNA (7)

3RT
Then c = (8)
M

In the above equations, p is the pressure in N m–2, V is the volume in m3, n is the number of moles, m is the
mass of the individual molecules (kg), c (or crms) represents the root mean square speed, and NA is the
Avogadro’s constant or number (6.022 x 1023 mol–1).

c12 + c22 + c32 + ...... + ci2 1 N 2

Root mean square speed can also be represented as c = =  ci (9)
N N i =1

Most Probable Velocity

There a large number of molecules, many of which are bound to have the same velocity. The most
probable velocity (cmp) is the velocity that most of the gas molecules possessed. It is represented
mathematically using Equation 10.

2RT
cmp = (11)
M

c c c cmp cmp
It is possible to compute the values of following relationships , , , , , etc.
c c cmp c c

Questions

1. A gas possesses 10 molecules with a speed of 5 m s –1, 8 molecules with a speed of 4 m s–1 and 5
molecules with a speed of 7.2 km h–1. Calculate (i) the average speed, (ii) root mean square speed and
(iii) the most probable speed of the gas molecules.
2. Calculate the average, room mean square speed and most probable velocities of nitrogen gas at 25 ºC.
{R = 8.314 J mol–1 K–1; π = 3.143; N =14}.
3. At what temperature would propane gas molecules have the same root mean square speed as
methane at 20 ºC? {C = 12; H =1}.
4. Estimate the ratio of average speed of oxygen and ozone at 25 ºC. {O = 16}.
5. A 5 L container contains 1.0 x 1023 of hydrogen molecules. If the pressure exerted by the gas is 2 atm,
calculate the root mean square speed of the gas. {H = 1; R = 8.314 J mol–1 K–1}.

The following relationships also exist:

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 3RT 3RT 3kBT 3pV 3pV 3p
c= = = = = = (12)
M N Am m nM m 

2RT 2RT 2kBT 2pV 2pV 2p

cmp = = = = = = (13)
M N Am m nM m 

8RT 8RT 8kBT 8pV 8pV 8p

c= = = = = = (14)
M  N Am m  nM m 

m
where ρ is the density;  = . Also, M = m  N A and N = n  NA
V

Collision Frequency and Mean Free Path

Collision frequency is the number of collisions that a gas molecule undergoes per second. Collision
frequency is also known as collision number or collision rate. It is represented by Z with SI unit of s–1. The
number of collisions that a given molecule will undergo in 1 s depends on the distance that the molecule
moves and the number of gas molecule per unit volume (i.e. pressure). At any instant, a molecule will
collide with any other molecule whose centre lies within the cross-sectional area of the cylinder.

2N A cp
Z= (15)
RT

where Z = collision frequency or collision rate or collision number (s–1); NA = Avogadro’s constant (6.022
x 1023 mol–1) and δ = collision cross-sectional area (m2).

 =  d2 (16)

where d = collision diameter (m); and  = 227 PV = RT (for 1 mole of an ideal gas; n = 1)

p 1
2 cN A N =
Z= = 2 c A (17) RT V
V V
NA R
N= KB =
Z = 2 cN (18) V NA

where N = number of molecules per m3 or number of spheres (mol–1 m–3); and V = volume of the gas
(cylinder) in m3.

2 cp
Z= (19)
K BT

where KB = Boltzmann’s constant (1.38 x 10–23 J K–1); and R = 8.314 J mol–1 K–1.

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The mean relative speed ( crel ) is the speed with which one molecule approaches another. The value of
c rel can be calculated using Equation 20.

crel = 2  c (20)

For two different molecules of masses MA and MB, the values of c rel can be evaluated using Equation 21
or Equation 23.

16K BT
crel = (mA = mB) (21)


mAmB
where  = reduced mass = (22)
mA + mB

m = mass of the gas.

8K BT
crel = (mA ≠ mB) (23)


Equation 15 can be written as Equation 24.

N A crel p
Z= (24)
RT

So also Z =  crel N (25)

 crel p
Z= (26)
K BT

The mean free path is the average distance a molecule travels before collision. It is denoted by λ. The SI
unit of mean free path is m (metre). If a molecule collides with frequency, Z, it will spend a time (1/Z) in
the free flight between collisions. Then distance = velocity x time.

The relationship between average speed/velocity and collision frequency is presented in Equation 27.

c
= (27)
Z

6
 distance travelled in 1 second
= (28)
number of collisions in 1 second

Substitution of Equation 28 into Equation 15 gives Equation 29.

c 1
= = (29)
 p   p 
2N A c   2N A  
 RT   RT 

Equation 29 is rearranged to give Equation 30.

RT
= (30)
2N A p

1
So also  = (31)
2 N

k BT
= (32)
2 p

3 d = density
Similarly,  = (33)
pd
η = viscosity of the gas

The mean collision time of the gas is represented by  coll . The SI unit of the mean collision time is
seconds (s). The formula for mean collision time is presented in Equation 34.

 m 1
 coll = =  (34)
crel 16K BT 2 N

The mean molecular collision rate is represented by Z'. The SI unit of Z' is s–1.

1
Z'= (35)
 coll

16K BT
Or Z ' = 2 N  = 2 Ncrel (36)
m

The rate of collision per unit volume of gas molecules is represented by Z" and has a unit of m–3 s–1. The
value of Z" can be obtained using Equation 37.

7
Z " = 12 Z ' N (37)

The total rate of collision per unit volume = Z ''V = ( 1

2 )
Z 'N V (38)

The SI unit of the total rate of collision per unit volume is s–1.

Questions

6. For oxygen gas at 20 ºC and a molar volume of 24.45 L at approximately 1 atm, if the radius of the gas
is 2 nm, calculate:

(a) the mean free path

(b) average velocity
(c) most probable velocity
(d) root mean square velocity
(e) collision frequency
(f) the mean collision time
(g) the mean molecular collision rate
(h) the rate of collision per unit volume
(i) total rate of collision {  =
22
7 ; O = 16; R = 8.314 J mol–1 K–1; NA = 6.022 x 1023 mol–1}.

7. Calculate the mean relative speed of nitrogen and oxygen molecules at 30 ºC {  =

22
7 ; N = 14; O = 16;
R = 8.314 J mol–1 K–1; NA = 6.022 x 1023 mol–1}.
8. The root mean speed of Heat at SATP is 2 m/s and its free mean path is 2.5 cm, calculate the collision
number.
9. A certain sample of air at 20 ºC contains dust particles of radius 5 nm and density 2500 Kg m –3.
Evaluate (a) the most probable speed (b) root mean square speed (c) average speed of the dust
particles by treating them as particles (d) rate of collision of a dust particle with another if their
density number is 1.0 x 109 m–3 and (e) the total rate of collision of the dust particles [NA = 6.022 x
1023 mol–1].
10. Calculate the collision frequency and mean free path for H2 gas at 25 ºC and a molar volume of 22.4 L.
Take the diameter of the gas as 4 cm [H = 1; R = 8.314 J mol–1 K–1; NA = 6.022 x 1023 mol–1].

Heat Capacities

Heat capacity is defined as the amount of heat needed to raise the temperature of a substance by 1 K. it
is usually represented by C. The specific heat capacity, CS, is the amount of heat required to raise the
temperature of 1 g of a substance by 1 K. The molar heat capacity, Cm, is the amount of heat required to
raise the temperature of 1 mole of a substance by 1 K.

quantity of heat supplied

CS = (39)
mass of substance  temperature rise

8
 q
CS = (40)
mT

q
Cn = (41)
nT

The temperature can be raised either at constant volume or constant pressure. For gases, Cp (the molar
hear capacity at constant pressure) is the amount of heat required to raise the temperature of 1 mole of a
gas by 1 K at a constant pressure. Similarly, Cv (the molar hear capacity at constant volume) is the amount
of heat required to raise the temperature of 1 mole of a gas by 1 K at a constant volume.

q =U +W (42)

dq = dU + dW dU = dq + dW
W = pdV
dq dU dV W = work
= +p (43)
dT dT dT q = heat energy
U = internal energy
dq  dU 
At a constant volume (V), = (44)
dT  dT V

dqV  dU 
CV = = (45)
dT  dT V

dH
CV = , then dU = CV dT = nCV (T2 − T1 ) (46)
dT

H = U + PV (47)
H = enthalpy
dH dU dV Enthalpy is the total heat
= +p (48)
dT dT dT content of a system

 dH   dU   dV 
At a constant pressure (p),   =  + p  (49)
 dT  p  dT  p  dT  p  dH 
Cp =  
 dT  p
dH
Cp =
dT

Therefore dH = C pdT (50)

dH = nCpdT = nCp (T2 − T1 ) (51)

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Similarly, H = U + pV (Note = pV = RT; n =1)

dH dU RT dU dT
= + = +R (52)
dT dT dT dT dT

dH dU
= +R (53)
dT dT

The relationship between Cp and Cv is given as C p = CV + R (54)

It is known that E = 32 RT (55) E=U

E 3
CV = = R (56) E = ETranslational
T 2

The CV is the rate of change of energy with temperature.

C p = CV + R = 32 R + R = 52 R (57)

Therefore, for monoatomic gas, CV = 32 R and C p = 52 R .

For diatomic gases, E = ETranslational + E = ERotational + E = EVibrational

CV = 32 R + R + R (58)

Then CV = 72 R and C p = 92 R .

Question(s)

11. Estimate the value of dU and dH in Joule on heating 64 g of O2 from 15 to 100 ºC. The values of Cp and
CV are 4.0 J mol–1 K–1 and 6.0 J mol–1 K–1, respectively {O = 16; R = 8.314 J mol–1 K–1}.

Average Kinetic Energy and total Kinetic Energy

The average kinetic energy of gas molecules is proportional to the absolute temperature of the gas. All
gases at the same temperature have the same average kinetic energy.

The kinetic gas equation can be represented by Equation 59.

pV = 13 mNc 2 (59)
e = 12 mc 2
e is the average kinetic
energy (KE)
pV = 32 N A  12 mc 2 (60)
E = total KE
E = NAe
10 n = number of moles
pV = 32 N Ae (61)

pV = 32 E (62)

But pV = nRT

Then from Equation 62, E = 2 nRT

3
(63)

Similarly, e = 32nRT
NA (64)

Note:

1. At a given temperature, molecules of different gases (H2, O2, etc) must all have the same average
kinetic energy of translational motion.
2. The average translational kinetic energy of a gas molecule is directly proportional to the Kelvin
temperature, T.

Question(s)

12. What is the average kinetic energy and total kinetic energy of 2 nmol of nitrogen gas at 25 ºC? {N =
14; R = 8.314 J mol–1 K–1; NA = 6.022 x 1023 mol–1}.

Real and Ideal Gases

Any gas can be described in terms of its pressure, temperature (in Kelvin), volume, and the number of
moles, n, present. Any three of these variables can be used to determine the fourth. The gas laws (Boyle’s,
Charles’s, and Avogadro’s laws) provide relationships among these four variables. An ideal gas (perfect
gas) is a gas that exactly or perfectly obeys the gas laws. Many real gases show slight deviations from
ideality. However, at normal temperatures and pressures, the deviations are usually small and can be
ignored.

1
Boyle’s law V (constant T and n) (65)
p

Charles’s law V  (constant P and n) (66)

Avogadro’s law V n (constant T and p) (67)

nT
Then V (68)
p

11
  nT 
Hence V = R  (69)
 p 

Equation 69 can be rearranged as pV = nRT (70)

Equation 70 is known as Ideal gas equation or ideal gas law. An ideal gas obeys pV = RT (n=1) at all
temperatures and pressures. R in Equations 69 and 70 is a constant (known as universal gas constant)
and the value of R depends on the units of p, V and T. The value of R (using SI units) is 8.314 J mol–1 K–1
and this value is derived as shown in Equation 71.

A 1.0 mol of an ideal gas occupies 22.414 L at 1.0 atm and 273.15 K (STP).

101325 Pa  0.022414 m3 Pa m3  N  m −2 m3 
R= = 8.314   (71)
1 mol  273.15 K mol K  mol K 

Note: 1 L = 1 dm3 = 1000 cm3 = 0.001 m3; and 1 m3 = 1000 L.

The value of R can also be expressed as 0.0821 L atm mol–1 K–1 (non-SI unit) and this value can be obtained
from Equation 72.

1.0 atm  22.414 L L atm

R= = 0.082057 (72)
1 mol  273.15 K mol K

Questions

13. What pressure, in atm and Pa, is exerted by 54.0 g of Xe in a 1-liter flask at 20 °C? (Xe = 131.3 g/mol).
(R = 0.0821 L atm mol–1 K–1 or 8.314 J mol–1 K–1)

14. Nitric acid (HNO3) is produced in the laboratory by dissolving the nitrogen dioxide (NO2) in water.
Calculate the density of NO2 gas in g/L at 1.24 atm and 50 °C (H = 1, N = 14, O = 16, R = 8.314 J mol–1 K–1).

As said earlier, under ordinary conditions most real gases do behave ideally; their p and V are predicted
by the ideal gas laws, so they obey the postulates of the kinetic–molecular theory of gases. According to
this theory, (1) volume of a gas is negligible (empty space) compared to the volume of the container, and
(2) the molecules of ideal gases do not attract one another because they are so far apart relative to their
own sizes. Under some circumstances, however, most gases can have pressures and/or volumes that are
not accurately predicted by the ideal gas laws and are not behaving entirely as postulated by the kinetic–
molecular theory of gases.

Real gases do not obey perfect or ideal gas law exactly and they deviate from ideal gas law because (i)
molecules do interact with one another, (ii) the actual volume of the gas is appreciable, and (iii) molecular
collisions may not be perfectly elastic.

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Nonideal gas behaviour (deviation from the ideal gas laws) is significant at high pressures and/or low
temperatures, that is, near the conditions under which a gas liquefies. At high pressures, a gas is
compressed so that the volume of the molecules themselves becomes a significant fraction of the total
volume occupied by a gas. At high temperature, the potential energy as a result of intermolecular
attractions is negligibly small compared with the high kinetic energy due to the rapid motion of the
molecules and to the great distances between them. When the temperature is low (low kinetic energy),
the molecules move so slowly that the potential energy, due to small attractive forces, becomes important.
This perturbation becomes even more important when the molecules are very close together (at high
pressure. Hence, gas molecules deviate from their straight-line paths and take longer time to reach the
walls and a few collisions will take place.

At higher pressures, a better description of other than pV = nRT is needed to describe real gases. Several
equations of state have been formulated for this reason. The first successful attempt to account for real
gases behaviours was introduced by van der Waals in 1873. Equation 73 is known as van der Waals
equation.

 an2 
 p +  (V − nb ) = nRT (73)
 V2 

where a and b are constants. These constants differ for different gases.

 RT  a V
If n =1, then we can have p =  − 2 (73a) Vm is the molar volume, and Vm =
 Vm − b  Vm n

pV 2 atm  L2
a= = = atm L2 mol −1 (73b)
n2 mol 2

V L
b= = = L mol −1 (73c)
n mol

(i) The factor nb corrects for the volume occupied by the molecules themselves. The volume of a gas is
not negligible. Larger molecules have greater values of b, and the greater the number of molecules in a
sample (higher n), the larger is the volume correction. The correction term becomes negligibly small,
however, when the volume is large. Then, the correction factor (nb) is subtracted from the volume, V, to
account for this reduction. Hence, we have V − nb .

 n2 
Where V is the measured volume; p is the measured pressure; p + a  2  is the ideal pressure; and
V 
V − nb is the ideal volume.

(ii) The large values of a indicate strong attractive forces. When more molecules are present (greater n)
and when the molecules are close together (smaller V in the denominator), the correction term becomes
larger. The correction term becomes negligibly small when the volume is large. The pressure is somewhat

13
less in real gasses than in real gases. Therefore, the correction factor is added to the pressure (actual
2
n
pressure) in van der Waals equation to make it up for the slightly reduced pressure. That is p + a  
V 

2
n
The a   is the difference between the measured p and the ideal value of p.
V 

When a and b are both zero, the van der Waals equation reduces to the ideal gas equation.

The extent by which a real gas departs or deviates from the ideal gas behaviour is known as
compressibility factor, which is denoted by Z. Compressibility factor is a measure of non-ideality of a gas.

pV = ZRT (74)

pV
Z= (75)
RT

For an ideal gas, Z =1; for real gases, the deviations from ideality depend on the temperature and pressure.
The magnitude of Z < 1 or Z > 1 value determines how big the deviation from ideality.

For real gases:

1. At a low pressure and a fairly high temperature, real gases show nearly ideal behaviour and the
ideal gas equation is obeyed.
2. At a sufficiently high pressure and a low temperature, perfect gases deviate noticeably from ideality
and ideal equation is not obeyed.
3. The closer the real gas to liquefaction point, the bigger the deviation from ideality.

Many other equations of state have been developed for description of real behaviour of real gases. Other
equations of state include:

pVm B B B
(i) Virial equation of state: = 1 + 2 + 32 + 43 + .... (76)
RT Vm Vm Vm

B = virial coefficient; and virial coefficients depend on T.

 a 
(ii) Berthelot equation of state:  p +  (Vm − b ) = RT (77)
 TVm2 

(iii) Dieteric equation of state: p  e (Vm − b) = RT (78)

Vm RT

14
 RT a
(iv) Redlich-Kwong equation of state: p = − 1 (79)
Vm − b T 2Vm (Vm + b)

RT a   (T )
(v) Soave modification of Redlich-Kwong equation of state: p = − (80)
Vm − b Vm (Vm + b)

2
  T 2 
1

where  (T ) = (1 + m ) 1 −   
 (80a) m = a constant, and Tc = critical
  Tc  

temperature.

(vi) Gibbons-Laughton modification of Redlich-Kwong equation of state:

T   T 2
 (T ) = 1 + X   − 1 + Y   − 1 (81) X and Y are constant parameters.
 Tc   Tc 

Question(s)

15. Evaluate the pressure exerted by 1.0 mole of methane gas in a 0.5 L container at 25 °C assuming (a)
ideal behaviour and (b) nonideal behaviour (a = 2.25 L2 atm mol–2; b = 0.0428 L mol–1; R = 0.0821 L atm
mol–1 K–1).

16. Repeat the calculations in question 15 using 10 L of methane gas while all other factors remain the
same. Comment on your answer.

Critical Phenomenon and Liquefaction of Gases

A gas can be liquefied by lowering the temperature and increasing the pressure.

1. Critical Temperature (Tc): gas cannot be liquefied above a certain temperature, regardless of how
much pressure is applied to it. Critical temperature is the temperature above which a gas cannot be
liquefied.
8a
Tc = (82)
27 Rb
2. Critical Pressure (Pc): The critical pressure of a gas is the minimum pressure required to liquefy it
at its critical temperature.
a
pc = (83)
27b 2
3. Critical Volume (Vc): the critical volume of a gas is the volume occupied by one mole of the gas at
critical conditions (temperature and pressure).

15
 Vc = 3b (84)

The change of a gaseous substance into a liquid state is known as liquefaction. Changes in physical
variables such as temperature, pressure, and volume cause this transformation. Thomas Andrew studied
the change of state from gases to liquids in Carbon dioxide (CO 2). It was discovered that most real gases
behave like CO2 and change from gases to liquids if optimum physical changes in temperature and
pressure are achieved.

With Andrew’s experiment on CO2, he concluded that at high temperatures, despite high pressure, the
gases cannot be liquefied. Similarly, with the increase in temperature, the gases show significant deviation
from the ideal behaviour. The gas molecules must be pushed closer together for liquefaction to take place.
Liquefaction of gases can be achieved by lowering the temperature and increasing the pressure. When
pressure of the gas is increased, the molecules come closer until they unite to form liquids at a certain
pressure. Similarly, when a gas’s temperature is reduced, the gas molecules will lose kinetic energy,
resulting in a considerable decrease in velocity. Slowly moving molecules cannot resist the force of
attraction, so they clump together to form a liquid.

Question(s)

17. The van der Waals constants for a gas are 3.6 L2 atm mol–1 and 40.5 L mol–1 for respective a and b
constants. Calculate the critical temperature, pressure and volume of the gas (R = 0.0821 L atm mol –1 K–
1).

16