Chemical Thermodynamics:

Basic Terminology:

Terms Explanation
System Part of the universe under investigation.
Open System A system which can exchange both energy and matter with its
surroundings.
Closed System A system which permits passage of energy but not mass, across
its boundary.
Isolated system A system which can neither exchange energy nor matter with
its surrounding.
Surroundings Part of the universe other than system, which can interact with
it.
Boundary Anything which separates system from surrounding.
State variables The variables which are required to be defined in order to
define state of any system i.e. pressure, volume, mass,
temperature, surface area, etc.
State Functions Property of system which depend only on the state of the
system and not on the path.

Example: Pressure, volume, temperature, internal energy,

enthalpy, entropy etc.
Intensive properties Properties of a system which do not depend on mass of the
system i.e. temperature, pressure, density, concentration,
Extensive properties Properties of a system which depend on mass of the system i.e.
volume, energy, enthalpy, entropy etc.
Process Path along which state of a system changes.
Isothermal process Process which takes place at constant temperature
Isobaric process Process which takes place at constant pressure
Isochoric process Process which takes place at constant volume.
Adiabatic process Process during which transfer of heat cannot take place
between system and surrounding.
Cyclic process Process in which system comes back to its initial state after
undergoing series of changes.
Reversible process Process during which the system always departs infinitesimally
from the state of equilibrium i.e. its direction can be reversed at
any moment.
Irreversible Process This type of process is fast and gets completed in a single step.
This process cannot be reversed. All the natural processes are
of this type
Heat, energy and work:

Heat (q):

Energy is exchanged between system and surrounding in the form of heat when they are at different
temperatures.

In any process, increase in energy of the system rises the temperature. Therefore, the heat absorbed,
q is proportional to the rise in the temperature, ∆T and also the quantity of the material taken.

i.e. q α ∆T

or q = C ∆T

where C is the heat capacity, defined as the heat required to rise the temperature of a body by 10C.

Heat added to a system is given by a positive sign, whereas heat extracted from a system is
given negative sign.

It is an extensive property.

It is not a state function.

Work (w):

A system may interact with its surroundings and transfer the energy in the form of work.

Work = Force (F) × Displacement(dx)

i.e. dw = [Link] = [Link] = P (Adx) = PdV

Work done on the system (for example, compression) is given by positive sign while work done
by the system (for example, expansion) is given negative sign.

Mechanical Work or Pressure-Volume Work: work associated with change in volume of a system
against an external pressure. Work done in reversible process:

𝑉2 𝑉2 𝑛𝑅𝑇 𝑉2 𝑑𝑉 𝑉
𝑊 = − ∫𝑉1 𝑃𝑑𝑉 = − ∫𝑉1 ( ) 𝑑𝑉 = − 𝑛𝑅𝑇 ∫𝑉1 = 𝑛𝑅𝑇 log (𝑉1 )
𝑉 𝑉 2

Or W = – 2.303 nRT log V2/V1 = –2.303 nRT log P1/P2

Unit: Joule.

Energy:

It is the capacity for doing work.

Energy is an extensive property.

Unit: Joule.

Internal Energy (E or U):

The energy associated with each substance is called so.

It can also be defined as, ΔU is the heat change for a reaction taking place at constant temperature
and volume.

ΔU is a state function.

It is an extensive property.

Value of ΔU is negative for exothermic reactions while it is positive for endothermic reactions.

First Law of Thermodynamics (Law of conservation of energy):

Energy can neither be created nor destroyed although it can be converted from one form to
another.

or

Energy of an isolated system is constant.

Mathematical Expression

Internal energy = Heat of the system + work

ΔU = q + w i.e. ΔU = q + PΔV
For an infinitesimal process

dU = dq + dw

If work is done on the system (compression), then the change in internal energy is given by,

ΔU = q + w

Otherwise, if work is done by the system (expansion), then ΔU = q - w

For an isolated system, dq=0

so, dU = dw or ΔU = w

At constant volume i.e. isochoric process, ΔV = 0 and hence PΔV = 0,

Therefore, ΔU = qv

For Isothermal Process, ΔU = 0

therefore, q = -W = -PdV

For adiabatic process, q = 0

Therefore, ΔU = W

Enthalpy (H):

The quantity U + PV is known as the enthalpy of the system and is denoted by H. It represents the
total energy stored in the system.

Thus, H = U + PV

It may be noted that like internal energy, enthalpy is also an extensive property as well as a state
function. The absolute value of enthalpy cannot be determined, however the change in enthalpy
can be experimentally determined.

ΔH = ΔU + Δ(PV) = ΔU + PΔV+ VΔP

At constant pressure, ΔH = ΔU + PΔV = qp

For system involving mechanical work only, dH = qP (At constant pressure)

For exothermic reactions:

dH = -ve
For endothermic reactions:

dH = +ve

Heat capacity:

Amount of heat required to raise temperature of the system by one degree.

C = q / dT

Specific heat capacity: Heat required to raise the temperature of 1 g of a substance by one degree.

Cs = Heat capacity / Mass in grams

Molar heat capacity: Heat required to raise the temperature of 1 mole of a substance by one
degree.

Cm = Heat capacity / Molar mass.

Heat capacity of system at constant volume:

Cv = qv/dT

CV = (U/T)V (since ΔU = q + PdV and at constant volume, PdV =0. So, ΔU =qv )

Heat capacity of system at constant pressure:

Cp = qp/dT

CP = (H/ T)P

CP – CV = R, the gas constant.

Second law of thermodynamics

NEED FOR THE SECOND LAW

• The First Law of Thermodynamics tells us that during any process, energy must be
conserved.
• However, the First Law tells us nothing about in which direction a process will proceed
spontaneously.
• It would not contradict the First Law if a book suddenly jumped off the table and
maintained itself at some height above the table.
• It would not contradict the First Law if all the oxygen molecules in the air in this room
suddenly entered a gas cylinder and stayed there while the valve was open.
Statement:

• The Kelvin formulation - It is impossible to construct an engine that, working in cycles,

shall produce no effect other than the extraction of heat from a reservoir and the production
of work.
• The Clausius formulation - It is impossible to construct an engine that, working in cycles,
shall produce no effect other than the transfer of heat from a colder to a hotter body.

Mathematically:

ΔS = qrev/T

Where, ΔS is entropy change.

• Entropy is a measure of the disorder (randomness) of a system. The higher the entropy of the
system, the more disordered it is.
• The second law states that the universe always becomes more disordered in any real process.
• The entropy (order) of a system can decrease, but in order for this to happen, the entropy
(disorder) of the surroundings must increase to a greater extent, so that the total entropy of the
universe always increases.

At equilibrium or reversible process, ΔStotal = ΔSsystem + ΔSsurrounding = 0

A spontaneous or irreversible process is always accompanied by an increase in entropy of the

system and surroundings.

i.e. ΔStotal = ΔSsystem + ΔSsurrounding > 0 or ΔSuniverse > 0

Entropy change in an isothermal reversible expansion of a gas

Physical Significance of Entropy:

1. It is a measure of the disorder of the system. Increase in entropy implies increase in

disorder.
2. It is also a measure of probability. According to Boltzmann,
S = k ln W + constant
Where k is Boltzmann’s constant and W is thermodynamic probability. A solid at absolute
zero temperature is considered to be in a most ordered state. In this case W is unity and S 0
= 0. The entropy of crystalline solids at absolute zero temperature is, therefore, taken as
zero.
OTHER STATE FUNCTIONS:

Determination of ∆Ssur is a complex process. Therefore, new terms have been defined and are
Gibbs free energy, G and Helmholtz free energy, A.

Helmholtz free energy or work function, A:

A = U – TS

Upon differentiation, ∆A = ∆U – T∆S – S ∆T

At constant temperature T, S ∆T = 0,

Therefore, ∆A = ∆U – T∆S

But, ∆S = qrev /T,

∆A = ∆U – T (qrev /T);
∆A = ∆U – qrev

From First law of thermodynamics, ∆U = q + w;

 wrev = ∆U – qrev

If the work is done by the system, then wrev will be -ve.

 ∆A = - wrev or -∆A = wrev

Wrev is the maximum work always possible.

 The decrease in the Helmholtz free energy (-∆A) is a measure of maximum work that can
be done by a system.

At equilibrium, ΔA = 0

For spontaneous process, ΔA < 0

Gibbs free energy(ΔG):

This is another thermodynamic quantity that helps in predicting the spontaneity of a process, is
called Gibbs free energy (G).

Gibbs free energy is the energy needed to create a system out of nothing in an environment at
constant pressure.
It is defined mathematically by the equation.

G = H - TS

Where H = heat content or enthalpy, S = entropy of the system, T = absolute temperature

For isothermal process,

ΔG = ΔH – TΔS

ΔG = change in Gibbs free energy of the system.

But ∆H = ∆U + P∆V

∆G = ∆U + P∆V – T∆S or ∆G = ∆U - T∆S + P∆V

Substituting ∆A = ∆U - T∆S = -wrev

∆G = - wrev + P∆V or - ∆G = wrev - P∆V

Where P∆V is mechanical work done by the system. Therefore, -∆G gives the measure of
maximum work other than volume change obtainable from a system. ie., net work

ie., net work = wrev - P∆V = - ∆G

It is that thermodynamic quantity of a system the decrease in whose value during a process at
constant temperature and pressure is equal to the maximum possible useful work (Wuseful) that can
be obtained from the system.

ΔG = - nRT ln Keq and ΔG = - nFEcell

At equilibrium, ΔG = 0

For spontaneous process, ΔG < 0

Criteria for reversible and irreversible processes:

1. At constant U, V & T, dS or ∆S ≥ 0
2. At constant S, V & T, dU or ∆U ≤ 0
3. At constant S & P, dH or ∆H ≤ 0
4. At constant T & V, dA or ∆A ≤ 0
5. At constant T & P, dG or ∆G ≤ 0

Where the sign “equal to” refers to a reversible process and the sign “greater than” or
“less than” refers to an irreversible process.
General Mathematical expressions to remember:

1. ΔU = q + w or ΔU = q + PΔV (in general)

2. ΔU = qv
3. H = U + PV and ΔH = ΔU + PΔV = qp
4. ΔS = qrev/T
5. A = U – TS and ∆A = ∆U – T∆S
6. G = H – TS and ΔG = ΔH – TΔS

Variation of Free energy change with Temperature and Pressure

G = H – TS ----------(1)
Since H = U + PV -------(2)
G = U + PV – TS-------(3)
Upon complete differentiation of equation (3),
dG = dU +PdV + VdP–TdS–SdT ------(4)
The first law equation for an infinitesimally small change is, dq = dU – dw
If the work is done by the system, (ie, expansion),
w = - PdV;  dq = dU + PdV ------(5)
For a reversible process, dS = dq/T ----(6)
From eqns (5) & (6), TdS = dq = dU + PdV---(7)
Substituting eqn (7) in eqn (4), we will get
dG = TdS+VdP–TdS–SdT
ie. dG = VdP – SdT -----(8)
At constant Pressure P, dP = 0.  dG = - SdT
Or, (G/T)P = - S
At constant temperature T, dT = 0,  dG = VdP
(G/P)T = V

Gibbs-Helmholtz Equation derivation

Suppose a system at initial state at temperature T, whose free energy is represented as G1.

If the temperature increases by an infinitesimally small quantity dT, the free energy at the
new temperature T + dT is G1 + dG1
 If the system is in final state, G2 at the same temperature T, and if the temperature is
increased by dT, free energy at T + dT is G2 + dG2

At constant pressure, dG = - SdT

 dG1 = -S1dT

dG2 = -S2dT

where S1 and S2 are the entropies of the system in the initial and final states respectively.

 d(G2 – G1) = - (S2 – S1)dT or d(∆G) = - ∆S dT

ie., ((∆G)/T)P = - ∆S

But ∆G = ∆H - T∆S

-T∆S = ∆G - ∆H

-∆S = (∆G - ∆H)/T

 ((∆G)/T)P = (∆G - ∆H) / T

∆G - ∆H = T (∆G)/T)P or -∆S=(∆G - ∆H)/T=((∆G)/T)P

 ∆G = ∆H + T((∆G)/T)P is called Gibbs – Helmholtz Equation

Significance

This equation is applicable to all processes occurring at constant pressure.

1. This is an equation used to calculate ∆H, the heat change for a process taking place at
constant pressure P, if the values of the free energy changes at two different
temperatures are known.
2. This can be used to calculate ∆Greaction at a temperature other than 298K.
3. Since ∆G0 = - RTlnKeq, where K is the equilibrium constant, the Gibbs – Helmholtz
equation can be used to calculate the effect of temperature change on the equilibrium
constant, K.
4. Change in entropy at different temperatures can be determined by using the Gibbs-
Helmholtz equation.

Similar to the above equation, another form of Gibbs-Helmholtz equation can be derived
between Helmholtz free energy, A and internal energy, U.

∆A = ∆U + T((∆A)/T)V
 ELECTROCHEMISTRY
Concept of electrochemistry
The branch of science which deals with the relationship between electrical energy and chemical
energy and their inter-conversion of one form to another is called electrochemistry. The chemical
changes which involve the flow of electric current are called electro chemical changes. They are
classified into two types:
• Electrolysis: The changes in which electrical energy causes chemical reaction to occur.
• Electrochemical cells: The changes in which electrical energy is produced as a result of chemical
change.
Conductors: The substances which allow the passage of electric current are called conductors.
Eg. Metals like Cu, Ag, Sn etc.
Insulators: The substances which do not allow the electric current to pass through them are called
non-conductors or insulators. Eg. Rubber, wood, wax, wool, glass etc.
Metallic conductors: These are the metallic substances which allow the electric current to pass
through them without undergoing any chemical change. The flow of electric current in metallic
conductors is due the flow of electrons in the metal atoms. Eg. Metals like Cu, Ag, Sn etc.
Electrolytes: These are the substances which allow the electric current to pass through them in their
molten states or in the form of their aqueous solutions and undergo chemical decomposition. The
flow of electric current through an electrolytic solution is called electrolytic conduction in which
charge is carried by ions. These substances do not conduct electricity in the solid state but conduct
electricity in the molten state or aqueous solutions due to movement of ions. Eg. Acids, bases and
salts.
Non-electrolytes: The substances which do not conduct electricity either in their molten state or
through their aqueous solutions are called non-electrolytes. Eg. Sugar, glucose, urea, ethyl alcohol
etc.

Galvanic Cells
• An electrochemical cell is a device which converts chemical energy into electrical energy.
• The redox reaction is utilized for generation of electrical energy.
• The electrochemical cells are commonly referred as Voltaic or Galvanic cells.
• The electromotive force (EMF) of such cell is directly proportional to intensity of chemical
reaction taking place in it.
• The electrochemical cell is divided into two half cells. The half-cell electrode where oxidation
(loss of electrons) occurs is called anode (negative electrode). The half-cell electrode where
reduction (gain of electrons) occurs is called cathode (positive electrode). An electrochemical
cell is the coupling of these two half cells.

1
Daniel cell
The Daniel cell is a typical example of Galvanic cell. It consists of a beaker containing copper rod
dipped in 1M CuSO4 solution which is connected to another beaker containing zinc rod dipped in
1M ZnSO4 solution by a salt bridge. Salt bridge is an inverted U-tube containing saturated solution
of some electrolyte such as KCl, KNO3, NH4NO3 which does not undergo chemical change during
the process. The saturated solution is generally taken in agar-agar jelly or gelatin. The salt bridge
allows the flow of ions to pass through it when the flow of electric current takes place. It completes
the electrical circuit and maintains the electrical neutrality of two half-cell solutions.

Figure: Daniel cell

When the circuit is completed, electric current flows through the external circuit as indicated by
an ammeter. The following observations are made:
1. Zinc rod gradually loses its weight.
2. The concentration of Zn2+ (aq) in the ZnSO4 (aq) solution increases.
3. Copper gets deposited on the electrode.
4. The concentration of Cu2+ (aq) in CuSO4 (aq) solution decreases.
5. The flow of electrons is from Zn-electrode (anode) to Cu-electrode (cathode).
6. The flow of electric current is from Cu-electrode (cathode) to Zn-electrode (anode).

The above observations can be explained as follows:

Zn is oxidized to Zn2+ ions which goes in the solution and therefore Zn rod gradually loses its
weight (oxidation half-cell).
Zn Zn2+ + 2e- (At anode)
The electrons released at the Zn electrode move towards Cu electrode through external circuit.
These electrons are accepted by the Cu2+ ions in the solution and gets reduced to copper which
gets deposited on the Cu-electrode (reduction half-cell).
Cu2+ + 2e- Cu (At cathode)

2
The oxidation of Zn occurs at anode (negative terminal) and reduction of Cu2+ occurs at cathode
(positive terminal). The flow of electrons is from negative terminal (anode) to positive terminal
(cathode).
Flow of electrons

(-) Anode Zn │ ZnSO4 ║ CuSO4 │ Cu Cathode (+)

Flow of electric current

Cell reactions: At Anode: Zn Zn2+ + 2e-

At cathode: Cu2+ + 2e- Cu

Overall Reaction: Zn + Cu2+ Zn2+ + Cu

Cell representation: Zn(s) │ ZnSO4 (aq) (1M) ║ CuSO4 (aq) (1M)│ Cu(s)
EMF of galvanic cell
The flow of electric current in Galvanic cell is due to potential difference between the two electrodes
which is known as electrode potential. Electrode potential is a measure of tendency of an electrode to
gain or lose electrons. Each electrode has a different tendency to lose or gain electrons.

Reduction potential (conventionally used) is the measure of tendency of an electrode to gain

electrons and oxidation potential is the measure of tendency of an electrode to lose electrons.
Electrodes with high reduction potential readily gains electrons and gets reduced. Electrodes with
low reduction potential (oxidation potential) readily loses electrons and gets oxidized.

• It is not possible to measure the absolute value of the single electrode potential
directly. Only the difference in potential between two electrodes can be measured
experimentally.
3
 • It is, therefore, necessary to couple the electrode with another electrode whose potential is
known. This electrode is termed as reference electrode. The EMF of the resulting cell is
measured experimentally.

Standard Electrode Potential

The potential difference developed between metal electrode and the solution of its ions of unit
molarity (1M) at 25°C (298 K) is called standard electrode potential. Standard reduction potential
of an electrode means that reduction reaction is taking place at the electrode. If the reaction is
reversed and written as oxidation reaction, the numerical value of electrode potential will remain
same but the sign of standard potential will have to be reversed. Thus

Standard reduction potential = - (Standard oxidation potential)

or

Standard oxidation potential = - (Standard reduction potential)

Reference Electrode
(Standard Hydrogen Electrode, SHE)
Hydrogen electrode is the primary standard electrode. It consists of a small platinum strip coated with
platinum black as to adsorb hydrogen gas. The platinum strip is placed in an acid solution which has
H+ ion concentration 1 M. Pure hydrogen gas is circulated at one atmospheric pressure. A part of the
gas is adsorbed and the rest escapes through holes. This gives an equilibrium between the adsorbed
hydrogen and hydrogen ions in the solution.

H+ (1M)│ H2 (1atm), Pt (half-cell representation when SHE acts as cathode)

Pt, H2 (1atm) │ H+ (1M) (half-cell representation when SHE acts as anode)

The temperature of the cell is maintained at 250C. By international agreement the standard hydrogen
electrode is arbitrarily assigned a potential of exactly ±0.000volt. The hydrogen electrode can act as
cathode or anode with respect to other electrode.
SHE half reaction Electrode potential
H2 → 2H + 2e
+ -
0.0 V (Anode)
2H + 2e → H2
+ -
0.0 V (Cathode)

Determination of Standard Electrode Potential of Zn/Zn 2+ Electrode:

The cell can be represented as
Cell Representation Oxidation half reaction Reduction half reaction
2+ +
Zn|Zn (aq)/Anode(-) || H (aq)| H2 (g), Pt/Cathode (+) Zn → Zn2+ + 2e- 2H+ + 2e- → H2↑

The EMF of the cell is 0.76 volt.

ECell = EoAnode + EoCathode

4
0.76 = EoAnode + 0 or EoAnode = +0.76 V

As the reaction on the anode is oxidation, i.e., Zn → Zn2+ + 2e, EoAnode is the standard oxidation
potential of zinc. This potential is given the positive sign. E oox (Zn/Zn2+) = +0.76 volt. So standard
reduction potential of Zn, i.e., Eo(Zn2+/Zn)= Eored = -(+0.76)= - 0.76 volt.

Determination of Standard Electrode Potential of Cu2+/Cu, Electrode:

The cell can be represented as

Cell Representation Oxidation half reaction Reduction half reaction
Pt, H2 (g)| H+ (aq) ||Cu2+ (aq) |Cu H2 → 2H+ + 2e- Cu2+ +2e- → Cu

The EMF of the cell is 0.34 volt.

EoCell = EoAnode + EoCathode

0.34 = 0 + EoCathode

Since the reaction on the cathode is reduction, i.e., Cu2+ + 2e- → Cu, EoCathode is the standard
reduction potential of copper. This is given the +ve sign. E°, i.e., standard reduction potential of
Cu2+/Cu = 0.34 volt. So E°ox standard oxidation potential of copper = -0.34 volt.

EMF of A Galvanic Cell

The emf of the cell or cell potential can be calculated from the values of electrode potentials of the
two half-cells constituting the cell. The following three methods are in use: When oxidation potential
of anode and reduction potential of cathode are taken into account,
EoCell = Oxidation potential of anode + Reduction potential of cathode
EoCell = Eoox (anode) + Eored (cathode)
When reduction potentials of both electrodes are taken into account:
EoCell = Reduction potential of cathode - Reduction potential of anode
EoCell = EoCathode - EoAnode = Eoright - Eoleft

Nernst Equation
The electrode potential and the EMF of the cell depend upon the nature of the electrode, temperature
and the activities (concentrations) of the ions in solution. The variation of electrode and cell potentials
with concentration of ions in solution and temperature can be obtained from thermodynamic
considerations. Consider, a general reduction reaction such as
Mn+ + ne- → M
occurring in the cell. According to Van’t Hoff reaction isotherm, the Gibbs free energy change is
given by the equation

5
 (or)

where aM and aMn+ represent the activities of product and reactant under a given set of conditions and
∆Go refers to free energy change for the reaction when the various reactants and products are present
at standard conditions. The free energy change of a cell reaction is related to the electrical work that
can be obtained from the cell, i.e.,
∆G = -nFE and ∆Go = -nFEo
On substituting these values in Eq. (ii) we get

Diving the above equation by –nF, we obtain

Eqn (iv) can also be written as,

This equation is known as Nernst equation. Substituting the values of R=8.314JK-1mo-1, T = 298 K
and F=96500 C, Eq. (v) reduces to

Applications: Nernst equation enables us to calculate the following:

1. Half cell potential or single electrode potential.
2. Cell potential or EMF of the cell at any temperature.
3. Equilibrium constant for the cell reaction.

Determination of cell potential using Nernst equation:

Let us consider a Daniel cell to explain the above equation. The concentrations of the electrolytes are
not 1 M.
Zn(s)+Cu2+(aq) Zn2+(aq) + Cu(s)
Cell Representation: Zn(s)|Zn2+(aq)||Cu2+(aq)|Cu
We know that, Emf of the cell, Ecell = Eox + Ered
or Ecell =reduction potential of cathode, E(Cu2+/Cu) – reduction potential of anode, E(Zn2+/Zn)
From the electrochemical series, we can get Eo(Zn2+/Zn) and Eo(Cu2+/Cu). To determine E(Zn2+/Zn)
and E(Cu2+/Cu), Nernst equation can be used and it involves the following steps:
1. Write down the reduction reactions of both the anode and cathode
2. Using eqn (v) or (vi), write the expressions for E(Zn2+/Zn) and E(Cu2+/Cu)
3. Then, Ecell = E(Cu2+/Cu) - E(Zn2+/Zn)

6
Potential at zinc electrode (Anode)
The anodic reaction is Zn → Zn2+ + 2e
To find out the reduction potential of E(Zn2+/Zn), the above equation should be written as,
Zn2+ + 2e → Zn
So, eqn (vi) becomes,
E(Zn2+/Zn) = E0(Zn2+/Zn) - (0.0591/n) log10{[Zn]/[Zn2+]}
Since the concentration or activity of pure metals is unity, it will be
E(Zn2+/Zn) = E0(Zn2+/Zn) - (0.0591/n) log10{1/[Zn2+]}
or Eanode = E0anode + (0.0591/n) log10[Zn2+] ------(vii)
Potential at Copper Electrode (Cathode)
The cathodic reaction is, Cu2+ + 2e → Cu, So, E
E(Cu2+/Cu) = E0(Cu2+/Cu) - (0.0591/n) log10[Cu]/[Cu2+]
Since [Cu] = 1,
E(Cu2+/Cu) = E0(Cu2+/Cu) - (0.0591/n) log10{1/[Cu2+]}
or Ecathode = E0cathode + (0.0591/n) log10[Cu2+] -------- (viii)

Emf of the cell, Ecell = Ecathode – Eanode

Ecell = E0cathode + (0.0591/n) log10[Cu2+] – (E0anode + (0.0591/n) log10[Zn2+])

or Ecell = E0cathode - E0anode + (0.0591/n) log10{[Cu2+]/[ Zn2+]}

where, E0cathode and E0anode are the standard reduction potentials of cathode and anode respectively
which can be taken from electrochemical series. The value of n represents the number of electrons
involved in the reaction and is 2 for both zinc and copper.

Find out the expression of EMF of the following cell, Cu|Cu2+||Ag+|Ag

Similarly by knowing Ecell, ∆G and equilibrium constant K can be determined.

7
Electrochemical series (Galvanic series)
By measuring the potentials of various electrodes versus standard hydrogen electrode (SHE), a series
of standard electrode potentials has been established. The arrangement of elements in increasing order
of their standard (electrode) reduction potentials as compared to that of Standard Hydrogen Electrode
(S.H.E) is called electrochemical series or galvanic series.

Standard Aqueous Electrode Potentials at 25°C: The Electrochemical Series

Electrode Standard Electrode Reduction

Element o
Reaction (Reduction) potential E , volt
Li Li+ + e- → Li -3.05
K K+ + e- → K -2.925
Ca Ca2+ + 2e- → Ca -2.87
Na Na+ + e- → Na -2.714
Mg Mg2+ + 2e- → Mg -2.37
Al Al3+ + 3e- → Al -1.66
Zn Zn2+ + 2e- → Zn -0.7628
Cr Cr3+ + 3e- → Cr -0.74
Fe Fe2+ + 2e- → Fe -0.44
Cd Cd2+ + 2e- → Cd -0.403
Ni Ni2+ + 2e- → Ni -0.25
Sn Sn2+ + 2e- → Sn -0.14
H2 2H+ + 2e- → H2 0.00
Cu Cu2+ + 2e- → Cu +0.337
I2 I2 + 2e- → 2I- +0.535
Ag Ag+ + e- → Ag +0.799
Hg Hg2+ + 2e- → Hg +0.885
Br2 Br2 + 2e- → 2Br- +1.08
Cl2 Cl2 + 2e- → 2Cl- +1.36
Au Au3+ + 3e- → Au +1.50
F2 F2 + 2e- → 2F- +2.87

Li+, K+, Ba+2, Ca+2, Na+, Mg+2, Al+3, Zn+2, Cr+3, Fe+2, Cd+2, Co+2, Ni+2, Sn+2, Pb+2, H, Cu+2, I2, Fe+3, Ag+, Hg+2, Pt+2, Au+3

* Increasing order of reduction potential

* Increasing power of oxidizing agent
* Decreasing order of oxidation potential
* Decreasing power of reducing agent

8
• Higher end of galvanic series acts as reducing agents (gets oxidized) and lower end of the series
acts as oxidizing agents (gets reduced).
• Higher end of galvanic series can displace hydrogen gas from dilute acids.
Zn + HCl ZnCl2 + H2
• Metals with lower reduction potentials can displace the metal with higher reduction potential.
Zn + CuSO4 ZnSO4 + Cu
Applications of galvanic series: The galvanic series give more information on the following
1. The relative corrosion tendencies of the metals.
2. Relative ease of oxidation or reduction of metals.
3. Replacement of tendency of metals.
4. Calculating the equilibrium constant.

Calomel Electrode
• It is a secondary reference electrode.
• It is a mercury-mercurous chloride (Hg-Hg2Cl2) electrode.
• The high purity mercury is placed at the tip of this tube and connected to the circuit by means of
Pt-wire, sealed in a glass tube.
• The surface of Hg is covered with a paste of mercurous chloride (calomel) and KCl electrolyte
solution
The potential of the calomel electrode depends upon the concentration of KCl.
Concentration of KCl 0.1N 1.0N Saturated

Electrode potential (V) 0.3335 0.2810 0.2422

Half cell representation of calomel electrode: Hg, Hg2Cl2(s)│ KCl (saturated solution)

9
APPLICATIONS OF NERNST EQUATION: POTENTIOMETRIC TITRATIONS

1. ACID-BASE TITRATION

Acid-base titrations involving the strong or weak acids against strong or weak bases are
conveniently carried out by using potentiometer or pH meter.

Suppose we want to titrate a solution of HCl against NaOH. Any electrode whose potential depend
on H+ ion concentration (e.g. hydrogen or glass electrode) is placed in the HCl solution. This
indicator electrode is connected to a reference electrode (e.g. Saturated Calomel Electrode, SCE)
to form a galvanic cell. It may be represented as

Pt| H2(1 atm), H+ (C=unknown) || KCl (saturated)| Hg2Cl2(s), Hg

The EMF of the cell is measured potentiometrically and is given by

Ecell = ER - EL = ECalomel – EHydrogen

= 0.2422 – 0.0591 log [H+]

Usually, the concentration of the titrant (NaOH) is 5 to 10 times higher than that of the solution to
be titrated so that the volume change is as small as possible. As the titration proceeds, the H + ion
concentration goes on decreasing, hence, according to the equation, the EMF of the cell goes on
increasing. It is evident that the EMF of the cell would increase by 0.0591V for every ten-fold
decrease in the concentration of H+ ion.

The EMF of the cell changes slowly at first but more and more rapidly as the end point approaches.
After the end point further addition of NaOH produces very little change in the H + ion
concentration and hence there is very little change in the EMF of the cell.

In the plot of E against the volume of NaOH added gives the equivalent point lies where the curve
is steepest. Because of the uncertainty in drawing a vertical line at the steep portion and finding
the accurate volume of NaOH, a first derivative graph of ∆E/∆V against volume of NaOH is made.
The resulting curve rises to a maximum at the equivalent point. Also a second derivative part of
∆2E/∆V2 vs volume of NaOH can be drawn. In this case the end point is at which ∆2E/∆V2= 0.
2. REDOX TITRATION

One of the widely used applications of emf measurements is to detect the end point of a titration
by measuring the emf of a cell consisting of an indicator electrode (electrode, whose potential
depends on the concentration of the reactant ions) and a reference electrode (e.g., SCE) as the
titration progresses. This is called a potentiometric titration (varying emf measured during the
progress of titration). Since the electrode potential of the reference electrode is constant, the
observed change in emf as the reaction progresses, is due to the change in the electrode potential
of the indicator electrode.

Let us consider the redox reaction,

Ce4+ + Fe2+ → Ce3+ + Fe3+ (1)

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:

Hg, Hg2Cl2(s) | KCl(sat) || Fe2+, Fe3+ | Pt(s)

The overall reaction can be described in terms of the two half cell reactions

Ce4+ + e → Ce3+ ; (2) Eo (Ce4+/Ce3+) = + 1.610 V and

Fe3+ + e → Fe2+ ; (3) Eo ( Fe3+/Fe2+) = + 0.771 V

Initially when no Ce4+ is added to the system, the potential of the electrode, is determined by the
Fe3+/Fe2+ couple, it is given by Eqn.

ER = 0.771 + 0.0591 log {[Fe3+]/[Fe2+]} (4)

Therefore, the EMF of the cell will be,

Ecell = (0.771 + 0.0591 log {[Fe3+]/[Fe2+]}) – ESCE

or Ecell = (0.771 + 0.0591 log {[Fe3+]/[Fe2+]}) – 0.2422 (5)

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 which causes the potential
to rise as more iron becomes oxidized.

At the equivalence point, the concentration of Ce (IV) and Fe(II) are minute; however, equivalence
point potentials are easily obtained. It has been observed that the reactions (2) & (3) are both in
equilibrium at the Pt electrode. So, the Nernst equations for these reactions are as follows:

ER = 0.771 + 0.0591 log {[Fe3+]/[Fe2+]} and ER = 1.61+ 0.0591 log {[Ce4+] / [Ce3+]}
i.e. 2ER = 0.771 + 1.61 + 0.0591 log {{[Fe3+][ Ce4+]/[Fe2+][ Ce3+]}

Since the two reactions are at equilibrium. i.e. [Ce4+] = [Fe2+] and [Ce3+] = [Fe3+], the ‘log’term is
unity and the corresponding half-cell potential will be

ER = (0.771 + 1.61)/2 = 1.19V

and hence the cell potential can be written as

Ecell = ER – ESCE = 1.19 – 0.2422 = 0.9483 V (6)

After the equivalence point is reached, the Fe2+ will have been totally consumed and the potential
will then be controlled by the concentration ratio of Ce3+/Ce4+ and is given by

ER = 1.61+ 0.0591 log {[Ce4+] / [Ce3+]} (7)

Therefore, the EMF of the cell will be,

Ecell = (1.61+ 0.0591 log {[Ce4+] / [Ce3+]}) – ESCE

or Ecell = (1.61+ 0.0591 log {[Ce4+] / [Ce3+]}) – 0.2422 (8)

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). The measurement
of actual cell potentials for various concentrations of all these species results in a titration curve as
shown in Fig 1. 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.

Fig1 Plot of Volume of Ce4+ vs EMF of the cell Fig 2. Plot of Volume of Ce4+ added vs ∆E/∆V

A better procedure to obtain the equivalence point is to make use of the fact that the slope of
∆E/∆V is large in the vicinity of the equivalence point. If ∆E/∆V is plotted against V (Fig. 2), the
sharp maximum corresponds to the equivalence point.
3. DETERMINATION OF SOLUBILITY PRODUCT CONSTANT FROM NERNST
EQUATION

Consider the general dissolution reaction below (in aqueous solutions):

ABn ⇌ An+ + nB- (1)

The Ksp of the above reaction can be written as,

Ksp = [An+] [B-]n (2)

Note that the reactant, ABn, is not included in the Ksp equation. Solids are not included when
calculating equilibrium constant expressions, because their concentrations do not change the
expression; any change in their concentrations are insignificant, and therefore omitted. Hence, Ksp
represents the maximum extent that a solid that can be dissolved in solution. Equation (2)
represents that the solubility product Ksp is an equilibrium constant and hence its value can be
predicted from a knowledge of the standard electrode potentials. The electrodes are chosen in such
a way, that the overall cell reaction is the solubility product equilibrium. A suitable galvanic cell
is thus set up and its EMF is determined experimentally. Even if measurements cannot be made, it
is possible to arrive at the approximate values of Ksp from appropriate half-cell reaction potentials.

Let us consider a sparingly soluble salt MX in equilibrium with its ions in a saturated solution,
MX(s)  M+(aq) + X-(aq)
The solubility product of the salt s given by assuming it an ideal solution, so that activities are
equal to concentrations.
Ksp = aM+ . aX- = [M+] [X-]
To determine the solubility product constant, the following cell can be constructed.
M | M+X-(sat) || MX(s) | M
The half-cell reactions are:
RHE : MX(s) + e-  M + X-
LHE : M  M+(aq) + e-
Overall reaction: MX(s)  M+(aq) + X-(aq)

For example, we will now illustrate the calculation of Ksp for Hg2Cl2(s) at 298 K from data on
electrode potentials. The reaction will be as follows:
Hg2Cl2(s) ⇌ Hg22+ + 2Cl- (1)
Thus, the solubility product can be written as
Ksp = [Hg22+] [Cl-]2 (2)
We need to look for a reaction in which Hg2Cl2 takes part and another reaction in which Hg22+ and
Cl- take part. These reactions are
Hg2Cl2(s) + 2e- ⇌ 2Hg + 2Cl- --------- (3) Eo = + 0.268 V
Hg22+ + 2e- ⇌ 2Hg ; --------- (4) Eo = + 0.789 V
Reaction (3) - Reaction (4) gives
Hg2Cl2(s) ⇌ Hg22+ + 2Cl- ; Eo = 0.268 - 0.789 = - 0.521 V
∆Go = - RT /n Keq = - nFEo ;
In the case of sparingly soluble salts, Keq = Ksp = [Hg22+] [Cl-]2
Ksp = exp[nFEo/RT] = 1.355 x 10-18
The solubility product constant, Ksp, is the equilibrium constant for a solid substance dissolving
in an aqueous solution. It represents the level at which a solute dissolves in solution. The more
soluble a substance is, the higher the Ksp value it has.
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