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 ELECTROCHEMISTRY

ELECTROCHEMISTRY

1. ELECTROCHEMISTRY the external circuit. Anode is assigned negative polarity

and cathode is assigned positive polarity. In Daniell Cell,
Electrochemistry is the study of production of electricity
Zn acts as the anode and Cu acts as the cathode.
from the energy released during a spontaneous chemical
reaction and the use of electrical energy to bring about 5. ELECTROLYTIC CELL
non-spontaneous chemical transformations.
These electrodes are dipped in and electrolytic solution
2. ELECTROCHEMICAL CELLS containing cations and anions. On supplying current the
ions move towards electrodes of opposite polarity and
A spontaneous chemical process is the one which can simultaneous reduction and oxidation takes place.
take place on its own and in such a process the Gibb’s
energy of the system decreases. It is this energy that 5.1 Preferential Discharge of ions
gets converted to electrical energy.The reverse process Where there are more than one cation or anion the process
is also possible in which we can make non-spontaneous of discharge becomes competitive in nature. Discharge
processes occur by supplying external energy in the form of any ion requires energy and in case of several ions
of electrical energy. These inter conversions are carried being present the discharge of that ion will take place first
out in equipments called Electrochemical Cells. which requires the energy.

3. TYPES 6. ELECTRODE POTENTIAL

Electrochemical Cells are of two types: It may be defined as the tendency of an element, when it is
placed in contact with its own ions to either lose or gain
3.1 Galvanic Cells electrons and in turn become positively or negatively charged.

Converts chemical energy into electrical energy The electrode potential will be named as oxidation or
reduction potential depending upon whether oxidation or
3.2 Electrolytic Cells
reduction has taken place.
Converts electrical energy into chemical energy.
oxidation
ZZZZZ
M s YZZZZ X M n  aq  ne 
reduction Z
4. GALVANIC CELL
M n  aq  ne  YZZZZ
reduction
Cell energy is extracted from a spontaneous chemical ZZZZZ X
ZM s
oxidation
process or reaction and it is converted to electric current.
For example, Daniell Cell is a Galvanic Cell in which Zinc 6.1 Characteristics
and Copper are used for the redox reaction to take place. (a) Both oxidation and reduction potentials are equal in
Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu(s) magnitude but opposite in sign.

Oxidation Half : Zn (s) Zn2+ (aq) + 2e– (b) It is not a thermodynamic property, so values of E are
not additive.
Reduction Half : Cu2+(aq) + 2e– Cu(s)
2+
7. STANDARD ELECTRODE POTENTIAL (EO)
Zn is the reducing agent and Cu is the oxidising
agent.The half cells are also known as Electrodes. The It may be defined as the electrode potential of an electrode
oxidation half is known as Anode and the reduction half is determined relative to standard hydrogen electrode under
called Cathode. Electrons flow from anode to cathode in standard conditions. The standard conditions taken are :
 Study Materials
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ELECTROCHEMISTRY

(i) 1M concentration of each ion in the solution. Zn(s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu EMF = +1.1V
(ii) A temperature of 298 K. (f) If an inert electrode like platinum is involved in the
construction of the cell, it may be written along with the
(iii) 1 bar pressure for each gas.
working electrode in bracket say for example, when a zinc
8. ELECTROCHEMICAL SERIES anode is connected to a hydrogen electrode.

The half cell potential values are standard values and are Zn s | Zn 2 C1 || H  C2 | H 2 | Pt s
represented as the standard reduction potential values
as shown in the table at the end which is also called 11. SALT BRIDGE
Electrochemical Series.
Salt bridge is used to maintain the charge balance and to
9. CELL POTENTIAL OR EMF OF A CELL complete the circuit by facilitating the flow of ions through it.
It contains a gel in which an inert electrolyte like Na2SO4 or
The difference between the electrode potentials of two
KNO3 etc are mixed. Negative ions flow to the anode and
half cells is called cell potential. It is known as electromotive
force (EMF) of the cell if no current is drawn from the cell. positive ions flow to the cathode through the salt bridge and
charge balance is maintained and cell keeps on functioning.
Ecell = Ecathode + Eanode

For this equation we take oxidation potential of anode and

reduction potential of cathode.

Since anode is put on left and cathode on right, it follows

therefore,

= ER + EL

For a Daniel cell, therefore

E ocell E oCu 2 / Cu  EoZn / Zn 2 0.34  0.76 1.10 V

10. CELL DIAGRAM OR REPRESENTATION

OF A CELL
The following conventions or notations are applied for writing
the cell diagram in accordance with IUPAC recommendations. 12. SPONTANEITY OF A REACTION
The Daniel cell is represented as follows : 'G = – nFECELL
2+ 2+
Zn(s) | Zn (C1) || Cu (C2) | Cu (s) For a spontaneous cell reaction ΔG should be negative
(a) Anode half cell is written on the left hand side while and cell potential should be positive.
cathode half cell on right hand side. If we take standard value of cell potential in the above
(b) A single vertical line separates the metal from aqueous equation we will obtain standard value of ΔG as well.
solution of its own ions.
ΔGo = – nFE0CELL
2 2
Zn s | Zn aq ; Cu aq | Cu s
Anodic chamber Cathodic chamber
13. TYPES OF ELECTRODES
(c) A double vertical line represents salt bridge
13.1 Metal-Metal Ion electrodes
(d) The molar concentration (C) is placed in brackets after
the formula of the corresponding ion. A metal rod/plate is dipped in an electrolyte solution
containing metal ions. There is a potential difference
(e) The value of e.m.f. of the cell is written on the extreme
right of the cell. For example, between these two phases and this electrode can act as a
cathode or anode both.
 ELECTROCHEMISTRY

Anode: M Mn+ + ne–

Cathode: Mn+ + ne– M

13.2 Gas Electrodes

Electrode gases like H2, Cl2 etc are used with their respective
ions. For example, H2 gas is used with a dilute solution of HCl
(H+ ions). The metal should be inert so that it does not react
with the acid.

Cathode :
Hg2Cl2(s) + 2e– 2Hg(l) + 2Cl–(aq)
Anode :
2Hg(l) + 2Cl–(aq) Hg2Cl2(s) + 2e–
This electrode is also used as another standard to measure
other potentials. Its standard form is also called Standard
Anode: H2 2H+ + 2e– Calomel Electrode (SCE).
13.5 Redox Electrode
Cathode: 2H+ + 2e– H2
In these electrodes two different oxidation states of the
The hydrogen electrode is also used as the standard to same metal are used in the same half cell. For example,
measure other electrode potentials. Its own potential is Fe2+ and Fe3+ are dissolved in the same container and an
set to 0 V as a reference. When it is used as a reference inert electrode of platinum is used for the electron transfer.
the concentration of dil HCl is taken as 1 M and the Following reactions can take place:
electrode is called “Standard Hydrogen Electrode (SHE)”. Anode: Fe2+ Fe3+ + e–

13.3 Metal-Insoluble salt electrode Cathode: Fe3+ + e– Fe2+

We use salts of some metals which are sparingly soluble 14. NERNST EQUATION
with the metal itself as electrodes. For example, if we use
AgCl with Ag there is a potential gap between these two It relates electrode potential with the concentration of ions.
phases which can be identified in the following reaction:
Thus, the reduction potential increases with the increase
in the concentration of ions. For a general electrochemical
AgCl(s) + e– Ag(s) + Cl–
reaction of the type.
This electrode is made by dipping a silver rod in a solution 

containing AgCl(s) and Cl– ions. aA  bB o

ne
cC  dD

Nernst equation can be given as

13.4 Calomel Electrode
c d
Mercury is used with two other phases, one is a calomel RT C D
E cell E o
 ln
paste (Hg2Cl2) and electrolyte containing Cl– ions. cell
nF A
a
B
b
ELECTROCHEMISTRY

c d concentrations and the solutions are connected through

2303 C D
E cell E o
cell  RT log a b
salt bridge, such cells are known as concentration cells.
nF A B For example

H2 | H+(c1) || H+ (c2) | H2
Substituting the values of R and F we get
Cu | Cu+2 (c1) || Cu2+(c2) | Cu
c d
0.0591 C D These are of two types :
E cell E ocell  log a b
,at 298 K
n A B
16.1 Electrode concentration cells

15. APPLICATIONS OF NERNST EQUATION H2 (P1) | H+ (C) || H+ (C) | H2(P2)

15.1 Equilibrium Constant from Nernst Equation

0.059 P
Ecell = 0 – log 2
For a Daniel cell, at equilibrium n P1

ª Zn 2  º where p 2  p1 for spontaneous reaction

log ¬ 2  ¼
2.303 RT
E cell 0 E ocell 
2F ¬ªCu º¼ 16.2 Electrolyte concentration cell

The EMF of concentration cell at 298 K is given by

ª Zn 2  º
log ¬ 2  ¼
o 2.303RT Zn | Zn2+ (c1) || Zn2+ (c2) | Zn
or E cell
2F ¬ªCu º¼
0.0591 c
E cell log 2 ,
n1 c1
ª¬ Zn 2  ¼º
But at equilibrium, ª 2  º Kc where c2 > c1 for spontaneous reaction
¬ Cu ¼
17. CASES OF ELECTROLYSIS
2.303 RT
E ocell log K c 17.1 Electrolysis of molten sodium chloride
2F
2NaCl (l ) U 2Na+ (l ) + 2Cl– (l )
2.303 u 8.314 u 298
E ocell log K c The reactions occurring at the two electrodes may be
2 u 96500 shown as follows :

At cathode :
0.0591
log K c
2 2Na+ + 2e– o 2Na E0 = – 2.71 V

At anode :
o 0.0591
In general, E cell log K c
n 2Cl– o Cl2 + 2e– E0 = – 1.36V

o Overall reaction :
n E cell
or, log KC =
0.0591 2Na+ (l ) + 2 Cl– (l ) 2Na (l ) + Cl2 (g)

16. CONCENTRATION CELLS or 2NaCl (l ) 2Na (l ) + Cl2 (g)

If two electrodes of the same metal are dipped separately At cathode At anode
into two solutions of the same electrolyte having different
 ELECTROCHEMISTRY

17.2 Electrolysis of an aqueous solution of sodium chloride 18.3 Mercury cells

NaCl (aq) Na+(aq) + Cl– (aq) These are used in small equipments like watches, hearing aids.

(almost completely ionized) Anode : Zn – Hg Amalgam

H2O (l ) U H+(aq) + OH–(aq) Cathode : Paste of HgO and carbon

(only slightly ionized) Electrolyte : Paste of KOH and ZnO

At cathode : Anode : Zn (Hg) + 2OH– ZnO (s) + H2O + 2e–

2Na+ + 2e– 2Na E0 = – 2.71V Cathode : HgO (s) + H2O + 2e– Hg (l) + 2OH–

2H2O + 2e– H2 + 2OH– E0 = – 0.83V Overall Reaction : Zn (Hg) + HgO (s) ZnO (s) + Hg (l)

Thus H2 gas is evolved at cathode value Na+ ions remain The cell potential is approximately 1.35V and remains
in solution. constant during its life.

At anode : 18.4 Secondary Batteries

2H2O O2 + 4H+ + 4e– E0 = – 1.23V Secondary cells are those which can be recharged again
and again for multiple uses. e.g. lead storage battery and
2Cl– Cl2 + 2e– E0 = – 1.36V Ni – Cd battery.
Thus, Cl2 gas is evolved at the anode by over voltage 18.5 Lead Storage Battery
concept while OH– ions remain in the solution.
Anode : Lead (Pb)
18. BATTERIES
Cathode : Grid of lead packed with lead oxide (PbO2)
When Galvanic cells are connected in series to obtain a
higher voltage the arrangement is called Battery. Electrolyte : 38% solution of H2SO4

18.1 Primary Batteries Discharging Reactions

Primary cells are those which can be used so long the Anode: Pb(s) + SO42–(aq) PbSO4(s) + 2e–
active materials are present. Once they get consumed the
cell will stop functioning and cannot be re-used. Example Cathode: PbO2(s) + 4H+(aq) + SO42–(aq) + 2e–
Dry Cell or Leclanche cell and Mercury cell.
PbSO4(s) + 2H2O(l)
18.2 Dry cell
Overall Reaction : Pb(s) + PbO2(s) + 2H2SO4(aq)
Anode : Zn container
2PbSO4(s) + 2H2O(l)
Cathode : Carbon (graphite) rod surrounded by powdered
MnO2 and carbon. To recharge the cell, it is connected with a cell of higher
potential and this cell behaves as an electrolytic cell
Electrolyte : NH4Cl and ZnCl2 and the reactions are reversed. Pb(s) and PbO 2(s) are
regenerated at the respective electrodes.These cells
Reaction : deliver an almost consistent voltage.
Anode : Zn Zn2+ + 2e– Recharging Reaction : 2PbSO4(s) + 2H2O(l) Pb(s) +

Cathode : MnO2 + NH 4 
e– MnO (OH) + NH3 PbO2(s) + 2H2SO4(aq)

The standard potential of this cell is 1.5 V and it falls as 19. FUEL CELLS
the cell gets discharged continuously and once used it
A fuel cell differs from an ordinary battery in the sense
cannot be recharged.
that the reactants are not contained inside the cell but are
ELECTROCHEMISTRY

externally supplied from an external reservoir. Fuel cell is and iron is protected. This method of protecting one metal
used in space vehicles and in this cell the two gases are by the other is also called Cathodic Protection.
supplied from external storages. In this cell carbon rods
are used as electrodes with KOH as the electrolyte.

Cathode : O2 (g) + 2H2O (l) + 4e– 4OH– (aq)

Anode : 2H2 (g) + 4OH– (aq) 4H2O (l) + 4e–

overall Reaction : 2H2(g) + O2 (g) 2H2O (l)

21. CONDUCTANCE (G)

It is the reciprocal of resistance and may be defined as the
ease with which the electric current flows through a
conductor.
1
G
R
SI unit is Siemen (S).

1 S = 1 ohm–1 (mho)

N)
22. CONDUCTIVITY (N
20. CORROSION
It is the reciprocal of resistivity (U).
It involves a redox reaction and formation of an
1 1 A A
electrochemical cell on the surface of iron or any other metal. N u Gu
U R A A
At one location oxidation of iron takes place (anode) and
Now if A = 1 cm and A = 1 cm2, then N = G..
at another location reduction of oxygen to form water takes
place (cathode). First Fe gets oxidised to Fe2+ and then in Hence, conductivity of an electrolytic solution may be
the presence of oxygen it forms Fe3+ which then reacts defined as the conductance of a solution of 1 cm length
with water to form rust which is represented by Fe2O3.xH2O. with area of cross-section equal to 1 cm2.
Anode : 2Fe (s) o 2 Fe2+ + 4e– Eº = + 0.44 V 23. FACTORS AFFECTING ELECTROLYTIC
Cathode : O2 (g) + 4H + 4e o 2H2O (l) Eº = 1.23 V
+ –
CONDUCTANCE
Overall R × N :
23.1 Electrolyte
2Fe (s) + O2 (q) + 4H+ o 2Fe2+ + + 2H2O Eºcell = 1.67 M
An electrolyte is a substance that dissociates in solution to
produce ions and hence conducts electricity in dissolved
or molten state.

Examples : HCl, NaOH, KCl (Strong electrolytes).

CH3–COOH, NH4OH (Weak electrolytes).

The conductance of electricity by ions present in the

solutions is called electrolytic or ionic conductance. The
Rusting of iron can be avoided by painting it or by coating following factors govern the flow of electricity through a
it with some other metals like Zinc. The latter process is
solution of electrolyte.
known as Galvanisation. As the tendency of Zn to get
oxidised is more than iron it gets oxidised in preference
 ELECTROCHEMISTRY

(i) Nature of electrolyte or interionic attractions : Lesser 25. MOLAR CONDUCTIVITY (/m)
the solute-solute interactions, greater will be the freedom
of movement of ions and higher will be the conductance. It may be defined as the conducting power of all the ions
produced by dissolving one mole of an electrolyte placed
(ii) Solvation of Ions : Larger the magnitude of solute-solvent
between two large electrodes at one centimeter apart.
interactions, greater is the extent of solvation and lower
will be the electrical conductance. Mathematically,

N u1000
(iii) The nature of solvent and its viscosity : Larger the solvent- /m N u V, / m
solvent interactions, larger will be viscosity and more will C
be the resistance offered by the solvent to flow of ions where, V is the volume of solution in cm3 containing 1
and hence lesser will be the electrical conductance. mole of electrolyte and C is the molar concentration.

(iv) Temperature : As the temperature of electrolytic solution N u 1000 S cm 1

rises solute-solute, solute-solvent and solvent-solvent Units : /m
C mol cm 3
interactions decreases, this results in the increase of
electrolytic conductance. = ohm–1 cm2 mol–1 or S cm2 mol–1

24. MEASUREMENT OF CONDUCTANCE 26. EQUIVALENT CONDUCTIVITY (/eq)

1 A It is conducting power of one equivalent of electrolyte
As we know, N u The value of Ncould be known,
R A placed between two large electrodes at one centimeter apart.
if we measure l, A and R. The value of the resistance of Mathematically :
the solution R between two parallel electrodes is
determined by using ‘Wheatstones’ bridge method / eq Nu v
(Fig.)
N u1000
/ eq
N

Where, v is the volume of solution in cm3 containing

1 equivalent of electrolyte and N is normality.

Units :
N u1000
/ eq
N
S cm1 Ohm1 cm 2 equivalent 1
equivalent cm 3 or S cm 2 equivalent 1

27. VARIATION OF CONDUCTIVITY AND MOLAR

It consists of two fixed resistance R3 and R4, a variable CONDUCTIVITY WITH DILUTION
resistance R1 and the conductivity cell having the unknown
resistance R2. The bridge is balanced when no current Conductivity decreases with decrease in concentration,
passes through the detector. Under these conditions, this is because the number of ions per unit volume that
carry the current in the solution decreases on dilution.
R1 R3 R 1R 4
or R2
R2 R4 R3
Molar conductivity / m N u V increases with decrease
in concentration. This is because the total volume V of
solution containing one mole of electrolyte also increases.
ELECTROCHEMISTRY

It has been found that the decrease in Non dilution of a Here, O o and Oo are the limiting molar conductivities of
solution is more than compensated by increases in its cations and anions respectively.
volume.
30. APPLICATIONS OF KOHLRAUSCH’S LAW
Graphic representation of the variation of / m vs c
30.1 (i) Calculation of molar conductivities of weak
electrolyte at infinite dilution

For example, molar conductivity of acetic acid at infinite

dilution can be obtained from the knowledge of molar
conductivities at infinite dilution of strong electrolyte like
HCl, CH3COONa and NaCl as illustrated below.

ªOo  OoNa º  ¬ª OHo   O Cl ¼º  ¬ªOoNa  OCl

o
 º
¬ CH3  COO ¼ ¼

i.e. / m CH3  COOH / mo CH3  COONa  / om HCl  / om NaCl

o

28. LIMITING MOLAR CONDUCTIVITY (/m) 30.2 (ii) Determination of Degree of Dissociation
The value of molar conductivity when the concentration of Weak Electrolytes
approaches zero is known as limiting molar conductivity or
molar conductivity at infinite dilution. It is possible to / cm
determine the molar conductivity at infinite dilution / m in
o Degree of dissociation D
/ mo
case of strong electrolyte by extrapolation of curve of
/ m vs c. On contrary, the value of molar conductivity of 30.3 (iii) Determination of Dissociation Constant
weak electrolyte at infinite dilution cannot be determined (K) of Weak Electrolytes:
by extapolation of the curve as the curve becomes almost
parallel to y-axis when concentration approaches to zero. cD 2
K
1 D
The mathematical relationship between / m and / om for
strong electrolyte was developed by Debye, Huckel and / cm
Onsagar. In simplified form the equation can be given as also D
/ fm
/m / fm  b c1/ 2 2 2
c / cm / / fm C / cm
where / f
is the molar conductivity at infinite dilution ? K
m
1  / cm / / fm / fm / fm  / cm
and b is a constant which depends on the nature of the
solvent and temperature. 31. USE OF 'G IN RELATING EMF VALUES OF
HALF CELL REACTIONS
29. KOHLRAUSCH’S LAW
When we have two half cell reactions such that on adding
It states that the limiting molar conductivity of an electrolyte
them we obtain another half cell reaction then their emfs
can be represented as the sum of the individual contributions
cannot be added directly. But in any case thermodynamic
of the anion and cation of the electrolyte. In general, if an
functions like 'G can be added and emf values can be related
electrolyte on dissociation gives v+ cations and v– anions
through them. Consider the following three half cell reactions:
then its limiting molar conductivity is given by
Fe2+ + 2e– o Fe E1
/ fm v O o  v  Oo
 ELECTROCHEMISTRY

Fe3+ + 3e– o Fe E2 / cm
5. D
Fe3+ + e– o Fe2+ E3 / fm
We can easily observe that the third reaction can be where, D = Degree of dissociation
obtained by subtracting the first reaction from the second.
But the same relation does not apply on the emf values. / cm = Molar conductivity at a given
That is, E3 z E2 – E1. But the 'G values can be related concentration
according to the reactions. That is, 6. For a weak binary electrolyte AB
'G3 = 'G2 – 'G1 c / cm
2
cD 2
K
– n3FE3 = – n2FE2 + n1FE1 1 D / fm / fm  / cm
– E3 = – 3E2 + 2E1 where, K = Dissociation constant
ŸE3 = 3E2 – 2E1 Eocell E ocathode  E oanode
= Eo Right + Eo left
NOTE 7. Nernst equation for a general electrochemical reaction

We should always remember that emf values are additive aA + bB 
ne
o cC + dD
only when two half cell reactions are added to give a c d
complete balanced cell reaction. In any other case we RT C D
E cell E o
 In
will be using 'G values to obtain relations between emf cell
nF A
a
B
b

values. c d
2.303RT C D
E cell E o
cell  log a b
32. FORMULAE nF A B

§A· A B
a b
1. R U ¨ ¸ Uu Cell constant E cell E o

0.059
log at 298 K
©A¹ cell
n c
C D
d

where, R = Resistance
n
A = Area of cross-section of the electrodes. 8. log Kc = E ocell
0.0591
U= Resistivity
where, Kc = Equilibrium constant.
1 9. 'r G o  nFE ocell (Creterion of spontaneity)
2. N u cell constant
R
'r G o 2.303RT log K c
where, N = Conductivity or specific conductance
where, 'rGo = Standard Gibbs energy of the reaction.
N u 1000
3. /m 10. Q=I×t
M
where Q = Quantity of charge in coulombs
where, / m = Molar conductivity I = Current in amperes
M = Molarity of the solution. t = Time in seconds
11. m=Z×I×t
4. / mf (Ax By) = x / fm (Ay+) + y / fm (Bx–)
where m = mass of the substance liberated at the
f
where, / = Molar conductivity at infinite dilution x and y electrodes
m

are the number of cations and anions produced by one Z = Electrochemical equivalent.
formula unit of the electrolyte on complete dissociation. where E = Equivalent weight = E/96500
ELECTROCHEMISTRY

STANDARD REDUCTION POTENTIALS AT 298 K.

IN ELECTROCHEMICAL ORDER

H4XeO6 + 2H+ + 2e– o XeO3 + 3H2O + 3.0 Hg 2SO 4  2e  o 2Hg  SO 24 + 0.62
F2 + 2e– o 2F– + 2.87
MnO 24  2H 2 O  2e  o MnO 2  4OH  + 0.60
O3 + 2H+ + 2e– o O2 + H2O + 2.07

S2O 82  2e  o 2SO 24 + 2.05 MnO 4  e  o MnO24 + 0.56

Ag2+ + e– o Ag+ + 1.98 I2 + 2e o 2I

– –
+ 0.54
Co3+ + e– o Co2+ + 1.81 Cu+ + e– o Cu + 0.52
H2O2 + 2H + 2e o 2H2O
+ –
+ 1.78 I 3  2e  o 3I  + 0.53
Au + e o Au
+ –
+ 1.69 NiOOH + H2O + e o Ni(OH)2 + OH – –
+ 0.49
Pb4+ + 2e– o Pb2+ + 1.67
Ag 2 CrO 4  2e  o 2Ag  CrO 24 + 0.45
2HClO + 2H+ + 2e– o Cl2 + 2H2O + 1.63
O2 + 2H2O + 4e o 4OH – –
+ 0.40
Ce4+ + e– o Ce3+ + 1.61
2HBrO + 2H+ + 2e– o Br2 + 2H2O + 1.60 ClO4  H 2 O  2e  o ClO3  2OH  + 0.36

MnO 4  8H   5e  o Mn 2  4H 2 O + 1.51 [Fe(CN)6]3– + e– o [Fe(CN)6]4– + 0.36

Cu + 2e o Cu
2+ –
+ 0.34
Mn3+ + e– o Mn2+ + 1.51
Hg2Cl2 + 2e o 2Hg + 2Cl
– –
+ 0.27
Au3+ + 3e– o Au + 1.40
AgCl + e o Ag + Cl– –
+ 0.22
Cl2 + 2e– o 2Cl– + 1.36
Bi + 3e o Bi
–
+ 0.20
Cr2 O 27   14H   6e  o 2Cr 3  7H 2 O + 1.33
Cu + e o Cu
2+ – +
+ 0.16
O3 + H2O + 2e– o O2 + 2OH– + 1.24 Sn + 2e o Sn
4+ – 2+
+ 0.15
O2 + 4H+ 4e– o 2H2O + 1.23 AgBr + e o Ag + Br– –
+ 0.07
ClO4  2H  2e 
o ClO3  H2O + 1.23 Ti + e o Ti
4+ – 3+
0.00
MNO2 + 4H + 2e o Mn + 2H2O
+ – 2+
+ 1.23 2H + 2e o H2
+ –
0, by definition
Br2 + 2e o 2Br
– –
+ 1.09 Fe + 3e o Fe
3+ –
– 0.04
Pu4+ + e– o Pu3+ + 0.97 O2 H2O + 2e– o HO 2  OH  – 0.08
NO3  4H   3e  o NO  2H 2 O + 0.96 Pb2+ + 2e– o Pb – 0.13
In + e o In
+ –
– 0.14
2Hg 2  2e  o Hg 22 + 0.92
Sn + 2e o Sn
2+ –
– 0.14
ClO– + H2O + 2e– o Cl– + 2OH– + 0.89
AgI + e– o Ag + I– – 0.15
Hg2+ + 2e– o Hg + 0.86
Ni + 2e o Ni
2+ –
– 0.23
NO3  2H   e  o NO 2  H 2 O + 0.80
Co + 2e o Co
2+ –
– 0.28
Ag+ + e– o Ag + 0.80 In + 3e o In
3+ –
– 0.34
Hg 22 
 2e o 2Hg + 0.79 Tl e o Tl
+ –
– 0.34
Fe3+ + e– o Fe2+ + 0.77 PbSO4 + 2e– o Pb + SO 24 – 0.36
BrO + H2O + 2e o Br + 2OH
– – – –
+ 0.76
 ELECTROCHEMISTRY

Ti3+ + e– o Ti2+ – 0.37 V2+ + 2e– o V – 1.19

Cd2+ + 2e– o Cd – 0.40 Ti + 2e o Ti

2+ –
– 1.63

In2+ + e– o In+ – 0.40 Al3+ + 3e– o Al – 1.66

Cr3+ + e– o Cr2+ – 0.41 U + 3e o U

3+ –
– 1.79

Fe2+ + 2e– o Fe – 0.44 Sc + 3e o Sc

3+ –
– 2.09

In3+ + 2e– o In+ – 0.44 Mg + 2e o Mg

2+ –
– 2.36

S + 2e– o S2– – 0.48 Ce + 3e o Ce

3+ –
– 2.48

In3+ + e– o In2+ – 0.49 La3+ + 3e– o La – 2.52

U4+ + e– o U3+ – 0.61 Na + e o Na

+ –
– 2.71

Cr3+ + 3e– o Cr – 0.74 Ca + 2e o Ca

2+ –
– 2.87

Zn2+ + 2e– o Zn – 0.76 Sr + 2e o Sr

2+ –
– 2.89

Cd(OH)2 + 2e– o Cd + 2OH– – 0.81 Ba + 2e o Ba

2+ –
– 2.91

2H2O + 2e– o H2 + 2OH– – 0.83 Ra2+ + 2e– o Ra – 2.92

Cr2+ + 2e– o Cr – 0.91 Cs + e o Cs

+ –
– 2.92

Mn2+ + 2e– o Mn – 1.18 Rb + e o Rb

+ –
– 2.93
K +e oK
+ –
– 2.93
Li + e o Li
+ –
– 3.05

REDUCTION
POTENTIALS IN ALPHABETICAL ORDER

Ag+ + e– o Ag + 0.80 Ca2+ + 2e– o Ca – 2.87

Ag + e o Ag
2+ – +
+ 1.98 Cd(OH)2 + 2e o Cd + 2OH – –
– 0.81
AgBr + e o Ag + Br
– –
+ 0.0713 Cd2+ + 2e– o Cd – 0.40
AgCl + e o Ag + Cl
– –
+ 0.22 Ce + 3e o Ce
3+ –
– 2.48

Ag2CrO4 + 2e– o 2Ag + CrO 24 + 0.45 Ce4+ + e– o Ce3+ + 1.61

Cl2 + 2e o 2Cl – –
+ 1.36
AgF + e– o Ag + F– + 0.78
ClO– + H2O + 2e– o Cl– + 2OH– + 0.89
AgI + e– o Ag + I– – 0.15
Al3+ + 3e– oAl – 1.66 ClO4  2H   2e  o ClO3  H 2 O + 1.23

Au+ + e– o Au + 1.69 ClO4  H 2 O  2e  o ClO3  2OH  + 0.36

Au3+ + 3e– oAu + 1.40
Co2+ + 2e– o Co – 0.28
Ba + 2e o Ba
2+ –
+ 2.91
Co3+ + e– o Co2+ + 1.81
Be2+ + 2e– o Be – 1.85
Cr + 2e o Cr
2+ –
– 0.91
Bi3+ + 3e– o Bi + 0.20
Cr2 O 72  14H   6e  o 2Cr 3  7 H 2 O + 1.33
Br2 + 2e– o 2Br– + 1.09
BrO– + H2O + 2e– o Br– + 2OH– + 0.76 Cr3+ + 3e– o Cr – 0.74
Cr + e o Cr
3+ – 2+
– 0.41

Lakshya Educare
ELECTROCHEMISTRY

Cs+ e– o Cs – 2.92 MnO4  2H 2O  2e  o MnO2  4OH  + 0.60

Cu + e o Cu
+ –
+ 0.52 Na+ + e– o Na – 2.71
Cu + 2e o Cu
2+ –
+ 0.34 Ni + 2e o Ni
2+ –
– 0.23
Cu2+ + e– o Cu+ + 0.16 NiOOH + H2O + e o Ni(OH)2 + OH – –
+ 0.49
F2 + 2e– o 2F– + 2.87
NO3  2H   e  o NO 2  H 2O – 0.80
Fe2+ + 2e– o Fe – 0.44
Fe3+ + 3e– o Fe – 0.04 NO3  4H   3e  o NO  2H 2 O + 0.96

Fe3+ + e– o Fe2+ + 0.77 NO3  H 2 O  2e  o NO 2  2OH  + 0.10

[Fe(CN)6] + e o [Fe(CN)6]
3– – 4–
+ 0.36 O2 + 2H2O + 4e– o 4OH– + 0.40
2H + 2e o H2
+ –
0, by definition O2 + 4H + 4e o 2H2O
+ –
+ 1.23
2H2O + 2e– o H2 + 2OH– – 0.83
O 2  e  o O 2 – 0.56
2HBrO + 2H+ + 2e– o Br2 + 2H2O + 1.60
2HClO + 2H+ + 2e– o Cl2 + 2H2O + 1.63 O2 + H2O + 2e– o HO 2 + OH– – 0.08

H2O2 + 2H+ + 2e– o 2H2O + 1.78 O3 + 2H+ + 2e– o O2 + H2O + 2.07

H4XeO6 + 2H+ + 2e– o XeO3 + 3H2O + 3.0 O3 + H2O + 2e o O2 + 2OH – –
+ 1.24
Pb + 2e o Pb
2+ –
– 0.13
Hg 22  2e  o 2Hg + 0.79
Pb + 2e o Pb
4+ – 2+
+ 1.67
Hg2Cl2 + 2e– o 2Hg + 2Cl– + 0.27
Hg2+ + 2e– o Hg + 0.86 PbSO4 + 2e– o Pb + SO 24 – 0.36
Pt2+ + 2e– o Pt + 1.20
2Hg2+ + 2e– o Hg 22  + 0.92
Pu + e o Pu
4+ – 3+
+ 0.97
Hg2SO4 + 2e– o 2Hg + SO 24  + 0.62 Ra + 2e o Ra
2+ –
– 2.92
I2 + 2e– o 2I– + 0.54 Rb + e o Rb
+ –
– 2.93
I 3   S + 2e o S
– 2–
 2e o 3I + 0.53 – 0.48
In+ + e– o In – 0.14 S2 O82  2e  o 2SO 24 + 2.05
In + e o In
2+ – +
– 0.40 SC + 3e o Sc
3+ –
– 2.09
In + 2e o In
3+ – +
– 0.44 Sn + 2e o Sn
2+ –
– 0.14
In + 3e o In
3+ –
– 0.34 Sn + 2e o Sn
4+ – 2+
+ 0.15
In + e o In
3+ – 2+
– 0.49 Sr + 2e o Sr
2+ –
– 2.89
K +e oK
+ –
– 2.93 Ti + 2e o Ti
2+ –
– 1.63
La3+ + 3e– o La – 2.52 Ti + e o Ti
3+ – 2+
– 0.37
Li+ e– o Li – 3.05 Ti + e o Ti
4+ – 3+
0.00
Mg2+ + 2e– o Mg – 2.36 Tl + e o Tl
+ –
– 0.34
Mn2+ + 2e– o M – 1.18 U + 3e o U
3+ –
– 1.79
Mn3+ + e– o Mn2+ + 1.51 U +e oU
4+ – 3+
– 0.61
MnO2 + 4H+ + 2e– o Mn2+ + 2H2O + 1.23 V + 2e o V
2+ –
– 1.19
V +e oV
3+ – 2+
– 0.26
MnO 4  8H   5e  o Mn 2  4H 2 O + 1.51
Zn + 2e– o Zn
2+
– 0.76
MnO 4  e  o MnO24 + 0.56
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