Conductor (Electronic) R

Ionic Conductor

L [S] or [-1]

Normalization
Geometry (1 m3)
Amount of charged species (1 mol) Amount of charge (ion 1 F, molecule 2F)
m= / c
c / mol dm C/mol.dm-3
3

[S m-1]
m

m = /c [S m2 mol-1] m
[S m2 mol-1]

Ionic Conductor Ionic Conductor

Volume which contains 1 molar electrolyte Vm / m 3

Sole Ion-Solvent Interaction

Unit area

Unit distance Unit cube

They are on the different level!

Conductivity

Kohlrausch's Square Root Law

1840-1910

m = A c m
m of an electrolyte of the

For strong electrolytes with sufficient dilution, the molar conductivity

concentration c is a linear function of the root of the concentration c. m = molar conductivity at infinite dilution; A = constant which is a function of the valence of the salt.
Physical institute, University of Wrzburg, Germany 1886

Strong electrolyte C
Why
m slightly up
ion interaction weak ion velocity increase

Weak electrolyte
m remarkably up
ionization degree up number of ion increase

Kohlrausch's Law

Law of Independent Migration of Ions

m = , + + , (equivalent charge) m m
Limiting Molar Conductivity of cation and anion

m = A c m

m = ( A + B ) c m m

m = + , + + , m m

(1 mole)

Kohlrausch's Law

Law of Independent Migration of Ions

m = , + + , m m

Measurement of m
a. b. c.

m ( Mx) m ( Nx) + m ( NA)

strong electrolyte

x , c m
m , c m
( strong electrolyte

= (MA)

Weak electrolyte

, + , , m m m

(weak electrolyte)

The concentration dependence of molar conductivity

(weak electrolyte)
HAc <==> H+ + Ac(Ac-: acetate ion)

There are two classes of electrolyte with dramatically different character Ions interact strongly with each other How to get the limiting molar conductivity or its approximation Ions move at different ways. The mobility H+ > OH- >> K+ > Na+ Degree of dissociation , dissociation constant K, can be obtained.

(1 - )c

K = 2c / (1- )
If is expressed as the ratio m

/ mo

C/mol.dm-3

1 / m = 1 / mo + c m/ K(mo)2

25C, Limiting Molar Conductivity of some ions(-1m2mol-1)

Ionic Conductor (Electrolyte Solution)

Microscopic

Dynamic

Macroscopic

m m
m , + ,m ,

Ui Ui ti ti

Ionic Move Velocity Electrolytic Cell

I

i
A A

Ionic move velocity

dE dE = U+ = U+ dl dl dE dE = U = U dl dl

i
E l E l

( I = I + + I- )

and ionic mobility Ui

- +

A e

+
Ui

e
Cathode

+
Anode

even E

Electrolyte

dE dl

Ionic mobility [m2s-1V-1] is defined as

dE = 1 Vm dl
1

the move velocity of ions when

Charge Flux (Electrochemical Current) by Ions Transfer

I = I+ + II = (U + + U )

MA c(1-)
I
+

M+ + Ac c
+

( I = I + + I- )

E A cF l

=
+

A cF

= U

E A cF l

I = U

E A cF l

A l I = = L = c Ac E = (U + + U ) F

=L l

l Ac

m = (U + + U ) F
= (U m, + + U m, ) F m

For a more general electrolyte M+ A -

(c 0)

m = (U + + U ) + z + F
, + = U + + z + F m , = U z F m

= , + + , m m m
, + = U m , + F m , = U m , F m

At 298Km,i and Ui of some ions in solution

ions
H+ Li+ Na+ K+ NH4+ Ag+ 1/2Cu2+ 1/2Zn2+
103m/ -1m2 mol-1 103U/m2 S-1 V -1

Microscopic View of Ions Motion under Electric Field in Solution

Force of electric field

ions
OHClBrI1/2CO32AcNO31/2SO42-

103m / -1m2 mol-1

103U / m2 S-1 V -1

34.98 3.86 5.01 7.35 7.35 6.19 5.66 5.28

36.2 4.0 5.2 7.6 7.6 6.4 5.9 5.5

19.86 7.74 7.81 7.68 6.93 4.09 7.15 8.0

20.6 7.9 8.1 8.0 7.2 4.2 7.4 8.3

F = zeE V E = ze l
i =
zeE = Ui E f

+
F

Force of Friction

f fric = fi

i
Ffric

f = 6a

Ui =

ze ze = f 6a

Atkins Physical Chemistry , p.836

Ui =
Cs+:

ze ze = f 6a

a = 0.17 10-9 m

Factors to influence ionic mobility ze ze m2 V-1 s-1 U= = f 6a

1) Nature of Ion
ChargeSolvation radius Interaction of ionsMechanism of transportation

=1.0 cP=1.0 10-3Kg m-1 s-1

U 5 10-8 m2 s-1 V-1
E = 1 V/cm (100 V/m)

i =

zeE = Ui E f

= 5 m s-1 Crossing over solvent molecules per second! ~104

2) Nature of Solvent
Viscosity (interaction of solvent molecules)

Structure of Water Near Ion

Effect of viscosity of solvent on ze ze U= = f 6a limiting molar conductivity of ions

Water Acetone Methanol 0.316 0.0082 0.0075 0.547 0.0054 0.0040 Ethanol 1.200 0.0022 0.0015

i 1/ ri
r(Li+) > r(Na+) > r(K+) U(Li+) < U (Na+) < U (K+)

/ mPas

1.0 0.00735 0.00387

m
(K+)

(Li+)

<m

(Na+)

<m

m
(Li+)

(K+)

Ui of H+ and OH- s are abnormally high!

Unique proton transport mechanism of H+(OH-)

Ions Interaction
Anion and cation are close to each other in a critical distance in highly concentrated solution

Forming Ion Pair

M + + M +

Transport Numbers
The fraction of the total current carried in a solution by a given ion.

ti =

I = I+ + I-

c z AF Ii Q = i = i i i = I Qi ci zi i AF

= 1

Hittorf method to measure transport number

For only one electrolyte in the solution

n+ 3 v+ = = n 1 v
t+ =

t+ =
t+ =
=

Q+ Q

t =

Q Q
I I

t+ + t = 1
I+ =
= U
+

n+ n v+ 3 = = + = = 0.75 v+ + v n+ + n Q 4

I+ I

t =

A cF

t =

n v = = n = 1 = 0.25 n+ + n Q 4 v+ + v

U U+ = U + + U U+ +U

E A cF l

U U
+

t =

U U + U

Hittorf method to measure transport number

,+ m

, m

In the strong electrolyte solution of low concentration, the equation can be expressed approximately as

ti = ni Q/ F
Q = n 1 z 1 F = n2 z 2 F By measuring the change of composition in the cathodic compartment, the anion transport number t- can be deduced.

t+

m, +

m m , + + m ,
t m,

ti =

ni Q/ F

ni(end) = ni(begin) +

ni(reaction)+

ni( transport

1. Suitable to any ions in either cathodic area or anodic area

2. n (reaction) > 0, electrode reaction generate ions n (reaction) < 0, electrode reaction consume ions

Q = niziF
ni(end) = ni(begin) + ni(reaction)+ ni( transport
ni should be ni (transport), that must exclude the portion generated by the electrode reaction

3.

ni( transport) = ni(end) - ni(begin) -

ni(reaction)

n (transport)

>0 <0

Moving in Moving out

2. Moving-Boundary Method

2. Moving-Boundary Method

MX C

MX D

MX and NX have the same anion

x The boundary, difference in color, refractivity, etc. should be sharp.

A NX B

t+ = =

Q+ Q

NX

+
t=0

+
t=t

c+ z +V+ F It

2. Moving-Boundary Method
t+ = Q+ c+ z +V+ F c+ z + xF = = Q It It

Conductivity Dependence on Temperature

38 % H2SO4 was used in acid-lead battery;

It can also be applied to measure ionic mobility

l U+ = +

x+ A t I

Hot electrolyte was used for electrolysis and electroplating

XYZ X X Y Y Z Z
1 2 3

CCFE
Current cleavage focusing electrophoresis
V1

E1

V2

E2

V3

E3

V4

X X X + Y Y Y + Z Z Z
1 2 3
40

E1 > E2 > E3 I1 > I2 > I3

CCFE
Current cleavage focusing electrophoresis
+
v

Separation in short channels using novel focusing electrophoresis technique:

Counter flow focusing electrophoresis Current cleavage focusing electrophoresis

x VF
Injection I: 800A V: 4 L / min t: 2.5 min

Il

State Key Laboratory for Physical Chemistry of Solid Surfaces

x
41

VEA

VEB

VEC

Europe patent:wo0235223 Chinese patent:98104828 00131582

How to calculate Ksp through ?

Conductivity Measurements and Applications

M + + M
+

z+

+ z

+ c( M z + ) c( A z ) K sp = o co c

= measurement water
Ordinary Multiple High purity

c=

Measuremen t water

m,+

m,

distilled water

Attention to the unit of c: m-3 dm-3

(S m-1)

10-3

10-4

510-6

o How to calculate K c through ?

o How to calculate K c through ?

(I-I valence weak electrolyte)

MA
c(1-)

M+ + Ac c

2 o c c = c Kc = (1 )c 1 c o o o

c c
co

2 co co = c K = (1 ) c 1 c o co
o c

c c

2 m =(mU =

+ Uc ) F

m=m m+ U m , ) F ( (U m , + ) c m

Conductometric titration

Conductometric titration

NaOH ----- HCl

BaCl2 ----- AgNO3

Conductometric titration

Ionic conductor(electrolyte solution)

Equilibrium

Dynamic Macroscoipc

i
Microscoipc

m m
NaOH ----- HAc

F F ti

Ui Ui ti

m = , + , , m m

Exercises:
: 2 6 The ionic mobility is about 510-8 m2s-1V-1 in aqueous solution. Is the corresponding current density small Why? 1 528

Atkins Physical Chemistry 7th Edition p. 858, 24.29(a)&(b); p.859, 24.13