Molecules in motion

Contents
Molecular motion in gases
24.1 The kinetic model of gases
24.2 Collisions with walls and surfaces
24.3 The rate of effusion
24.4 Transport properties of a perfect gas

Molecular motion in liquids

24.5 Experimental results
24.6 The conductivities of electrolyte solutions
24.7 The mobilities of ions
24.8 Conductivities and ion-ion interactions

Diffusion
24.9 The thermodynamic view
24.10 The diffusion equation
 Transport properties

• Diffusion: the migration of matter down a concentration

gradient.
• Effusion: the emergence of a gas from a container through
a small hole.
• Thermal conduction: the migration of energy down a
temperature gradient.
• Electric conduction: the migration of electric charge
along an electric potential gradient (=electric field).
• Viscosity: the migration of linear momentum down a
velocity gradient.
 The kinetic model of gases
1. The gas consists of molecules of mass m
in ceaseless random motion.
2. The size of the molecules is negligible
(their diameters are much smaller than
the average distance traveled between
collisions.

3. The molecules interact only through

brief, infrequent, and elastic collisions.
(the total translational kinetic energy of
the molecules is conserved.) Free paths

Mean free path=average of free paths

Pressure and molecular speeds
Perfect gases
1 M  mN A
pV  nMc2 EOS
3
pV  constant Constant T

pV  nRT
1
 3RT  2
c 
 M 
Maxwell distribution of speeds

3
 M   Mv 2
f v   4 
2

2 2 RT
v e
 2RT 

The gas continuously

redistribute the speeds
among the molecules
Fraction in the range v1 to v2   f v dv
v1

v2

 Given a narrow range of speeds

f(v)v

 In a range of speeds, we have to

evaluate the integral
Engel and Reid,
3rd ED, 2013
 Using Maxwell Distribution
• Evaluating Maxwell distribution
– Over narrow range, v,evaluate f(v) v
v2
– Over wide range, numerically integrate, f(v1  v 2 ) 
v 1
f(v)dv
 Mean speed of particle
» Mean speed (not mean root speed) is calculated by
integrating the product of each speed and the
probability of a particle having that speed over all
possible speeds
3
  M  2 2 Mv

3
 M  2  1 
  c  4    
2
/ 2RT
c  vf(v)  v  4   v e 2RT  2(M / 2RT )2 
0 0 2RT 
 M  2 2R 2 T 2 4 * 2R 2 T 2 M 1.5 
3 3
  M  2 3  Mv
0 c  4     2 
/ 2RT
1.5 
2

c 4   v e   
2RT  2RT  M 2
 2RT  M 
3
 M  2  3  Mv 2 / 2RT 21.5 R 0.5T 0.5 
c  4  
2RT  0 v e c  
  0.5M 0.5 



Math moment :
8RT 0.5
 1 c   
0 3 ax 2
x e   M  Mean speed
2a
 The most probable speed
The speed with largest probability
3
  2 
f v   4 
2 2
M Mv
 ve 2 RT

 2RT 
df ( v )
|
dv v  c *
0
1
  2 RT  2
c  
 M  v=c*

ćrel=21/2ć Relative mean speed, mean speed with which one

molecule approaches another
 Collisions
Hit
• Collision diameter, d - distance > which no
collision occurs, i.e., no change in p of
either molecule
– Not necessarily molecular diameter, except
for hard spheres
• N2, d = 0.43 nm
• Collision frequency, z - number of collisions made by molecule per unit time
z = s x crel x N
s = collision cross section = πd2
N = # molecules per unit volume = N/V
crel = relative mean speed
• For ideal gas, in terms of pressure ,
z = (s crel p)/kT
– As T increases, z increases because the rel. mean speed a T1/2
– As p increases, z increases because the # of collisions a density of gas a N/V

Kinetic model enables us to calculate the frequency with which

molecular collisions occur and the distance a molecule travels on
average between collisions.
 Collisions
• Mean free path, l - average distance between collisions (the average
distance a molecule travels between collisions)
l = mean speed collision frequency
If collision frequency is z, and c is mean speed, l  c z
s c rel p
But, z  and c  2  c rel so
kT
s c 2 p 
l  c  



 kT 
kT
l
2s p

• Doubling pressure halves l

• At constant V, for ideal gas, T/p is constant so l independent of T
• the distance between collisions is determined by the number of molecules
present in the given volume, not by the speed at which they travel
• Collision Flux, zw - # collisions per unit time and area
zw = p/(2πmkT)0.5
Collisions with walls and surfaces

Collision with walls and surfaces -

= transport in the gas phase
- rate at which molecules strike an area

* no. of collisions per unit area per unit time, (ZW)

p
ZW 
2mkT 1/2
 Collisions with walls and surfaces
The number of molecules colliding with the wall
per second and per unit area :
ZW  NAt  v x f v x dvx / At  N v x f v x dvx
 

0 0

 N v x (  m vx2 / 2 kT
 1/ 2
m
2kT ) e dvx
0

 N( 2mkT )1/ 2
1 p
 kT 
 N
2
1
 cN
ZW 
ZW 
 2m  4 2mkT  21

Using the probability distribution of velocities

 Experimental fact of effusion:
Graham’s Law

Rate of effusion reffuse  1

molar mass  1
M

Effusion t ime  r 1effuse  molar mass  M


t effuse , A MA
t effuse ,B MB

The rate at which they strike the area of the hole is also inversely
proportional to M1/2
 The rate of effusion

pA0 pA0 N A
ZW A0  
A0 2mkT  2 2MRT  2
1 1

Using the expression for the rate of collisions: detailed expression

Transport properties of a perfect gas
Diffusion:
dN
J (matter ) 
dz
dN
J (matter )   D
dz
Thermal conduction:
dT
J (energy ) 
dz
dT
J (energy )  
dz

Viscosity:

dvx
J ( x  component_of_momentum)  
dz
 molecular motion
rate of migration of a property
= measured by its flux, J
 flux, J = quantity of that property passing
through per unit area per unit time
 experimental observation
= flux of a property is usually proportional to the
slope of the variation of a related property
with distance
 molecular motion
 the flux of matter
dN
J(matter) 
dz
 also called Fick’s first law of diffusion

* similarly, the rate of thermal conduction

(flux of the energy)
dT
J(energy) 
dz
 molecular motion
 if flow of matter occurs down a gradient - ( high
to low )
dN
 < 0
dz
but, J is positive (flow to the right)

- therefore, the coefficient of proportionality

= D (diffusion coefficient)
thus,
dN
J(matter)  D
dz
 molecular motion

similarly,
dT
J(energy)   
dz

 = coefficient of thermal conductivity

The rate of transport is a to the spatial derivative (gradient) of

some property
 molecular motion
 for viscosity -
= consider a fluid in a state of Newtonian flow
 a fluid at laminar flow
* layer next to the wall is stationary
* velocity of the succeeding layers varies
linearly with the distance (z) from the wall
* because fast layer are retarded and slow layer
are accelerated by arriving molecules
= layers tend towards a uniform velocity
~ retarding effect
= fluid’s viscosity
Origin of viscosity
 molecular motion
 = the flux of the x-component of momentum  dvx
dz
= since there is no net flux when all the layers move
at the same velocity,
dv
J(x  component of momentum)  x
dz
and,
J(x  component of momentum)   dvx
dz
 = coefficient of viscosity or simply viscosity
(constant of proportionality, kg m-1s-1)
 molecular motion
Property Transport Simple kinetic theory Units
Quantity
Diffusion matter m2 s1
D = lc
1
3
 1 1 1
Thermal energy  = 1 lc [A] J K m s
C V,m
Conductivity 3
cC V,m

 
3 2 sN A
Viscosity momentum  = 1 l cmN kg m1s1
3
mc

 
3 2s
Diffusion 1
D  lc
3
l, as the pressures is , so D
decreases with increasing
pressure
Gas molecules diffuse more
slowly
 with T, so, D with T
Molecules in a hot sample
diffuse more quickly than those
in a cool sample
Mean free path when the
collision cross-section of the
molecules decreases, D, is
greater for small molecules
 Proof
 dN 
N (l )  N (0)  l  
 dz 0
A0N  l ct
1
 N  l c
Z A t 1
J ( L  R)  A t  4 W 0

A0 t
0
4

J ( L  R)   N  l c
1
4
 dN 
N (l )  N (0)  l  
 dz 0
J z  J( L  R )  J( L  R )
=
1   dN     dN   
 cN (0)  l     N (0)  l   
4   dz 0    dz 0  
1
1  dN 
  cl  
D  lc
2  dz 0 2
Correction to diffusion coefficient
due to collision

1
D  lc
2

1
D  lc
3
 Thermal conduction
T

  l cCV ,m A
λ 1
0

-λ
3
 Thermal conduction: Proof
  kT    degree of freedom
1
2

T J ( L  R)  cN  l 
1
4
  dT  
  l   vk T  l   
z   dz 0 

  dT  
J ( L  R)   cN l 
λ 1  l   vk T  l   
  dz  0 
4
0 1  dT 
J z  J ( L  R)  J ( L  R)   vkl cN  
2  dz 0
-λ
1
  vkl cN
2
1  dT 
J z   vkl cN   (after including collision effect)
3  dz 0
  l cCV ,m A
1
N  N /V 
1 CV .m  kN A
  vkl cN nN A / V  N A [ A]
3
3
 Thermal conduction and pressure

  l cCV ,m A
1
3
l
kT
1
[ A]  n / V  p / RT
2 2 sp
1
  l cCV , m [ A]  3 1 2
c CV ,m
(independent of p)
sN A
3
At low pressure when the mean free path is larger than the
Dimension of container,
kT
l 1
2 2 sp

  [ A]  p
Viscosity of a perfect gas

  Ml cA
1
3
 Proof
mvx (l )  mvx (0)  ml ( dzx )0
dv

mvx (l )  mvx (0)  ml (

dv x
)
dz 0

J  14 Nc{[mvx (l )  mvx (0)  ml ( dzx )0 ]

dv

 [mvx (l )  mvx (0)  ml ( dzx )0 ]}

dv

  12 Nmlc ( dvdzz )0
 | no collision  Ml cA
1
2

After collision effect is considered,

  Ml cA
1 1
  Nml c
3 3
Viscosity and temperature (Argon gas)

1
  Ml c[ A]  1 cM
3 2 sN A
3
1
 8RT  2
c 
 M 

 T
Independent of pressure
 Measuring viscosity: Poiseuille’s
formula for rate of flow

dV


p  p r 2
1
2
2  4

dt 16lp 0
Dependence of viscosity
on pressure and temperature
p1 2r p0 p2 can be measured based on
this formula.
l
Summary of transport properties
of perfect gases
 Molecular motion in liquids
24.5 Experimental results
24.6 The conductivities of electrolyte solutions
24.7 The mobilities of ions
24.8 Conductivities and ion-ion interactions
 Experimental results
Nuclear Magnetic Resonance (NMR)
Electron spin resonance (ESR)
(mobilities of molecules)

Inelastic neutron scattering

Small molecules in nonviscous

fluids typically jump through
about 57o in each step

Large molecules in viscous

fluids typically rotate in series
of small steps (~ 5o).
 Experimental results

Viscosity measurement:
Larger viscosity means small mobility.

For a molecule to move in a liquid, Ea

Mobility of the molecules in the liquid Ea

should follow this temperature
dependence
e Ea / RT

Intermolecular interactions govern Ea

Conductivities of electrolyte solutions
A 1
G R
conductance
l
1 S = 1000 mS= 1 Ω-1 = 1 C V-1 S-1
κ: conductivity, unit: S m-1

Molar conductivity: 
 conductivity of a solution
m 
depends on the number of ions
c
present, Unit: mS m-2 mol-1

Strong electrolytes
and weak electrolytes
Conductivities of electrolyte solutions
- + -
- electric charge equilibriu m :
+ - +
- + +
+ - + - - z    z  
- +
+ - -z- +z+ +
-
- + + - -
+ +
- +
A binary electrolyte solution: Aν++Bν-
+ - + + + - - -+
+- - - + +
+ - +- - -
- + +- - + +
- - - ++ +- - --
+ ++ - - + + +

A quatiary electrolyte solution: Aν++Bν-+Cν++Dν-

Strong electrolytes

 m    Kc 0
m
1/ 2

Kohlrausch’s law

Λ0m: limiting molar conductivity

Law of independent migration of ions:

for a binary strong electrolyte solution
Aν+Bν-,
   l  l
0
m    
Conductivities of weak electrolytes
HA(aq)  H 2 O(l )  H 3O  (aq)  A (aq)

a H O  a A [ H 3O  ][ A  ]
Ka  3
 [ HA]
aHA
α: degree of ionization
(degree of deprotonation
for weak acids)
[ H 3O  ]  ac
HA  (1  a )c
A   ac


a 2c
Ka 
1a

K  4c 
1 2

a a 1    1
2c  K a  

 m  a0m
 Ostwald’s dilution law
and measurement of limiting molar conductivity
1 ac
 1
a Ka
 m  a 0
m

1 1  mc
 0 
 m  m K a 0m   2

(Ostwald’s dilution law)

Intercept at c=0 (by extrapolation) gives 1/Λ0m .

 The mobilities of ions
+ s-
- -
+ - Balance of forces:
+- + +
+ - - - Electric field +
- + + - + Friction (retarding force
- + +
-
- + + - - Caused by viscosity)
+ + =0
- +
Electric field E=Δø/l
+ l
-
ze
Electric field: E   Force: F  zeE  l
l
f  6a
Stokes formula: F fric  fs
a: hydrodynamic radius
 The mobilities of ions
s
- + - -
+- + -
- + +
+ + - -
- + + - - F-----2a------
elec=zeE Ffric=fs
+ + S +
-
- + + - -
+ + - +
Electric field E
+ -
zeE
Drift speed s :
s s  uE
f
ze ze
Mobility: u 
f 6a
 zeE zeE
s 
 therefore: f 6a

- drift speed governs the rate at which charge is transported

expected: conductivity decreases with increase

viscosity and size

 predictions were confirmed by experiments

*confirmed: true for bulky ions
(R4N- and RCOO-)

- large conductivities for small ions, highly charged ions and

solvents of low viscosity
 Mobility and conductivity
= ionic mobility - provides a link between
measurable and theoretical quantities
= ionic mobility - is related to its molar conductivity:
= ionic conductivity :
l = zF

applies to the cations and anions
Mobility and conductivity
s
- + - -
+- + -
- + +
+ + - -
- + + - -
- + +
- + + - -
+ + - +
Electric field E
+ -

l  zuF Faraday constant : F  N Ae

 9.64853 10 Cmol
4 -1
 Mobility and conductivity
 therefore,
= for a solution in the limit of zero concentration

oM = (z+++ + z   1)F

since, om = l++ + l 

= for symmetrical electrolyte z:z

oM = z(+ +  )F
 Mobility and conductivity
Transport Numbers
  transport number, t,
= the fraction of total current carried by a
specific ion
 for a solution with 2 kinds of ions
* cation transport number: t + = I+ / I
* anion transport number: t = I / I
* since I = sum of the cation and anion current,
then, t+ + t = 1
 Transport numbers
• The contributions of cations and anions to the total
electric current may be different:

The transport number:

I z u 
t   z u   zu 
I
END
Conductivity and ion-ion interactions

Kohlrausch law (for strong electrolytes):

m   0
m  Kc 1 2