GUIDELINES OF ELECTROCHEMISTRY

BY
Mr. YUV RAJ SAHU
Assistant Professor
(Chemistry)
9852049175

Department of Applied Sciences,

Purwanchal Campus, Dharan
Institute of Engineering, Tribhuvan University
 CHAPTER-1
ELECTRO-CHEMISTRY

TOPICS:
1. Introduction, Fundamentals, Type of cells
2. Electro-chemical cells, Electrolytic cells , Comparison ,
Applications
3. Electrode potentials, types, single and standard electrode
potentials, emf (cell potentials) of cells
4. Standard hydrogen electrode, cell notation (representation)
5. Electrochemical series, characteristics and applications
6. Nernst’s equation and numerical
7. Buffer , types, mechanism , Henderson’s equation, numerical
8. Corrosion, influencing factors and prevention
 BUFFER SOLUTION
Solutions which can resist change in pH value and tends to maintain pH to a
constant value even after addition of a small amount of extra acid or base are
commonly termed as Buffer solutions. Human blood is an excellent example of
natural buffer solution. Artificial buffer solution can be classified into two
classes:- 1) Acidic buffer 2) Basic buffer
1) Acidic Buffer :- Buffer solutions prepared by intermixing equi-molar quantities
of a weak acid and soluble ionic salt of that weak acid from any strong base are
called acidic buffer. For example, equi-molar mixture of (1) Acetic acid
(CH3COOH) and its soluble salt from NaOH ie. Sodium acetate (CH3COONa)
(2) Acetic acid (CH3COOH) and its soluble salt from KOH ie. Potassium
acetate (CH3COOK) (3) Formic acid (HCOOH) and its soluble salt from NaOH
ie. Sodium Formate (HCOONa) (4) Formic acid (HCOOH) and its soluble salt
from KOH ie. Potassium Formate (HCOOK) etc.
2) Basic Buffer :- Buffer solutions prepared by intermixing equi-molar quantities
of a weak base and soluble ionic salt of that weak base from any strong acid
are called basic buffer. For example, equi-molar mixture of (1) ammonia or
ammonium hydroxide (NH3/NH4OH) and its soluble ionic salt from HCl ie.
NH4Cl (2) ammonia or ammonium hydroxide (NH3/NH4OH) and its soluble
ionic salt from HNO3 ie. NH4NO3 (3) ammonia or ammonium hydroxide
(NH3/NH4OH) and its soluble ionic salt from H2SO4 ie. (NH4)2SO4
 DIFFERENT BUFFER SOLUTIONS

Human Blood acts as a natural buffer with a pH value of 7.4.

S. N. Component Conjugate Acid-Base Pair pH ranges

1. Glycine/Glycine Hydrochloride 1.0 – 3.7

2. Phthalic acid/ Potassium hydrogen phthalate 2.2 – 3.38

3. Acetic acid/ Sodium acetate 3.7 – 5.6

4. Boric acid/ Borax 6.8 – 9.2

5. Ammonium hydroxide/ammonium chloride 10

6. NaH2PO4/Na2HPO4 5.8 – 8

7. Na2HPO4/ Na3PO4 11 - 12
 MECHANISM OF ACIDIC BUFFER
According to Le Chatelier’s Principle, buffer solutions maintain their pH values
by following Common ion effect.
1) Mechanism of Acidic Buffer : Assume that an acidic buffer is prepared by
intermixing equi-molar mixture of acetic acid and sodium acetate solutions where
acetate ion acts as the common ion present in both of solutions. Acetic acid is a
weak acid that ionizes quite poorly providing less number of proton (H+) and
acetate ions while sodium acetate is obtained from acetic acid with strong base
NaOH and hence sodium acetate acts as a strong electrolyte undergoing almost
complete ionization which contains greater number of acetate ions and sodium ions.
2) CH3COOH + H2O CH3COO- + H3O+ ( Feeble ionization, slow)
3) CH3COONa → CH3COO- + Na+ ( complete ionization, fast)
Addition of strong acid:- When we add strong acid like HCl, HCl provides more and
more Hydrogen ions [H+] and tend to decrease pH but whole of H+ ions get
neutralized by common acetate ions in order to regenerate fresh acetic acid
according to common ion effect. Due to reformation of freshly regenerated
CH3COOH by consuming H+ ions, equilibrium shifts to left side and pH remains
unaltered.
HCl → H+ + Cl- (Fast ionization)
CH3COO- + H+ CH3COOH
(from common ion) (Fresh and regenerating un-ionized acetic acid molecules)
Addition of strong base:- Assume that a strong base like NaOH is added into that system which
increases more and more OH- ions to increase pH. Whole of OH- ions get neutralized by H+
ions generated from earlier acetic acid as well as freshly generated acetic acid. Hence pH of
such acidic buffer does not alter by shifting the equilibrium into right side.
NaOH → Na+ + OH- ( Fast ionization)
H+ (From CH3COOH) + OH- ⇄ H2O (Neutralizing)
MECHANISM OF BASIC BUFFER
Assume that a basic buffer is prepared by mixing equi-molar quantities of Ammonium
hydroxide and ammonium chloride solutions together. These components undergo ionization
as-
NH4OH ⇄ NH4+ + OH- (poorly ionized)
NH4Cl → NH4+ + Cl- (completely ionized)
This solution contains a large concentration of ammonium ions as common ion as well as enough
chloride ions but concentration of hydroxide ion is quite limited. Ammonium ions are
obtained from both NH4OH & NH4Cl.
Addition of strong acid:- When we add a strong acid like HCl, H+ ion concentration increases
rapidly trying to reduce pH of solution but whole of H+ ions get neutralized by OH- ions from
ammonium hydroxide by shifting the equilibrium into right side. Hence pH of system
remains unaltered.
HCl → H+ + Cl- (Fast ionization)
OH- + H+ (From HCl) ⇄ H2O (Neutralizing)
(from earlier NH4OH & freshly regenerated)
Addition of strong base:- When we add small amount of any strong base like NaOH,
concentration of OH- ions increases rapidly tending to elevate pH of buffer. Regenerated fresh
ammonium ions which act as common ion trap these OH- ions for rapid neutralization purpose.
Further ionization of ammonium hydroxide gets suppressed (decreased) in accordance with
common ion effect. Hence equilibrium shifts to left side and pH of system remains unaltered.
NaOH → Na+ + OH- ( Fast ionization)
NH4+ + OH- ⇄ NH4OH (Re-generated)
(from common ion) (from NaOH)
Henderson- Hasselbalch Equation
In 1908, Lawrence Joseph Henderson developed an equation to describe the use of carbonic acid
as a buffer solution. Karl Albert Hasselbalch re-expressed those equations in logarithmic
terms to study metabolic acidosis. Hence the equation was named as Henderson-
Hasselbalch equation.
A) Henderson’s equation for acidic buffer:- Consider an acidic buffer solution prepared by
mixing a weak acid (H+A-) where H+ is proton and A- is any electronegative radical ( like
acetate from acetic acid or sodium acetate) , such acid has quite lower degree of ionization
and hence can produce just limited number of H+ ions as well as A- ions. The soluble ionic
salt of HA with strong base like NaOH is Na+A- .
Na+A- → Na+ + A- (strong electrolyte, complete ionization in water)
HA + H2O ⇄ H3O+ + A- (weak acid, poor ionization)
Equilibrium constant for weak acid can be given as:-
Kc = {[H3O+] [A-]} / {[HA][H2O]}
Or, Kc x [H2O] = {[H3O+] [A-]} / [HA]
Or, Ka = {[H3O+] [A-]} / [HA]
Or, [H3O+] = Ka x [HA]/ [A-]
Taking log on both sides, we get
Or, log [H3O+] = log {Ka x [HA]/ [A-]}
Or, log [H3O+] = log Ka + log [HA] / [A-] (multiply both sides by -)
Or, - log [H3O+] = - log Ka - log [HA] / [A-]
Or, - log [H3O+] = - log Ka + log [A-] / [HA] {Since log(a/b) = - log(b/a)}
Since we know that , - log [H3O+] = - log[H+] = pH and –log Ka = pKa
Similarly, [HA] denotes weak acid molarity and [A-] denotes the molarity of
soluble ionic salt of that weak acid and strong base or simply molarity of salt,
above equation can be rewritten in the form of-
 pH = pKa + log [Salt] / [Weak Acid] …..(1)
 pH = pKa + log [Conjugate Base] / [Acid]……..(2)
This is the required Henderson’s equation for calculation of pH of acidic buffer.
B) Henderson- Hasselbalch equation for basic buffer:- Consider a basic buffer
solution prepared by mixing a weak base (B) like NH3 or (BH+)OH- like NH4OH
where BH+ is any electropositive radical (like ammonium from NH4OH or NH4Cl)
, such base has quite lower degree of ionization and hence can produce just limited
number of OH- ions as well as B+ ions. The soluble ionic salt of B with strong acid
like HCl is BH+ Cl-like NH4+ Cl- (NH3.H+).Cl-
B + H2O BH+ + OH- (poor ionization)
(BH+)A- → BH+ + A- (complete ionization)
Equilibrium constant of such weak base can be given as-
Kc = [BH+][OH-]/ {[B][H2O]}
Or, Kc x [H2O] = [BH+][OH-]/ [B]
Or, Kb = [BH+][OH-]/ [B]
Or, [OH-] = Kb x [B]/ [BH+]
Taking log on both sides, we get,
Or, log[OH-] = log {Kb x [B]/ [BH+]}
Or, log [OH-] = log Kb + log [B]/ [BH+]
Or, - log [OH-] = - log Kb - log [B]/ [BH+]
Or, - log [OH-] = - log Kb + log [BH+]/ [B]
Or, pOH = pKb + log [BH+]/ [B]
 pOH = pKb + log [Salt] / [Base] = pKb + log [Conjugate acid] / [Base]…..(2)
 This is the required equation for calculation of pH of basic buffer solution.
 We know that :- pH + pOH =14
BUFFER RANGE AND BUFFER CAPACITY
Buffer range is the pH range where a buffer effectively neutralizes added acids and
bases, while maintaining a relatively constant pH. Buffering range can be
simply defined as the pH range wherein the solution can resist drastic changes
in pH upon addition of small amounts of an acid or a base. Buffers are generally
good over the range pH = pKa ± 1. The ammonia buffer would be effective
between pH = 8.24 - 10.24. The acetate buffer would be effective of the pH
range from about 3.74 to 5.74. Outside of these ranges, the solution can no
longer resist changes in pH by added strong acids or bases.
Buffer capacity- The amount of protons or hydroxide ions a buffer can absorb
without a significant change in pH. Large buffering capacity means it contains a
large amount of buffering components and it can absorb a lot of
protons/hydroxide ions and show little pH change. The pH of a buffered solution
is determined by [A-]/[HA]. The capacity is determined by how large [HA] and
[A-] are presented.
Buffer capacity (ß) is a measure of a buffers ability to keep the pH stable in a
narrow range and is calculated as follows:- H where ∆n is the

equivalents of strong base or acid added per volume liter and ∆pH is the change
in pH. This can be measured by titrating the buffer with an acid or a base and is
reflected of the slope of the titration curve.
 NUMERICAL PROBLEMS
1.Calculate the pH of a basic buffer solution that contains 0.06M NH4Cl and 0.05M
NH3 if Kb of ammonia is 1.8 x 10-5.
Solution :- We know that, p Kb = -log Kb = - log 1.8 x 10-5 = 4.74
Now by using Henderson- Hasselbalch Equation,
pOH = pKb + log [Salt] / [Base]
= 4.74 + log 0.06/0.05 = 4.74 + 0.07918 = 4.8191
Since, pH + pOH =14 or, :- pH = 14 - pOH = 14 – 4.8191 = 9.1809 Ans.
2.What amount of sodium acetate should be used to prepare 500 ml of acidic
buffer which is deci-molar with respect to acetic acid along with pH of 5.1?
Solution :- Given that pKa of acetic acid = 4.74
Now by using Henderson- Hasselbalch Equation,
pH = pKa + log [Salt] / [Acid]
Or, 5.1 = 4.74 + log [Sodium Acetate]/ 0.1
Or, 5.1 - 4.74 = log [Sodium Acetate]/ 0.1
Or, 0.36 = log [Sodium Acetate]/ 0.1 = log [Sodium Acetate] – log 0.1
Or, 0.36 = log [Sodium Acetate] +1 or, log [Sodium Acetate] = 0.36 – 1 = - 0.64
[Sodium Acetate] = antilog (-0.64) = 0.229086 M
Number of mole of Sodium Acetate = Molarity x volume in L = 0.229 x 0.5 = 0.1145
Amount of Sodium Acetate required = 0.1145 x molecular weight of Sodium Acetate
= 0.1145 x 82 = 9.389 g Ans.
3.The pH of human blood stream is maintained by a proper balance of
carbonic acid (H2CO3) and sodium bi-carbonate (NaHCO3) concentration.
What volume of 5M NaHCO3 solution should be mixed with 10ml of blood
sample which is 2M in H2CO3 in order to maintain a pH of 7.4? Given that
ionization of carbonic acid in human blood is 7.8 x 10-7.
Solution:- Let V be the required volume of 5M NaHCO3 solution. Total volume of
blood system becomes (10 + V) ml.
Carbonic acid ionizes as- H2CO3 H+ + HCO3-
Molarity of HCO3- = [HCO3- ] = 5M { V/ (10 + V)…..(1)
Molarity of H2CO3 = [H2CO3] = 2M { V/ (10 + V)…..(2)
By using the Henderson’s equation,
Ph = pKa + log { [HCO3-]/ [H2CO3]
Or, 7.4 = - log Ka + log { 5M V/2M x 10 ml}
Or, 7.4 = -log 7.8 x 10-7 + log (V/ml) (1/4)
Or, 7.4 = 6.108 + log ¼ + log (V/ml)
Or, log (V/ml) = 7.4 – 6.108 + 0.062 = 1.894
or, V/ ml = antilog(1.894) = 78.34
 V = 78.34 ml Ans.
4. Calculate the pH of 1 x 10-7 M HCl solution at 25℃.
Solution:- For 1 x 10-7 M HCl solution , the concentration of H+ ion due to ionization
(dispropornation) of water will not be negligible in comparison to the concentration
of H+ ion from HCl solution.
[H+]Total = [H+]Acid + [H+]Water…………….(1)
Since water produces equal amounts of H+ and OH- ions, above equations can be
expressed in the form of –
[H+]Total = [H+]Acid + [OH-]Water
In aqueous solution, H+ and OH- are related by the equation-
Kw = [H+] x [OH-] ( where [H+] = [OH-] == 1 x 10-7 ion / L)
Or, [OH-] = Kw / [H+] Total…………………….(2)
where Kw is the ionization constant or ionic product of water ( Kw = 1 x 10-14 )
Substituting the value of eqn (2) in eqn (1), we get-
Or, [H+]Total = [H+]Acid + Kw / [H+] Total {
Or, [H+]2Total = [H+]Acid [H+]Total + Kw {
Or, [H+]2Total - [H+]Acid [H+]Total – Kw = 0
Using the quadratic equation to solve [H+]Total, we get-
[H+]Total = {[H+]Acid + √{[H+]2Acid + 4Kw}/ 2
Or, [H+]Total = 10-7 +√(10-7)2 + 4 (10-14) / 2 = (10-7 + 2.24 x 10-7 )/2 = 1.62 x 10-7 M
pH = - log [H+] = - log 1.62 x 10-7 = 6.79 Ans.
5.Calculate the pH of an aqueous solution of 1.0 M Ammonium Formate solution
assuming its complete ionization if pKa of formic acid is 3.8 and pKb of
ammonia is 4.8.
Solution :- Hydrolysis of ammonium formate can be given as –
(HCOO-)NH4+ + H2O NH4OH + HCOOH
Ionization constant of ammonium formate can be given as –
Kc = [NH4OH] [HCOOH]/[HCOO- ] [NH4+ ][H2O]
Hydrolysis constant of ammonium formate can be given as –
Kc x [H2O] = Kh = [NH4OH] [HCOOH]/[HCOO- ] [NH4+ ]…..(1)
Ionization constant of formic acid can be given as –
Ka = [HCOO-] [H+]/ [HCOOH]…………………(2)
Ionization constant of ammonium hydroxide can be given as –
Kb = [NH4+] [OH-]/[NH4OH]…………………(3)
Upon substitution, Kh =[OH-]/Kbx{[H+]/Ka}=[H+][OH-]/Ka Kb =Kw/Ka Kb …..(4)
From the question, [NH4OH] = [HCOOH] and [HCOO- ] = [NH4+ ]
Eqn (1) becomes- Kh = [HCOOH]2 / [HCOO-]2
Using eqn (2) and (4) , we get, Kw/Ka Kb =[H+]2/ Ka2
Or, [H+]2 = Kw x Ka / Kb , Taking log both sides, we get,
Or, 2 log [H+] = log Kw + log Ka - log Kb
Or, - 2 log [H+] = -log Kw - log Ka - (- log Kb )
Or, 2pH = pKw + pKa - pKb
Or, pH = (pKw + pKa - pKb )/2 = (14 + 3.8 – 4.8)/ 2 = 6.5 Ans
 CORROSION
The serious consequences of corrosion process have become a common problem
among worldwide significance. In addition to our everyday encounters with this
form of degradation, waste of valuable resources, loss or contamination of
expensive products, reduction in efficiency, costly maintenance and expensive
overdesign. It can also jeopardize safety and inhibit technological process.
Corrosion degrades the useful properties of materials and structures including
strength, appearance and permeability to liquids and gases.
Corrosion is the gradual destruction of surface materials (generally metals) from its
surface due to the unwanted chemical or electrochemical redox reaction of metals
with their environment. For example- (1) Formation of multiple layers of red
brown scale or hydrated ferric oxide (Fe2O3) on the surface of iron, also called
Rusting of iron (2) Formation of green film of basic copper carbonate
[CuCO3.Cu(OH)2] on the surface of copper when exposed into moist air
containing carbon dioxide (3) Tarnishing of silver wares in hydrogen sulphide air
due to formation of silver sulphide etc.
Factors affecting corrosion
Corrosion or rate of corrosion is a spontaneous and continuous redox process which is
directly/indirectly being affected by different factors like (1) nature, physical state
and position of metal undergoing corrosion in the electrochemical series (2) nature
of oxide film, solubility and products of corrosion (3) relative surface area of anode
and cathode (4) temperature, humidity, salinity, air, moisture and pH (5) presence of
impurities in the surroundings as well as in metal (6) nature of electrolyte and
impurities dissolved in it (7) strains in metals like dent, scratches etc.
Cause of corrosion
Metals are electropositive in nature. Besides few noble metals like gold, platinum
etc. other metals are found in nature in the form of their ores. Metals are
obtained form ores by extraction process. As long as metals exist in the form of
ores, these are stable due to lower energy state. After extraction, metals become
less stable due to higher energy state than in the ionic state. Metals have natural
tendency to turn into their ionic state and hence metal atoms become prone to
corrosion by environment.
Types of corrosion
1. Chemical /dry corrosion:- It involves the direct chemical interference of
atmospheric gases like CO2, O2, H2S, SO2, halogen, moisture (least/rare) and
inorganic acid vapours on target metals.
2. Electrochemical/wet corrosion:- It occurs due to setting up of several galvanic
cells inside metals due to presence of impurities and moisture. In fact,
impurity or more active metal acts as anode while original metal acts as
cathode, it means anode area gets corrosion.
Main differences between dry and wet corrosion can be listed as:-

S. N. Dry corrosion Wet corrosion

1. It occurs in the absence of It occurs in the presence of
moisture (l). moisture/conducting medium.

2. It involves direct interference of It involves clear formation of

chemicals from atmosphere on electrochemical cells.
metal surface.
3. It is quite slowly. It is quite rapidly.

4. Corrosion products are formed at Corrosion occurs at anode and

the site of corrosion. corrosion products /rust gets deposited
at cathode.
5. Process of corrosion is uniform Process of corrosion depends on the
and dry corrosion may occur by size of the anodic part of the target
oxidation process or by other gases metal.
or liquid metal corrosion.
Theories of corrosion
There are three main theories of corrosion like:-
1. Acid theory of corrosion
2. Dry or chemical theory of corrosion
3. Electrochemical or wet theory of corrosion
Acid theory of corrosion
This theory suggests that metal, mainly iron, gets corroded because of acids or
acidic materials present around the metal. Iron metal gets corroded by
atmospheric carbon dioxide, moisture and oxygen. Corrosion products are the
mixture of Fe(HCO3)2, Fe(OH)CO3 and Fe(OH)3.
Plausible chemical reaction:-
Fe + 2CO2 + H2O + ½ O2 → Fe(HCO3)2
2 Fe(HCO3)2 + H2O + ½ O2 → 2Fe (OH)CO3 + 2CO2 + 2H2O
Fe (OH)CO3 + 2H2O → 2 Fe(OH)3 ↓ + 2CO2
(Red brown ppt)
.
Dry or chemical theory of corrosion
Corrosion on the surface of a metal is due to interaction of atmospheric gases like
oxygen, halogens, oxides of sulphur, oxides of nitrogen, hydrogen sulphide and
fumes of chemicals with metals. Chemical corrosion may occur by oxidation, by
gases or liquid metal corrosion.
Electrochemical or wet theory of corrosion
In 1824, Humphrey Davy first proposed cathodic protection principles. In 1830,
Swiss physicist Auguste de la Rive attributed rapid attack by acid on impure zinc to
the electrochemical interaction between the zinc and the impurities.
Electrolyte :- CO2 + H2O → H2CO3 2H+ (aq) + CO3--
Anodic reaction:- 2Fe(s) → 2Fe++ (aq) + 4e-
Cathodic reaction:- O2 (g) + 4H+ (aq) + 4e- → 2H2O (l)
Overall reaction:-2Fe(s) + O2 + 4H+ → 2Fe++ (aq) + 2H2O (l)
Reaction at surface:-
2Fe++ (aq) + 2H2O (l) + O2 (g) →2Fe2O3 (s) + 8H+ (aq)
Fe2O3 (s) + x H2O (l) → Fe2O3 .x H2O (rust)
 PREVENTION OF CORROSION
There are several methods of protecting metals against corrosion.
1. Barrier protection 2. Alloying protection
3. Sacrificial protection 4. Cathodic protection
1. Barrier protection:- A thin layer is developed between the surface of iron and
atmosphere by one of the following methods-
a) Painting the surface of iron
b) Coating the surface of iron with a thin film by non-corrosive metal like Nickel,
Chromium, Copper etc. Resistant coating is made between the metal surface
and environment. Thin coating of Zn on iron surface (Galvanization), coating
of Cu, Ni or Cr on iron surface in the presence of electricity (electroplating),
coating of Tin (Sn) on iron (Tin plating), dusting of Zn powder on iron surface
by heating (Sheradizing) etc are some of modern methods for coating.
Application of organic paint like paint, enamel, varnishes, lacquers can prevent
metals from corrosion. Similarly, some inorganic coatings like oxide or
phosphates coating also reduce corrosion.
2. Alloying protection:- Conversion of metal into alloy is another way for corrosion
resistant. For example, stainless steel (in which ordinary steel is alloyed with
Chromium and Nickel).
Types of alloying
a) Homogeneous alloying - Solid solutions in which components are completely
soluble in one another like stainless steel.
b) Heterogeneous alloying – Mixture of two or more separate phases in which
components of such alloy are not soluble and exist as separate phase like
Chromium (used for alloying metals of iron and Nickel), Chromium (used for
alloying metals of iron and Nickel), Silicon (used for alloying Si-Fe alloy).
3. Sacrificial protection:- Surface of iron is converted with a more electropositive
metal like Zn, Al etc. Such active metals lose electrons readily than iron, rusting
is prevented till the active metal is present as external coating. Such method of
prevention from corrosion is called sacrificial protection.
4. Cathodic protection:- It protects the parent metal from corrosion by connecting
with a more active metal like Zn, Al, Mg etc in which such active metal acts as
anode and supply electrons while parent metal acts as cathode and gains
electrons. In this way, the connecting metal undergoes corrosion by protecting
the parent metal and such prevention method is called cathodic protection.
Depth of study in accordance with syllabus
demands much more concentration. So
you are advised to collect some more
numerical problems for complete study
from different text-books/references or any
other sources.