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SMJC 2233 Physical Chemistry

ELECTROCHEMICAL CELLS
Coverage:  Atkins, Chapter 6.
 Gilbert W. Castellan, Chapter 17.
 David W. Ball, Chapter 8.

Dr. Kamyar Shameli


Environmental and Green Technology Department
Chemical Energy Conversions and Applications (ChECA) i-Kohza
MJIIT, UTM, 54100 Kuala Lumpur, Malaysia
E-mail: kamyar@utm.my
CHARGES
Coulomb made accurate measurements of the force of
attraction or repulsion between small charged spheres
and found that:
 Attraction or repulsion is dictated by the types of the charges
on the spheres
 The magnitude of the interaction between any two spheres
(attraction or repulsion, F) is dependent on the distance
between the two small spheres, r :
Charles-Augustin de
Coulomb (1736–1806)
 The force between charged objects is proportional to the was a French physicist
magnitude of the charges (q1 and q2) on the objects. who used very delicate
instrumentation to
make measurements on
 This equation is known as Coulomb’s law. In order to get the the force of attraction
correct unit of force, newtons, an additional expression is between charged
bodies.
included in the denominator of the equation.

“epsilon naught” is called the permittivity of free space. Its value is 8.854×10-12 C2/(Jm).
q can be + or - by convention F is + for forces of repulsion and - for forces of attraction.
EXAMPLES
Calculate the force between charges in the following cases.
a. +1.6 ×10-18 C and +3.3×10-19 C at a distance of 1.00×10-9 m

• We used the fact that 1 J=1 N.m.


The positive value for the force indicates that it is a force of repulsion.
This is a very small force for macroscopic objects, but a very large force for atom-
sized systems, like ions.
b. +4.83×10-19 C and -3.22 ×10-19 C at a distance of 5.83 Å

• Because the force is negative, it represents a force of attraction between the two
charged bodies.
PREVIOUS EXAMPLES INVOLVE THE FORCE DUE TO
ELECTRICAL CHARGES IN A VACUUM.
 If the electrical charges are in some medium other than vacuum, then a correction
factor called the dielectric constant, ɛr, of that medium appears in the denominator of
the equation for the force.
Dielectric constant = ɛr
For water ɛr = 78
ɛr is unitless. The higher the ɛr, the smaller the force between the charged particles.
 The Electric field (E) of a charge q1 interacting with another charge q2 is defined as
the force between the charges divided by the magnitude of the charge itself.

ɛr need to be added for any medium

 The magnitude of the electric field E (the electric field is technically a vector) is the
derivative with respect to position of some quantity called the Electric potential ɸ:
ELECTRIC POTENTIAL REPRESENTS HOW MUCH ENERGY AN
ELECTRIC PARTICLE CAN ACQUIRE AS IT MOVES THROUGH THE
ELECTRIC FIELD .
We can rewrite this equation and integrate with respect to position r :

We have an expression for E in terms of r, after substitute:


electric potential
This integral is solvable, since it is a function of r (that is, r to the second power in the
denominator; all other variables are constant). We get:

Evaluating:

The units for electric potential, is J/C. Since we will be working with
electric potentials quite a bit, we define a new unit, volt (V) 1 V=1 J/C
The unit volt is named in honor of the Italian physicist Alessandro Volta (1745-1827)
INTRODUCTION TO CELLS: TERMINOLOGY AND BACKGROUND
WHY IS IT PAINFUL TO BITE AL FOIL?
You may experienced a severe pain in teeth after accidentally eating a piece of sweet rapper.
Metal fillings in the teeth
Sweet wrapper made of aluminium metal ‘silver paper’. Al dissolves readily in acidic,
conductive electrolytes (saliva pH: 6.5–7.2) This dissolution is an oxidative process.
The pain comes through those teeth filled with metal (silver dissolved in mercury to
form a solid – we call it a silver amalgam)

An electrochemical cell is ‘two or more half-cells in


contact with a common electrolyte’.

• Al as the more positive pole (the anode)


• Fillings acting as the more negative pole (the
cathode).
• Saliva completes this cell as an electrolyte.

Anode
Cathode
ELECTROCHEMISTRY

Electrochemistry is the branch of physical


chemistry that studies chemical reactions which
take place at the interface of an electrode,
usually a solid metal or a semiconductor, and an John Daniell (left) and
ionic conductor, the electrolyte. These reactions Michael Faraday (right),
both credited as founders
involve electric charges moving between the of electrochemistry today.
electrodes and the electrolyte.
An electrochemical cell can be defined as a
single arrangement of two electrodes in one or
two electrolytes which converts chemical energy
into electrical energy or electrical energy into
chemical energy.
TYPES OF ELECTROCHEMICAL CELLS

A spontaneous reaction generates Absorb free energy from an electrical source


electrical energy to drive a nonspontaneous reaction
Galvanic Cells
A galvanic cell is an electrochemical cell that
produces electricity as a result of the
spontaneous reaction occurring inside it.
Galvanic cell generally consists of two
electrodes dipped in two electrolyte
solutions which are separated by a porous
diaphragm or connected through a salt
bridge. To illustrate a typical galvanic cell,
we can take the example of Daniel cell.
DANIEL CELL.

At the anode: Zn → Zn 2+ + 2e-


At the cathode: Cu 2+ + 2e- → Cu
Net reaction: Zn(s)+Cu 2+ (aq)→ Zn 2+ (aq)+ Cu(s)
REPRESENTATION OF GALVANIC CELL
Anode Representation:

Zn│Zn2+ or Zn ; Zn2+
Zn │ ZnSO4 (1M) or Zn ; ZnSO4 (1M)
Cathode Representation:

Cu2+ │ Cu or Cu2+ ;Cu


Cu2+ (1M) ; Cu or CuSO4(1M) │ Cu
Cell Representation:
Zn │ ZnSO4 (1M)║ CuSO4(1M) │ Cu
ELECTROLYTIC CELL
An electrolytic cell is an electro –chemical cell in which a non-
spontaneous reaction is driven by an external source of current
although the cathode is still the site of reduction, it is now the negative
electrode whereas the anode, the site of oxidation is positive.
LIQUID JUNCTION POTENTIAL.
Unlike Daniel cells, in the cells with 2 different electrolytes, there is
additional source of potential difference. Difference between the electric
potentials developed in the two solutions across their interface.
Examples:
Contact between two different electrolytes (ZnSO4/ CuSO4).
Contact between same electrolyte of different concentrations (0.1M HCl /
1.0 M HCl).

Electrolyte concentration cells always have a liquid junction; electrode


concentration don’t have.
SALT BRIDGE.
The liquid junction potential interferes with the
exact measurement of the electromotive force of
a chemical cell, so its effect should be
minimized as much as possible for accurate
measurement.
The liquid junction potential can be reduced (to
about 1 to 2 mV) by joining the electrolyte
compartments through a salt bridge.
Function Of Salt Bridge
 It provides electrolytic contact between the two
electrolyte solutions of a cell.

 It avoids or at least reduces junction potential in


galvanic cells containing two electrolyte solutions
in contact.
ELECTROMOTIVE FORCE (EMF) OF A CELL.
The difference of potential, which causes a current to flow from the
electrode of higher potential to one of lower potential.
Ecell = Ecathode- Eanode
The E Cell depends on:
The nature of the electrodes.
Temperature.
Concentration of the electrolyte solutions.

Standard emf of a cell (Eo cell) is defined as the emf of a cell when the
reactants & products of the cell reaction are at unit concentration or unit
activity, @ 298 K and at 1 atmospheric pressure.
STANDARD CELL.
It is one which is capable of giving constant and reproducible emf.

It has a negligible temperature coefficient of the emf.

The cell reaction should be reversible.

It should have no liquid junction potential.

E.g. Weston Cadmium Cell. The emf of the cell is 1.0183 V at 293 K
and 1.0181 V at 298 K.
WESTON CADMIUM CELL
Cell representation:
Cd-Hg/Cd2+// Hg2SO4/Hg

At the anode:
Cd (s) → Cd2+ + 2e-

At the cathode:
Hg2SO4(s) + 2e- → 2 Hg (l)+ SO42-(aq)

Cell reaction:
Cd + Hg 2+ → Cd2+ + 2Hg
ORIGIN OF SINGLE ELECTRODE POTENTIAL.
Consider Zn(s)/ ZnSO4
Anodic process: Zn(s) → Zn2+(aq)
Cathodic process: Zn2+(aq) → Zn(s)

 At equilibrium: Zn(s) ↔ Zn2+(aq)

Metal has net negative charge and solution has equal positive
charge leading to the formation of an Helmholtz electrical layer.
Helmholtz double layer
 Electric layer on the metal has a potential Ø(M).
 Electric layer on the solution has a potential Ø(aq)
 Electric potential difference between the electric
double layer existing across the electrode
/electrolyte interface of a single electrode or half cell.
MEASUREMENT OF ELECTRODE POTENTIAL.

It is not possible to determine experimentally the potential


of a single electrode.
It is only the difference of potentials between two
electrodes that we can measure by combining them to give a
complete cell.
By arbitrarily fixing the potential of reversible hydrogen
electrode as zero it is possible to assign numerical values to
potentials of the various other electrodes.
SIGN OF ELECTRODE POTENTIAL.
The electrode potential of an electrode:
Is positive: If the electrode reaction is reduction when coupled with the
standard hydrogen electrode.
Is negative: If the electrode reaction is oxidation when coupled with standard
hydrogen electrode. According to latest accepted conventions, all single electrode
potential values represent reduction tendency of electrodes.
when copper electrode is combined with SHE, When zinc is coupled with S.H.E. zinc
copper electrode acts as cathode and electrode acts as anode and hydrogen
undergoes reduction hydrogen electrode acts electrode acts as cathode.
as anode. Zn → Zn2+ +2e-
H2(g) → 2H+ +2e- (oxidation) 2H+ + 2e-→ H2.
Cu2+ +2e- → Cu (reduction) Hence, electrode potential of zinc is negative.
Hence electrode potential of copper is The standard electrode potential of zinc
assigned a positive sign. Its standard electrode is -0.74 V.
electrode potential is 0.34 V.
NERNST EQUATION.
Nernest received the 1920 Nobel Prize in
Chemistry for his contributions in thermodynamics.
Having recognized the validity of the following
two equations:
Walther Hermann von Nernst
(1864–1941), a German chemist
first formulated an equation relating
the potential of an electrochemical
reaction to the instantaneous
One can combine them to yield conditions of the products and
reactants. His Nobel Prize (1920),
was awarded in honor of his
Solving for E, the nonstandard electromotive force: pioneering work to establish the
third law of thermodynamics.

Nernst equation

Recall that Q is the reaction quotient, which is expressed in terms of the


instantaneous (nonequilibrium) concentrations, pressures, activities, or fugacities of
reactants and products.
EXAMPLES.
Given the nonstandard concentrations for the following
reaction, calculate the instantaneous E of the Daniell cell.

which is Q= 0.00444/0.0333= 0.133. Given that the voltage under standard


conditions,
E°= 1.104 V, we have

All of the units cancel except for the expression J/C, which equals the unit volt.
Solving:

slightly greater than the standard voltage


A galvanic cell consists of copper plate immersed in 10 M solution of
CuSO4 and iron plate immersed in 1M FeSO4 at 298K. If E0cell=0.78
V, write the cell reaction and calculate E.M.F. of the cell.

Solution:

Cell reaction: Fe + Cu2+ ↔ Fe2+ + Cu


E Cell= E0Cell - 0.0592/2 log [Fe2+ ]/[Cu2+]
E Cell= 0.78 + 0.0296 log 10/1= 0.8096V
Calculate E.M.F. of the zinc – silver cell at 25˚C when [Zn2+]
= 1.0 M and [Ag+] = 10 M (E0cell=1.56V at 25˚C). Write
the cell representation and cell reaction

Solution:
Cell representation Zn/ Zn2+((1M)//Ag+(10M) /Ag
Cell reaction:
Zn + 2Ag+ ↔ Zn2+ + 2Ag
ECell= E0Cell-0.0592/2 log [Zn2+ ]/[Ag+]2
ECell= 1.56 + 0.0592 log 10/1.0 =1.6192 V
The emf of the cell

(0.01M)║
Mg│ Mg 2+ Cu 2+ /Cu is measured to be 2.78 V at 298K. The
standard eletrode potential of magnesium electrode is -2.37 V. Calculate the
electrode potential of copper electrode

Cell reaction:

Mg + Cu2+ ↔ Mg2+ + Cu

E= Eo - 0.0592/n log 1/[Mn+]


EMg= EoMg-0.0592/2 log 1/[Mg2+] = -2.4291V
E cell= E Cu- E Mg
2.78 = E Cu-[-2.429] E Cu =2.78-2.429 = 0.3509 V
E ° VARIATION WITH TEMPERATURE
The Nernst equation is very useful for estimating the voltage of electrochemical cells at
nonstandard conditions of concentration or pressure. But despite the fact that the equation
contains temperature, T, as a variable, it has limited use at temperatures other than 25°C.
That’s because E° itself varies with temperature.
We want to estimate how E°varies
with temperature:

Combining

where we have now included the ° symbol on G, E, and S. Solving for the change
in E°with respect to the change in temperature

rearrange and approximation


temperature
where ΔT is the change in temperature (from the 25°C). coefficient of the
reaction
The new EMF at the nonreference temperature is
CHANGE IN S°
Previuos equations are approximations, but fairly good ones. We aren’t even
considering the change in S° as the temperature changes.
Since F is a relatively large number, the change in E° is slight as the temperature
changes, but there can be a noticeable effect for some common electrochemical
reactions.
We can easily rearrange to get an
expression for ΔS°:
Now that we have expressions for ΔG° and Δ S° , we can find an expression for
Δ H°. Using the original definition for Δ G (that is, Δ G = Δ H-T Δ S), we get

We rearrange this algebraically to get

This equation allows us to calculate H°


for a process using electrochemical
information.
EXAMPLES.
Estimate E for the following reaction at 500 K:

This is the chemical reaction for fuel cells, which among other uses provide
electrical power to the space shuttle.
First, we determine E°under standard conditions. The above reaction can be
broken down into the half-reactions

The standard EMF for the


reaction is therefore 1.229 V.

ΔS° for the reaction is determined by looking up S°values for H2, O2, and H2O (all in
the gaseous state). We get

for the molar reaction. The change in temperature is 500 K-298 K=202 K. Now, we can
estimate the change to E°:

the approximate voltage of the reaction at 500 K is


Consider the following formation reaction for H2O (l):

If ΔH°= 571.66 kJ at 25 °C and n =4 for this reaction, determine the


temperature coefficient of the standard potential E°.
ENERGETICS OF CELL REACTIONS; DETERMINATION OF
THERMODYNAMIC FUNCTIONS
Net electrical work performed by the cell reaction of a
galvanic cell:
W= QE ------(1)
Charge on 1mol electrons is F(96,500) Coulombs.
When n electrons are involved in the cell reaction,
the charge on n mole of electrons = nF
Q = nF
Substituting for Q in eqn (1)
W = nFE ----------(2)
The cell does net work at the expense of
-ΔG accompanying. ΔG = -nFE
-ΔG = nFE
From Gibbs – Helmholtz equation.
ΔG = ΔH + T [δ(ΔG)/ δT]P ------- (2)
-nFE = ΔH – nFT (δ E/ δT)P
ΔH = nFT (δ E/ δ T)P – nFE
ΔH = nF[T(δ E/ δT)P –E]
We know that, [δ (∆G)/ δT]P = - ΔS
ΔS = nF (δE/ δT)P

Problem: Emf of Weston Cadmium cell is 1.0183 V at 293 K


and 1.0l81 V at 298 K.
Calculate ∆G, ΔH and ΔS of the cell reaction at 298 K.
Solution:- ∆G: ∆G = - n FE
n = 2 for the cell reaction; F = 96,500 C
E= 1.0181 V at 298 K
∆G = -2 x 96,500 x 1.0181 J = -196.5 KJ

∆H: ∆H = nF [ T (δE /δT)P – E]


(δE/δT)p = 1.0181 – 1.0183 / 298-293 = -0.0002 / 5
= -0.00004VK-1
T = 298 K
∆H = 2 x 96,500 { 298 x (-0.00004) – 1.0181)
= -198. 8 KJ
ΔS: ΔS = nF (δE / δT) P
= 2 x 96,500 x (0-00004) = -7.72JK-1
CLASSIFICATION OF ELECTRODES.
Conventional electrodes as half cells for electroanalytical techniques involve redox
reactions (electrodes of zeroth, 1st, 2nd and 3rd kinds) as follows:

Class 0: Inert metals used in oxidation-reduction electrolytic cells. Ideal inert


materials exchange electrons reversibly with the electrolyte components and are not
subject to oxidation or corrosion themselves, i.e., “ideally” polarizable electrodes.
Example: Gas electrode (Hydrogen H2/H+ electrode)

Class 1: Reversible metal/metal ion (ion exchanging metals bathed in electrolytes


containing their own ions), for Example Ag/Ag+.

Class 2: Reversible metal/metal ion with saturated salt of the metal ion and excess
anion X- , for Example Ag/AgX/X-.

Class 3: Reversible metal/metal salt or soluble complex/second metal salt or


complex and excess second cation, for example Pb/Pb-oxalate/Ca-oxalate/Ca2+ or
Hg/Hg-EDTA2-/Ca-EDTA2-/Ca2+.

At a gas-electrode one component of the redox couple is in the gaseous state.


Ion-selective electrodes (ISEs) based on thin films or selective membranes as
recognitive elements are equivalent to other half-cells.
CLASS 0
GAS ELECTRODE.
It consists of gas bubbling over an inert metal wire or foil immersed in a solution
containing ions of the gas.
Standard hydrogen electrode (SHE) is the primary reference electrode, whose
electrode potential at all temperature is taken as zero arbitrarily.

Representation:
 The electrode reaction is Pt,H2(g)/H+
reversible as it can undergo
either oxidation or reduction
depending on the other half
cell.

 If the concentration of the H+


ions is 1M, pressure of H2 is
1atm at 298K it is called as
standard hydrogen electrode
(SHE).
CONSTRUCTION.
STANDARD HYDROGEN ELECTRODE (SHE).
APPLICATIONS.
To determine electrode potential of other unknown electrodes.
To determine the pH of a solution.
E=Eo- 2.303 RT/nF log [H2]1/2/[H+]
= 0 -0.0591 log 1/[H+]
= -0.0591pH.

pH = E(cell)/ 0.0592
Cell Scheme: Pt,H2,H+(x)// SHE

LIMITATIONS.
Construction and working is difficult.
Pt is susceptible for poisoning.
Cannot be used in the presence of oxidizing agents.
CLASS 1
METAL –METAL SALT ION ELECTRODE .
These electrodes consist of a metal and a sparingly soluble salt of the same metal
dipping in a solution of a soluble salt having the same anion.
E.g. Ag/AgCl E.g. Calomel
electrode. reference
electrode
# A much more common
reference electrode.

# It much easier to work


with-no gas

# Hg/Hg2Cl2(sat),
KCl//KCl is used to
maintain constant ionic
strength.
Representation: Hg; Hg2Cl2 / KCl

It can act as anode or cathode depending on the nature of the other


electrode.

As anode: 2Hg + 2Cl- → Hg2Cl2 + 2e-

As Cathode: Hg2Cl2 + 2e- → 2Hg + 2 Cl-

The NERNST EQUATION for this reaction is:

αHg is the Activity for the mercury cation (the activity for a liquid of 1 Molar is 1).
This activity can be found from the solubility product of the reaction.

By replacing the activity in the Nernst equation with the value in the solubility
equation, we get:
The only variable in this equation is the activity (or concentration) of the chloride anion. But
since the inner solution is saturated with KCl, this activity is fixed by the solubility of KCl.

When saturated the redox potential of the CALOMEL ELECTRODE is +0.2444 V


vs. SHE at 25 °C, but slightly higher when the chloride solution is less than saturated.

For example, a 3.5M KCl electrolyte solution increases the reference potential to +0.250 V
vs. SHE at 25 °C, and a 0.1 M solution to +0.3356 V at the same temperature.

ITS ELECTRODE POTENTIAL DEPENDS ON THE CONCENTRATION OF KCL

CONC. OF CL- ELECTRODE POTENTIAL

0.1 M 0.3335 V

1.0 M 0.2810 V

Saturated 0.2422 V
APPLICATIONS.
 Since the electrode potential is a constant it can be used as a secondary
reference electrode.
 To determine electrode potential of other unknown electrodes.
 To determine the pH of a solution.
Pt, H2/H+(X) // KCl, Hg2Cl2,Hg
pH = E(cell) – 0.2422/ 0.0592
ION SELECTIVE ELECTRODE.
It is sensitive to a specific ion present in an electrolyte.
The potential of this depends upon the activity of this ion
in the electrolyte.
Magnitude of potential of this electrode is an indicator
of the activity of the specific ion in the electrolyte.
*This type of electrode is also called indicator electrode.
SCHEME OF TYPICAL PH GLASS ELECTRODE

A sensing part of electrode,


1. A bulb made from a specific glass sometimes
electrode contain small amount of AgCl precipitate
inside the glass electrode.
3 Internal solution, usually 0.1M HCl for pH electrodes
4.Internal electrode, usually silver chloride electrode or
calomel electrode.
5. Body of electrode, made from non-conductive glass or
plastics.
6. Reference electrode, usually the same type as 4
7. Junction with studied solution, usually made from
ceramics or capillary with asbestos or quartz fiber.
The hydration of a pH sensitive glass membrane involves an ion-exchange
reaction between singly charged cations in the interstices of the glass lattice
and protons from the solution.

H+ + Na+ Na+ + H+

Soln. glass soln. glass

Eg = Eog – 0.0592 pH
POTENTIAL OF GLASS ELECTRODE.
The overall potential of the glass electrode has three components:
 The boundary potential Eb
 Internal reference electrode potential Eref.
 Asymmetric potential Easy.- due to the difference in
response of the inner and outer surface of the glass bulb
to changes in [H+].
 Eg = Eb + Eref. + Easy. Eg = Eb + EAg/AgCl + Easy.

Eb = E1 – E2 = L + RT/nF ln C1 + EAg/AgCl + Easy.


= Eog + RT/nF ln C1
= RT/nF ln C1 – RT/nF ln C2 = Eog + 0.0592 log [H+]
= L + RT/nF ln C1
Eb depends upon [H+] Eg = Eog – 0.0592 pH.
ADVANTAGES:
1. It can be used without interference in solutions containing strong
oxidants, strong reductants, proteins, viscos fluids and gases as the
glass is chemically robust.
2. It can be used for solutions having pH values 2 to 10. With some
special glass (by incorporation of Al2O3 or B2O3) measurements can
be extended to pH values up to 12.
3. It is immune to poisoning and is simple to operate
4. The equilibrium is reached quickly & the response is rapid
5. It can be used for very small quantities of the solutions. Small
electrodes can be used for pH measurement in one drop of solution
in a tooth cavity or in the sweat of the skin (micro determinations
using microelectrodes)
6. If recently calibrated, the glass electrode gives an accurate response.
7. The glass electrode is much more convenient to handle than the
inconvenient hydrogen gas electrode.
DISADVANTAGES:
1. The bulb of this electrode is very fragile and has to be used
with great care.
2. The alkaline error arises when a glass electrode is employed to
measure the pH of solutions having pH values in the 10-12 range
or greater. In the presence of alkali ions, the glass surface
becomes responsive to both hydrogen and alkali ions. Low pH
values arise as a consequence and thus the glass pH electrode
gives erroneous results in highly alkaline solutions.
3. The acid error results in highly acidic solutions (pH less than zero)
Measured pH values are high.
4. Dehydration of the working surface may cause erratic electrode
performance. It is crucial that the pH electrode be sufficiently
hydrated before being used. When not in use, the electrode should
be stored in an aqueous solution because once it is dehydrated,
several hours are required to rehydrate it fully.
5. As the glass membrane has a very high electrical resistance (50
to 500 mΩ), the ordinary potentiometer cannot be used for
measurement of the potential of the glass electrode. Thus special
electronic potentiometers are used which require practically no
current for their operation.
6. Standardization has to be carried out frequently because
asymmetry potential changes gradually with time. Because of an
asymmetry potential, not all glass electrodes in a particular
assembly have the same value of EoG . For this reason, it is best to
determine EoG for each electrode before use.
7. The commercial version is moderately expensive.
LIMITATIONS.
The bulb is very fragile and has to be used with great
care.
In the presence of alkali ions, the glass surface
becomes responsive to both hydrogen and alkali ions.
Measured pH values are low.
In highly acidic solutions (pH less than zero) measured
pH values are high.
When not in use, the electrode should be stored in an
aqueous solution.
APPLICATIONS.
Determination of pH:
Cell: SCE ║Test solution / GE
E cell = Eg – Ecal.
E cell = Eog – 0.0592 pH – 0.2422

pH = Eog -Ecell – Ecal. / 0.0592


PROBLEMS
The cell SCE ΙΙ (0.1M) HCl Ι AgCl(s) /Ag
gave emf of 0.24 V and 0.26 V with buffer having pH value 2.8 and
unknown pH value respectively. Calculate the pH value of unknown buffer
solution. Given ESCE= 0.2422 V

Eog= 0.0592pH +Ecell + Ecal.


= 0.0592x2.8 +0.24 + 0.2422
=0.648 V
pH = Eog -Ecell – Ecal. / 0.0592
= 0.648 -0.26-0.2422/0.0592
= 2.46
CONCENTRATION CELLS.
 Two electrodes of the same metal are in
contact with solutions of different concentrations.
Emf arises due to the difference in concentrations.
Cell Representation:
M/ Mn+[C1] ║ Mn+/M[C2]
CONSTRUCTION.
At anode: Zn →Zn2+(C1) + 2e-

At cathode: Zn2+(C2) + 2e-→ Zn


Ecell = EC-EA
= E0 + (2.303RT/ nF)logC2-
[E0+(2.303RT/nF)logC1]
Ecell = (0.0592/n) log C2/C1
Ecell is positive only if C2 > C1
Anode - electrode with lower electrolyte
concentration.

Cathode – electrode with higher electrolyte


concentration.

Higher the ratio [C2/C1] higher is the emf.

Emf becomes zero when [C1] = [C2].


PROBLEMS
Zn/ZnSO4(0.001M)||ZnSO4(x)/Zn is 0.09V at 25˚C. Find the concentration
of the unknown solution.

Ecell = 0.0592/n log C2/C1


0.09 =(0.0592/2) log ( x / 0.001)
x =1.097M

2. Calculate the valency of mercurous ions with the help of the following cell.
Hg/Mercurous ||Mercurous/Hg
nitrate (0.001N) nitrate (0.01N) when the emf observed at 18˚ C is
0.029 V
Ecell=(2.303 RT/nF) log C2/C1
Ecell=(2.303 RT/nF) log C2/C1

0.029 = 2.303RT/n) log (0.01/0.001)


0.029 =0.057 x 1/ n
n = 0.057/0.029 =̃ 2
Valency of mercurous ions is 2, Hg2 2+
Assignment
Answer the following questions:
1.Distinguish between electrolytic and galvanic cells.
2.Explain the origin of electrode potential. What are the sign
conventions for electrode potential?
3.Give reasons for the following.
i) The glass electrode changes its emf over a period
of time.
ii) KCl is preferred instead of NaCl as an electrolyte
in the preparation of salt bridge
4. What is meant by a standard cell? Give an example
5. Quote any four limitations of glass electrode
6.Define liquid junction potential. How it can be eliminated
or minimized?
7.Derive Nernst equation for the single electrode potential.
8.Describe potentiometric determination of emf of a cell.
9.Writ e construction and working of Calomel Electrode
10.What are concentration cells? Show that emf of
concentration cell becomes zero at a certain point of its
working.