DIRECT AND INDIRECT REDOX REACTIONS

DIRECT AND INDIRECT REDOX REACTIONS

• DIRECT REDOX REACTION:
• In a direct redox reaction, both oxidation and
reduction reactions take place in the same vessel.
• Chemical energy is converted to heat energy in a direct redox
reaction
• Electron produced doesn’t travel to large distance.
• In direct redox reactions, the transference of electrons from the
reducing agent to the oxidizing agent takes place in the same
container. Hence, no useful electric work is obtained.
Important observations when zinc rod is
placed in copper sulphate solution
• Zn rod starts dissolving and loses its mass gradually
• Blue colour of CuSO4 solution slowly fades
• Reddish brown deposits of Cu
• The reaction is slightly exothermic
Indirect redox reaction
• Oxidation and reduction occurs in different vessels
• The electron so produced has to travel a certain distance that leads to the
generation of the current
• Transfer of electrons between oxidising and reducing agent take place indirectly
through the conducting wires
• The decrease in energy during indirect redox reaction appears as electrical
energy
Electrochemical cell
• The device for carrying out indirect redox reaction is called electrochemical cell or
Voltaic cell or Galvanic cell.
• A Daniell cell is a Voltaic or Galvanic or an electrochemical cell in which
chemical energy is converted into electrical energy.
• A Daniell cell is the best example of a galvanic cell which converts
chemical energy into electrical energy.
• The main difference between Daniell cell and galvanic cell is that
Daniell cell uses only copper and zinc as electrodes whereas a galvanic
cell can have a variety of metals as electrodes.
• The Daniell cell consists of two electrodes of dissimilar metals,
Zn and Cu; each electrode is in contact with a solution of its own
ion; Zinc sulphate and copper sulphate respectively.
• The electrode at which oxidation occurs is called anode and is
negatively charged(in electrochemical cell)
• The electrode at which reduction takes place is called cathode and
is positively charged
 OXIDATION HALF CELL

OXIDATION HALF CELL REDUCTION HALF CELL

DANIELL CELL
Indirect redox raection
When key is inserted,the following are observed:

• There is deflection in voltmeter which indicates the flow of electrons through

wires
• Electron(s) flow from anode towards the cathode
• Zn rod loses mass and cu rod gains mass
• The flow of electrons stop after some time due to accumulation of charges (
positive charges at anode and negative charges at cathode)
• Therefore a salt bridge is used .
 Salt bridge
• A salt bridge consists of an inverted U-shaped glass tube. It is filled
with a concentrated solution of a salt such as KCl, KNO3 or NH4NO3 in
agar agar or gelatin to make a semisolid paste.. The two open ends
are closed with glass-wool plugs.
•
FUNCTIONS OF SALT BRIDGE

• COMPLETION OF CIRCUIT: it completes the circuit by connecting two

half cells and helps the current to flow.
• MAINTENANCE OF ELECTRICAL NEUTRALITY: It maintains electrical
neutrality of the solutions by allowing the migration of ions through
it. Thus it prevents the accumulation of charges.
REPRESENTATION OF A GALVANIC CELL
• 1. Half cell is constituted by redox couple ,represented by
M/Mn+ or Mn+/M where M is the symbol of the element and
Mn+ is the cation in electrolyte
• Slash(/) is the interface between two phases such as
solid/liq etc
• Zn/Zn2+ ----- oxidation half cell Zn → Zn2+ + 2e
• Cu2+/Cu ------ reduction half cell
• 2. oxidation half cell( anodic half cell) is written on LHS
whereas reduction half cell(cathodic half cell) is written on
RHS
• 3. These half cells are separated by two vertical lines which
indicate salt bridge
• Zn-CuSO4 cell → Zn/Zn2+ // Cu2+/Cu
• Q : Represent the cell in which the net cell reaction is
• Fe + Sn2+ → Fe2+ + Sn
• Fe/Fe2+ // Sn2+/Sn

• Name the cathode: Sn and anode: Fe

• Name the negatively charged electrode: Fe(anode)
• What is the direction of flow of electron? Fe to Sn
Electrode potential [ E ]
• When a strip of metal is placed in contact with the
solution of its own ions, it has either of two tendencies:
• a) Tendency of oxidation: metal strip develops a
negative charge due to accumulation of electrons
released and at the same time, solution develops a
positive charge due to formation of positive ions.
• b) Tendency of reduction: Mn+ + e → M, metal ions may gain
electron and get reduced and are deposited as metal ,the solution is
negative charge and strip becomes positive.
• There is separation of charges and it results into
potential difference being set up between strip and its
solution.
ELECTRODE POTENTIAL
• Electrical potential difference set up between metal and its
solution is called half cell electrode potential or single
electrode potential.
• According to present convention, half reactions are always
written as reduction half reaction and their potential are
represented by reduction potential.
• Ered(tendency to gain e) and Eox (tendency to lose e) are
numerically equal but have opposite signs
• For example : E0red of Zn2+/Zn = -0.76V
• E0oxid of Zn /Zn2+= +0.76V
Standard reduction potential( E0red)and cell
potential

• standard electrode potential: An electrode

potential measured under standard conditions
(298 K, 1 atm, and 1 M).
• standard reduction potential: (E0red ): Reduction
potential measured under standard conditions
(298 K, 1 atm, and 1 M).
•
Std EMF OR E0cell = E0 cathode – E0 anode

• E0cell = E0 (right)– E0(left)

• Calculate the Std EMF of the cell in which the following
reaction takes place
• Zn + Ni2+ →Zn2+ + Ni
• E0Zn2+/Zn = -0.76 V and E0Ni2+/Ni = -0.25 V

• E0 (cell)= E0 (cathode) – E0(anode)

• = -0.25 –(--0.76) = 0.51V
• Depict(represent) the galvanic cell for this reaction:
• Zn/Zn2+// Ni2+/Ni
Reference electrode
• It is not possible to measure the single electrode potential
or half cell electrode potential because independently half-
cell reaction cannot occur.

• It is not possible to measure the absolute value of

the single electrode potential directly. Only the difference
in potential between two electrodes can be measured
experimentally. It is, therefore, necessary to couple
the electrode with another electrode whose potential is
known.
• The commonly used reference electrode is Standard
Hydrogen Electrode (SHE) or also called as Normal
Hydrogen Electrode (NHE).
Standard hydrogen electrode (she)
• Standard Hydrogen Electrode is used as a reference
electrode when calculating the standard electrode potential
of a half cell.
• The electrode whose potential is arbitrarily fixed or is
exactly known at the given constant temperature is a
reference electrode.
• The standard reduction potential of SHE is arbitrarily fixed
as zero
Standard Hydrogen Electrode

• A platinum electrode which is covered in finely powdered

platinum black (platinized platinum electrode).
• A solution of acid having a H+ molarity of 1 mole per cubic
decimeter.
• Pure and dry hydrogen gas is bubbled through HCl solution
from a inlet at a constant pressure of 1 atm
• Hydrogen gas is adsorbed on the platinum plate and acts
as hydrogen electrode
• If SHE acts as anode , then the reaction is
• H2(g) →2H+(aq) + 2e

• If SHE acts as cathode , then the reaction is

2H+(aq) + 2e → H2(g)
Representation of she
• If it acts as an anode,
• Pt, H2(g)(1atm)/H+(aq) (1M)

• If it acts as a cathode,
• H+(aq) (1M)/ H2(g)(1atm),Pt
• An Electrochemical Cell Is Setup in which a zinc rod is dipped in
1 M zinc Sulphate solution. This half-cell is combined with a
standard hydrogen electrode through a salt bridge. The deflection
of the voltmeter indicates that current is flowing from hydrogen
electrode to metal electrode or the electrons are moving from
zinc rod to hydrogen electrode. Hence the zinc electrode acts as
an anode and the hydrogen electrode acts as cathode .in this
case the reading (EMF) by the voltmeter is 0.76 V. The cell can be
represented as

• Zn + 2H+ → Zn2+ +H2

• Calculations

• The EMF of the cell is 0.76 volt

• E0Cell = EoCathode - EoAnode

• 0.76 = 0 - EoZn2+/Zn or EoAnode = -0.76 V

• Hence reduction potential of zinc will be – 0.76 V

Determination of Standard Electrode
Potential of Cu2+/Cu Electrode:

• An Electrochemical Cell Is Setup in which a copper rod is dipped in 1 M copper

Sulphate solution. This half-cell is combined with a standard hydrogen electrode
through a salt bridge. The deflection of the voltmeter indicates that current is
flowing from copper electrode to hydrogen electrode or the electrons are
moving from hydrogen rod to copper electrode. Hence the copper electrode acts
as an cathode and the hydrogen electrode acts as anode. In this case the
reading (EMF) by the voltmeter is 0.34 V. The cell can be represented as

• Cu2+ + H2 → 2H+ + Cu
• Calculations

• The EMF of the cell is 0.34 volt

• E0 Cell = Eo Cathode - Eo Anode

• 0.34 = Eo Cathode - 0

• Hence reduction potential of copper is +0.34V

Electrochemical series
• The electrochemical series is built up by arranging various
redox equilibria in order of their standard electrode
potentials (redox potentials).
• The standard reduction potentials of a large number of
electrodes have been measured using standard hydrogen
electrode as the reference electrode. These various
electrodes can be arranged in increasing or decreasing
order of their reduction potentials.
• The greater the reduction potential of an element the more
easily it will be reduced. Meanwhile, elements that have low
reduction potential will get oxidized much quickly and
easily.
Application of Electrochemical Series

• 1. Oxidising and Reducing Strengths

• Electrochemical series helps us to identify a good oxidising
agent or reducing agent.
• All the substance appearing on the top of the electrochemical series are a
good oxidising agent i.e., they have positive Value of standard reduction
potential
• whereas those appearing on the bottom of the electrochemical series are
a good reducing agent i.e., they have a negative value of standard
reduction potential.
• For Example, F2 electrode with the standard reduction potential value of
+2.87 is a strong oxidising agent and Li+ with standard reduction potential
value of -3.05 volts is a strong reducing agent.The more is the reduction
potential, more is the oxidizing power
2. Calculation of Standard emf (E0) of Electrochemical
Cell

• As oxidation takes place at anode and reduction takes place

at the cathode. Hence,
• Eocell = Eo cathode – Eo anode
• For a reaction, 2Ag+ (aq) + Cd → 2Ag + Cd+2(aq)
• The standard reduction potential given are: Ag+/ Ag =0.80
volt, Cd+2/ Cd = -0.40 volt
• From the reaction, we can see that Cd losses electron and
Ag+ gains. Hence, oxidation half cell or anode is Cd.
• Using the formula,
• Eocell = Eocathode – Eoanode
• =0.80 -(-0.40)
• = 1.20 V
PREDICTING THE FEASIBILITY OF A REDOX
REACTION
• For example, let us find out whether we can store
copper sulphate solution in a nickel vessel or not.
• Given: Ni+2/ Ni = -0.25 volt, Cu+2/Cu = 0.34 volt
• Ni + CuSO4 → NiSO4 + Cu
• We want to see whether Ni metal will displace copper
from copper sulphate solution to give NiSO4 by
undergoing oxidation reaction.
• Ni(s) + Cu+2(aq) → Ni+2(aq) + Cu(s)
• From the above reaction, it is clear oxidation terminal
will be Ni electrode.
• Eocell = Eocathode – Eoanode
• = 0.34 – (-0.25)
• = 0.59 volt
• As the emf comes out to be positive, it implies copper
sulphate reacts when placed in a nickel vessel and
hence cannot be stored in it.
Ques
• The standard reduction potential at 250C for the following half-
reaction are given below:
• Zn+2(aq) + 2e– → Zn(s); -0.76 volt
• Cr+3 (aq) + 3e– → Cr(s); -0.740 volt
• Cu+2(aq) + 2e– → Cu(s); 0.34 volt
• Fe+3 + e– → Fe+2 ; 0.77 volt
• Which is the strongest reducing agent
1.Zn
2.Cr
3.Cu
4.Fe+3
The standard reduction potential at 250C for the
following half-reaction are given below:
Zn+2(aq) + 2e– → Zn(s); -0.76 volt
Cr+3 (aq) + 3e– → Cr(s); -0.740 volt
Cu+2(aq) + 2e– → Cu(s); 0.34 volt
Fe+3 + e– → Fe+2 ; 0.77 volt
• Solution : Option 1
• Reducing agent is a chemical species that loses an
electron to another chemical species in a redox
chemical reaction. Since, reducing agent loses
electron so it is oxidised. Out of the following given
half-reaction, the reduction of Zn+2 has the lowest
reduction potential(-0.762). We know that
• Oxidation potential = -(reduction potential)
• So in terms of standard oxidation potential Zinc will
have the highest oxidation potential i.e, 0.762 volts.
Therefore, zinc is the strongest reducing agent.
Ques
• . The standard oxidation potential, E0 for the half-reactions are
as follows,
• Cu → Cu+2 + 2e; E0 = +0.34 volts
• Fe → Fe+2 + 2e ; E0 = - 0.41 volts
• Calculate the emf of the cell, Cu+2 + Fe → Cu + Fe+2
• Solution:
• Eocell = Eocathode – Eoanode

• Eocell = 0.34-(-0.41)
• Eocell = 0.75 V
QUESTIONS
• 1.A cell is prepared by dipping a Cu rod in 1M CuSO4
solution and a nickel rod in 1M NiSO4 solution. The standard
reduction potentials of Cu and Ni are 0.34V and -0.25V
respectively.

• i) Which electrode will work as anode and which as

cathode? Ni = anode Cu= cathode
Ii)Write the overall cell reaction.
Iii)How is cell represented?
Iv)Calculate standard EMF of the cell. 0.59 V
• At anode : Ni → Ni2+ + 2e
• At cathode : Cu2+ + 2e → Cu
• --------------------------------------------------------
• Net reaction : Ni + Cu2+ → Ni2+ + Cu
• n factor : total e lost or gained during a redox
reaction= 2

• Ni/Ni2+// Cu2+/Cu
q2
• 2.Two half cells are Al3+(aq) /Al and Mg2+(aq) /Mg.The
reduction potentials of these half cells are --1.66V and
-2.36V respectively.
i)Calculate the cell potential. E 0= -1.66-(-2.36) =0.70 V
ii)Write the cell reaction also.
iii) Indicate the n factor and identify the negatively charged
electrode.
n factor – total e gained or lost during a redox reaction