Oxidation-Reduction

Course Tittle: Pharmaceutical Inorganic Chemistry-II

Course No.: PHAR-1205

Md. Shahin Sarker

Lecturer, Dept. of Pharmacy
Jashore University of Science & Technology (JUST)
 Oxidation-Reduction
• Oxidation and Reduction
• Oxidation is a reaction in which an atom or an ion loses one or more electrons and thus increases its
valency, i.e. in oxidation the atomic or ionic system loses one or more electrons and is changed into more
electropositive or less electronegative state. Due to the loss of electrons, oxidation is also called
dcelectronation.
• Reduction is a reaction in which an atom or an ion gains one or more electrons and thus decreases its
valency, i.e. in reduction the atomic or ionic system gains one or more electrons and is changed into less
electropositive or more electronegative slate.
 Oxidation number
• Oxidation number of an element is defined as the formal charge which an atom of that element
appears to have when electrons are counted. Oxidation number of an atom may be positive or
negative. For example (i) oxidation number of K and Br in KBr is +1 and - 1 respectively. (ii)
Oxidation number of N in NH3 is -3. In ionic compounds the oxidation state of an element is the
same as the charge on the ion formed from the atom of the element. For example in KBr, K is said
to be in + 1 oxidation state while Br is said to be in - 1 oxidation state.

• Rules for assigning oxidation numbers.

1. The oxidation number of an element in its elemental form is 0 (zero).
2. The oxidation number of a simple ion is equal to the charge on the ion. Both the size and the
polarity of the charge are part of the oxidation number: an ion can have a +2 oxidation number
or a -‐2 oxidation number. The “+” and “-‐“ signs are just as important as the number
3. The oxidation numbers of group 1A and 2A (group 1 and group 2) elements are +1 and +2
respectively.
4. In compounds, the oxidation number of hydrogen is almost always +1. The
most common exception occurs when hydrogen combines with metals; in this case
the oxidation number of hydrogen is typically –1.
5. In compounds, the oxidation number of oxygen is almost always –2. The most
common exception is in peroxides, when the oxidation number is –1. Peroxides are
compounds having two oxygen atoms bonded together. For example, hydrogen
peroxide is H-‐O-‐O-‐H. In hydrogen peroxide, each oxygen atom has a -‐1
oxidation number. When oxygen is bonded to fluorine, as in hypofluorous acid
(HOF), the oxidation number of oxygen is 0. Oxygen-‐fluorine compounds are
relatively rare and not too terribly important for our studies.
6. In compounds, the oxidation number of fluorine is always –1. The oxidation
number of other halogens (Cl, Br, I) is also –1, except when they are combined
with oxygen. The oxidation number of halides (except fluorine) combined with
oxygen is typically positive. For example, in ClO-‐, chlorine’s oxidation number is +1.
7. For a complex ion, the sum of the positive and negative oxidation numbers of all
elements in the ion equals the charge on the ion.
8. For an electrically neutral compound, the sum of the positive and negative oxidation
numbers of all elements in the compound equals zero
 Redox Reactions and Half Reactions
• Since loss or gain of electrons are relative terms, the gain or loss of electrons takes place simultaneously
in a chemical reaction. Thus the oxidation (i.e. loss of electrons) and reduction (i.e. gain of electrons)
reactions go hand in hand and such reactions in which oxidation and reduction take place simultaneously
are known as oxidation-reduction reactions or redox reactions. For example the reaction between Zn
and CuSO4 solution shown as

This is a redox reaction, since Zn atom (valency = 0) by losing two electrons is oxidized to Zn2+ion
(valency = +2) while Cu2+ ion (valency = +2) by gaining the same number of electrons lost by Zn atom gets
reduced to Cu atom (valency = 0). Thus we see that a redox reaction consists of two reactions—one
involves oxidation (e.g. Zn > Zn2+ ) and the other involves reduction (e.g. Cu2+ > Cu). Each of these
reactions is called half reaction. The reaction showing oxidation is called oxidation half-reaction while
that representing reduction is called reduction half-reaction. Thus the two half-reactions of which the
redox reaction (A) is composed of are
 Oxidising Agent (Oxidant) and Reducing Agent (Reductant
• An oxidising agent (atom, ion or molecule) is that substance which oxidises some other substance,
and is itself reduced to a lower valency state by gaining one or more electrons while a reducing
agent (atom, ion or molecule) is that substance which reduces some other substance, and is itself
oxidised to a higher valency state by losing one or more electrons.
 Equivalent Weights of Oxidizing Agents
• The equivalent weight of an oxidising agent (molecule or ion) is its that weight which can take up one electron,
i.e. the equivalent weight of an oxidizing agent is equal to its molecular weight or ion weight divided by the
number of electrons gained by its per molecule or per ion.
 Equivalent Weights of Reducing Agents
• The equivalent weight of a reducing agent (molecule or ion) is its that weight which can loss one electron.
i.e. the equivalent weight of a reducing agent is equal to its molecular weight or ion weight divided by the
number of electrons lost by its per molecule or per ion.
 Balancing Redox Equations by Oxidation Number Method
Balance the following equation by oxidation number method
The given equation shows that the oxidation number of Cu decreases from +2 (in CuO) to 0 (in Cu) while that of N increases
from -3 (in NH3) to 0 (in N2) and hence

In order to equalise the total increase in O.N. (= 3) to the total decrease in O.N. (= 2), we should have three
atoms of Cu for every two atoms of N and hence the equation should be written as

Now in order to balance O-atoms we should add 3H2O molecules to the right hand side. Thus
 Balance the following equation by oxidation number method.

The given equation shows that O.N. of Cr decreases from +6(in K2Cr2O7) to +3 [in Cr2(SO4)31 while that of Fe
increases from +2 (in FeSO4) to +3 [in Fe2(SO4)31 and hence

In order to equalise the total increase in O.N. (= 1) to the total decrease in O.N. (= 3) we should have one atom of Cr for every
three atoms of Fe or two atoms of Cr for every six atoms of Fe and hence above equation should be written as

In order to balance Fe atoms we should write the above equation as

Now in order to balance O-atoms we add 7H2O molecules to the right hand side and to balance H-atoms we write 7H2SO4 in
place of H2SO4 on the left hand side. Thus the equation in its balanced form becomes
 Oxidation-Reduction potential
• Electrode Potential: The potential difference between a metal and a solution containing its own
ions in a equilibrium is called electrode potential of that metal or electrode.
• Oxidation-Reduction potential or Redox potential: if the electrode is of oxidation-reduction
type and is dipped into a solution containing ions in two different oxidation states, then the
potential of the electrode is known as the oxidation-reduction or redox potential.
• For example, for a typical redox electrode, Sn/Sn++, the electrode reaction is:
• Sn ↔ Sn+2+ 2e ……………………….E = +0.15 v
• In the above redox reaction, the redox potential is +0.15 volt.
• Depending on the tendency of a metal to lose or gain electrons, the electrode potential may be two
types namely oxidation potential and reduction potential.
• Oxidation potential: It indicates the electron losing tendency of the metal.
• Reduction potential: It indicates the electron gaining capacity of the metal.
• Standard electrode potential: Standard electrode potential (E°) is the measure of individual
potential of a reversible electrode at standard state which is with solutes at an effective
concentration and gases at the pressure of 1 bar. The values are most often regulated at 25°C.
Standard hydrogen gas electrode is usually taken as a standard electrode potential.
 Oxidation-Reduction titration
• Principle : In oxidation-reduction titration, the oxidation potential of the solution undergoes a
more or less abrupt change near the equivalence point. Therefore, if a platinum electrode is
immersed in the solution to be titrated and the resultant half-cell is connected to a standard half-cell
of accurately known potential (e.g. a standard hydrogen electrode or a calomel electrode), then a
cell is constructed and the e.m.f. of which changes sharply near the equivalence point. Therefore, if
this e.m.f. is measured periodically by means of a potentiometer during the titration, the sharp
change of e.m.f. shows when the equivalence point is reached. This is the principle of oxidation-
reduction/ potentiometric titration of oxidizing and reducing agents.
• Application: The potentiometric method greatly extends the applicability of volumetric analysis
and is of great practical importance. It is used in the determination of the oxidation potential of
oxidizing and reducing agent as well as the oxidation-reduction reaction. It can also be applicable
in the neutralization method. For this the solution being titrated can be converted into a hydrogen
half-cell, which is then connected to a suitable standard half-cell and the e.m.f. of the resultant cell
is measured during the titration. Since in this -case, the e.m.f. depends on the H+ ion concentration
in the solution being titrated and this concentration changes abruptly at the equivalence point, the
latter can be easily detected.
Figure : Titration curve for the titration of 50.0 mL of 0.100 M
Fe2+ with 0.0200 M MnO4– at a fixed pH of 1 (using H2SO4). The
equivalence point is shown by the red dot.