Conductivity, Ionic Mobilities, Transport

Number

Common materials
at room temperature

Conducting media
Insulators: small amount of charge carrying particle
Metals:
electrons are the charge carrying
particles.
Electrolyte solutions:
ions are the charge carrying
particles.
Semiconductors: band structure determines the
number of charge carriers.

Resistance:

l
A

- specific resistivity
l length of wire
A cross sectional area of wire
G

Conductance:
Conductivity:

Band gaps

Molar conductivity:

1
R

Ge
InN
InGaN
Si
InP
GaAs
AlGaAs
AlAs
SiC 6H
SiC 4H
GaN
Diamond

0.67 eV
0.7 eV
0.7 - 3.4eV
1.11 eV
1.34 eV
1.43 eV
1.42 - 2.16 eV
2.16 eV
3.03 eV
3.28 eV
3.37 eV
5.46 - 6.4 eV

-1 = S (Siemens)

unit: m-1 -1 = S m-1

m

unit: if c is given in mol m-3,

than S m2 mol-1

m is concentration and temperature dependent, m = f(c,T),.

In general, increasing the number of charge carriers increases the conductivity.
Number of ions present in a solution of unit volume (concentration) depends on
the concentration in a complicated way. weak electrolytes
The Coulomb interactions prevents the molar conductivity vs. concentration
function to show ideal behaviour. strong electrolytes.
Conductivity 2008

Figure 1. The variation of the molar conductivity m with the concentration of

the electrolyte.
When a straight line is fit to the points of m vs. c function for a strong
electrolyte the intercept gives m0 .
Measuring conductance: conductivity cell
Noble metal electrodes electrolysis
alternating current polarization
Strong electrolytes
Kohlrauschs law:

m m0 k c1 / 2

1.

m0 - limiting molar conductivity

m m0 . The distance of ions in the

In the condition: c 0,
solution is so large, that there is no interaction between them.

k depends principally on the stoichiometry of salt, rather than specific

identity.

Conductivity 2008

Figure 2. The m vs. c1 / 2 function. The circles represent experimenal points,

while the solid lines are theoretical lines calculated with the Debye-Hckel0
0
1/ 2
Onsager theory ( m m P Q m c ).
Independent migration of ions
m

2.

and are the numbers of cations and anions per formula

for NaCl, CuSO4
1, 2 for BaCl2.

Each ion is assumed to make its own contribution to molar conductivity,

irrespective the nature of other ion with which it is associated.

Table. Limiting ionic conductivities of sodium and potassium salts in water at

298 K, / mS m2 mol-1
m0
m0
Electrolyte
Electrolyte
Difference
KCl
149.79
NaCl
126.39
23.4
KI
150.31
NaI
126.88
23.4
K2SO4
153.48
Na2SO4
130.1
23.4

Conductivity 2008

The difference between the m values of sodium and potassium salts is

irrespective of the anions, as it can be seen from Table 1
Weak electrolytes
A part of the amount of dissolved substance appears in the solution as ions,
according to the ionization equilibrium.
vant Hoffs experimental findings for osmotic pressure, measurements in
weak electrolytes:
m0 R T
, i m0 R T

3.

where m0 is the concentration in mol/kg determined from mass measurement.

The effective concentration, i m0 is usually greater. The number of ionic and
non-ionic particles present in a solution is given by i
i m0 m0 1 m0

The molecule dissociates ions, and is the degree of ionization (1 > > 0).
Example: weak acid.
CH3COOH H+ + CH3COOAcetic acid dissociates into two ionic species, therefore = 2, and
i m0 2 m0 1 m0 m0 1

vant Hoff found to be proportional the ratio of molar conductivities,

m
m0

4.

When m0 0, then = 1, therefore m0 m . In dilute solution of weak

electrolytes the ionization is complete.
Eq. 4 is used to determine equilibrium constant for ionization processes.
Data can be calculated from conductivity measurements.
For general case, a weak acid dissociates

Conductivity 2008

HAc H+ + AcThe thermodinamic equilibrium constant:

Ka

a Ac a H
a HAc

For dilute solutions (c < 10-4 molal) concentrations can be used instead of
activities.
The equilibrium concentrations for a weak acid dissociation,
[H+] = [Ac-] = c, and [HAc] = (1 )c.
Ka

a Ac a

aHAc

c c
2
c
c 1
1

5.

Equation 5. is a quadratic equation in ,

c 2 Ka Ka 0

Transforming Eq. 5.
1 c

2
, and divided by
Ka

1 c

Ka

Using Eq. 4 we get, one of the forms of Ostwalds dilution law

m0

1 c 0 m
m
m Ka

or in a more applicable form

1
1

0 c 0 2m
m m
m Ka

6.

Plotting the data for Eq. 6. in a linearized form

Conductivity 2008

Figure 5. Graph used to determine 0m from the intercept, and Ka from the slope.
1

Intercept = 0
m
Slope =

0m 2 K a

Ionic Mobilities, Transport (transference) Number

Electric force field directs migrating ions parallel to the force field lines and
accelerates them toward the electrodes. A counter force prevents their speed to
exceed a limit. This is the friction force resisting the relative motion of fluid
layers.
The condition for mechanical equilibrium of transporting ion,
F friction F field

Conductivity 2008

1.

In a short time after the electric field has been switched on, the ions, e.g. the
cations migrate with a constant speed, s toward the negative electrode.
F friction s 6 r

F field zeE ze

A potential difference at a distance l produces E electric field which make

spherical ions with radius, r move against friction, that is caused mainly by
solvent molecules.
When net force is zero (see Eq. 1.) the speed, s, at a migrating ion travels can be
given as
s

zeE
6r

As , the viscosity of liquid or the radius of migrating ion increases the speed
lowers.
The hydrodynamic radius should be taken into account. For alkali metal ions
(Li Cs) the hydrodynamic radius of Li+ is the greatest, though its radius
without hydration shell is the smallest. The surface charge density of Li+ is the
greatest in the first column of periodic system.
Migration speed can be referred to unit field:
u

s
ze

E 6r

2.

the quantity u is called ionic mobility. The ion mobility is independent of the
magnitude of electric field.
Table 1. Ionic mobilities in water at 298 K, u / 10-8 m2 s-1 V-1
H+
Na+

OHCl-

36.23
5.19

Mobility as a function of conductivity = f(u)

Definitions
Electroneutrality principle, example: H2SO4

Conductivity 2008

20.64
7,91

formula
charge number
charge
ion concentration
electroneutrality

+ = 2
z+ = 1
z+e
c+
z+ + = z- -

- = 1
z- = 2
z-e
c-

An experimental cell is set in which a strong electrolyte of concentration c is

filled. The noble electrode metal pair is polarized at a potential which
maintains an electric field, E (V/cm).

Figure. In the calculation of the current, all the cations within a distance s+t
(i.e. those in volume As+t) will pass through the area A. Likewise anions
The ion flux:

J ion

N
A t

3.

The number of ions, N pass through area, A at a time t producing ion flux.
Each of the positive or negative ion concentration is chosen the same flux can be
observed (electroneutrality).
ion concentration

c+

Number density,

N
V

c- , in general: c

can also be given in terms of ion concentration. If nion = n, than

Conductivity 2008

N NA N
n

N A ion N A c
V N AV
V
N
N A c
V

N
N A c
V

Volume can be given by speed s

V s t A

5.

From Eqs. 3. 4. and 5.

J ion

stA cN A
s cN A
A t

Number of ions number of charges conversion:

J ch arg e J ion ze
J ch arg e s cN A ze s c zF

s uE , and E

Introducing:
J ch arg e u

c zF
l

Current can be given as:

I u

(NA e = F, the Faraday constant)

I J ch arg e A

c zF A
l

6.

Current can also be given from Ohms law:

I

G
A
R
l

7.

Comparing Eq. 6. and 7. we get

u c zF

Defining individual molar conductivity:

Conductivity 2008

u zF
c

8.

Eq. 8. tells us the relation between a theoretical quantity, mobility of an ion and
an experimentally determined quantity, molar conductivity.
In the limit of zero concentration
m0 F z u z u

9.

Eq. 9. simplifies for electrolytes with z+ = z-, i.e. z : z electrolytes

(KCl with z = 1, CuSO4 with z =2).
m0 zF u u

Transport number, t
It is the fraction of the current carried by each ion that is present in solution
t

Ii
I

10.

i 1

The sum of transport numbers in a solution should give one,

t t 1

where t and
respectively.

are the sum of the transport number for cations and anions

When a solution contains c1 concentration of NaCl and c2 concentration of

KNO3 the transport number of Na+ can be given as

t Na

u Na Na z Na c1 FA
FA

u Na Na z Na c1 uCl Cl zCl c1 uK K z K c2 u NO NO z NO c2
l
3

We used Eq. 6. for substituting the current caused by different ions. This long
equation is simplified by the following facts:
Na = 1, zNa = 1, K = 1, zK = 1, Cl = 1, zCl = 1, NO3 = 1, zNO3 = 1

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t Na

u Na c1
c1 u Na uCl c2 uK u NO

11.

When we have a single z : z electrolyte with mobilities u+ and u-, the transport
number of anion is
t

u
u u

This equation can also be given in molar conductivity representation

t

The migration of H+
The actual mechanism is not the transport of the H3O+ through the solution, but
the transfer of the proton to the next water molecule. A similar effect occurs
with OH-.

Figure 1. Schematic explanation why H3O+ has a much higher ionic mobility than

for instance the alkali cations.

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The reason being that the H3O+ does not have to migrate but transfers its proton
to the solvation water molecule.

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