Unit-2

Electrochemistry and Corrosion

 •Electrochemistry is the branch of chemistry which deals with the transformation of  electrical energy to chemical energy
and vice versa. In brief it deals with the chemical  applications of electricity.

• Electrical Energy                                            Chemical Energy

• Electric current is a flow of electrons generated by a battery, when the circuit is completed.  Electrolysis is one process where
electrical energy causes chemical changes. It is carried out  in an apparatus called electrolytic cell. The cell contains electrolyte
and electrodes. The  electrode connected to the positive pole of the current source is called anode. The electrode  connected to
the negative pole of the current source is called cathode. When an electric  current is passed through the electrolytic solution,
cations move towards cathode (-ve  electrode and anions move towards anode (+ve electrode)
• Ex: Electrolysis of water yields H2 and O2
• In other process, certain chemical reactions takes place in a vessel and produce electric  energy. The device is called
electrochemical cell. Eg. Galvanic cell, batteries and fuel cells  Broadly we can classify the cells as electrolytic cells and
electrochemical cells.

• Electrolytic cell: A device which converts electrical energy to chemical energy

• Electrochemical cell: A device which converts chemical energy to electrical energy
•Electric conductors are two types
1.Metallic conductors: They conduct electricity by free electrons, mobile, valance electrons and involve flow of
electrons. There is no chemical decomposition during conductance. E.g.; metals, alloys, certain solid salts and oxides.
2.Electrolytic conductors: The substance which allows the electricity to pass-through them in their molten state or in
their aqueous solution are called electrolytic conductors or electrolytes. They undergo chemical decomposition.

•Eg: Acids and bases.

•Non-Electrolytes: Non-Electrolytes do not dissociate into ions even at low dilutions. Eg: Glucose, Sugar.

•Electrolytes are classified into two types:

•Strong electrolytes: The electrolytes which completely dissociates in solution at all concentrations. Their
conductance is very high. Eg. NaCl, HCl, NaOH.

•Weak Electrolytes: The electrolyte which partially dissociates at moderate concentration. Their conductance is low as
they dissociate only to a small extent even at very high dilutions. Eg: CH3COOH, NH4OH, sparingly soluble salts like
AgCl, AgBr, AgI, BaSO4, PbSO4 etc
•Types of Conductors:
•Electrical Conductors: Substances which allow electric current to pass through them are 
known as electrical conductors. Eg. All metals, graphite, fused salts, aqueous solutions of 
acids and bases and salts.5
•Semi conductors: The substances which partially conduct electricity are called semi-
conductors. The conducting properties of semi-conducting properties are increased by
the addition of certain impurities called “dopping”.
•Ex: ‘Si’ and Ge on addition of V group elements like P produces n-type semi- conductor.
On addition of III group element like B, Al, produces p-type of semi- conductor.
•Non-conductors or Insulators: The substances which do not allow electricity are called
non- conductors. . Eg. Rubber, wood, paper, all non-metals except carbon.
•Conductance: The capacity of a conductor to allow the passage of current through it
called conductance. It is a property of conductor which facilitates flow of electricity
through it.
Specific resistance (⍴ ): is the resistance offered by a conductor (metallic) of unit
length and unit area of cross section.
                             or
Is the resistance offered by a conductor of unit volume.
According to IUPAC it is also called Resistivity.
    R= ⍴. l/a        or    ⍴ =Ra/l
R=resistance , a= area of cross section, l= length of the material and 
 ⍴ = specific resistance.
Units: Ω cm (or) mho −1 cm
Specific conductance or Conductivity (ks kappa):
In the case of electrolytic conductors, we consider their conductance instead
of resistance.
  ks= 1/ ⍴  =   l/Ra
Units: Ω−1 cm−1(or) mho cm−1 
Molar conductance or molar conductivity or molecular conductance ( μv)v :
The conductance of solution containing one mole of electrolyte in a given volume of solution.
  μv = ks.v  = ks.1000/M
Units: Ω−1 cm2 mol −1 
Relation between molar and equivalent conductance
                               μv = n λv 
                               n= valency
Cell constant(k): It is the constant characteristic of the cell in which the electrolyte is
taken.
It is the ratio of the distance between the two electrodes to the area of cross section of
each electrode.
cell constant(k)= distance between2electrodes /area of cross section of each
electrode
cell constant(K) = l/a 
  a= area of cross section, l= length of the material
 Relation between cell constant and specific conductance
Specific conductance (ks)= l/Ra = cell constant/R

Specific conductance (ks)= cell constant(k) . Observed conductance

Cell constant= specific conductance/observed conductance
Effect of dilution on conductance
Specific conductance(ks) Equivalent conductance(λv )

ks= 1/ ⍴ = l/Ra λv = ks.v

as dilution increases more and more, When volume increases λv also increases
electrolyte ionizes more and more ie.
Ionisation increases and specific conductance Number of ions of the electrolyte solution
decreases because ks is the conductance of increase on dilution
ions present per 1cmcube of solution. On
dilution number of current carrying particles
or ions present per cm cube of solution
become less and less
  Ionisation increases on dilution till the whole of the electrolyte substance has
ionized. Further addition of water produces no change in equivalent
conductance . This limiting value is known as equivalent conductance at infinite
dilution(λα).
   λv/ λα = α = degree of ionzation

                                                     ⍴ =Ra/l
                                                   λv =  ks.v
                                                   λv =  ks.v
                                         μv = ks.v  = ks.1000/M
                                                    μv = n λv 
                                                       K = l/a
•ELECTRODE POTENTIAL:
 When a metal rod is dipped in its salt solution (electrolyte), the metal atom tends either to lose electrons
(oxidation) or to accept electrons (reduction).

 The process of oxidation or reduction depends on the nature of metal.

 In this process, there develops a potential between the metal atom and its corresponding ion called the electrode
potential.
 It is a measure of tendency of a metallic electrode to lose or gain electrons when it is in contact with its own ions
in solution
.
 Reduction potential: The tendency of an electrode to gain electrons and to get reduced is called
reduction potential, its value is +x volts.

 Oxidation potential: Similarly the tendency of an electrode to lose electrons and to get oxidized is
called oxidation potential, its value is –x volts

 The potential develop between electrode and electrolyte by the formation of charges and these charges are formed
Helmholtz electrical double layer, through which potential develop between electrode and electrolyte.
•Anode Cathode Helmholtz Electrical Double Layer

Anode Cathode

Helmholtz Electrical Double Layer

Single electrode potential (E)
It is the potential developed at the electrode electrolyte interface when an
electrode is dissolved in solution (electrolyte) other than 1M concentration and
temperature may or may not be 250c
E can be determined and has to be connected to a half cell ie. A standard
reference electrode , the circuit is completed and emf is measured.
Standard electrode potential(E0)
It is the potential developed at the electrode electrolyte interface when an
electrode is dissolved in solution (electrolyte) whose concentration is 1M and
temperature is 250c .
If the electrode is a gaseous electrode then the pressure is 1atm and
temperature is 250c
GALVANIC CELL (ELECTROCHEMICAL CELL)
• In this cell chemical energy is converted into electrochemical energy.
• Electricity is generated due to the chemical reaction taking place.
• Galvanic cell has 2 half cells.
• Anodic half cell consisting of a zinc rod dipped in zinc sulphate solution.
• cathodic half cell consisting o fa copper rod dipped in copper sulphate solution.
• Both the half cells are connected externally by a wire (metallic conductor) and
internally by a salt bridge.
salt bridge
• Salt bridge is an inverted ‘U’ shaped tube filled with an inert electrolyte like saturated
KCl,KNO3 , agar agar , K 2SO4 etc.
• The mobility of the ions of the inert electrolyte must be the same.
• Salt bridge maintains electrical neutrality
• Electrons flow from anode to cathode , ie anode has negative polarity
• When electrons flow from anode to cathode ,a charge difference is established , which
has to be balanced by a salt bridge.
• If the charge difference is not balanced current will not flow.
• Salt bridge allows passage of ions and prevents intermixing of the solution or
prevents accumulation of charge around the electrons.
• Current flows from cathode to anode.
• Anode – Oxidation occurs at this electrode.
• Cathode – Reduction occurs at this electrode.
• Salt bridge – Contains electrolytes which are required to complete the
circuit in a galvanic cell.
• Half-cells – reduction and oxidation reactions are separated into
compartments.
• Cell reactions:
• At cathode(reduction): Cu 2+ + 2e– → Cu
• At anode(oxidation): Zn → Zn2+ + 2e–
• Overall cell reaction: Zn +Cu2+ ----------------  Zn2+ + Cu
•Electromotive Force or Cell Potential (EMF):
•The flow of electricity from one electrode to another electrode in a galvanic
cell  indicates that the two electrodes have different potentials. The difference of
potentials  between the electrodes of a cell which causes flow of current from an
electrode at higher  potential to other electrode at lower potential is known as
electromotive force or cell  potential. 

•The EMF of the cell depends on (a) temperature (b) nature of reactants and (c)
concentration of solutions in two half cells.
• Working of Galvanic Cell
• In a galvanic cell, when an electrode is exposed to the electrolyte at the electrode-electrolyte interface,
the atoms of the metal electrode have a tendency to generate ions in the electrolyte solution leaving
behind the electrons at the electrode. Thus, making the metal electrode negatively charged.
• While at the same time metal ions in the electrolyte solution too, have a tendency to deposit on a
metal electrode. Thus, making the electrode positively charged.
• Under equilibrium condition, charge separation is observed and depending on the tendencies of two
opposing reactions, the electrode can be positively or negatively charged. Hence, a potential
difference is developed between the electrode and electrolyte.
• This potential difference is known as electrode potential.
• Out of two electrodes, the electrode at which oxidation takes place is called anode while the electrode
at which reduction takes place is called cathode.
• The anode has a negative potential with respect to the solution while the cathode has a positive
potential with respect to the solution.
• Thus, a potential difference develops between two electrodes of the galvanic cell. This potential
difference is known as cell potential.
• When no current is drawn from the galvanic cell, cell potential is known as the electromotive force of
the galvanic cell.
• When the switch is set on, due to the potential difference, electrons flow from the negative electrode
to the positive electrode.
According to IUPAC ..at right ---------------cathode (more SRP)
at left ----------------anode (less SRP)
Cell representation:
Zn(s)/ZnSO4(1M)//CuSO4(1M)/Cu(s)
or
Zn(s) | Zn2+ (aq) || Cu2+ (aq)| Cu(s)
Calculation of EMF:
Ecell = E cathode –E anode

=E reduction potential of cathode –E reduction potential of anode

=E reduction potential of right hand electrode –E reduction potential of left hand electrode

SRP E 0
cu2+ /Cu = +0.33v
E 0
Zn2+/Zn = -0.761v

E 0
cu2+ /Cu -E 0
Zn2+/Zn =0.33 –(-0.761) = 1.1v
Q1)Standard electrode potentials of Cu and Cd are 0.337v and -0.403 v. Construct a galvanic cell ,
give cell reactions and calculate EMF of the cell and ∆G0

Q2)A conductance cell has 2 parallel electrodes of 1.25sq cm area and placed 10.5 cm apart when
filled with a solution of electrolyte, the resistance was found to be 1995Ὼ. Calculate cell constant and
specific conductance of the cell.

Q2)Ans:
                 cell constant(K) =l/a =10.5/1.25=8.4cm-1+
Specific conductance = cell constant . observed conductance
= 8.4 . 1/1995 =0.00421 Ω−1 cm−1
Q1) Ans:
Cd(s)/Cd2+ (1M) //Cu2+ (1M) /Cu(s)
At cathode(reduction) Cu2+ + 2e----------- Cu
At anode(oxidation) Cd ------------------- Cd2+ + 2e
overall cell reaction: Cu2+ + Cd ----------- Cu+ + Cd2+
Calculation of EMF:
E0cell = E 0cathode –E 0anode
=0.337 - (-0.403) =0.74v
∆G = -nFE0 = -2 .96500 .0.74 =-1428
Q3)Calculate EMF of cell Zn/Zn2+//Ag+/Ag and write the cell reactions.
E 0
Zn2+/Zn = -0.761v
E 0
Ag+/Ag = 0.8v

Q3)Ans:
At cathode(reduction) (Ag2+ + e----------- Ag) 2
At anode(oxidation) Zn ------------------- Zn 2+ + 2e
2Ag+ + Zn ----------- Ag + Zn2+
Calculation of EMF:
E0cell = E 0
cathode –E 0
anode

=0.8- (-0.762) =1.562v

Q4) A cell whose resistance when filled with 0.1NKCl is 192.3ῼ was found to be 6306 ῼ when filled with 0.01N
NaCl. (Ks of 0.1N KCl is 0.01289 and λv at infinite dilution of NaCl is 126.450 )Calculate
a)Cell constant
b)Specific conductance of NaCl solution
c) Equivalent conductance of NaCl solution
d) Degree of dissociation of NaCl solution
Q5) Specific conductance of N/50 of KCl at 250c is 0.002765Ω−1 cm−1. If resistance of cell containing
this solution is 400 Ω what is cell constant.
Ans: Ks = 1/R . l/a
0.002765= 1/400.l/a
l/a= 0.002765 . 400
l/a = 1.106 cm−1

Q6) The resistance of a decinormal solution of salt occupying a volume between 2 platinum
electrodes 1.8cm apart and 5.4 cm2 area was found to be 25 Ω. Calculate equivalent conductance.
Ans:
λv = Ks . 1000/N
Ks = 1.8/5.4 .(25 )
λv =133.3 Ω−1 cm2 equiv −1
Q7) Calculate useful electrical energy obtained from Daniel cell under standard conditions
Ans:
∆G = -nFE=-2 . 96500 . 1.1 = 212.3 KJ
 Nernst equation
It gives the relation between electrode potential or emf and concentration of
products and reactants. 
m1A + m2B ------------- n1C+  n2D --------------------  (1)
The free energy change of this reaction is given by Vant Hoff’s isotherm We import
this equation from thermodynamics.
∆G = ∆G 0 +RT ln [C]n1 [D]n2  / [A]m1[B]m2  ---------------------(2)(vanthoff isotherm)
Where ∆G =free energy change
             ∆G 0 =standard free energy change
 we know
∆G   = -nFE   ---------------------------------- (3)
 ∆G 0= -nFE 0 ---------------------------------- (4)
Substituting values of ∆G and ∆G 0 in equation 2 we get
 -nFE = - nFE 0 +RT ln. [C]n1 [D]n2  / [A]m1[B]m2   ---------------(5) 
Dividing equation (5) with nF  we get,
-E = - E 0 +RT/nf ln. [C]n1 [D]n2  / [A]m1[B]m2   ---------------(6) 
Changing the sign we get, 
  E =  E 0 -RT/nF .ln [C]n1 [D]n2  / [A]m1[B]m2         ---------------(7)  
                  or 
E= E 0  - RT/. ln[ Products] / [Reactants]                 ---------------(8) 
At 250c 
   T= 273+25= 298K
R= gas constant= 8.315KJ/mole
n= number electrons transferred
E = electrode potential or emf
F=  96500 faraday 
E 0  =standard electrode potential or standard emf 

E  = E0  -2.303(8.315) (298)/n(96500)  . log Products/ Reactants 

    
                         or 

   E  = E 0 -0.0596)/n  . Log K
 E=E0 -2.303(8.315) (298) /n(96500) . log [Products]/[reactants]

E = E0 - 0.05916/n . log [Products]/[reactants]

E = E0 - 0.05916/n . logk
Where K= equilibrium constant
Nernst equation can be applied for a cell or a single electrode.
Applying Nernst equation to a cell
Eg. Daniel cell
Zn +Cu2+ ----------------  Zn2+ + Cu
Ecell= E0cell - RT/2. ln[Zn2+ ][ Cu] / [Zn ]+[Cu2+ ]
Concentrations of solid terms are eliminated as it is unity
Ecell= E0cell - RT/2. ln [Zn2+ ] / [Cu2+ ]
At 250c
E = E0 - 0.0591/2. log [Zn2+ ] / [Cu2+ ]
Applying Nernst equation to a single electrode

Mn+ +ne ------------------M (reduction)

E= E0 - 0.0591/n. log 1 / [Mn+ ]

M-----------------Mn+ +ne (oxidation)

E= E0 - 0.0591/n. log [Mn+ ]

Importance and applications of Nernst equation:

1) It is used to calculate equilibrium constant
2) It helps to calculate the free energy change in a reaction
3) It helps in calculating the spontaneity and feasibility of a reaction.
4) It is used to calculate electrode potential of any electrode at different concentrations.
5) It is used to calculate number of electrons involved.
6) It is used to calculate the concentration of products and reactants
Calculate emf of the following
Q1) Zn(s) | Zn2+ (aq) || Cu2+ (aq)| Cu(s) at 250c E0cell =1.1v
a=1 a=1
Zn +Cu2+ ----------------  Zn2+ + Cu
Ecell = E0 - 0.0591/n . log [Products]/[reactants]
cell

Ecell= 1.1 - 0.0591/2. log [Zn2+ ] / [Cu2+ ]

Ecell= 1.1 - 0.0591/2. log [1] / [1]
Ecell= 1.1v

Q2) Zn(s) | Zn2+ (aq) || Cu2+ (aq)| Cu(s) at 250c E0cell =1.1v

a=0.01 a=1
Zn +Cu2+ ----------------  Zn2+ + Cu
Ecell = E0 cell - 0.0591/n . log [Products]/[reactants]
Ecell= 1.1 - 0.0591/2. log [Zn2+ ] / [Cu2+ ]
Ecell= 1.1 - 0.0591/ 2 log [0.01] /[1] = 1.1 - 0.0591(- 2 )
Ecell= 1.159v
Calculate E (reduction potential) of Zn electrode , when activity of Zn 2+ is 0.1
Zn2+ + 2e-------------- Zn
E = E0 - 0.0591/n . log 1 / [Zn2+]
E=-0.761 – 0.0591/2 . log 1/[0.1]
E= -0.761- 0.0591/2 log (10)
E= -0.761-0.0295
E= -0.7905V