Solutions of

Electrolytes
Electrolysis
Electrolyte is a substance which when dissolve in water
dissociate into ions and its aqueous solutions conduct electric
current.
These are also called electrolytic conductors
The electronic conductors, such as metals, conduct electric
current by transfer of electrons.
When an electric current is passed through the electrolytic
conductors (such as solution of CuCl
2
in water) the cations
move towards the cathode and anions move towards the anode.
The process of decomposition of electrolyte by the passage of
electric current through its solution is called electrolysis.



Faradays law of electrolysis
Faradays first law
The amount of substance W deposited or dissolved at the
electrode is proportional to quantity of electricity Q passed
through the solution.
W Q
W= ZQ
W=Zit
Where I is the current in amperes passed through the solution
for t secs;
Z is the electrochemical equivalent of the element deposited at
the electrode.

Faradays second law

The amounts of different substances deposited or dissolved by the passage of the
same quantity of electricity are proportional to their chemical equivalents.

Let Q coulombs of electricity be passed through the solutions of two substances of
chemical equivalent weights E
1
and E
2
resp.
W
1
E
1

W
2
E
2


W
1
= eE
1
W
2
= eE
2
where e is a constant

W
1
/W
2
=E
1
/E
2

One gm equivalent weight of any substance is deposited or dissolved by 96500
coulombs of electricity. This quantity (96500 coulombs) is called a Faraday of
electricity.
Electrolytic conductance
The resistance, R, in ohms of a metallic or electrolytic
conductor of uniform thickness is proportional to its length ,
l and is inversely proportional to its area of cross section,
A in cm
2
. Thus,
R l/A
R = . l/A
Where is the proportionality constant and is called the specific
resistance of the metal.
This equation is also applicable to the electrolytic solutions.
l is the length of the liquid column between the two
electrodes of cross-sectional area of A, then is the specific
resistance of the solution.
R=l when l=1 and A=1 sq.cm and hence specific resistance of a
solution may be defined as the resistance of 1 cm length of the
solution of 1 sq.cm cross sectional area.



Conductance C of a solution is the reciprocal of its resistance
C
= 1/R
C = (1/p).A/l
C = KA/l where k is specific conductance.
When l=1cm,A=1sq.cm, hence specific conductance may be
defined as the conductance of cube of solution of 1cm side
placed between two electrodes

Conductance is expressed in mhos/cm
Specific conductance,

K = C.l/A =1.l/R.A



Equivalent conductance
Solutes of equal normality produce the same number of ions
when completely dissociated and equivalent conductance
measures the current carrying capacity of this given number of
ions.
Specific conductance measures the current carrying capacity of
all the ions in a unit volume of solution.
Equivalent conductance is the conductance of a solution
containing 1 gm equivalent weight of the electrolyte, when
whole of the solution is placed between two parallel electrodes
1 cm apart.
If V cc of the solution contains 1 gm equivalent of the solute,
then there will be V number of cubes of 1 cm side between two
electrodes separated by a distance of 1 cm.

Equivalent conductance c at a concentration of c gram
equivalents per liter is calculated from the product of the
specific conductance and the volume V in cm
3
that contains 1
gram equivalent of solute.
V=(1000 cm
3
/liter)/(c Eq/liter) = 1000/c cm
3
/Eq
It is obtained when is multiplied by V, hence c is expressed
in units of mho cm
2
/Eq and it is given by expression
c = * V = 1000 /c mho cm
2
/Eq


Molecular conductance
is the conductance containing 1 gm mole of the solute when
placed between two parallel electrodes 1 cm apart.

= k.V
Where k is the specific conductance and V is the volume
of the solution in cc containing 1 gm mole of the solute.
Transference or Transport Number or
Hittorfs number
The fraction of total current carried by the cations or by anions
is known as the transport or transference number t
+
or t
-
t
+
= Current carried by cations/total current
t
-
= Current carried by anions/total current
The sum of the two transference numbers is equal to unity.

t
+
+ t
-
=1
Transference number are related to velocities of ions, the faster
moving ion carrying the greater fraction of current.
Velocities of ions in turn depend on hydration as well as ion
size and charge.
Speed and transference numbers are not same for positive and
negative ions.

Determination of Transport Number
There are two methods for determination of the transport
number of an ion:
1. Hittorfs method
2. Moving boundary method
Hittorfs method:
Acc. To this rule, the loss of concentration around any
electrode is proportional to the speed of the ion moving away
from that electrode.
The apparatus consist of two vertical glass tubes joined
together through a U-tube in the middle.
All the three tubes are provided with stopcocks at the bottom.
The U- tube is also provided with stopcocks at the tops of the
two limbs.
By closing these stopcocks, the communication between the
solutions in the cathode and anode limbs can be stopped.


The silver anode is sealed in a glass-tube and the cathode is a
piece of freshly silvered foil.
The apparatus is filled with a solution of silver nitrate and a
steady current of about 0.01 ampere is passed for two or three
hours.
It is an important precaution that the current is passed only for
a short time so that too large a change in conc. does not take
place.
The apparatus is connected with a silver or copper coulometer.
When the current has been passed for near about 2-3 hrs, the
stopcocks at the top of the U-tube are closed.
The whole of the liquid in the anode compartment is carefully
drained into a weighed flask and its weight determined.
Its silver content is determined by titrating against a standard
solution of potassium thiocyante.
The weight of silver deposited in the silver coulometer is also
determined.
If copper coulometer is used in place of silver coulometer, the
weight of silver equivalent to the copper deposited is
calculated by multiplying it with 108/31.5.
In the above expt. has been performed by using silver
electrodes, I this case nitrate ions attack the silver anode.
The same expt can also be performed by using platinum
electrodes to avoid the attack of anions at the anode.
Calculations:
Two different cases may arise:
Case I: When electrodes are unattackable (Pt electrodes are
used)
After passing electric current:
Let the weight of anodic solution taken out = a g
Weight of AgNO3 present in it by titration = b g
Weight of water = (a- b) g



Before passing electric current:
Let weight of AgNO3 in (a - b) g of water before passing electric
current be = c g
Fall in conc. = (c - b) g of AgNO3
= (c b)/170 g eqvt of AgNO3
= d (say)
Let the weight of silver deposited in silver coulometer be = w1 g
= w1/108 g eqvt of Ag
= W (say) g eqvt of Ag
Transport number of Ag+ (t Ag+) = d/W
And transport number of NO3- ion (t No3-) = 1- d/W
Case II: When electrode are attackable (Ag electrodes are
used).
Increase in conc. Of anodic sol. = (b c) g of AgNO3
= (b c)/170 * 108 g of Ag
= e (say)
If no Ag+ ions had migrated from the anode, the increase in
conc. Of Ag+_ ions would have been equal to W
Fall in concentration due to migration of Ag+ ion = W e
Hence, Transport number of Ag+ ion (tAg+) = W e / W
And transport number of NO3- ion (t NO3-) = 1- (W e / W)

The moving boundary method
It is based on the direct observation of migration of ions under
the influence of applied potential.
This method is very accurate and has been used in recent years
for precision measurement.
The apparatus used consist of a long vertical tube fitted with
two electrodes at the two ends
The tube is filled with a solution of cadmium chloride(CdCl2)
at the lower end and hydrochloric acid at the upper end in way
that there is a sharp boundary between the two (due to
differences in refractive indices.)
The platinum cathode dipped in HCl solution is inserted at the
top and the anode (cadmium stick) is introduced at the
bottom.
On passing electric current through the apparatus, hydrogen
gas is evolved at the cathode and H+ ions move towards the
cathode.



The H+ ions are replaced by Cd
++
ions and hence the boundary
line moves in the upward direction. By noting the length
through which the boundary moves and the quantity of
electricity passed through the cell, the transport number of H
+

ion can be calculated.
If the transport number of a cation A
+
is to be determined, the
electrolyte AX solution is taken in the upper part of the
apparatus and a layer of another electrolyte BX having the
common ion X
-
is introduced in the lower part of the apparatus.
The electrolyte BX is selected so that the velocity of B
+
ion is
less than that of A
+
ion.



Equivalent conductance of strong and weak
electrolytes
As the solution of strong electrolyte is diluted the specific
conductance decreases because the number of ions per unit
volume of solution is reduced.
Equivalent conductance of a solution of strong electrolyte
steadily increases on dilution. According to definition quantity
of strong electrolyte remains constant at 1 gm equivalent but
the ions are less hindered by neighbor ions in dilute solution
and hence moves faster.
Equivalent conductance of weak electrolyte also increases on
dilution.
Kohlrausch first investigated this phenomenon.


He found that equivalent conductance was linear function of
square root of the concentration for strong electrolytes in dilute
solutions.
Equivalent conductance at concentration c (Eq/L),
c =
0
- bc
where
0
is the intercept on vertical axis and it is known as
equivalent conductance at infinite dilution.
Constant b is the slope of the line for strong electrolytes
Kohlrausch concluded that the ions of all electrolytes migrate
independently as the solution is diluted and the ions are so far
that they do not interact with each other.
So the
0
is the sum equivalent

conductance

of the cations l
c

and the anions l
a
at infinite dilution

0 =
l
c
+ l
a


Arrhenius theory of electrolytic dissociation
When electolytes are dissolved in water the solute exist in the
form of the ions in the solution.
Ionic compound
H
2
O + Na
+
Cl
-
Na
+
+ Cl
-
+ H
2
O (strong electrolyte)
Covalent compound
H
2
O + HCl H
3
O
+
+ Cl
-
(strong electrolyte)
Covalent compound
H
2
O + CH
3
COOH H
3
O+ + CH
3
COO
-
(weak electrolyte)
The first reaction indicates that sodium chloride exist as ions
in crystalline state as shown by + and - signs.
If the electrodes are placed in a mass of fused sodium chloride
and attached to a source of electric current then the molten
compound conduct the electric current because the crystal
lattice of pure salt consists of ions.



The addition of water to the solid dissolves the crystal and
separates the ions in the solution.
In the second reaction, hydrogen chloride exist as neutral
molecule rather than as ions in pure form and does not conduct
electricity.
But when it reacts with water it ionizes according to reaction
shown and there is formation of hydronium or oxonium ion.
In the third reaction, sodium chloride and hydrochloric acid are
strong electrolytes because they exist completely in the ionic
form in aq. solutions. Most inorganic and organic salts are
highly ionized and belong to the class of strong electrolytes.
In the fourth reaction, acetic acid is weak electrolyte and
equilibrium is established between the molecules and the ions
produced.
Most of organic acids and bases and some inorganic compounds,
some salts and complex ions belong to class of weak electrolyte.




Degree of Dissociation
According to Arrhenius strong electrolytes ionized completely
except in extremely dilute solutions.
He differentiated between strong and weak electrolytes by the
fraction of molecules ionized i.e. the degree of dissociation .
He determined the degree of dissociation directly from the
conductance measurement.
He recognized that the equivalent conductance at infinite
dilution,
0
was a measure of complete dissociation of the
solute into ions and that c represented the number of solutes
particles presented as ions at a concentration c.
Hence, the degree of dissociation was expressed by eq.
= c /
0
in which c /
0
is known as the conductance ratio.



Vant HOFF FACTOR i
It is used to express the departure of concentrated solutions of
non-electrolytes from the laws of ideal solutions.
It can be explained on the same basis as deviations of real
solutions from Raoults law.
The Vant HOFF FACTOR i can be connected with the degree
of dissociation by following way.
The i factor equals to unity for an ideal solution of non-
electrolyte, but an extra term is added for the particles
produced when the molecules of an electrolyte dissociates.
For an electrolyte yielding v ions,
i = 1 + (v - 1)
from which we can obtain an expression for the degree of
dissociation
= (i 1) / (v - 1)
Cryoscopic method is used to determined i from the
expression
T
f
= iK
f
m or i = T
f
/K
f
m

Debye-Huckel Theory
Derived an equation based on the principles that strong
electrolytes are completely ionized in dilute solutions and that
the deviations of electrolytic solutions from ideal behavior are
due to the electrostatic effects of the oppositely charged ions.
This equation relates the activity co-efficient of a particular ion
or the mean ionic activity coefficient of an electrolyte to the
valence of the ions, the ionic strength of the solution, and the
characteristics of the solvent.
Acc. to the theory, the activity coefficient,
i
, of an ion of
valence z
i
is given by the expression
Log
i
= - Az
i
2

This equation gives the measure of the activity coefficient of
an ion species up to an ionic strength, , of about 0.02.
For water at 25C, A, a factor that depends only on the
temperature and the dielectric constant of the medium, is
appro. equal to 0.51.
The Debye-Huckel equation for a binary electrolyte consisting
of ions with valences of z+ and z- and present in a dilute
solution ( < 0.02) is
Log
+
= - Az+z-
The symbol z+ and z- stand for valences or charges.
The coefficient in above equation should actually be
x
, the
rational activity coefficient but in dilute solutions for which
the Debye-Huckel equation is applicable,
x
can be assumed to
be equal also to the practical coefficients,
m
and
c
, on molal
and molar scales.
Thus the activity coefficient of a strong electrolyte in dilute
solution depends on the total ionic strength of the solution, the
valence of the ions involved, the nature of the solvent, and the
temp. of the solution.

Extension of Debye-Huckel Theory to higher
concentrations
The last two equations are not satisfactory above an ionic
strength of about 0.02.
A formula that applies up to an ionic strength of perhaps 0.1 is
Log
+
= - Az+z- / 1+ a
i
B
The term a
i
is the mean distance of approach of the ions and is
called the mean effective ionic diameter or the ion size
parameter. Its significance is not known but it is analogous to
the term b in Vander Waals gas equation.
The term B, like A, is a constant influenced only by the
solvent and the temperature.
The product of ai and B is approximately unity, then the above
equation simplifies to
Log
+
= - Az+z- / 1+


For higher concentrations i.e. at ionic strength above 0.1 the
activity coefficient for some electrolytes pass through minima
and then increase with concentration and in some cases they
become greater than unity.
To account for increase in
+
at higher concentrations, an
empirical term C can be added to the Debye-Huckel equation
Log
+
= - (Az+z- / 1+ a
i
B )+ C
This equation gives results in solutions of concentrations as
high as 1M.
The mean ionic activity coefficient obtained from above
equation is x.



Coefficients for expressing colligative
properties
The L value
The vant Hoff expression T
f
= iK
f
m can be modified slightly
for convenience in dilute solutions by substituting molar conc.
c and by writing iK
f
as L, so that
T
f
= Lc
The value of L varies with the conc. of solution.
For a drug conc. that is isotonic with the body fluids,
L = iK
f
is designated here as Liso.
It has a value equal to about 1.9 for non electrolytes, 2.0 for
weak electrolytes, 3.4 for univalent electrolytes and larger
values for electrolytes of high valences.

Osmotic Coefficient
As the solution becomes more dilute, i approaches v, the
number of ions into which an electrolytes dissociates, and at
infinite dilution, i = v, or i/v = 1.
For more concentrated solutions, i/v becomes less than unity.
The ratio i/v is designated as g and is known as the practical
osmotic coefficient when exposed on a molal basis.
In case of weak electrolytes it provides a measure of the
degree of dissociation.
For strong electrolytes, g is equal to unity for complete
dissociation, and the departure of g from unity, i.e. 1 g, in
moderately concentrated solutions is an indication of the inter-
ionic attraction.
Osmotic coefficients, g, for electrolytes and non-electrolytes
are plotted against ionic concentration, vm.
Because g = i/v or i = gv in a dilute solution, the cryoscopic
equation can be written T
f
= gvK
f
m


Osmolality
Osmotic Pressure is generally in atmospheres but in clinical
practice it is expressed in terms of osmols (Osm) or
milliosmols (mOsm).
A solution containing 1 mole ( 1 gram molecular weight) of a
non-ionizable substance in 1 kg of water ( a 1 m solution) is
referred to as 1-osmolal solution. It contains 1 osmol (Osm) or
1000 milliosmols (mOsm) of solute per kg of solvent.
Osmolality measures the total number of particles dissolved in
1 kg of water i.e. osmols per kg of water, and depends on the
electrolytic nature of the solute.
For an electrolyte that dissociates into ions in a dilute solutions
osmolality and milliosmolality can be calculated from
Milliosmolality (mOsm/kg) = i.mm
i is approximately the number of ions formed per molecule and
mm is the millimolal concentration.
If no ionic interactions occurred in a solution of sodium
chloride, i would equal 2.0.
For a 1:1 electrolyte in dilute solution, i is approx. 1.86, owing
to ionic interaction between positively and negatively charged
ions.
Osmolarity is used more frequently than osmolality in labeling
parenteral solutions in hospital.
Osmolarity = (measured osmolality) * (solution density in
g/mL anhydrous solute concentration in g/mL)
Osmolality is converted to osmolarity using equation
mOsm/liter solution = mOsm/ (kg H
2
O) * [d
1
(1-0.001 v
2
)]
d
1
= density of solvent v
2
= partial molal volume of the
solute at infinite dilution.


Colligative properties such as freezing point depression are
related to osmolality through equations
T
f
= K
f
im
Where i = gv and im = gvm is osmolality
Kohlrausch
Law
By Kohlrausch - The difference in the conductance at infinite
dilution of potassium and sodium salts having common anion
remained constant.
Hence, he concluded that each ion has a definite contribution
to equivalent conductance at infinite dilution.
The values for KCl,NaCl,KNO
3
and NaNO
3
at 20
0
C are
130,109,126.5,105.4 respectively.


KCl
-

NaCl
=130-109 =21 units

KNO3
-

NaNO3
=126.5-105.4 =21.1 units
This shows that K
+
and Na
+
ions will have a definite
contribution to the equivalent conductance at infinite dilution.



Kohlrauschs law of independent Migration of
ions
Each ion has a definite contribution to the equivalent
conductance at infinite dilution.
For a binary electrolyte such as KCL we can write,

KCl
=

K+
+

Cl-
Where,

K+
and

Cl-
are respective ion conductance at infinite
dilution.
Or in general

+
+

=

ku
+
+ ku
-

Since equivalent conductance of cation and anion are
proportional to the velocity (speed) of the cation and anion viz
u
+
and

u
-
resp.






Application of Kohlrauschs law

The equivalent conductance of strong electrolyte at infinite
dilution can be determined experimentally, by extrapolating the
plot of vs concentration. This can not be done in case of weak
electrolyte.
It can be determined using the Kohlrauschs law.
Eg. Equivalent conductance for the salt CH
3
COONa, for NaCl
and HCl is determined experimentally from the plot of vs
concentration.

From Kohlrauschs law of independent migration of ion we can write:

CH3COONa

=

CH3COO-

+

Na+1

HCl

=

H+

+

Cl-2

NaCl

=

Na+

+

Cl-3

Adding equation 1 and 2 and subtracting
3rd we get,

CH3COO-

H+

=

CH3COONa

+

HCl

-

NaCl


Since all the terms on the RHS of above equation can be experimentally
determined, the LHS ie

CH3COOH
can be calculated

Note: conductance at infinite dilution of CH3COONa, HCl and NaCl being
strong electrolytes can be determined by extrapolation of conc plots.






Conductometric titration
Titrations in which conductance measurements are made in
determining the end point of acid-alkali reactions,
displacements reactions or precipitation reactions are called
conductometric titrations.
Advantage is taken of the fact the conductance of a solution at
a constant temperature depends upon the number of ions
present in it and their mobility.
Titrant is added from a burette into a measured volume of the
solution to be titrated which is taken in a conductance cell and
the conductance readings corresponding to the various
additions are plotted against the volume of the titrant.
Principle of conductometric titrations
At infinite dilutions ions act independent of each other and
they contribute to the conductance of the solution.
Both cations and anions have varying degree of ionic
mobilities (or conductance values).
Thus, when a solution of one electrolyte is added (as a titrant)
to the solution of another electrolyte the overall conductance
of the solution (after addition) will depend whether a reaction
occurs or not.
If no chemical reaction occurs between the electrolyte solution
and another added to it the overall conductance of the solution
will increase. All ions will contribute to the conductance of the
solution.
When a chemical reaction occurs, replacement or substitution
of ions takes place and depending upon ionic conductance of
replacing and replaced ions conductance will either increase or
decrease.


Principle of conductometric titration is based upon the
substitution of ions of one mobility (conductance) by the ions
of another mobility. Thus,
A
+
B
-
+ C
+
D
-
= A
+
D
-
+ C
+
B
-
The conductance will increase or decrease depending upon
whether the mobility of C
+
ion is greater or lesser than that of
ion A
+
.
In conductometric titrations, titrant is added in small volume
and conductivity is measured
The points thus obtained after the addition of each increment
of titrant are plotted to give a graph which consists of two
straight lines intersecting at the equivalence point.
Accuracy of the method is greater when the angle of
intersecting line is more acute.
Conductance of weak electrolyte is largely dependant upon
the degree of ionization, which in turn is dependent upon the
dilution and temperature.
Types of conductometric titrations
Strong acid with strong base:
In the titration of HCl with
NaOH, initial fall in
conductance is due to
replacement of H+ ions of high
ionic mobility (350) with slow
mobility Na+ (50) ions. After
the end point conductance rises
due to excess of OH- ions (199)
being added.
Strong acid with weak base
The titration of HCl or H
2
SO
4
with
dil. NH
4
OH solution.
The progressive fall in
conductance is due to the
disappearance of hydrogen ions of
high ionic mobility during
neutralization.
After the end point the graph
becomes almost horizontal
because ionization of ammonia is
prevented in the presence of
NH
4
Cl or NHSO
4
formed during
neutralization reaction.
Weak acid with strong base
Titration of weak acid like acetic acid
or boric acid with strong base like
NaOH, the shape of graph will depend
upon the conc. and dissociation
constant of the acid.
Thus in neutralization of acetic acid
initial conductance is due to ionization
of small amount of acetic acid.
The progressive salt formation
increases conductance which in turn
repress ionization of acetic acid.
These two opposing influences show
fall followed by rise in conductance.
After the neutralization a break occurs
showing rise in conductance due to OH
-

ions.
Weak acid with weak base
Titration of weak acid like acetic
acid or phenol with weak base aq.
Ammonia solution shows the this
graph.
The neutralization curve upto end
point of weak acid is similar to that
obtained with NaOH.
Conductance rises due to the salt
formation of weak acid.
After the equivalence point an
excess of aq. Ammonia solution has
no effect upon the conductivity
because of suppression of
ionization of ammonia by the salt
formed
Very weak acid with strong base
Titration of boric acid with NaOH
solution.
Initial conductance is very small but
increases progressively as
neutralization proceeds.
This is because of salt formation
which accounts for rise in
conductance due to hydrolysis.
After the equivalance point the sharp
rise in conductance is due to excess
OH
-
ion added as titrant.
Mixture of HCl (strong acid) and acetic acid
(weak acid) with strong base
Initially conductance falls due to
neutralization of strong acid and then
rises as the weak acid is converted into
its salt.
After the complete neutralization of both
acids conductance finally rises more
steeply as the excess of OH ions are
introduced.
Two end points a and b for
neutralization are observed.
Titration of mixture of acids with weak
base (NH
4
OH) will show graph similar
upto neutralization of both acids.
Afterwards conductance remains same
due to suppression of ionization of weak
base


Displacement titrations
Titration of salt of weak acid (sodium acetate)
with strong acid (HCl) a and that of salt of
weak base (NH
4
Cl) with strong base (NaOH) b
can be followed by conductometer.
In sodium acetate titration with HCl, the initial
increase in conductivity is due to slightly greater
ionic mobility of chloride ions than that of the
acetate ion.
Until replacement is complete, solution contains
sufficient sodium acetate to suppress the
ionization of liberated acetic acid.
Near equivalence point the acetic acid is
sufficiently ionized to give rise in conductance.
Beyond equivalence point the excess of HCl
accounts for high conductance.
Similarly in titration of NH
4
Cl with NaOH, the
initial fall in conductance is due to replacement
of ammonium ion (high mobility) by the sodium
ion (low mobility).











After equivalences point steep
rise in conductance is due to
OH
-
of NaOH

Precipitation and complex formation titrations
Conductometric titrations of this
type can be satisfactorily
performed provided that:
The reaction product is
sparingly soluble,
Forms stable complex and
The precipitate do not have
strong adsorbent properties.
The solubility of precipitate and
its dissociation is kept below 5 %
by addition of ethanol.
A slow rate of precipitation
prolongs the time of titration.
Titration of AgNo
3
with KCl or
NaSo
4
with BaCl
2
Advatages:
Even coloured solutions can be titrated as no indicator is
required to judge the end point.
Precipitation reaction can also be studied by this method.
Care must be taken to use dilute solutions so that the
electrodes are not covered by the precipitate.
Eg. NaCl solution may be titrated against standard AgNO
3
.

Redox Titrations
The redox type of titrations are not possible by conductometer.
In most of redox reactions a large excess of acid or base is
used for completion of reaction.
This interferes by masking the changes in conductance.
Hence redox titrations are not performed by using
conductometer.
Solubility of a sparingly
soluble salt
The solubility of a sparingly soluble salt such as AgCl or
PbSO
4
can be determined by conductivity experiment.

The specific conductance of water (k
water
) is 1.6 x 10
-6
ohm
-
1
cm
-1
at 25
0
C; and is determined by a conductivity meter.

Also the specific conductance of saturated solution of AgCl.
k
AgCl(salt)
in distilled water is determined using a conductivity
meter.


= 1000k/c




Since the AgCl solution is very dilute solution may be
replaced by for AgCl and the value of c, the concentration
in gm.equivalents of AgCl/litre may be replaced by the
saturation solubility of AgCl viz s and hence , we can write,

= 1000k/s
s=1000k/


= 100 (k
AgCl(salt)
k
water
) /

Equivalent conductance of a weak electrolyte
at infinite dilution
The plot of equivalent conductance vs concentration is a
straight line for solution of strong electrolytes and it is possible
to extrapolate the straight line to obtain the equi conductance
at infinite dilution.
The Kohlrauschs law can be used to determine the equivalent
conductance at infinite dilution of a weak electrolyte, since in
the case of weak electrolytes extrapolation of vs c plot to
obtained is not justified.

Eg:

CH3COOH
is determined by determining

CH3COONa
,

HCl
,

NaCl

CH3COOH
=

CH3COONa
+

HCl
-

NaCl

=

CH3COO-
+

Na+
+

H+
+

Cl -
-

Na+
-

Cl


(By Kohlrauschs law)
=

CH3COO-
+

H+