Professional Documents
Culture Documents
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
The degree of dissociation of weak electrolyte such as NH 4OH, 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=KCΛ 02/Λ-KCΛ 0
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
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++ λ-
F U+ = λ+
FU+ =+ λ-
Example
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
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]
C6H5NH3Cl==== C6H5NH3++Cl-
C6H5NH3++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.