BRANCH :- CHEMICAL ENGINEERING

SEMESTER :- 4 Th

SUBJECT :- PHYSICAL AND INORGANIC CHEMISTRY

TOPIC :- ELECTROCHEMISTRY

NAME ENROLLMENT NO
CHAUHAN AJAY 140280105007
CHAUHAN NISHIL 140280105009
GOL RAJAN 140280105015
VADHIYA BHAVIN 140280105058

GUIDED BY :-Prof. N.J MODI

 INTRODUCTION:
ELECTOCHEMISTRY is the study of processes involved in interconversion of
electrical energy and chemical energy. ELECTROCHEMISTRY is the study of the equilibrium
and kinetic properties of ions in solution, production of electricity from energy released during
spontaneous chemical reactions or its reverse when electrical energy is used to bring about non-
spontaneous chemical transformation.

HALF REACTION:
Let us consider the reaction,

2Na + Cl2 2Na + + 2Cl

It occurs by the transfer of electrons from Na to Cl. Na loses an electron and is
said to be oxidized to Na+ ion. At the same time, gains an electron and is reduced to Cl ion.
Such a reaction which is brought about by loss of electrons (oxidation) and gain of electrons
(reduction) simultaneously, is called an Oxidation-Reduction reaction or Redox-reaction in
brief. It may be noted that in the overall redox reaction no free electrons are generated.
The redox reaction can be considered as made up of two reactions. For
example, the redox reaction.

2Na + Cl2 2Na + + 2Cl

It is composed of two reactins.

2Na 2Na+ +2e-

Cl2 +2e-2Cl-

Each of the two reactions shows just its oxidation or just the reduction
portion of the overall redox reaction. Being half components of the redox reaction, these
reactions are called Half-reactions. The first half-reaction that proceeds by oxidation is often
referred to as the Oxidation half-reaction. The second half-reaction that occurs by reduction, is
referred to as the Reduction half-reaction. When the two half-reactions are added together, the
sum is the net redox reaction.

Cell potential or emf :

In a Zn-Cu voltaic cell, electrons are released at the anode and it becomes
negatively charged. The negative electrode pushes electrons through the external circuit by
electrical repulsions. The copper electrode gets positive charge due to the discharge of Cu2+ ions
on it. Thus electrons from the outer circuit are attracted into this electrode. The flow of current
through the circuit is determined by the 'push', of electrons at the anode and 'attraction' of
electrons at the cathode. These two forces constitute the 'driving force' or 'electrical pressure' that
sends electrons through the circuit. This driving force is called the electromotive force
(abbreviated emf) or cell potential. The emf of cell potential is measured in units of volts (V)
and is also referred to as cell voltage.

Cell reaction:
The flow of electrons from one electrode to the other in an electrochemical cell is caused by
the half-reactions taking place in the anode and cathode compartments. The net chemical
change obtained by adding the two half-reactions is called the cell reaction. Thus, for a simple
voltaic cell described above, we have
(a) Half-reactions

Cu 2+ (aq) + 2e- Cu(s)

Zn(s) Zn 2+ (aq) + 2e

(b) Cell reaction by adding up the half-reactions:

Zn(s) + Cu 2+ (aq) Zn 2+ (aq) + Cu(s)
Calculating the emf of a cell :
The emf of a cell can be calculated from the half-cell potentials of the two cells
(anode and cathode) by using the following formula

Ecell = Ecathode - Eanode

= ER - EL

where ER and EL are the reduction potentials of the right-hand and left-hand electrodes
respectively. It may be noted that absolute values of these reduction potentials cannot be
determined. These are found by connecting the half-cell with a standard hydrogen electrode
whose reduction potential has been arbitrarily fixed as zero.

Nernest Equation:
We know experimentally that the potential of a single electrode or half-cell varies
with the concentration of ions in the cell. In 1889 Walter Nernst derived a mathematical
relationship which enable us to calculate the half-cell potential, E, from the standard electrode
potential, E, and the temperature of the cell. This relation known as the Nernst equation can be
stated as
.
E= E- logk
Here,
R = gas constant
T = Kelvin temperature
n = number of electrons transferred in the half-reaction
F = Faraday of electricity
K = equilibrium constant for the half-cell reaction as in equilibrium law
E = standard electrode potential

ELECTROCHEMICAL CELLS:
A device for producing an electrical current from a chemical reaction is called an
electrochemical cell.

PRODUCTION OF ELECTRIC CURRENT BY REDOX

REACTIONS:
When a bar of zinc is dipped in a solution of a copper sulphate,copper metal is
deposited on the bar.The net reaction is

Zn(s)+ Cu2+ (aq) Zn+2 (aq)+ Cu(s)

This is redox reaction and the two half reactions are:

Cu2+ (aq) + 2e- Cu(s)

Zn(s) Zn+2 (aq) + 2e-

In this charge Zn is oxidized and gives Zn+2 ions and Cu2+ ions reduced toCu atoms.The
electrons released in the first half-reaction are used up by the second half-reaction. Both the half-
reactions occur on the zinc bar itself and there is no net charge.
Now, let the two half-reactions occur in separate compartments which are connected by a
wire.The electrons produced in the left compartment flow through the wire to the other
compartment. However the current will flow for an instant and then stop. The current stops
flowing because of the charge build up in the two compartments. The electrons leave the left
compartment and it would become positively charged. The right compartment receives
electrons and becomes negatively charged. Both these factors oppose the flow of electrons
(electrical current) which eventually stops.
The problem can be solved very simply. The solutions in the two compartments may be
connected, say, by a salt bridge. The salt bridge is a U-tube filled with an electrolyte such as
NaCl, KCl, or k2SO 4. It provides a passage to ions from one compartment to the other
compartment without extensive mixing of the two solutions. With this ion flow, the circuit is
complete and electrons pass freely through the wire to keep the net charge zero in the two
compartments.
 VOLTAIC CELLS
A Voltaic cell, also known as a galvanic cell is one in which electrical current is generated
by a spontaneous redox reaction. A simple voltaic cell is shown in figure.Here the spont
aneous reaction of zinc metal with an aqueous solution of copper sulphate is used.
Zn(s)+ Cu2+ (aq) Zn+2 (aq)+ Cu(s)
A bar of zinc metal (anode) is placed in zinc sulphate solution in the left container. A bar of
copper (cathode) is immersed in copper sulphate solution in the right container. The zinc and
copper electrodes are joined by a copper wire. A salt bridge containing potassium sulphate
solution interconnects the solutions in the anode compartment and the cathode compartment.
The oxidation half-reaction occurs in the anode compartment.
Zn(s) Zn+2 (aq) + 2e-
The reduction half-reaction takes place in the cathode compartment.
Cu2+ (aq) + 2e- Cu(s)
When the cell is set up, electrons flow from zinc electrode through the wire to
the copper cathode. As a result, zinc dissolves in the anode solution to form Zn2+ ions. The
Cu2+ ions in the cathode half- cell pick up electrons and are converted to Cu atoms on the
cathode. At the same time, SO4-2 ions from the cathode half-cell migrate to the anode half-cell
through the salt bridge. Likewise, Zn2+ ions from the anode half-cell move into the cathode half-
cell. This flow of ions from one half-cell to the other completes the electrical circuit which
ensure continuous supply of current. The cell will operate till either the zinc metal or copper ion
is completely used up.
 A simple Voltoic cell

DANIELL CELL:
It is a typical voltaic cell. It was named after the British chemist John Daniel. It is a simple
zinc- copper cell like the one described above.
 In this cell the salt-bridge has been replaced by a porous pot. Daniel cell resembles the above
voltaic cell in all details except that Zn2+ ions and SO4 -2 ions flow to the cathode and the anode
respectively through the porous pot instead of through the salt-bridge. Inspite of this difference,
the cell diagram remains the same.

WESTON STANDARD SELL:

A standard cell is one which provides a constant and accurately known emf. The
Weston cadmium cell is most widely used as a standard cell. It is constructed in a H-
shaped glass tube .The positive electrode consists of mercury covered with a paste of
solid mercurous sulphate (Hg2SO 4) over which is placed a layer of cadmium sulphate crystals.
The negative electrode is 12.5% cadmium amalgam, Cd(Hg), covered with cadmium sulphate
crystals. The entire cell is filled with saturated cadmium sulphate solutions and sealed

CELL REACTIONS:
(A) At anod:- Cd + SO4-2 CdSO4 + 2e-2
(B) At cathode:- Hg2SO4 +2e- 2Hg + SO4-2
(C) Overall reaction:- Cd + Hg2SO4 CdSO4 + 2Hg

REVERSIBLE CELLS:
A familiar example of a reversible cell is the Daniel cell. We know that electrons flow
from zinc electrode to copper electrode due to the net cell-reaction.
Zn(s)+ Cu2+ (aq) Zn+2 (aq)+ Cu(s)
 Reversible Daniel Cell
However, when the two electrodes are connected to an external battery that opposes the cell
emf, the above reaction is reversed (Figure b) Cu from the copper electrode dissolves to form
Cu2+ ion and Zn2+ ion is discharged on the zinc electrode to give Zn atom.

(A) At cathod:- Cu2+ (aq) + 2e- Cu(s)

(B) At anod:- Zn(s) Zn+2 (aq)

(C) Overall reaction:- Zn(s)+ Cu2+ (aq) Zn+2 (aq)+ Cu(s)

With the help of a potentiometer, the cell emf is exactly balanced by the external emf. At the
balance point, no current will flow through the circuit. Now let the external emf increase and
then decrease by an infinitesimal amount. A minute current will flow first to the left and then to
the right. This reversal of the cell current is accompanied by a corresponding change in the
direction of the cell reaction. This type of reversible behaviour is a feature of the reversible cells.
A reversible cell may be defined as : a cell that operates by reversal of the cell current and
direction of cell reaction by infinitesimal change of emf on either side of the balance point.
All voltaic cells are reversible cells

Single electrode potential :-

An electrochemical cell consists of two half-cells. With an open-circuit, the metal electrode
in each half-cell transfers its ions into solution. Thus an individual electrode develops a potential
with respect to the solution. The potential of a single electrode in a half-cell is called the Single
electrode potential. Thus in a Daniel cell in which the electrodes are not connected externally,
the anode Zn/Zn 2+ develops a negative charge and the cathode Cu/Cu 2+, a positive charge. The
amount of the charge produced on individual electrode determines its single electrode potential.
The single electrode potential of a half-cell depends on : (a) concentration of ions in solution;
tendency to form ions; and (c) temperature

Standard emf of a cell:-

The emf generated by an electrochemical cell is given by the symbol E. It can be measured
with the help of a potentiometer. The value of emf varies with the concentration of the
reactants and products in the cell solutions and the temperature of the cell. When the emf of a
cell is determined under standard conditions, it is called the standard emf. The standard
conditions are (a) 1 M solutions of reactants and products; and (b) temperature of 25C. Thus
standard emf may be defined as : the emf of a cell with 1 M solutions of reactants and
products in solution measured at 25C.
Standard emf of a cell is represented by the symbol E. With gases 1 atm pressure is a
standard condition instead of concentration.For a simple Zn-Cu voltaic cell, the standard emf, E,
is 1.10 V. This means that the emf of the cell operated with [Cu 2+] and [Zn 2+] both at 1 M and
25C is 1.10 V.

TYPES OF ELECTRODE:-
STANDARD HYDROGEN ELECTRODE:-
The standard hydrogen half-cell or Standard Hydrogen Electrode (SHE), is selected for
coupling with the unknown half-cell. It consists of a platinum electrode immersed in a 1 M
solution of H+ ions maintained at 25C. Hydrogen gas at one atmosphere enters the glass hood
and bubbles over the platinum electrode. The hydrogen gas at the platinum electrode passes
into solution, forming H+ ions and electrons.

H22H+ +2e-

The emf of the standard hydrogen electrode is arbitrarily assigned the value of zero volts.
So, SHE can be used as a standard for other electrodes.
The half-cell whose potential is desired, is combined with the hydrogen electrode and the
emf of the complete cell determined with a voltmeter. The emf of the cell is the emf of the half-
cell.
 HYDHROGEN ELECTRODE

OTHER REFERENCE ELECTRODE:-

The standard hydrogen electrode (SHE) is not the most convenient standard electrode
to use in the laboratory. The gas has to be carefully controlled and hydrogen gas can form
explosive mixtures with air. Any other electrode system whose potential has been determined
relative to the SHE can also be used as Secondary standard electrode.

(1) The Standard Silver-Silver Electrode:-

In this electrode system, silver wire (or strip) is covered with silver chloride (a highly
insoluble substance). It is dipped in potassium chloride solution in which the concentration of Cl -
ion is 1 M This electrode can be represented as
Ag,AgCl | Cl - (1 M)
The half-cell reaction of theAg-AgCl electrode is
AgCl + e- Ag+ + Cl-

We can set up a cell involving this electrode and the hydrogen electrode with a KCl salt bridge
connecting the two solutions .The emf of the combing cell is found to be 0.2224.
 The standard Ag -Ag electrode

(2)The Calomel Electrode :-

It is the most commonly used secondary standard reference electrode. The standard
calomel electrode, SCE, consists of a wide glass-tube with a narrow side-tube. It is set up as
illustrated in following figure. A platinum wire is dipping into liquid mercury covered with solid
mercurous chloride (Hg2Cl2 ,calomel). The tube is filled with a 1 M solution of KCl (or
saturated KCl solution). The side-tube containing KCl solution provides the salt bridge which
connects the electrode to any other electrode.

The half reaction is

Hg2Cl2 + 2e- 2Hg + 2Cl-

The emf of cell at 25C is + 0.280 V. That is, the calomel electrode emf with
respect to the standard hydrogen electrode is + 0.280 V. This means that 0.280 must be added
to any electrode potential measured against a calomel electrode. This would give the
standard potential on the standard hydrogen scale.
Determination of emf of the standard zinc half-cell using calomel electrode:-

The zinc half-cell is connected with the standard calomel electrode as shown in Fig. 29.14.
The emf of the complete cell is then measured with the help of a voltmeter. It is found to be
1.040 V. Since zinc forms the negative electrode of the cell, its emf with respect to calomel
electrode will be - 1.040 V. The addition of 0.280 gives the standard electrode potential of zinc.
(- 1.040 + 0.280) = - 0.76 V

The calomel electrode

(3)DIPPING CALOMEL ELECTRODE:-
For many purpose, a calomel electrode is manufactured as a self-contained unit. It is
used by simply dipping the tip of the electrode in the solution of another electrode whose
emf is to be determined. This type of electrode is often referred as the dipping calomel
electrode.
The mercury and calomel (Hg2Cl2) are held in a narrow central tube by a porous cotton wool
plug. A platinum wire dips into the mercury. The KCl saturated solution contained in the
electrode makes contact with the other electrode solution through a sintered glass disc. This disc
functions as a 'salt bridge' between the two electrode solutions. Thus a galvanic cell is set
up and its emf is measured with the help of a voltmeter.
 Dipping calomel electrode

(4)The Glass Electrode:-

A commonly used secondary standard electrode is the so-called glass electrode. Its
emf is determined by coupling with a standard calomel electrode (SCE). The glass electrode
provides one of the easiest methods for measuring the pH of a given solution.

A simple type of glass electrode consists of a glass tube having a thin-walled bulb at the
lower end. The bulb contains a 1M HCl solution. Sealed into the glass-tube is a silver wirecoated
with silver chloride at its lower end.The lower end this silver wire dips in to the HCl. acid,
forming silver-silver chloride electrode. The glass electrode may be represented as

Ag,AgCl | 1M HCl| H+ (Test solution)

When placed in a solution, the potential of the glass electrode depends on the H +
ion concentration of the solution. The potential develops across the glass membrane as a
result of a concentration difference of H + ions on the two sides of the membrane. This happens
much in the same way as the emf of a concentration cell develops. The potential of a glass
electrode can be determined against a standard calomel electrode (SCE).
 Glass electrode

FARADAYS LAWS OF ELECTROLYSIS:-

Michael faraday studied the quantitative aspect of electrolysis. He discovered that there
exists a definite relationship between the amount of product liberated at the electrodes and the
electrodes and the quality of electricity used in the process . in 1834, he formulated two laws
which are known as faradays law of electrolysis.

FIRST LAW:-
The amount of given product liberated at an electrode during electrolysis is directly
proportional to the quantity of electricity which passes through the electrolytes solution.

SECOND LAW:-
When the same quantity of electricity passes through solutions of different electrolytes,
the amounts of the substances liberated at the electrodes are directly proportional to their
chemical equivalents.
 BUFFER SOLUTION:-
It is often necessary to maintain a certain pH of a solution in laboratory
and industrial processes. This is achieved with the help of buffer solutions, buffer
systems or simply buffers.

A buffer solution is one which maintains its pH fairly constant even upon the
addition of small amounts of acid or base.

In other words, a buffer solution resists (or buffers) a change in its pH. That is, we can
add a small amount of an acid or base to a buffer solution and the pH will change very
little. Two common types of buffer solutions are :

(1) a weak acid together with a salt of the same acid with a strong base. These
are called Acid buffers e.g., CH3COOH + CH3COONa

(2) a weak base and its salt with a strong acid. These are called Basic buffers. e.g.,
NH4OH + NH4Cl.

Let us illustrate buffer action by taking example of a common buffer system consisting of
solution of acetic acid and sodium acetate (CH3COOH/CH3COONa).

CH3COOH H+ + CH3COO

Na + + CH3COO
CH3COONa

Since, the salt is completely ionized , it provides the common ions CH3COO in
excess. The common ion effect suppresses the ionisation of acetic acid. This reduces
the concentration of H+ ions which means that pH of the solution is raised. Thus, a 0.1
M acetic acid solution has a pH of 2.87 but a solution of 0.1 M acetic acid and 0.1 M
sodium acetate has a pH of 4.74. Thus is the Ph of the buffer. On addition of 0.01 mole
NaOH the pH changes from 4.74 to 4.83, while on the addition of 0.01 mole HCl the pH
changes from 4.74 to 4.66. Obviously the buffer solution maintains fairly constant pH
and the changes in pH could be described as marginal.

HOW BUFFER
OPERATES?
We have already stated that a buffer solution containing equimolar amounts (0.10
M) of acetic acid and sodium acetate has pH 4.74. Now we proceed to discuss how the
addition of a small amount of HCl or NaOH to the buffer solution affects its pH.
The buffer solution (CH3 COOH/CH3COONa)
has a higher PH than the acid it self.

The pH of buffer changes only slightly upon

addition of an acid (0.01 moles)
or bases (0.01 moles) or bases(0.01 mole NaoH)
The pH of the buffer is governed by the equilibrium,

CH3COOH H+ + CH3COO -----------------------------------------------------------------------(1)

The buffer solution has a large excess excess of CH3COO ions produced by complete
ionisation of sodium acetate,

Na + + CH3COO
CH3COONa ---------------------------------------------------------(2)

(1) Addition of HCl. Upon the addition of HCl, the increase of H+ ions is counteracted
by association with the excess of acetate ions to form unionised CH3COOH. Thus the
added H+ ions are neutralised and the pH of the buffer solution remains virtually
unchanged. However owing to the increased concentration of CH3COOH, the
equilibrium (1) shifts slightly to the right to increase H+ ions. This explains the
marginal increase of pH of the buffer solution on addition of HCl

(2) Addition of NaOH. When NaOH is added to the buffer solution, the additional
OH ions combine with H+ ions of the buffer to form water molecules. As a result the
equilibrium (1) shifts to the right to produce more and more H+ ions till practically all the
excess OHsystem
equilibrium ions are neutralised
is set and [CH
up in which the 3original
COOH]buffer pHthan
is lower restored.
it wasHowever, a new
in the original
+
buffer. Consequently [H ] is also slightly less and pH slightly higher than the buffer pH
values.
Operation of a Basic buffer as NH4OH/NH4Cl can also be explained on the same lines as of
an acid buffer upon addition of HCl the H+ ions combine with OH ions of the buffer to form
water.

NH4OH NH4+ + OH-

The equilibrium is shifted to the right till all the additional H+ ions are
neutralised and the original buffer pH restored. When NaOH is added to th4 e buffer
solution, OH ions associate with excess of NH+ions to for unassociated NH4OH.
Thus the pH of the buffer is maintained approximately constant.
 HENDERSON-HASSELBATCH EQUATION:-

The PH/POH of a buffer solution can be calculated from the initial

concentration of the weak acid/base and the salt provided ka is given .
The relationship between PH, ka and initial concentration of acid and base is given as
follows.

[]
PH=Pka + log[]

OR
[]
POH=Pkb + log[]
Above equation is called the HANDERSON-HASSELBATCH EQUATION or
simply HANDERSON EQUATION.