In the name of GOD

Advanced
Electrochemistry
2
1
ADELK
For electrolytic solution:
electric conductance (G) : G = 1/R
G=   l
Dimension: -1, mho, Siemens, S

conductivity () or spedific conductance:

Definition:  = 1/ 
Dimension: -1 m-1 OR S m-1
 Solution Electric Conductivity (Sm-1)

Seawater 5
Drinking water 0.0005 to 0.05
Deionized water 5.5 x 10-6
Influential factors for
conductivity
Concentration

Temperature
Type of electrolyte
Influential factors for
conductivity
Concentration

Temperature
Type of electrolyte
Influential factors for
conductivity
Concentration
Temperature

Type of electrolyte
 Strong and Weak Electrolytes

strong electrolyte
substance that dissociates or ionizes completely when dissolved in water

HCl  H O 

weak electrolyte
substance that ionizes only partially when dissolved in water
 
CH 3 COOH  H 2 O  CH 3 COO
 H3 O
nonelectrolyte
substance that does not produce ions when dissolved in water
 Influential factors for
conductivity
• Concentration.

• Type of electrolyte

• Temperature

1. Acids and bases have higher

conductance
2. C < 5 mol dm-3,  increases with C

3. For CH3COOH conductance does not

depend on C
 Molar conductivity
The conductivity of a solution is approximately
proportional to the concentration

1) Definition
m  
C
m is the conductivity contributed by 1 mole of
electrolyte between electrodes of 1 m apart
 Molar conductivity

Example:

The specific conductivity of a KCl solution with a concentration of 1

mol/dm3 at 25 degrees and a pressure of 1 atmosphere is equal to
0.112 -1cm-1. What is the molar conductivity of KCl in this
solution?

 m,KCl   
0.1121cm1 103
cm3 C
 Dependence of molar conductivity on concentration

m decreases with
concentration.

Due to the interaction

between ions:
interionic attraction
 Plotted Kohlrausch replotted
m against m against C1/2
C
 Kohlrausch empirical formula

 m  m  A c 

To extrapolate the linear part of m ~ C1/2 at low

concentration to C = 0, m can be obtained.

m the limiting value of  m at infinite

dilution: limiting molar conductivity. It is the
conductivity of 1 mol of solution at infinite
dilution.
 Electrolyte m° (S cm2 mol-1)
HCl 426.16
HBr 428.10
Kohlrausch law
NaOH 248.10
NaCl 126.45

m  m Ac KBr 151.80
KCl 149.86
 NaNO3 121.55
KNO3 144.96
NH4Cl 149.70
KHCO3 118.00
 Kohlrausch law

 m  m  A c

 Kohlrausch’s law of independent ionic
mobilities

m
 
 

 m
m
At infinite dilution, m should be
 of the separate contributions
sum the of the
ions
Kohlrausch law was also able to establish experimentally that
°m
can be expressed as the sum of contributions from its
individual ions.

 and − are the limiting molar conductivity of cations and anions

 and − are the numbers of cations and anions per formula unit of electrolyte

 −1 for HCl, NaCl

 −1 for CuSO4
   1,  −  2 for MgCl2
Cation °+ / Scm2mol-1 Anion °- / Scm2mol-1
H+ 349.6 OH- 197.8
Li+ 38.7 Cl- 76.4
Na+ 50.1 Br- 78.2

K+ 73.5 I- 76.8

Fe2+ 108.0 CH3COO- 40.9

Fe3+ 204 CO2-3 138.6

NH4+ 73.4 NO-3 71.5

Ba2+ 127.3 SO2-4 160.0

For acetic acid CH COOH ("HAc"), we combine the λ values for
3 0

3H O and CH COO given in the table:

+
3
–

 (CH COOH)  v   v 
3  
 

 1(349.6) 1(40.9)
 390.5 Scm2 mol1
limiting molar conductivity of
weak electrolyte
 (HAc)   (H )   ( Ac )
    
m m m

  (H  )   (Cl )   (Na ) 
m m m
m ( Ac )   (Nam  )   (Clm  )

   (HCl)    (NaAc)   
(NaCl)
m m m
 Kohlrausch law:
 ° sum of contributions from its individual ions
m

Calculate m° for a weak electrolyte NH4OH from the ° values

for
these strong electrolytes:
NH4Cl: 149.7 Scm2mol-1
NaCl: 126.5 Scm2mol-1
NaOH:248.1 Scm2mol-1

(NH 4OH )  (NH 4Cl )  (NaOH )  (NaCl )

 149.7  248.10 126.5
 271.3
 Uses of Kohlrausch’s law

Calculation of Degree of dissociation and Dissociation Constant
for weak electrolytes


Calculation of solubility of sparingly soluble salt


Calculation of Molar Conductivity for weak electrolytes at infinite
dilution