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Srikanth K V K
 OXIDATION
• Oxidation is the loss of electrons during a reaction by a
molecule, atom or ion. Oxidation occurs when the
oxidation state of a molecule, atom or ion is increased.
 2Mg + O2  2Mgo (Addition of Oxygen)
 2FeCl2 + Cl2  2FeCl3 (Addition of electro negative
element)
 H2s + Cl2  2HCl + S (Removal of hydrogen)
 Hg2Cl2 + SnCl4  2HgCl2+ SnCl2 (Removal of electro
positive element)

loses one or more electrons -

Oxidation
 REDUCTION
• Oxidation is the gain of electrons during a reaction by a
molecule, atom or ion. Reduction involves a half-reaction in
which a chemical species decreases its oxidation number,
usually by gaining electrons.
 H2 + Cl2  2HCl (Addition of hydrogen)
 2HgCl2 + SnCl4  Hg2Cl2 + SnCl4 (Addition of electro positive
element)
 ZnO + C  Zn + CO (Removal of oxygen)
 2FeCl3 + H2S  2FeCl2 + 2HCl + S (Removal of electro
negative element)

Gains one or more elections - Reduction

 OXIDIZING AGENT
Supplies oxygen to electro negative element
Removes hydrogen from electro positive element
An oxidizing agent (often referred to as an oxidizer
or an oxidant) is a chemical species that tends to oxidize
other substances, i.e. cause an increase in the oxidation
state of the substance by making it lose electrons.
Common examples of oxidizing agents include
halogens (such as chlorine and fluorine), oxygen, and
hydrogen peroxide (H2O2).

 MnO2 + 4 HCl  MnCl2 +Cl2 +2H2O

 K2Cr2O7 + 3SO2 + H2SO4  Cr2 (SO4)3 + K2SO4 + H2O
 10HNO3 + I2  10NO2 + 2HIO3 + H2O
 REDUCING AGENT
A substance which loses electrons to other substances
in a redox reaction and gets oxidized to the higher
valancy state is called a reducing agent.
A reducing agent is one of the reactants of an oxidation-
reduction reaction which reduces the other reactant by
giving out electrons to the reactant. If the reducing
agent does not pass electrons to other substance in a
reaction, then the reduction process cannot occur.

 Fe2O3 + 3CO  2Fe + 3CO2

 CuO + C  CO + Cu
 Fe2O3 + 2Al  2Fe + Al2O3
Oxidation state of an atom
• The oxidation state of an atom (sometimes referred to as the
oxidation number) in a chemical compound provides insight
into the number of electrons lost it and, therefore, describes
the extent of oxidation of the atom.
• Oxidation number, also called oxidation state
• The iron ion Fe3+, for example, has an oxidation number of +3
because it can acquire three electrons to form a chemical
bond, while the oxygen ion O2− has an oxidation number of −2
because it can donate two electrons. In an electronically
neutral substance, the sum of the oxidation numbers is zero;
for example, in hematite (Fe2O3) the oxidation number of the
two iron atoms (+6 in total) balances the oxidation number of
the three oxygen atoms (−6).
 Zn + 2HCl  ZnCl2 + H2
Zn  Zn2+ +2e-
H+ + e-  H2
• Free State: Oxidation state  0 (Zero)
Ex: H,P,O,Fe, Br2, O2, P4 etc
• Cation/ Anion (A+/B-)  Magnitude of Charge
Ca  Ca2+  +2
Al  Al3+  +3
Cl  Cl-  -1
• Algebraic sum of oxidation numbers of all atoms of neutral
compound is Zero
• Algebraic sum of oxidation numbers of all atoms of an ion is
equal to charge on the ion
• Oxidation state of alkali metals (IA group) is +1
• Oxidation state of alkali earth metals (IIA group ) is +2
• Generally Hydrogen  +1
But when in metallic hydrides like KH, NaH, MgH2  -1
• Oxygen  -2
In peroxide  -1
But for OF2 - +2
O2F2  +1
KO2  - ½
• Fluorine (electro negative element)  -1
• Halogens  -1
• IF7  +7
• KClO3  +5
• Each atom in an element either in its free or un combined state holds up an oxidation number
of zero. Clearly, each atom in H2, Cl2, P4, Na, Al, O2, O3, S8, and Mg, has an oxidation number
zero.
• The oxidation number of ions which comprise of only one atom is equal to the actual charge on
the ion.
• In most of the compounds, the oxidation number of oxygen is –2. There are two exceptions
here.
• Peroxides- Every oxygen atom is allocated an oxidation number of –1. Example, Na 2O2
• Super oxides- Every oxygen atom is allocated an oxidation number of –(1/2). Example, KO 2
• Oxygen is bonded to fluorine- Example, di-oxygen di-fluoride where the oxygen atom is allocated an
oxidation number of +1.
• Hydrogen’s oxidation number is +1, excluding when it is bonded to metals containing two
elements. For example, CaH2, its oxidation number equals to –1.
• Fluorine and other halogens have an oxidation number –1 when they appear as halide ions in
their compounds. When iodine, chlorine, and bromine are combined with oxygen, their
oxidation number is positive.
• When the oxidation number of the atoms of a compound are added together the algebraic sum
must be equal to zero. In case of polyatomic ion, when the oxidation number of the atoms of
an ion are added together the algebraic sum must be equal to the charge on the ion. Consider
(CO3)2– the algebraic sum of oxidation number of one carbon atom and three oxygen atom is
 Rules for Assigning Oxidation States
• The oxidation state (OS) of an element corresponds to the
number of electrons, e-, that an atom loses, gains, or appears to
use when joining with other atoms in compounds. In determining
the oxidation state of an atom, there are seven guidelines to
follow:
• The oxidation state of an individual atom is 0.
• The total oxidation state of all atoms in: a neutral species is 0 and
in an ion is equal to the ion charge.
• Group 1 metals have an oxidation state of +1 and Group 2 an
oxidation state of +2
• The oxidation state of fluorine is -1 in compounds
• Hydrogen generally has an oxidation state of +1 in compounds
• Oxygen generally has an oxidation state of -2 in compounds
• In binary metal compounds, Group 17 elements have an
oxidation state of -1, Group 16 elements of -2, and Group 15
elements of -3.
Ex 1
Assigning Oxidation States
Determine the Oxidation State of the bold element in each of the
following:
• Na3PO3
• H2PO4-
Solutions
• The oxidation numbers of Na and O are +1 and -2. Because sodium
phosphite is neutral, the sum of the oxidation numbers must be zero.
• Let x be the oxidation number of phosphorus, 0= 3(+1) + x + 3(-
2). x=oxidation number of P= +3.
• Hydrogen and oxygen have oxidation numbers of +1 and -2. The ion
has a charge of -1, so the sum of the oxidation numbers must be -1.
Letting y be the oxidation number of phosphorus, -1= y + 2(+1) +4(-
2), y= oxidation number of
P= +5.
Ex 2
Determine the Oxidation States of each element in the following
reactions:
• Fe(s)+O2(g)→Fe2O3(g)Fe(s)+O2(g)→Fe2O3(g)
• Fe2+Fe2+
• Ag(s)+H2S→Ag2S(g)+H2(g)Ag(s)+H2S→Ag2S(g)+H2(g)
Solutions
• Fe and O2 are free elements; therefore, they each have an
oxidation state of 0 according to Rule #1. The product has a total
oxidation state equal to 0, and following Rule #6, O has an
oxidation state of -2, which means Fe has an oxidation state of +3.
• The oxidation state of Fe corresponds to its charge; therefore, the
oxidation state is +2.
• Ag has an oxidation state of 0, H has an oxidation state of +1
according to Rule #5, S has an oxidation state of -2 according to
Rule #7, and hence Ag in Ag2S has an oxidation state of +1.
Electro chemical cell

Galvanic cell or
Voltaic cell
Spontaneous
chemical reaction
Non spontaneous
chemical reaction
Electrolytic cell
Electro chemical cell
 Galvanic cell or Voltaic cell
• It was invented by a British chemist John F Daniel in
1836. And in this cell ZINC and COPPER electrodes and
electrolyte is used.

It has two half - cells, each having a beaker containing a

metal strip that dips in its aqueous solution. The metal strips
are called electrodes and are connected by an conducting
wire. Two solutions are connected by a salt bridge.
It converts Chemical energy to Electrical Energy
LAON – Left/ Anode/ Oxidation/ Negative
RCRP – Right/ Cathode/ Reduction/ Positive
 Parts of Galvanic Cell

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.

External circuit – Conducts the flow of electrons between

electrodes

Load – A part of the circuit utilizes the electron to flow to

perform its function.
Electrode potential
• Potential difference that exists between
electrolytes and the electrode is known as
Electrical Potential

Oxidation potential
• It is a measure of the tendency of a chemical
species to lose elections and thereby be
oxidized
Reduction potential
• It is a measure of the tendency of a chemical
species to acquire elections and thereby be
reduced

Zn (s)  Zn2+ + 2e- Oxidation

Potential

Cu2+ (aq) + 2e-  Cu (s)

Reduction
Potential
IF ZINC IS REDUCED????
Zn2+ + 2e-  Zn (s)

• It is called Reduction potential of Zn.

E0red

E red = - E oxd
0 0

E0Zn2+l Zn = - E0 Zn lZn2+
 STANDARD POTENTIAL

• Concentration of all electrolytic solutions are 1 Molar

• Temperature = 298 K or 25 degree centigrade
• Pressure = 1 atm
When the concentrations of all species involved in a half cell
is unity, then the electrode potential is known as Standard
Potential. It is denoted with E0
NOTE IMP

• If there is no mention of oxidation or reduction

potential in the problem, assume that it to be
REDUCTION POTENTIAL

• E0Zn2+l Zn = -0.76 V
• E0Cu2+l Cu = +0.34 V
SHORTHAND NOTATION FOR
GALVANIC CELL
SHORTHAND NOTATION FOR
GALVANIC CELL
Free energy changes for cell reaction
• The free energy change ΔG (thermo chemical
quantity) and the cell potential E
(Electrochemical quantity) both measure the
driving force of a chemical reaction.
Example

• Calculate E0 cell of (at 298 K),

Zn(s)/ZnSO4 ll CuSO4/Cu given that
E0 Zn lZn2+ = 0.76 V, E0 Cu lCu2+ = -0.34 V
• Soln:
EoCell = (SRP)Cathode - (SRP)Anode
= 0.34 – (- 0.76)
= 1.1 V
Example

• Given that E0 Cu2+/Cu = 0.337 V and E0 Cu lCu2+ = - 0.153 V. Then Calculate E0 Cu+ lCu-
• Soln:
Cu2+ + 2e-  Cu ΔG1
Cu+  Cu2+ + 2e- ΔG2
After adding

Cu+ + e-  Cu
ΔG1 + ΔG2 = ΔG3 We know ΔG = -nFE

-2FE01 – FE02 = -FE03

E3 = 2 E01 + E02

= 2 x 0.337 - 0.153 = 0.647 – 0.153 = 0.521 V

 NERNST EQUATION
 The Nernst equation provides a relation between the cell potential
of an electrochemical cell, the standard cell potential, temperature,
and the reaction quotient. Even under non-standard conditions, the
cell potentials of electrochemical cells can be determined with the
help of the Nernst equation.
 The Nernst equation is often used to calculate the cell potential of
an electrochemical cell at any given temperature, pressure, and
reactant concentration. The equation was introduced by a German
chemist Walther Hermann Nernst.
 Nernst equation is an equation relating the capacity of an atom/ion
to take up one or more electrons (reduction potential) measured at
any conditions to that measured at standard conditions (
standard reduction potentials) of 298K and one molar or one
atmospheric pressure.
NERNST EQUATION FOR SINGLE
ELECTRODE POTENTIAL
THERMODYNAMICS OF CELL
POTENTIAL
 ΔGo = -nFEocell
 ΔG = -nFEcell
 G = H – TS
Gibbs free energy G is defined as G = H - TS where H, T, and S
are the enthalpy, temperature, and entropy. The SI unit for
Gibbs energy is the kilojoule.
From thermodynamics
H = E + PV (Enthalpy function)
G = E + PV – TS
THERMODYNAMICS OF CELL
POTENTIAL
G = E + PV – TS
By partial differentiation
dG = dE +PdV + VdP – TdS – SdT ---------------- (i)
According to 1st law of thermodynamics
E = q +W
Where,
ΔU or E = change in internal energy of the system.
q = algebraic sum of heat transfer between system and
surroundings.
W = work interaction of the system with its surroundings.
 THERMODYNAMICS OF CELL
POTENTIAL
 E = q +W
First law of Thermodynamics for a Closed System
Work done for a closed system is the product of pressure
applied and the change in volume that occurs due to applied pressure :
 W = − P ΔV dW = -PdV
Where P is the constant external pressure on the system,
and ΔV is the change in volume of the system. This is specifically called
“pressure-volume” work.
E = dq – PdV
dq = dE + PdV ---------- (2)
 THERMODYNAMICS OF CELL
POTENTIAL
According to 2nd law of thermodynamics

 The first law of thermodynamics provides the definition of the internal energy
of a thermodynamic system, and expresses the law of conservation of energy.
The second law is concerned with the direction of natural processes.
dQ = TdS --------- (3)
From (i), (ii) and (iii)
dG = dE +PdV + VdP – TdS – SdT --------- (i)
dq = dE + PdV - --------- (2)
dq = TdS --------- (3)
dG = VdP - SdT
THERMODYNAMICS OF CELL
POTENTIAL
dG = VdP – SdT
At constant pressure, which is actually the condition for
all normal cell reactions
dG = - SdT
S=
ΔS =
We know that ΔG = -nFEcell
ΔS = +nF
THERMODYNAMICS OF CELL
POTENTIAL
 dEcell/dT = temperature coefficient of cell
reaction
ΔG = ΔH – TΔS
ΔH = ΔG + TΔS
Where ΔS = +nF and ΔG = -nFEcell
ΔH = -nFEcell + nFT (dEcell/dT)
Faraday’s law of electrolysis
 First law
The mass of deposited/ released/ produced of any
substance during electrolysis is proportional to the
amount of charge passed into the electrolyte
W∞Q
W = ZQ where I = Q/t ; Q = it
Z – electrochemical equivalent of the
substance
Z = W/Q = mass/ coulomb = kg/C or g/C
Faraday’s law of electrolysis
 Equivalent mass (E) : mass of any substance produced when 1
mole of electrons are passed through the solution during
electrolysis.
 E=