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Electrochemistry

B.R.Thorat
Department of Chemistry
Govt. of Maharashtra

Ismail Yusuf College, Jogeshwari (E), Maharashtra 400060

Electrochemistry
Branch of chemistry which deals with relationship between chemical reactions
(Redox reaction, Chemical Energy) and Electrical Energy
With proper arrangement

Converts Chemical energy


into Electrical energy

Converts Electrical energy


into Chemical energy

Galvanic cell / Voltaic cell

Electrolytic cell

ELECTROLYTIC CELL:
It is the arrangement in which electric energy is used to begin about a chemical change or it
is a device which can convert electric energy into chemical energy.
E.g. Charging of lead storage battery

GALVANIC CELL:
It is the arrangement in which chemical energy can be transformed into electrical energy.
E.g. Discharging of lead storage battery, Daniel cell.

Electrodes: Conduct
electricity between cell and
surroundings

Inactive
electrode: sites
for oxid. & red.

Electrolyte: Mixture of the


ions involved in reaction or
carrying charge

Active electrode:
Participate in
redox reaction

Salt bridge: Used to


completes circuit (provides
charge balance)
Cathode: Reduction occurs
at the cathode.

Anode: Oxidation occurs at


the anode.

Cell

A cell is a single arrangement of two electrodes and


an electrolyte capable of yielding electricity due to
chemical change in the cell or of producing chemical
change due to passage of electricity through the cell

Battery

A battery is a combination of two or


more cells arranged in series or
parallel

E.g.:- An ordinary 6-volt lead storage battery is a combination of 3-volt cells connected
in series

ORGINE OF THE EMF


CONCEPT OF ELECTRODE POTENTIAL (NERNST THEORY):An electrode is the combination of metal/element and its ionic solution.
E.g.:- Cu | Cu2+(aq), Zn | Zn2+(aq), Pt, H2(g) | H+(aq), Cd | Cd2+(aq).
According to the Nernst theory (1889) of electrode potential, the electrons are liberated or accepted
due to the electro nation and de-electro nation which occurs at the surface of electrodes.
DE-ELECTRONATION (OXIDATION):Certain metals when dipped into their salt
solution, they shows tendency to enter into the
solution in the form of cations leaving behind the
electron on the surface of metal. These
tendencies of metals are known as solution
pressure (Ps). Due to the free electrons on the
surface of metal, the metallic electrode becomes
a negatively charged and the excess cations in
the solution create positive charge in the
solution. Due to electrostatic force, the further
transfer of the metal to the solution is prevented
and an electrical double layer is formed at the
electrode. This is known as de-electronation.

(1) Zn(S) Zn2+(aq) + 2e-,


(2) Cd(S) Cd2+(aq) + 2e(3) H2(g) 2H+(aq) + 2e(4) Cu(S) Cu2+(aq) + 2e(5) M(S) Mn+(aq) + ne-.

ELECTRONATION (REDUCTION):Some metals when dipped into its salt solution


cation have a tendency to deposit on the surface
of metal in the form of metal. This tendency of
the metal ion is known as osmotic pressure (Po).
Due to this process, the negative charge density
of anion increased in the solution and metallic
electrode become positive charged. Due to the
electrostatics force further deposition of metallic
ion is prevented and an electric double layer is set
up at the electrode. This is known as electro
nationMetal rod
Vessel

+ +
+ +
+ +
+ +
++ +

(1) Cu2+(aq) + 2e- Cu(S),


(2) Ag+(aq) + e- Ag(S),
(3) Mn+(aq) + ne- Mn(S)

salt solution
electric double layer

RELATION BETWEEN PS AND PO


The metal when dipped into its salt solution gives an electrode, these electrode has
solution pressure (Ps) of the metal and osmotic pressure (P o) of the cation in the solution
simultaneously. The magnitude and sign of the potential difference between the metal
and solution is determined from the relative magnitude of P s and Po.

There are three cases as(1) PS >PO:In such case, positive (metal ) ions passed more rapidly into solution leaving behind the
electrons on the surface of the electrode so that the electrode become negative charged
and solution become positive charged for example- Active metals like Zn ,Cd , Mn Ni
alkali metals etc.
Zn Metal rod
Zn
Vessel
+
+
+
+
+
+
+ + +

+
+
+
+
+
+
+

ZnSO4
salt solution
electric double layer

(2) Po >Ps:
In such case, the positive ions of metals in the solution are
deposited more rapidly on the metal rod, so that the
electrode become positively charged and solution become
negatively charged for example less active metals like Cu,
Ag, Au etc. in its salt solution.

Cu Metal rod
Cu
Vessel
+ +
+ +
+ +
+ +
++ +

CuSO4 salt solution


electric double layer

(3)Ps = Po:In such case, neither the metal ion into the solution nor the metal
ion deposited ion on the surface of metal rod, so that metal and
solution do not acquire any charge and no potential difference
can be exist such electrode is called as null electrode.

For construction of electrochemical cell it is necessary to have one electrode negatively


charged and the other positively charged, so that electron can flow from the negative electrode
to positive electrode through the external circuit.

ELECTROCHEMICAL CELL
Electrochemical cell is a device is used to generate
electrical energy at the expense of spontaneous
oxidation-reduction.
The electrochemical cell is also called Galvanic cell or
Voltaic cell i.e. the electrochemical cell can be convert
chemical energy into electrical energy.
A single electrochemical cell is formed by the
combination of two electrodes One act as anode
(negative electrode) and other act as cathode
(positive electrode).

E.g.:- A simple galvanic cell is set up by dipping Zinc and copper rods / plates
into sulphuric acid solution or by dipping Zinc and Copper rods or plates into the
solution of their respective salts.
The electrical neutrality is maintained by using the porous partition or by a salt
bridge. These can be explaining with the help of typical example- Daniel cell.

DANIEL CELL
[Zn(s) | ZnSO4 | CuSO4 | Cu(s)]
(A) CONSTRUCTION:
A Daniel cell consist of two half electrodes. The metallic copper is dipped into its salt
solution such as CuSO4. This half cell can be represented as- Cu | CuSO4 or Cu | Cu++
and the another half cell is the metallic Zinc is dipped into its salt solution such as
ZnSO4 .This half cell can be represented as- Zn | Zn++ or Zn | ZnSO4.
The single vertical line indicates the electrode-electrolyte interface. These two half cells
are combined by using three difference methods are-

(a) BY
USING
POROUS
PARTITION:
A porous partition is kept in the vessel which
divides it into two compartments. A one
compartment containing ZnSO4 solution and
another containing a CuSO4. The Zinc and
copper rods are dipped into its respective salt
solution. This zinc and copper electrodes are
connected by the metallic wire. The electron is
flow from the zinc to copper electrode.

BY USING POROUS POT


There are two different methods of combining two half cells by using porous pot.

It consists of glass vessel containing a


solution of CuSO4. A porous spot
containing ZnSO4 solution which is
immersed in the copper sulphate
solution. A copper and zinc rod are
dipped into its salt solution. The zinc
and copper rods are connected by the
metallic wire. The current is flow from
zinc electrode to copper electrode

e
Zn electrode

e
+
Copper vessel (Cu electrode)
porous spot

ZnSO4 solution
CuSO4 solution

e
Cu electrode

Zn electrode
Glass vessel
porous spot
ZnSO4 solution
CuSO4 solution

It consists of an outer copper vessel


containing a CuSO4 solution. A porous
spot containing ZnSO4 solution & is
dipped into CuSO4 solution. A zinc rod is
dipped into its salt solution. Zinc rod and
a copper vessel are connected by a
metallic wire. The electron is flow from
zinc rod to copper vessel

USING A SALT BRIDGE

The two half cells are connected by the salt bridge. The solution of CuSO4 and ZnSO4
are taken into two different vessels containing zinc and copper rod in respective salt
solution. These two vessels are connected by a salt bridge. The zinc and copper
electrode are connected by a metallic wire. The electron flows from zinc to copper
electrode.

Connected this way the reaction starts


Stops immediately because charge builds up.

H+

MnO4-

Fe+2

Galvanic Cell
Salt
Bridge
allows
current
to flow
H+

MnO4-

Fe+2

Electricity

travels in a complete circuit

H+

MnO4-

e-

Fe+2

Voltmeter

Zn ()

Zn2+

Salt bridge
Na+
SO42

(+) Cu

Cu2+

Voltmeter
e
Anode Salt bridge
+
Zn () Na
SO 2

(+) Cu

Zn2+
Oxidation half-reaction
Zn(s)
Zn2+(aq) + 2e

Cu2+

e
2e lost
per Zn atom
oxidized

Zn

Zn2+

Voltmeter
e
Anode Salt bridge
+
Zn () Na
SO 2

(+) Cu

Zn2+
Oxidation half-reaction
Zn(s)
Zn2+(aq) + 2e

Cu2+

e
2e lost
per Zn atom
oxidized

Zn

Zn2+

Voltmeter
e
e
Anode Salt bridge Cathode
+
Zn () Na
SO 2 (+) Cu
4

Zn2+

Cu2+

Oxidation half-reaction
Zn(s)
Zn2+(aq) + 2e
Reduction half-reaction
Cu2+(aq) + 2e
Cu(s)

e
2e gained
per Cu2+ ion
reduced

2e lost
per Zn atom
oxidized

Zn

Cu2+
Zn2+

Cu e

Voltmeter
e
e
Anode Salt bridge Cathode
+
Zn () Na
SO 2 (+) Cu
4

Zn2+

Cu2+

Oxidation half-reaction
Zn(s)
Zn2+(aq) + 2e
Reduction half-reaction
Cu2+(aq) + 2e
Cu(s)

e
2e gained
per Cu2+ ion
reduced

2e lost
per Zn atom
oxidized

Zn

Cu2+
Zn2+

Cu e

Voltmeter
e
e
Anode Salt bridge Cathode
+
Zn () Na
SO 2 (+) Cu
4

Zn2+

Cu2+

Oxidation half-reaction
Zn(s)
Zn2+(aq) + 2e
Reduction half-reaction
Cu2+(aq) + 2e
Cu(s)
Overall (cell) reaction
Zn2+(aq) + Cu(s)
Zn(s) + Cu2+(aq)

*** SALT BRIDGE***


Salt bridge consists of a U-tube containing a saturated solution of the KCl or
KNO3 or NH4NO3 in agar gel with glass wool plug at the two ends. The
functions of salt bridge are listed below(1) It connects the two half-cells internally.
(2) It avoids diffusion of solutions between the two half cells.
(3) It maintains the electrical contact between the solutions by means of ionic
conductance.
(4) It helps to maintain electrical neutrality in the two electrolytes.
(5) The liquid Junction potential has been always eliminated or minimized
by using salt bridge.

LIQUID JUNCTION POTENTIAL


Consider electrochemical cell- Daniel cell- Zn | ZnSO4 solution | CuSO4 solution | Cu or
Ag | AgNO3 (conc. C1) | AgNO3 (conc. C2) | Ag
The liquid junction potential is developed because the speeds of diffusion of two ions
(cations and anions) of two electrolytes are different. When cations are moves faster than
anions from solution 1; then cations diffuse more rapidly in solution 2; than anions and so
that solution 2 will becomes positively charged with respect to solution 1. Therefore, one
side of the boundary becomes positively charged and other is negatively charged and
forming electrical double layer at the Junction of two liquids. Therefore, potential difference
is developed at the junction of the solution of the two electrolytes. The potentials of this kind
are called liquid Junction potential (Fj).
When two solutions of the same or of different electrolytes are brought in contact, a
difference of potential will be set up at the junction between them because of ionic
transference. The liquid junction potential is calculated experimentally after calculating the
Ecell, and electrode potential (ELHS and ERHS) by using the relationEcell = ELHS + ERHS + Ej.
The liquid Junction potential is eliminated or minimized by using salt bridge because salt
bridge contains KCl or KNO3 or NH4Cl. In KCl | KNO3 | NH4Cl the cations and anions
are moves almost with equal speeds. Due to this the liquid junction potentials developed
at the two ends of the bridge cancel with each other. The eliminating of liquid junction
potential is indicated by a pair of vertical lines between two half- electrodes

(B) WORKING OF THE DANIEL CELL (CELL


REACTIONS):-

(B) WORKING OF THE DANIEL CELL (CELL REACTIONS)


NET CELL REACTION:The overall or net cell reaction is obtained by
adding these two half cell reactions
Zn(s) + Cu++ Zn(s) + Cu++

Anode (-ve charge)


Oxidation Reaction
Zn(s) Zn++ + 2eThe zinc metal has a greater tendency to
ionize than the copper. Therefore zinc atoms
inter into the solution in the form of cations
leaving behind the electrons on the metal
rod. This process is called Oxidation of Zn

Cathode (+ve charge)


Reduction reaction

Cu++ + 2e- Cu
The liberated electron at zinc electrode travel
towards the copper electrode through an
external circuit. The Cu2+ ions in the solution
of CuSO4 go and get discharged at Cuelectrode by taking electrons which is coming
from the Zn rod. It is called reduction of Cu++

The current is flow from the Cu- electrode (cathode) to Zn- electrode (anode). At anode Znatoms from the rod enter into solution as Zn++ therefore, size of zinc rod reduces continuously
and at cathode Cu- atoms deposited on the copper electrode, so that size of copper-rod
increases.
Represented of cell: - Zn(s) | ZnSO4 || CuSO4 | Cu(s).

(1) The negative electrode or electrode having oxidation potential is written to the
left hand side in the cell. The oxidation reactions take place at negative electrode

(2) The positive electrode or electrode having reduction potential is


written to the right hand side in the cell. The reduction reactions
take place at positive electrode
(3) A single vertical line between the electrode and salt solution or in
between two salt solutions indicates the direct contact between theE.g.:- Zn- | ZnSO4 (aq) | CuSO4 (aq) | Cu+ or Zn- | Zn++ | Cu++ | Cu+

(4) The double vertical line between two salt solutions indicates indirect contacts between
them .i.e. two half cells are connected by salt bridge.
E.g.:- Zn- | ZnSO4 (aq) || CuSO4 (aq) | Cu+
(5) In case of gas-electrode, inert metal conductor is used for electrical contact & for ionization. E.g.: In the hydrogen electrode, platinized platinum foil is dipped into dilute HCl
solution and over which hydrogen gas bubbled. Pt, H2 | HCl (aq), Pt, Cl2 |Cl- (aq).
(6) When concentrations or activities of solution and pressures of gases are required, these
are written in the bracket.
Zn- | ZnSO4 (0.1m) || CuSO4 (0.1m) | Cu+; Pt-, H2 (1atm) | HCl (aH+ = 1), AgCl (s) |Ag+.
(7) For spontaneous cell reaction, electrons are flows from LHE to RHE, where as current
is flows in opposite direction.

(8) The total emf of a cell is the sum of oxidation potential of LHS electrode and reduction
potential of the RHS electrode. Ecell = EOx (LHS) + ERed (RHS) = EOx (LHS) EOx (RHS).

Standard cell
The accuracy of the measurement of emf will be depends on the accuracy of the emf of
standard cell. There are some condition which must satisfied by the standard cell-

1. It should show the characteristic reversibility and does not damage permanently
due to passage of current through it.
2. Standard cell potentials are reproducibly constant with time and well known.
3. Standard cell have low temperature coefficient of emf.
The cell which satisfied all these properties is the Western saturated and unsaturated
standard cell

CONVENTION REGARDING SIGN OF EMF


The net electric work performed by a reaction yielding an emf E and producing a quantity
of electricity Q is = E x Q.
Each equivalent reacting Q = faradays constant 96486 (F) x number of electrons involved
in the cell reaction (n).
Therefore net electric work performed by the cell reaction isNet Electric Work = n x F x E
... (1)
But any work performed by the cell can be accomplished only at the expense of or
decrease in the free energy of the cell. When the electric work is maximum, then cell can
be operate reversibly; the decrease in free energy (G), must be equal the electric work
done... Electric work done = -G
... G = - nFE
(2)
By using equation (2), emf of any reversible cell can be determined by the free energy
change of the reaction occurring in the cell. The relation between spontaneity of the
reaction and sign of emf and G can be summarized belowReaction
G
E
Spontaneous
+
Nonspontaneous
+
At equilibrium
0
0

According to Gibbs-Helmholtz equation, the decrease in energy free of a system at


constant pressure is
-G = -H T [(G)/T]P
... (3)
From equation (2) and (3)nFE = -H - T [ (-nFE)/T]P
= -H + nFT (E/T)P
... (4)
OR
E = -H/nF + T (E/T)P
...........(5)
Where, (E/T)P is the temperature coefficient of emf of the cell; at constant pressure
and is determined whether the electric energy would be equal to, more or less than the
heat of reaction. There are three different casesCase 1] When temperature coefficient is zero i.e. (E/T)P = 0
... From equation (5), -H = nFE
Case 2] when the temperature coefficient is positive i.e. (E/T)P > 0
... From equation (5), nFE > -H
The additional energy will come either from the surrounding or the temperature of
the cell would falls.
Case 3] when temperature coefficient is negative i.e. (E/T)P < 0
... From equation (5), nFE < -H
The excess energy will be either to surrounding or the temperature of the cell would
rise.

The equation (4) can be rearranged as- (-G = nFE);


-G + H = nFT (E/T)P
.... (6)
From equation (3) and (6)- [eq. 3 is -G +H = -T [(G)/T]P ]
- T [ (G)/T]P = nFT (E/T)P
OR
[ (G)/T]P = -nF (E/T)P
....(7)
The equation (4) can be rearranged as
H = -nFE + nFT (E/T)P
H = nF [T (E/T)P E] ...(8)
The equation (8) can be used to measured H from the emf and temperature coefficient
of emf of the reaction; or (E/T)P from H and E. The H can be obtained in joules
when E is in volts and F is in coulombs.
Also, we know thatG - H = -TS
.... (9)
From equation (6) and (9)- [eq. 6 is -G + H = nFT (E/T)P]
-nFT (E/T)P = -TS
OR
S = nF (E/T)P
... (10)
The entropy change of a reaction can be readily calculated from the temperature
coefficient of emf of cell.

***SINGLE ELECTRODE POTENTIALS***


Each individual electrode developed a potential with respect to the solution. The potential of a
single electrode in a cell is called the single-electrode potential.
The algebraic sum of the single electrode potentials of two half-cell gives the total emf of cell.
Ecell = Eox (LHE) + Ered (RHE)
OR
Ecell = Eox (LHE) - Eox (RHE)
{... Ered = - Eox}
OR
Ecell = Ered (RHE) Ered (LHE)
The single electrode potential of half cell depends on(i) Concentration of ion in solution, (ii) Tendency to form ions & (iii) Temperature.
The emf of cell can be measured by using potentiometer, which is summation or difference of
two single electrode potential of two electrodes, but not its absolute values.
The single electrode potential can be measured by coupling the half-cell /electrode with
another half-cell; whose potential is either zero or accurately known.
But there is no electrode, having true zero potential; therefore it is necessary to select another
standard or reference electrode.
The electrode whose single electrode potential is determined is coupled with standard hydrogen
electrode (SHE) and Ecell can be obtained potentiometrically asEcell = Eelectrode + ESHE
Eelectrode = Ecell - ESHE = Ecell
Thus, Single electrode potential of the given electrode is itself the emf of cell, when the cell is
constructed by coupling the electrode with standard hydrogen electrode. If calomel electrode is
used as reference electrode.
... Eelectrode = Ecell Ecalomel

***REFERANCE OR STANDARD ELECTRODE***


The electrode whose potential is accurately known is called standard or
reference electrodes.
The EMF of electrode is determined under standard condition is called as
standard EMF.
The standard conditions are:
(1) 1M solution of reactants and product,
(2) Temperature is 250C.
The standard electrodes are of two types(1) Primary reference (or standard) electrodes,
(2) Secondary reference (or standard) electrodes.

1. PRIMARY REFERENCE ELECTRODES (STANDARD HYDROGEN ELECTRODE


SHE) CONSTRUCTION:A standard hydrogen electrode is consist of platinized platinum electrode (plate) emerged in a 1
M solution of H+ ions at 250C. The hydrogen gas at one atmosphere pressure enters the glass
hood. Bubbles over the platinum plate.
The potential of standard hydrogen electrode is zero at all the temperatures. It is represented as
Pt, H2(1atm) | H+ (aH+=1) E0SHE = 0.0 volts
The hydrogen gas at the platinized plate is ionized and shows the equilibrium with H+ ions
present in the solution. The following reaction is occurred at the electrode
1
2

+
H (aq)

H2 (g)

inner glass tube


Cu wire
hydrogen gas
outlet

outer glass jacket


hydrogen gas at one atm pressure.

Hg
salt bridge

Pt wire
Platinised platinum plate
1M HCl solution

***DRAWBACKS OF STANDARD HYDROGEN ELECTRODE***


(1) SHE is not easily setup.
(2) Platinum plate is easily poisoned the impurities present in the solution; therefore
adsorbing capacity of platinum is decreased.

(3) It is difficult to maintain unit activity of hydrogen ions in the solution.


(4) It is difficult to maintain the pressure of hydrogen as 1 atm.
(5) It is difficult to prepare pure hydrogen and is become impure when passed over
the platinum plate. Therefore, hydrogen gas is not reused.

Therefore, instead of SHE, some other secondary reference electrodes are used whose
potentials are known exactly, and its construction is simple. The calomel electrode is
quite satisfactory as secondary reference electrode.

SECONDARY REFERENCE ELECTRODE (CALOMEL ELECTRODE)


Calomel electrodes are very stable and good reversible electrodes.
0.1M calomel

1 M calomel

0.1M KCl

1 M KCl
Hg2Cl2 (S) + 2e- 2Hg(l) + 2Cl-

KCl solution saturated


with
Hg2Cl2
Cu wire
Side arm
Hg
Paste of Hg + Hg2Cl2

Pt wire

Saturated Calomel

Sat. KCl

It consists of a glass tube with


side arms. Pure mercury is
placed at the bottom of tube and
it is then covered with a paste
of mercurous chloride
(calomel) and mercury. The
KCl solution
tube is then filled with KCl
solution of known
concentration (0.1M KCl or
Hg
1.0M KCl or saturated KCl at
250C), which is saturated with
Paste of Hg + Hg2Cl2
mercurous chloride. A copper
wire is introduced into
Porous plug
mercury for the external
circuit. The other side tube acts
Sintered glass disc
as a salt bridge during the
coupling it with other half
electrode.

The potentials of various calomel electrodes depend on the


temperature and concentration of the potassium chloride with
which the electrode vessel is filled.
The emf is highest for the 0.1M calomel and that of less for
saturated electrode, because 0.1M calomel has smallest
temperature coefficient of emf, while the saturated electrode has
the highest.

***SINGLE ELECTRODE POTENTIAL***


The single electrode potential as half cell potential is the difference of potential
between the metal and the solution around it at equilibrium.
There are two types of single electrode potentials as oxidation potential and reduction
potentials.
1. OXIDATION POTENTIALS ( Eoxi) :It is the difference of potential between the metal and the solution around it in
equilibrium due to the oxidation.
2. REDUCTION POTENTIALS (Ered):It is the difference of potential between the metal and the solution around it in
equilibrium due to the reduction.

The reduction potential of an electrode is equal to the oxidation potential for the
same electrode but having different (reversed) sign.
... E(oxi) = - E(red)

***NERNST EQUATION***
In electrochemical cell- one electrode undergoes oxidation where as other get reduction. Therefore, the total
electrode potential is the algebric sum of the single electrode potentials:
Ecell = E(oxi) + E(red) = Eox(LHE) + Eox(LHE)
The value of the single electrode potential of electrode undergoes oxidation as:
M Mn+ + ne... According to the Nernst equation Eox = Eox0 RT/nF ln a+
Where, a+ is the activity or concentration of the metallic ion in the solution.

Oxidation

The value of the single electrode potential of electrode undergoes reduction as:
Reduction
Mn+ + ne- M
... According to the Nernst equation Ered = Ered0 - RT/nF ln 1/a+
Where, Eox0 = Standard oxidation potential, Ered0 = Standard reduction potential, R = Gas constant =
8.314 Joules, T = Absolute temperature of electrode, F = Faradays constant = 96500 joules, n = number
of electrons involved in the oxidation or reduction process.
For the dilute solutions the activity can be expressed in term of concentration. At 250C considering the
value of R, F and ln = 2.303 log10, therefore above equation can be written asEox = Eox0 0.059/n log10 a+
Ered = Ered0 0.059/n log 1/ a+
In general, the Nernst equation can also be stated asEox = Eox0 RT/nF ln aoxidant/areductant
Ered = Ered0 RT/nF ln areductant/aoxidant
And

Ecell = Ecell0 RT/nF ln aproduct/areductant

Redox

Calculation of cell emf from single electrode potentials:If the single electrode potentials and its reactions are available, the cell reaction and its emf
can be calculated by using following steps1) The standard oxidation or reduction potential of each electrode can be determined by
coupling the electrode with SHE at 250C.
2) The electro-chemical cell which is under study can be written with the convention with
respect to the cell reaction.

3) The electrode potential of anode and cathode can be determined by using Nernst equation
after knowing the activity of the cations in the solutions.
Eox = Eox0 RT/nF ln a+ = Eox0 RT/nF ln aoxidant/areductant
Ered = Ered0 RT/nF ln 1/a+ = Ered0 RT/nF ln areductant/aoxidant
4) The emf of the cell is the algebric sum of the two electrode potentials forming the cell,
thus Ecell = Eox + Ered
And the standard cell potentials (E0cell) is determined after knowing Ered0 and Eox0 of the
electrodes forming the cell.
Ecell0 = E0ox + E0red
5) The emf of the cell is directly calculated after knowing the activities of the ions in their
solutions by using Nernst equation.
Ecell = Ecell0 RT/nF ln acC x adD x . / aaA x abB x .

Summary of Rules:The various rules introduced above with respect to cell reactions and emfs are
summarized below1) Any cell reaction is the sum of the single electrode reactions as they occur in cell
a) At anode, the oxidation reaction can be take place. b) At cathode, the reduction
reaction can be occurred.
2) The cell emf is the algebric sum of the single electrode potentials: Ecell = Eox + Ered
3) The negative electrode can be written at the left hand side and the positive
electrode can be written at the right hand side. So that the electrons can flow from
left to right through an external circuit, the cell reaction deduced by the rule- a) Is
spontaneous and emf deduced by the rule, b) Is positive.
4) If the wrong assumption is done with respect to the polarity of the electrode, the emf
of cell is negative and cell reaction is non spontaneous.
5) Oxidation potential of all metals above hydrogen in electro-chemical series is
positive and those below are negative.

6) Activities of pure solid, liquid, insoluble solids and pure gases with unit
atmospheric pressure are taken as unity.
7) The oxidation or reduction potential of the SHE is assumed to be zero.

Classification of the electrodes:The electrodes are in two types- ion selective electrodes and ion specific electrodes.
Ion specific electrodes:These electrodes are reversible to its own ions in the solution with which it is directly
contact. They are constructed by using solid metal rod/trip/wire in contact with its
aqueous solution or gas molecules. The various electrodes used in electrochemical work
are classified into following five groupsi) Metal-metal ion electrodes.
ii) Amalgam electrodes.
iii) Gas electrodes.
iv) Metal-insoluble salt electrodes.
v) Oxidation-reduction electrodes.
Ion selective electrodes:These are electrochemical sensors. They are used for the potentiometric determination
of activity of particular ion in presence of other ions.
The selective membrane can be prepared from glass, solid crystalline ceramic or
polymer. The change in activity of certain ion in the sample causes change of membrane
potential and therefore electrode.
1) Glass electrode.
2) Solid crystalline ceramic electrode.

1. Metal-metal ion electrode:The electrodes of this type involve a metal in equilibrium with a solution
of its ion. The electrode consists of a rod or a strip of metal dipped in a
solution containing its ion. All these electrodes operate on the general
reaction.
M Mn+ + neThe electrode potential corresponding to the oxidation can be calculated
by using the following equationEm = E0m RT/nF ln amn+
Where, amn+ is activity of metal ions. Each of these electrodes is said to
be reversible to its own ions. Examples are the Zinc, Copper, Cadmium
and Sodium electrodes.

2. Amalgam electrode:In same cases of metal-metal ion electrodes, the pure metals are too active and not stable in its
metallic form in aqueous solution.
E.g. - K, Na, Ca etc. are highly active metals and can not be used in their pure form in metal
electrode. The activity of such metals can be lowered some what by dilution in the mercury i.e.
forming its amalgam. These amalgams can be used to construct the electrode. Therefore it is
called as amalgam electrode. They are constructed by dipping the amalgam of the desired metal
in solution of its salt.
The general reaction take place at the electrode is
M(Hg) Mn+ + ne- + Hg
The corresponding oxidation electrode potential can be calculated by using the equationEa = E0m (RT/nF) ln (amn+/am)
Where, Ea = Electrode potential
amn+ = Activity of metallic ions in the solutions
am = Activity of metal in the amalgam.
The amalgam electrodes have some advantageous over the metallic electrodes1) The equilibrium between the metals and their ions can be established rapidly than the pure
metal electrodes.
2) Due to amalgamation, the impurities present in the metals are diluted; therefore, they do not
affect practically the behavior of the electrodes and gives satisfactory and reproducible results.
3) If the amalgam is saturated with metal, then electrode becomes equivalent to metal-metal ion
electrodes; (i.e. am =1), it is because the chemical potential of a component in its saturated
solution equals the chemical potential of pure metal.

3. Gas Electrode:Gas electrodes consist of inert metal wire or foil immersed in a solution
containing ions to which gas molecules are reversible. The gas bubbling
about the inert metal; so that gas is absorbed over the surface of the inert
metal and become saturated. The absorbed gas molecules and their ions
in solutions are brought in contact through the inert metal. The metal foil
established the equilibrium between the gas and its ions in solution. The
most common inert metal used is platinumPt, M2 (g) (PM2) | Mn+ (aMn+)
E.g. M2 (g) Mn+ + neThe oxidation potential is E = E0M2 RT/nF ln (amn+/a1/2M2)
At low pressure the activity of the gas is equal to pressure of gas in
atmosphere.
E = E0M2 RT/nF ln (amn+/PM2)

4. Metal-insoluble salt electrode:The various types of calomel electrodes, the silver-silver chloride electrode, the lead-lead
sulphate electrode, silver-silver bromide electrode etc. are the examples of such type of electrode.
These electrodes consist of a metal in contact with one of its sparingly soluble salt and solution
containing the ion present in the salt other than the metal.
For example- Silver-Silver chloride electrode composed of a silver wire coated with silver
chloride and dipped in the solution of chloride ions. In the Lead-Lead sulphate electrode the lead
metal is used in its amalgam is covered with a crystal of lead sulphate and surrounded by the
sulphate. In all instances these electrodes are reversible to the ions other than those of metal
present in the insoluble salt e.g. Silver-silver chloride electrode is reversible to the chloride ions.
Consider the silver electrode dipping in the solution of chloride ions and is saturated by the
silver chloride. If the electrode is acts as ordinary metal-metal ion electrode, then silver ion will
pass from the electrode into the solution according to the equationAg(S) Ag+ + eBut the solution is saturated with silver chloride and the introduction of any silver ions into the
solution distributed the solubility product principle of the salt, therefore to re-establish the new
equilibrium, backward reaction (reaction between Ag+ and Cl-) can be take place forming undissociated AgCl.
Ag+ + Cl- AgCl
Therefore the over all reaction occurring at the electrode is Ag + Cl- AgCl + eIt indicates that the electrode is reversible with respect to Cl- ion. For this reaction the electrode
potential isEAg/AgCl = E0Ag/AgCl RT/F ln 1/aCl-

5. Oxidation-reduction electrode:In the oxidation-reduction electrode, the ions of a substance in two different oxidation
states are present in the same.
For example:- When a platinum wire is immersed in a solution containing Ferrous and
Ferric ions or in a solution containing both- Cerous-Ceric ions, Stannous-Stannic ions
etc a potential is developed called redox potential. This potential can be arises by the
electrode due to spontaneous conversion of one oxidation state of metal ion into another
stable oxidation state.
Fe3+ + e- Fe2+
Ce3+
Ce4+ + eThe function of platinum wire is to facilitate the exchange of electron from one species
to another and provides the electric contact to the electrode. The other redox electrodes
areSn2+ Sn4+ + 2eMn2+ + 4H2O MnO-4 + 8H+ + 5eHydroquinone [C6H4(OH)2] quinine (C6H4O2) + 2H+ + 2eIn general the equilibrium between oxidized and reduced state of the same substance
can represented asReduced state Oxidized state + neThe electrode potential can be derived by using the following Nearst equation.
ERedox = ERedox0 RT/nF ln aoxid state/aredu state

Classification of electrochemical calls:A large number of electrochemical calls are obtained from the combination of
various electrodes. The cells are broadly classified into two types1) Chemical cells, 2) Concentration cells.
Electrochemical cells

Chemical cells

Without transference

Concentration cells

With transference

Electrode concentration cells


without transference

Without transference

With transference

Electrolyte concentration cells


without transference

1. Chemical cells:It is a class of electrochemical cells in which the free energy of a cell is converted
into a electric energy, and
2. Concentration cells:It is a class of electrochemical cells in which electric energy can be generated due
to transfer of matter from one half cell into another half cell on account difference
in- Electrode composition or Concentration of the electrolyte.

Solubility product and emf


In the saturated solution of the sparingly soluble salt, such as AgBr
AgBr(S) Ag+ + Br- is dissociated in the solution. The product of activities of the two ions is equal
to the solubility product of the AgBr. But the solubility product Ks is equilibrium constant and its
value can be determined from the E0 value of a cell in which the above reaction can be occurs.
Therefore finding two electrodes, whose reactions leads to overall dissociation reaction of the
sparingly soluble salt, combining their E0 values, and it is possible to calculate Ks of that salt.
E.g.:
Calculation of solubility product of AgBr.
Combining the two electrodes-silver and silver-silver bromide electrodes. The oxidation reaction
takes place at silver electrodeAg (S) Ag+ + eAnd the reduction can be occurs at silver-silver bromide electrode.
AgBr(S) + e- Ag (S) + BrNet cell electrode- AgBr(S) Ag+ + BrThe E0 value of the silver electrode at 25 0C is E0 = - 0.7991 volt and E0 value of the silver-silver
bromide electrode for reduction is- E0 = +0.0711.
... Ecell0 = E0Ag + E0Ag-AgBr
= - 0.7991 + 0.0711
= - 0.7280 volt
Substituting the value E0cell in the equationEcell0 = 2.303RT/nF log Ks
... log KS = -0.7280/0.05916
... log KS = 4.6 x 10-13

Determination of solubility product of the silver chloride


Determination of a solubility of the sparingly soluble salt involves the measurement of the
single electrode potential of an electrode which is reversible to one of the ions of the salt and
in the solution saturated with this salt.
Consider the solution of chloride (0.1M KCl solution) and is saturated with AgCl by adding
few drops of AgNO3. A silver wire is dipped into this solution and the silver electrode is
combined with a reference Calomel electrode to form the cell.
Ag(s) | KCl (0.1M) [AgCl sat.] | Calomel electrode
The emf of the reference 0.1N Calomel electrode at 250C is 0.3338 volt for reduction. The emf of
cell at 250C is 0.0494 volt.
... Ecell = EAg + EC
... EAg = 0.0494 - 0.3338
= -0.2844 volt.
But
EAg = E0Ag RT/F ln aAg+
- 0.059 x log aAg+ = - 0.2844 + 0.7991 = 0.5147
... log aAg+ = - 0.5147/0.05916
= - 8.700
.
. . aAg+ = 2.00 x 10-9
The activity of chloride ion in 0.1M KCl is product of molality 0.1 and mean activity coefficient
of KCl at this concentration is 0.769. The KS of AgCl isKS = aAg+ x aCl= (2.00 x 10-9) (0.1 x 0.769)
= 1.54 x 10-10

Buffer solutions
1. The solution of a weak acid or weak base and its salt with strong base or strong acid.
2. It resist the change in pH of the solution by the addition of small amounts of strong acid
or base or upon dilution
e.g. A buffer of carbonic acid (H2CO3) and bicarbonate (HCO3-) is present in human blood
plasma to maintain pH between 7.35 and 7.45.

There are two types of buffer solutions as- acidic buffer and basic buffer.
Acidic buffer: It is the solution of weak acid and its salt with strong base. E.g. acetic acid
+ sodium acetate.
Basic buffer: It is the solution of weak base and its salt with strong acid. E.g. ammonium
hydroxide + ammonium chloride.

Buffer solutions
Hendersons equation for acidic and basic buffer solutions
Acid buffer solution: It is made from weak acid HA and its salt with strong base BA.
HA is weak electrolyte therefore dissociated partially and exist equilibrium with A- ions.
HA (aq)
H+(aq) +
A-(aq)
According to the Le Chateliers principle (or common ion effect), in presence of salt the
equilibrium will be shifted towards left. The salt BA will get dissociated completely into B+ and Awhich increases the concentration of A- and decreases the dissociation of acid HA. The equilibrium
constant isKa = [H+(aq)] [A-(aq)]/[HA(aq)]
Or
[H+(aq)] = Ka [HA(aq)] / [A-(aq)]
.. (1)
Taking the negative logarithum of both sides, we havepH = pKa + log[A-(aq)]/[HA(aq)]
.. (2)
Assume that [A (aq)] is only due to salt BA i.e. [BA] [A (aq)] i.e. amount of A- present in the
solution at equilibrium is approximately the same as the amount of salt AB present initially. Also very
small amount of acid undergoes dissociation therefore amount of acid in equilibrium is same as the acid
added initially.
pH = pKa + log[salt]/[acid]
.. (3)
The above equation is called as the Hendersons equation for acid buffer solution.
Base buffer solution: Similarly the Henderson equation for base buffer solution,
pOH = pKb + log[salt]/[base]
.. (4)
But
pH = 14 - pOH
Therefore, equation (4) become,
pH = 14 - {pKb + log[salt]/[base]}