Electrochemical Technology in Pollution Control

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

Module IV
Lecture – 06
Properties of solution 3

We will continue our discussion on the Electrochemical Technology. I have been trying
to introduce you to solution chemistry as part of the course. We had discussed about
activity and activity coefficient in the last class.

(Refer Slide Time: 00:48)

Here I have written an equation it is a plus b going to ab. But instead of concentrations
thermodynamically we should write,

a
 A
  aB 

K a
a AB

Here a represents the activity of A, aB+ represents activity of B and aAB represents the
activity of AB (product).
(Refer Slide Time: 01:34)

Activity is defined as the concentration into activity coefficient. We had also discussed
about the ionic strength. That is the activity is nothing but activity coefficient into
concentration. We have defined ionic strength as the total number of ions present and
their ionic concentration and valency of sum of that, approximately 50 % as the ionic
strength.

(Refer Slide Time: 02:07)

Then we discussed about the acid base equilibrium reaction. We have written

CH3COOH + H2O ⇌ H3O+ + CH3COO-

K = [CH3COO-⦎ [H+⦎ / [CH3COOH⦎

If one gram equivalent is there and a small portion that is alpha dissociates into the
products. I can write undissociated product would be (1 - ɑ) .

(Refer Slide Time: 02:55)

I can write instead of H3O+ and CH3COO-. I can write

K α
1  α  V
2
αc
(1  α)

This is the dissociation constant and the values of alpha can be determined
experimentally by determining the equivalent conductance. Because, these H3O+ and
CH3COO- contribute to the conductance this will not contribute.

I can determine the conductance and take 50 % has H3O+ and 50 % as CH3COO- of the
total conductivity that is λC of the analytical solutions. We assume that, it is the
conductance at infinite dilution. The dissociation constants of weak acids are available in
the literature.
Now we are going to discuss about the weak basis. That is dissociation of weak basis.
Just like acids we also have bases. Basis can be strong bases and weak basis. Sodium
hydroxide, potassium hydroxide they are all strong basis. Ammonia is a weak base. You
can smell ammonia very easily. Because, it is a weak base.

Ammonia will react with water to give you ammonium hydroxide. The reaction is
represented like this

NH3+ + H2O ⇋ NH4+ + OH-.

There is another equilibrium that is present in aqua solutions, that is water itself can
dissociate as H+ + OH- ⇋ H2O.

I can write Kb is

 NH   OH 

4
-

K b

 NH  3

That is the product. We do not write the concentration of water. Because, it is very large
compared to NH3. We assumed that it is 1. All others are very small. Dissociation
constant of ammonia is nothing but NH4+ . OH- / NH3.

I can write an equilibrium constant because this is equally available. Simultaneously

Kb =Kw / Ka

This is the equivalent concentrations of water is written as K w. I can write similar

Since values of Kb and Ka vary over several powers of 10 that is 1.85 × 10 -5. As we
defined pK has negative log of K to the base of 10. If I write 10-5, it will be 4.87 ×10-5

Larger the pk, weaker is the acid and stronger is the base. This is the ultimate conclusion
of the pk value. If you see the value of pK, it means you are seeing the value of negative
log of 10 K. If pK is larger, the acid is weak and base is strong. larger pKb weaker is the
base and stronger is the acid. This is a about the dissociation constant.

Now I will discuss about the common ion effect. That is, concentration of a particular ion
in a solution can be increased by the addition of another compound which produces the
same cation or anion. I want you to imagine that, we are having a particular solution of
acetic acid. Now acetic acid will dissolve into acetate ion and H + ion that is, CH3COOH
going to CH3COO- and H+. To this if we add sodium acetate, then what happens is, we
have another equilibrium in this system.

Here I am writing,

CH3COOH ⇋ CH3COO- + H+.

To this solution we are going to add sodium acetate. Now we have another equilibrium
for sodium acetate separately. What is that equilibrium? Sodium acetate will decompose
into CH3COO- and Na+. Now there will be two equilibriums in the same solution. One is,
acetic acid another is sodium acetate. But, this CH 3COO- is common in both reactions. In
general you have to understand that, sodium salts are ionized 100%.

If I add sodium acetate to acetic acid, what I am going to add is 100% ionized salt. So, I
am going to add CH3COO- ions to the same solution and 100% of sodium ions plus come
from acetic acid in this case. So, in the solution, we have CH 3COO- coming from one
reaction and another CH3COO- coming from another reaction and remaining is Na+ and
H+. CH3COO- is common. This edition of CH3COONa will have on the dissociation
constant of CH3COOH.

(Refer Slide Time: 11:27)

Unlike acetic acid sodium acetate is 100 % ionized. Therefore the concentration of
CH3COO- will be much more than what is produced by the dissociation of acetic acid.
This induces the backward reaction of the acetic acid with a result that the acetate more
acetate ions will be converted into acetic acid.

(watch the video) Remember Le Chatelier’s principle, if I add additional CH 3COO- into
another system, the system should try to remove the addition. How it will remove the
addition of CH3COO- is, it will combined more with H+ and go back to CH3COOH. That
means, the dissociation of acetic acid will become less to the extent of CH 3COO- coming
from sodium acetate. This effect is known as common ion effect. Le Chatelier’s principle
is at work here. It will induce more of the acetate ions to get converted into acetic acid.
This is the principle of common ion effect.
(Refer Slide Time: 13:26)

Now we are going to talk about the solubility product. So far I have been trying to
introduce you to different concepts of the aqueous chemistry. Now we have discussed
about activity, concentration, dissociation and then common ion effect etc.

Now, I am going to introduce to you one more property of the aqueous solutions. That
means, they contain solutes dissolved in the solvents. Earlier we had talked about
solubility. Now I am going to talk about the solubility product. I have a product salt AB
(s), s represents solid.

Sparingly soluble salt means, it is soluble to a very less extent. That means, even if you
take the solid put it in water, it will remain as such but water will be saturated with the
ions of the salt. Very little salt will be dissolved in water. Such thing is known as
sparingly soluble salt.

For example silver chloride, if you add silver nitrate solution to a solution containing
chloride, silver chloride will precipitate. Why silver chloride will precipitate? Because,
the solubility of silver chloride is very less in water. Such a substance, whenever there is
a precipitation reaction happening it means the solubility is very less. Such product like
silver chloride is known as sparingly soluble salt. It may be of the order of few
milligrams per liter, few milligrams per liter or it may be few grams per liter etc. Not
more than that.
We are going to talk about salts which are very sparingly soluble in water. All dissolved
salts in water dissociate into their corresponding anion and cations. Positively charged
cations and negatively charged anions. Sodium chloride will give you positively charged
sodium and negatively charged chloride ion.

I am going to write an equation for the equilibrium between undissociated salt and
dissociated salt in aqueous solution. Consider

AgCl ⇋ Ag+ + Cl-

We can write an equilibrium constant for this reaction involving both forward and
reverse reactions just like a dissociation constant. I can write an equilibrium constant

K = [Ag+] [ Cl-] / AgCl.

You should remember that AgCl is a solid. Because, it is very sparingly soluble. The
product AgCl at the bottom is a solid. So concentration of solid is always 1. You must
always remember that, concentrations of solids in their solid form is 1. If the
denominator is 1, I can write [Ag+] [Cl-] = K because AgCl is 1.

SAgCl = [Ag+] [Cl-]

That is forward reaction. For the reverse reaction I should write,

AgCl / [Ag+] [Cl-]

I can write K2 = AgCl / [Ag+] [Cl-]

The ratio of K1 / K2 is nothing but the product of Ag+ and Cl- because AgCl is 1. So, a
large database exists again for the solubilities of sparingly soluble salts in water and
several other solvents.
(Refer Slide Time: 21:13)

I want to introduce you to another property of the solutions that is ionic product of water.
One molecule of water may react with one more molecule of water to give you H 3O+ and
OH-. We can apply the same law of mass action or equilibrium constant to this reaction
then I can write

a H  a OH
 

aH O 2

 H   OH 
 -


fH   f OH _

[H O ] 2
fHO 2

I can convert it into concentration because it is only pure water. The reaction can be
written in terms of concentrations and activity products.

Activity products are one almost in all water solutions. So, I can write the product of [H+⦎
[OH-⦎ = Kw = 1 × 10-14 .

The value of H+ would be 10-7 and OH- also would be equal to 10-7. Then only Kw would
be 1×10-14.
This Kw is known as ionic product of water. [H+] is equal to 10-7 and [OH-] ion
concentration is equal to 10-7. So, it is called as neutral solution. If H+ is greater than 10-7
we call is as acidic solution and if [H+] is less than 10-7 then it is called as base solution.

(Refer Slide Time: 25:01)

pH.

S.P.L Sorensen proposed that, instead of writing 10-7, 10-8 etc., we simply write it as
negative log of concentration that will be very simple number.

He suggested that, use logarithm to the base of 10. This is very widely accepted all over
the world.

pH = -log of [H+] = log10 1 / [H+]. This is can also be written like 10-H or 10-OH

If [H+⦎= 10-7, [OH-⦎ = 10-7, Kw = 10-14 and pKw = 14

pH 7 is a neutral solution. Anything above that is a basic solution. If it is less than that it
is acidic solutions.
(Refer Slide Time: 28:20)

The hydrolysis of the salts. Many of the salts dissolve in water and that process is known
as hydrolysis. There are four kinds of salts.

1. Salt of strong acid and strong bases. Like sodium chloride, potassium chloride,
potassium nitrate etc., .

2. Salts of strong acids and weak bases. Like ammonium chloride.

3. Salt of weak acid and strong base. CH3COONa; this is a strong base.

4. Salts of weak acid and weak base. Ammonium acetate, COONH4 or (CH3COO)3Al
(Refer Slide Time: 31:33)

In case 1, here strong acid and strong base, that is H+ and OH- ion equilibrium is not
disturbed and the solution remains neutral. If I take salt of a strong acid and strong base
that is H+ and OH- ions are not disturbed.

In NaCl, H+ and OH- ions are not there but Na+ and Cl- will be there. So the pH will
remain constant. It will not change if I put it in water.

If I take weak acid and strong base salt, pH would be the half of this pKw that is

pH = 1/2 pKw + 1/2 p Ka + 1/2 log C

This expression is usually used to determine the pH of a solution containing a salt of a

If I know the concentration of the salt, pKw is known and pKa values are available from
database. So, I can always calculate pH.

If I have a salt of strong acid and weak base. I can write an expression like this

1/2 pKw - 1/2 pKb - 1/2 log C.

That will give me the pH. If I know the concentration of the salt I can simply calculate
the pH and check whether it is correct or wrong.
In case 4, that is weak acid and weak base, here also we can write pH is nothing but

pH = pKa+ log (Salt/Acid) or

pOH = pKb + log (Salt/Acid)

Just like pH we can write pOH, if I know the pKb.

(Refer Slide Time: 34:59)

What is Hydrolysis? I can write

H2O+ ⇋ H+ + OH-

MA ⇋ M+ + A-.

M represents metal. It maybe sodium, potassium or anything. A maybe acetic acid or any
other salt. A- ions will react with H+ to give HA.

H++ A- ⇌ HA

Since part of H+ ions are consumed, H+ ion concentration will decrease. Part of H+ is
consumed so HA is 1. This is undissociated, so the pH should degrees.

Disrupting the equilibrium in equation of H2O+ ⇋ H+ and OH-. So to compensate for this
decrease more water will dissociate producing H+ and OH- ions. Hence Le Chatelier
principle is applicable here. Since OH- ions increase the solution, solution becomes more
alkaline. Hence we can write

A- + H2O ⇌ OH- + HA

The reverse reaction in this case is more predominant.

(Refer Slide Time: 36:25)

The interaction between the ions of the salt and ions of water is known as hydrolysis.
The hydrolysis of weak acid and strong base produces a weak acid or a weak base or
both a weak acid and weak base.

aOH   a HA 
OH   HA 

f
 OH
  f HA  Kh
aA  A  
fA 

The degree of hydrolysis is the fraction of each gram molecule hydrolyzed at

= Degree of hydrolysis= Kh
(Refer Slide Time: 37:30)

Degree of hydrolysis leads us to the situation of Buffer solutions. Consider a mixture of

pH  pK  log
 salt  
a  acid  K b

pH is equal to pKa. Thus We add a small quantity of 0.1 normal acetic acid, then

H+ + CH3COO- ⇋ CH3COOH.

It will combined with acetate ions from undissolved acetic acid. Similarly, if I add a
small concentration OH- ions it will combined with H+ to form undissolved water. pH
remains unaffected.
(Refer Slide Time: 38:51)

In either case the pH of the solution will not change appreciably, since the concentration
of the acid will remain unchanged. Such solutions are called buffer solutions.

Buffer capacity is maximum when acid to salt is 1 : 1 ratio.

For acid to salt is 1:3, pH is given by this expression,

pKa - log 1/3 = pKa - 0.48.

The approximate pH range for buffer capacity is, if you add 10 times acid or salt pH will
not change appreciably. The buffer solutions find many applications in chemical
preparations, quantitative analysis, precipitations, electrodeposition etc.

Here we we come to the end of our general chemistry introduction to electrochemical

We will continue our discussion in the next class.

Thank you very much.