Electrochemical Technology in Pollution Control

Dr. J. R. Mudakavi
Department of Chemical Engineering
Indian Institute of Science, Bangalore

Lecture - 05
Typical Properties of the Solutions

We will continue our discussion on Typical Properties of the Solutions. There are many
properties of solutions which are connected with this decrease of vapour pressure in the
systems.

(Refer Slide Time: 00:53)

They include; relative lowering of vapour pressure of the solvent, depression of freezing
point, elevation of boiling point and osmotic pressure of the solution.

All these properties depend upon the number of solute particles irrespective of their
nature, relative to the total number of particles present in the solution. Such properties
are called as colligative properties. Because, they depend upon the total number of solute
particles irrespective of their nature.
(Refer Slide Time: 01:37)

Here I give a brief introduction to relative lowering of the vapour pressure. The vapour
pressure of a solvent in solution is less than that of the pure solvent. Raoult established
that, the lowering of the vapour pressure depends only on the concentration of the solute
particles. That is independent of their identity. That means, it mainly dependent upon the
solvent. Equation establishes a relationship between vapour pressure and mole fraction
of the solvent.

(Refer Slide Time: 02:36)

Here I write,
 P1 = X1. P01.

The reduction in the vapour pressure is given as

∆P1= p01 - p1.

Because, p1 will be lower than that. Because it contains solute. So, this will be I can write
it as

∆p1 = x2. p01.

(Refer Slide Time: 03:27)

In a solution containing several non volatile solutes, the lowering of the vapour pressure
depends on the sum of the mole fractions of different solutes. Suppose there is one
component p1 and it will lower the vapour pressure a little bit less, another component is
there p2 that also will lower to some extent. Like that there will be different solutes that
will lower the vapour pressure of the substance that depends on the sum of the mole
fractions of the different solutes. Suppose there are two, then the sum of two mole
fractions. Then we can write the equation like this,

0
p p p 2
0
1
 1
0
1
 x
p 1
p 1
 0 n
p p n x  2
2
n n
1 1 2

You can write as, p
0

1
n n1 2 since 1 2

Here, n1 and n2 are the number of moles of the solvent and solute respectively present in
the solution. For dilute solutions n2 should be much lower than n1. Hence neglecting n2 in
the denominator

(Refer Slide Time: 05:27)

Then we can write,

0
p p1 1 n 2

n
0
p 1
1

This is because, we are neglecting n2 in the denominator. It should have been n2 because,
it is much lesser than n1. So, we can write this as,

0
p p1 1 w M 2 1

p
0

1
M w 2 1
Here w1 and w2 are the masses and M1 and M2 are the molar masses of the solvent and
solute respectively.

From this equation knowing all other quantities, the molar mass of solute M 2 can be
calculated.

(Refer Slide Time: 06:18)

Now we go to another feature that is essentially a colligative property that is, elevation of
boiling point. The boiling point of a solution is always higher than that of the boiling
point of the pure solvent in which the solution is prepared as shown in the figure.

(watch the video) Here I have a boiling point of the solvent and atmospheric pressure,
vapour pressure and temperature. I have a solution that is boiling point is given at this
temperature. This is the boiling point of the solvent. But, if I dissolve a substance boiling
point curve will go like this.
(Refer Slide Time: 07:51)

Similar to lowering of the vapour pressure, the elevation of boiling point also depends on
the number of solute molecules rather than their nature. That is irrespective of the nature
of the chemical. Whatever you put in a liquid its boiling point will increase. You can find
out whether a substance is a pure liquid or not pure liquid just by looking at the boiling
point. Depending upon the increase in the boiling point, you can say how much has been
dissolved. It may not tell you exactly what is dissolved, but the solvent is pure only to
some extent.

A solution of 1 mole of sucrose in 1000 grams of water boils at 373.52 at one

atmospheric pressure. This is a simple explanation. Because, water should boil at 100
degree centigrade. So 273, it should boil. A solution of 1 mole of sucrose if I dissolve it
in water, instead of 373.00 it boils at 373.52 Kelvin at one atmospheric pressure.
(Refer Slide Time: 09:45)

(watch the video) Look at the previous diagram now; Here I have written T b and T r.

Delta Tb that is, increase in the boiling point of a solution is Tb - T0b. That represents as,

0
T b  T b  T b

Experiments are shown that for dilute solutions the elevation of boiling point is directly
proportional to the molal concentration of the solute in a solution.

We can write,

∆Tb α m

Or ∆Tb = Kb m

m is the number of moles of solute dissolved in 1 kg of the solvent and constant of

proportionality, Kb is called boiling point elevation constant or molal elevation constant.
It is also known as ebullioscopic constant.
(Refer Slide Time: 10:56)

The unit of Kb is K kg per mole. If w 2 gram of the solute of solar mass M 2 is dissolved in
w1 gram. Then I can write,

1000w K
M 2

T w
2 b

b 1

(Refer Slide Time: 11:48)

Depression of freezing point. Similar to elevation of boiling point, depression of freezing

point also happens. Depression of freezing point is a similar situation that is irrespective
of the nature of the substance. When boiling point increases, the freezing point
decreases. We can write an expression something like this,

∆ Tf α m.

Then we have, ∆ Tf = Kf m.

This is essentially similar equation like what we have seen for elevation of boiling point.
It is also known as depression constant or molal depression constant or cryoscopy
constant. The unit of Kf should be kilogram in a degrees Kelvin per mole.

Kf  w 2  1000
M2 
T  w
f 1

(Refer Slide Time: 14:00)

Here is an anti elevated figure. That shows you the depression of freezing point. It keeps
on increasing as you keep on adding a solute. Delta Tf is the depression of freezing point.
(Refer Slide Time: 14:28)

For determining the molar mass of the solutes, we should know the quantities of w1, w2
and delta Tf along with the molar freezing point.

If we know all other things, the values of Kf and Kb depend on the nature of the solvent
and they can be ascertained from the following relations.

(Refer Slide Time: 14:48)

R and M1 stand for the gas constant and molar mass of the solvent and T f and Tb denote
the freezing point and the boiling point of the pure solvents in degree Kelvin. Further ∆,
change in the heat of fusion and ∆ change in the enthalpy of the vaporization represents
the enthalpies for the fusion and vaporization of the temperature. These two equations
will tell us exactly what is the problem.

(Refer Slide Time: 15:42)

Now we discuss another property that is known as osmosis and osmotic pressure.
Assume that we have only solvent molecules passing through semipermeable membrane.
I think most of you have heard of RO (Reverse Osmosis). They contain a semipermeable
membrane in which water will pass through and whatever is dissolved in water will not
pass through. That is a semi permeable membrane. Impermeable membrane means no
water, no salt. Permeable membrane means everything will pass through. Semipermeable
membrane will preferentially allow the solvent to go through holding the solute back.

Theoretical basis is fairly simple. What happens is, assume that solvent molecules like
water it will pass through a membrane. If this membrane is placed between a solvent and
the solution, solvent molecules will fall through and solute molecules are held back in
the solution. This process of flow is called as osmosis. There is certain amount of
pressure that is exerted during osmosis that is known as osmotic pressure. Osmotic
pressure is proportional to the morality of the solution at any given temperature.

So, I can write

  CRT
Here R is gas constant and π is the osmotic pressure, T is temperature. I can write
concentration as number of molecules divided by volume.

  (n / V ) RT
2

(Refer Slide Time: 18:23)

V is the volume of the solution in liters containing n 2 moles of the solute. If w2 grams of
solute, of molar mass M2 is present in the solution. Then,

w RT
M 2
 2

Π V

If there are two solutions having same osmotic pressure, then they are called as isotopic
solutions.
(Refer Slide Time: 19:01)

What is reverse osmosis? The direction of the osmosis can be reversed; if I put a pressure
larger than the osmotic pressure. That is applied to the solution side.

(Refer Slide Time: 19:20)

Here I am drawing a picture of reverse osmosis. We have semipermeable membrane and

I have put salt water and pressure is there. I put pressure on this solution and it is allow
fresh water on the other side

In normal osmosis; salt water will remain this side and in fresh water will remain that
side. Only that much will go through that is exerted by the osmotic pressure. If I put
additional pressure then reverse osmosis occurs when a pressure larger than the osmotic
pressure is applied. This will force the solution to go into this, but not the solutes.

Fresh water I am collecting this side, what remains here is, more of the salt water that is
remaining here. This is the principle of all RO’s what we have in our houses. The
direction of the osmosis can be reversed if a pressure larger than the osmotic pressure is
applied. So, the pure solvent flows out of the solution.

(Refer Slide Time: 20:49)

We want to talk about other properties of the electrolytic dissociation. Nearly 95 % of

the chemical reactions take place in aqueous solutions.

Let us make this make an attempt to understand basic concepts of chemical analysis
useful for electrochemical technology. I am going to define several chemical terms
associated with chemical reactions. I want to define an acid. Acid is defined as a
substance it gives a hydrogen ion in aqueous solution. Its dissociation in aqueous
solutions it will dissociate as H+ and Cl-, but it may also live because there are a lot of
water molecules in HCl solutions.

HCl ⇌ H+ + Cl-

This H+ will react with one more molecule of water to give you H3O+.

HCl + H2O ⇌ H3O+ + Cl-

That has got independent existence as an ion. The H+ does not have an independent
existence, but it will not remain like H+. This is a very standard way of writing in all
modern textbooks that, HCl dissociates to give you H+ and Cl-.

HCl ⇌ H+ + Cl-

I can write acid is in equilibrium with proton and its conjugated base. What is the base?
What remains if you take out the proton is base. Normally, our concept of base is that
sodium carbonate is a base, sodium hydroxide is a base, potassium hydroxide is a base,
calcium hydroxide is a base like that. But we are extending the same definition that, acid
is one in which a proton is there along with its conjugate base in equilibrium with the
undissociated acid. Some part of acid dissociates.

It is also a tendency to lose a proton. This is the definition of acid from the Bronsted
theory. Examples are BF3, AlCl3, BCl 3, SO2 in an inert solvent. Here you can see that in
HCl there is H+ in acid there is proton and proton is nothing but H +. But in BF 3 there is
no hydrogen here. Still it is an acidic solution. Similarly, aluminum chloride, BCl 3, SO2
etc.

(Refer Slide Time: 24:59)

This is the definition of an acid that is known as Lewis acid. BF3, aluminum chloride
BCl3 these are all called as Lewis acid. Here we define acid as one which has got a
tendency to accept electrons that is Lewis acid.
A base is one which is which when dissolved in water should dissociate to give you a
hydroxide ion. The other part that is cation and anion. OH- is anion and Na+ is cation.

NaOH ⇌ Na+ + OH-

Suppose it is KOH; then it will give K+ and OH-.

KOH ⇋ K+ + OH-

OH- is very common in all bases. It exhibits a tendency to accept a proton. It need not
dissociate. This is Brönsted concept. A base is one which can react with water to accept
one hydrogen from here. NH3 will become NH4+ because it is a proton, it will be NH4+.
Once this loses H+, what remains is two electrons are remaining here extra OH- is
produced.

NH3 + H2O ⇌ NH4+ + OH-

This is a Brönsted concept. All these definitions represent the acid base concept.

We also have another definition that is Lewis concept. It must exhibit a tendency to
release electron. That means, it must be electron rich. For example, two chlorine atoms
can give you chlorine chloride ions and 2e-.

2 Cl → Cl2 + 2e-

Strong acids and strong bases are those which are dissociated 100% in aqueous
solutions. Some acids are strong, some acids are weak acids. For example, hydrochloric
acid, nitric acid they are all very strong acids. If they fall on your hands your hand will
burn. HF is a very strong acid and NaOH is a strong base. We also come across in our
day to day life.

Citric acid is a very weak acid. There are lots of weak acids and weak bases around us
and they are those which do not dissociate 100 % in aqueous media. That is how the
definition goes.

Salts we defines as substances which dissociate partially or 100 % in aqueous media

(water).
(Refer Slide Time: 29:30)

If I take sodium chloride (salt), I put it in water. What it will give? It gives Na+ and Cl-.

NaCl → Na+ + Cl-

This will be totally dissolved. Totally dissolved means, all the salt that we put in water is
contained as sodium ions and chloride ions. Then we have sodium benzoate (C6 H5
COONa). Sodium benzoate can also dissociate into benzoic acid (anion) and sodium
(cation).

C6H5COONa ⇌ C6H5COO- + Na+

All these things you must remember that, I have an equilibrium sign and one single
arrow. This single arrow shows that, there is no equilibrium. Whatever you put is totally
ionized. In another case it is partially ionized. Whenever you put benzoic acid in solution
part of it will dissolve to give you C6H5COO- and Na+ and some of the undissociated
sodium benzoate. Sodium benzoate is used as a preservative.

A solution of sodium benzoate will contain benzoic acid minus and Na plus ion.

Consider we are going to write a chemical reaction at a constant temperature. We write

A plus B going to C plus D.

A + B ⇌ C + D
Reactant A will react with reactant B to give you a product C and another product D. The
velocity with which the forward reaction goes is proportional to their concentrations.

I can write,

V1 = k1 [A] [B]

Concentration of A is multiplied by concentration of B. The proportionality constant is

k1.

Similarly, we can write,

V2 = k2 [C] [D]

That is the reverse reaction. So, C plus D is also going to A plus B now.

(Refer Slide Time: 33:34)

For this reaction, I can write another equation like this at equilibrium. Forward reaction
should be equal to the backward reaction. So, k 1 into AB should be equal to k 2 into C D.
If they are going on simultaneous way and if they are equal k1 by k2 should be equal to C
D by A B.

K  k1 
 C   D 
k 2  A    B
You measure the concentration of the products divided by the concentration of the
reactants. You will get another constant that is known as K. That is equilibrium constant.
It means, the concentration of the products divided by the concentration of the reactants.

(Refer Slide Time: 34:41)

Now I define another concept that is, activity and activity coefficient. In the previous
equation we had written concentrations in their square brackets. That is equilibrium
constant. But its not actually the concentration calculated from the existing system. But,
a rigorous thermodynamic equilibrium constant of the reaction tells us that, the
concentrations are not exactly the same what it should have been. For example, I can
write an equation like this,

a
 A
  aB 

K a
a AB

Here I write it is not the concentration, but it is the another product related to the
concentration that is known as activity. Activity is replacing concentration. Here we are
going to write an equation like A plus B going to C. Instead of concentration of C A and
C B; I have got C AB. Here it is A B. So, instead of writing CA: I am going to write
activity of A into activity of B divided by activity of AB.
These things represent the activities of A+ and B- and AB respectively. In this equation
what do we do is, we write activity as a effective concentration of a species. It will not be
very different from concentration, but slightly different. But thermodynamically we
should not write CA concentration terms. So, we define activity as, activity is equal to
concentration into activity coefficient. That is, A+ that is activity and activity coefficient
is fA+. That is a notation normally accepted.

Activity = concentration × activity coefficient

= ⦏A+⦎. fA+

(Refer Slide Time: 37:56)

I can write,

  B
 A
 
fA  fB
 

K 
a
 AB f AB

That is for the forward reaction. But, they should be multiplied by activity coefficients. If
I want to do the correct technical representation of the reaction. This concentration of A+
that will represent activity of A and B+ will represents the activity of B. This will
represent AB. That is the product.
We also define another term that is I. I is ionic strength. It is approximately 0.5 times. all
the concentrations of all the ions present in the solution and their charge Z1 is a discharge
valency of the ions. Here Ci is the ionic concentration in gram molar liter and zi is the
valency.

in
2
I  0.5 c z
i 1
i 1

So, the activity coefficient depends upon the total ionic strength of the solution. For
weak electrolytes activity coefficient approaches unity. For very dilute solutions activity
coefficient becomes unity.

Activity coefficient depends upon the total ionic strength of the solution. For weak
electrolytes activity coefficient approaches unity hence KA and Ka become equal.

(Refer Slide Time: 40:48)

We continue our discussion regarding the acids and bases a little bit more. I can write for
a weak electrolyte such as, acetic acid react with water gives H3O+ and CH3COO-.

CH3COOH + H2O ⇌ H3O+ + CH3COO-

K = ⦏CH3COO-⦎ ⦏H+⦎ / ⦏CH3COOH⦎

If 1 gram equivalent of the acid is dissolved in V liters and if alpha is the degree of
dissociation at equilibrium then amount of unionized acid will be (1 - ɑ). Alpha is
dissociation constant. So, maximum concentration is 1. (1 - ɑ) gram equivalent would be
the undissociated. The amounts of ionized electrolytes will be alpha.

I can write this is as,

2 2

K α or
c
1    V (1   )

(Refer Slide Time: 43:12)

This is the mathematical expression for weak acids. The value of alpha can be
determined experimentally by determining the equivalent conductance of the analytical
solution and conductance at infinite dilution. The dissociation constants of weak acids
are available in data bases and for acetic acid it is about 1.85 × 10 -5.

we will continue our discussion on weak bases in the next class.

Thank you.