Chem Unit3 Ans

UNIT-III
ELECTROCHEMISTRY
PART A
1. What is electrode potential?
The tendency of an electrode to lose or gain electrons, when it is in contact
with its own ions.

2. What is an electrochemical cell?
A device used to convert the chemical energy produced in a redox reaction
into electrical energy.

3. Write the Nernsts equation for the electrode reaction?
M
n+
(aq) + ne
-
M(s)
E
Mn+/M
= E
0
Mn+/M
+ 2.303 RT/ nF log [M
n+
(aq)]

4. Define a reference electrode?
The tendency of an electrode to lose electrons, when it is in contact with
solution of its own ions.

5. Why glass electrode cannot be used for solution of pH above 9.0?
At pH above 9.0, the ions of the solution affect the glass interface and
render the electrode useless.

6. Glass electrode is preferred to quinhydrone electrode in measuring pH of a
solution. Give reason.
Glass electrode is simple, not easily oxidized and attains equilibrium
rapidly. It can safely be used up to pH of 10. On the other hand, quinhydrone
electrode can be used upto a pH of 8 only. Moreover, it cannot be used in solutions
containing redox system. Hence, use of glass electrode in pH measurement is
preferred over quinhydrone electrode.

7. Electrode potential of zinc is assigned a negative value; whereas that of
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copper a positive value.
Zn electrode is anodic wrt to SHE, so its electrode potential is assigned a
negative sign. On the other hand, Cu electrode is cathodic wrt to SHE, so its
electrode potential is assigned a positive sign.
8. What is galvanic cell or voltaic cell?
It is a simple device of producing electrical energy by chemical reaction, e.g.,
Daniel cell. Such a cell is also known as electrochemical cell.

ZnSO
4 CuSO4
Zn -------- > Zn
+2
+ 2e~ (oxidation)
Cu
2+
+ 2e --------- > Cu (reduction)

In the above cell Zn-electrode is anode and Cu-electrode is cathode.
9. What is an electrolytic cell?
It is a device used for converting electrical energy into chemical energy.

10. What do you mean by electrode potential (E)?
It is the tendency of an electrode in a half cell to lose or gain electrons when it is
in contact with the solution of its own ions.

11. What are reduction and oxidation potentials?
Reduction potential is the tendency of an electrode in a half cell to gain electrons
and oxidation potential is the tendency of an electrode in a half cell to lose electrons.
12. What do you mean by standard electrode potential (E)?
It is the electrode potential of a metal in contact with its ions when the
concentration of ions is 1 M (1 molar).

13. What is a salt bridge?
It is an inverted U-tube containing an electrolyte (e.g., KC1, KNO
3
). It connects
(acts as a bridge) the solutions of the two half cells.

14. What is the E.M.F. of a cell?
It is defined as the potential difference between the two terminals of the cell
when no current is drawn from it.
15. Define normal hydrogen electrode.
It is a reference or standard reference electrode. Its electrode potential is taken
as zero at all temperatures. A normal hydrogen electrode generally consists of a Pt-
foil coated with platinum, dipped in solution having 1 M H
+
ion concentration
and hydrogen gas at 1 atmospheric pressure constantly bubbled over it. It can be
represented as:
16. What do you mean by potentiometry?
Potentiometry is an electrochemical method of analysis based on
measuring the potential difference (e.m.f.) between two half cells, one of which
is an indicating electrode and the other is a reference electrode.

17. What is an indicating electrode?
It is an electrode in balance with an redox couple, the potential of which is
given by Nernst equation.

18. What are reference electrodes?
These are the electrodes whose potential is constant and independent
of the composition of the contacting solution.
The most widely used are saturated calomel electrodes (G = + 0.246 V) and
the silver-silver chloride electrode (e = + 0.222 V).
19. Define the electrochemical series?
When the standard reduction potentials of the electrodes are arranged in an
increasing order, the series so obtained is known as electrochemical series.

20. How do you increase the value of reduction potential of an electrode?
By increasing the concentration of metal ions in contact with metal
electrode or increasing the temperature.

PART-B
1. How do you measure EMF of a cell?
The difference of potential which causes flow of current from an electrode of
higher potential to an electrode of lower potential is called electromotive force.
Measurement of EMF of a cell:
The emf of a cell can be measured using a potentiometer. This measurement is
based on poggendorffs compensation principle. In this method, the emf to be measured
is opposed by the emf of another cell or battery until the two emfs become equal and
there is no net flow of current in the circuit.The electrical assembly used is known as
potentiometer.

It consists of a uniform wire AC of high resistance. A storage battery of constant
emf is connected at the ends A and C by the wire.
The cell X, the EMF of which is to be determined is included in the circuit by
connecting the positive pole to A and the negative pole to the sliding contact J through a
galvanometer. The sliding contact is moved along the wire AB till no current flows
through the galvanometer.The distance AD is noted. The emf of the cell E
x
is
proportional to the distance AD,
i.e.,E
x
AD ------(1)
The cell X is replaced by a standard cell of known emf,E
s
. The position of the
sliding contact is readjusted by moving it the wire AB, as before ,till no current flows
through the galvanometer, i.e., the null point,is reached again at D as shown in the
figure.
Now the emf of the cell is proportional to the distance AD,
i.e., E
s
AD --------(2)
From (1) & (2)
E
x
/ E
s =
AD/ AD
E
x=
E
s
AD/ AD
Hence the emf of unknown cell is measured.

2. Write notes on calomel electrode
This electrode consists of mercury, mercurous chloride and a solution of saturated
KCl. The cell is represented as;
Pt,Hg,Hg
2
Cl
2
/KCl(sat)
Mercury is placed at the bottom of the electrode. Mercury is covered by a paste of
mercurous chloride and a solution of saturated KCl is introduced above the paste. A
platinum wire sealed in to a glass tube serves to make electrical contact of the electrode
with the circuit.

Calomel electrode
If the electrode acts as anode, the electrode reaction will be;
2Hg + 2Cl
-
Hg
2
Cl
2
+2e-

If the electrode acts as cathode the electrode reaction will be;
Hg
2
Cl
2
+2e-

2Hg + 2Cl
-

The electrode potential can be written as
E= E -0.0591/2 log[Cl
-
]
2
or E= E -0.0591 log[Cl
-
]
The electrode potential depends on the concentration of chloride ion.

3. Discuss the construction of glass electrode.
It is an electrode, which produces current in response to a specific ion present in
the solution. This electrode is otherwise known as ion selective electrode.
Construction:

A glass membrane electrode consists of thin walled glass bulb containing AgCl
coated Ag electrode or platinum wire in 0.1M HCl. There is an equilibrium exist between
H
+
ions of solution and Na
+
ions of glass. For a particular type of glass the electrode
potential depends on the concentration of H
+
ions. This can be represented as;
AgCl, Ag, HCl (0.1M)/Glass or Pt, HCl (0.1M)/Glass
If this electrode acts as anode , the electrode reaction will be;
H
2
H
+
+ e
-

If this electrode acts as cathode , the electrode reaction will be;
H
+
+ e
-
H
2

The electrode potential can be written as;
E= E
g
-0.0591 log[H
+
] -----------(oxidation potential)
E = E
g
+0.0591p
H
Determination of p
H
with the help of glass electrode: The electrode is
dipped into the solution where p
H
is to be determined and is usually
combined with a reference electrode generally calomel electrodeto
form a complete cell. The potential of the glass electrode varies linearly with
pH .
`

Solution of unknown p
H

Ecell= E
R
- E
L

E
cell
= Ecalomel - Eglass
E
cell
= +0.2422- ( Eglass -0.0591log [H
+
]
E
cell
= +0.2422- Eglass -0.0591p
H

p
H
=+.2422 - E
G
-E
cell
/.0591

5. What is meant by EMF series? Explain the importance of EMF series.
The electrode potentials of various electrodes are arranged in the order of
increasing standard reduction potentials with respective to hydrogen scale.This
arrangement is known as electrochemical series
Importance of electrochemical series:

Saturated
calomel electrode

Glass
electrode
Calculation of standard EMF of a cell:
The standard EMF of a cell can be calculated using the standard reduction
potentials of right hand side and left hand side electrodes from the emf series.

E
cell
= E
R
- E
L

Relative ease of oxidation and reduction:
Higher the value of standard reduction potential, greater is the tendency to get
reduced. For example, in the electrochemical series, fluorine has high positive value of
reduction potential (+2.87 V) and is reduced. Lower the value of standard reduction
potential, greater is the tendency to get oxidized. In the electrochemical series, lithium
has the lower negative reduction potential value (-3.05V) and is oxidized.

Predicting spontaneity of a reaction:
The spontaneity of a reaction can be determined from the standard emf of the cell.
If the emf of a cell is positive, the reaction is spontaneous. If it is negative, the reaction is
non spontaneous.
Ecell= E
R
- E
L
= + ive (spontaneous)
Ecell= E
R
- E
L
= - ive (non spontaneous)

Displacement behaviour of hydrogen:
If zinc electrode is immersed in H
2
SO
4
solution, it displaces hydrogen from acid
solution.
Zn + H
2
SO
4
ZnSO
4
+H
2

If silver electrode is immersed in H
2
SO
4
solution, it will not displace
hydrogen from acid solution. Because it has higher reduction potential value.

Ag + H
2
SO
4
No reaction

6. Derive Nernst equation for electrode potential.

Nernst equation for electrode potntial:
Consider the following redox reaction:
M
n+
+ ne
-
M

For such a redox reversible reaction, the free energy change (G) and its equilibrium
constant (K) are inter related as

G= - RTlnK + RTln [Product]/ [reactant]

G = G
+ RTln [Product]/ [reactant] [ G
= - RTlnK ]

Where G
=Standard free energy change

The above equation is known as Vant Hoff reaction isotherm. The decrease in free
energy in the above reversible reaction will produce electrical energy.

-G = nFE and G
=- nFE

Where E is the electrode potential, E
is the standard electrode potential, F = 96500

coulombs and n is the number of electrons transformed.
Comparing equations (1) and (2),it becomes

- nFE = -nFE
+ RTln [ M]/ [M
n+
] (consider the reduction reaction)

- nFE = -nFE
+ RTln 1/ [M
n+
] ([M] = 1)

Dividing eqn (3) by nF

E = E
- RT/nF ln 1/ [M
n+
]
or
E = E
+ RT/nF ln [M
n+
]

E = E
+ 2.303 RT/nF log [M

n+
]

Where R =8.314 J/K/mole, F = 96500coulombs, T = 298K, the above equation becomes

E = E
+ .0591 /n log [M
n+
] This the Nernst equation for reduction potential

For oxidation potential

E = E
- .0591 /n log [M
n+
]

Application:
i) It is used to calculate electrode potential of unknown metal.
ii) It can be used to calculate the emf of a cell.

7. Write notes on potentiometric redox titrations.

Potentiometric Titrations:
A titration in which concentration change is followed by potential change is called
a potentiometric titrations. Two electrodes are required to measure the potential of the
test solution. The potential of one electrode should be constant while that of the other
should change with concentration of the test species. The former is called reference
electrode and the latter is called an indicator electrode which is different for different
types of titrations. For a redox titration (Fe
2+
Vs Cr
6+
), calomel electrode is used as a
reference electrode and platinum is used as an indicator electrode. The two electrodes are
connected to a potentiometer.

Redox Titration:( Fe
2+
Vs Cr
6+
)

Titration of ferrous sulphate vs potassium dichromate is Fe
2+
Vs Cr
6+
.When
K
2
Cr
2
O
7
is added to ferrous sulphate in acid medium, ferrous ion is oxidized to ferric ion
hexavalent Cr is reduced to trivalent state. The potential of this system depends on ratio
of ferrous to ferric.

trivalent Cr will be present. So the potential of this system will follow the concentration
ratio of hexavalent Cr to trivalent Cr. When the potential is plotted against the volume of
dichromate added, the following graph is obtained.

The potential is found to increase with the addition of K
2
Cr
2
O
7.
Initially the
increase in potential is gradual but at the end point, the increase is very steep because
almost all Fe
2+
would have been converted to Fe
3+
.Thereafter Fe
2+
will not be present.
Beyond the end point , addtion of excess Cr
6+
established equilibrium with Cr
3+
present in
the solution. The potential now depends on Cr
6+
/Cr
3+
.The diffential graph is drawn for
getting more accurate end point.

The mid point of the curve is known as the end point. The cell is represented as
Pt, Hg, Hg
2
Cl
2
/ KCl(sat)//Fe
2+
, Fe
3+
(H
+
)/ Pt .

8. Write notes on conductivity Acid- Base Titration.
Strong Acid Vs Strong Base:
A known amount of acid (HCl) is taken in a beaker and alkali (NaOH) is taken in
the burette. A conductivity cell is introduced into the beaker solution. Initially the
conductivity of HCl is high, this is due to the presence of fast moving H
+
ions. As NaOH
is added gradually, conductance will be going on decreasing until the acid has been
completely neutralized. This is due to yhe replacement of fast moving H
+
ions by slow
moving Na
+
ions. The point B indicates the complete neutralization of all H
+
ions.


HCl +NaOH NaCl + H
2
O

Further addition of NaOH will introduce fast moving OH
-
ions.Therefore the
conductance value will begin to increase. On plotting conductance against volume of
NaOH added, the two lines intersect at a point B which corresponds to the neutralization
point.

Advantages:
i) Conductometric titrations give more accurate end point.
ii) It can be used to titrate col,oured solutions where the colour change of the
indicator is not clear.
iii) It can be used for titratig dilute solutions.
iv) There is no need to have keen observation near the end point, as it is
determined graphically.

Problems
1. Calculate the emf of a cell at 25 C, when the concentration of ZnSO4 and
CuSO4 are 0.001 M and 0.1 M, respectively. The standard potential of cell is
1.2 V.
Solution
Cell is: Zn(s) | Zn
2+
(0.001 M) || Cu
2+
(0.1 M) | Cu(s)
E
cell
= E
o
cell
+ (0.0592 /2) log [Cu
2+
]/ [Zn
2+
]
= 1.2 + 0.0296 2
= 1.2 + 0.0592
= 1.2592 V
2. What is concentration of Ni2+ in the cell at 25C, if the emf is 0.601 V?
Ni(s) | Ni
2+
(a = ?) || Cu
2+
(0.75 M) | Cu(s)
Given
E
o
Ni/Ni
2+
= 0.25 V ; E
o
Cu
2+
/Cu

= 0.34 V
Solution
E
cell
= E
o
cell
+ (0.0592 /2) log [Cu
2+
]/ [Ni
2+
]
0.601 = (0.34-(-0.25) + 0.0296 log [0.75/a]
0.011 = 0.0296 log 0.75/a
log 0.75/a = 0.011 / 0.0296
0.75/a = Antiliog 3.7162
a = 0.75 / 2,3529
= 0.3188 M.

Chem Unit3 Ans

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UNIT-III

+ RTln [Product]/ [reactant] [ G

=Standard free energy change

is the standard electrode potential, F = 96500

+ 2.303 RT/nF log [M

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