APPLICATION OF EMF

MEASUREMENT
PRESENTED BY –
MONIKA MAHAWAR
ROLL NO.- B23CI1024
BATCH – A5

Definition of electromotive force –

The electromotive force (EMF) is the maximum
potential difference between two electrodes of a
galvanic or voltaic cell. This quantity is related to the
tendency for an element, a compound or an ion to gain
or lose electrons. The EMF of a cell is mainly used to
determine whether an electrochemical cell is galvanic or
not.

Application of EMF measurement

some of application are described here -
1. Determination of equilibrium constant
2.determination of solubility of sparingly soluble salt.
3.Determination of valence
4.determination of thermodynamics functions
5.determination of ph of a solution
6.potentiometric titration
7. Determination of activity coefficient
8.determination of transference number

1. Determination of equilibrium
constant
To calculate the equilibrium constant for an electrochemical
cell we need to know:
 The standard state potential for a cell

 the half-reactions involved

The Nernst equation is used in calculating the equilibrium

constant.

At equilibrium Q = K. Substituting in K for Q, and the values

for R, T, and F, we get:
Derivation of equation

When an electrochemical cell runs down the cell voltage is

zero. The system is now in a state of equilibrium. The Nernst
equation can be used to estimate the value of the equilibrium
constant.
Ecell = Eocell - (RT/nF) ln Q
R is the thermodynamic constant, 8.31 joules/mole K. F is
Faraday's constant, 96,485 C/mole e-. At 25°C, or 298K and 1
atm pressure this equation simplifies to
Ecell = Eocell - (0.0257/n) ln Q
At equilibrium the cell potential is zero and Q =
K. Substituting these into the equation we get
0 = Eocell - (0.0257/n) ln K
In terms of log10 the equation becomes
0 = Eocell - (0.0592/n) log K
Rearranging this equation to solve for Eocell we get
Eocell = (0.0592/n) log K
By substituting into the equation the values for Eocell and n, we
can solve for log K. The anitlog can then be calculated with
the aid of a calculator.
log K = x
K = 10x
2.determination of solubility of sparingly
soluble salt.

This is a useful technique to evaluate the solubility product of

sparingly soluble salt such as AgCI. The saturated solution of
AgCl in water is so dilute that it is completely ionized as:
AgCl(s)Ag+(aq)+Cl-(aq)
(9)
The solubility product is given by:
Ksp=aAg+ x
aC1-
(10)
For solutions of high dilution and activity may be replaced
by concentration. Ksp for AgC1 may be determined from Emf
measurements by employing a suitable cell whose overall cell
reaction will be that given by eqn 9 above. A suitable cell
would be
Ag(s)/Ag+(aq)//Cl-(aq)/AgCI(s)/Ag
Left electrode: Ag Ag+ + e
E0= -0.799V
Right electrode: AgCI + e Ag + Cl- E° =
+0.2225V
Overall: AgCl Ag+ + Cl- E°cell
= -0.5765
The cell Emf is given by:
E=E0 - — In aAg+x aCl-
E=E0 - — In Ksp
At equilibrium the cell would not be able to perform any
useful work and hence ECell = 0.
We also know that
G0 = -nE0F = -RT In Ksp
or
E0 = In Ksp
At 298K
E°=0.0591 log Ksp
Log Ksp =

Therefore Ksp = 1.76 x 10-10 mol2 dm-6

The solubility of AgCl may be evaluated from the solubility
product. Since the concentration of Ag+ equals that of C1, we
may write
[Ag+]= [Cl-] = (Ksp)1/2 = (1.76 x 10-10)1/2
Hence the solubility of AgCl is 1.32 x 10-5 mol dm-3

Determination of valence
3.
• The valency of mercurous ion can be determined by
determining the EMF of a concentration cell of the type given
below.
Hg/ Hg2(NO3)2(C1) // Hg2(NO3)2(C2) / Mercury
• The EMF of the cell, E, is given by the expression
• C1
= 0.1M) the EMF was 0.0295V. Therefore, the valency of
mercurous ion is 2, and it should be represented as .
0.059 C
E= log 2
n C1
It was found that when C2/C1 was 10, (i.e. C2 = 1M and
2Hg+2

4.determination of thermodynamics
functions
Determining thermodynamic functions such as entropy (ΔS),
enthalpy (ΔH), and Gibbs free energy (ΔG) using EMF
measurements involves analyzing how EMF changes with
temperature. Here's how it's done:

1. Entropy (ΔS): The change in entropy can be determined

using the relationship:ΔS=−T/ΔH+nFRln(Q) Where:
 ΔH is the enthalpy change.

 T is the temperature in Kelvin.

 R is the gas constant (8.314 J/mol·K).

 Q is the reaction quotient.

 n is the number of moles of electrons transferred in

the cell reaction.

 F is Faraday's constant (96,485 C/mol).

2. Enthalpy (ΔH): The change in enthalpy can be

calculated using the Van't Hoff equation: ΔH=−ndTdE∘
Where:
 ΔH is the enthalpy change.

 n is the number of moles of electrons transferred in

the cell reaction.

 dTdE∘ is the rate of change of standard EMF with

temperature.
3. Gibbs Free Energy (ΔG): The change in Gibbs free
energy can be determined using the relationship:
∘ΔG=−nFE∘ Where:
 ΔG is the change in Gibbs free energy.

 E∘ is the standard EMF of the cell.

 n is the number of moles of electrons transferred in

the cell reaction.

 F is Faraday's constant.

By analyzing EMF data at different temperatures and applying

these relationships, the thermodynamic functions of
electrochemical cells can be determined, providing valuable
insights into the energetics of chemical reactions and the
feasibility of electrochemical processes.

5. Determination of pH

One of the most important applications of Emf measurements

is the determination of the pH of solution. In principle, the
activity of hydrogen ions or the concentration of hydrogen
ions can be determined by setting a cell in which one of the
electrodes is reversible to hydrogen ions.
In practice the hydrogen electrode is combined with another
reference electrode such as standard hydrogen electrode
(SHE) or a saturated calomel electrode (SCE) or any other
reference electrode. ..
For the single hydrogen electrode Pt/H2(1atm)/H+, the
electrode reaction is
1/2H2H++e
The electrode potential is given by
E= In aH+ since E° H+/H2 = 0
By definition pH = -log10aH+Hence the above equation
becomes
E = + ()pH
At 298K
E=+0.0591pH
(11)
Thus the Emf of the cell is linearly dependent on the pH value
of the solution. The hydrogen electrode may be combined
with a reference calomel electrode to obtain the cell;
Pt/H2 (1atm)/H+(a1)//Cl-(a2)/Hg2Cl2/ Hg
As seen from above the potential of the hydrogen electrode is
given by:
EH2= In aH+
Since the calomel electrode is a reference electrode its
potential will be constant and hence its potential may simply
be referred to as reference potential written as E. The Emf of
the cell is given by;
Ecell= ER – EL
= Eref – EH2
= Eref -0.0591 log aH+
=Eref + 0.0591 pH
pH = at 298K
Thus by measuring the Emf of a cell such as the one given
above which has a reference electrode of known potential, the
pH of the solution can be determined.

Potentiometric titrations
In many situations, accurate determination of an ion
concentration by direct measurement of a cell potential is
impossible due to the presence of other ions and a lack of
information about activity coefficients. In such cases it is often
possible to determine the ion indirectly by titration with some
other ion. For example, the initial concentration of an ion such
as Fe2+ can be found by titrating with a strong oxidizing agent
such as Ce4+. The titration is carried out in one side of a cell
whose other half is a reference electrode:
Pt(s) | Fe2+, Fe3+ || reference electrode
Initially the left cell contains only Fe2+. As the titrant is added,
the ferrous ion is oxidized to Fe3+ in a reaction that is virtually
complete:
Fe2++Ce4+→Fe3++Ce3+
The cell potential is followed as the Fe2+ is added in small
increments. Once the first drop of ceric ion titrant has been
added, the potential of the left cell is controlled by the ratio of
oxidized and reduced iron according to the Nernst equation
E=0.68−0.059log]Fe3+][Fe2+]
which causes the potential to rise as more iron becomes
oxidized.

potentiometric titration curve

When the equivalence point is reached, the Fe2+ will have been
totally consumed (the large equilibrium constant ensures that
this will be so), and the potential will then be controlled by the
concentration ratio of Ce3+/Ce4+. The idea is that both species
of a redox couple must be present in reasonable concentrations
poise an electrode (that is, to control its potential according to
the Nernst equation.) If one works out the actual cell potentials
for various concentrations of all these species, the resulting
titration curve looks much like the familiar acid-base titration
curve. The end point is found not by measuring a particular cell
voltage, but by finding what volume of titrant gives the
steepest part of the curve.

4.Determination of Activity Coefficients

Consider a cell where a silver-silver chloride electrode is

combined with a hydrogen electrode to give the following
cell:
Pt/H2(1atm)/HCl(m)/AgCl/Ag
The overall cell reaction of the above cell is
1/2H2(g) + AgCl(s) Ag(s) + H+(aq) + Cl-(aq)
The Emf of the cell is:
E =ER –EL =E0Ag/AgCl – E0H+/H2 -
(13)
By definition E0H+/H2=0, and aAgCl =1
Also (PH2)1/2= 1 since PH2 =1 atm
Hence
E=E°Ag/AgCl - In
aH+aCl- (14)

The mean activity a± of HCl is defined as:

a±2 =aH+aCl-
and
a± =m+
where ± is the mean activity coefficient
E=E°Ag/AgCl - In
m- In± (15)
Directly measurable quantities are rearranged on the left to
give:
E + In m= E°Ag/AgCl -
In±

(16)
At298K
E+0.1181og m=E°Ag/AgCl -
0.1181og± (17)

By measuring the Emf of the cell at different molalities of

hydrochloric acid, the quantity (E+0.1181og m ) can be
calculated at various molalities. If we plot(E+0.1181og m )
against m and extrapolate to zero m, we determine the value
of E° because at zero m± is unity so ln± = 0. Once we know
the value of E°, the mean activity coefficient can be found at
a particular value of m.
8.determination of transference number
Calculation of Transference Number: The transference
number of a specific ion (ti) can be calculated using the
following relationship: ti= jλi /∑ jλi Where:
 λi is the molar conductivity of the ion of interest.

 λj is the molar conductivity of all ions in the solution.

 The sum is taken over all ions present in the solutio