Formula sheet of
Electrochemistry
1. Introduction and cells
a. Introduction and Types of cells
REPRESENTATION OF A CELL (IUPAC CONVENTIONS)
Let us illustrate the convention taking the example of Daniel cell.
(i) Anodic half cell is written on left and cathodic half cell on right
hand side.
Zn(s)|ZnSO4 (sol) || CuSO4 (sol) | Cu(s)
(ii) Two half cells are separated by double vertical lines:
Double vertical lines indicate salt bridge or any type of porous partition.
(iii) EMF (electromotive force) may be written on the right hand side of
the cell.
(iv) Single vertical lines indicate the phase separation between
electrode and electrolyte solution.
Zn| Zn2+|| Cu2+|Cu
(v) Inert electrodes are represented in the bracket
Zn|ZnSO4|| H+|H2. (Pt)
2. Electrochemical cells
https://www.acadza.com/dosts/formula-sheet/672d85d667d34828fc045a4b 20/11/2024, 8 53 AM
Page 1 of 20
:
a. Electrode potential, SOP and SRP
Depending on the nature of the metal electrode to lose or
gain electrons, the electrode potential may be of two
types:
(i) Oxidation potential: When electrode is negatively
charged with respect to solution,
i.e., it acts as anode. Oxidation
occurs.
M ® Mn+ + ne-
(ii) Reduction potential : When electrode is positively
charged with respect to solution.
i.e., it acts as cathode. Reduction
occurs.
Mn+ + ne-® M
EMF of cell may be calculated as:
Ecell = Reduction potential of cathode - Reduction potential
of anode
Similarly, standard e.m.f. of the cell (Eo) may be
calculated as
Eocell = Standard reduction potential of cathode - Standard
reduction potential of anode
Ecell = R.P. (Cathode) - R.P.(Anode)
= R.P.(Cathode) + O.P.(Anode)
b. Working of Electrochemical cells and Electrochemical Series
Oxidation takes place at anode :
https://www.acadza.com/dosts/formula-sheet/672d85d667d34828fc045a4b 20/11/2024, 8 53 AM
Page 2 of 20
:
Zn(s) ® Zn2+ + 2e- (loss of electron : oxidation)
Reduction takes place at cathode :
1. Cu2+ + 2e- → Cu(s) (gain of electron ; reduction)
Over all process :
Zn (s) + Cu2- ®Cu (s) + Zn2+
In galvanic cell like Daniell cell ; electrons flow from anode
(zinc rod) to the cathode (copper rod) through external circuit
; zinc dissolves as Zn2+ ; Cu2+ ion in the cathode cell picks up
two electron and become deposited at cathode.
c. Half cells, full cells and feasibility of cells
Types of Electrodes :
1. Metal in contact with its ions :
M/Mn+ is written as:
M(s) ® Mn+ (1.0M) + ne- (oxidation electrode)
Mn+ / M is written as:
M n+(1.0M) + ne- ® M(s) (reduction electrode)
2. Gaseous electrode:
https://www.acadza.com/dosts/formula-sheet/672d85d667d34828fc045a4b 20/11/2024, 8 53 AM
Page 3 of 20
:
Its electrode potentials are represents as:
(oxidaion potential)
(reduction potential)
(standard oxidation
potential)
(standard reduction
potential)
3. Redox Electrodes :
Electrode representation : Pt/Fe3+, Fe2+
Electrode reaction: As cathode: Fe3+ (aq.) + e - ® Fe2+
(aq.)
As anode: Fe2+(aq.) → Fe3+(aq.) + e-
Another example: Pt/MnO-4, Mn2+, H+
As cathode: MnO-4 (aq.) + 8H+ (aq.) + 5e- ®Mn2+ (aq.) +
https://www.acadza.com/dosts/formula-sheet/672d85d667d34828fc045a4b 20/11/2024, 8 53 AM
Page 4 of 20
:
4H2O( )
Redox electrodes can also be made using substances that
exist in two different oxidation states. Quinhydrone is an
equimolar mixture of benzoquinone (Q) and hydroquione
(H2Q)
Electrode representation : Pt / H2Q, Q, H*
Electrode reaction : As anode :
4. Calomel Electrode:
Electrode representation: Hg/ Hg2Cl2/Cl-
Electrode reaction : As cathode :
Hg2Cl2(s) + 2e- 2 Hg( ) +
2Cl- (aq.)
As anode :
2 Hg( ) + 2Cl-(aq.) Hg2Cl2
(s) + 2e-
5. Silver - Silver Chloride Electrode :
https://www.acadza.com/dosts/formula-sheet/672d85d667d34828fc045a4b 20/11/2024, 8 53 AM
Page 5 of 20
:
Electrode representation : Ag/AgCI/Cl-
Electrode reaction : As cathode:
AgCl(s) +e- Ag(s) + Cl-(aq.)
= 0.222 V
As anode :
Ag(s) + Cl-(aq) AgCl(s) +e-
6. Mercury - Mercurous Sulphate Electrode:
Electrode representation : Hg/Hg2SO4/SO42-
Electrode reaction : As cathode:
Hg2SO4(S)+ 2e- ® 2 Hg( )+
SO42-(aq.)
= 0.616V (w.r.t.
SHE)
As anode: 2 Hg( )+ SO42-(aq.) ® Hg2SO4(S)+ 2e-
[2] The potential of metal - metal ion electrode and
metal-metal insoluble salt-slat anion electrode is same while
their standard potentials are not same. Standard
potential are related by the following equation.
7. Amalgam electrodes:
https://www.acadza.com/dosts/formula-sheet/672d85d667d34828fc045a4b 20/11/2024, 8 53 AM
Page 6 of 20
:
This is the modified version of Metal/Metal - ion
electrode in which metal strip is replaced by metal amalgam.
e.g. Na (in Hg at c1 M)/Na+ (c2M)
RELATIONSHIP BETWEEN D G AND ELECTRODE
POTENTIAL
\DG = - nFE
Under standard state DG0 = -nFE0
Reactions DG E
Spontaneous (-) (+)
Non-spontaneous (+) (-)
Equilibrium 0 0
d. Nernst Equation and applications
Nernst Equation and applications
https://www.acadza.com/dosts/formula-sheet/672d85d667d34828fc045a4b 20/11/2024, 8 53 AM
Page 7 of 20
:
aA + bB ®cC + dD, the EMF can be calculated as:
(ii) Determination of equilibrium constant:
We know, that
At equilibrium, the cell potential is zero because cell reactions
are balanced, i.e. E=0
\From Eq. (i), we have
e. Standard Hydrogen cell and Calomel Electrode
Its electrode potentials are represents as :
Electrode Gas concentration cell:
https://www.acadza.com/dosts/formula-sheet/672d85d667d34828fc045a4b 20/11/2024, 8 53 AM
Page 8 of 20
:
Pt,H2(P1) | H+(C) | H2(P2), Pt
(i) Calomel electrode:
Electrode representation: Hg / Hg2Cl2 / Cl-
Electrode reaction: As cathode: Hg2Cl2(s) + 2e-
2Hg( ) + 2Cl-(aq.)
As anode: 2Hg( ) + 2Cl-(aq.)
Hg2Cl2(s) + 2e-
f. Concentration Cell, type and define spontaneity of cell
https://www.acadza.com/dosts/formula-sheet/672d85d667d34828fc045a4b 20/11/2024, 8 53 AM
Page 9 of 20
:
g. Relation between Standard Electrode Potential and Equilibrium
Constant
3. Commercial Cells
a. Primary, secondary cell & fuel cell
Dry Cell Battery
https://www.acadza.com/dosts/formula-sheet/672d85d667d34828fc045a4b 20/11/2024, 8 53 AM
Page 10 of 20
:
Cathode, reductions: 2NH4+ (aq) + 2e- ® 2NH3(g) +H2(g)
Anode, Oxidation: Zn(s) ® Zn2+ (aq) + 2e-
SECONDARY OR RECHARGEABLE BATTERIES
https://www.acadza.com/dosts/formula-sheet/672d85d667d34828fc045a4b 20/11/2024, 8 53 AM
Page 11 of 20
:
An automobile battery-
Cathode, reduction: PbO2(s) + 4H+(aq) + SO42-(aq) + 2e-
® PbSO4(s) + 2 H2O(l)
Anode, oxidation: Pb(s) + SO42-(aq) ® PbSO4(s) + 2e-
--------------------------------------------------------------------------
------------------------
Net cell reaction Pb(s) + PbO2(s) + 2H2SO4(aq) ®
2PbSO4(s) + 2H2O(l)
The discharging process of the storage cell is based on the
principles of electrochemical cell, whereas the charging
process is based upon the principles of electrolytic cells.
https://www.acadza.com/dosts/formula-sheet/672d85d667d34828fc045a4b 20/11/2024, 8 53 AM
Page 12 of 20
:
Nickel - Cadmium ("Ni-Cad") batteries,
Cathode, reduction : NiO(OH)(s) + H2O(l) + e- ®
Ni(OH)2(s) + 2OH-(aq)
Anode, Oxidation: Cd(s) + 2OH- ® Cd(OH)2(s) + 2e-
Net cell reaction: 2NiO(OH)(s) + Cd(s)+H2O(l) ®
2Ni(OH)2(s) + Cd(OH)2(s)
FUEL CELLS AND HYBRID CARS
i
Cathode, reduction: O2(g) + 2H2O(l) + 4e- ® 4OH-(aq)
Anode, Oxidation: H2(g) ® 2H+(aq) + 2e-
https://www.acadza.com/dosts/formula-sheet/672d85d667d34828fc045a4b 20/11/2024, 8 53 AM
Page 13 of 20
:
EFFICIENCY OF A FUEL CELL
(∆G )
η= ×100
(∆H )
4. Electrolytic cell
a. Electrolytic cell and Electrolysis
(i) Electrolysis of sodium chloride solution
NaCl ⇌ Na+ + Cl
H 2O ⇌ H+ + OH-
At cathode At anode
H+ + e- ® H Cl- ® Cl + e-
2H ® H2 2 Cl ® Cl2
Thus, Na+ and OH- ions remain in solution and the solution
when evaporated yields crystals of sodium hydroxide.
(ii) Electrolysis of copper sulphate solution using
platinum electrodes
CuSO4 ⇌ Cu2+ + SO42-
H 2O ⇌ H+ + OH-
At cathode At anode
Cu2+ + 2e- ® Cu 2 OH- ® H2O + O + 2e-
O + O ® O2
https://www.acadza.com/dosts/formula-sheet/672d85d667d34828fc045a4b 20/11/2024, 8 53 AM
Page 14 of 20
:
(iii) Electrolysis of sodium sulphate solution using inert
electrodes
Na2SO4 2Na+ + SO42-
H2O H+ + OH-
At cathode At anode
H+ + e- ® H 2 OH- ® H2O + O + 2e-
2H ® H2 O + O ® O2
(iv) Electrolysis of copper sulphate solution using copper
electrodes
CuSO4 Cu2+ + SO42-
At cathode, copper is deposited.
Cu2+ + 2e– ® Cu
At anode, the copper of the electrode is oxidised to Cu2+ ions
or ions dissolve equivalent amount of copper of the anode.
Cu ® Cu2+ + 2e-
Or Cu + ® CuSO4 + 2e-
(V) Electrolysis of silver nitrate solution using silver
electrodes
AgNO3 Ag+ + NO-3
At cathode, silver is deposited.
Ag+ + e– ® Ag
At anode, the silver of the electrode is oxidised to Ag+ ions
which go into the solution or NO3− ions dissolve equivalent
amount of silver of the electrode.
https://www.acadza.com/dosts/formula-sheet/672d85d667d34828fc045a4b 20/11/2024, 8 53 AM
Page 15 of 20
:
amount of silver of the electrode.
Ag ® Ag+ + e-
Ag + NO3− ® AgNO3 + e-
b. Selective Electrolysis
The decreasing order of discharge potential for cations is
given below.
K+ > Na+ > Ca2+ > Mg2+ > Al3+ > Zn2+ > H+ > Cu2+ > Hg2+ >
Ag+
The decreasing order of discharge potential for anions is
given below.
−
SO2−
4
> NO3− < OH > Cl- > Br- > I-
c. Faraday's law of Electrolysis
(i) First law of electrolysis :
mount of substance deposited or liberated at an electrode
is directly proportional to amount of charge passed (utilized)
through the solution.
wµQ
W = weight deposited, Q = charge in coulomb
W = ZQ
Z = electrochemical equivalent
when Q = 1 coulomb, then w = Z
E E
\ 1 Coulomb will liberate gm; By definition, Z =
96500 96500
ItE
\W=
96500
https://www.acadza.com/dosts/formula-sheet/672d85d667d34828fc045a4b 20/11/2024, 8 53 AM
Page 16 of 20
:
(ii) Second law of electrolysis :
When same amount of charge is passed through different
electrolyte solutions connected in series then weight of
substances deposited or dissolved at anode or cathode are in
ratio of their equivalent weights .i.e.
w1/w2 = E1/ E2
5. Conductance
a. Conductance and Specific Conductance
Conductance
1 1
Conductance (G) = = ......(i)
Resistance R
Conductivity (K):
l l
Rα or R = ρ .....(ii)
A A
Conductivity (k) = Conductance (G) x cell constant (G*)
b. Molar and Equivalent Conductance
Molar conductance ( ùm)
1000
Ùm = k where c is the concentration of the solution in M
c
Equivalent Conductance (Ùeq)
At concentration c (in gm-equivalent/L i.e., normality),
https://www.acadza.com/dosts/formula-sheet/672d85d667d34828fc045a4b 20/11/2024, 8 53 AM
Page 17 of 20
:
equivalent conductance is denoted by Ùeq.
1000 × conductivity (ohm −1 cm −1 ) 1000 × k
⇒ ^eq = ⎡⎢ ⎤⎥ ×
c ⎢⎣ or Norma lity ⎥⎦ N
c. Effect of dilution, Kohlrausch law and Ionic Mobility
(a) Strong Electrolytes:
When infinite dilution is approached, the conductance of a
solution of strong electrolyte approaches a limiting value and
can be obtained by extrapolating the curve between ^m and
c as shown: (Note: the behavior/variation is linear)
The molar conductivity of strong electrolytes is found to vary
with concentration as:
^m = ^0m −b c
Weak Electrolytes : When infinite dilution is approached, the
conductance of a solution of weak electrolyte increases very
rapidly and thus, cannot be obtained through extrapolation.
Also, the variation between ^m and c is not linear at low
concentrations.
https://www.acadza.com/dosts/formula-sheet/672d85d667d34828fc045a4b 20/11/2024, 8 53 AM
Page 18 of 20
:
lim ^m = ^0m and lim ^eq = ^0eq
c →0 c →0
d. Application of Kohlrausch law and Conductometric Titration
(i) Solubility Product of a Sparingly Soluble Salt:
saturated solution.
(ii) Degree of dissociation:
(iii) lonisation constant of weak electrolytes:
https://www.acadza.com/dosts/formula-sheet/672d85d667d34828fc045a4b 20/11/2024, 8 53 AM
Page 19 of 20
:
https://www.acadza.com/dosts/formula-sheet/672d85d667d34828fc045a4b 20/11/2024, 8 53 AM
Page 20 of 20
:
