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Applications of Kohlrausch Law

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**1-Calculation of molar conductivity of a weak electrolyte at
**

infinite dilution

It is not possible to determine the value of ∧∞m for weak electrolytes since we cannot

obtain the limiting value of the molar conductivity for a weak electrolyte. This is done

indirectly by the molar ionic conductance for the individual ions of the weak

electrolyte as follows:

For e.g. molar conductance of acetic acid at infinite dilution can be calculated from

the molar conductance at infinite dilution of hydrochloric acid, sodium acetate and

sodium chloride as follows:

∧0 HCl = λH+ + λ Cl- --------------(1)

∧0 CH3COONa = λ0 Na+ + λ0 CH3COO- ---------------(2)

∧0 NaCl = λ0 Na++ λ0 Cl- -------------- (3)

Add eq. 1 and 2 and subtract 3 we get:

∧0 HCl + ∧0 CH3COONa - ∧0 NaCl = λ0 H+ + λ0 Cl- + λ0 Na+ + λ0 CH3COO- - λ0

Na+ - λ0Cl

Example

The limiting molar conductivities of KCl, KNO3, and AgNO3 are 14.99 mSm2mol-1,

14.50 mSm2mol-1and 13.34 mSm2mol-1 respectively at 25°C. Calculated the

limiting molar conductivity of AgCl at this temperature?

Solution

∧0 AgCl= ∧0 KCl + ∧0 AgNO3 - ∧0 KNO3

=(14.99+13.34-14.5) mSm2mol-1

= 13.83 mSm2mol-1

**2- Calculation of Degree of Dissociation of Weak Electrolytes
**

The degree of dissociation of weak electrolyte such as NH4OH, acetic acid can be

determined by measuring the molar conductivity Λ, of the solution of the electrolyte

at any given dilution. For e.g. the degree of dissociation (α) of a weak electrolyte at

the concentration C mole per liter may be given by the following relation:

α = ∧/∧0

**Where, Λ is the equivalent conductance of electrolyte at any concentration and Λ0 is
**

the equivalent conductance of the same electrolyte at infinite dilution. Hence,

measurement of Λ permits evaluation of ‘α’ if Λ0 is known.

Let us consider dissociation of acetic acid:

CH3COOH+H2O==CH3COO-+H3O+

(1- α)C

αC

αC

**Where C is the equivalent concentration .Dissociation constant is represents as
**

following:

KC=[ H3O+][ CH3COO-]/[ CH3COOH ]

KC=(αC)( αC)/ (1-α)C

KC = α2C/1-α

KC = (∧/∧0)2/1-(∧/∧0)

ΛC=KCΛ02/Λ-KCΛ0

By plotting this equation,KC can be calculated.

Example

Equivalent conductance of 0.001028 N acetic acid solution is 48.15 ohm-1cm2 and

390.6 ohm-1cm2 of infinite diluted solution. Calculate the degree of dissociation.

Solution

α=Λ/Λ0

α=48.15 ohm-1cm2 /390.6 ohm-1cm2

α=0.1232

KC = α2C/1- α

KC=(0.1232)(0.001028)/(1-0.1232)

=1.781x10-5

3- Determination of Solubility of Sparingly Soluble Salts

**Salts like AgCl, BaSO4, CaCO3, Ag2CrO4, PbSO4, PbS, Fe(OH)3 etc. are ordinarily
**

regarded as sparingly soluble and have a very small but definite solubility in water.

The solubility of such sparingly soluble salts is obtained by determining the specific

conductivity (κ) of a saturated salt solution.

AgCl ⇌ Ag+ + ClAssume concentration of solid is a constant.

Concentration of Ag+= concentration of Cl- = C

Ksp = [Ag+aq] [Cl-aq]

Ksp = C2

The measurement of the specific conductivity, κ of the saturated solution leads to a

value of the concentration.

C = κ / Λ0

i.e.

or

S= κ / Λ0

**i.e C is the solubility(S).Units of S is the same of that C,equi.cm3
**

As, Ksp = C2

Ksp = (κ / Λ0)2

Example

Specific conductivity of saturated AgCl solution at 25oC is 3.41x10-6 ohm-1cm-1,while

the specific conductance of water that used as solvent is 1.6x10-6 ohm-1cm-1.Calculate

the solubility of AgCl in .water at this temperature in units of mol L-1.Given that

equivalent conductance of infinite diluted AgCl solution is 138.3 equi ohm-1 cm2.

Solution

κAgCl= κsolution- κwater

=3.41x10-6 ohm-1cm-1-1.6x10-6 ohm-1cm-1

=1.81x10-6 ohm-1cm-1

As AgCl is 1:1 electrolyte

S = κ / Λ0

=(1.81x10-6 ohm-1cm-1)/ (138.3 equi ohm-1 cm2)

=1.31x10-8 equi-1 cm-3

=1.31x10-5 equi-1 L-1

4- Determination of ionic product of water

**With the help of specific conductivity of water, the ionic product of water can be
**

determined. The ionization of water may be represented as,

H2O H+ + OHThe product of the concentrations of H+ and OH– ions expressed in mol/L is called

ionic product of water and is represented by Kw.

[H+] [OH-] = Kw

The measured specific conductivity of the purest form of water is 0.055 x 10-6 S cm-1.

The molar conductance is given by

Λm = Kv x 18

Thus, = 0.055 x 10-6 x 18

= 0.990 x 10-6 Scm2mol-1

The molar conductance of water at infinite dilution can be obtained by

∧∞m (H2O) = Λ (H+) + Λ (OH-)

Therefore, Λ∞ (H2O) = 349.8 + 198.5 = 548.30 Scm2mol-1

and for water, α = Λm / Λ∞

= 0.055 x 10-3 x 18/ 548.3

CH+= COH= 0.055 x 10-3 x 18/ 548.3

(Concentration of water = 1000/18 = 55.55 M

CH+= COH= α x 55.55 x 10-9

= 1.806 x 55.55 = 1.003 x 10-7

Kw = (1.003 x 10-7)

= (1.006 x 10-14)

6- Determination of Ionic Mobility of an Ion

Hypothesis a solution contains C equi of 1:1 electrolyte. the applied voltage is E

,volt.cm-1.The passing current is:

I=E/R

If the electrolyte is strong=C++C- .The cation cross U+ distance in sec toward cathode

and anions cross U- distance in sec toward anode.i.e

**C+U+ equivalents of cations move to cathode and C- U- equivalents of anions move to
**

anode. The total equivalent concentrations that move toward two electrodes is(C+ U+)(

C- U-) .The total current is represents as:

L=F(C+ U+ + C-U-)

L=CF(U+ +U-)

Λ=L/C=F(U+ +U-)

Λ=F(U+ +U-)

Λ= λ++ λF U+ = λ+

FU+ =+ λExample

Calculate the specific conductance of 0.1 NaCl solution at 250C given that ionic

mobilities of sodium and chloride ions are 42.6 x10-5 and 68x10-5 volt-1 cm2 sec-1

respectively.

Solution

C=0.1/1000=0.0001 equi cm3

L=CF(U+ +U-)

=(0.0001 equi cm3)(96500 C equi-1)[42.6 x10-5 volt-1 cm2 sec-1+68x10-5 volt-1 cm2

sec-1]

=0.01067 ohm-1 cm-1

6- Determination of hydrolysis constant of salts

When aniline chloride is dissolved in water ,it is hydrolysis as following:

C6H5NH3Cl==== C6H5NH3++ClC6H5NH3++H2O==== C6H5NH2+H3O+

(1- α)C

αC

αC

**Where is the hydrolysis degree and C is the salt equivalent concentration, thus:
**

Λs=(1- α) ΛC +αΛa+α Λb

**Where S,C,a,and b are a salt,concentration,acid and base respectively. Where a is HCl
**

and base is aniline. While equivalent conductance of weak base is too small ,so it cam

be negligible.

Λs=(1- α) ΛC +αΛa

α= (Λs- ΛC)/ Λa- ΛC

ΛC can be determined from measurements of equivalent conductance of aniline

chloride dissolved in aniline. The aniline is a weak base ,so it retarded the dissolution

of salt and ΛC is somewhat equal of equivalent conductance of non decomposed salt..

while Λa is determined from ionic conductance of its ions.

The hydrolysis constant(Kh) of aniline chloride can be represents as following:

Kh=[ H3O+][ C6H5NH2]/ [C6H5NH3+]

Kh=(αC) (αC)/(1-α)C

Kh=α2C/1-α

Kh can be used to calculation of decomposition constant of base(Kb) as following:

Kh=Kw/Kb

Where Kw is a ion product of water.

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