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CHEM 1301 | KINETIC THEORY OF GASES

 A gas refers to a fluid state of matter which will fill a container

Properties

 Static properties: pressure, volume, temperature

 Transport properties: diffusion / effusion1 (Graham’s law of effusion), viscosity

(resistance to flow)

 Heat capacity

 Chemical properties: reactions between gases

Boyle’s Law

constant
 At constant T, pV = constant or p=
V

 When the pressure of gas is doubled, the volume halves

 Reason: pressure results from molecular collisions with the wall

 Pressure = Force / Area (As F increases, and A decreases, p increases)

Charles’ Law

 At constant p, V = constant x (T/oC + 273.15)

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Effusion refers to the escape of gas from a container
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 Charles’ Law implies a natural minimum temperature of –273.15oC / 0 K

T/K = T/oC + 273.15

 Another form of Charles’ Law: At constant V, p = constant x (T/K)

 Hence, p  0 as T  0, which is an example of a limiting law

pV
 Overall, =constant
T

 Avogadro’s Law states that all molar volumes of gases should be the same

V
V m= or V = constant x n
n

 Standard temperature and pressure refers to 1 atm (101325 Pa) and 273.16 K

 Volume of 1 mole of ideal gas = 22.414 dm3

pV 101325× 22.414 ×10−3

 Constant = = = 8.31441 J K mol-1
nT 1× 273.16

 Per molecule: k (Boltzmann constant) = R / NA

 Ideal gas equation pV = nRT

 For a fixed amount of ideal gas, the surface shows the only states that can exist in
equilibrium

 Real gases behave more like ideal gases at low p, and obey pV = nRT as p  0

3 Central Assumptions

1. The gas consists of molecules of mass m and diameter d in ceaseless random

motion
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2. The volume occupied by the molecules is negligible compared to the volume of the
gas

3. The molecules do not interact when they collide, making perfectly elastic collisions

 Elastic collision occurs when total KE is conserved (no energy goes into the internal
energy of the molecule)

Using the model to predict pressure

 The pressure results from molecules hitting the vessel walls, p = force / area

d dv
Force = rate of change of momentum = ( mv ) = m = ma
dt dt

 Calculate the change in momentum for one molecule hitting the wall and scale up to
the total change in momentum in a given time per unit area

Momentum change on hitting the wall

Before collision,

Momentum vector quantity = mv

Component momentum towards wall = mvx

After collision,

Component momentum towards wall = –mvx

Change in momentum = (–mvx) – (mvx) = –2mvx

Note: 2mvx transferred to wall in 1 collision

 In a given time, t, a molecule travels a distance of vx.t along the x axis

 All molecules closer than vx.t from the wall and travelling towards it will reach the
wall in t
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Defines a distance
from the wall

 Molecules have to be within vxDt of the wall and going in the right direction

 For a unit area A of wall, molecules have to be in a ‘collision volume’ of vx.Dt.A

No of molecules per unit vol =

No in collision vol = D

No colliding with wall in time Dt = D

Reason: Gases occupy volumes homogenously, so half

of the molecules are travelling towards the wall

 Total change in momentum = no of collisions x momentum change per collision

A .V x . t . n . N A
= x 2mvx
2V

 Note: m.NA = M (molar mass)

nMA V 2x
 Rate of change of momentum = total change / Dt = = Force
V

nM V 2x
 Hence, pressure = force / area =
V

 However, molecules have a range of vx and an average of vx2 should be considered

(<vx2>)

 Molecules move randomly and there is no net flow in one direction,

<vx2> = <vy2> = <vz2>

 Mean square speed of molecules (c2) = <vx2> + <vy2> + <vz2> = 3<vx2>

c2
 <vx2> =
3
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nM c 2 nM c 2
p= or pV =
3V 3

Comparing Experimentally

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 Experimentally, pV = nRT while the model result predicts pV = nMc2
3

 If c2 depends only on T, then at constant T, model predicts pV = constant

(Boyle’s Law)

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 Also, it implies RT = M c2
3

2 3 RT
 Mean square speed: c =
M

3 RT 3 kT
 Root mean square (rms) speed: c=
√ M
=
√ m
(after dividing by Avogadro’s no)

 Note: T increases as c increases and M increases as c decreases

 Example: rms speed of Ar atoms at 298 K

3 × 8.31× 298
c=
√ 39.95 ×10−3
= 431 ms-1

 Note: change relative atomic mass of atom from g mol-1 to kg mol-1

 Speeds of individual molecules are wide ranging

Kinetic Energy

 For 1 molecule, KE = ½ mv2

 Total KE = N. ½ mc2 (where c2 = mean square speed of molecules)

1 1
 pV = nM c 2 = Nm c 2
3 3

 Note: N.m = n.M where n = no of moles, N = no of molecules, M = mass of a mole, m

= mass of a molecule

2 3
 Hence, pV = KE or KE = pV
3 2
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3
 For an ideal gas, pV = nRT hence total KE = nRT
2

 Translational (kinetic) energy [energy resulting from motion] is the only energy for the
ideal model gas

 Considering c2= <vx2> + <vy2> + <vz2>,

Total KE = N. ½ mc2
= N. ½ m<vx2> + N. ½ m<vy2> + N. ½ m<vz2>

Since <vx2> = <vy2> = <vz2>,

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 Total KE = nRT
2

 KE = ½ nRT for each translational degree of freedom (each axis motion contributes
½ nRT)

Molecular Speeds

 Experimentally, pV = constant (at fixed T) = nRT and kinetic theory predicts that
1
pV = Nmc2
3

 Thus, pV = constant if c2 depends on T only

 Comparison of theory and experiment gives mean square speed of the molecule,
c2 = (3RT/M)

Range of Molecular Speeds

 Since molecules collide many times in their constant motion, molecular speeds are
wide ranging

 The range of speeds is represented as a probability density function / probability

distribution function (pdf)

 Data from the histogram enables <x> (mean value) to be calculated

 The probability of a measurement occurring is proportional to Ni (no of times that

value of x appears)

 The probability of a value occurring within a range of x depends on pi and on the

width of the range (i.e. Pi = fi x)
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❑
 Therefore, <x> = ∑ f i . ∆ x . xi
i

x2

 Probability = ∫ f ( x ) dx (for a smooth curve) = area under curve

x1

 Total area under the entire curve = 1 (i.e. ∫ f ( x ) dx=1)

−∞

∞ ∞
Since <x> = ∑ x i . f ( x ) . ∆ x = ∫ xf ( x ) dx, in general, <x > = ∫ x f ( x ) dx
n
 n
i
−∞ −∞

Distribution of Molecular Speeds, s

 The distribution function showing the range of speeds of molecules:

2
3 −m s
m
(
f ( s )=4 π
2 πkT ) .s e
2 2 2 kT

 To verify the Maxwell distribution, experiments use a velocity selector where only
molecules with a specific speed pass through the slots of the rotating discs to the
detector

 The most probable speed, s*, is at the peak of the Maxwell distribution
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 Since the distribution is asymmetric, s* is lower than the mean speed <s> which is in
turn lower than the root mean square speed <s*>½ (i.e. s* < <s> < <s*>½)

Expression in Ratio to most

Speeds
units (RT/M) ½ probable speed
Most probable 2½ 1
1
8
Mean () π
2
1.128

Root mean
3½ 1.225
square

Molecular Collisions and Transport Properties

 The Maxwell Distribution shows that the mean speed of molecules

1
8 kT 2
¿s>= c= ( πm )
 Relative mean speed, srel =
c rel

 Relative speed
c rel = 0

 Relative speed
c rel = 2 c

 Mean direction of approach – how quickly they approach each other

Mean Speed of Approach

 Resolve the molecular speed into 2 components (orthogonal: perpendicular)

a2 +a2=c 2
2a2 =c 2
c
a=
√2
c
 Component of mean speed towards other molecule = √2
c
2 =√ 2c
 Mean relative speed = √2
 If molecules have different masses, reduced mass, , is used in the expression for
c rel
m A mB
μ=
m A +m B
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 If mA = mB,  = mA / 2 Thus, mA = 2
8 kT 12
c= ( πm )
1 1 1
8 kT 2 8 kT
c rel=√ 2 c=2 2
πm ( ) ( )
=
πμ
2

Collisions Between Molecules

 Consider all molecules except one to be static and give the moving molecule a speed
c rel

 In time t, the molecule effectively travels a distance of c rel .t and it will hit any
other molecule when the centre of separation of the molecule is < d (assuming the
molecules are the same size)

 Hence, the molecule sweeps out a ‘collision tube’ of diamter 2d and length c rel .t

 The molecule hits any other molecule in the collision tube in our defined time t

 Note: A pair of molecules will collide whenever the centres of the 2 molecules within
a distance d (the collision diameter) of each other

 Cross sectional area of tube =  = d2

 Vol of tube = .
c rel .t

 No of collisions made by a molecule in time t = .

c rel .t.(N/V) (where N/V = no of
molecules per unit vol)

 No of collision made by one molecule per unit time / collision frequency =

ZA = 
c rel (N/V) = .2½. c rel (N/V) = .2½. c rel .(p/kT)

 Units for ZA = s-1 and note: pV = NkT = nRT where k = R/NA

 Typical values of  range from 0.2 to 1 nm2

Molecule Collision cross-section / nm2

He 0.21
N2 0.43
Ar 0.36
CO2 0.52
C6H6 0.88
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Example ZA for Ar at 298 K and 1 atom

8kT 12 8×1.381×10−23×298
( )
Mean speed of Ar atoms = c =
πm
=
(
3.142×
39.95×10
(
−3

6.02×10 23 ) )
=397ms−1

Z Ar =σ ×√ 2×c× ( kTp )=0 . 36×10 −18

×√ 2×397×
101325
−23
1 . 381×10 ×298
=4 . 98×109 s−1

Mean Free Path

 If a molecule collides at frequency ZA (collisions per second),

time between collisions = 1/ZA

 Distance between collisions = c / ZA =  (where  = mean free path)

 For Ar,  = 79.4 nm, from which dAr can be calculated from

Ar = 0.36 x 10-18 m2 = .dAr2

dAr = 3.39 x 10-10 m = 3.39 Angstrom (approximately 100 times lower than mean free
path)

Total No of Collisions

 If a single molecule in a sample of gas undergoes ZA collisions per unit time,

Total no of collisions = ZA (NA / 2V) = ZA (p / 2kT)

 Note: 2V is used to avoid double counting

 Example, for Ar gas at 298 K and 1 atm, ZAA = 6 x 1034 s-1 m3 (note units)

 ZAA = total collision frequency and could indicate how quickly chemical reactions can
occur

dB / 2 B
Collisions between Different Molecules
A
 Consider one molecule of A in a gas B dA / 2

2
d A +d B
 Collision cross-section, AB = π
2( )
 Hence, ZB (frequency / rate) = AB
c rel (N /V) s-1
B
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 Total collision frequency (no of A—B collisions per unit time, per unit vol)

ZAB = ZB (NA / 2V) s-1 m-3

 From diagram, it shows that in order to collide, the centre of B has to within the
dotted circle

Collision Frequency

 Can be used to develop a theory to explain the kinetics (rates) of reactions

 Importance: Allows us to understand / test reaction mechanisms (fundamental) and

to apply reactions environmentally and industrially (practical)

Gas Phase Reaction Kinetics

aA + bB  cC + dD

−1 d [ A] −1 d [B ] 1 d [C ] 1 d [D]
r= = = =
a dt b dt c dt d dt

 The stoichiometric no ensures that r is the same for a given reaction regardless of
which species is monitored (removes ambiguity, obtain same measure of rate)

 Note: r is negative for reactants as they are decreasing while r is positive for products
as they are formed

 Experimentally, the rate equation shows the dependence of r on the concentrations

of reactants

−1 d [ A] α β
r= =k [ A ] [B ]
a dt

 Where k = rate constant and  and  are the orders of reaction wrt A and B
respectively

 Overall order of reaction =  + 

 ,  and k are experimentally determined

 However, if a reaction is found to be elementary (takes place in a single step; no

mechanism), then the order of reaction = molecularity

 Molecularity of an elementary reaction refers to the no of reactant molecules taking

part
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 An elementary bimolecular reaction, in the gas phase, can be considered as a

collisional process

 Collision theory involves 2 assumptions:

1 The reactants must collide

2 On collision, the reactants must have enough energy to react

Theoretical reaction rate = ZAB x fraction of molecules with enough energy to react

Where ZAB = collision rate / frequency

 The probability distribution function for energies: Boltzmann distribution

 Where  (Ea) is the minimum energy needed for reaction to occur, f(E>) is the area
under f(E) above  (shaded area)

Boltzmann Distribution
−E
1
f ( E )= e kT
kT

For fraction of molecules with E > ,

∞ −E ∞ −E −E
1 kT 1 1 1
f ( E> ε )=∫ e dE= ∫ e kT dE= [−kT .e kT ]∞ε = ¿
ε kT kT ε kT kT
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Theoretical and Experimental Rate of Reaction

 Theoretical rate

−ε
kT N A N B −ε
kT
−ε
2 [ A ] [B] kT
r =Z AB e =❑ AB ć rel e =❑ AB ć rel L e
V 2V 2

 Note: L = Avogadro’s no = 6.02 x 1023

Where (NB / V) = [B].L (convert molecular units  molar units)

 Experimental rate

r = k[A][B]

❑ AB ć rel L2 −ε
 Thus, equating both equations, theory predicts that k = e kT
2

 Many reactions show a rate constant that follows the Arrhenius equation

−E a
RT
k=Ae

 Where A = pre-exponential factor and Ea = activation energy (in kJ mol-1 / J mol-1)

−ε
2 [ A ] [B]
 Theoretical rate constant k = ❑ AB ćrel L e kT
2

 Thus, good agreement for the general form of k

Ea
 A=
[ A ] [B]
Example

CH3 + CH3  C2H6

 Experimentally, A = 2.4 x 1010 mol-1 dm3 s-1 (same units as rate constant k)

 Theoretically, Atheo = 1.1 x 1011 mol-1 dm3 s-1

 Good agreement for a crude model

Steric Factors

 However, collision theory usually overestimates the experimental reaction rate

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 Reason: Molecules do not always react on collision. They must have the correct
orientation. (not all molecules are spherical)

A experimental
 The steric factor, P, is defined as and is usually < 1
Atheoretical

 Note: The lower the steric factor, the more specific the alignment / orientation of
molecules must be for the molecules to react (e.g. H2 + C2H4)

Effusion

 Defined as the emergence of a gas from a small hole in a container

 Can be thought of in the same way pressure is derived (i.e. finding how many
molecules hit a given area of wall) and taking away the wall

 In time t, molecules travel a distance of vx.t in the direction towards the wall

 For an area A of wall, molecules in a ‘collision volume’ of vx.t.A hit the wall

 We need to use the mean vx going towards the wall

 For vx, the distribution is given by:

2
−m v x
m 1
( )
f ( V x )= ( 2 πkT ) 2
e 2 kT

 Note: this is the distribution of molecular velocity, not speed

 Vx is a vector and can have positive and negative values, indicating direction
(symmetrical about 0 – since gas fills a container homogeneously)

 Mean vx towards the wall is the mean value of positive vx only

2
∞ 1 ∞ −m v x
m ( ) dx=¿ kT 12 8 kT 12 1
¿ v x ≥∫ v x . f ( v x ) dx=¿
0 2 πkT ( ) ∫ vx
2

0
e 2 kT
( ) (
2 πm
=
16 πm )
= ć ¿ ¿
4

 No of molecules hitting the wall, in a unit time per unit area:

N N kT 12 p kT 12 p N ć p ć
ZW =¿ v x > =
V V 2 πm
= ( )
kT 2 πm
= ( ) (2 πmkT)
1
2
= . = .
V 4 kT 4

 Example, for Ar, Zw = 2.45 x 1023 s-1 cm-2

Graham’s Law of Effusion

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 States that the rate of effusion of a gas from a small hole is inversely proportional to
(molar mass) ½

1
 In other words, no of molecules escaping 
√M
 If the wall has a small hole in it of area AO, and gas emerges from the hole,

p . AO p . AO . L
Rate of effusion = ZW . AO = 1
= 1
2 2
(2 πmkT ) (2 πMRT )

 Measuring very low vapour pressures indicates the nature of intermolecular forces of
attraction

 Knudsen applied Graham’s law to measure vapour pressures of solids and liquids

 In time t, mass loss from a container through effusion

∆ m=Z W . A O .m . ∆ t

∆m
ZW =
A O . m. ∆ t

p ∆m
=
1
2
A O .m . ∆ t
(2 πmkT )
1 1 1
∆m ∆ m 2 πkT ∆ m 2 πRT
p=
AO . m. ∆ t
(2 πmkT ) 2 =
AO . ∆ t m ( ) 2
= (
AO . ∆ t M ) 2