Chapter 24b: Molecules in Motion

Conductivity and Ion Mobility

Homework:
Exercises (a only) :25, 26, 27, 28
Problems:8

Conductance in Solution
Conductance, G, is the inverse of electrical
resistance
G = 1/R
Units ohm
-1
, O
1
, or mhos
SI unit, S, siemens: 1 S = 1 O
11
= 1C/(Vs)
Conductance decreases with length and increases
with area
G = kA/l
k is conductivity (S/m)
l = length (m)
A = area (m
2
)
Molar conductivity, A
m
, where A
m
= k/c
Variation of with concentration - function of the
number of ions in solution and interaction between
ions
Strong electrolyte - weak dependence
Weak electrolyte - strong dependence
Variation of Molar Conductivity
Strong Electrolytes
Strong Electrolytes
Fully ionized in solution
At low concentrations, A o c
A = A
m
- Kc (Kohlraushs Law)
A
m
- limiting molar conductivity
A A
m
as c 0
Sum of contributions from individual ions
A
m
= v
+

+
+ v
-

-
(Law of Independent Migration of Ions)

+
,
-
molar conductivity of cations and anions
v
+
, v
-
# of cations and anions per formula unit
(MgCl
2
: v
+
= 1; v
-
=2)
K depends on stoichiometry of electrolyte
Limiting Ionic Conductivities
(Water 25C)
Ion

+
(mSm
2
mol
-1
)
Ion

-
(mSm
2
mol
-1
)
H
+
34.6 OH
-
19.91
Na
+
5.01
Cl
-
7.63
K
+
7.35
Br
-
7.81
Zn
2+
10.56 SO
4
2-
16.00
Variation of Molar Conductivity
Weak Electrolytes
Not fully ionized in solution
For weak Brnsted acids and bases (e.g., acetic acid,
ammonia)
HA(aq) + H
2
O(l) A
-
(aq) + H
3
O
+
(aq)
Conductivity depends on degree of ionization, o, (degree
of deprotonation - weak acids)
[H
3
O
+
] = o c [A
-
] = o c [HA] = (1-o)c

Ignoring activity coefficients,


Solving for o,

The molar conductivity, A
m
, becomes A
m
= o A
m

K
a
=
a
H
3
O
+ a
A

a
HA
K
a
=
o
2
c
2
1o ( )c
=
o
2
c
1o ( )
o =
K
a
2c
1+
4c
K
a
|
\


|
.
|
|
1 2
1

`

)






Variation of Molar Conductivity
Weak Electrolytes - Ostwalds Dilution Law
If you plot 1/ A
m
vs. A
m
c, the intercept (c=0) is 1/A
m

Youll do this in Lab 7!
K
a
=
o
2
c
1o
K
a
o
=
oc
1o
or
1
o
=
oc
K
a
1o ( )
Re arranging
1o ( )
o
=
oc
K
a
or
1
o
=1+
oc
K
a
But , o =
A
m
A
m
o
so substituting for o
A
m
o
A
m
=1+
A
m
A
m
o
c
K
a
=1+
A
m
c
K
a
A
m
o
Dividing by A
m
o
,
1
A
m
=
1
A
m
o
+
A
m
c
K
a
A
m
o
2 Ostwalds Dilution Law
Mobilities of Ions
Drift speed - terminal speed of an ion moving in an electric field
Accelerating forces balanced by viscous drag forces
Accelerating force
Electric field, E = A|/l
l is separation between electodes and A| is potential difference
Force, F, on an ion of charge ze is
F = zeE = zeA|/l
Cations go to negative electrode, anions to positive
Drag force, F
fric
, estimated from Stokes relation
On sphere of radius a and speed, s, moving through a fluid
of viscocity, q
F
fric
= f s where f = 6aq
Net force is zero when F = F
fric
or

s = zeE/f
Re-writing, define ionic mobility, u, such that s = uE
u = ze/f = ze/ 6aq
Ionic Mobilities
(Water 25C)
Ion u
(m
2
s
-1
V
-1
)
Cations
H
+
36.23 x 10
8
Na
+
5.19 x 10
8
K
+
7.62 x 10
8
Zn
2+
5.47 x 10
8
Anions
OH
-
20.64 x 10
8
Cl
-
7.91 x 10
8
Br
-
8.09 x 10
8
SO
4
2-
8.29 x 10
8
Mobility, Ionic Size and Conductivity
Drift speed governs rate of charge transport
Solution viscosity important
Effect of ionic size on drift speed
Ionic radius -
Bulky ions (RN+) larger ionic radius lowers conductivity
Other ions (e.g. alkali metals) hydrodynamic (Stokes)
radius rather than ionic radius important
Accounts for hydration sphere of ions which move with ions
Small ions have higher charge density than large ions and larger hydration sphere
Exception
H
+
- high conductivity and mobility
May due to rapid reorientation of water molecules
NH
+
in liquid ammonia
Mobility and Conductivity
Molar conductivity () o mobility: =zuF (F = Faradays const.)
For solutions in limit of infinite dilution: A A
m

Recall A
m
= v
+

+
+ v
-

-
so A
m
= (v
+
z
+
u
+
+ v
-
z
-
u
-
)F
If | z
+
| = | z
-
| = z, A
m
= (

u
+
+ u
-
)zF

Ionic Mobilities
(Water 25C)
Ion u
(m
2
s
-1
V
-1
)
Ionic
Radius
(pm)
H
+
36.23 x 10
8
Li
+
4.01 x 10
8
59
Na
+
5.19 x 10
8
102
K
+
7.62 x 10
8
138
Rb
+
7.92 x 10
8
149
Zn
2+
5.47 x 10
8
Transport Numbers
Transport Number, t

- fraction of total current carried by ions of a specified type

Cations - t
+
; Anions t
-
If I is total current, then t

= I

/I
Since current carried by anions and cations in solution, t
+
+ t
-
= 1
Limiting Transport Number, t

- fraction of total current carried by ions of specified

type in the limit of infinite dilution (c=0)
Current related to ionic mobility: I = (zuvcFA)(A|/l) [1]
Thus,







[2]

c = concentration,
F= Faradays const.
A = area
A|/l =potential gradient
t

o
=
I

I
=
I

I
+
+ I

Substituting from [1]

t

o
=
(z

) cFAA| ( )/ l
z
+
v
+
u
+
cFAA| ( )/ l
( )
+ z

cFAA| ( )/ l
( )
t

o
=
z

z
+
v
+
u
+
+ z

But , for any electrolyte , z

+
v
+
= z

= z

, so
t

o
=
u

u
+
+ u

Transport Numbers and Ionic Conductivity

Because of this relationship ionic conductivities can
be determined from limiting transport numbers
Earlier we saw how to get A
m

Plot of A
m
vs cA
m

A variety of independent ways to get t

Since is related to mobility ( =zuF), u can also
be determined from transport numbers
t

o
=
z

z
+
v
+
u
+
+ z

But , A
m
o
= z
+
v
+
u
+
+ z

( )
F
t

o
=
z

F
A
m
o
Re call = zuF so
t

o
=
v

A
m
o
or v

= t

o
A
m
o