Contents of Atkins’ Physical Chemistry

• Equilibrium (Thermodynamics: chap 1-6)

• Structure (Quantum theory and spectroscopy: Chap 7-14)
• Change (Chemical kinetics: chap 20-23)

Thermodynamics Quantum theory

Matter in bulk Individual atoms and molecules
Macroscopic view ‘structure of molecule’
Microscopic (molecular) view
Statistical Mechanics
Provides the link between the
microscopic properties of matter
and its bulk properties

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 Part 3 of Atkins: Change
Chemistry is the science of change
Rates of reactions by considering the motion of molecules

cf.
• Thermodynamics: treat the properties of matter in bulk
interchanges among different forms of energy

• Quantum Theory (quantum mechanics, quantum chemistry):

how these properties stem from the behavior of individual
atoms or molecules

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 Chap 20. Molecules in motion
• The random motion of molecules of perfect gas
accounts for
– The pressure of a gas
– The rates at which molecules and energy migrates through gases

• Molecular mobility in liquids: ionic motion in electric

field -> generalize to handle neutral motion in the absence of E field

• The diffusion equation: shows how matter and energy spread

through media of various kinds.

• The transport properties

– Diffusion: the migration of matter down a concentration gradient
– Thermal conduction: the migration of E down a T gradient
– Electric conduction: the migration of electric charge along an φ gradient
– Viscosity: the migration of linear momentum down a velocity gradient

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 Assigned Problems
Chapter 20 in the 9th edition
•Numerical Problems: 1, 5, 9, 10, 12, 13, 15, 18, 19
• Theoretical Problems: 22, 24, 26
• Applications: 31, 32, 34, 35, 36

In the 10th edition

• Problems in Chapter 19: 19A.1, 19A.3, 19A.4, 19B.6
19B.7, 19B.8, 19C.1, 19C.5, 19C.12, 19C.13

• Problems in Chapter 1: 1B.1, 1B.5, 1B.7, 1B.10

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 Molecular motion in gases
The kinetic model of a perfect gas as a starting point for the
discussion of its transport properties
(KE of the molecules is the only contribution to E of the gas)

20.1 The kinetic model of gases

Three assumptions
1. The gas consists of molecules of mass m in ceaseless random motion
2. The size of the molecule is negligible (if d << average distance travelled)
3. The molecules interact only through brief, infrequent and elastic collision

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20.1 (a) Pressure and molecular speeds-1a
p of a perfect gas according to the kinetic model
nMc 2
=
pV = nRT
1 M = mN A 3
pV = nMc 2 12 3RT
3 c = v2 ∴ c2 =
M
Momentum change of a molecule after collision:
∆Pa molecule =
2mv x
1  nN A 
Number of colliding molecule in ∆t : ( Avx ∆t )  
2  V 
nN A Av x ∆t nMAv x2 ∆t
∴∆Ptotal = 2mv x =
2V V
∆P nMAv x2
=
F =
∆t V
F nMv x2 nM v x2 nMc 2
=
p = → →
A V V 3V
where c 2 = v 2 = v x2 + v 2y + vz2
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 20.1 (a) Pressure and molecular speeds-1b
∞ π v x − direction KE =
1
mv x 2
∫
− ax 2
e dx =
−∞ a 2
∞ Probability having v x , ( −∞ ≤ v x ≤ ∞ )
∫ f ( v x ) dv x
−∞
E mv x 2
− −
f ( vx ) ∝ e
2
=e
mv x
∞ − kT 2 kT

∫=
Ne dv x 1
−∞
2 kT
1 2

 m  − 2 kTx
mv
2π kT f ( vx ) = 
2
N =1  e
m  2π kT 
 m 
 a ≡  : Maxwell-Boltzmann
 2kT 
velocity distribution

3
Mv 2
 M  −
f ( v ) = 4π 
2
2
 ve
2 RT
molar mass, M = mN A
 2π RT 
gas constant, R = kN A
Maxwell distribution of speeds

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 20.1 (a) Pressure and molecular speeds-1c
v x − direction v x ~ v x + dv x
1
mv x 2 v y ~ v y + dv y
 m  −
f ( vx ) = 
2
 e
2 kT
v z ~ v z + dv z ,
 2π kT 
v= vx 2 + v y 2 + vz 2
dv x dv y dv z = v 2 sin θ dvdθ dφ

f ( v y ) dv y ∫
v x + dv x v y + dv y v z + dv z
∫ f ( v x ) dv x ∫ f ( v z ) dv z
vx vy vz

3 2 2 2
mv
 m  − 2 kTx − 2 kT − 2 kTz
mv mv
v x + dv x v y + dv y v z + dv z 2y

=∫ ∫ ∫   e e e dv x dv y dvz
vx vy vz
 2π kT 
3 2

 m  − 2 kT 2
mv
v + dv π 2π 2
=∫ ∫ ∫   e v sin θ dvdθ dφ
v 0 0
 2π kT 
3 2

 m  − 2 kT 2
mv
v + dv v + dv
 e v dv = ∫v f ( v ) dv
2
3 = 4π ∫ 
Mv 2 v
 2π kT 
 M  −
f ( v ) = 4π 
2
2
 ve
2 RT
molar mass, M = mN A
3 2

 m  2 − 2 kT
mv

 2π RT  ∴ f ( v ) = 4π 
2
 ve gas constant, R = kN A
 2π kT 

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 20.1 (a) Pressure and molecular speeds-2
3 2

 M  2 − 2 RT
Mv
f (v) (0 ≤ v ≤ ∞) 1 π
2
4π   ve
∞
∫0 e − ax dx =
2

 2π RT  2 a
∞ 1
Root mean square speed
∫0
− ax 2
xe dx =
1 2a
 3RT 
1
2
=c =
v 
2 2
 ∞ π
∫ x 2e − ax dx = a −3 2
2

 M  0 4
∞ 1
∫0
3 − ax 2
x e dx =
Mean speed 2a 2
1 ∞ 3 π −5 2
∫0
4 − ax 2
 8RT  2 x e dx = a
c =  8
 πM  ∞
∫ vf ( v ) dv
c≡ v =
0
∞
∫ f ( v ) dv
c2 ≡ v2 = 2
v
Most probable speed 0
1
 2 RT  2
c* =  
 M 

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20.1 (a) Pressure and molecular speeds-3
3
Mv 2
 M  2 −
f ( v ) = 4π 
2
 ve
2 RT
Relative mean speed  2π RT 

crel = 2c
1
 8kT 2 m AmB
=
 πµ  where µ
  m A + mB

A velocity selector

Ex 20.1 c of N2 molecules in air at 298K.

8RT 8 × 8.314 JK −1mol −1 × 298K

=c = = 475 ms −1
πM π × ( 28.02 × 10 kg mol )
−3 −1

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 20.1 (b) The collision frequency, z
(c) The mean free path, λ
σ crel p
z σ=
crel N collision crosssection,
kT σ ≡ πd2
c 1 kT
λ= = =
z 2σ N 2σ p freeze the position of all the molecules except one
Ν p
number density, N ≡ =
V kT
For 1 atm of N2 molecules at 298K. ( pV = nRT = nN AkT = ΝkT )
Ν
σc p
z = rel = )  / ∆t Nσ crel
z  (σ crel ∆t=
kT V 

=
0.43 × 10−18 m 2 × ( )
2 × 475 ms −1 × (101325 Nm −2 )
1.38 × 10−23 JK −1 × 298K
= 7.1 × 109 s −1

c 475 ms −1
λ= = = 67 nm (~ 200 times of d )
z 7.1 × 109 s −1
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 Review 20-1
nMc 2
pV =
3
• The collision frequency
1
z = σ crel N
2

 m  − 2 kTx
mv
f ( vx ) = 
2
 e
 2π kT 
3
Mv 2
 M  2 −
• The mean free path
f ( v ) = 4π 
2
 ve
2 RT

 2π RT  1
1 λ=
 3RT  2σ N
1
2
=c =
v2 2
 
 M 
1
 8RT  2
c = 
 πM 

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 20.2 Collisions with walls and surfaces
The collision flux, Zw
(the number of collisions per a given time and area)

1 1 8kT p p
=
Zw = cN =
4 4 π m kT 2π mkT

number of molecules collide with wall

For 1 bar of O2 molecules at 300K.
NAv x ∆t
p
= ∞
( NAv ∆t ) f ( v ) dv
∫=
Zw
2π mkT =Zw 0
x x x 1
Nc
100000 Nm −2 A∆t 4
= 2

 m  ∞ − 2 kTx
mv
2π × 32 × 10 kg ÷ 6.02 × 10 × 1.38 × 10
−3 23 −23 −1
JK × 300 K ∞
v x f ( v x ) dv x = 
∫0
 2π kT
 ∫0 v x e

dv x
 kgms −2m −2 −2 −1 −4 −2 −1

= 26893 × 10 23
=
m s = 10 cm s  1
 kg × kgm s
2 − 2   kT  2 1
 
= =  c
 2π m  4
≈ 3 × 1023 cm −2 s −1

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 20.3 The rate of effusion
The emergency of a gas from a
Rate of effusion through a hole of area A0 container through a small hall

pA0 pA0 N A pA0 N A 1 : Graham’s law of effusion

Z=
w A0 = =
2π mkT 2π MRT 2π RT M

Knudsen method
(vapor pressure determination for liquids and solids with low vapor pressure using effusion rate)
mass loss in an interval ∆t due to effusion
Ex 20.2 Cs in container was heated to 773K. After
100 s, 385 mg is lost through d = 0.50 mm opening. ∆
=w Z w A0m∆t
What is the vapor pressure of Cs at 773K? ∆w p
= Zw =
2π RT ∆w A0m∆t 2π mkT
p=
M A0 ∆t 2π kT ∆w 2π RT ∆w
=∴p =
2π × 8.314 × 773 J 385 × 10−6 kg m A0 ∆t M A0 ∆t
=
π ( 0.25 × 10−3 m ) × 100 s
2
0.1329 kg

 kg  760
10808  m 2 s −2 2 =
= kgm −1s −2 =
Nm −2 =
Pa  =
10808 × Torr =
81 Torr
 m s  101325
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 20.4 Transport properties of a perfect gas-1
commonly expressed in terms of a number of phenomenological equations
Flux, J (the quantity of a property passing through unit area per unit time)
ex, matter flux (diffusion), energy flux (thermal conduction)

dN
J ∝ gradient of a property Fick’s 1 st law of diffusion
J matter∝
dz Diffusion coefficient
dN molecules  m 2  molecules 1
Jz =−D 2
=  s 
dz ms   m3 m
dT
J energy ∝
dz Coefficient of thermal conductivity
dT J  J K
Jz = −κ =
 
dz m 2 s  Kms  m
dv
J momentum ∝ x
dz Coefficient of viscosity
dv x kgms −1  kg  ms −1
Jz = −η =  
 ms  m
2
dz ms
gcm −1s −1 ≡ P( poise), kgm
= −1 −1
s =
10 P, cP 10−2 P
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20.4 Transport properties of a perfect gas-2
Newtonian flow (laminar flow):
a series of layers moving past
one another
- layers tend towards a uniform
velocity
- interpret the retarding effect of
the slow layers on the fast layers
as the fluids viscosity

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 Review 20-2
1 1 8kT p p
Collision flux:=
Zw = cN =
4 4 π m kT 2π mkT

2π kT ∆w 2π RT ∆w
=
Knudsen method: p =
m A0 ∆t M A0 ∆t

dN molecules  m 2  molecules 1
J matter , z =
−D 2
=  3
dz ms  s  m m
dT J  J K
−κ
J energy , z = =  
dz m 2 s  Kms  m
dv x kgms −1  kg  ms −1
−η
J momentum , z = =
 
  m
2
dz ms ms
gcm −1s −1 ≡ P( poise), kgm −1s −1 =
10 P, cP = 10−3 kgm −1s −1
10−2 P =

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20.4 Transport properties of a perfect gas-3
The molecules within a mean free path can pass A0
1
J ( L → R )= cN ( −λ )
4
1
J ( R → L ) =cN (λ )
4
Net flow, J z = J ( L → R ) − J ( R → L )
1
c ( N ( −λ ) − N (λ ) )
=
Jz
4
1  dN   dN 
= c   N ( 0) − λ + ⋅⋅⋅  −  N ( 0 ) + λ + ⋅⋅⋅  
=4  dz z 0=   dz z 0 
1  dN  1 dN  2  Some path may not
≈ c  −2λ  =
− λ c  ×  reach the wall
=4  dz 
z 0= 2 dz z 0 3

1 kT 8kT
=
∴D λc =(λ = , c )
3 2σ p πm
T↑ D↑
p↑ D↓
larger molecule: σ ↑ D↓
(2015) Chemical Kinetics by M Lim 18
20.4 Transport properties of a perfect gas-4
Each molecule carries on average energy ε = νkT
1
J ( L → R=
) cN ε ( −λ )
4
1 For a perfect gas
J ( R → L ) =cN ε (λ )
4 CV=
,m ν=
R ν kN A
 dT  Ν nN A
ε (=
±λ ) ν k  T ± λ + ⋅⋅⋅  =
N =
 dz 0  V V
N n p p
1  dT   2  = = [ A=] =
Jz ≈ cN  −2ν k λ ×  NA V RT kN AT
4  dz 0   3 

1 1 cCV ,m
∴κ
= λ=
cν kN λ cCV ,m [ A] =
3 3 3 2σ N A
κ : independent of p at high p
At low p, if λ is greater than dimensions of the apparatus
κ depends on p

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20.4 Transport properties of a perfect gas-5
1
J ( L →=
R) cNmv x ( −λ )
4
1
J ( R → L ) =cNmv x (λ )
4
 dv x 
=
mv x ( ± λ ) m  x
v (0) ± λ + ⋅⋅⋅ 
 dz 0 
1  dv   2 
Jz ≈ cN  −2mλ x   × 
4  dz 0   3 

1 mc 1
∴η
= λ=
cNm λ
(= )
3 3 2σ 2σ N
η : independent of p
8kT
η∝ T (c = )
πm
cf . for liquid, T ↑ η ↓

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