Chem

Introduction
Substances like salts and inorganic acids and bases when dissolved in water or other solvents yield
solutions which conduct electricity. These substances are called electrolytes. Properties of
electrolytic solutions, works done to account their behaviour like Van’t Hoff factor and Arrhenius
dissociation are discussed in Topic 1. Classification of electrolyte and Ionic strength of strong
electrolytes will be tackled in Topic 2. applications to biochemical systems will be discussed in this
unit.
Topic 3.1 colligative properties, Van’t Hoff factor I and Arrhenius theory of dissociation of
electrolytes
Introduction
The properties like freezing point lowering, boiling point elevation, vapour pressure lowering and
osmotic pressure arises from the presence of solute. The amount of solute present in the solution
determine the change in property. The discussion on colligative properties in physical chemistry for
engineers 1 is strictly for non-electrolytes.
Electrolytes have higher colligative properties compared with those of non-electrolytes which are
mainly due to the concentration of solute. Relationship of the Van’t Hoff factor i with the colligative
properties and dissociation of electrolytes are discussed below.
Learning Objectives: at the end of the topic, the students should be able to
a) Predict and compare colligative properties of ionic substances in solution
b) Relate the colligative properties of non-electrolyte and electrolyte using the Van’t Hoff
factor
c) Relate the Va’t Hoff factor with degree of dissociation of electrolyte
Lesson Proper
A. Freezing point Depression of Electrolytes
Recall the formula of the freezing point depression which relate the molality and the change
in freezing point,
∆t f = k f m where K f is the molal freezing point lower or cryogenic constant.
RT o2
Kf= = 1.86 for water as solvent.
∆ H f n1
∆T f
The ratio should approach a value of 1.86 o per mole per 1000 gm for dilute aqueous
m
solution. The table below show higher values. The limit approached is not the same. It varies
with the number of ions: substances with two ions like HCl and NH4Cl, the ratio is 2(1.86)=
3.72 while substances with three ions have a ratio of 3(1.860)= 5.58 and 4(1.86)= 7.44 for
potassium ferricyanide.
Table 13-1. ∆T f/m for aqueous solution of electrolytes(Maron and Lando)

m HCl HNO3 NH4Cl CuSO4 H2SO4 CoCl2 K2SO4 K3Fe(CN)6
0.0005 - - - - - - - 7.3
0.0010 3.690 - - - - - 5.280 7.10
0.0020 3.669 - - - - 5.35 - 6.87
0.0025 - - - 3.003 5.052 - 5.258 -
0.0050 3.635 3.67 3.617 2.871 4.814 5.208 5.150 6.53
0.0100 3.601 3.64 3.582 2.703 4.584 5.107 5.010 6.26
0.0500 3.532 3.55 3.489 2.266 4.112 4.918 4.559 5.60
0.1000 3.523 3.51 3.442 2.08 3.940 4.882 4.319 5.30
0.2000 3.54 3.47 3.392 1.91 3.790 4.946 4.044 5.0
0.4000 - 3.46 - - 3.68 5.170 3.79 -
1.0000 3.94 3.58 3.33 1.72 4.04 6.31 - -
2.0000 4.43 3.79 3.34 - 5.07 8.51 - -
4.0000 4.65 4.16 3.35 - 7.05 - - -
Van’t Hoff suggested the factor I, which is the ratio of the colligative effect by a concentration m of
electrolyte divided by the same effect observed for the same concentration of non-electrolyte.
This factor I is represented below from the different colligative properties. The numerator being
greater than the denominator makes the Van’t Hoff factor, I > 1
∆T f ∆T b ∆P π colligative property of electrolyte

I= = = = =
( ∆ T f ) o ( ∆ Tb ) o (∆ P) o πo colligative property of non−electrolyte
Using the table above and the formula ∆T f= i K f . m , values of I are reflected below. Note that I
approaches a limit of 2 for substances containing two ion; 3 for substances containing 3 ions and a
limit of 4 for potassium ferricyanide.
Van’t Hoff factor I for various electrolytes.
m HCl HNO3 NH4Cl CuSO4 H2SO4 CoCl2 K2SO4 K3Fe(CN)6

0.0005 - - - - - - - 3.92
0.0010 1.98 - - - - - 2.84 3.82
0.0020 1.97 - - - - 2.88 - 3.70
0.0025 - - - 1.61 2.72 - 2.83 -
0.0050 1.95 1.97 1.95 1.54 2.59 2.80 2.77 3.51
0.0100 1.94 1.96 1.92 1.45 2.46 2.75 2.70 3.31
0.0500 1.90 1.91 1.88 1.22 2.21 2.64 2.45 3.01
0.1000 1.89 1.89 1.85 1.12 2.12 2.62 2.32 2.85
0.2000 1.90 1.87 1.82 1.03 2.04 2.66 2.17 2.69
0.4000 - 1.86 - - 1.98 2.78 2.04 -
1.0000 2.12 1.92 1.79 0.93 2.17 3.40 - -
2.0000 2.38 2.04 1.80 - 2.73 4.58 - -
4.0000 2.04 2.24 1.80 - 3.79 - - -
The colligative properties of electrolytes are solved using the following formulas.
Freezing point lowering, ∆T f= I x K f x m
Boiling point elevation, ∆T b = I x Kb x m
Vapour pressure depression, ∆P= I N solute x Po
RT Po
Osmotic pressure, ∏= I CRT= I x ln
V Psolution
Arrhenius Theory of electrolytic dissociation

Svante Arrhenius(1887) proposed that electrolytes in solution dissociates into ions in such a way that
the total number of positively charged ions is equal to the number of negatively charged ions. The
net results is a solution as a whole is neutral in spite of the presence of electrically charged particles.
He pointed that an electrolyte in solution may partially dissociates to yield an ions in chemical
equilibrium with the unionized molecule of the substance. It may be anticipated from the law of
chemical equilibrium that the degree of dissociation vary with concentration, becoming greater as
the concentration is lowered. At finite concentration, the electrolyte will partially ionize to a degree
dependent on the nature of the substance and concentration.
The concept of partial dissociation was used by Arrhenius to explain the colligative properties of
electrolyte. This theory of electrolytic dissociation is satisfactory to the colligative property, electrical
conductance and ionic equilibria of WEAK ELECTROLYTE.
Computation of Van’t Hoff factor I for weak electrolyte.

Consider an electrolyte AxBy which dissociates into x ions of A with a charge of z+ and y ions of B
with a charge z-.
AxBy = xA z+ + yBz-
The ICE of the ionic equation results to the total number of moles mt,
Mt= m(1-α) + x(mα) + y(mα) = m[ 1 + α(x + Y -1)]
Mt= m[1 +α(v-1) where v is the total number of ions formed.

The freezing point lowering becomes
∆T f = Kf m[1 + α(v-1)]
Previous equation ∆T f = ikf m
i−1
Equate the two equations to give the degree of dissociation, α=
v−1
i−1
Percent dissociation, % α= x 100
v−1
Learning Activity on Colligative Properties and Van’t Hoff Factor i.

Problem 2/548 Marlon and Lando was given as a Board Problem.
A 0.4 molal aqueous solution of K2SO4 freezes at -1.52 oC. Assuming i is constant with
temperature, calculate the vapour pressure at 25 oC and the normal boiling point of the solution.
Given: ∆T f= -1.52 oC , m= 0.4 molal K2SO4 solution

For water: K f = 1.86 oC/mol and Kb = 0.52 oC/mol, normal boiling point = 100 oC
Normal pressure at 25 oC, P o = 23.76 mm Hg
Required: a)Vapor pressure of the solution
b) normal boiling point of the solution
Solution:
Determine first the value of the Van’t Hoff Factor from ∆T f = iKf x m
∆T f = tf o – t f solution= 0 oC – (-1.52 oC) = 1.52 oC
1.52 oC
∆T f
Van’t Hoff Factor i= = oC = 2.043
Kf m 1.86 x 0.4 mole
mol
Use this factor in the computation of boiling point elevation.
∆T b= ix Kb m = 2.043(0.52 oC/mol)(0.4 mol)= 0.425 oC
∆T b= T solution – T bo
0.425 oC= T solution- 100 oC → T solution= 100.425 oC
In Vapor pressure lowering a different concentration unit is used. ∆P= ix N solute x Po
Change the molal concentration to normal concentration.
mole K 2 SO 4
0.4 molal K2SO4= → m K2SO4= 0.4 moles
1 kg of H 20
1000 gm
Moles of water= = 55.6 moles ( Note: basis is 1kg of water)
18 gm/mole
n K 2 SO 4
Mole fraction of solute= mole fraction of K2SO4= =
n K 2 SO 4+n H 2O
0.4 moles
0.4+55.6 moles
N K2SO4= 7.14 x 10 -3
The change in vapour pressure, ∆P= 2.043(7.14 x 10 -3) ( 23.76 mm Hg)= 0.35 mm Hg
P solution = Po - ∆P= 23.76 – 0.35= 23.41 mm Hg
Answers: a) vapour pressure of solution, P solution= 23.41 mm Hg
b) normal boiling point of solution, Tb solution = 100.425 oC
Learning Activity on Van’t Hoff factor and degree of dissociation
5/548 Maron and Landon

A 0.01 molal solution of K3Fe(CN)6 freezes at -0.062 oC. What is the apparent % of dissociation?
Given: t f solution= -0.062 oC, concentration: 0.01 molal K3Fe(CN)6
For water: K f= 1.86 oC/mol and t f o= 0 oC
Required: percent dissociation of K3Fe(CN)6
Solution:
Dissociation of Ferric cyanide K3Fe(CN)6 = 3 K+ + 1 Fe(CN) 6 3-
Total number of ions produce, v= 3 + 1= 4
Freezing point depression, ∆t f = t fo- tf solution= 0 oC – (-0.062 oc) = 0.062 oC
The other Equation of Freezing point depression, ∆T f= I x K f m
0.062 oC
∆t f
I= = oC = 3.33
K f m 1.86 (0.01mol)
mol
i−1 3.33−1
Percent dissociation, % α = x 100 = x 100 = 77.67%
v−1 4−1
Answer: %α= 77.67%
For your self learning solving problem activity, solve # 1,2,3,4 &6 on page 548

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Introduction

Table 13-1. ∆T f/m for aqueous solution of electrolytes(Maron and Lando)

∆T f ∆T b ∆P π colligative property of electrolyte

Van’t Hoff factor I for various electrolytes.

m HCl HNO3 NH4Cl CuSO4 H2SO4 CoCl2 K2SO4 K3Fe(CN)6

Arrhenius Theory of electrolytic dissociation

Computation of Van’t Hoff factor I for weak electrolyte.

Mt= m[1 +α(v-1) where v is the total number of ions formed.

Previous equation ∆T f = ikf m

Learning Activity on Colligative Properties and Van’t Hoff Factor i.

Given: ∆T f= -1.52 oC , m= 0.4 molal K2SO4 solution

Learning Activity on Van’t Hoff factor and degree of dissociation

5/548 Maron and Landon

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