Debye Onsager theory

1. Ionic atmosphere, Debye-Hckel theory

Ions are not randomly distributed throughout the

solution

Ions are distributed under ionic

spherically atmosphere concepts
(the ionic atmosphere is spherically
symmetric)
Zone
of oppositely charged ion around the central ion
Ionic atmosphere

2. Debye-Onsager theory of conductivity

+

The electrophoretic effect

The relaxation effect

2. Debye-Onsager theory of conductivity

2.1 The electrophoretic effect
Move in opposite
direction
Frictional force
Ideal solution

Ffriction 6rv c

Non-Ideal solution

Ffriction 6r(v c v a )
With r is the radius of the moving ion
4

2. Debye-Onsager theory of conductivity

2.2 The relaxation effect
the charge density behind is
greater than in the front

Electrostatic interaction

3. Debye Onsager equation

The electrophoretic force by Debye - Hckel:

Felectrophoretic z i erE

(3.1)

The relaxation force by Onsager:

Frelaxation

with

e3 z i
2q

zz
E
6 40kT
1 q

zz

q

z z z z

(3.2)

(3.3)

 The effective force on the moving central ion once the

electrophoretic and relaxation effects are taken into
consideration will be:

e3 z i
2q
z i eE z i erE
zz
E
6 4 0kT
1 q

(3.4)

Since the ion moves at a constant velocity, this force (Eq 3.1)
will be balanced by the viscous drag on the ion exerted by the
solvent irrespective of the effects of the ionic atmosphere

e3 z i
2q
6rvi z i eE z i erE
zz
E
6 40kT
1 q

(3.5)

Electric force
Relaxation force
Frictional force of solvent

Electrophoretic force

Divide by 6r :

zi eE z i eE
e3 z i
2q
vi

zz
E
2
6r 6 6 6 4 r 0kT
1 q
E = 1V/cm

zie
zi e
e3z i
2q
vi

zz
2
6r 6 6 6 4 r 0kT
1 q
At infinite dilution, = 0, Eq3.6 follows:

(3.6)

zi e
ui v
6r
o
i

And for finite concentrations Eq3.6 follows that:

3
z
e

e
zi
2q
o
i
ui ui

zz
2
6 6 6 4 r 0kT
1 q

Since

Fu io io ( dn in ng lng):

3
z
e

F
e
z i F
2q
o
i
Fu i Fu i

zz
2
6 6 6 4 r 0kT
1 q

zi e
o
Replacing the terms
in the final term by u i gives:
6r
2
o
z
e

F
e

Fu
2q
o
i
i
Fu i Fu i

zz
6 6 4 0kT
1 q
2
o
z
e

F
e

2q
o
i
i
i i

zz
6 24 0kT
1 q

(3.7)

e2 N A
1.26456 1020
2
2

C
z

C
z
ii
ii
0kT
T
2

With:

N A 6.02214 1023 mol 1

e 1.60218 10 19 C 4.80298 10 10 c.g.s.e.s.u of ch arg e

F 9.6485 104 Cmol 1

k 1.38066 1023 J K 1
0 8.85419 1012 J 1C 2 m 1
3.14159
Then Eq3.7 becomes:

29.15z
i

i
o
i

1/2

1.98 106

3/2

q
o
zz
i
1 q

C z 2 C z 2

(3.8)

10

Thay

If C is a normality (equivalent/L) then:

29.15z
i

i
o
i

1/2

1.98 106

3/2

q
o
zz
i
1 q

C z z

dn in ng lng ca cht in li bng tng dn in ca cc ion

ring ca cht in li. T phng trnh ta c:

29.15 z z

1/2

1.98 106

3/2

q
zz
o
1 q

C z z
11

29.15 z z

1/2

z z

1.98 106

3/2

zz

q
z z
o
1 q

o ( * * o ) C

8.20 105
o

o
1/2
3/2
T
T

82.4

12

Question 2.11:
Using data from the book ( tables: 2.7, 2.12, 2.13), give
the related expression between and concentration of
solution at .

From the 2.7 table:

= +
= 130.1

13

=0.4813

w=
is electrolyte 1:2
Suppose that are parameters just depends on
the charge of ions, not the nature of electrolytes.

14


From
the 2.12 table on page 133, we have:
,
Thus:
= 0.7629

15


Question 2.12:
Using data from the book ( tables: 2.7, 2.12, 2.13),
give the related expression between and
concentration of HCl solution at .
From

the 2.7 table, we have:

16

 Temperature
coefficient of the conductivity:

;
At :

17

HCl

is separated into 2 ions, thus g = 0.500;

W=1.00.
From 2.12 table on page 133 :
Therefore:
= 0.2299

18