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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
Diffusion
24.9 The thermodynamic view
24.10 The diffusion equation
Transport properties
pV nRT
1
3RT 2
c
M
Maxwell distribution of speeds
3
M Mv 2
f v 4
2
2 2 RT
v e
2RT
v2
c 4 v e
2RT 2RT M 2
2RT M
3
M 2 3 Mv 2 / 2RT 21.5 R 0.5T 0.5
c 4
2RT 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
2RT
df ( v )
|
dv v c *
0
1
2 RT 2
c
M v=c*
p
ZW
2mkT 1/2
Collisions with walls and surfaces
The number of molecules colliding with the wall
per second and per unit area :
ZW NAt v x f v x dvx / At N v x f v x dvx
0 0
N v x ( m vx2 / 2 kT
1/ 2
m
2kT ) e dvx
0
N( 2mkT )1/ 2
1 p
kT
N
2
1
cN
ZW
ZW
2m 4 2mkT 21
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 2mkT 2 2MRT 2
1 1
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,
dT
J(energy)
dz
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
cN (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 cA
1
3
Proof
mvx (l ) mvx (0) ml ( dzx )0
dv
12 Nmlc ( dvdzz )0
| no collision Ml cA
1
2
Ml cA
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 16lp 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)
Viscosity measurement:
Larger viscosity means small mobility.
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-
+ - + + + - - -+
+- - - + +
+ - +- - -
- + +- - + +
- - - ++ +- - --
+ ++ - - + + +
m Kc 0
m
1/ 2
Kohlrausch’s law
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
1a
K 4c
1 2
a a 1 1
2c K a
m a0m
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
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:
I z u
t z u zu
I
END
Conductivity and ion-ion interactions
m 0
m Kc 1 2