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Ionic Conductor Normalization: Kohlrausch's Law
Ionic Conductor Normalization: Kohlrausch's Law
Ionic Conductor Normalization: Kohlrausch's Law
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]
Conductivity
1840-1910
m = A c m
m of an electrolyte of the
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
m = A c m
m = ( A + B ) c m m
m = + , + + , m m
(1 mole)
Kohlrausch's Law
Measurement of m
a. b. c.
x , c m
m , c m
( strong electrolyte
= (MA)
Weak electrolyte
, + , , m m m
(weak electrolyte)
(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
Microscopic
Dynamic
Macroscopic
m m
m , + ,m ,
Ui Ui ti ti
i
A A
i
E l E l
( I = I + + I- )
- +
A e
+
Ui
e
Cathode
+
Anode
even E
Electrolyte
dE dl
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
(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
ions
OHClBrI1/2CO32AcNO31/2SO42-
103U / m2 S-1 V -1
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
Ui =
Cs+:
ze ze = f 6a
a = 0.17 10-9 m
i =
zeE = Ui E f
2) Nature of Solvent
Viscosity (interaction of solvent molecules)
i 1/ ri
r(Li+) > r(Na+) > r(K+) U(Li+) < U (Na+) < U (K+)
/ mPas
m
(K+)
(Li+)
<m
(Na+)
<m
m
(Li+)
(K+)
Ions Interaction
Anion and cation are close to each other in a critical distance in highly concentrated solution
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
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
,+ 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
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(reaction)
n (transport)
>0 <0
2. Moving-Boundary Method
2. Moving-Boundary Method
MX C
MX D
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
l U+ = +
x+ A t I
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
CCFE
Current cleavage focusing electrophoresis
+
v
x VF
Injection I: 800A V: 4 L / min t: 2.5 min
Il
x
41
VEA
VEB
VEC
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
(S m-1)
10-3
10-4
510-6
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
Conductometric titration
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