Electrochemistry

Electrolyte solutions
Introduction
The solutions can be classified in non-electrolyte solutions and electrolyte solutions.
The electrolytes (IInd order conductors) are substances, which in molten state or when
they are dissolved in a polar solvent, they conduct the electric current because they dissociate in
particles with positive and negative charge, so - called ions. The dissociation process in mobile
ions is called electrolytic dissociation and is independent of electric current passing.
The property of an electrolyte to conduct the electric current is named electrical
conductibility and the physical parameter associated to the phenomenon is named conductivity.
The real electrolytes (ionofor) in solid states crystallize in ionic lattice (ex. NaCl, KCl) so
the ions exist in a crystalline lattice. The ionic bond from crystals can be stabilized through
substance melting resulting in an ionic conducting substance, or through the dissolution in a
polar solvent, when the ions pass into the solution and ion-dipole bonds are formed.
Example:

Na Cl

H 2 O Na Hydrated Cl Hydrated

(4.1)

The potential electrolytes (ionogene) in solid state crystallize in molecular lattice. In

lattice node of the crystalline lattice there are polar molecules formed by atoms covalent bonded.
The ions appear when the electrolyte dissolve in water or in another polar solvent, as a
consequence of polarization of the covalent bond and its breaking under the action of solvent
polar molecules.
Example:

H Cl H 2O H 3 O

Cl Hydrated

(4.2)

The real electrolytes dissociate completely in ions when they are dissoluted in polar
solvents. The potential electrolytes dissociate completely when the polarity of the covalent bond
is high and dissociate partially when the polarity bond is low.
The electrolyte solutions are ionic conductors (II nd order). As in the case of I st order
conductors, the Ohms law can be applied:

E RI

(4.3)

where: E the voltage expressed in volts, [V];

1

R the resistance expressed in Ohm, [];

I the intensity of the current expressed in amperes [A].
The resistance of the Ist order conductors (electronic conductors or metallic) is given by
the relation:
R

l
S

(4.4)

where: - resistivity or specific resistance, [.cm], l the length of the conductors or the
distance between the electrodes [cm], S section of the conductor, [cm2].
From the relation (4.4) we have:
R

S
l

(4.5)

The conductance G is the parameter that is inverse to the resistance and is expressed in
[-1] or Siemens [S].
G

1
R

(4.6)

The conductivity is the inverse of the resistivity, and is expressed in -1cm-1 or Scm-1.
It represents the conductance of a 1cm3 column of electrolyte solution that is between two inert
electrodes with the same surface of 1 cm2 and 1 cm distance one from the other.

(4.7)

In order to measure the electrical conductivity of the electrolyte solution, conductivity

cells are used. The measurements are done by means of a conductivity cell connected to a
conductometer. The conductivity cell is formed of two electrodes of an inert metal (Pt). They are
characterized by the cell constant, K.
Kl S

(4.8)

where, l the distance between the electrodes, [cm];

S the surface of electrodes, [cm2].
The conductivity of the electrolyte solution varies with the concentration f c . It
increases with increasing concentration, reaching a maximum and than decreases on continuing
to increase concentration.
The position of the maximum depends on the nature of the electrolyte and on
temperature. The variation of the conductivity is larger for strong electrolytes than for weak
2

electrolytes. Generally, in dilute solution, is increasing with concentration, because the number
of charge carriers is greater, while in concentrated solution, decreases with concentration
because of the process of ion association.

4.1. The variation of the conductivity and pH of an electrolyte solution in

function of concentration
The aim of this practical work is to determine the degree of dissociation , the
dissociation constant, Kd,, and the pH for an weak electrolyte, acetic acid (CH3COOH) and also,
for a strong electrolyte, natrium chloride (NaCl) and to establish the variation of the conductivity
and of the pH in function of their concentration.
In order to compare, from the point of view of electrical conductivity of the different
electrolyte solution, another parameter will be defined, the equivalent conductivity, , which
represent the conductivity, , reported to one equivalent gram of electrolyte in a volume V
(cm3) of solution.
V

, where

V 1 c

and represents the dilution

(4.1.1)
(4.1.2)

V is the volume expressed in cm3 of solution that contains one chemical equivalent
from the considered electrolyte and c is his normal concentration.
V 1000 c

and

1000 c

(4.1.3)

[-1cm2/equiv] or [Scm2 / equiv]

(4.1.4)

The equivalent conductivity is increasing with the dilution and tends to a maximum
value 0, reached at infinite dilution, when the dissociation of the electrolyte is complete. For the
determination of 0 , first will be calculated for different concentration of an electrolyte
solution and then, a extrapolation will be done for c0.
The dissociation of an electrolyte is quantitatively expressed by two parameters:
-

Kd dissociation constant the equilibrium constant of the reversible equilibrium

process that take place between the ions and non-dissociated molecules of the
electrolyte.

- dissociation degree a physico- chemical parameters introduced by Arrhenius ; it

represents the ratio between the number of dissociated molecules and the total number
of dissolved molecules and it can be express as the ratio between and 0.

(4.1.5)

Kd and represent a classification criteria for the electrolyte solution :

Kd > 1 and = 1 - strong electrolytes, totally dissociated in solutions of concentration
between 0.1 and 0.001M.
Kd < 10-2 and < 0.5 weak electrolytes, solution with c < 0.01M
10-2 < Kd < 1 and 0.5 < < 0.8 medium electrolyte
Kd

2c
- the Ostwald dilution law
1

(4.1.6)

The dilution law express the connection between K d and and can be apply only for
weak electrolytes, because in the case of strong electrolytes, increases with the dilution and Kd
doesnt indicate a constant value.
Replacing from the relation (4.1.5.) in relation from (4.1.6.), we obtain:
Kd

2c
0 ( 0 )

(4.1.7)

The electrolyte can be solution of: acids, base or salts. Below, the processes of
dissociation are presented for a strong electrolyte:
Dissociation
Strong acid
H2SO4 2H+ + SO4 2c 2H c SO 2
4
Kd
c H 2SO 4

Dissociation
Strong base
Ca(OH)2 Ca2+ + 2HOKd

c Ca 2 c 2HO
c Ca(OH) 2

Dissociation
Salt
NiSO4 Ni2+ + SO42c Ni 2 c SO 2
4
Kd
c NiSO 4

where c is the concentration of the electrolytes.

In the case of weak electrolytes: water is a very weak electrolytes, is just one molecule
dissociated from another 550000.
or

H2O H++ HO-

(4.1.8)

2H2O H3O++ HO-

(4.1.9)
4

because H+ is not free. The dissociation constant will be:

Kd

[H ] [HO ]
;
H 2O

but, Kd[H2O]= const. = [H+][HO-] = Kw = the water ionic product.

At 250C, Kw=10-14 [mol/L2]. For neutral water: [H+] = [HO-] = 10-7[mol/L].
Comparing with neutral situation, the solution can be:
- acid if [H+] > 10-7
- basic if [H+] < 10-7
CH3COOH H+ + CH3COO-

Kd

(4.1.10)

c CH COO c H

(4.1.11)

c CH 3COOH

The acidity of a solution can be expressed through the physico chemical parameter
named pH.

In the case of ideal solution: pH lg c
In the case of ideal solution: pH lg c H

(4.1.12)

(4.1.13)

where aH+ - the active concentration or the activity.

a H c H

(4.1.14)

c CH COO c H c

(4.1.15)

where the mean activity factor of the electrolyte, depends on the nature of the substances,
of temperature and concentration. It value tends to 1 when the dilution is increasing:
1 and a c, when c 0

c concentration of the electrolyte solution

In the case of aqueous solution, the pH is comprised in the domain (014). If pH < 7, the
solution has acidic character, if pH > 7 the solution has basic character. For pH = 7, the solution
is neutral.
Apparatus and substances:
Conductometer, conductivity electrode, pH electrod, Berzelius beaker, solutions of CH3COOH
and NaCl of different concentration, KCl solution 0.01N.
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Experimental
o The conductivity electrode from the Berzelius vessel with distilled water is taken off,
dried with filter paper and than it is connected to the conductometer.
o The conductivity electrode is introduced successively in the 4 Berzelius vessels with
CH3COOH (0.001N, 0.01N, 0.1N and 1N), starting with the smallest concentration;
o The same operations will be performed for NaCl solutions;
o The pH electrode will measure the pH of the solution, respecting the same procedure as
for the conductivity measurements;
o At the end, the apparatus will be switched off; the two electrodes will be washed and
placed in their special solution.
Results
The following table will contain the experimental data obtained and calculated:
Solution

cN

CH3COOH

NaCl

[S/cm]

[Scm2]

Kd

c H+

pH

pH

(calculated)

measured

0.001
0.01
0.1
1
0.001
0.01
0.1
1

For the solution of weak electrolyte, (CH3COOH), it will be calculated:

o

The equivalent conductivity with the relation (4.1.4.)

The dissociation degree using the relation (4.1.5.), knowing that 0= 380 Scm2;

The dissociation constant Kd , based on the relation (4.1.6.)

The concentration of hydrogen ions (cH+) with the relation (4.1.15) and pHcalc. with
the relation (4.1.13)
In the case of strong electrolytes, (NaCl):

It will be calculated and plotted the dependence f c 1 2 . Through extrapolation, the

value of 0 will be established. Than calculate , , Kd, cH+ and pHcalc.

Plot the graph f c and pH cal f c for all electrolyte solution.

Applications:
1. A conductivity cell has the following characteristics: the surface area of electrodes S = 2 cm 2,
the distance between the two electrodes l = 2.5 cm, the concentration of the solution is c = 1N
and its resistance R = 50 . Calculate the conductivity, the equivalent conductivity and the
degree of dissociation of the electrolyte, knowing that 0 = 125-1cm2.
2. The resistance of a conductivity cell with KCl solution, experimentally determined is R = 100
. Knowing that cKCl = 0.02N, = 0,024 -1cm-1, calculate the cells constant and the equivalent
conductivity of the solution.
3. Calculate the pH for the following solutions: (a) 0,1 M NH4Cl (aq); (b) 0,1 M CH3COOH(aq);
c) 0.25 M CH3COOH