CHB-301 Section (B) Physical: Syllabus

B.Sc. Semester-III, CHB-301, M(B) Batch

Unit 1. Electrochemistry: Migration of ions: transference number and their determination (Hittorf method), molar and equivalent
conductances and their measurements, Kohlrausch law of independent migration of ions, ionic mobilities, conductance measurements and
Course: applications to conductometric titrations, acid dissociation constant and solubility product determination.
Free energy change and emf of cells, Nernst equation, single electrode potentials, reference electrodes (SHE, calomel, silver-
CHB-301 Section (B): Physical Chemistry-II silver chloride electrodes), emf measurements, potentiometric titrations (acid – base, redox), buffer solutions, pH determination using
(Credits 2) quinhydrone and glass electrodes, concentration cells, liquid junction potential, acid-base indicators, indicator constant.

Unit 2. Phase Equilibria: Thermodynamics of phase transition, Clapeyron-Clausius equation, phase rule, phase diagrams of one-
component (water) and two component (phenol-water & Pb-Ag) systems, distribution law, application to cases for dissociation and association,
Unit 1: Electrochemistry determination of equilibrium constant (KI + I2 = KI3).
Unit 2: Phase equilibria
Unit 3. Solid State: Crystal lattices, space lattice, unit cell, crystal systems, law of rational indices, Miller indices, Bragg’s equation,
Unit 3: Solid State crystal structure of NaCl, graphite and diamond, Schottky and Frankel defects.

Books Recommended:
1. Physical Chemistry, P. C. Rakshit, 5th Edition (1988), 4th Reprint (1997), Sarat Book House, Calcutta.
2. Principles of Physical Chemistry, B. R. Puri, L. R. Sharma and M. S. Pathania, 44th Edition (2009), Vishal Publishing Co., Jalandhar.
3. Physical Chemistry, K. J. Laidler and J. M. Meiser, 3rd Edition, (1999) Houghton Mifflin Comp., New York, International Edition.

By
Dr. S. MANIVANNAN
2

What is Electrochemistry

Electrochemistry:
“Electrochemistry is the science that unites electricity and chemistry. It is the study of the transfer of electrons.
If a chemical reaction is driven by an external applied voltage, as in electrolysis, or if a voltage is created by a chemical
reaction, as in a battery, it is an electrochemical reaction.

⚫ Electrochemistry is the study of the chemical reactions which take place at the interface of an electrode usually a
solid, metal or semiconductor and an ionic conductor, the electrolyte.

Unit 1. Electrochemistry ⚫ Electrochemistry deals with the interaction between electrical energy and chemical change.

3 4
 Terminology in Electrochemistry Electrochemical Cell

Conductance is the measure of how easily electricity flows along a certain path through an electrical element, and
since electricity is so often explained in terms of opposites, conductance is considered the opposite of resistance.
LEO GER
Loss of Electron Oxidation
Gain of Electron Reduction
Ohm's law states that the current through a conductor between two points is directly proportional to the
voltage across the two points.
Where there is oxidation,
Cathode Anode there is reduction
The ampere (symbol: A) is the SI base unit of electric current equal to one coulomb per second. Positively Negatively
Charged Ion Charged Ion
Cation
Anion
Ohm is a unit for measuring electrical resistance.
Negative Positive
The volt (symbolized V) is the Standard International (SI) unit of electric potential or electromotive force. A Electrode Electrode Substance oxidized Substance reduced
potential of one volt appears across a resistance of one ohm when a current of one ampere flows through that loses electron(s) gains electron(s)
resistance.
Electrolyte
5 6
Solution

Applications of
Electrochemistry

• Torches.
• Electrical appliances such as
cellphones (long-life alkaline batteries)
• Digital cameras (lithium batteries)
• Hearing aids (silver-oxide batteries)
• Digital watches (mercury/silver-
oxide batteries)
• Military applications (thermal
batteries)

7 8
 Arrhenius Theory of Ionisation Arrhenius Theory of Ionisation (Cont.)

(2) The ions present in solution constantly reunite to form neutral molecules.
In 1903 Svante August Arrhenius (1859–1927) received the Nobel Prize in Chemistry for Thus, there is a state of equilibrium between the undissociated molecules and the ions.
his electrolytic theory of dissociation, which states that molecules of acids, bases, and salts dissociate
into ions when dissolved in water. AB A+ + B-

- Arrhenius studied the conduction of current through water solutions of electrolytes. [𝑨+ ][𝑩− ]
Applying the Law of Mass Action to the ionic equilibrium we have, = K,
- He came to believe that the conductivity of solutions was due to the presence of ions. 𝑨𝑩
where K is called the Dissociation constant.
- In 1884, Arrhenius put forward his theory of ionisation.
Arrhenius theory of ionisation may be stated as :
(1) When dissolved in water, neutral electrolyte molecules are split up into two types of charged particles.
(3) The charged ions are free to move through the solution to the oppositely charged
These particles were called ions and the process was termed ionisation.
electrode.
- The positively charged particles were called cations and those having negative charge were called anions.
-This movement of the ions constitutes the electric current through electrolytes.
- In its modern form, the theory assumes that the ions are already present in the solid electrolyte, and these are held
-This explains the conductivity of electrolytes as well as the phenomenon of electrolysis.
together by electrostatic force.
- When placed in water, these neutral molecules dissociate to form separate anions and cations.
(4) The electrical conductivity of an electrolyte solution depends on the number of ions
present in solution (Concentration of the electrolyte is directly proportional to current).
Thus, AB A+ + B- (Old view); A+B- A+ + B- (Modern view);
-Thus, the degree of dissociation of an electrolyte determines whether it is a strong
electrolyte (Ex: NaCl) or a weak electrolyte (Ex: CH3COOH).
- For that reason, this theory may be referred to as the theory of electrolytic dissociations.
9 10

Migration Migration of ions

Migration of Ions: During the electrolysis, the electrolyte dissociates and

move towards their opposite charge at different speeds and this
process is referred as migration of ions.

We know that electrolytes dissociate in solution to form positive ions (cations)

and negative ions (anions).

𝑨𝒈𝑵𝑶𝟑 𝑨𝒈+ + 𝑵𝑶−

𝟑 𝑪𝒖𝑺𝑶𝟒 𝑪𝒖𝟐+ + 𝑺𝑶𝟐−
𝟒 𝑯𝟐 𝑺𝑶𝟒 𝟐𝑯+ + 𝑺𝑶𝟐−
𝟒
Migration: movement from one part of something to another. 𝒆− 𝒆−
- Animal migration refers to the movement of animals over a long distance, usually in line with changes in the seasons. ➢ As the current is passed between the electrodes of the
- A simple movement of animals over a substantial distance cannot be considered a migration. electrolytic cell, the ions migrate to the opposite electrodes.
- A migration is animal movement due to reasons like changes in the season such as when birds in the Northern Hemisphere 𝑵𝑶−
𝟑 𝒊𝒐𝒏𝒔 𝒎𝒊𝒈𝒓𝒂𝒕𝒊𝒏𝒈
escape to the south during winter. ➢ Thus, in the electrolytic solution of AgNO3, the cations (Ag+) will 𝒕𝒐 𝒂𝒏𝒐𝒅𝒆
- A migration can also occur if there is a major change in the habitat of an animal such as when a young one leaves the move to the cathode and anions (𝑵𝑶𝟑− ) will move to the anode. 𝑨𝒈+ 𝒊𝒐𝒏𝒔 𝒎𝒊𝒈𝒓𝒂𝒕𝒊𝒏𝒈
habitat of birth and moves to adult habitats. 𝒕𝒐 𝒄𝒂𝒕𝒉𝒐𝒅𝒆
➢ Usually, different ions move with different rates.
Signs of Migration: (a) movement in a relatively straight line, (b) relocation of a species on a massive scale, and
(c) a movement that redistributes members of a species in a population. (d) seasonal movement. ➢ The migration of ions through the electrolytic solution can be
11 12 understood from the given figure. Migration of ions through electrolytic solution to opposite electrodes.
 Migration of ions: (1) Lodge’s Moving Boundary Experiment Migration of ions: (2) Movement of Coloured Ions

Anode Cathode
Fig: Experiment showing the ➢ The lower part of a U-tube is filled with a 5 % water-solution of agar-agar Cathode Anode
migration of H+ ions as indicated by
the movement of the red boundary with a small amount of copper dichromate (CuSO4 + K2Cr2O7).
through the agar-agar jelly. ➢ The dark green colour sets to a jelly.
𝑺𝑶𝟐−
𝟒 𝑵𝒂𝟐 𝑺𝑶𝟒 ➢ The surface of the green solution in the two limbs of the U-tube is
KNO3 Solution
𝑫𝒊𝒍. 𝑯𝟐 𝑺𝑶𝟒 𝑯+ 𝑺𝒐𝒍𝒖𝒕𝒊𝒐𝒏 Phenolphthalein Indicator marked by a small amount of charcoal.
𝑯+ ➢ In both the limbs is then placed a layer of solution of potassium nitrate
KNO3 in Jelly
𝐶𝑢2+

Yellow
and agar-agar.
➢ This is also allowed to set. Over this second layer is placed some solution

Blue
of pot. nitrate in pure water and the two electrodes are inserted in it. 𝐶𝑟2 𝑂72−
Charcoal
Agar-Agar jelly containing alkali coloured ➢ As the current is turned on, the blue colour of Cu2+ ions rises into the jelly
red by adding phenolphthalein under the cathode.
➢ The apparatus used consists of a U-tube which has a long horizontal portion. ➢ The reddish yellow dichromate ions (𝐶𝑟2 𝑂72− ions) move up under the
➢ It is fitted with electrodes in the side limbs. anode. CuCr2O7
➢ The horizontal portion is filled with a jelly of agar-agar treated with a trace of alkali. ➢ After some time the two types of ions are seen rising with well-defined Solution in Jelly
➢ This is then made red by addition of a few drops of phenolphthalein. boundaries.
➢ When the jelly is set, dilute H2SO4 is added in the anodic limb of the tube. ➢ The use of jelly in this experiment prevents the mixing of the solutions by Fig: Apparatus for demonstrating the
➢ Na2SO4 solution is added in the cathodic limb. diffusion. migration 𝐶𝑢2+ and 𝐶𝑟2 𝑂72− ions.
➢ On passing the current, H+ ions in the left limb solution eventually move into the agar-agar jelly.
➢ Their passage is marked by the gradual discharge of the red colour due to the neutralisation of the alkali by H+ ions.
13 14
➢ The movement of the red boundary through the agar-agar jelly shows that H+ ions migrate to the cathode limb.

Hittorf’s Theoretical Device (Or) Relative Speed of Ions During Hittorf’s Theoretical Device (Or) Relative Speed of Ions During
Electrolysis Electrolysis (Cont.)
• We knew that ions move to the oppositely charged Now let us consider the following cases:
(i) Let the anions alone be capable of movement
A B electrodes during electrolysis. A B - two anions have moved towards the anode, we get the position as
Anode Middle Cathode • But the speeds of cations and anions migration are not Anode Middle Cathode shown in II. The cations have not moved at all. -But inspite of that the
A Compartment Compartment Compartment C necessarily the same. A Compartment Compartment Compartment C number of discharged anions and cations is the same viz., 2. The
• However, the speed of a cation moving away from the concentration in the anode compartment, however, has not altered while in
the cathode compartment it has fallen by two ion-pairs.
I anode will be proportional to the fall of concentration I
of these ions at the anode and vice versa. (ii) Let the anions and cations move at the same rate
-When two ions of each type have crossed over towards the opposite
• Hittorf studied such changes experimentally and gave a electrodes, we get the condition as shown in III. The number of
II general rule known as the Hittorf’s Rule. II
discharged anions and cations is the same viz., 4. The concentration of
• It states that : the loss of concentration around any both the anode compartment and the cathode compartment has fallen to
electrode is proportional to the speed of the ion moving the same extent viz, by two ion-pairs.
III away from it. III (iii) Let the cations move at twice the speed of the anions
• In Fig, A is anode and C is cathode. AA′ and BB′ are -In this case, when cations have moved to the cathode compartment,
one anion passes into the anode compartment. The state of affairs is
two imaginary planes which divide the cell into three shown in IV. The total number of discharged anions and cations is again
IV compartments, the anode compartment, the middle IV the same viz., 3. Although the concentration in the cathode compartment
compartment and the cathode compartment. has fallen by one ion-pair, the concentration in the anode compartment
• The sign (+) represents a cation while the sign (–) decreases by two ion-pairs.
A’ B’ represents an anion. A’ B’ • It is evident from the above considerations that ions are always
discharged in equivalent amounts on the opposite electrodes. It is
• Before electrolysis, let there be 13 ion-pairs in the really due to the difference in the speeds of anions and cations that
Fig: Scheme showing that the loss of concentration around any cell. The number of ion-pairs in the two outer Fig: Scheme showing that the loss of concentration around any the changes in concentration around electrodes are caused.
electrode
15
is proportional to the speed of the ion moving away compartments is 4 each and there are 5 ion-pairs in the electrode
16
is proportional to the speed of the ion moving away • Hence, loss in concentration around any electrode is proportional
from it. middle compartment (Position I). from it. to the speed of the ion moving away from it.
 Relative Speed of Ions: Hittorf’s Rule Migration Speed of 𝑨𝒈+ and 𝑵𝑶−
𝟑 ions

Hittorf’s Rule. Definition: Anode Cathode

A B
Anode Middle Cathode 𝑭𝒂𝒍𝒍 𝒂𝒓𝒐𝒖𝒏𝒅 𝑨𝒏𝒐𝒅𝒆 𝑺𝒑𝒆𝒆𝒅 𝒐𝒇 𝑪𝒂𝒕𝒊𝒐𝒏 𝝂+
A Compartment Compartment Compartment C = =
𝑭𝒂𝒍𝒍 𝒂𝒓𝒐𝒖𝒏𝒅 𝑪𝒂𝒕𝒉𝒐𝒅𝒆 𝑺𝒑𝒆𝒆𝒅 𝒐𝒇 𝑨𝒏𝒊𝒐𝒏 𝝂−
I III
- where 𝝂+ and 𝝂− is the speed of cations and anions
II respectively.
Fig: With Silver electrodes, concentration around the cathode falls while it increases around the anode.
- In deriving the above relation, an important assumption
⚫ Let us study the electrolysis of a solution of AgNO3 in a cell of the type described above but using silver electrodes.
III has been made, namely, the discharged ions do not react ⚫ Here, instead of a fall in concentration of AgNO3 around the anode, it increases.
with the material of the electrodes. ⚫ This is due to the fact that every 𝑁𝑂3− ion that arrives at the anode dissolves from it one Ag+ ion to form AgNO3.
⚫ If the electrodes were of platinum, the state of affairs would be as shown in Hittorf's theoretical device when ions moved at the same
IV - However, in many cases they combine with the rate.
material of the electrodes rather than depositing on it. ⚫ That is, there should have taken place a fall in concentration by 2 ion-pairs in each compartment.
⚫ It is clear that the concentration around the cathode has fallen from 4 to 2 ion-pairs but around the anode it has increased from 4 to 6
ion-pairs.
A’ B’ - This results in an increase in concentration around such an
⚫ It is very easy to calculate the speed ratio of ions in this case as well by putting a Ag coulometer in the circuit.
electrode instead of a decrease. ⚫ This would give us the total current passed or increase in concentration around the anode as if no silver ions had migrated towards the
Fig: Scheme showing that the loss of concentration around any cathode.
electrode is proportional to the speed of the ion moving away ⚫ The difference of the total increase and the actual increase around the anode would give the fall in concentration around the anode due
17 18 to the migration of Ag+ ions.
from it.

Solved Problem-1 Transference Number (Or) Transport Number

➢ During electrolysis the current is carried by the anions and the cations.
➢ The fraction of the total current carried by the cation, or the anion is termed its Transport number or Hittorf’s number.
➢ If, 𝝂+ represents the speed of migration of the cation and 𝝂− that of the anion,

Problem: In an experiment, the increase in concentration of AgNO3 around the silver anode was 5.6 mg of silver. 10.73 mg the transport number of the transport number of
of silver were deposited by the same current in the silver coulometer placed in series. Find the speed ratio of Ag+ and ν+ (𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝐷𝑒𝑐𝑟𝑒𝑚𝑒𝑛𝑡 𝑎𝑡 𝐶𝑎𝑡ℎ𝑜𝑑𝑒) ν− (𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝐺𝑟𝑎𝑑𝑖𝑒𝑛𝑡 𝑎𝑡 𝐴𝑛𝑜𝑑𝑒)
Cation = Anion =
𝑁𝑂3− ions. ν+ + ν− (𝑇𝑜𝑡𝑎𝑙 𝐷𝑒𝑐𝑟𝑒𝑚𝑒𝑛𝑡 𝑜𝑓 𝑡ℎ𝑒 𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛) ν+ + ν− (𝑇𝑜𝑡𝑎𝑙 𝐷𝑒𝑐𝑟𝑒𝑚𝑒𝑛𝑡 𝑜𝑓 𝑡ℎ𝑒 𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛)

The transport number of the cation is represented by 𝒕+ and that of the anion by 𝒕− .
Solution: Fall of concentration around cathode (= rise of concentration around anode) = 5.6 mg
- If no Ag+ ions had migrated from the anode, the increase in concentration around the anode would have been 10.73 ν+ ν−
mg silver. Thus 𝒕+ = and 𝒕− =
ν+ + ν− ν+ + ν−
- But the actual increase is 5.6 mg. ∴ Fall around the anode due to migration of Ag+ = (10.73 – 5.6) = 5.13 𝑡+ ν+
Or = and 𝒕+ + 𝒕− = 1
𝑡− ν−

𝑭𝒂𝒍𝒍 𝒂𝒓𝒐𝒖𝒏𝒅 𝑨𝒏𝒐𝒅𝒆 𝑺𝒑𝒆𝒆𝒅 𝒐𝒇 𝑨𝒈+

𝟓. 𝟏𝟑 ν+
= = = 𝟎. 𝟗𝟏𝟔 If the speed ratio be denoted by r, we have,
𝑭𝒂𝒍𝒍 𝒂𝒓𝒐𝒖𝒏𝒅 𝑪𝒂𝒕𝒉𝒐𝒅𝒆 𝑺𝒑𝒆𝒆𝒅 𝒐𝒇 𝑵𝑶− 𝟓. 𝟔 ν−
𝟑

𝑡+ 1
r = 𝑡𝑡+
−
=
1 − 𝑡+
and 𝒕− =
1+𝑟
19 20
 Solved Problem-2 Coulometry

Coulometry: Electrochemical method based on the quantitative oxidation or reduction of

analyte
-amount of the analyte can be measured by measuring the amount of current and To constant-current source
time required to complete the reaction
Mercury
Problem: The speed ratio of silver and nitrate ions in a solution of silver nitrate electrolysed between silver electrodes is Charge (Q) = Current (i) x time in coulombs
0.916. Find the transport number of the two ion.
Def: Coulometry determines the amount of matter transformed during an electrolysis Electrolyte
reaction by measuring the amount of electricity consumed or produced. It can be solution
Generator
Solution: 1 used for precision measurements of charge, and the amperes even used to have a Electrode Counter
We know that 𝒕− = coulometric definition. Electrode
1+𝑟 Stirring
bar Sintered
where 𝒕− is the transport number of the anion and r is the speed ratio of the anion and the cation. Coulomb: a unit of electric charge, equal to the quantity of electricity carried in one second by glass disk
one ampere (= one unit of current).
Magnetic stirrer
1 C = As Where, C = coulomb, A = ampere, s = second
𝒕𝒉𝒆𝒓𝒆𝒇𝒐𝒓𝒆, 𝒕𝑵𝑶− = = 0.521 𝒂𝒏𝒅 𝒕𝑨𝒈+ = 1 - 𝒕𝑵𝑶− = 1 - 0.521 = 0.479
𝟑 1 + 0.916 𝟑
Example: Coulometric Titration of Cl-
Ag electrode is used to produce Ag+. By measuring the amount of current and time required to complete the following reaction,
amount of Cl- can be determined.
Ag (s) Ag+ + e-

21 22 Ag+ + Cl- AgCl (ppt.)

Migration of ions: Transference Number and their

Hittorf’s Method (Cont.)
Determination (Hittorf method)
There are two methods for determination of the transport number of an ion :
(1) Hittorf’s method (Traditional)
(2) Moving Boundary method (Advanced)_Not in our Syllabus
Variable ⚫ When the current has been passed for about three hours, the Variable
Ammeter Ammeter
⚫ According to Hittorf’s rule, the loss of concentration around any Resistance Resistance
stopcocks at the top of the U-tube are closed.
electrode is proportional to the speed of the ion moving away from that AgNO3 ⚫ The whole of the liquid in the anode compartment is carefully AgNO3
electrode.
Solution drained into a weighed flask and its weight determined. Solution
⚫ The transport number of an ion is calculated from the changes in
Silver ⚫ Its silver content is determined by titrating against a standard Silver
concentration found experimentally around the electrodes.
Voltameter solution of potassium thiocyanate. Voltameter
⚫ The apparatus used in this method consists of two vertical glass tubes ⚫ The weight of silver deposited in the silver coulometer is also
joined together through a U-tube in the middle. noted.
⚫ All the three tubes are provided with stopcocks at the bottom. ⚫ If a copper coulometer is used in place of silver coulometer, the
⚫ The U-tube is also provided with stopcocks at the tops of the two limbs. weight of silver equivalent to the copper deposited is calculated
⚫ By closing these stopcocks, the communication between the solutions in Anode Cathode by multiplying it with 108/31.5. (AgNO3/Cu(NO3)2) Anode Cathode
the cathode and anode limbs can be stopped. Compartment Compartment ⚫ There should be no change in the concentration of the solution in Compartment Compartment
⚫ The silver anode is sealed in a glass-tube and the cathode is a piece of the U-tube if the experiment has been successfully performed.
freshly silvered foil. ⚫ If the above experiment has been performed by using silver
⚫ The apparatus is filled with a solution of silver nitrate and a steady electrodes, in this case nitrate ions attack the silver anode.
current of about 0.01 ampere is passed for two to three hours. ⚫ Consequently, there is an increase in concentration of Ag+ ions
⚫ It is an important precaution that the current is passed only for a short Middle rather than decrease. Middle
time so that too large a change in concentrating does not take place. Compartment ⚫ The same experiment can also be performed by using platinum Compartment
⚫ The apparatus is connected with a silver or copper coulometer as shown in electrodes to avoid the attack of anions on the anode.
Figure, which shows the circuit for the experiment.
23 Fig: Hittorf's apparatus for determining Transport numbers. 24 Fig: Hittorf's apparatus for determining Transport numbers.
 Hittorf’s Method Calculations: Case 1. When electrodes are unattackable Hittorf’s Method Calculations: Case 2. When electrodes are attackable

Two different cases may arise:

Case 1. When electrodes are unattackable (Pt electrodes are used).
Case 2. When electrodes are attackable (Ag electrodes are used).
Variable Variable
1a. After passing electric current: Ammeter Ammeter
Resistance Increase in conc. of anodic solution Resistance
Let the weight of anodic solution taken out = a g = (b – c) g of AgNO3
AgNO3 AgNO3
weight of AgNO3 present in it by titration = b g (𝒃−𝒄)
Solution Solution
weight of water = (a – b) g =
𝟏𝟕𝟎
x 108 g equivalent of Ag
Silver Silver
1b. Before passing electric current: Voltameter (𝒃−𝒄) Voltameter
Let weight of AgNO3 in (a – b) g of water before passing we have, g equivalent of Ag = e (for example)
𝟏𝟕𝟎
electric current be = c g
∴ Fall in concentration If no Ag+ ions had migrated from the anode, the increase in concentration of 𝐴𝑔+
= (c – b) g of AgNO3 = (c-b)/170 g equivalent of AgNO3 ions would have been equal to “W”.
Anode Cathode Anode Cathode
= (c-b)/170 g equivalent of Ag = d (for example) Compartment Compartment ∴ Fall in concentration due to the migration of 𝐴𝑔+ ion = W – e Compartment Compartment

Let the weight of silver deposited in silver coulometer be = w1 g 𝑊−𝑒

Transport number of 𝐴𝑔+ (𝑡𝐴𝑔+ ) =
= w1/108 g equivalent of Ag 𝑊
𝑊−𝑒
= W (for example) g equivalent of Ag Transport number of 𝑁𝑂3− (𝑡𝑁𝑂3− ) = 1 -
Middle 𝑊 Middle
𝐹𝑎𝑙𝑙 𝑖𝑛 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑎𝑟𝑜𝑢𝑛𝑑 𝑎𝑛𝑜𝑑𝑒 𝑖𝑛 𝑔 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑑 Compartment Compartment
Transport number of 𝐴𝑔+ (𝑡𝐴𝑔+ ) = =
𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝐴𝑔 𝑑𝑒𝑝𝑜𝑠𝑖𝑡𝑒𝑑 𝑖𝑛 𝑔 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑊
𝑑
Transport number of 𝑁𝑂3− (𝑡𝑁𝑂3− ) = 1 -
25 𝑊 Fig: Hittorf's apparatus for determining Transport numbers. 26 Fig: Hittorf's apparatus for determining Transport numbers.

Solved Problem-3 Solved Problem-4

Problem: A solution of silver nitrate containing 12.14 g of silver in 50 ml of solution was electrolysed between platinum Problem: In an electrolysis of copper sulphate between copper electrodes the total mass of copper deposited at the
electrodes. After electrolysis, 50 ml of the anode solution was found to contain 11.55 g of silver, while 1.25 g of metallic cathode was 0.153 g and the masses of copper per unit volume of the anode liquid before and after electrolysis were 0.79
silver was deposited on the cathode. Calculate the transport number of 𝐴𝑔+ and 𝑁𝑂3− ions. and 0.91 g respectively. Calculate the transport number of the 𝐶𝑢2+ and 𝑆𝑂42− ions.

Solution:
Weight of Ag in 50 ml of the solution before electrolysis = 12.14 g Solution:
Weight of Ag in 50 ml of the solution after electrolysis = 11.55 g Wt. of copper in the anode liquid before electrolysis = 0.79 g
∴ Fall in concentration of Ag = 12.14 – 11.55 Wt. of copper in the anode liquid after electrolysis = 0.91 g
= 0.59 g Increase in weight = 0.91 – 0.79 = 0.12 g
= 0.0055 g eq Increase in weight of copper cathode in the coulometer = 0.153 g
Weight of Ag deposited in silver coulometer = 1.25 g This means that if no copper had migrated from the anode,
= 1.25/108 eq increase in weight would have been 0.153 g.
= 0.0116 But actual increase = 0.12
∴ Fall in concentration due to the migration of 𝐴𝑔+ ion = W – e Fall in concentration due to migration of Cu2+ ions = 0.153 – 0.12 = 0.033

𝐹𝑎𝑙𝑙 𝑖𝑛 𝑐𝑜𝑛𝑐. 𝑎𝑟𝑜𝑢𝑛𝑑 𝑎𝑛𝑜𝑑𝑒 0.0055 0.033

Transport number of 𝐴𝑔+ (𝑡𝐴𝑔+ ) = = = 0.474 Transport number of 𝐶𝑢+ (𝑡𝐶𝑢+ ) = = 0.215
𝑁𝑜.𝑜𝑓 𝑔 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑑𝑒𝑝𝑜𝑠𝑖𝑡𝑒𝑑 𝑖𝑛 𝑠𝑖𝑙𝑣𝑒𝑟 𝑐𝑜𝑢𝑙𝑜𝑚𝑒𝑡𝑒𝑟 0.0116 0.153

Transport number of 𝑁𝑂3− (𝑡𝑁𝑂3− ) = 1 -0.474 = 0.526 Transport number of 𝑆𝑂42− (𝑡𝑆𝑂42− ) = 1 - 0.215 = 0.78

27 28
 Transport Number of Electrolytes: Examples Factors which Determines the Transport Number

➢ The fraction of the total current carried by the cation, or the anion is termed its Transport number or Hittorf’s number.
1. Property of Electrolyte
- In addition to the migration speed, ion’s transport number is dependent of the ion attached with it.
Electrolyte (0.02 N) 𝒕+ Electrolyte (0.02 N) 𝒕+ - Ex: NaCl = 0.604, HCl = 0.166
HCl 0.823 ZnSO4 0.395
2. Concentration of the Electrolyte
LiCl 0.338 CuSO4 0.397 - Migration speed is dependent of electrolyte concentration hence, transport number also varies little.
NaCl 0.395 BaCl2 0.449
3. Hydration of Ions
KCl 0.490 AgNO3 0.461 - Transport number of chloride salts in 𝐿𝑖 + < 𝑁𝑎+ < 𝐾 + (ascending)
- But concerning their size, the order should be 𝐿𝑖 + > 𝑁𝑎+ > 𝐾 + (descending) (K+ is bigger in size)
KBr 0.488 K2SO4 0.483
- 𝐿𝑖 + 𝑖𝑠 𝑠𝑚𝑎𝑙𝑙𝑒𝑟 𝑖𝑛 𝑠𝑖𝑧𝑒, ℎ𝑎𝑣𝑖𝑛𝑔 ℎ𝑖𝑔ℎ 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑖𝑐 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 ℎ𝑒𝑛𝑐𝑒, 𝑎𝑡𝑡𝑟𝑎𝑐𝑡𝑠 𝑚𝑜𝑟𝑒 𝑤𝑎𝑡𝑒𝑟 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠.
- On contrary, 𝐾 + 𝑎𝑡𝑡𝑟𝑎𝑐𝑡𝑠 𝑙𝑒𝑠𝑠 𝑤𝑎𝑡𝑒𝑟 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠.
- After the hydration, the size of ions are viz, 𝐾 + < 𝑁𝑎+ < 𝐿𝑖 + (Li+ ion is more crowded by the water molecules, low speed)
S. Solution Electrolyte
No Concentration
HCl NaCl KNO3 K2SO4 BaCl2 CdI2
(N)
4. Co-ordination complex formation between the ions
1 0.01 0.025 0.392 0.508 0.483 0.440 0.449 𝐶𝑑𝐼2 𝐶𝑑 2+ + 2𝐼 −
2 0.05 0.822 0.388 0.509 0.487 0.432 0.402
3 0.10 0.831 0.385 0.510 0.489 0.425 - 𝐶𝑑𝐼2 + 2𝐼 − 𝐶𝑑𝐼4 2−

4 0.20 0.884 0.385 0.512 0.491 0.416 0.131 5. Temperature

5 0.50 - - - 0.491 0.399 0.005 - while increasing the temperature, the transport number of both cations and anions are nearing 0.5.
29 30

Ionic Mobility Determination of Ionic Mobility

◆ During the electrolysis, boundary between the two electrolytes will be moving, by
S. No Electrolyte λ∞ (mol. cm2) measuring such moving boundary distance Ionic Mobility can be determined.
◆ Although, at infinite dilution, all electrolytes are completely dissociated,
their molar conductances differ vastly from one another. (Total 1 HCl 426.15 ◆ Ex. Measurement of Ionic Mobility of the 𝐾 + ions: Pt
conductance of the 1 molar solution is referred as molar conductance) Cathode
2 NaCl 126.46 ◆ KCl: Primary Solution. CdCl2: Boundary indicator solution. Both have Chloride ion as common.
◆ This is because of differences in speeds of the ions.
3 KCl 129.86 ◆ Migration Speed: 𝑪𝒅𝟐+ > 𝑲+
◆ At the vertical setup, CdCl2 is taken at the bottom and KCl is taken at the top. Pt Anode at
◆ Ex. The molar conductance at infinite dilution of HCl is more than three 4 LiCl 115.03 the bottom and Pt Cathode at the top are connected. b b'
times as high as that of NaCl. Since chloride ion is common, it follows that ◆ During the electrolysis both 𝑪𝒅𝟐+ 𝒂𝒏𝒅 𝑲+ are migrating towards the Cathode hence Moving
KCl
the speed of hydrogen ion is more than three times of the speed of sodium 5 KBr 151.92 boundary (a-a’) between the CdCl2-KCl is also moving towards cathode (upward: b-b’). Solution Boundary
ion. ◆ Lets consider that “E volt” as electro motive force of the current applied and distance
6 CH3COOH 390.70 a a'
between the two electrodes is 1 cm.
◆ Speed of an ion varies with the potential applied. ◆ Besides, at time “t” assume that boundary has moved a distance “X cm”.
7 NaNO3 105.20
◆ “Ionic mobility is defined as the distance travelled by an ion per 8 AgNO3 133.63 𝑿 𝑬
second under potential gradient of 1 volt per meter” Ionic Mobility of 𝑲+ = 𝒄𝒎. 𝒔−𝟏 ; Voltage drop = 𝒗𝒐𝒍𝒕. 𝒄𝒎−𝟏
𝒕 𝒍 CdCl2
9 BaCl2 139.98 Solution
◆ Potential gradient is given by the potential difference applied at the 𝑺𝒑𝒆𝒆𝒅 𝑿Τ𝒕 𝑿𝒍
electrodes divided by the distance between the electrodes. 10 MgSO4 131.86 therefore, Ionic Mobility of 𝑲+ = 𝑽𝒐𝒍𝒕𝒂𝒆 𝒅𝒓𝒐𝒑
𝒄𝒎. 𝒔−𝟏 𝑬Τ𝒍 =
𝑬𝒕
𝒄𝒎𝟐 . 𝑽𝒐𝒍𝒕−𝟏 𝒔−𝟏 Pt
Anode Coulometry
Cadmium
Stick

31 32
 Conductance Measurements and Applications to
Conductometric Titrations

◆ Titrations in which conductance measurements are made use of in

Table: Ionic Mobility of different ions determining the end-point of acid-alkali reactions, some displacement
reactions or precipitation reactions are called Conductometric titrations.
◆ In these titrations, advantage is taken of the fact that the conductance
S. No Ions λ∞ (mol. cm2) of a solution at a constant temperature depends upon the number of
+ ions present in it and their mobility.
1 𝐻 0.003624
◆ For this purpose, the titrant is added from a burette into a measured
2 𝑁𝑎+ 0.000519 volume of the solution to be titrated which is taken in a conductance cell
and the conductance readings corresponding to the various additions are
3 𝐾+ 0.000761 plotted against the volume of the titrant.
◆ In this way two linear curves are obtained, the point of intersection of
4 𝐵𝑎2+ 0.000660 which is the end-point.
◆ Several phenomena like hydrolysis of reactants or products or partial
5 𝑁𝐻4+ 0.000760
solubility of a precipitated product give rise, however to a curvature in the
6 𝑂𝐻 − 0.002050 curves.
◆ The shapes of curves obtained in certain types of titration are discussed
7 𝐶𝑙 − 0.000791 below :

8 𝑁𝑂3− 0.000740

9 𝑆𝑂42− 0.000827
−
10 𝐶𝐻3 𝐶𝑂𝑂 0.000425
33 34

Conductometric Titrations: (1) Titration of a Weak acid Vs. Conductometric Titrations: (1) Titration of a Weak acid Vs.
Strong alkali Strong alkali (Cont.)

(1) Titration of a Strong acid against a Strong base:
◆ Consider the reaction in which hydrochloric acid (HCl) solution is titrated against a
solution of sodium hydroxide (NaOH).
◆ Take 20 mL of the acid solution in the conductance cell placed in a thermostat and
determine its conductance.
◆ Now add 1 mL sodium hydroxide solution from the burette at a time.
◆ After each addition, determine the conductance of the solution after through mixing and
plot the conductance of the solution against the volume of the alkali added.
◆ It will be observed that the points lie on two lines which are almost straight.
◆ The point of intersection of the interpolated lines will be the end point and the volume of
alkali corresponding to this point is the volume of alkali required to neutralize 20 mL of
the acid (Figure).
◆ The reason for this is that before the addition of alkali, the conductance of the solution is
due to presence of 𝐻 + and 𝐶𝑙 − ions.
◆ Since hydrogen ions possess the greatest mobility of any ion, the greater part of the
conductance is due to it.
◆ As alkali solution is added, the hydrogen ions are removed by combination with the
hydroxyl ions forming feebly ionised water molecules and their place is taken up by
comparatively slow-moving 𝑁𝑎+ ions.
𝑯+ + 𝑪𝒍− + 𝑵𝒂+ + 𝑶𝑯− 𝑵𝒂+ + 𝑪𝒍− + 𝑯𝟐 𝑶 (𝒇𝒆𝒆𝒃𝒍𝒚 𝒊𝒐𝒏𝒊𝒔𝒆𝒅)
Figure: Conductometric titration curve for
HCl Vs NaOH
(1) Titration of a Strong acid against a Strong base:
Figure: Conductometric titration curve for
◆ As a result of this, the conductance of the solution decreases and continues to fall with HCl Vs NaOH
every subsequent addition of alkali till the end-point is reached.
◆ After the equivalence point, the further addition of sodium hydroxide solution results in
an increase of conductance since the hydroxyl ions are no longer removed in the chemical
reaction in the form of feebly ionised water.
◆ The point of minimum conductance, therefore, coincides with the end-point of the
titration.
◆ In order to get accurate results, the volume change during titration should be as little as
possible.
◆ The titrant should, therefore, be about 10 times as strong as the acid solution in the
conductance cell in order to keep the volume change small.
◆ If this is not so, a correction to the readings has to be applied viz,
𝒗+𝑽
actual conductance = x observed conductance
𝑽
where v is the volume of the titrant and V is the original volume of the solution to be titrated.

35 36
 Conductometric Titrations: (2) Titration of a Weak acid Vs. Conductometric Titrations: (3) Titration of a Strong acid Vs.
Strong alkali Weak base
(2) Titration of a Weak acid against a Strong alkali:
◆ When a weak acid like acetic acid (CH3COOH) is titrated against a strong alkali like
sodium hydroxide (NaOH), we get a curve of the type shown in Figure. Figure: Curve for titration of a Figure: Curve for titration of a HCl Vs NH4OH
◆ The initial conductance of the solution is low because of the poor dissociation of the CH3COOH Vs NaOH (3) Titration of a Strong acid against a Weak base:
weak acid.
◆ On adding alkali, highly ionised sodium acetate is formed. 𝑯+ + 𝑪𝒍− + 𝑵𝑯𝟒 𝑶𝑯 𝑵𝑯+ −
𝟒 + 𝑪𝒍 + 𝑯𝟐 𝑶 (𝒇𝒆𝒆𝒃𝒍𝒚 𝒊𝒐𝒏𝒊𝒔𝒆𝒅)
◆ The acetate ions at first tend to suppress the ionisation of acetic acid still further
due to Common Ion Effect but after a while the conductance begins to increase ◆ After the end-point has been reached, the addition of ammonium
because the conducting power of highly ionised salt exceeds that of the weak acid. hydroxide will not cause any appreciable change in conductance value as
it is a weak electrolyte, and its conductance is very small compared
𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 + 𝑵𝒂+ + 𝑶𝑯− 𝑪𝑯𝟑 𝑪𝑶𝑶− + 𝑵𝒂+ + 𝑯𝟐 𝑶 (𝒇𝒆𝒆𝒃𝒍𝒚 𝒊𝒐𝒏𝒊𝒔𝒆𝒅) with that of the acid or its salt.
◆ The shape of this part of the curve will, therefore, be as shown in the
◆ Immediately after the end point, further addition of sodium hydroxide introduces the figure.
fast-moving hydroxyl ions.
◆ Thus, the conductance value shows a sharp increase. ◆ The curve obtained for the titration of a strong acid against a weak
◆ The point of intersection of the two curves, gives the end-point. base is shown in Figure.

◆ In this case, the conductance of the solution will first decrease due to
the fixing up of the fast-moving 𝐻 + ions and their replacement by slow
moving 𝑁𝐻4+ ions.

37 38

Conductometric Titrations: (4) Titration of a Weak acid Vs.

Conductometric Titrations: (5) Precipitation Reactions
Weak base

Figure: Curve for titration of CH3COOH Vs NH4OH (5) Precipitation reactions:

Figure: Titration of AgNO3 Vs KCl
◆ The end-point in precipitation reactions can be accurately determined by
(4) Titration of a Weak acid against a Weak base:
conductometric titration.
◆ The accuracy is further increased by working with fairly dilute solutions and
◆ The conductometric method is particularly suitable as such titrations do
addition of alcohol which reduces the solubility of the precipitate and
not give a sharp end-point with indicators.
prevents adsorption.
◆ Consider the titration of acetic acid with ammonium hydroxide.
◆ In the titration of potassium chloride (KCl) against silver nitrate (AgNO3), for
◆ The complete titration curve is shown in Figure.
example, the change in conductance on the addition of silver nitrate (AgNO3)
◆ The initial conductance of the solution in this case is also low due to the
is not much since the mobility of the potassium ion (𝐾 + ) and the silver ion (𝐴𝑔+ )
poor dissociation of the weak acid.
is of the same order.
◆ But it starts increasing as the salt CH3COONH4 is formed.
◆ Thus, the curve is nearly horizontal.
◆ After the equivalence point, the conductivity remains almost constant
because the free base NH4OH is a weak electrolyte.
◆ The end-point is quite sharp.
𝑨𝒈+ + 𝑵𝑶− +
𝟑 + 𝑲 + 𝑪𝒍
− 𝑲+ + 𝑵𝑶−
𝟑 + 𝑨𝒈𝑪𝒍 (𝒑𝒑𝒕)

After the end-point, there is a sharp increase in conductance due to an increase

in the number of free ions in solution.

39 40
 Advantage of Conductometric Titrations Differences Between Conductometric and Volumetric Titrations

Advantage of Conductometric Titrations:

(1) Coloured solutions where no indicator is found to work satisfactorily can be successfully titrated by this method.

(2) This method is useful for the titration of weak acids against weak bases which do not give a sharp change of colour with
indicators in ordinary volumetric analysis.

(3) More accurate results are obtained because the end -point is determined graphically.

Precautions:

(i) It is necessary to keep the temperature constant throughout the experiment.

(ii) In acid-alkali titrations, the titrant should be about 10 times stronger than the solution to be titrated
so that the volume change is as little as possible.

41 42

Molar and Equivalent Conductances and their Measurements Molar and Equivalent Conductances and their Measurements

Specific Conductance: or conductivity is defined as the conductance of unit volume of a cell.

It is reciprocal of resistivity.

Resistance: is a measure of the opposition to current flow in an electrical circuit. 𝒍 𝒂𝑹 𝒍 𝒍

Resistance is measured in ohms, symbolized by the Greek letter omega (Ω). 𝐊= 𝒂𝒏𝒅 𝝆 = , therefore, 𝐊= or K = 𝑖𝑠 𝑐𝑎𝑙𝑙𝑒𝑑 𝑐𝑒𝑙𝑙 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡.
𝝆 𝒍 𝒂𝑹 𝒂
Specific conductance has units as ohm-1cm-1. SI unit of specific conductance is Sm-1 where S is Siemen.
Insulators: Materials that present high resistance and restrict the flow of electrons.

Equivalent Conductance: The equivalent conductance of an electrolyte is defined as the conductance of

a volume of solution containing one equivalent weight of dissolved substance when placed
Specific Resistance: the electrical property of a material that determines the resistance of a piece of given between two parallel electrodes 1 cm apart, and large enough to contain between them all of
dimensions (1 cm length and 1 cm2 cross-sectional area). the solution.

𝟏𝟎𝟎𝟎 𝑲
It is equal to
𝑙
R = ρ 𝑎, where R is the resistance, a the cross-sectional area, and ‘l’ the length, and ‘ρ’ is the reciprocal of conductivity. 𝝀= where, N = Normality of the electrolyte. Unit: mol.cm2
𝑵
It is measured in ohms. Symbol: ρ.
Molar Conductance: is defined as the conducting power of all the ions produced by 1 mole of an electrolyte in the given solution.

Conductance: (also known as electrical conductance) is defined as the potential for a substance to conduct electricity. Symbol = μ. μ = K x V
𝟏𝟎𝟎𝟎 𝑲
Conductance is the measure of how easily electrical current (i.e. flow of charge) can pass through a material. μ= where, M = Molarity of the electrolyte. Unit: mol.cm2
Conductance is the inverse (or reciprocal) of electrical resistance, represented as 1/R. 𝑴
Note: 1. Specific conductance is used to measure the conductance of the metallic conductors.
2. To determine the conductance of the electrolyte, Equivalent or Molar conductance is used.
43 44
 Measurements of Conductances Measurements of Conductances

1. Conductivity Cell: A conductivity cell is a device that is comprised of electrodes that sense the electrical conductivity of a 2. Conductivity Water:
substance, such as water.
Common configurations include two electrode cells and four electrode conductivity cells. The conductivity of water is a measure of the capability of water to pass electrical flow. This ability is directly dependent on the
concentration of conductive ions present in the water.
- the solution whose resistance is to be determine, is taken in a conductivity cell.
- the cell basically consist of a glass container, in which two electrodes are fixed. - Specific capacitance of conductivity water is 5 x 10-8 mol. cm-1.

Connecting
Connecting Wires
Wires

Platinized Pt
Electrodes

Platinized Pt Electrode Platinized Pt Electrode

Figure: Two different types of conductivity cells

45 46

Measurements of Conductances Measurements of Conductances

𝒍 4. Alternating Current, A. C.:

3. Cell Constant: ( )
𝒂 - During the conductance measurements, if we use the Direct Current, DC, concentration of the electrolyte is decreasing
and due to the polarization effect of the electrodes, solution resistance also increasing.
In a conductivity cell, distance between the two electrodes (l) and cross-section of the electrode area (a) are
𝒍 - In order to overcome this issue, Alternating Current, AC (100 cycles/s) is used.
constant. Hence, is a constant and it is referred as Cell Constant. -to identify the electric equivalent point, instead of Galvanometer, Telephone head or magic eye is used.
𝒂

𝒍
𝑺𝒑𝒆𝒄𝒊𝒇𝒊𝒄 𝒄𝒐𝒏𝒅𝒂𝒖𝒄𝒕𝒂𝒏𝒄𝒆, 𝒌 = 𝑪 𝒙
𝒂

47 48
 Measurements of Specific Conductance by Measurements of Specific Conductance by
Wheatstone Bridge Method Wheatstone Bridge Method (Cont.)

Specific Conductance: or conductivity is defined as the conductance of unit volume of a cell. Specific Conductance: or conductivity is defined as the conductance of unit volume of a cell.

D Method: D ⚫ Resistance of “AO” and “OB” will be equal at every unit

distance. Hence,
Resistance Box ⚫ Target solution is taken in container “C” and connected in Resistance Box
C a circuit as shown in the figure. C 𝑺𝒐𝒍𝒖𝒕𝒊𝒐𝒏 𝑹𝒆𝒔𝒊𝒔𝒕𝒂𝒏𝒄𝒆 𝑨𝑶 − 𝑳𝒆𝒏𝒈𝒕𝒉
⚫ “AB” is rod having uniform diameter and made up of =
𝑹𝒆𝒔𝒊𝒔𝒕𝒂𝒏𝒄𝒆 𝒂𝒕 𝑹𝒆𝒔𝒊𝒔𝒕𝒂𝒏𝒄𝒆 𝒃𝒐𝒙 𝑶𝑩 − 𝑳𝒆𝒏𝒈𝒕𝒉
Platinum-Iridium alloy.

Conductivity Cell

Conductivity Cell
O ⚫ Current is passing through two ways; “AOB” and “ADB”. O
A A
𝐓𝐡𝐞𝐫𝐞𝐟𝐨𝐫𝒆,
B B

⚫ Through the resistance box, a particular resistance is appl

Telephone head T J B ied to move the Jockey (J) over “AB”. Telephone head T J B 𝑨𝑶−𝑳𝒆𝒏𝒈𝒕𝒉
𝑺𝒐𝒍𝒖𝒕𝒊𝒐𝒏 𝑹𝒆𝒔𝒊𝒔𝒕𝒂𝒏𝒄𝒆 = 𝑶𝑩−𝑳𝒆𝒏𝒈𝒕𝒉 𝐱 𝐑𝐞𝐬𝐢𝐬𝐭𝐚𝐧𝐜𝐞 𝐚𝐭 𝐛𝐨x
Secondary S Secondary S
⚫ When “J” is at the point “O” there is mild sound coming
Primary Thermostat out. Primary Thermostat ⚫ Hence, by measuring the distance of AO and OB, solution
Test Solution Test Solution resistance can be calculated.
⚫ Lets assume this point as mute point.
Induction Coil ⚫ Now, at point D and O, voltage is equal. Hence, Induction Coil
𝐁𝐞𝐬𝐢𝐝𝐞𝐬,
Figure: Determination of Specific Conductivity. 𝑺𝒐𝒍𝒖𝒕𝒊𝒐𝒏 𝑹𝒆𝒔𝒊𝒔𝒕𝒂𝒏𝒄𝒆 𝑨𝑶 − 𝑹𝒆𝒔𝒊𝒔𝒕𝒂𝒏𝒄𝒆 Figure: Determination of Specific Conductivity. 𝟏
= 𝑺𝒐𝒍𝒖𝒕𝒊𝒐𝒏 𝑪𝒐𝒏𝒅𝒖𝒄𝒕𝒂𝒏𝒄𝒆 =
𝑹𝒆𝒔𝒊𝒔𝒕𝒂𝒏𝒄𝒆 𝒂𝒕 𝑹𝒆𝒔𝒊𝒔𝒕𝒂𝒏𝒄𝒆 𝒃𝒐𝒙 𝑶𝑩 − 𝑹𝒆𝒔𝒊𝒔𝒕𝒂𝒏𝒄𝒆 𝑹
By using the Wheatstone bridge method, By using the Wheatstone bridge method,
specific conductance of the solution is measured. specific conductance of the solution is measured. -Hence, solution conductance can be measured

49 50

(i) Measurement Cell Constant (ii) Measurement of Specific Conductance

𝒍
Cell Constant: ( )
𝒂
In a conductivity cell, distance between the two electrodes (l) and cross-section of the electrode area (a) are
𝒍
constant. Hence, is a constant and it is referred as Cell Constant.
𝒂
⚫ Electrolyte solution should be taken in a conductivity cell of know cell constant.
𝒍 𝒍 𝑺𝒑𝒆𝒄𝒊𝒇𝒊𝒄 𝑪𝒐𝒏𝒅𝒖𝒄𝒕𝒂𝒏𝒄𝒆, 𝒌
𝑺𝒑𝒆𝒄𝒊𝒇𝒊𝒄 𝒄𝒐𝒏𝒅𝒂𝒖𝒄𝒕𝒂𝒏𝒄𝒆, 𝒌 = 𝑪 𝒙 𝒆𝒒𝒏 (𝟏) 𝑪𝒆𝒍𝒍 𝑪𝒐𝒏𝒔𝒕𝒂𝒏𝒕, = eqn (2) ⚫ Subsequently, conductance is measured.
𝒂 𝒂 𝑪𝒐𝒏𝒅𝒖𝒄𝒕𝒂𝒏𝒄𝒆,𝑪 ⚫ By using the following equation, specific conductance, K can be measured.

⚫ 0.01 N or 0.1 N or 1 N KCl is taken in a conductivity cell, and its conductance is measured.
⚫ From the table we know the specific conductance value hence, by using the equation 2, Cell Constant can be measured. 𝒍 𝒍
𝑺𝒑𝒆𝒄𝒊𝒇𝒊𝒄 𝒄𝒐𝒏𝒅𝒂𝒖𝒄𝒕𝒂𝒏𝒄𝒆, 𝑲 = 𝑪 𝒙 , where, C = conductance and is the cell constant
𝒂 𝒂

Table: Specific Conductance (K) values of KCl at different concentrations and temperatures.

Specific Conductance (mol. cm-1)

S. No Concentration
273 K 291 K 298 K
1 0.01 N 0.0007751 0.0012227 0.0014114
2 0.1 N 0.007154 0.011192 0.012886
3 1N 0.06543 0.0982 0.11173
51 52
 (iii) Measurement of Equivalent Conductance Solved Problem

Problem: 1
At 291 K, resistance of 0.1 N KCl is 55 Ω hence, calculate the cell constant of the conductivity cell? Assume that
Specific conductance of the solution is 0.0112 mol. cm-1.
⚫ If we know the target electrolyte’s concentration (N), then from its specific conductance value, equivalence
conductance can be measured. Solution:

𝒍 𝑺𝒑𝒆𝒄𝒊𝒇𝒊𝒄 𝑪𝒐𝒏𝒅𝒖𝒄𝒕𝒂𝒏𝒄𝒆, 𝑲 𝟏 𝒍
𝑪𝒆𝒍𝒍 𝑪𝒐𝒏𝒔𝒕𝒂𝒏𝒕, 𝒂 = 𝑪𝒐𝒏𝒅𝒖𝒄𝒕𝒂𝒏𝒄𝒆,𝑪
eqn (1) 𝑪𝒐𝒏𝒅𝒖𝒄𝒕𝒂𝒏𝒄𝒆, 𝑪 =
𝑹
(2) 𝑪𝒆𝒍𝒍 𝑪𝒐𝒏𝒔𝒕𝒂𝒏𝒕, = 𝑲𝑹 cm-1 (3)
𝒂
𝟏𝟎𝟎𝟎 𝒙 𝑺𝒑𝒆𝒄𝒊𝒇𝒊𝒄 𝒄𝒐𝒏𝒅𝒖𝒄𝒕𝒂𝒏𝒄𝒆, 𝑲
𝑬𝒒𝒖𝒊𝒗𝒂𝒍𝒆𝒏𝒕 𝒄𝒐𝒏𝒅𝒂𝒖𝒄𝒕𝒂𝒏𝒄𝒆, 𝛌 =
𝑵 Solution resistance, R = 55 Ω
Specific conductance, K = 0.0112 mol. cm-1.

Equivalent Conductance: The equivalent conductance of an electrolyte is defined as the conductance of 𝒍

a volume of solution containing one equivalent weight of dissolved substance when placed 𝑻𝒉𝒆𝒓𝒆𝒇𝒐𝒓𝒆, 𝑪𝒆𝒍𝒍 𝑪𝒐𝒏𝒔𝒕𝒂𝒏𝒕, = 𝟎. 𝟎𝟏𝟏𝟐 𝒙 𝟎. 𝟔𝟏𝟔 cm-1
𝒂
between two parallel electrodes 1 cm apart, and large enough to contain between them all of
the solution.

𝟏𝟎𝟎𝟎 𝑲
𝝀= where, N = Normality of the electrolyte. Unit: mol.cm2
𝑵

53 54

Solved Problem Solved Problem

Problem: 3
Problem: 2
At 291 K, in a conductivity cell 0.1 N KCl solution was taken and the solution resistance was measured as 87 Ω. Specific conductance of
At 298 K, resistance of 0.01 N solution is 210 Ω. Cell constant is 0.88 cm-1 hence, calculate the equivalent conductance
this solution is 0.011192 mol. cm-1. In a same conductivity cell, solution resistance of 203 Ω was measured while taking 0.05 N NaCl hence,
of the solution?
calculate the specific and equivalent conductance of the 0.05 N NaCl solution?
Solution: KCl NaCl
𝒍 𝒍
𝑺𝒑𝒆𝒄𝒊𝒇𝒊𝒄 𝒄𝒐𝒏𝒅𝒖𝒄𝒕𝒂𝒏𝒄𝒆, 𝑲 = 𝑪 𝒙 , where, C = conductance and is the cell constant Concentration (N) 0.1 N 0.05 N
𝒂 𝒂
𝟏 𝟏 Resistance, R 87 Ω 203 Ω
K = 𝟎. 𝟖𝟖 𝒙 = 0.00419 mol. cm-1 (𝑪 = )
𝟐𝟏𝟎 𝑹
Specific conductance, K 0.011192 mol. cm-1 ??
𝟏𝟎𝟎𝟎 𝑲 Equivalent conductance, λ - ??
𝑬𝒒𝒖𝒊𝒗𝒂𝒍𝒆𝒏𝒕 𝒄𝒐𝒏𝒅𝒖𝒄𝒕𝒂𝒏𝒄𝒆, 𝝀 = where, N = Normality of the electrolyte. Unit: mol.cm2
𝑵
Solution 1: Calculation of Cell constant from KCl Solution 2: Specific conductance of NaCl Solution 3: Equivalent conductance of
𝟏𝟎𝟎𝟎 𝒙 𝟎. 𝟎𝟎𝟒𝟏𝟗 Solution NaCl
𝝀= = 𝟒𝟏𝟗 𝒎𝒐𝒍. 𝒄𝒎𝟐 𝒍
𝟎. 𝟎𝟏 𝒍 𝑺𝒑𝒆𝒄𝒊𝒇𝒊𝒄 𝒄𝒐𝒏𝒅𝒖𝒄𝒕𝒂𝒏𝒄𝒆, 𝑲 = 𝑪 𝒙 𝟏𝟎𝟎𝟎 𝑲
𝑪𝒆𝒍𝒍 𝑪𝒐𝒏𝒔𝒕𝒂𝒏𝒕, = 𝑲𝑹 cm-1 𝒂
𝒂 𝑬𝒒𝒖𝒊𝒗𝒂𝒍𝒆𝒏𝒕 𝒄𝒐𝒏𝒅𝒖𝒄𝒕𝒂𝒏𝒄𝒆, 𝝀 =
𝑵
𝟎.𝟗𝟕𝟑
= 0.011192 x 87 = 0.973 cm-1 K= = 0.00479 mol. cm-1
𝟐𝟎𝟑 𝟏𝟎𝟎𝟎 𝒙 𝟎. 𝟎𝟎𝟒𝟕𝟗
𝝀= = 𝟒𝟏𝟗 𝒎𝒐𝒍. 𝒄𝒎𝟐
𝟎. 𝟎𝟓
𝟏
(𝑪 = )
𝑹

55 56
 Effect of Dilution on Conductivities Effect of Dilution on Conductivities (Cont.)

⚫ In an Electrolyte solution, its ions are conducting the current flow.

Table: Specific and Equivalent Conductance values of KCl at 291 K.
⚫ During dilution, dissociation speed become high consequently, number of ions are increasing.
⚫ As an impact, value/ ability of all the conductances (Specific, Equivalent and Molar) should increase. S. No Concentration (N) Volume of 1 g equivalent solution Specific conductance Equivalence conductance
(cm3) (mol. cm-1) (mol. cm2)
⚫ On contrary, during dilution specific conductance is decreasing and Equivalent and Molar conductances are increasing.
1 1.0 1000 0.982 98.2
⚫ During dilution, number of ions are increasing as well as volume.
⚫ In comparison with the increasing ions, volume increase is very high. 2 0.1 10,000 0.0112 112.0
⚫ Eventually, increase in volume led to decrease in concentration. i.e., in 1 cm3, no of ions are decreasing. And specific conductance is 3 0.01 1,00,000 0.001223 122.3
directly proportional to the number of ions present in 1 cm3 solution. Hence, Specific conductance is decreasing.
4 0.001 10,00,000 0.0001273 127.3
⚫ But Equivalent conductance = Specific conductance x Volume of 1 g equivalent electrolyte (cm3) 5 0.0001 1,00,00,000 0.00001291 129.1
⚫ Hence, the volume increase is compensating the decrement of specific conductance and overall equivalent conductance is increasing.
6 0.00001 10,00,00,000 0.000001291 129.1
⚫ But after certain dilution stage, there is no increase in Equivalence conductance.
⚫ This stage is referred as “Infinite Dilution” or “Zero Concentration” 7 0.000001 1,00,00,00,000 0.0000001291 129.1

⚫ At infinite dilution, electrolyte is completely dissociated, further dilution will not contribute in increasing the number of ions.
⚫ Hence, there is no change in Equivalence conductance at infinite dilution.
⚫ Equivalence conductance at the infinite dilutions is termed as λ0 or λ∞.

57 58

Calculation of Dissociation Constant by

Solved Problem
Equivalent Conductance
⚫ Equivalent conductance of the certain concentrated solution (λc) is dependent of dissociation constant of an Electrolyte (α) solution.
Problem: At 298 K, specific conductance of 0.01 N CH3COOH is 0.000163 mol. cm-1. Its λ0 is 390 mol. cm2 hence,
⚫ But equivalent conductance at the infinite dilution (λ0 or λ∞) is dependent of number of ions dissociated out of electrolyte (α = 1). calculate the dissociation constant (α) 0.01 N solution?
𝝀𝒄
Hence, 𝒅𝒊𝒔𝒔𝒐𝒄𝒊𝒂𝒕𝒊𝒐𝒏 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕, 𝜶 = .
𝝀𝟎
❑ Equivalent conductance of a Weak electrolytes at moderate concentration is bit low. Solution:
❑ Upon further dilution, its value is quickly increasing.
𝟏𝟎𝟎𝟎 𝑲
𝑬𝒒𝒖𝒊𝒗𝒂𝒍𝒆𝒏𝒕 𝒄𝒐𝒏𝒅𝒖𝒄𝒕𝒂𝒏𝒄𝒆, 𝝀 = where, N = Normality of the electrolyte. Unit: mol.cm2
❑ But equivalent conductance of a Strong electrolytes is bit high even at moderate concentration. 𝑵
❑ Upon dilution, it is slowly increasing.
𝟏𝟎𝟎𝟎 𝒙 𝟎.𝟎𝟎𝟎𝟏𝟔𝟑
Such trend can be understood from the following table: For 0.01 N CH3COOH, 𝝀𝒄 =
𝟎.𝟎𝟏
Equivalent Conductance (mol cm2)
Strong Electrolyte Weak Electrolyte 𝝀𝒄 = 16.3 𝒎𝒐𝒍. 𝒄𝒎𝟐
S. No Concentration (N) 𝝀 𝟏𝟔.𝟑
HCl NaCl CH3COOH NH4OH Therefore, dissociation constant (α) = 𝝀 𝒄 = = 𝟎. 𝟎𝟒𝟏𝟕𝟗
𝟎 𝟑𝟗𝟎
1 1.0 332.8 89.9 - -

2 0.1 391.3 106.7 5.2 3.6 i.e., 4.179 % of CH3COOH is dissociated.

3 0.01 412.0 118.5 16.3 11.3
Slow Rapid
4 0.001 421.4 Increase 123.7 49.2 34.9 Increase

59 5 0.0005 422.1 124.5 67.7 46.9 60

 Measuring Equivalent Conductance at Infinite
Kohlrausch Law of Independent Migration of Ions
Dilution (λ0)
❑ From a study of the equivalent conductances of different electrolytes at infinite dilution (λ∞ ), Kohlrausch discovered that each ion
contributes to the conductance of the solution.
𝝀𝟎 𝒐𝒓 𝝀∞ (Not touching the Y-axis)
❑ In 1875, he enunciated a generalisation which is called the “Kohlrausch’s Law”.
❑ It states that : the equivalent conductance of an electrolyte at infinite dilution is equal to the sum of the equivalent conductances of the
component ions.
⚫ For strong electrolytes, plot of 𝝀𝒄 𝑽𝒔. 𝑪 gives straight lines.
The law may be expressed mathematically as : 𝝀∞ = 𝝀𝒂 + 𝝀𝒄
⚫ Furthermore, extrapolating these lines to “Zero Concentration”, 𝝀𝟎 𝒐𝒓 𝝀∞ where 𝝀𝒂 is the equivalent conductance of the anion and 𝝀𝒄 that of the cation.
𝝀𝟎 𝒐𝒓 𝝀∞ can be obtained. ❑ For example, the equivalent conductance of NaCl at infinite dilution at 25°C is found to be 126.45.
The equivalent conductance of 𝑵𝒂+ and 𝑪𝒍− ion is 50.11 𝑜ℎ𝑚−1 and 76.34 𝑜ℎ𝑚−1 respectively.

Conductance,
Strong
Thus, 𝝀∞ (NaCl) = 𝝀𝑪𝒍− + 𝝀𝑵𝒂+ or 126.45 = 50.11 + 76.34

Equivalent
⚫ As shown in the figure plot of 𝝀𝒄 𝑽𝒔. 𝑪 for weak electrolyte Electrolyte
like CH3COOH, curved line is obtained. like KCl ❑ This is in conformity with the Kohlrausch’s Law. Table: 𝝀𝟎 values of few electrolytes at 291 K. for better understanding

λ
S. No Electrolytes Pair having 𝝀𝟎 (𝒎𝒐𝒍. 𝒄𝒎𝟐) Difference S. No Electrolytes Pair having 𝝀𝟎 (𝒎𝒐𝒍. 𝒄𝒎𝟐) Difference
⚫ Hence, 𝝀𝟎 𝒐𝒓 𝝀∞ can not be obtained by using this graphical-
Weak Electrolyte Common Anions Common Cations
extrapolating method.
like CH3COOH 1 KF 112.2 21.1 9 KCl 130.0 18.8
⚫ 𝝀𝟎 𝒐𝒓 𝝀∞ can be obtained b using another method which is 𝑪
2 NaF 90.1 10 KF 111.2
based on “Kohlrausch Law ”. 3 KCl 130.0 21.1 11 NaCl 108.9 18.8
𝑪𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 4 NaCl 108.9 12 NaF 90.1
5 KNO3 126.3 21.1 13 KNO3 126.3 27.8
6 NaNO3 105.2 14 KIO3 98.5
7 KIO3 98.5 21.1 15 NaNO3 105.2 27.8
61 62 8 NaIO3 77.4 16 NaIO3 77.4

Kohlrausch Law: Explanation Applications of Kohlrausch’s Law: 1. Ionic Conductance (ν)

❑ In an electrolyte if, 𝑵𝒂+ is there instead of 𝑲+ , 𝝀∞ is decreased about 21.1 mol. cm2. ❑ Each ion has the same constant Ionic Conductance at a fixed temperature, no matter of which electrolyte it forms a part.
❑ This difference is independent of anions (𝑪𝒍− and 𝑭− ). ❑ It is expressed in ohm– 1 cm2 and is directly proportional to the speeds of the ions.
❑ Likewise, 𝑪𝒍− is there instead of𝑭− , 𝝀∞ is decreased about 18.8 mol. cm2.
❑ Again, this difference is independent of cations (𝑵𝒂+ and 𝑲+ ). 𝝀𝒂 ∝ ν− 𝒐𝒓 𝝀𝒂 = 𝒌 𝒙 ν− and 𝝀𝒄 ∝ ν+ 𝒐𝒓 𝝀𝒄 = 𝒌 𝒙 ν+
❑ This trend is possible only when each ion (cation and anion) of an electrolyte contributes their portion to the 𝝀∞ .
Kohlrausch explained it as follows; where k is the proportionality constant.
Kohlrausch law: At the infinite dilution, each ion contributes its portion/value to the 𝝀𝟎 and this value is independent of the ion attached Also
with it. 𝝀∞ ∝ (λ𝒂 + 𝝀𝒄 ) = 𝒌 ( ν− + ν+ )
i.e., 𝝀∞ = 𝝀𝒂 + 𝝀𝒄
where 𝝀𝒂 is the equivalent conductance of the anion and 𝝀𝒄 that of the cation λ𝒂 𝒌ν− ν−
where 𝝀𝒂 is the equivalent conductance of the anion and 𝝀𝒄 that of the cation.
therefore, λ∞
=𝒌 = ν− + ν+
= 𝑡− ……..(1)
(ν− + ν+ )

λ𝒄 𝒌ν− ν+
and λ∞
=𝒌 = ν− + ν+
= 𝑡+ = 1 − 𝑡− ……..(2)
(ν− + ν+ )

𝜆𝑎 𝑡−
Diving equation (1) by (2), we have = ……..(3)
𝜆𝑐 1 − 𝑡−

With the help of the expression (3), we can determine ionic conductances from the experimental values of the transport number of
the ions.
63 64
 Applications of Kohlrausch’s Law: 2. Calculation of λ∞ for Weak Electrolytes Ionic Conductance: Experimental Values

❑ Weak electrolytes do not ionise to a sufficient extent in solution and are far from being completely ionised even at very great dilution.
❑ The practical determination of λ∞ in such cases is, therefore, not possible. Table: Ionic Conductance values of few electrolytes at 298 K.
❑ However, it can be calculated with the help of Kohlrausch’s law.

S. No Cation λ𝟎𝒄 S. No Anion λ𝟎𝒂

𝜆𝑎 𝑡−
= 1 𝐻 +
349.83 1 𝑂𝐻 −
198.50
𝜆𝑐 1 − 𝑡−
2 𝐿𝑖 + 38.70 2 𝐶𝑙 − 76.34
𝝀𝒂 - 𝒕− 𝝀𝒂 = 𝒕− 𝝀𝒄 3 𝑁𝑎+ 50.11 3 𝐵𝑟 − 78.40

4 𝐾+ 73.52 4 𝐼− 76.80
𝝀𝒂 = 𝒕− ( λ𝒂 + λ𝒄 )
5 𝑁𝐻4+ 73.40 5 𝑁𝑂3− 71.44
= 𝒕− 𝝀 ∞ 6 𝐴𝑔+ 61.92 6 𝐻𝐶𝑂3− 44.50
❑ Thus the ionic conductance of an ion is obtained by multiplying the equivalent conductance at infinite dilution of any strong 7 𝐵𝑎+ 63.65 7 𝑆𝑂42− 79.80
electrolyte containing that ion by its transport number.
❑ In this manner, the ionic mobilities of the two ions present in the weak electrolyte can be calculated. 8 𝐶𝑎+ 59.46 8 𝐶𝐻3 𝐶𝑂𝑂𝐻 − 40.89
❑ Thus we can get the equivalent conductance of the electrolyte at infinite dilution by adding up these two values.

65 66

Solved Problem Solved Problem

Problem: At 25°C the transport number of 𝑯+ ion in 𝑯𝑪𝒍 and 𝑪𝑯𝟑 𝑪𝑶𝑶− ion in 𝑪𝑯𝟑 𝑪𝑶𝑶𝑵𝒂 are 0.81 and 0.47 respectively.
The equivalent conductances at infinite dilution of 𝑯𝑪𝒍 and 𝑪𝑯𝟑 𝑪𝑶𝑶𝑵𝒂 are 426 𝑜ℎ𝑚−1 𝑐𝑚2 𝑒𝑞𝑣𝑡 −1 and
Problem: Calculate the equivalent conductance at 20°C of NH4OH at infinite dilution.
91.0 𝑜ℎ𝑚−1 𝑐𝑚2 𝑒𝑞𝑣𝑡 −1 respectively. Calculate the equivalent conductance of acetic acid at infinite dilution.
Given :
Solution: 𝝀∞ 𝑵𝑯𝟒 𝐂𝐥 = 𝟏𝟑𝟎 𝝀∞ 𝑶𝑯− = 𝟏𝟕𝟒 𝝀∞ 𝑪𝒍− = 𝟔𝟔
Conductance of 𝑯+ ion = 𝝀∞ 𝐇𝐂𝐥 𝒙 𝒕𝑯+
Solution:
= 426 x 0.81 = 345.06
Applying Kohlrausch’s law,
Conductance of 𝐶𝐻3 𝐶𝑂𝑂𝐻 − ion = 𝝀∞ 𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 𝒙 𝒕𝑪𝑯𝟑 𝑪𝑶𝑶− 𝝀∞ 𝑵𝑯𝟒 𝑶𝑯 = 𝝀∞ 𝑵𝑯𝟒 𝑪𝒍 + 𝝀∞ 𝑶𝑯− − 𝝀∞ 𝑪𝒍−
= 91 x 0.47 = 42.77
= 130 + 174 – 66
Therefore, Conductance of 𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 at infinite dilution is = 𝝀𝒂 + 𝝀𝒄
= 42.77 + 345.06 = 238 𝑜ℎ𝑚−1 𝑐𝑚2 𝑒𝑞𝑣𝑡 −1
= 387.83 mhos

67 68
 Applications of Kohlrausch’s Law: 3. Calculation of Absolute Ionic Mobilities Solved Problem

❑ The absolute ionic mobility of an ion is defined as the velocity of an ion in centimetres per second under a potential gradient of one
volt per centimetre. Problem: The molecular conductance at infinite dilution of KCl is 130.1. The Hittorf number, 𝒕− for the chloride ion in very dilute
❑ (Potential gradient = applied EMF/distance between (the electrodes). solution is 0.505. Calculate the mobilities in 𝒄𝒎 𝒔𝒆𝒄−𝟏 of potassium and chloride ions.
❑ It is expressed in cm sec–1.
❑ For example, let the velocity of the ion at infinite dilution be U cm per second when the distance between the electrodes is 20 cm
and the voltage 100 V. Solution:
❑ Then the potential difference is 100/20 i.e., 5 volts per cm and the ionic mobility is U/5 cm sec–1.
❑ It has been found that the ionic conductance is directly proportional to the ionic mobility i.e., Ionic Conductance of 𝑪𝒍− ion, 𝝀𝒂 = λ∞ 𝒙 𝒕−

𝝀𝒂 ∝ 𝑼𝒂 and 𝝀𝒄 ∝ 𝑼𝒄 Therefore, Ionic Mobility of 𝑪𝒍− ion, 𝑼𝒂 =

𝟏𝟑𝟎.𝟏 𝒙 𝟎.𝟓𝟎𝟓
= 𝟎. 𝟎𝟎𝟎𝟔𝟖𝟏 𝐜𝐦 𝒔𝒆𝒄−𝟏
(Or) 𝟗𝟔,𝟓𝟎𝟎

𝝀𝒂 ∝ 𝒌𝑼𝒂 and 𝝀𝒄 ∝ 𝒌𝑼𝒄 Ionic Conductance of 𝑲+ ion, 𝝀𝒄 = λ∞ (𝟏 − 𝒕− )

➢ where ‘k’ is the proportionality constant. 𝟏𝟑𝟎.𝟏 𝒙 𝟎.𝟒𝟗𝟓

➢ Its value is equal to the charge on one gram-equivalent of the ion under the potential gradient of 1 volt per cm i.e., k = 96,500 Therefore, Ionic Mobility of 𝑲+ ion, 𝑼𝒄 = = 𝟎. 𝟎𝟎𝟎𝟔𝟔𝟕 𝐜𝐦 𝒔𝒆𝒄−𝟏
𝟗𝟔,𝟓𝟎𝟎
coulomb (1 Faraday).
➢ Therefore, the ionic mobility is obtained by dividing the ionic conductance by 96,500 coulombs.

λ#
𝑈# = λ# = 𝐹𝑈#
96,500
69 70

Solubility Product Applications of Kohlrausch’s Law: 4. Calculation of Solubility of Sparingly Soluble Salts

Definition:
❑ Solubility product,𝑲𝑺𝑷 is the mathematical product of its dissolved ion concentration raised to the power of their stoichiometric
⚫ Substance like AgCl or PbSO4 which are ordinarily called insoluble do possess a definite value of solubility in water.
co-efficients.
❑ (Or) The maximum product of the ionic concentrations or activities of an electrolyte from the saturated solution that at one
⚫ This can be determined from conductance measurements of their saturated solutions.
temperature can continue in equilibrium with the undissolved phase is referred as 𝑲𝑺𝑷
Water Alcohol Water Salt Water Oil ⚫ Since a very small amount of solute is present it must be completely dissociated into ions even in a saturated solution so that
the equivalent conductance κV is equal to equivalent conductance at infinite dilution.

⚫ This according to Kohlrausch’s Law is the sum of the ionic mobilities.

Saturated i.e., 𝒌𝑽 = 𝝀∞ = λ𝒂 + 𝝀𝒄
brine Excess AgCl
Salt
(Water insoluble) knowing 𝒌 𝒂𝒏𝒅 𝝀∞ , V can be found out which is the volume in ml containing 1 g equivalent of the electrolyte.
Unlimited Solubility Limited Solubility No Solubility
❑ Many ionic compounds are only Slightly soluble in water: ex. Ag salts, sulfides.
❑ Equations are written to represent the equilibrium between the compound and the ions present in a saturated aqueous solution.
❑ If we know the solubility of the salt, we can learn the concentration of the ions. Therefore, 𝑲𝑺𝑷 can be calculated.
❑ Lets consider “S” as solubility of the AgCl;
𝐴𝑔+ [𝐶𝑙 − ] 𝑏𝑢𝑡 𝐾𝑐 [𝐴𝑔𝐶𝑙] = 𝐴𝑔+ [𝐶𝑙 − ] 𝐾𝑆𝑃 = 𝐴𝑔+ [𝐶𝑙 − ]
𝐴𝑔𝐶𝑙 𝑠 ⇄ 𝐴𝑔+ 𝑎𝑔 + 𝐶𝑙 − (𝑎𝑔) 𝐾𝑐 =
(1-S) S S [𝐴𝑔𝐶𝑙] = S x S = S2
71 72
 Solved Problem Acid Dissociation Constant

Problem: The specific conductance of saturated solution of silver chloride at 18°C is 1.24 × 10–6 mhos after subtracting that of water.
The mobilities of 𝐴𝑔+ and 𝐶𝑙 − ions at this temperature are 53.8 and 65.3 respectively. Calculate the solubility of silver chloride (AgCl) in
grams per litre.

⚫ Most acidic substances are weak acids; that is acids are only partially ionised in aqueous solution.
Solution:
Here K = 1.24 × 10–6 mhos ⚫ If we represent a general weak acid as HA, we can write the equation for its ionization reaction as follows.
and 𝝀∞ = λ𝑨𝒈 + 𝝀𝑪𝒍 = 𝟓𝟑. 𝟖 + 𝟔𝟓. 𝟑 = 𝟏𝟏𝟗. 𝟏
+
𝐻𝐴(𝑎𝑔) + 𝐻2 𝑂(𝐼) ⇌ 𝐻3 𝑂(𝑎𝑔) + 𝐴−
(𝑎𝑔)
Now 𝝀∞ = 𝐊 𝐱 𝐕 𝐨𝐫 𝟏𝟏𝟗. 𝟏 = 𝟏. 𝟐𝟒 𝐱 𝟏𝟎−𝟔 𝒙 𝑽
⚫ Since 𝐻2 𝑂 is removed from equilibrium expressions in aqueous solutions,
119.1 119.1
Therefore 𝑉= 1.24 𝑥 10−6
𝑚𝐿 i.e.,
1.24 𝑥 10−6
mL contains AgCl = 1 g − eqvt = 143.5
𝐻3 𝑂+ [𝐴− ]
Equilibrium constant Expression 𝐾𝑎 =
143.5 𝑥 1.24 𝑥 10−6 [𝐻𝐴]
Therefore 1000 mL contain 𝐴𝑔𝐶𝑙 = x 1000
119.1

143.5 𝑥 1.24
= 𝑥 10−3
119.1

= 𝟏. 𝟒𝟗𝟒 𝒙 𝟏𝟎−𝟑 𝒈

73 74

Applications of Kohlrausch’s Law: 5. Calculation of Degree of Dissociation or

Conductance Ratio Solved Problem

❑ The apparent degree of dissociation, α, of an electrolyte at the dilution V is given by

λ𝑉
α= Problem: The equivalent conductance at 18° of a normal solution of KCl is 98.2 and for infinite dilution at the same temperature 131.
λ∞
Calculate the degree of dissociation of KCl at this dilution.
where 𝝀𝑽 is the equivalent conductance of the electrolyte at the dilution V and 𝝀∞ is its equivalent conductance at infinite
dilution.
❑ This is according to Kohlrausch’s Law is the sum of 𝝀𝒂 and 𝝀𝒄 . Solution:
λ𝑉
We know α=
Problem: The conductance of silver ion at 18° is 55.7 and of the nitrate ion 60.8. If the specific conductance of AgNO3 in a decinormal λ∞
solution at 18° is 0.00947 mhos, what will be the percentage of dissociation of the salt at this concentration ?
Here, 𝝀𝑽 = 𝟗𝟖. 𝟐 and 𝝀∞ = 𝟏𝟑𝟏
Solution:
Specific conductivity (κ) in N/10 solution = 0.00947 mhos λ𝑉 98.2
Volume containing 1 g equivalent = 10,000 ml Therefore, α= = = 0.75
∴ Eqvt conductance at this dilution = 0.00947 × 10,000 λ∞ 131
= 94.7 mhos
94.7 Hence the degree of dissociation of KCl in normal solution is 0.75.
Eqvt conductance at infinite dilution = 55.7 + 60.8 = 116.5 α= = 0.8128
116.5

Hence the salt is 81.28% dissociated.

75 76
 Applications of Kohlrausch’s Law: 6. Calculation of the Ionic Product for Water Electrochemical Cells: Preview
(General principles of electrochemical cells and with some of their more important applications)

❑ The observed specific conductance of the purest water at 25° C is 5.54 × 10–8 mhos. ❑ Concerning the galvanic cells, in which a chemical reaction produces an
Electrolytic Cell Galvanic Cell
❑ The conductance of one litre of water containing 1-gram eqvt of it would be : electric potential difference between two electrodes.
❑ The chemical reactions occurring at the two electrodes cause a flow Voltmeter
of electrons in the outer circuit. Battery
λ𝐻2𝑂 = 5.54 𝑥 10−8 𝑥 1000 = 5.54 𝑥 10−5 𝑚ℎ𝑜𝑠 ❑ It is impossible to measure the electromotive force (emf) of a single
electrode, and the convention is to use a standard hydrogen
At the same temperature the conductance of 𝐻 + 𝑎𝑛𝑑 𝑂𝐻 − ions 𝝀𝑯+ =349.8 mhos and 𝝀𝑶𝑯− = 𝟏𝟗𝟖. 𝟓 mhos electrode as the left-hand electrode in a cell.
❑ With another standard electrode on the righthand side, the cell emf
is then taken to be the standard electrode potential for the
According to Kohlrausch’s Law λ𝐻2𝑂 = 𝝀𝑯+ + 𝝀𝑶𝑯−
right-hand electrode.
❑ Such standard electrode potentials are useful for predicting the
= 𝟑𝟒𝟗. 𝟖 + 𝟏𝟗𝟖. 𝟓 = 𝟓𝟒𝟖. 𝟑 𝒎𝒉𝒐𝒔 direction of a chemical reaction.
❑ The thermodynamic relationship between the Gibbs energy change and
− ion the emf of a galvanic cell leads to the determination of equilibrium
One molecule of water gives one 𝐻 + ion and one 𝑂𝐻 𝐻2 𝑂 = 𝐻 + + 𝑂𝐻 − constants.

Assuming that ionic concentration is proportional to conductance, we have 𝐻 + = 𝑂𝐻 − =
The ionic product of water is then 𝐾𝑤
For most purposes, the value of 𝐾𝑤
77
5.5 𝑥 10−5
❑ An equation due to Nernst relates the cell emf to the activities of solutions in the cell.
= 1.01 𝑥 10−7 𝑔 𝑖𝑜𝑛 𝑙𝑖𝑡𝑟𝑒 −1 ❑ The Nernst potential is the potential difference established across a membrane when two different solutions are on opposite sides of it.
548.3
❑ An important type of cell is a redox cell, in which oxidation-reduction processes occur in a special way.
❑ Practical applications of emf measurements include the determination of pH, activity coefficients, equilibrium constants,
= 𝐻+ 𝑂𝐻− = 1.02 𝑥 10−14 𝑔 at 25°C
solubility products, and transport numbers.
❑ Certain electrochemical cells are useful devices for the generation of electric power.
𝑖𝑠 𝑡𝑎𝑘𝑒𝑛 𝑡𝑜 𝑏𝑒 10−14 . ❑ In a fuel cell, for example, the reacting substances are continuously fed into the system.
❑ Photogalvanic cells are electrochemical cells in which radiation induces a chemical process that gives rise to an electric current.
78

Daniell Cell Procedure Followed While Writing Cells

⚫ In an old version, zinc electrode immersed in dilute sulfuric acid and a copper 1). Daniell Cell:

⚫
electrode immersed in a cupric sulfate solution.
Cell gave a more stable voltage if the sulfuric acid was replaced by zinc sulfate
𝑍𝑛 𝑠 ⃓ 𝑍𝑛𝑆𝑂4 𝑎𝑞 ⃒⃒ 𝐶𝑢𝑆𝑂4 (𝑎𝑞) ⃓ Cu (s)
Voltmeter John Frederic Daniell (Solution) a = 0.1 (Solution) a = 0.1
⚫
solution, and present version of "Daniell cell" is shown in figure.
The voltage produced by the cell depends on the activities of the Zn2+ and
𝑒− 𝑒− (1790-1845)
Oxidation reaction @ Anode: 𝑍𝑛 → 𝑍𝑛2+ + 2𝑒 −
To describe the electrochemical cell following procedures are followed:
Cu2+ ions in the two solutions. 2+
𝐶𝑢 + 2𝑒 − → 𝐶𝑢
Zn

⚫ If the molalities of the two solutions are 1 M, the cell is called a standard Daniell cell. V Reduction reaction @ Cathode:
1). Anode should come first (left-hand side) and Cathode next (right-hand side) in which
⚫ When a Daniell cell is set up, there is a flow of electrons from the zinc to the -
copper electrode in the outer circuit. Anode
Salt Bridge/Porous + Cathode electrodes’ metal part must be place outside. Cell Reaction: 𝑍𝑛 + 𝐶𝑢2+ → 𝐶𝑢 + 𝑍𝑛2+
Partition
⚫ This means that positive current is moving from left to right in the cell itself (Oxidation) (Reduction)
⚫ By convention, a potential difference corresponding to an external flow of
2). Phases (Gas, Liquid, Solid) of the electrode substrates must be mentioned in brackets 2). Clarke Cell:
Zn
Zn KCl
Zn Cu
Zn and to be placed lower.
electrons from the left-hand electrode to the right-hand electrode is 𝑍𝑛 𝑠 ⃓ 𝑍𝑛𝑆𝑂4 𝑎𝑞 ⃒⃒ 𝐻𝑔2 𝑆𝑂4 (𝑎𝑞) ⃓ Hg (s)
said to be a positive potential difference. (Solution) a = 0.1
3). Concentrations (M) of the solutions and pressures (atm) of the gases must be (Sat. Solution)
⚫ Since positive electricity in the form of positive ions moves from left to right within
the cell, zinc metal dissolves to form Zn2+ ions, Zn metal 𝐹𝑙𝑜𝑤 𝑜𝑓 𝑍𝑛2+ 𝑖𝑜𝑛𝑠
Cu metal is mentioned. Oxidation reaction @ Anode: 𝑍𝑛 → 𝑍𝑛2+ + 2𝑒 −
plated on
dissolves 2+
𝑍𝑛 → 𝑍𝑛2+ + 2𝑒 − electrode
4). If the electrodes are connected by the salt-bridge, ⃒⃒ symbol must be written in Reduction reaction @ Cathode: 𝐻𝑔2 + 2𝑒 − → 𝐻𝑔
𝐹𝑙𝑜𝑤 𝑜𝑓 𝑆𝑂42− 𝑖𝑜𝑛𝑠 between the two electrodes.
⚫ Some of these zinc ions pass through the membrane into the right-hand
𝑍𝑛 + 𝐻𝑔22+ → 𝑍𝑛2+ + 2 Hg
1 M CuSO4
1 M ZnSO4 Cell Reaction:
solution, and at the right-hand electrode cupric ions interact with ZnSO4 CuSO4 Solution
Solution 5). While mentioning the electro motive force (emf) of the cell, temperature (° C) must be
electrons to form metallic copper:
mentioned.
𝐶𝑢2+ + 2𝑒 − → 𝐶𝑢 (𝑠) 3). 𝑃𝑡, 𝐻2 ⃓ 𝐻𝐶𝑙⃒⃒ 𝐾𝐶𝑙, 𝐻𝑔2 𝐶𝑙2 (𝑆) ⃓ Hg (s)
𝑍𝑛 𝑠 + 2𝑒 − → 𝑍𝑛2+ 𝐶𝑢2+ + 2𝑒 − → 𝐶𝑢 (𝑠) (Gas) (Solution) (Solution) (Solid)
⚫ Every time a zinc atom dissolves, and a copper atom is deposited, = 1atm a = 0.1 a = 0.1
two electrons travel round the outer circuit.
Oxidation reaction @ Anode: 𝐻2 → 2𝐻 + + 2𝑒 −
⚫ Cells of this kind can be made to behave in a reversible fashion, by balancing 𝑍𝑛 𝑠 ⃓ 𝑍𝑛𝑆𝑂4 𝑎𝑞 ⃒⃒ 𝐶𝑢𝑆𝑂4 (𝑎𝑞) ⃓ Cu (s)
their potentials by an external potential so that no current flows. Reduction reaction @ Cathode: 𝐻𝑔2 𝐶𝑙2 + 2𝑒 − → 2𝐻𝑔 + 2𝐶𝑙−

79 80 Cell Reaction: 𝐻2 + 𝐻𝑔2 𝐶𝑙2 → 2𝐻𝑔 + 2HCl

 Reversible and Irreversible Cells Measurement of EMF of a Cell

Let's consider that an Electrochemical Cell (Daniell Cell) is connected to external Electro Motive Force (EMF): “The difference of potential which causes flow Poggendorff’s "compensation" method: An unknown voltage is balanced
power supply (battery) now; of current from one electrode of higher potential to the other electrode of lower against a voltage drop obtained from constant current passing through
Potential”. an adjustable resistance dividing network.
Voltmeter ❑ The magnitude of the emf developed is a measure of the relative tendencies of the two
1). emf of the battery = emf of Daniell cell, NO REACTION in the Cell. No Electron Flow.
𝑒− 𝑒− processes. W
❑ (Or) Potential difference between the two electrodes in an electrochemical cell.
2). emf of the battery < emf of Daniell cell, REACTION in Cell. Outward Electron Flow.
Zn
V ❑ Thus, the emf of a galvanic cell can be calculated using the following relationship. - + Rheostat (R)
0 0 0
𝑍𝑛 + 𝐶𝑢2+ → 𝑍𝑛2+ + 𝐶𝑢 𝑒− - Salt Bridge/Porous + Cathode 𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑟𝑖𝑔ℎ𝑡 − 𝐸𝑙𝑒𝑓𝑡 F
Anode Partition
(Oxidation) (Reduction) ❑ A current is passed through a uniform slide wire AB, along which there is a linear Potentiometer Cell/ Working
potential drop (W), the magnitude of which can be adjusted by a rheostat (R). Battery
Zn
Zn KCl
Zn Cu
Zn Current
3). emf of the battery > emf of Daniell cell, OPPOSITE REACTION in Cell. ❑ The cell under investigation (X) is connected in order to oppose the emf of (W) through
Slide wire (S) S CS’
a tap-key switch and a galvanometer (G) to one end (A) of the slide wire and to a movable
Inward Electron Flow.
contact C.
A B
Cu metal is Sliding Contact (C)
Zn metal 𝐹𝑙𝑜𝑤 𝑜𝑓 𝑍𝑛2+ 𝑖𝑜𝑛𝑠
❑ The contact is moved along the slide wire until, when the switch is depressed, no current
𝐶𝑢 + 𝑍𝑛2+ → 𝐶𝑢2+ + 𝑍𝑛 𝑒− dissolves
plated on
electrode
passes through the galvanometer. (S: Equalizer point): length “AS” is noted = Ex. Cell under
❑ The potential difference produced by the cell is then exactly balanced by the potential Investigation (X)
𝐹𝑙𝑜𝑤 𝑜𝑓 𝑆𝑂42− 𝑖𝑜𝑛𝑠 difference between points A and C. S
1 M CuSO4 (Or) Standard Cell
1 M ZnSO4 ❑ The potentiometer wire can be calibrated by use of a standard cell, such as the Weston
If a cell obeys the above three conditions: Reversible Cells ZnSO4 CuSO4 Solution G
Solution cell. (S: Equalizer point): length “AS is noted = Es.
❑ When the electric potential of a cell is exactly balanced in this way, the cell is operating Galvanometer (G)
If not, Irreversible Cells.
reversibly, and its potential is then referred to as the emf of the cell.
𝑍𝑛 𝑠 + 2𝑒 − → 𝑍𝑛2+ 𝐶𝑢2+ + 2𝑒 − → 𝐶𝑢 (𝑠)
Daniell Cell obeys the all three condition hence, it is a reversible cell. Its overall 𝐸𝑥 𝑃𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 𝑑𝑟𝑜𝑝 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 𝐴 𝑎𝑛𝑑 𝑆 𝐴𝑆−𝑅𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝐴𝑆−𝐿𝑒𝑛𝑔𝑡ℎ
cell reaction can be written as follows; = = =
𝐸𝑠 𝑃𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 𝑑𝑟𝑜𝑝 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 𝐴 𝑎𝑛𝑑 𝑆′ 𝐴𝑆 ′ −𝑅𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝐴𝑆 ′ −𝐿𝑒𝑛𝑔𝑡ℎ Tap-key Rheostat (R)
𝑍𝑛 𝑠 ⃓ 𝑍𝑛𝑆𝑂4 𝑎𝑞 ⃒⃒ 𝐶𝑢𝑆𝑂4 (𝑎𝑞) ⃓ Cu (s)
𝐴𝑆−𝐿𝑒𝑛𝑔𝑡ℎ switch (K)
𝑍𝑛 + 𝐶𝑢2+ ⇄ 𝑍𝑛2+ + 𝐶𝑢 Therefore, 𝐸𝑥 = 𝑥 𝐸𝑠
𝐴𝑆 ′ −𝐿𝑒𝑛𝑔𝑡ℎ Figure: A potentiometer circuit used for determining the
81 82 reversible emf of a cell.
𝐸𝑠 (𝑒𝑚𝑓 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑐𝑒𝑙𝑙 𝑖𝑠 𝑘𝑛𝑜𝑤𝑛)

Standard Cell Single Electrode Potentials

⚫ The Weston standard cell is a wet-chemical cell that produces a highly stable voltage “When a metal (Ag) is placed in its salt solution (AgNO3), following two opposite reactions
irrespective of temperature as well as suitable as a laboratory standard for calibration Weston Cell is having the structure of letter “H” do occur in a electrochemical cell.
of voltmeters.
Reaction 1 (Oxidation): Due to the affinity of the metal of being solution, metal atoms are oxidized ions Metal Solution
⚫ Invented by Edward Weston in 1893, it was adopted as the International Standard for Saturated and dissolves in salt solution (electrolyte) thereby leaving the electrons in the
EMF from 1911 until superseded by the Josephson voltage standard in 1990. Solution of metal (electrode).
CdSO4 Reaction 2 (Reduction): Simultaneously, ions from the salt solution deposits over the metal due to the
Weston Standard Cell Reaction can be written as follows; diffusion process.
8 Metal become –Ve charged when Reaction 1 is dominant: due to the static electric attractive force
𝐶𝑑(𝐻𝑔)𝑥 ⃓ 𝐶𝑑𝑆𝑂4 . 𝐻2 𝑜 𝑠 ⃒⃒ 𝐶𝑑𝑆𝑂4 (𝑆𝑎𝑡𝑢𝑟𝑎𝑡𝑒𝑑)⃓ 𝐻𝑔2 𝑆𝑂4 , Hg the +Ve ions surrounds the metal. This process leads to the development of “Electrical Double layer”
3

Oxidation reaction @ Anode: Reduction reaction @ Cathode: ❑ Metal become +Ve charged when Reaction 2 is dominant: due to the static electric attractive force
the now -Ve ions surrounds the metal. This process leads to the development of another/parallel
𝐶𝑑 → 𝐶𝑑2+ + 2𝑒 − “Electrical Double Layer”
= Solvent Molecule
−
𝐻𝑔2 𝑆𝑂4 (𝑠) + 2𝑒 → 2𝐻𝑔 + 𝑆𝑂42− ❑ Potential difference between these two “Electrical Double Layers” is referred as ‘Electrode Potential’
= Adsorbed Anion
𝐶𝑑2+ + 𝑆𝑂42− → 𝐶𝑑𝑆𝑂4 (𝑠) CdSO4
= Solvated Cation
CdSO4
Crystals ❑ When electrode is preferred to oxidize, its electrode potential is referred as Oxidation Potential.
𝐶𝑑 + 𝑆𝑂42− → 𝐶𝑑𝑆𝑂4 (𝑠)+ 2𝑒 − Crystals Paste of
❑ When electrode is preferred to reduce, its electrode potential is referred as Reduction Potential. IHP OHP Diffuse
Hg + Region
❑ Both oxidation and reduction processes are happening at opposite direction to each other in a
Hg2SO4
single reaction. Ex:
Cell Reaction: 𝐶𝑑 + 𝐻𝑔2 𝑆𝑂4 (𝑠) ⇄ 𝐶𝑑𝑆𝑂4 (𝑠) + 2Hg
𝑂𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 ∶ 𝐴𝑔 → 𝐴𝑔+ + 𝑒 − 𝑅𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛: 𝐴𝑔+ + 𝑒 − → 𝐴𝑔
Hg 12.5 % Electrical double layer. Depiction of the electrical double
Hg-Cd layer that builds up at the electrode solution interface
Amalgam ❑ Hence, both oxidation and reduction reaction will be having equal electrode potential values with when a metal is placed in solution.
⚫ At 298 K, EMF of the Weston Standard cell is 1.01845 Volt.
opposite signs. i.e.,
𝑑𝐸
+ P1wire
Pt1- - Pt2P-wire
1 Reduction Electrode Potential = - Oxidation Electrode Potential In the solution there are three distinct layers:
⚫ Its Temperature co-efficient, = 0.00004 𝑣𝑜𝑙𝑡. 𝑑𝑒𝑔𝑟𝑒𝑒 −1 1. Inner Helmholtz Plane (IHP),
𝑑𝑇 (Or) Oxidation Electrode Potential = - Reduction Electrode Potential 2. Outer Helmholtz Plane (OHP), and
Figure: The Weston standard cell, which is the most 3. Diffuse layer.
83 84 For example: Zn⃓ Zn2+ Reduction Potential = -0.76 V and Oxidation Potential = 0.76 V
widely used standard cell.
 Measurement of Electrode Potential Reference Electrode/Standard Hydrogen Electrode

❑ There are two electrodes in an electrochemical cell, Cathode and Anode. ❑ In order to determine the electric potential of the electrode, we need a Reference electrode.
❑ EMF of the cell is sum of electrode potentials of the two electrodes with their signs. ❑ In this regard, Standard Hydrogen Electrode (SHE) is widely used to serve this purpose. Cu Wire
❑ Where 1 M concentration of 𝐻 + 𝑖𝑜𝑛𝑠 (1 𝑀 𝐻𝐶𝑙) is taken as electrolyte in which Platinum coated Platinum
Therefore, EMF of a Cell: electrode is placed as shown in the figure.
❑ With this cell setup high pure 𝐻2 gas is purged continuously. (𝐻2 gas do adsorb over Platinum electrode and
= Anode’s Oxidation Potential + Cathode’s Reduction Potential EMF of a Cell: reaction precedes)
❑ Cell: 𝑃𝑡, 𝐻 ⃓ HCl 2
= Anode’s Oxidation Potential - Cathode’s Oxidation Potential = Calomel electrode’s Oxidation Potential + +
Cu electrode’s Reduction Potential (gas) a = 1 atm (Solution) 𝑎𝐻 =1M
= Cathode’s Reduction Potential – Anode’s Reduction Potential ❑ Electrode potential of the SHE at all temperature is fixed as “ZERO”. i.e., 𝑬𝟎𝑯𝟐 =0
Therefore,
❑ EMF is measured by connecting the two electrodes in a cell. If one electrode’s reduction
Cu electrode’s Reduction Potential: ❑ Note: Apart from SHE, other electrodes potentials are “never taken as ZERO”
or oxidation potential is known means another electrode’s reduction or oxidation
potential can be measured. 1
= EMF - Calomel electrode’s Oxidation Potential Electrode reaction: 𝐻2 ⇄ 𝐻 + + 𝑒 − H2 Cu
2 C

⚫ Example: Measuring Cu electrode’s potential immersed in CuSO4 solution.

u

+ + H2
= 0.0955 – (-0.2415) 2.303 𝑅𝑇 𝑎𝐻 2.303 𝑅𝑇 𝑎𝐻
Corresponding Nernst Equation, 𝐸𝐻2 = 𝐸𝐻02 − log 1 =− log 1 (a = conc. & p = pressure) at 1 atm Cu Pt
By connecting with calomel reference electrode, following cell reaction can be written; = 0.0955 + 0.2415 𝐹 2
𝐹 2
𝑝𝐻 𝑝𝐻 pressure electrode
= 0.3370 V 2 2
+
At SHE, 𝑝𝐻2 = 1 (1 atm); 𝑎𝐻 = 1 (1 M). Hence, 𝐸𝐻2 = 0 (log 1 = 0)
𝐻𝑔⃓ 𝐻𝑔2 𝐶𝑙2 𝑠 , 𝐾𝐶𝑙 𝑆𝑎𝑡. ⃒⃒ 𝐶𝑢𝑆𝑂4 (𝑆𝑜𝑙)⃓ Cu Hence, Cu electrode’s Reduction Potential : - 0.3370 V +
For other electrodes, 𝑝𝐻2 ≠ 1 ; 𝑎𝐻 ≠ 1 . Hence, 𝐸𝐻2 ≠ 0 H2 gas Diaphragm
EMF of the cell is 0.0955 V.
Oxidation Potential of Calomel Electrode is -0.2415 V ❑ SHE is connected with another electrode to construct the electrochemical cell and EMF is measured.
❑ EMF is nothing but, sum of two electrode potentials. 1 M HCl
❑ 𝐸𝐻2 = 0, hence unknown electrode’s potential, 𝐸𝑥 can be measured. Solution

85 86 𝐸 = 𝐸𝑥 + 𝐸𝐻02 (𝐸𝐻02 = 0) therefore, 𝐸 = 𝐸𝑥

Secondary Reference Electrodes: Calomel Electrode Secondary Reference Electrodes: Silver-Silver Chloride Electrode

❑ Fabrication and handling SHE is such a difficult job since, it involves the use of H2 gas.
❑ Hence, secondary reference electrodes comes into picture. ❑ Ag-AgCl Cell Configuration:
❑ In this regard, Calomel Electrode and Ag-AgCl electrodes are widely in use.
Glass vessel
A𝑔⃓ 𝐴𝑔𝐶𝑙 𝑠 , KCl (Sol)
Ag
❑ Calomel Electrode: Bent side Electrode Reaction:
Pt wire Ag
Ag

tube AgCl
+ −
Ag
❑ As shown in the picture, special glass apparatus is used for its fabrication. KCl solution A𝑔 → 𝐴𝑔 + 𝑒
❑ Pure Hg is taken at the bottom, over that Hg2Cl2 (Calomel) + Hg paste is placed.
❑ Filled with KCl solution and Platinum wire is used as connecting probe. 𝐴𝑔+ + 𝐶𝑙− → 𝐴𝑔𝐶𝑙 (𝑠)
Glass wool Hg + Hg2Cl2 paste
❑ Cell: 𝐻𝑔⃓ 𝐻𝑔2 𝐶𝑙2 𝑠 , KCl (Sol) plug Hg 𝐴𝑔 + 𝐶𝑙− → 𝐴𝑔𝐶𝑙 (𝑠) + 𝑒 − 3.5 M KCl
Solution

Electrode Reaction:
0
Oxidation Potential: Nernst Equation, 𝐸𝐶𝑎𝑙𝑜𝑚𝑒𝑙 = 𝐸𝐶𝑎𝑙𝑜𝑚𝑒𝑙 −
2.303 𝑅𝑇
log
𝑎𝐻𝑔2 𝐶𝑙2
0 2.303 𝑅𝑇 𝑎𝐴𝑔𝐶𝑙
2𝐹 − )2
(𝑎𝐻𝑔 )2 (𝑎𝐶𝑙 2𝐻𝑔 ⇄ 𝐻𝑔22+ + 2𝑒 − Oxidation Potential: Nernst Equation, 𝐸𝐴𝑔,𝐴𝑔𝐶𝑙 = 𝐸𝐴𝑔,𝐴𝑔𝐶𝑙 − log
𝐹 𝑎𝐴𝑔 .𝑎𝐶𝑙−
0 2.303 𝑅𝑇 1 𝐻𝑔22+ + 2𝐶𝑙− ⇄ 𝐻𝑔2 𝐶𝑙2 (𝑠)
𝑎𝐻𝑔2𝐶𝑙2 = 1 and 𝑎𝐻𝑔 = 1. Therefore, 𝐸𝐶𝑎𝑙𝑜𝑚𝑒𝑙 = 𝐸𝐶𝑎𝑙𝑜𝑚𝑒𝑙 − log 0 2.303 𝑅𝑇 1
2𝐹 − )2
1 (𝑎𝐶𝑙
2𝐻𝑔 + 2𝐶𝑙− ⇄ 𝐻𝑔2 𝐶𝑙2 (𝑠)+ 2𝑒 − 𝑎𝐴𝑔𝐶𝑙 = 1 and 𝑎𝐴𝑔 = 1. Therefore, 𝐸𝐴𝑔,𝐴𝑔𝐶𝑙 = 𝐸𝐴𝑔,𝐴𝑔𝐶𝑙 −
𝐹
log 1 .𝑎 −
𝐶𝑙
0 2.303 𝑅𝑇 −
𝐸𝐶𝑎𝑙𝑜𝑚𝑒𝑙 = 𝐸𝐶𝑎𝑙𝑜𝑚𝑒𝑙 + log 𝑎𝐶𝑙
𝐹
0.1 N KCl - 0.3338 V ❑ Hence, Ag, AgCl electrode potential is dependent of 𝑎𝐶𝑙 − .
−
❑ Hence, Calomel electrode potential is dependent of 𝑎𝐶𝑙 . ❑ By connecting with SHE, 𝐸𝐴𝑔,𝐴𝑔𝐶𝑙 can be measured.
❑ By connecting with SHE, 𝐸𝐶𝑎𝑙𝑜𝑚𝑒𝑙 can be measured.
1.0 N KCl - 0.2800 V ❑ After knowing the 𝐸𝐴𝑔,𝐴𝑔𝐶𝑙 , other electrodes potential can be determined.
❑ Different KCl solution is used.
❑ After knowing the 𝐸𝐶𝑎𝑙𝑜𝑚𝑒𝑙 , other electrodes potential can be determined.
Sat. KCl - 0.2415 V
87 88
 Van’t Hoff Equation (From CHB 201) Van’t Hoff Reaction Isotherm (From CHB 201)

KP = 𝑒 −Δ𝐺°/𝑅𝑇 𝑜𝑟 ΔG° = - RT ln KP 𝑜𝑟 ΔG° = - RT ln KP + RT ln QP ⚫ The Van't Hoff isotherm equation is used for estimating the equilibrium shift during a chemical reaction.
⚫ We can also derive the Van't Hoff isotherm equation using the Gibbs-Helmholtz equation which gives a relation between the change in
free energy with respect to the changing temperature.
This equation is known as the van’t Hoff reaction isotherm. And it is very important one which permits the calculation of ΔG° of the reaction
from the known value of the equilibrium constant Kp and vice-versa. QP is the pressure ratio.
KP = 𝑒 −Δ𝐺°/𝑅𝑇 𝑜𝑟 ΔG° = - RT ln KP 𝑜𝑟 ΔG° = - RT ln KP + RT ln QP
Deriving The vant’ Hoff Equation: Significance of The vant’ Hoff Equation:
➢ When QP < Kp, ΔG < 0, Reaction proceeds towards the positive way.
⚫ If you run the same reaction at different temperature, T1 and T2: ➢ If ΔH = 0, no heat is evolved or absorbed in the reaction, ➢ When QP = Kp, ΔG = 0, Reaction is in the equilibrium state.
𝑲𝟐 𝑲𝟐
➢ When QP > Kp, ΔG > 0, Reaction proceeds towards the opposite way.
Δ𝐻° Δ𝑆° Δ𝐻° Δ𝑆° ln = 0, i.e. = 1 or K1 = K2
𝑲𝟏 𝑲𝟏
ln K1 = – + ; ln K2 = – + i.e., the equilibrium constant does not change with temperature.
𝑅𝑇1 𝑅 𝑅𝑇2 𝑅
➢ If ΔH = +Ve, endothermic reaction,
-then subtraction yields:
Δ𝐻° 1 1 𝑲𝟐
ln K2 – ln K1 = ( – ) ln
𝑲𝟏
= +Ve, or K2 > K1
𝑅 𝑇1 𝑇2
i.e., the equilibrium constant increases with the increase in
-Which equals: temperature.
𝑲𝟐 𝜟𝑯° 𝟏 𝟏
ln = ( – ) van’t Hoff equation ➢ If ΔH = -Ve, exothermic reaction,
𝑲𝟏 𝑹 𝑻𝟏 𝑻𝟐
𝑲𝟐
ln = -Ve, or K2 < K1
So, if you know the equilibrium constant at any temperature, and the 𝑲𝟏
standard enthalpy of reaction, you can determine the what K would be at any i.e., the equilibrium constant decreases with the increase in
89 90
other temperature. temperature.

Nernst Equation for EMF of Cells Solved Problem

⚫ In electrochemistry, the Nernst equation is an equation that relates the reduction potential of a reaction (half-cell or full cell reaction)
to the standard electrode potential, temperature, and activities (often approximated by concentrations) of the chemical species 𝑍𝑛 𝑠 ⃓ 𝑍𝑛𝑆𝑂4 𝑎𝑞 ⃒⃒ 𝐴𝑔𝑁𝑂3 (𝑎𝑞) ⃓ Ag (s)
undergoing reduction and oxidation.
⚫ It was named after Walther Nernst, a German physical chemist who formulated the equation. (Mentor: Kohlrausch; Student: Langmuir)
Walther Hermann Nernst
(1864-1941)
𝑎𝑍𝑛2+ = 0.1 𝑎𝐴𝑔+ = 10
⚫ During the reaction in an electrochemical cell, decrement in the free energy
Lets consider following cell reaction precedes at Volta Cell:
change (– ΔG ) is equivalent to the electrical energy (nFE) obtained from the
Problem: Standard EMF (E°) of the above cell is 1.56 V hence, calculate Oxidation reaction @ Anode: 𝑍𝑛 → 𝑍𝑛2+ + 2𝑒 −
cell.
𝐴 + 𝐵 ⇄ 𝐶 + 𝐷 ……(1) – ΔG = nFE … . … (6) the EMF of the cell at 298 K? Reduction reaction @ Cathode: 2𝐴𝑔 + 2𝑒 − → 2𝐴𝑔
+
⚫ From the Vant Hoff Isotherm, free energy change during the reaction, ΔG (Or) ΔG = – nFE … . … (7)
can be obtained. Cell Reaction: 𝑍𝑛 + 2𝐴𝑔+ → 𝑍𝑛2+ + 2𝐴𝑔
Here, “E” is the EMF of the cell, “n” is the no. of electrons transferred. “F” is Solution:
𝑎 𝑎
– ΔG = RT ln K – RTln 𝐶 𝐷 … . … (2) Faraday constant (96 485.332 12... C mol-1)
𝑎𝐴 𝑎𝐵 Besides, ΔG° = – nFE° … . … (8) 0.0591
2
𝑎 2+ 𝑎𝐴𝑔
Here, “K” is the equilibrium constant
At 298 K, Nernst equation, E = E° + log 𝑍𝑛 2
2 𝑎𝑍𝑛 𝑎𝐴𝑔+
- 𝑎𝐴 , 𝑎𝐵 , 𝑎𝐶 𝑎𝑛𝑑 𝑎𝐷 𝑎𝑟𝑒 𝑡ℎ𝑒 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛𝑠 𝑜𝑓 𝐴, 𝐵, 𝐶 𝑎𝑛𝑑 𝐷 𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚. Here, “E°” is the standard EMF of the cell, substituting eqn (7) and (8) in eqn (5);
𝑎 𝑎
- Lets assume that at the equilibrium each species concentration is – nFE = – nFE° +RTln 𝐶 𝐷 … . … (9) Here E° = 1.56 V, n= 2, 𝑎𝐴𝑔 = 𝑎𝑍𝑛 = 1 and 𝑎𝐴𝑔+ = 10 , 𝑎𝑍𝑛2+ = 0.1
one (a = 1) 𝑎 𝐴 𝑎𝐵
Dividing eqn (9) by – nF,
– ΔG° = RT ln K … . … (3) 𝑅𝑇 𝑎𝐶 𝑎𝐷 Therefore E = 1.64865 V
Here, “ΔG°” is the standard free energy change
E = E° + ln … . … 10 ∶ 𝑁𝑒𝑟𝑛𝑠𝑡 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛
𝑛𝐹 𝑎𝐴 𝑎𝐵
Substituting eqn (3) in eqn (2) we get, Note: 2.303 𝑅𝑇 2.303 𝑥 8.314 𝑥 298
𝑎𝐶 𝑎𝐷 At 298 K, = = 0.0591
– ΔG = – ΔG° – RTln … . … (4) 𝐹 96500
𝑎𝐴 𝑎𝐵 0.0591 𝑎𝐶 𝑎𝐷
E = E° + ln … . … 11
𝑎𝐶 𝑎𝐷 𝑛 𝑎𝐴 𝑎𝐵
91 (Or) ΔG = ΔG° +RTln … . … (5) Hence, by knowing the E° and species concentration, EMF of the cell at 92
𝑎𝐴 𝑎𝐵 particular temperature can be calculated
 Nernst Equation for Electrode Potential Standard Electrode Potentials (E°)

⚫ In a reversible electrochemical cell, two electrodes also having reversible behavior.

⚫ Hence, Nernst equation for measuring the EMF can be used to measure the single electrode potential.
⚫ Irrespective of the type of the electrode, electrode reaction can be written as follows;

Reduction State ⇄ Oxidation State + 𝑛𝑒 − ⚫ At 298 K, if activities of the each species of a electrode is (a = 1) means its potential is referred as standard electrode potential (E°).

⚫ When there is oxidation reaction at the electrode, it is called as standard oxidation potential.
2.303 𝑅𝑇 𝑎𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 𝑠𝑡𝑎𝑡𝑒
Therefore, E = E° – = 𝑙𝑜𝑔 ⚫ When there is reduction reaction at the electrode, it is called as standard reduction potential.
𝑛𝐹 𝑎𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝑠𝑡𝑎𝑡𝑒
Example 1: 𝑍𝑛⃓ 𝑍𝑛+
⚫ An electrode can be connected with a reference electrode through which EMF of the cell can be measured.
Here, E = oxidation potential of the electrode
and E° = standard oxidation potential of the electrode. 𝑍𝑛 → 𝑍𝑛2+ + 2𝑒 − here, n = 2 ⚫ From the measured EMF, E, oxidation potential of the electrode can be calculated (Nernst equation).

0 2.303 𝑅𝑇
𝐸𝑍𝑛, 𝑍𝑛+ = 𝐸𝑍𝑛, 𝑍𝑛 + − 𝑙𝑜𝑔𝑎𝑍𝑛+ 2.303 𝑅𝑇 𝑎𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 𝑠𝑡𝑎𝑡𝑒
Example 1: 𝐴𝑔⃓ 𝐴𝑔+ 2𝐹 Therefore, E = E° – = 𝑙𝑜𝑔
𝑛𝐹 𝑎𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝑠𝑡𝑎𝑡𝑒
+ −
A𝑔 → 𝐴𝑔 + 𝑒 here, n = 1

2.303 𝑅𝑇 𝑎𝐴𝑔+ ⚫ Therefore, by knowing the concentration of the electrode’s species, standard electrode potential of the particular electrode can be calculated.
0
Electrode Reaction: 𝐸𝐴𝑔,𝐴𝑔+ = 𝐸𝐴𝑔, 𝐴𝑔+ − log
𝐹 𝑎𝐴𝑔
0 2.303 𝑅𝑇
= 𝐸𝐴𝑔, 𝐴𝑔 + − 𝑙𝑜𝑔𝑎𝐴𝑔+
𝐹
Because 𝑎𝐴𝑔 = 1

93 94

Sign of Electrode Potentials Electrochemical Series

As pe the IUPAC standard protocol, assigning sign of the electrode potential is followed as follows; ⚫ Potential of the Standard Hydrogen Electrode (SHE) is ZERO.

⚫ Potential of the Standard Hydrogen Electrode is ZERO. ⚫ In comparison with the SHE, other electrodes’ standard reduction or standard oxidation potentials are determined.

⚫ To measure the EMF, electrochemical cell to be constructed by connecting Standard Hydrogen Electrode and TARGET ELECTRODE. ⚫ By arranging these standard electrode potentials in the descending order, ELECTROCHEMICAL SERIES can be obtained.

⚫ During the above process, if there is reduction at the TARGET ELECTRODE, its electrode potential must carry +Ve (+) sign. At 298 K, electrode potentials of the few electrodes are summarized below:

⚫ On contrary, if there is a oxidation reaction, then TARGET ELECTRODE caries –Ve (-) sign.
S. No Electrode Electrode Reaction Electrode
Potential (V)
Example 1: Example 2:
1 𝐾⃓ 𝐾 + 𝐾 ⇄ 𝐾 ++ 𝑒 − 2.925
𝑍𝑛 𝑠 ⃓ 𝑍𝑛𝑆𝑂4 𝑎𝑞 ⃒⃒ 𝐻𝐶𝑙 ⃓ 𝐻2 , Pt
𝑃𝑡, 𝐻2 ⃓ 𝐻𝐶𝑙⃒⃒ 𝐶𝑢𝑆𝑂4 ⃓ Cu 2 𝑁𝑎⃓ 𝑁𝑎 +
𝑁𝑎 ⇄ 𝑁𝑎++ 𝑒 − 2.714
(Gas) (Solution) (Solution) (Solution) (Gas)
= 1atm a = 1 a = 1 atm
a=1 3 𝑀𝑔⃓ 𝑀𝑔2+ 𝑀𝑔 ⇄ 𝑀𝑔2+ + 2𝑒 − 2.340

4 𝑍𝑛⃓ 𝑍𝑛2+ 𝑍𝑛 ⇄ 𝑍𝑛2+ + 2𝑒 − 0.761

In this electrochemical cell, Cu electrode’s reduction potential = + 0.34 V In this electrochemical cell, Zn electrode’s oxidation potential = - 0.76 V
5 𝐹𝑒⃓ 𝐹𝑒 2+ 𝐹𝑒 ⇄ 𝐹𝑒 2++ 2𝑒 − 0.441
2+ 2+ −
6 𝐶𝑑⃓ 𝐶𝑑 𝐶𝑑 ⇄ 𝐶𝑑 + 2𝑒 0.402

7 𝐶𝑜⃓ 𝐶𝑜 2+ Co ⇄ 𝐶𝑜 2+ + 2𝑒 − 0.280

95 96
 Significance of Electrochemical Series Significance of Electrochemical Series (Cont.)

Electrochemical series is helpful in obtaining the following conclusions; 2. A metal will react with diluted acid or not?
With help of electrochemical series, it can be identified that whether a Example 2 Ag Vs. H2SO4?:
reaction between a metal and diluted acid do liberate the Hydrogen gas or not.
1. Construction of the Electrochemical Cell 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛: 2 𝐴𝑔 + 𝐻2 𝑆𝑂4 → 𝐴𝑔2 𝑆𝑂4 +𝐻2
Example 1 Zn Vs. H2SO4?:
Standard EMF of a Cell = Anode’s standard Oxidation Potential + Cathode’s standard Reduction Potential Or 2𝐴𝑔 + 2𝐻 + → 2𝐴𝑔+ +𝐻2
𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛: 𝑍𝑛 + 𝐻2 𝑆𝑂4 → 𝑍𝑛𝑆𝑂4 +𝐻2
⚫ Hence, E° of the two electrode cell can be measured.
Or 𝑍𝑛 + 𝐻 + → 𝑍𝑛2+ +𝐻2 Besides, reaction expanded as follows;
⚫ When E° = +Ve = free energy change ΔG° = -Ve because, – ΔG° = nFE° . So reaction is spontaneous, system can act as a electrochemical cell.
Besides, reaction expanded as follows; Oxidation reaction @ Anode: 2𝐴𝑔 → 2𝐴𝑔+ +2𝑒 −
⚫ When E° = -Ve = free energy change ΔG° = +Ve . NO REACTION takes place, system can not act as a electrochemical cell.
Reduction reaction @ Cathode: 2𝐻 + 2𝑒 − → 𝐻2
+
⚫ At this situation, Anode should be connected as cathode and vice versa, now the new system will work as electrochemical cell because, E° = +Ve. Oxidation reaction @ Anode: 𝑍𝑛 → 𝑍𝑛2+ + 𝐻2
Example: Reduction reaction @ Cathode: 2𝐻 + + 2𝑒 − → 𝐻2
Cell Configuration: 𝐴𝑔 ⃓ 𝐴𝑔+ ⃒⃒ 𝐻+ ⃓ 𝐻2 , 𝑃𝑡
(Gas)
1 𝑍𝑛 ⃓ 𝑍𝑛2+ ⃒⃒ 𝐶𝑢2+ ⃓ Cu Cell Reaction can be easily derived after knowing the configuration of the cell
Cell Configuration: 𝑍𝑛 ⃓ 𝑍𝑛2+ ⃒⃒ 𝐻 + ⃓ 𝐻2 , 𝑃𝑡
(Gas)
0 0
0
Here, 𝐸 0 = 𝐸𝑍𝑛,𝑍𝑛 0
2+ 𝐸𝐶𝑢2+ ,𝐶𝑢 = 0.76 + 0.34 = 1.10 V
For example:
𝑍𝑛 ⃓ 𝑍𝑛2+ ⃒⃒ 𝐶𝑢2+ ⃓ Cu Here, 𝐸 0 = 𝐸𝐴𝑔, 𝐴𝑔+ 𝐸𝐻 + , 𝐻2 = -0.80 + 0 = -0.80 V
2+ −
Oxidation reaction @ Anode: 𝑍𝑛 → 𝑍𝑛 + 2𝑒
0 0
Here, 𝐸 0 = 𝐸𝑍𝑛, 𝑍𝑛2+ 𝐸𝐻 + , 𝐻2 = 0.76 + 0 = +0.76 V
2 𝐶𝑢 ⃓ 𝐶𝑢2+ ⃒⃒ 𝑍𝑛2+ ⃓ Zn Reduction reaction @ Cathode: 𝐶𝑢2+ + 2𝑒 − → 𝐶𝑢 E° = -Ve, Ag metal do not react with diluted sulphuric acid and do not
liberate Hydrogen gas.
Cell Reaction: 𝑍𝑛 + 𝐶𝑢2+ → 𝑍𝑛2+ + 𝐶𝑢 E° = +Ve, Zn metal do react with diluted sulphuric acid and liberate
0 0
Here, 𝐸 0 = 𝐸𝐶𝑢, 𝐶𝑢2+ 𝐸𝑍𝑛2+ , 𝑍𝑛 = -0.34 + (-0.76) = -1.10 V
Hydrogen gas.

97 Hence, system (2) do not act as an electrochemical cell. 98

Applications of EMF Measurements: Calculation of

Solved Problem
Thermodynamic Quantities
⚫ During the reaction in an electrochemical cell, decrement in the free energy ⚫ From the Vant Hoff Isotherm, std. free energy change during the reaction,
Problem: At 25 °C, EMF (E) of the following cell is 0.6753 V and at 0 °C it is 0.6915 V. Hence, calculate the electrochemical cell’s free energy
change (– ΔG ) is equivalent to the electrical energy (nFE) obtained from the ΔG° can be, change (ΔG), enthalpy change (ΔH), entropy change (ΔS).
cell.
– ΔG = nFE … . … (1)
ΔG° = – RT ln K – nFE° = – RT ln K RT ln K = nFE° Oxidation reaction @ Anode: 𝐶𝑑 → 𝐶𝑑2+ + 2𝑒 −
(Or) ΔG = – nFE … . … (2)
𝐶𝑑 (𝑠)⃓ 𝐶𝑑𝐶𝑙2 𝑎𝑞 ⃒⃒ 𝐴𝑔𝐶𝑙 (𝑎𝑞) ⃓ Ag (s) Reduction reaction @ Cathode: 2𝐴𝑔 + 2𝑒 − → 2𝐴𝑔
+
Here, “E” is the EMF of the cell, “n” is the no. of electrons transferred. “F” is nFE°
Faraday constant. ln K = ….. (10) Cell Reaction: 𝐶𝑑 + 2𝐴𝑔+ → 𝐶𝑑2+ + 2𝐴𝑔
Besides, ΔG° = – nFE° … . … (3) “E°” is the standard EMF of the cell. 𝑅𝑇
Solution 1: free energy change (ΔG) Solution 2: enthalpy change (ΔH) Solution 3: entropy change (ΔS)
As per the Gibbs-Helmholtz equation,
Significance:
ΔG = – nFE 𝐽𝑜𝑢𝑙𝑒𝑠 – ΔH 𝜕𝐸 𝜕𝐸
ΔG = ΔH +T
𝜕Δ𝐺
… . … (4) E= +T ΔS = nF
𝑛𝐹 𝜕𝑇 𝑃 𝜕𝑇 𝑃
𝜕𝑇 𝑃 1). Measurement of E
Substituting eqn (2) in eqn (4), Here, E = 0.6753 V, n = 2, F = 96500 coulomb 𝜕𝐸 ΔE 0.6915−0.6753
= –2 x 96500 x 0.00065
ΔT = –
𝜕𝑬 2). Subject to knowing the standard EMF, E° =
– nFE = ΔH – nFT … . … (5) 𝜕𝑇 𝑃 25
𝜕𝑇 𝑃 ΔG = – 2 x 96500 x 0.6753 𝐽𝑜𝑢𝑙𝑒𝑠
Dividing eqn (5) by – nF, 𝜕𝐸 = –0.00065 V degree –1 = –125. 5 J degree –1
3). Temperature co-efficient, measurement.
𝜕𝑇 𝑃 Therefore,
– ΔH 𝜕𝑬 = – 130.33 kJ
E=
𝑛𝐹
+T 𝜕𝑇 𝑃
… . … (6) – ΔH
4). If no. of electrons (n) transferred in a cell reaction is known, 0.06753 = + 298 (–0.00065 )
following thermodynamic quantities can be measured; 2 𝑥 96500
Besides, ΔG = ΔH–T ΔS … . … (7)
Comparing eqn (4) and eqn (7), ΔG, ΔG°, ΔS, ΔH and K. ΔH = – 167.772 kJ
𝜕Δ𝐺 𝜕(– nFE) 𝜕𝐸
ΔS = – … (8) =– ΔS = nF … (9)
99 𝜕𝑇 𝑃 𝜕𝑇 𝑃 𝜕𝑇 𝑃 100
 Applications of EMF Measurements: Determination of pH of a
Solved Problem
Solution
Problem: At 25 °C, calculate standard free energy change (E°) and equilibrium constant (K) of the following reaction at equilibrium?
“pH is the measurement of hydrogen ion concentration in a given solution”
1 1 1
𝐶𝑢 𝑠 + 𝐶𝑙 (𝑔𝑎𝑠) ⇄ 𝐶𝑢2+ + 𝐶𝑙−
2 2 2 2 ⚫ Acids are defined as proton donors and bases are defined as proton acceptors.
⚫ pH of the pure water is 7 at 25 °C
0 0
𝐸𝐶𝑙 − ,𝐶𝑙 = –1.36 V
2
𝐸𝐶𝑢 2+ ,𝐶𝑢 = –0.34 V ⚫ pH falls below 7 means solution is acidic, pH raises above 7 means solution is alkaline.
⚫ It is important that pH involves taking the negative log of hydrogen ion (H+) concentration.
⚫ Therefore, each degree decrease or increase in pH value denotes 10 times more or less number of H +, respectively.
Solution 1: free energy change (ΔG°) Solution 2: Equilibrium constant (K)
Biological Importance:
1 1
Oxidation reaction @ Anode: 𝐶𝑢 → 𝐶𝑢2+ +𝑒 −
nFE°
2 2 ⚫ Most of the living cells have a range of tolerance for pH.
1
ln K =
𝑅𝑇 ⚫ The shapes of molecules such as proteins can be affected by pH causing denaturation and loss of function.
Reduction reaction @ Cathode: 𝐶𝑙 + 𝑒 − → 𝐶𝑙 − pH is an important homeostatic for all living things –organisms must work to maintain stable pH values through the use of buffering compounds.
2 2 ⚫
nFE°
𝐶𝑢 (𝑠)⃓ 𝐶𝑢2+ 𝑎𝑞 ⃒⃒ 𝐶𝑙− (𝑎𝑞) ⃓ 𝐶𝑙2 𝑔 , Pt (s) log K = 2.303 𝑅𝑇 Significance of Soil pH:

⚫ Soil organisms prefer different pH levels

0 0 +98430
𝐸 0 = 𝐸𝐶𝑢 2+ ,𝐶𝑢 – 𝐸𝐶𝑙 − ,𝐶𝑙 = –0.34 + 1.36 = +1.02 V
2 log K = = 17.3 ⚫ Acid-sulfate soils-soils that are rich in inorganic sulfide minerals, such as pyrites,
2.303 𝑥 8.314 𝑥 298 - Can lead to the formation of excessive levels of sulfuric acid through oxidation. Soil pH dives to very low levels.
- Causes solubilisation of toxic levels of aluminium, manganese and iron from soil minerals.
- Plants prefer most alkaline soils; a few which need acidic soils.
ΔG° = – nFE° 𝐽𝑜𝑢𝑙𝑒𝑠 Therefore, K = Antilog of 17.3 = 2 𝑥 1017
ΔG° = – 1 x 96500 x 1.02 𝐽𝑜𝑢𝑙𝑒𝑠

101 = – 98,430 J 102

The pH Scale and Buffer Solutions Available Methods for the Determination of pH of the Solution

BUFFERS:
“Buffers are solutions which can resist changes in pH when acid or alkali is added”

Types of Buffer:

(a), mixtures of weak acids with their salt with a strong base or
(b) Mixtures of weak bases with their salt with a strong acid.

Few examples are:

1. Bicarbonate buffer
2. Acetate buffer
3. Phosphate buffer Use of Buffers in Research

pH electrode- Portable type

Titrimetric Method based Instruments -widely used in
Litmus Paper Dip Method -more reliable Research Labs
Blue to Red : Acid

103 104
 pH Determination using Quinhydrone Electrode pH Determination using Quinhydrone Electrode (Cont.)
Significance
⚫ When 𝐻 + ions are present in the electrolyte solution, electrochemical cell’s single electrode Potentiometer 𝑖𝑛 𝑡ℎ𝑒 𝑠𝑎𝑡𝑢𝑟𝑎𝑡𝑒𝑑 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑜𝑓 𝑄𝑢𝑖𝑛ℎ𝑦𝑑𝑟𝑜𝑛𝑒, 𝑎𝑄 = 𝑎𝑄𝐻2 (equilibrium)
potentials are dependent of 𝐻 + ions concentration [𝐻 + ].
2.303 𝑅𝑇
⚫ Hence, by measuring the electrodes potentials, [𝐻 + ] and pH of the solution can be determined. Therefore, = 𝐸 0 𝑄𝐻2 ,𝑄 − log 𝑎𝐻 + ⚫ Fabrication of quinhydrone electrode is easy
𝐹
KCl Inlet
0 ⚫ Minimal solution is sufficient.
⚫ For this purpose, Standard Hydrogen Electrode (SHE) is not suitable since, it have following
=𝐸 𝑄𝐻2 ,𝑄 − 0.0591 log 𝑎𝐻 +
Pinch of
limitations; Quinhydrone ⚫ Within short time equilibrium is reached.
- Fabrication and handling difficulties = 𝐸 0 𝑄𝐻2 ,𝑄 + 0.0591 (− log 𝑎𝐻 + )
- Not suitable for oxidizing agents and unsaturated compounds KCl Sol ⚫ No need to remove dissolved oxygen.
- Can't be used in the presence of metal ion (Copper, Gold) solutions 𝐸 0 𝑄𝐻2 ,𝑄 = 𝐸 0 𝑄𝐻2 ,𝑄 + 0.0591 (pH)
- Corrosion of Pt electrode surface due to cyanide, arsenic, antimony, alkaloids, colloids. ⚫ Can be used for unsaturated compounds, metal ion (Copper, Gold) solutions.
Hg2Cl2 𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒 𝑝𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 𝑜𝑓 𝐸 0 𝑄𝐻2 ,𝑄 = −0.6996
⚫ Quinhydrone Electrode Fabrication:
-given solution to be taken in a clean beaker.
-To this Quinhydrone (1 g for 100 mL) is added to prepare saturated solution. Mercury 𝐸 0 𝑄𝐻2 ,𝑄 = −0.6996 + 0.0591 (pH)
-Platinum wire is inserted to in the solution and circuit is completed by connecting with Fabricated quinhydrone electrode is connected with Calomel Electrode to obtain the
Calomel Reference electrode. following electrochemical cell Limitations
HCl Solution
𝐻𝑔⃓ 𝐻𝑔2 𝐶𝑙2 𝑠 , KCl (sat. sol) ⃒⃒𝐻 + 𝑠𝑜𝑙 𝑄𝐻2 𝑠𝑎𝑡 ⃓ 𝑃𝑡 (𝑠)
At 298 K, its electrode potential,
⚫ In basic solutions, hydroquinone tends to ionize, hence it can not be used to
2
EMF = Oxidation Potential of Calomel Electrode measure the unknown solution pH beyond 8.5.
2.303 𝑅𝑇 𝑎𝑄 𝑎𝐻 + 𝑃𝑡 𝑠 , 𝑄𝐻2 𝑆𝑎𝑡. 𝑆𝑜𝑙 ⃒ 𝐻 + (𝑎𝑞)
𝐸 0 𝑄𝐻2 ,𝑄 = 𝐸 0 𝑄𝐻2 ,𝑄 − log + Reduction Potential of Quinhydrone Electrode
2𝐹 𝑎𝑄𝐻2 Cell Reaction:
⚫ Not suitable for high temperature, above 303 K.
𝐸 = −0.2415 − (−𝐸 0 𝑄𝐻2 ,𝑄 ) = −0.2415 − (−0.6996 + 0.0591 𝑝𝐻)
⚫ Salt Error: There is a variation in quinhydrone electrode’s potential while
= 𝐸 0 𝑄𝐻2 ,𝑄 −
2.303 𝑅𝑇 𝑎
log 𝑄 −
2.303 𝑅𝑇
log 2
𝑎𝐻 𝐶6 𝐻4 𝑂𝐻 2 ⇄ 𝐶6 𝐻4 𝑂2 + 2𝐻 + + 2𝑒 − 0.0591 pH = 0.6996 − 0.2415 − E measuring the high concentrated neutral salt solution and it is referred as salt
+
2𝐹 𝑎𝑄𝐻2 2𝐹 error.
+ −
Q𝐻2 ⇄ 𝑄 + 2𝐻 + 2𝑒 0.6996 − 0.2415 − 𝐸
105 106 therefore, pH =
0.0591

Solved Problem pH Determination using Glass Electrode

Principle Modern Setup

Problem: At 298 k, unknown solution’s EMF was measured as 0.2000 V. Cell was constructed using saturated solution of Quinhydrone and ⚫ Haber and Klemensiewicz found that when two electrolytes are separated by a glass diaphragm, electric potential is Wires to pH Meter
developing at the diaphragm.
Calomel electrode (filled with saturated KCl). Hence, calculate the pH of the unknown solution? ⚫ It is referred as “glass electrode potential (𝐸𝐺 )” and it is dependent of pH of the two solutions.
⚫ Hence, glass electrode behave like Standard Hydrogen Electrode (SHE) Filling hole
Solution : pH determination ⚫ With respect the solution pH, 𝐸𝐺 is varies as follows;
Configuration
⚫ Glass Electrode (A) is made up of a glass bulb-diaphragm having AgCl covered
𝐸 0 𝑄𝐻2,𝑄 = − 0.6996 𝑉 2.303 𝑅𝑇
𝐸𝐺 = 𝐸𝐺0 − log 𝑎𝐻 + low melting point and high conductance. Ag wire
𝐹 ⚫ Bulb is filled with 0.1 N HCl or KCl + CH3COOH, either Pt wire or Ag/AgCl
consider the oxidation reduction potential of Calomel electrode as − 0.2415 V At 298 K, 𝐸𝐺 = 𝐸𝐺0 + 0.0591 (− log 𝑎𝐻 + )
Ag/AgCl wire is pierced for contact.
Reference
reference
⚫ This setup is taken in a beaker filled with unknown pH (B) electrode
electrode
0.6996 − 0.2415 − 𝐸 0.6996 − 0.2415 − 0.2000 𝐸𝐺 = 𝐸𝐺0 + 0.0591 (pH) solution thereby Glass Electrode is Constructed.
Internal solution
therefore, pH = = = 4.37 ⚫ Subsequently, Glass Electrode is connected with Calomel
Electrode (C) to complete the circuit/to get cell.
0.0591 0.0591 Classical Setup
Permeable
Pt⃓ 0.1 N HCl ⃓ Glass Membrane ⃓ 𝐻 + (𝑆𝑜𝑙. ) ⃒⃒𝐻𝑔2 𝐶𝑙2 𝑠 , KCl (sat. sol)⃓ 𝐻𝑔 (𝑠) porous
C Voltmeter
EMF = Oxidation Potential of Glass Electrode
Glass electrode junction
A internal solution
Glass membrane
+ Reduction Potential of Calomel Electrode
Calomel Reduction potential of Calomel electrode: −0.2415 V Another Method for pH determination
Calome
Electrode
l
Electro Glass Electrode
𝐸 = 𝐸𝐺0 + 0.0591 pH + (−0.2415) 𝐸 = 𝐸𝐺0 + 0.0591 pH + 0.2415
de

0.0591 pH = 𝐸 − 𝐸𝐺0 − 0.2415 𝐸1 = 𝐸𝐺0 + 0.0591 pH1 + 0.2415

Δ𝐸 = 𝐸1 − 𝐸 = 0.0591 (pH1 − pH)
𝐸 − 𝐸𝐺0 − 0.2415
B Solution of therefore, pH = ℎ𝑒𝑛𝑐𝑒 𝑏𝑦 𝑢𝑠𝑖𝑛𝑔 𝑡ℎ𝑒 𝑠𝑎𝑚𝑒 𝑟𝑒𝑓𝑒𝑟𝑒𝑛𝑐𝑒
0.0591 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒, 𝑖𝑓 𝑜𝑛𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑝𝐻 𝑖𝑠 𝑘𝑛𝑜𝑤𝑛,
Unknown pH
107 108 ℎ𝑒𝑛𝑐𝑒 𝑏𝑦 𝑘𝑛𝑜𝑤𝑖𝑛𝑔 𝐸𝐺0 , 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑝𝐻 𝑐𝑎𝑛 𝑏𝑒 𝑚𝑒𝑎𝑠𝑢𝑟𝑒𝑑 𝑜𝑡ℎ𝑒𝑟 𝑜𝑛𝑒 ′ 𝑠 𝑝𝐻 𝑐𝑎𝑛 𝑏𝑒 𝑐𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒𝑑.
Determination of pH using Glass Electrode
 pH Determination using Glass Electrode (Cont.) Applications of EMF Measurements: Potentiometric titrations
Significance
Solved Problem 1. Principle:
-During a titration, there is change in the ions concentrations Digital
-Consequently, electrodes (having the corresponding ions concentrations in the Potentiometer
⚫ Fabrication and handling of Glass Electrode is easy. Problem: At 298 k, unknown solution’s EMF was measured as 1.2 V. Cell electrode reactions) potentials also changing
was constructed using Glass electrode and Calomel electrode (filled -Hence, by measuring the electrodes’ potential during the titration,
⚫ Minimal solution is sufficient to measure pH.
with saturated KCl). Hence, calculate the pH of the unknown solution? equivalent/end point can be determined. 84.2 mV
⚫ Suitable for all types of solutions, means not affected by oxidizing-, reducing
agents and organic compounds. Solution : pH determination ⚫ Potentiometric titration is a chemical method of analysis in which the equivalence point is
detected with help of indicator electrode.
0 ⚫ The change in potential in the indicator electrode is recorded as a function of amount of
⚫ Normal range pH 0 – pH 10. 𝐸𝐺0 = 0.700 𝑉 𝑎𝑛𝑑 𝐸𝐶𝑎𝑙𝑜𝑚𝑒𝑙 = 0.2415 𝑉 titrant added.
⚫ Special Glass Electrode can be used to measure solution having above pH 10
too. 𝐸 − 𝐸𝐺0 − 0.2415 2. Advantages
Reference
therefore, pH = 1. No indicator / no undesired reactions with indicators
0.0591 2. Provides more reliable data Electrode, 𝐸𝑟𝑒𝑓
3. Can be conducted for turbid or precipitation reaction
Limitations
1.2 − 0.700 − 0.2415 4. Lack of titration error
pH = 5. Lesser time consumption
0.0591 6. Suitable for diluted and Coloured solutions
⚫ Due to the high resistance of the diaphragm-glass bulb, usual potentiometer Metallic Indicator
7. Weak acid Vs Weak base equivalent point can be detected more accurately
can not be used. pH = 4.37 8. By using the suitable electrodes, concurrent titration of mixture of different species Salt Bridge, Electrode, 𝐸𝑖𝑛𝑑
can be titrated.
⚫ To overcome this, Vacuum tube potentiometer or Electronic voltmeter is 𝐸𝑗
required. 3. Potentiometric Titration Curve Analyte Solution
Potentiometric titration curves are obtained by plotting the potential of the indicator Porous
electrode against the volume of titrant. In case of acid-base titration, pH value is plotted Membrane
instead of potential. 𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑖𝑛𝑑 − 𝐸𝑟𝑒𝑓 + 𝐸𝑗
109 110

Applications of EMF Measurements: Potentiometric titrations Applications of EMF Measurements: Potentiometric titrations
(Cont.) (Cont.)
Acid-base titration Procedure:
⚫ 1 N NaOH titrant is dispensed to 0.1 N HCl solution taken in the beaker.
Example. HCl Vs. NaOH

4. Evaluation of Equivalence Point - 100 mL 0.1 N HCl is taken in a clean beaker. 𝐻 + + 𝑂𝐻 − → 𝐻2 𝑂

⚫ The equivalence point is evaluated based on the titration curve (Figure). - Platinum coated Platinum plate is placed in the beaker.
⚫ With every unit addition of titrant, potential increases. - H2 gas (1 atm) passed over Platinum electrode continuously. (SHE) ⚫ Due to the above reaction concentration of 𝐻 + ions is decreasing hence, EMF
- This SHE is connected with Calomel Reference electrode to complete the is increasing.
⚫ When the potential or pH change is large, the curve is steep/sharp. circuit and following cell is obtained. ⚫ During the titration, initially EMF is slowly increasing, while reaching the
⚫ The equivalence point is corresponding to the titrant volume connecting dE d2 E equivalent point it is quickly increasing, afterwards slowly increasing.
half height of the steep (Fig. a). end Pt,𝐻2 (𝑔𝑎𝑠, 1 𝑎𝑡𝑚) ⃓ 0.1 N HCl ⃒⃒𝐻𝑔2 𝐶𝑙2 𝑠 , KCl (sat. sol)⃓ 𝐻𝑔 (𝑠)
E point dV dV 2 ⚫ Plot between volume of the NaOH Vs. EMF would give the following graph.
⚫ Another convenient way of determining equivalence point is finding point EMF = Oxidation Potential of Hydrogen Electrode equivalence point is evaluated based on the titration curve (Figure).
of maximal. − Oxidation Potential of Calomel Electrode
𝑑𝐸 𝑑𝐸
⚫ The maximum of slope is obtained by plotting first derivative curve, Oxidation potential of Calomel electrode: + 0.2415 V ⚫ The maximum of slope is obtained by plotting first derivative curve, (Fig.
𝑑𝑉 𝑑𝑉
𝑑2 𝐸 (a) Titrant Volume (mL) (b) Titrant Volume (mL) (c) Titrant Volume (mL) 𝐸 = 𝐸𝐻2 − 𝐸𝑐𝑎𝑙𝑜𝑚𝑒𝑙 𝑑2 𝐸
(Fig. b) or second derivative curve, d2E/dV2 (Fig. c) against titrant b) or second derivative curve, d2E/dV2 (Fig. c) against titrant volume.
𝑑𝑉 2 𝑑𝑉 2
volume. At 298 K, 𝐸𝐻2 = 𝐸𝐻0 2 − 0.0591 log 𝑎𝐻 +
Figure. (a) Titration Curve (b) First Derivative Titration Curve (c) Second Derivation Titration Curve 𝐸 = 𝐸𝐻02 − 0.0591 log 𝑎𝐻+ − 𝐸𝑐𝑎𝑙𝑜𝑚𝑒𝑙

𝐸 = (𝐸𝐻02 − 𝐸𝑐𝑎𝑙𝑜𝑚𝑒𝑙 ) − 0.0591 log 𝑎𝐻+ end

point
𝐸 = 𝐶𝑂𝑁𝑆𝑇𝐴𝑁𝑇 − 0.0591 log 𝑎𝐻 +
𝐸 = 𝐶𝑂𝑁𝑆𝑇𝐴𝑁𝑇 + 0.0591 pH ……(1)
111 112
ℎ𝑒𝑛𝑐𝑒 𝐸𝑀𝐹 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑒𝑙𝑙 𝑖𝑠 𝑑𝑖𝑟𝑒𝑐𝑡𝑙𝑦 𝑝𝑟𝑜𝑝𝑜𝑟𝑡𝑖𝑜𝑛𝑎𝑙 𝑡𝑜 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑝𝐻
 Applications of EMF Measurements: Potentiometric titrations Liquid-junction Potential (𝑬𝒋 )
(Cont.)
Oxidation-reduction titration ⚫ Hence, till reaching the following equilibrium EMF value is slowly increasing; ⚫ There are two electrodes in an electrochemical cell.
⚫ Assume that both electrolytes are separated by a diaphragm. (a) 0.1 M HCl 0.01 M HCl
Example. FeSO4 Vs. K2Cr2O7 ⚫ Due to the “Reverse Osmosis” ions do exchange between the electrolytes.
2+ 3+
- 100 mL 0.1 N FeSO4 + 100 mL of diluted H2SO4 are taken in a clean beaker.
𝐹𝑒 ⇄ 𝐹𝑒 ⚫ Variations in the migration speed between the cations and anions will led to the
- To which 1N K2Cr2O7 dispensed from burette. [𝐹𝑒 3+ ] concentration gradient in the both electrolytes
⚫ After reaching the equilibrium, there is no change in -value. Porous
[𝐹𝑒 2+ ]
- 𝐹𝑒 2+ 𝑖𝑜𝑛𝑠 𝑎𝑟𝑒 𝑜𝑥𝑖𝑑𝑖𝑠𝑒𝑑 𝑖𝑛𝑡𝑜 𝐹𝑒 3+ 𝑖𝑜𝑛𝑠. ⚫ K2Cr2O7 added after the equilibrium led to the formation
-i.e., in one electrolyte cations may be high and in another electrolyte Membrane
anions may be high.
- Consequently, Pt/𝐹𝑒 2+ , 𝐹𝑒 3+ electrode is produced, and it is connected 2+ 2−
𝐶𝑟 − 𝐶𝑟2 𝑂7 electrode. Hence, EMF is slowly increasing. -Subsequently, electrostatic interaction would try compensate the (b) 0.1 M HCl 0.01 M HCl
with Calomel Reference electrode to complete the circuit and following cell is ⚫ At the end point EMF is suddenly changing because system is transforming concentration gradient.
obtained. from 𝐹𝑒 2+ − 𝐹𝑒 3+ electrode (A) to 𝐶𝑟 2+ − 𝐶𝑟2 𝑂72− electrode (B). -Consequently, “Electrical Double Layer (EDL)” will be created at the
𝐻𝑔 ⃓ 𝐻𝑔2 𝐶𝑙2 𝑠 , KCl (sat. sol) ⃒⃒ 𝐹𝑒 3+ ⃓ 𝐹𝑒 2+ , 𝑃𝑡 (𝑠) ⚫ Plot between volume of the K2Cr2O7 Vs. EMF would give the following graph. junction where both electrolytes meet with each other.
equivalence point is evaluated based on the titration curve (Figure). -This EDL is generating electric potential and it is referred as “Liquid
Excess 𝐶𝑙 − Excess 𝐻 +
EMF = Oxidation Potential of Calomel Electrode Junction Potential”
− Oxidation Potential of 𝐹𝑒 2+ , 𝐹𝑒 3+ Electrode ⚫ Note: ⚫ It is noted as 𝑬𝒋 , while measuring the EMF of the cell, 𝑬𝒋 must be considered.
2.303 𝑅𝑇 𝑎𝐹𝑒3+ - If the potential difference between the “A” and “B” region is less means Salt bridge
𝐸 = 𝐸𝑐𝑎𝑙𝑜𝑚𝑒𝑙 − 𝐸𝐹𝑒 2+ 𝐹𝑒 3+ = 𝐸𝑐𝑎𝑙𝑜𝑚𝑒𝑙 − (𝐸𝐹𝑒 2+ 𝐹𝑒 3+ + log ) equivalent point cannot be measured accurately. Example: 𝑍𝑛 ⃓ 𝑍𝑛𝑆𝑂4 ⃒ 𝐶𝑢𝑆𝑂4 ⃓ 𝐶𝑢
2𝐹 𝑎𝐹𝑒2+

𝑎
At 298 K, = 𝐸𝑐𝑎𝑙𝑜𝑚𝑒𝑙 − (𝐸𝐹𝑒 2+ 𝐹𝑒 3+ + 0.0591 log 𝑎𝐹𝑒 )
3+ 𝐸 = 𝐸𝑍𝑛,𝑍𝑛2+ − 𝐸𝐶𝑢,𝐶𝑢2+ + 𝐸𝑗
𝐹𝑒2+
B These type of cells are called as chemical cells with transference (no salt
Coating
𝑎[𝐹𝑒 3+ ] bridge) of Ag/
= (𝐸𝑐𝑎𝑙𝑜𝑚𝑒𝑙 − 𝐸𝐹𝑒 2+ 𝐹𝑒 3+ ) + 0.0591 log To measure the 𝐸𝑗 following equation is used. AgCl
𝑎[𝐹𝑒 2+ ]
end

𝐸 = 𝐶𝑂𝑁𝑆𝑇𝐴𝑁𝑇 + 0.0591 log

[𝐹𝑒 3+ ]
……(1)
point 2.303 𝑅𝑇 𝑎2
[𝐹𝑒 2+ ]
A 𝐸𝑗 = (𝑡− −𝑡+ ) log
𝐹 𝑎1
[𝐹𝑒 3+ ]
During the titration 𝐹𝑒 2+ 𝑖𝑜𝑛𝑠 𝑎𝑟𝑒 𝑜𝑥𝑖𝑑𝑖𝑠𝑒𝑑 𝑖𝑛𝑡𝑜 𝐹𝑒 3+ 𝑖𝑜𝑛𝑠 , -value is Galvanic Cell without Galvanic Cell with Liquid
[𝐹𝑒 2+ ]
113 Note: in addition to the activities, transport numbers also involved.
114 Liquid Junction Junction
increasing

Eliminating the Liquid-junction Potential (𝑬𝒋 ) Concentration Cells

⚫ By connecting the both electrolytes via salt bridge, Liquid-junction Potential ⚫ In the cells we have considered so far there is a net chemical change.
can be eliminated. (a) 0.1 M HCl 0.01 M HCl ⚫ Such electrochemical cells are classified as chemical cells. Electrochemical Cells
⚫ There are also cells in which the driving force, instead of being a chemical
⚫ “SALT BRIDGE“ is the saturated solution of KCl or KNO3 or NH4NO3. reaction taking place between electrodes and solute ions, is a dilution process.
⚫ In these salts, migration speed of both cations and anions are almost same. Porous
Such cells are known as concentration cells.
Membrane ⚫ The changes in concentration can occur either in the electrolyte or at the
⚫ First, hot and saturated Agar-Agar solution is prepared in a beaker. electrodes. Chemical Cells Concentration Cells
⚫ Subsequently, KCl or KNO3 or NH4NO3 salt is added till saturation. (b) 0.1 M HCl 0.01 M HCl
⚫ This mixture is filled in “U” shaped glass tube and allowed to cool. ⚫ Examples of concentration changes at electrodes are found with electrodes
⚫ Agar-Agar gel is now holding the saturated salt inside the glass tube. made of amalgams or consisting of alloys and with gas electrodes (e.g., the Pt,
Amalgam or Alloy
H2 electrode) when there are different gas pressures at the two electrodes.
Without With electrodes (6)
⚫ When connected, potential created at the junction of left side salt bridge- Excess 𝐶𝑙 − Excess 𝐻 + ⚫ Figure shows a classification of electrochemical cells.
electrolyte interface will be having same potential at the right side but differ ⚫ A sub classification of chemical and concentration cells relates to whether or transference (1) transference (2)
in sign (For ex: +0.2 and -0.2). Thereby it is believed that Liquid-junction is not there is a boundary between two solutions.
eliminated. Salt bridge Gas
⚫ Examples: Electrolyte
Concentration Cells Electrodes (7)
Example:

𝑍𝑛 ⃓ 𝑍𝑛𝑆𝑂4 ⃒⃒ 𝐶𝑢𝑆𝑂4 ⃓ 𝐶𝑢
Coating
𝐸 = 𝐸𝑍𝑛,𝑍𝑛2+ − 𝐸𝐶𝑢,𝐶𝑢2+ of Ag/ Redox Cells (3)
AgCl Cells in which the With
chemical reaction Transference (5)
Without
These type of cells are called as chemical cells without transference (Salt involves in the
Transference (4)
bridge is present) electrodes

Galvanic Cell without Galvanic Cell with Liquid

115 Liquid Junction Junction 116
 Amalgam Electrode Concentration Cells Gas Electrode Concentration Cells

⚫ By using a single metal two different amalgams (Metal-Mercury) are prepared Oxidation reaction at Cathode: Ag → 𝐴𝑔+ + 𝑒 − ⚫ Two metal plates kept in an electrolyte, in which gas is supplied at two
as two different electrodes. different pressures for each metal plate, thereby gas electrode concentration
+
⚫ These two electrodes are kept in their salt solution, thereby concentration 0 2.303 𝑅𝑇 𝑎 cell is fabricated.
cell is fabricated.
Its oxidation potential 𝐸2 = 𝐸𝐴𝑔 − 𝐹 log 𝑎𝐴𝑔
𝐴𝑔
1. 𝐴𝑔(𝐻𝑔) ⃓ 𝐴𝑔𝑁𝑂3 ⃓ 𝐴𝑔(𝐻𝑔) ⚫ Examples: 𝑃𝑡, 𝐻2 (𝑔)⃓ 𝐻𝐶𝑙 ⃓𝐻2 (g) , Pt
⚫ Examples: 2.303 𝑅𝑇 𝑎𝐴𝑔+
𝑎𝐴𝑔 = 𝑎1 𝑆𝑜𝑙. 𝑎𝐴𝑔 = 𝑎2 0
= 𝐸𝐴𝑔 − log 𝑝𝐻2 = 𝑃1 𝑆𝑜𝑙. 𝑝𝐻2 = 𝑃2
𝐹 𝑎2
2. 𝐶𝑑(𝐻𝑔) ⃓ 𝐶𝑑𝑆𝑂4 ⃓ 𝐶𝑑(𝐻𝑔) EMF = Oxidation Potential of Anode − Oxidation Potential of Cathode 𝐸 = 𝐸1 − 𝐸2 𝑃𝑡, 𝐶𝑙2 (𝑔)⃓ 𝐻𝐶𝑙 ⃓𝐶𝑙2 (g) , Pt
𝑎𝐶𝑑 = 𝑎1 𝑆𝑜𝑙. 𝑎𝐶𝑑 = 𝑎2
𝑆𝑜𝑙. 𝑝𝐶𝑙2 = 𝑃2
+ +
0
𝐸 = (𝐸𝐴𝑔 −
2.303 𝑅𝑇 𝑎𝐴𝑔
log 𝑎 0
) −(𝐸𝐴𝑔 −
2.303 𝑅𝑇 𝑎𝐴𝑔
log 𝑎 ) 𝑝𝐶𝑙2 = 𝑃1
𝐹 1 𝐹 2 Note:
3. 𝑍𝑛(𝐻𝑔) ⃓ 𝑍𝑛𝑆𝑂4 ⃓ 𝑍𝑛(𝐻𝑔) - Hence EMF (E) from the eqn (1) can be measured for the gas electrode
2.303 𝑅𝑇 𝑎𝐴𝑔+ 2.303 𝑅𝑇 𝑎𝐴𝑔+ EMF of the Hydrogen gas concentration cell,
𝑎𝑍𝑛 = 𝑎1 𝑎𝑍𝑛 = 𝑎2 0
= 𝐸𝐴𝑔 − log 0
− 𝐸𝐴𝑔 − log concentration cells.
𝑆𝑜𝑙. 𝐹 𝑎1 𝐹 𝑎2
2.303 𝑅𝑇 𝑎
+
2.303 𝑅𝑇 𝑎
+ - To obtain +Ve “E” value, 𝑃1 > 𝑃2 (ΔG = – nFE, Spontanous reaction)
⚫ Let's take the following concentration cell for our analysis
2.303 𝑅𝑇 𝑎𝐴𝑔+ 2.303 𝑅𝑇 𝑎𝐴𝑔+ 𝐸 = (𝐸𝐻02 − log 𝐻 ) −(𝐸𝐻02 − log 𝐻 ) - Hence, in the gas electrode concentration cells, high pressured electrode do
𝐹 𝑃1 𝐹 𝑎𝑃2
= log − log act as an “ANODE”.
𝐴𝑔(𝐻𝑔) ⃓ 𝐴𝑔𝑁𝑂3 ⃓ 𝐴𝑔(𝐻𝑔) 𝐹 𝑎1 𝐹 𝑎2
2.303 𝑅𝑇 𝑃
𝑎𝐴𝑔 = 𝑎1 𝑆𝑜𝑙. 𝑎𝐴𝑔 = 𝑎2 2.303 𝑅𝑇 𝑎𝐴𝑔
+
𝑎1 E = log 1 …..(1)
= log 𝑥 + 𝐹 𝑃2
𝐹 𝑎2 𝑎𝐴𝑔
+ −
Oxidation reaction at Anode: Ag → 𝐴𝑔 + 𝑒 2.303 𝑅𝑇 𝑎
+
E =
𝐹
log 1
𝑎2
…..(1)
0 − 2.303 𝑅𝑇 log 𝑎𝐴𝑔
Its oxidation potential 𝐸1 = 𝐸𝐴𝑔 𝐹 𝑎𝐴𝑔
Note:
- Hence EMF (E) from the eqn (1) can be measured for the amalgam
0
2.303 𝑅𝑇 𝑎𝐴𝑔+ concentration cells.
= 𝐸𝐴𝑔 − log
𝐹 𝑎1 - To obtain +Ve “E” value, 𝑎1 > 𝑎2 (ΔG = – nFE, Spontanous reaction)
117 - Hence, in the amalgam concentration cells, high concentrated electrode do act 118
as an “ANODE”.

Electrolyte Concentration Cells Concentration Cells with and without Transference

⚫ In an electrolyte concentration cell, both electrodes are same, but their Oxidation reaction at Cathode: Ag → 𝐴𝑔+ + 𝑒 −
electrolyte concertation is different.
+
⚫ Both electrolytes must be separated by the “SALT BRIDGE” 0 − 2.303 𝑅𝑇 log 𝑎𝐴𝑔
Its oxidation potential 𝐸2 = 𝐸𝐴𝑔 𝐹 𝑎𝐴𝑔
⚫ Examples: 1. 𝐴𝑔 ⃓ 𝐴𝑔𝑁𝑂3 ⃒⃒ 𝐴𝑔𝑁𝑂3 ⃓ 𝐴𝑔
0
2.303 𝑅𝑇
𝑎𝐴𝑔+ = 𝑎1 𝑆𝑜𝑙. 𝑆𝑜𝑙. 𝑎𝐴𝑔+ = 𝑎2 = 𝐸𝐴𝑔 − 𝑙𝑜𝑔𝑎2 𝑏𝑒𝑐𝑢𝑎𝑠𝑒, 𝑎𝐴𝑔 = 1
𝐹
2. 𝑍𝑛 ⃓ 𝑍𝑛𝑆𝑂4 ⃒⃒ 𝑍𝑛𝑆𝑂4 ⃓ 𝑍𝑛 EMF = Oxidation Potential of Anode − Oxidation Potential of Cathode 𝐸 = 𝐸1 − 𝐸2
𝑎𝑍𝑛2+ = 𝑎1 𝑆𝑜𝑙. 𝑆𝑜𝑙. 𝑎𝑍𝑛2+ = 𝑎2 0 2.303 𝑅𝑇 0 2.303 𝑅𝑇
1. Concentration cells with transference (𝐸𝑡 ):
𝐸 = (𝐸𝐴𝑔 − 𝐹
𝑙𝑜𝑔𝑎1 ) −(𝐸𝐴𝑔 − 𝐹
𝑙𝑜𝑔𝑎2 ) In an electrolyte concentration cell, if two electrolytes are in contact with each other means it is referred as concentration
⚫ Let's take the following concentration cell for our analysis
cell with transference.
0 2.303 𝑅𝑇 0 2.303 𝑅𝑇
1. 𝐴𝑔 ⃓ 𝐴𝑔𝑁𝑂3 ⃒⃒ 𝐴𝑔𝑁𝑂3 ⃓ 𝐴𝑔 = 𝐸𝐴𝑔 − 𝑙𝑜𝑔𝑎1 − 𝐸𝐴𝑔 − 𝑙𝑜𝑔𝑎2
𝐹 𝐹
𝑎𝐴𝑔 +
= 𝑎1 𝑆𝑜𝑙. 𝑎𝐴𝑔+ = 𝑎2 2. Concentration cells without transference:
𝑆𝑜𝑙.
2.303 𝑅𝑇 2.303 𝑅𝑇 In an electrolyte concentration cell, liquid-junction potential (Ej) is eliminated by the salt bridge means it is referred as
= 𝑙𝑜𝑔𝑎2 − 𝑙𝑜𝑔𝑎1
Oxidation reaction at Anode: Ag → 𝐴𝑔+ + 𝑒 − 𝐹 𝐹 concentration cell without transference.
2.303 𝑅𝑇 𝑎
𝑎𝐴𝑔
+
E = log 𝑎2 …..(1)
Its oxidation potential 𝐸1 = 0
𝐸𝐴𝑔 − 2.303
𝐹
𝑅𝑇
log 𝑎𝐴𝑔
𝐹 1

Note:
0
2.303 𝑅𝑇
= 𝐸𝐴𝑔 − 𝑙𝑜𝑔𝑎1 𝑏𝑒𝑐𝑢𝑎𝑠𝑒, 𝑎𝐴𝑔 = 1 - Hence EMF (E) from the eqn (1) can be measured for the electrolyte
𝐹 concentration cells.
- To obtain +Ve “E” value, 𝑎2 > 𝑎1 (ΔG = – nFE, Spontanous reaction)
- Hence, in the electrolyte concentration cells, less concentrated electrolyte do
act as an “ANODE”.

119 120
 Applications of Concentration Cells: Determination of Valency
Applications of Concentration Cells
of Ions
⚫ By measuring the EMF of the concentration cells, a suspected valency of ions
can be determined.

⚫ Example: Determination of Valency of Mercurous Ions

𝐻𝑔⃓𝑀𝑒𝑟𝑐𝑢𝑟𝑜𝑢𝑠 𝑛𝑖𝑡𝑟𝑎𝑡𝑒 𝑆𝑜𝑙 ⃓𝑀𝑒𝑟𝑐𝑢𝑟𝑜𝑢𝑠 𝑛𝑖𝑡𝑟𝑎𝑡𝑒 (𝑠𝑜𝑙)⃓ 𝐻𝑔
Note:
𝐶1 𝐶2 -Hence valency of the mercurous ion is 2.
EMF of the above concentration cell is as follows; -So, Mercurous ion should be written as 𝐻𝑔22+
1. Valency of Ions
2.303 𝑅𝑇 𝑎2
2. Determination of Transport Number E =
𝐹
log
𝑎1
…..(1)
3. Determination of Solubility of the sparingly soluble salt
4. Determination of activity co-efficient 2.303 𝑅𝑇 𝐶
E = 𝐹
log 𝐶2 …..(2)
1

0.0591 𝐶
At 298 K, E = log 2 …..(3)
𝑛 𝐶1

𝐶2
When = 10, EMF of the above cell was measured as 0.0295 V
𝐶1

0.0591
0.0295 = log10 …..(3) (log 10 = 1)
𝑛

0.0591 0.0591
0.0295 = ;n= =2
121 122 𝑛 0.0295

Applications of Concentration Cells: Determination of Applications of Concentration Cells: Determination of

Transport Number Solubility of Sparingly Soluble Salts
⚫ Transport number can be determined via constructing without and with ⚫ Example: Determination of solubility product of AgCl
transference concentration cell followed by measuring their EMF. Dividing eqn (2) by eqn (1),
2.303 𝑅𝑇 𝑎2 -0.01 N KCl solution is taken in a clean beaker.
⚫ Example: Determination of transport number of 𝑁𝑂3− 𝑖𝑜𝑛𝑠 𝐸𝑡 = (2𝑡− ) log ……(2) - A drop of AgNO3 is added to gel saturated AgCl solution. Note:
𝐹 𝑎1
- In which Ag wire is inserted to fabricate 𝐴𝑔⃓𝐴𝑔+ electrode. - Hence by measuring
1. 𝐴𝑔 ⃓ 𝐴𝑔𝑁𝑂3 ⃒⃒ 𝐴𝑔𝑁𝑂3 ⃓ 𝐴𝑔
- 𝐴𝑔⃓𝐴𝑔+ electrode is connected with another 𝐴𝑔⃓𝐴𝑔+ electrode to 𝐸𝑀𝐹 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑒𝑙𝑙, 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴𝑔+ 𝑖𝑜𝑛𝑠 𝑝𝑟𝑒𝑠𝑒𝑛𝑡 𝑖𝑛 𝐾𝐶𝑙 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛, 𝐶 𝑐𝑎𝑛 𝑏𝑒 𝑐𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒𝑑
𝑎𝐴𝑔+ = 𝑎1 𝑆𝑜𝑙. 𝑆𝑜𝑙. 𝑎𝐴𝑔+ = 𝑎2 2.303 𝑅𝑇 𝑎 fabricate the following concentration cells;
𝐸𝑡 (2𝑡− ) log 2
= 2𝑡−
𝐹 𝑎1
EMF of the above cell (concentration cell without transference) = 2.303 𝑅𝑇 𝑎 Note:
𝐸 log 2 𝐴𝑔 ⃓ 𝐴𝑔𝑁𝑂3 , 0.01𝑁 𝐾𝐶𝑙⃒⃒ 0.01 𝑁𝐴𝑔𝑁𝑂3 ⃓ 𝐴𝑔
𝐹 𝑎1 - The concentration of 𝐶𝑙 − = 0.01 (KCl solution is completely dissociated).
2.303 𝑅𝑇 𝑎2 𝑎𝐴𝑔+ = 𝐶 𝑆𝑜𝑙. 𝑆𝑜𝑙. 𝑎𝐴𝑔+ = 0.01
E = log …..(1)
𝐹 𝑎1 therefore solubility of AgCl,
Note: EMF of the above cell (concentration cell without transference)
2. 𝐴𝑔 ⃓ 𝐴𝑔𝑁𝑂3 ⃓ 𝐴𝑔𝑁𝑂3 ⃓ 𝐴𝑔
- Hence by measuring 𝐸 𝑎𝑛𝑑 𝐸𝑡. 𝐸𝑁𝑂3− can be measured. 2.303 𝑅𝑇 𝑎2 𝐾𝑠𝑝 = 𝐴𝑔+ 𝐶𝑙 −
𝑎𝐴𝑔+ = 𝑎1 𝑆𝑜𝑙. 𝑆𝑜𝑙. 𝑎𝐴𝑔+ = 𝑎2 E = log …..(1)
𝐹 𝑎1 = 𝐶 𝑥 0.01 = 𝑆 = 𝐾𝑠𝑝 = 𝐶 𝑥 0.01
EMF of the above cell (concentration cell with transference, 𝐸𝑡 ) Or E =
2.303 𝑅𝑇
log
𝐶2
…..(2)
𝐹 𝐶1
hence, solubility product of the AgCl can be measured.
𝐸𝑡 = 𝐸 + 𝐸𝑗
2.303 𝑅𝑇 0.01
E = log …..(3)
𝐹 𝐶
2.303 𝑅𝑇 𝑎2 2.303 𝑅𝑇 𝑎2
= log + (𝑡− − 𝑡+ ) log 0.01
𝐹 𝑎1 𝐹 𝑎1 At 298 K, E = 0.0591 log …..(4)
𝐶
2.303 𝑅𝑇 𝑎2
𝐸𝑡 = (1 + 𝑡− −𝑡+ ) log here(𝒕+ + 𝒕− = 1 (or) 𝒕− = 1- 𝒕+ )
𝐹 𝑎1

2.303 𝑅𝑇 𝑎2
𝐸𝑡 = (2𝑡− ) log ……(2)
𝐹 𝑎1
123 124
 Applications of Concentration Cells: Determination of Activity
Acid-Base Indicators
Co-efficient (γ)
⚫ Example: Determination of Average Activity Co-efficient of KCl solution

𝐾 𝐻𝑔 ⃓𝐾𝐶𝑙 𝑠𝑜𝑙 ⃓𝐴𝑔𝐶𝑙 𝑠 ⃓𝐴𝑔⃓𝐴𝑔𝐶𝑙 𝑠 ⃓𝐾𝐶𝑙 (𝑠𝑜𝑙) ⃓𝐾(𝐻𝑔)

𝑎1 𝑎2
Note:
EMF of the above concentration cell without transference is as follows; 𝑚2
- Here KCl solutions is known hence EMF (E) can be measured, subsequently
2.303 𝑅𝑇 𝑎2 𝑚1
E =
𝐹
log
𝑎1
…..(1) γ2
can be measured.
γ1
Let’s assume that m1, m2 are the molar concentrations of the KCl solutions and γ1, - If more diluted KCl solutions (diluted m2) is used, then by using debye-huckel
γ2 are the average activity co-effcients equation

E =
2.303 𝑅𝑇
𝐹
(𝑚 γ )2
log (𝑚2 γ2 )2
1 1
…..(2) (a = (mγ)2) 𝑙𝑜𝑔γ± = 0.5 𝑍+ 𝑍− 𝜇
2.303 𝑅𝑇 𝑥 2 𝑚 γ γ-value can be measured.
= 𝐹
log 𝑚2γ2 …..(3)
1 1 Hence, KCl solution’s γ-value can be calculated.
2.303 𝑅𝑇 𝑥 2 𝑚 2.303 𝑅𝑇 𝑥 2 γ
𝐸 = log 2 + log 2 …..(4)
𝐹 𝑚1 𝐹 γ1

125 126

Indicator Constant

127 128
 Introduction: Phase Equilibria

Phase equilibria is the application of the principles of thermodynamics to the study of equilibrium relationships within or
between phases, corresponding to homogeneous and heterogeneous phase equilibria, respectively.

Unit 2. Phase Equilibria Phase equilibrium is the study of the equilibrium which exists between or within different states of matter namely solid, liquid
and gas. Equilibrium is defined as a stage when chemical potential of any component present in the system stays steady with
time.

The criteria for phase equilibrium, established over 100 years ago by Gibbs, are that: (1) the temperature and pressure of the
phases are equal, (2) the chemical potentials of each of the components in each of the phases that it is present are equal, and
(3) the global Gibbs free energy is a minimum.

129 130

Introduction: Phase Rule Definitions

System: An assembly of materials that is isolated in some manner from rest of the universe.
❑ isolated system: one that does not exchange matter or energy with its surroundings.
For a system at equilibrium the phase rule relates: ❑ closed system: one that exchanges only energy with its surroundings.
❑ open system: one that exchanges both matter and energy with its surroundings.
P = number of phases that can coexist, to ❑ adiabatic system: a system with changes in energy caused only by a change in volume
C = number of components making up the phases, and as pressure changes.
F = degrees of freedom.
When an heterogenous system is in equilibrium without having the impact of gravitational-, electric- and electromagnetic force, these Equilibrium: The lowest energy state of a system in which there is no tendency for a
three variables are related in the equation. Which is referred as “Phase Rule” spontaneous change.
Metastable Equilibrium: state of a system which is not in its lowest energy state at the
P + F = C + 2 (Or) F = C-P+2 imposed conditions but cannot spontaneously change due to high activation energy for change.
The degrees of freedom represent the environmental conditions which can be independently varied without changing the number of phas
All chemical reactions are broadly classified into 2 types:
es in the system.
1) Irreversible Reactions: Zn + H2SO4 −−−−−> ZnSO4 + H2 ↑
Conditions include: Temperature, Pressure, Chemical Composition, Oxygen Fugacity ,etc .
2) Reversible reactions:
(a) Homogeneous reversible reactions
▪ The reversible reactions are represented by 2 arrows in
the opposite directions.
▪ The homogeneous reversible reactions can be studied by
the law of mass action and the heterogeneous reversible
reactions using the phase rule, given by
Willard Gibbs (1874) which is defined as,
PHASE RULE:
• If the equilibrium between any numbers of phases is not in
fluenced by gravitational/electrical/ magnetic forces but is
influenced by pressure, temperature and concentration,
then the number of degrees of freedom (F) is related to
the number of components (C) and the number of
phases (P) as:
F=C−P+2

Ex: N2 (g ) + 3H2 (g) ⇌ 2NH3 (g)

(b) Heterogeneous reversible reactions

Ex: CaCO3 (s) ⇌ CaO (s) + CO2 (g)

131 132
 Explanation of the Terms with Examples: Phase (P) Explanation of the Terms with Examples: Component (C)

PHASE (P): Other examples: COMPONENT (C): When CaCO3 and CaO are considered as components, the chemical equations are:
PHASE is defined as, “any homogeneous physically distinct and mechanically
separable portions of a system which is separated from other parts of the 1) A water system has 3 phases namely one solid, one liquid and one gaseous phase. • Component is defined as, “the minimum number of independent variable
constituents, by means of which the composition of each phase can be S. No Phase (P) Components (C)
system by definite boundaries”.
Ice(s) Water(l) Vapour(g) expressed in the form of a chemical equation.
• Besides, Component is element or a compound present in a system. I CaCO3 CaCO3 + 0 CO2
a) Gaseous phase (g):
• All gases are completely miscible and have no boundaries between them. 2) A solution of a substance in a solvent constitutes only one phase.
CaO 0 CaCO3 + CaO
• Hence all gases constitute a single phase. (e.g.) Sugar solution in water.
Examples: CO2 CaCO3 - CaO
Eg: Air, a mixture of O2, H2, N2, CO2 and water vapor, etc., 3) An emulsion of oil in water forms two phases (a) Consider a water system consisting of three phases.
constitutes a single phase. S. No Phase (P) Components (C)
4) MgCO3 (s) ⇌ MgO (s) + CO2 (g) Ice(s) Water(l) Vapour(g)
(b) Liquid Phase (l): II CaCO3 CaCO3 + 0 CO2
• The number of liquid phases depends on the number of liquids present and It involves 3 phases, solid MgCO3, solid MgO and gaseous CO2. • The chemical composition of all the three phases is H2O.
their miscibility’s. • Hence the number of component is one. CaO CaCO3 - 0 CO2
(i) If two liquids are immiscible, they will form two separate liquid phases. 5) Rhombic sulphur (s) −−−−> Monoclinic sulphur (s).
CO2 0 CaCO3 + CO2
(e.g.) Benzene – Water system. (b) Sulphur exists in 4 phases namely rhombic, monoclinic, liquid and vapour, but
It forms 2 phases. the chemical composition is only sulphur.
(ii) If two liquids are completely miscible, they will form only one liquid phase. -Hence it is a one component system. S. No Phase (P) Components (C)
(e.g.) Alcohol - Water system. 6) Consider the following heterogeneous system.
(c) Thermal decomposition of CaCO3 III CaCO3 CaO + CO2
(c) Solid Phase (s): CuSO4(s) + 5H2O (l) ⇌ CuSO4 . 5H2O (s)
• Every solid constitutes a separate single phase. CaCO3 (s) ⇌ CaO (s) + CO2 (g) CaO CaO + 0 CO2
(e.g.) Decomposition of CaCO3 It involves 3 phases namely, 2 solids and 1 liquid phase. CO2 0 CaO + CO2
• The system has 3 phases namely, solid CaCO3, solid CaO and gaseous CO2
CaCO3 (s) ⇌ CaO (s) + CO2 (g) and 2 components, as the composition of each of the above phases can be
expressed as equations considering any two of the three components present.
Hence, no. of Components in this system is 2.
It involves 3 phases namely solid CaCO3, solid CaO and gaseous CO2
133 134

Explanation of the Terms with Examples: Component (C) Explanation of the Terms with Examples: Degree of Freedom (F)

COMPONENT (C): Degree of freedom is defined as, “the minimum number of independent variable factors like temperature, pressure and
When NH3 (g) and HCl (g) are present in equivalent quantities: concentration, which must be fixed in order to define the system completely”.
(d) PCl5 (s) ⇌ PCl3 (l) + Cl2 (g) One Component System
A system having 1, 2, 3 or 0 degrees of freedom are called as univariant, bivariant, trivariant and non-variant systems, respectively.
This system has 3 phases and 2 components namely, PCl3 and Cl2. S. No Phase (P) Components (C)
(1) For a gas, PV = RT
(e) An aqueous solution of NaCl is a two-component system. I Gas (NH3 + HCl) NH4Cl -Hence, pressure, P; Volume, V; are determined means system will be having a particular temperature, T.
-likewise, if P, T are determined then system will be having volume, V.
The constituents are NaCl and H2O. Solid NH4Cl NH4Cl -therefore, out of P,V,T by determining two of the variable factors is sufficient to describe the system.
-Hence, degree of freedom, F is two.
(f) CuSO4. 5H2O (s) ⇌ CuSO4.3H2O (s) + 2H2O (g) Examples:
(a) Consider the following equilibrium
It is also a two-component system as components are CuSO4. 3H2O and H2O.
Ice(s) ⇌ Water(l) ⇌ Vapour(g)
(g) In the dissociation of NH4Cl , the following equilibrium occurs. When NH3 (g) and HCl (g) are not in equivalent quantities:
Two Component System
-These 3 phases will be in equilibrium only at a particular temperature and pressure.
NH4Cl (s) ⇌ NH3 (g) + HCl (g) -Hence, this system does not have any degree of freedom, so it is non-variant (or) zero-variant (or) in-variant system.
S. No Phase (P) Components (C)
▪ The system consists of 2 phases namely solid NH4Cl and the gaseous mixture (b) Consider the following equilibrium
containing NH3 + HCl. I Gas (x NH3 + y HCl) y NH3 + y HCl + (x-y) NH3 + y NH4Cl
▪ When NH3 (g) and HCl (g) are present in equivalent quantities the + (x-y) HCl Liquid Water(l) ⇌ Water-vapour(g)
composition of both the phases can be represented by NH4Cl and hence the Solid NH4Cl NH4Cl + 0 NH3
system will be a one component system. -Here liquid water is in equilibrium with water vapour.
-Hence any one of the degrees of freedom such as temperature (or) pressure has to be fixed to define the system.
-Therefore, the degree of freedom is one.

(c) For a gaseous mixture of N2 and H2, both the pressure and temperature must be fixed to define the system. Hence, the system is bivariant.
135 136
 Derivation of Phase Rule Phase Diagram

When a homogenous system is in equilibrium, -Hence, concentration of a component in a phase is known means,
-Consider that it have Phases (P) and components (C). (P-1) concentration also become known. Phase diagram is a graph obtained by plotting one degree of freedom against the other.
-the minimum number of independent variable factors like temperature, Phase Diagram
pressure and concentration, required to describe the system is referred as -That is, component, (P-1) concentration become auto determined. Types of Phase Diagrams
degree of freedom (F).
-So, when system is having “C” components, C(P-1) concentration become (i) P-T Diagram
(1) For a gas, PV = RT auto determined. D
-Hence, pressure, P; Volume, V; are determined means system will be -If the phase diagram is plotted between temperature and pressure, the diagram is called
having a particular temperature, T. Therefore, Variants to be determined P -T diagram. P -T diagram is used for one component system.
-likewise, if P, T are determined then system will be having volume, V. = (total Variants of the system) – (Variants auto determined) 1 (atm)
-therefore, out of P,V,T by determining two of the variable factors is (ii) T-C Diagram
sufficient to describe the system. I.e., Degree of Freedom,
-If the phase diagram is plotted between temperature and composition, the diagram is called
C

Pressure
-Hence, Out of all components present (C) in a phase (P), determining the F = [P(C-1) + 2] – [C(P-1)] T-C diagram. Solid Liquid
concentration of (C-1) will lead to the determination of other components. -T- C diagram is used for two component system
= PC-P + 2-PC + C
-Hence, each phase (P) have (C-1) as constant. Uses of Phase Diagram:
F = C-P + 2 ……(2)
Therefore, total no. of constants in a system = P (C-1) + 2 It helps in B
Eqn (2) is the mathematical form the Phase Rule.
-Based on thermodynamics, concentration of an element of a system (i) Predicting whether a eutectic alloy (or) a solid solution is formed on cooling a homogeneous liquid A Gas
present in equilibrium will be equal at all its phases (solid, liquid and gas). containing mixture of two metals.
Temperature
- Let's assume that component “1” is present in phases a, b, c, its chemic (ii) Understanding the properties of materials in the heterogeneous equilibrium system.
al pressure is
(𝑎) (𝑏) (𝑐) (iii) Studying of low melting eutectic alloys, used in soldering.
μ1 = μ1 = μ1 = 1 ………………(1)

137 138

Thermodynamics of Vapor Pressure: The Clapeyron Equation Clapeyron-Clausius Equation

⚫ Criterion for two phases of a pure substance to coexist is that their Gibbs 𝑑𝑃 𝑆𝑚 𝑉 −𝑆𝑚 𝑙 Δ𝑆𝑚 ⚫ After 30 years of Clapeyron equation, Clausius introduced a modification that Δ𝑣𝑎𝑝 𝐻𝑚
Rearranging eq (4), = = …..(5) We thus obtain, ‫ 𝑑 ׬‬ln 𝑃′′ = 𝑅
‫ 𝑇 ׬‬−2 𝑑𝑇 ….(4)
energies must be equal at a given temperature and pressure. 𝑑𝑇 𝑉𝑚 𝑉 −𝑉𝑚 𝑙 Δ𝑉𝑚 improved the versatility of the expression.
⚫ However, if either T or P is varied, with the other held constant, one of the Δ𝑣𝑎𝑝 𝐻𝑚
phases will disappears Thus, if we are at a particular point on one of the phase- -If the molar enthalpy change at constant pressure for the phase transformation Assumptions: ln 𝑃′′ = − + 𝐶 ….(5) (y = mx +c)
𝑅𝑇
equilibria lines on a P-T diagram (gas-liquid, liquid-solid, solid-gas, or even solid- Δ𝐻 1. When one of the phases in equilibrium is a vapor phase , we assume that
is Δ𝐻𝑚 , then the term Δ𝑆𝑚 may be written as 𝑇𝑚 and eq (5) becomes ⚫ Where C is a constant of integration.
solid), Problem becomes how to vary P and T while maintaining equilibrium. 𝑉𝑚 𝑉 is so much larger than 𝑉𝑚 𝑙 that we may neglect 𝑉𝑚 𝑙 in comparison to 1
𝑑𝑃 Δ𝐻𝑚
⚫ A plot of ln 𝑃′′ Vs
Δ 𝐻
= …..(6) 𝑉𝑚 𝑉 when the pressure is near 1 bar. (For water, the volume of vapor is at should be linear. Slope of the line is 𝑣𝑎𝑝𝑅 𝑚.
𝑑𝑇 T Δ𝑉𝑚 𝑇
⚫ In 1834 Benoit Clapeyron (1799-1864) published a solution for the case of a least a thousand times that of a liquid.) 1
liquid and its vapor. 2. The second assumption is to replace 𝑉𝑚 𝑉 by its equivalent from the Ideal ⚫ A plot of R ln 𝑃′′ Vs can also made in which the intercept on the R ln 𝑃′′
⚫ The general form of eq (6) is known as the Clapeyron equation and may be 𝑇
⚫ Researchers do investigate the vapor pressure because, since the vapor gas law, axis will give the value of Δ𝑣𝑎𝑝 𝑆𝑚 .
applied to vaporization, sublimation, fusion, or solid phase transitions of a pure
generally behaves as an ideal gas, it provides, through thermodynamics, one of 𝑅𝑇 𝑑𝑃 Δ𝐻𝑚
the most important means of determining the properties of either a solid or a
substance. ; = …..(1) ⚫ Deviations from linearity occur as a result of the temperature variation of
⚫ Its derivation involves no assumptions and is thus valid for the general 𝑃 𝑑𝑇 T Δ𝑉𝑚 Δ𝑣𝑎𝑝 𝐻𝑚 and of nonideal gas behavior of the vapor.
liquid.
process of equilibrium between any two phases of the same substance.
- In order to use the Clapeyron equation, molar enthalpy of the process must be -eqn (1) becomes, Another useful form of eqn (5) may be obtained by integrating between specific
⚫ Let's start with the statement of phase equilibrium for a single pure substance 𝑑𝑃 Δ𝑣𝑎𝑝 𝐻𝑚 𝑃
in the liquid and vapor states.
known along with the equilibrium vapour pressure. = …..(2) limits:
- Hence, to integrate eqn (6) both Δ𝐻𝑚 and Δ𝑉𝑚 must be known as functions of 𝑑𝑇 𝑅𝑇 2 𝑃2 Δ𝑣𝑎𝑝 𝐻𝑚 𝑇2 −2
⚫ If the pressure and temperature are changed infinitesimally in such a way that
temperature and pressure; however, they may be considered constant over 𝑑 ln(
𝑃
) Δ𝑣𝑎𝑝 𝐻𝑚
‫ 𝑑 𝑃׬‬ln 𝑃′′ = 𝑅
‫… 𝑇𝑑 𝑇 𝑇׬‬..(6)
𝑑𝑃 1 1
equilibrium is maintained,
short temperature ranges. or at standard pressure of 1 atm, = 𝑎𝑡𝑚
= …..(3)
𝑑𝐺𝑉 = 𝑑𝐺1 ……(1) 𝑃 𝑑𝑇 𝑑𝑇 𝑅𝑇 2
- For solid-to-liquid transitions, Δ𝐻𝑚 is almost invariably positive. 𝑃2 Δ𝑣𝑎𝑝 𝐻𝑚 1 1
- Δ𝑉𝑚 is usually positive except in a few cases, such as H20, Bi, and Ga, where it
ln =− ( − ) ….(7)
𝑃1 𝑅 𝑇1 𝑇2
-Since this expression depends only on T and P, the total derivatives may be is negative.
written as - Expression (3) is known as the Clausius-Clapeyron equation.
𝜕𝐺𝑉 𝜕𝐺𝑉 𝜕𝐺1 𝜕𝐺1
⚫ It should be pointed out that the enthalpies of sublimation, fusion, and • It is immediately evident that one may calculate Δ𝑣𝑎𝑝 𝐻𝑚 (or Δ𝑠𝑢𝑏 𝐻𝑚 for
dP + dT = dP + dT ……..(2) vaporization are related at constant temperature by the expression sublimation from a similar expression) by measuring the vapor pressure of a
𝜕𝑃 𝑇 𝜕𝑇 𝑃 𝜕𝑃 𝑇 𝜕𝑇 𝑇 -For pressure expressed in other units, P" is used to indicate the numerical value
- We have Maxwell relations from thermodynamics, for 1 mol substance, of the pressure. substance at two different temperatures.
𝜕𝐺𝑚
= 𝑉𝑚 and
𝜕𝐺𝑚
= −𝑆𝑚 ……..(3) Δ𝑠𝑢𝑏 𝐻𝑚 = Δ𝑓𝑢𝑠 𝐻𝑚 + Δ𝑣𝑎𝑝 𝐻𝑚 ……..(7) • It is generally convenient to let P1 = 1 atm so that T1 = Tb.
𝜕𝑃 𝑇 𝜕𝑇 𝑃 This is as expected since enthalpy is a state function, and the same amount of -In order to make use of eq (3), integration is performed assuming Δ𝑣𝑎𝑝 𝐻𝑚 to be • Even if curvature exists in the plot, the enthalpy change may be calculated by
- From eq (3) we may partially substitute eqn (2), heat is required to vaporize a solid directly as to go through an intermediate independent of temperature and pressure, drawing a tangent to the curve at the temperature of interest.
139 𝑉𝑚 𝑉 𝑑𝑃 − 𝑆𝑚 𝑉 𝑑𝑇 = 𝑉𝑚 𝑙 𝑑𝑃 − 𝑆𝑚 𝑙 𝑑𝑇 ……..(4) melting stage to reach the final vapor state. 140 • Fairly good results are obtained if the equilibrium vapor density is not too high.
 Thermodynamics of Phase Transition One Component Systems

❑ During the change in Temperature, Pressure, and (ii). Solid ⇄ Vapour

Concentration, changes occurring at the phases as Phase Diagram
well as possibility of existence of multiple phases can Based on Clapeyron-Clausius Equation, Phase Rule: F = C-P + 2
be identified from the “Phase Diagram” D
𝑑𝑃 Δ 𝐻𝑠 Δ𝑆 For One Component System, F = 1-P + 2
= =
❑ In the Phase diagram, 𝑑𝑇 𝑇(𝑉𝑔𝑎𝑠 − 𝑉𝑠𝑜𝑙𝑖𝑑 ) (𝑉𝑔𝑎𝑠 − 𝑉𝑠𝑜𝑙𝑖𝑑 ) 1 (atm)
- Two variant is represented by “Area” F = 3-P
- One variant is represented by “Line” 𝑡𝑜 ℎ𝑎𝑣𝑒 + 𝑉𝑒, Δ𝑆-value; 𝑉𝑔𝑎𝑠 > 𝑉𝑠𝑜𝑙𝑖𝑑 (𝑉𝑔𝑎𝑠 − 𝑉𝑠𝑜𝑙𝑖𝑑 ) = +Ve
- Zero variant is represented by “dot” In this system, at lest one phase (P) will be there, then
𝑑𝑃
C

Pressure
Hence. become +Ve Solid
One variant system is indicative of following equilibrium 𝑑𝑇 Liquid F = 3-1 = 2
state;
Means, solid ⇄ Vapour system will be having +Ve slope Hence, degree of freedom, F for this system is “TWO”
(i). Liquid ⇄ Vapour Besides, slope of Δ 𝑆𝑠𝑜𝑙𝑖𝑑 > 𝑠𝑙𝑜𝑝𝑒 𝑜𝑓 Δ 𝑆𝑙𝑖𝑞𝑢𝑖𝑑
Besides, minimum degree of freedom for this system might have “ZERO”
Based on Clapeyron-Clausius Equation, (iii). Solid ⇄ Liquid B therefore,
A Vapour 0 = 3-P. (Or) P = 3
𝑑𝑃 Δ 𝐻𝑉 Δ𝑆 Based on Clapeyron-Clausius Equation,
= =
𝑑𝑇 𝑇(𝑉𝑔𝑎𝑠 − 𝑉𝑙𝑖𝑞𝑢𝑖𝑑 ) (𝑉𝑔𝑎𝑠 − 𝑉𝑙𝑖𝑞𝑢𝑖𝑑 ) It is indicating that in this system, “THREE” phases might be in equilibrium
𝑑𝑃 Δ 𝐻𝑓 Δ𝑆 Temperature at the same time/point.
= =
𝑑𝑇 𝑇(𝑉𝑙𝑖𝑞𝑢𝑖𝑑 − 𝑉𝑠𝑜𝑙𝑖𝑑 ) (𝑉𝑙𝑖𝑞𝑢𝑖𝑑 − 𝑉𝑠𝑜𝑙𝑖𝑑 )
𝑡𝑜 ℎ𝑎𝑣𝑒 + 𝑉𝑒, Δ𝑆-value; 𝑉𝑔𝑎𝑠 > 𝑉𝑙𝑖𝑞𝑢𝑖𝑑 (𝑉𝑔𝑎𝑠 − 𝑉𝑙𝑖𝑞𝑢𝑖𝑑 ) = +Ve
𝑚𝑜𝑠𝑡𝑙𝑦(𝑉𝑙𝑖𝑞𝑢𝑖𝑑 − 𝑉𝑠𝑜𝑙𝑖𝑑 ) = +Ve but sometimes, -Ve
𝑑𝑃
Hence. 𝑑𝑇
become +Ve 𝑑𝑃
Ex: Ice ⇄ Water: = +Ve or –Ve.
𝑑𝑇
Means, Liquid ⇄ Vapour system will be having +Ve slope
Consequently, its slope appearing almost vertical (B-D)
141 142

Phase Diagrams of One-component (water) System

Phase Diagrams of One-component (water) System
(Cont.1)
-In a Water system there are ICE, WATER, VAPOUR, three phases.
-Among which it have H2O as a single component.
Phase Diagram of Water (2) Lines:- Phase Diagram of Water
(a) Consider the following equilibrium
-Hence, Water system is single component system.
-Its Phase diagram can be explained as follows; C C
Liquid Water (l) ⇌ Water-vapor (g)
(1) Areas:-
Considering liquid and vapor Phase in the diagram,
Critical Pressure Critical Pressure
F = C-P + 2 ; F = 1-2 + 2 = 1
Considering only liquid Phase in the diagram, F = C-P + 2 ; F = 1-1 + 2 = 2 218 atm A 218 atm A
Fusion Curve b ⚫ Hence, this system is a univariant system. Fusion Curve b
⚫ Hence, this system is a bivariant system.
⚫ Line ‘OA’ is the indicative of this univariant system.
⚫ Area ‘AOC’ is the indicative of this bivariant system. Solid Ice Liquid Water Solid Ice Liquid Water
c y ⚫ Line ‘OA’ is explaining the relationship between Temperature and Pressure c y
⚫ In this region, at particular pressure, there is possibility of different
Vapour Pressure x for this equilibrium. This line is known as “Vapor Pressure Curve” Vapour Pressure x
temperature.
⚫ Lets consider the point ‘Y’, if we raise the Temperature to point “Z” system
Pressure

Pressure
⚫ Ex; at 1 atm, liquid phase exist any of the temperature between 273 K and Curve z Curve z
1 atm become Vapor. 1 atm
373 K.
X Y Z Z’ ⚫ On contrary, if we lower the Temperature to point “X” system become Ice. X Y Z Z’
⚫ Similarly, at particular temperature, there is a possibility of several
⚫ Similarly, at particular Temperature, if we raise the pressure system become
pressures.
⚫ Hence, to describe the point in the liquid phase, both Temperature and 4.58 mm O water. 4.58 mm O
⚫ On contrary, if we decrease the pressure, system become Vapor.
Pressure variants are to be determined. Hence, it is referred as bivariant Metastable Triple Water Vapour Metastable Triple Water Vapour
system. Equilibrium Point Equilibrium Point
m Liquid Water (l) ⇌ Water-vapor (g) m
⚫ Similar to liquid phase of Water, Vapor as well as Ice phases are also a A’ n t
A’ n t
bivariant systems. Sublimation s Critical Sublimation s Critical
- Hence, this equilibrium can exist only at particular Temperature and Pressure
⚫ In the phase diagram, area “AOB” and “BOC” are for Vapor and Ice, Curve Temperature Curve Temperature
respectively.
B u M.P. B u M.P.
⚫ Hence, by determining either Temperature or Pressure would led to the
0° 0.0075° 100° 374° determination of another one automatically due to this reason it is univariant 0° 0.0075° 100° 374°
system.
Temperature ⚫ Line “OA” is extending up to the critical temperature of 647 K (critical Temperature
143 144pressure: 218 atm). Afterwards, there is no liquid phase.
 Phase Diagrams of One-component (water) System Phase Diagrams of One-component (water) System
(Cont.2) (Cont.3)
(2) Lines:- (2) Lines:-
(b) Consider the following equilibrium
Phase Diagram of Water (c) Consider the following equilibrium
Phase Diagram of Water

Ice (s) ⇌ vapor (g) C Ice (s) ⇌ water (l) C

Considering solid and vapor Phase in the diagram, Considering solid and vapor Phase in the diagram,
F = C-P + 2 ; F = 1-2 + 2 = 1 Critical Pressure F = C-P + 2 ; F = 1-2 + 2 = 1 Critical Pressure
218 atm A 218 atm A
⚫ Hence, this system also a univariant system. Fusion Curve ⚫ Hence, this system also a univariant system. Fusion Curve
b b
⚫ Line ‘OB’ is the indicative of this univariant system. ⚫ Line ‘OC’ is the indicative of this univariant system.
⚫ Line ‘OB’ is explaining the relationship between Temperature and Pressure Solid Ice Liquid Water ⚫ Line ‘OC’ is explaining the relationship between Temperature and Pressure Solid Ice Liquid Water
for this equilibrium. This line is known as “Sublimation Curve” c
x
y for this equilibrium. This line is known as “Fusion Curve” c
x
y
⚫ Lets consider the point ‘S’, if we raise the Pressure to point “m” system Vapour Pressure Vapour Pressure

Pressure

Pressure
become Ice. Curve z - Hence, this equilibrium can exist only at particular Temperature and Pressure Curve z
1 atm 1 atm
⚫ On contrary, if we lower the Pressure to point “u” system become Vapor.
⚫ Similarly, at particular Pressure (n), if we raise the Temperature system X Y Z Z’ ⚫ (𝑉𝑤𝑎𝑡𝑒𝑟 − 𝑉𝑖𝑐𝑒 ) is –Ve for H2O (Clapeyron-Clausius Equation) hence, slope of X Y Z Z’
become Vapor (t). the Line “OC” is having –Ve.
⚫ On contrary, if we decrease the Temperature, system become Ice (n). 4.58 mm O 4.58 mm O
Metastable Triple Water Vapour ⚫ Means, while increasing the pressure, melting point of the ice is decreasing. Metastable Triple Water Vapour
Ice (s) ⇌ vapor (g) Equilibrium m Point Equilibrium m Point
A’ n t
A’ n t
- Hence, this equilibrium can exist only at particular Temperature and Pressure Sublimation s Critical Sublimation s Critical
B Curve u Temperature B Curve u Temperature
⚫ Hence, by determining either Temperature or Pressure would led to the M.P. M.P.
determination of another one automatically due to this reason it is univariant 0° 0.0075° 0° 0.0075°
100° 374° 100° 374°
system.
⚫ Line “OB” is extending lower up to 0 K.
𝑀𝑜𝑙𝑎𝑟 𝑒𝑛𝑡𝑟𝑜𝑝𝑦 𝑜𝑓 𝑠𝑢𝑏𝑙𝑖𝑚𝑎𝑡𝑖𝑜𝑛, Δ𝑠𝑢𝑏 𝑆𝑚 > Δ𝑣𝑎𝑝 𝑆𝑚 , Molar entropy of vaporization
Temperature Temperature
145 146
hence, slope of Line “OB” > slope of Line “OA”.

Phase Diagrams of One-component (water) System Phase Diagrams of One-component (water) System
(Cont.4) (Cont.5)
(2) Lines:- (3) Triple Point:-
Phase Diagram of Water Phase Diagram of Water
(d) Metastable equilibrium
C Considering the situation of Ice, Water and Vapor are in equilibrium, C
⚫ It is possible to freeze the water below to its freezing point under extreme
precaution and care. F = C-P + 2 ; F = 1-3 + 2 = 0
Critical Pressure Critical Pressure
⚫ At this state, water is referred as “Reversible Cold Water”. 218 atm A ⚫ Hence, this system is a Zero variant or Non-variant. 218 atm A
⚫ Though it is stable, become ice when stirred or addition of small amount of
Fusion Curve ⚫ Point ‘O’ is the indicative of this Zero variant system. And it is referred as Fusion Curve
ice. Hence it is referred as “Metastable Equilibrium”. b
“Triple Point”.
b

Solid Ice Liquid Water ⚫ At this point Lines ‘OA’, ‘OB’ and ‘OC’ are meeting together. Solid Ice Liquid Water
⚫ Line OA’ is the indicative of this Metastable equilibrium of Water phase- c y ⚫ By keeping the Triple point’s Pressure as constant, if we lower the c y
Vapour Pressure x Vapour Pressure x
Vapor phase. Temperature then both Vapor and water transform into Ice.
Pressure

Pressure
⚫ Besides, Line OA’ is above to Line OB of Ice (s) ⇌ vapor (g). Curve z Curve z
1 atm 1 atm
⚫ On contrary, by keeping the Temperature constant, if we increase the
⚫ Hence, at particular temperature, “Reversible cold water” will be having high X Y Z Z’ pressure then Vapor transform into Water. X Y Z Z’
pressure than Ice.
4.58 mm O ⚫ I.e., if there is a change in Temperature or Pressure of the Triple Point, One 4.58 mm O
⚫ Means, below to point “O”, Ice phase is stable, and water will be in Metastable Metastable Triple Water Vapour or Two phases do disappear. Metastable Triple Water Vapour
equilibrium (unstable). Equilibrium Point Equilibrium Point
m m
A’ n - Hence, this “Triple Point” can exist only at particular Temperature (273.0075 A’ n
t K) and Pressure (4.58 mm Hg) t
Sublimation s Critical Sublimation s Critical
B Curve u Temperature B Curve u Temperature
M.P. ⚫ Means, its temperature and pressure are not to be determined to fix the M.P.

0° 0.0075° system hence, this system is being a Zero variant system. 0° 0.0075°
100° 374° 100° 374°

Temperature Temperature
147 148
 Different Forms of Ice Two Component Systems (Solid-Solid)

Different forms of Ice When two component system will be having only one phase,
⚫ When pressure high as 50,000 atm is applied to freeze the water, seven
different types of Ice crystals are forming and are called as follows;
What is the phase of 𝐻2 𝑂 at 25 °C and 1 atm? Phase Rule: F = C-P + 2 = 2-1 + 2 = 3
⚫ 1. Ice-I (usual Ice), 2. Ice-II, 3. Ice-III, 4. Ice-IV, 5. Ice-V, 6. Ice-VI and 7.
Ice-VII. Hence, degree of freedom, F for this system is “THREE”
20,000 atm

⚫ Except Ice-I, all the other types are having high density. Ice VII So, system will be having Pressure, Temperature, and Concentration as minimum independent variables to describe it.

⚫ Except Ice-IV, all are highly stable. (Ice-IV does not exist in the diagram)
Ice VI Hence, 3-dimensional plot is required to explain the “Phase equilibria”

⚫ Given phase diagram is explaining the stability of each Ice at particular Ice V But, by making any one of the variable as constant, this issue can be overcome.
window of Pressure and Temperature. Ice II
Ice III In a SOILD-LIQUID system, impact of the pressure is less, it can be taken as a constant (ex: 1 atm),
Thereby system’s VAPOR PHASE can be omitted.

Pressure
⚫ Diagram further explains that three or two different types of Ices are in
equilibrium with the Water phase. C At this junction, system is referred as “CONDENSED SYSTEM”.
⚫ Besides, at 25,000 atm and 373 K, indicative of Ice-VII is melting into water.
Since, PRESSURE is constant for condensed system, so its phase rule can be given as,
25 °C and 1 atm
A F = C-P + 1 …..(1)
Ice I Liquid Water
eqn (1) is called as REDUCED PHASE RULE.

Now, when two component system will be having only one phase,
O Gaseous Water Phase Rule: F = C-P + 1 = 2-1 + 1 = 2

-50° C 0° C 100° C Hence, system can be described by taking two of the variable (T, V) to derive the Phase Diagram.
149 150
Temperature

Simple Eutectic Systems Simple Eutectic Systems (Cont.1)

⚫ At liquid phase, two components mix with each other well. Simple Eutectic System - “B” is the melting point of the Pure component “B”. Simple Eutectic System
⚫ There won't be any chemical reactions.
⚫ By freezing this liquid mixture, mixture of two solid components can be - Freezing point of component “B” is decreasing when it is mixed with
X Y Z X Y Z
obtained. component “A” and parabola “BE” is indicative of it. And it is referred as
⚫ In this mixture of solids, one can see their crystals are so close to each B FREEZING LINE of component “B”. B
other and this mixture is called “EUTECTIC” then the system is referred as A 𝐿3 A 𝐿3
“Simple Eutectic System” 𝐿1
Liquid Only 𝑇3 - Freezing Line “BE” is explaining the nature of equilibria between solid “B” and 𝐿1
Liquid Only 𝑇3
𝑇1 b liquid melt. 𝑇1 b
Liquid Ice II 𝐿4 a Liquid Ice II 𝐿4 a
Temperature

Temperature
+A 𝑇4 +A 𝑇4
- “A” is the melting point of the Pure component “A”. 𝑇2 𝐿2 Liquid - In this system (BE), Two phases such as Solid component “B” and Liquid melt 𝑇2 𝐿2 Liquid
b a 𝐿𝐸 +B are in equilibrium hence, b a 𝐿𝐸 +B
- Freezing point of component “A” is decreasing when it is mixed with 𝑇𝐸 F = 2-2 + 1 = 1 𝑇𝐸
𝑇𝐸 𝑇𝐸
component “B” and parabola “AE” is indicative of it. And it is referred as
E E
FREEZING LINE of component “A”.
Solid A + Solid B Hence, it is a UNIVARIANT System Solid A + Solid B
- Freezing Line “AE” is explaining the nature of equilibria between solid “A” and Means, determining either TEMPERATURE or CONCENTRATION is
liquid melt. sufficient to describe the system.
0 20 𝑋𝐸 60 80 100 0 20 𝑋𝐸 60 80 100
- In this system (AE), Two phases such as Solid component “A” and Liquid melt A Composition % B A Composition % B
are in equilibrium hence,
F = 2-2 + 1 = 1

Hence, it is a UNIVARIANT System

Means, determining either TEMPERATURE or CONCENTRATION is
sufficient to describe the system.

151 152
 Simple Eutectic Systems (Cont.2) Simple Eutectic Systems (Cont.3)

- Let's consider point “X”, on freezing until reaching the point 𝑳𝟏 , no change in
- Parabolas “AE” and “BE” are meeting at point “E”. Simple Eutectic System Simple Eutectic System
phase (liquid).
- at this point “E” two solid phases (A and B) and one liquid phase, in total - At 𝑳𝟏 , “X” will attain temperature 𝑻𝟏 , in here Solid “A” starts solidifying
X Y Z from the liquid. X Y Z
THREE PHASES are in equilibrium, hence
- Now Solid “A” is in equilibrium with liquid
B B
F = 2-3 + 1 = 0 A 𝐿3 A 𝐿3
𝐿1
Liquid Only 𝑇3 F = 2-2 + 1 = 1 (Univariant) 𝐿1
Liquid Only 𝑇3
Hence, it is a ZEROVARIANT or NON-VARIANT System. 𝑇1 b 𝑇1 b
Liquid Ice II 𝐿4 a Liquid Ice II 𝐿4 a

Temperature

Temperature
This point “E” is referred as “EUTECTIC POINT”. - On further freezing lead to lowering the temperature along with phase
+A 𝑇4 +A 𝑇4
𝑇2 𝐿2 Liquid change, means Solid “A” become crystal. 𝑇2 𝐿2 Liquid
At this point, two solid components are getting solidified/crystalized at the b a 𝐿𝐸 +B b a 𝐿𝐸 +B
same time from the liquid melt. 𝑇𝐸 - Now in solution composition of Solid “B” is increasing, when reaching 𝑇𝐸
𝑇𝐸 𝑇𝐸
E temperature 𝑻𝟐 , Solid “A” will be in equilibrium with concentration “a” E
There is no liquid being present below to this point “E” - Hence, with respect to temperature, Solid “A” is equilibrium with liquid’s
Solid A + Solid B Solid A + Solid B
concentration.
Temperature at this point “E” is referred as EUTECTIC TEMPERATURE (𝑇𝐸 )
0 20 𝑋𝐸 60 80 - When reaching EUTECTIC POINT (E), solid “B” also started to become 0 20 𝑋𝐸 60 80
And this 𝑇𝐸 is the lowest freezing point of this system 100 100
crystal.
A Composition % B - Now, there are THREE Phases are in equilibrium (A-Liquid-B); ZERO A Composition % B
Above to the Parabolas “AE” and “BE” only one phase, liquid is present VARIANT.

F = 2-1 + 1 = 2 - On further freezing, both A and B become crystals with the composition of
𝑿𝑬 .
Hence, it is a BIVARIANT System. - Temperature remains constant until complete crystallization of A and B.
Means, determining point in this area, both TEMPERATURE and
CONCENTRATION are sufficient to describe the system. - Besides, freezing below 𝑻𝑬 , system will be having two phases (crystal A and
153 154B): UNIVARIANT.
- Similar explanation for Solid B.

Phase Diagrams of Two Component: Pb-Ag System

Freezing Mixtures
(Example for Simple Eutectic System)
Phase Diagram of Pb-Ag System
- Freezing Point of ICE is 273 K.
B 961° - Let's consider adding a SALT to ICE.
- When ICE is meting, resultant water will be having salt composition too Ice-Melted Away
(SALT SOLUTION). Frozen Road
Liquid Melt
- Now, ICE, SOLID SALT and SALT SOLUTION will be in equilibrium.
A = 600 K; B = 1234 K; C = 576 K.
- F = 2-3 + 1 = 0 (ZEROVARIANT)
Eutectic Concentration = 2.6 % Ag, 97.4 % Pb. p
A - Possibility of existence of the above equilibrium is only at “Eutectic Point”. Pouring Freezing Mixture
327° - Hence, system will be moving towards the “Eutectic Point”.
Temperature

Pattinson's Process, or pattinsonisation is a method for

Temperature

Liquid + Solid Silver - Besides, ICE will get melt, issue water and the salt do get dissolve in it.
removing silver from lead discovered by Hugh Lee Pattinson in 1829 and S. No System Eutectic Eutectic
- During these processes, TEMPERATURE of the system go down till reaching
patented in 1833.
Liquid q the “Eutectic Point”. Temperature, K Composition
+ (% Salt)
The process is dependent on the fact that lead which has least silver in it
- TEMPERATURE become constant once, “Eutectic Point” is reached.
solidifies first on liquefaction, leaving the remaining liquid richer in silver. Solid Pb - This constant Temperature is the lowest temperature of the system. 1 KI + Ice 250 52
303°
In the Pattinson’s process, this phase diagram is used to increase the Ag% in C 2 NaCl. 2H2O + Ice 251 23
Solid Solid Silver
the Argentiferous ore.
Lead + + - Based on the given explanation, water can be freeze below 273 K.
- Hence this ICE + SALT is referred as “Freezing Mixtures” 3 NH4Cl + Ice 257 20.1
Eutectic Eutectic
- Some of the “Freezing Mixtures” are given in the Table. 4 NH4NO3 + Ice 255 43
100% Pb 2.6% Ag 100% Ag
0% Ag Composition 0% Pb 5 NaNO3 + Ice 255 33.3
155 156 6 CaCl2. 6H2O 217 15.2
 Cooling Curves and Thermal Analysis Drawing Thermal Analysis Graph

a ⚫ In order to determine the equilibrium between the SOILD and

LIQUID Phase of the TWO COMPONENT system, Thermal analysis a Phase Diagram
A is in use and it is based on the Freezing parabolas. B Different Compositions of TWO different components….

- Freezing Parabola can be obtained by plotting Time Vs. Temperature. (i) 100% + 0% B (ii) 80% + 20% B
Readings can be taken while freezing a LIQUID at different A
d intervals of TIME. (iii) 60% + 40% B (iv) 40% + 60% B
b
Temperature

Temperature
- (A): During cooling, Temperature is gradually decreasing (a-b). Liquid Solution
(v) 20% + 80% B (vi) 0% + 100% B
- At point “b”, solid getting separated (solidification) d B
b
c ⚫ Liquid solutions are prepared as given above.

Temperature
- Now, Both SOLID and LIQUID are having same composition and will
e be in equilibrium. e ⚫ Freezing lines are drawn for each solution. Solid A + Solid B +
Liquid Liquid
F = 1-2 + 1 = 0 (ZEROVARIANT) ⚫ Simple Eutectic Systems will be having two barriers in general;
x O y
Time - Means, there is no temperature change till complete freezing Time ⚫ By connecting the “UPPER BARRIER” points Liquid line is obtained. Solid A and Solid B
(b-d). Besides, rate of freezing is ZERO.
- On continuing the freezing, gradual decrease in Temperature (d-e). ⚫ By connecting the “LOWER BARRIER” points Solid line is obtained.
A: Pure Components B: Solution of Two Components
A (100%) B (100%)
-If the composition of solid obtained at point “b” is different with the ⚫ Point “O” is having only “ONE BARRIER” point and which is indicative of
Composition %
Liquid means, Pure compound A, Pure compound B and mixture Pure AB will be having
F = 1-2 + 1 = 0 (ZEROVARIANT) F = 2-2 + 1 = 1 (UNIVARIANT) F = 2-2 + 1 = 1 (UNIVARIANT)
only one barrier point as EUTECTIC POINT.

-This difference in composition between the Solid and Liquid at point

“b” causing the interference in the cooling rate. Means, temperature
drop is too slow (b-c).
-Besides, temperature remains constant (b-c), when Solid and Liquid
157 compositions become equal (Point “c”). 158

Two Component Systems (Liquid-Liquid) Completely Miscible Liquid-Liquid Systems: Ideal Solutions

(1) One liquid is mixed with another liquid at all different concentrations Ideal Solution: Liquid-Liquid system which obeys the Raoult’s law is referred as
Ideal solution.
While mixing the two different liquids together:-
In this Liquid-Liquid system, Liquid is in equilibrium with its vapor phase, Examples:
(i) One liquid is mixed with another liquid at all different concentrations.
Ex: Methanol-Water mixture F = C-P + 2 ; F = 2-2 + 2 = 2
Benzene Toluene
⚫ Hence, this system is a Bivariant.
(ii) One liquid can mix with another partially. Water Methanol
Ex: Phenol-Water mixture ⚫ Hence, out of Temperature, Pressure and Concentration, any of the two
variants need to be fixed to describe the system. n-hexane n-heptane

(iii) Completely immiscible with each other ⚫ Besides, in these systems, Vapor pressure is dependent of solution Benzene Ethylene chloride
Ex: Benzene-Water mixture concentration.
Chloro benzene Bromo benzene
(A) Ideal Solutions:
Ethylene chloride Ethylene bromide
Raoult’s law:
Ethylene bromide Propylene bromide
At constant temperature, partial vapor pressure (𝑃𝐴 ) of the easily volatile
component of the solution is equivalent to the multiplication of VAPOR n-butyl chloride n-butyl bromide
PRESSURE (𝑃𝐴0 ) of the Component with its MOLE FRACTION (𝑋𝐴 ).
Carbon tetra chloride Silicon tetra chloride
𝑃𝐴 = 𝑃𝐴0 𝑋𝐴 ; 𝑃𝐵 = 𝑃𝐵0 𝑋𝐵
Cyclohexane Carbon tetra chloride
Here, 𝑋𝐴 𝑎𝑛𝑑 𝑋𝐵 are mole fractions,
𝑃𝐴0 and 𝑃𝐵0 are vapor pressure of each components.
159 160 𝑃𝐴 and 𝑃𝐵 are partial vapor pressures.
 Fractional Distillation (Not in Syllabus) Azeotropic Mixtures (Not in Syllabus)

Phase Diagram

𝐷
Vapour
𝑇𝐴 Composition 𝑃𝐴0
𝑃𝐵0

Vapour Pressure
𝑇1

Temperature, T
𝑇 0 X1 X 𝑍 Y Y1 1

Mole Fraction
Thermometer

Cork 𝑇2
Water Outlet
Clamp
𝑇𝐵
Fractionating
Column 𝑃𝐴0
Cork Water 0 𝑦 𝑥 𝑥2 𝑥1 𝑧 1

Vapour Pressure
Condenser
t 𝑃𝐵0
Distilation Flask Mole Fraction of “B” Composition 𝐶
Cold Water
Mixture of Acetone
inlet
and 0 X X1 𝑍 Y1 Y 1
Water
161 Acetone 162 Mole Fraction

Obtaining Absolute Alcohol from Azeotropic Mixtures

Partially Miscible Liquid-Liquid Systems: Conjugate Solutions
(Not in Syllabus)

Lets consider, mixture of two liquids A and B:-

(i) Liquid “A” can be completely dissolved in liquid “B” thereby a saturated solution can be
obtained.

(ii) Likewise, Liquid “B” can be completely dissolved in liquid “A” thereby a saturated solution can
be obtained.

(iii) Now at the equilibrium, these two saturated solutions are referred as conjugate solutions.

(iv) In some of the systems, while raising the temperature, solubility of one in another become
increasing. When reaching a particular temperature, system became a HOMOGENOUS
MIXTURE. And this temperature is referred as Upper Critical Solution Temperature (UCST).

(v) In some of the systems, while decreasing the temperature, solubility of one in another become
increasing. When reaching a particular temperature, system became a HOMOGENOUS
MIXTURE. And this temperature is referred as Lower Critical Solution Temperature (LCST).

(ii) Few systems do exhibit both UCST and LCST.

Ex: Phenol-Water system

163 164
 Phase Diagrams of Two Component: Phenol-water System
Phase Diagrams of Two Component: Phenol-water System
(Cont.)
Lets consider, mixing Phenol with Water, we get mixture out of two components. ⚫ Concerning point “D”, when concentration of Water is lower than “a” or higher
Phase Diagram of Phenol-Water System Phase Diagram of Phenol-Water System
When the added Phenol exceeds 8% we get the following two layers:- than “b”, system do exist in homogenous solution (°Y or °W) (one phase:
bivariant).
(i) Water dissolved in Phenol
⚫ On contrary, when the concentration of Water is in between “a” and “b” then
(ii) Phenol dissolved in Water 1. Phenol in Water and
2. Water in Phenol equilibrium systems do exist (two phases).
⚫ Parabola “AB” is indicative of Water’s increasing solubility in Phenol while 𝑩 °Z 𝐵 °Z
68.1 T= 68.1
increasing the temperature. ⚫ At point “B” two conjugate solutions are having the same concentration,
-here two conjugate solutions (two phases) and one homogenous
⚫ Parabola “CB” is indicative of Phenol’s increasing solubility in Water while solution (one phase) are in equilibrium,
increasing the temperature. - hence, F = C-P + 2 ; F = 2-3 + 1 = 0 (Zerovariant)

Temperature °C

Temperature °C
⚫ Hence, point “B” is referred as “Zerovariant point”
⚫ Both parabolas, “AB” and “CB” are meeting at point “B” and this point is ⚫ At this point “B” the composition between Phenol and Water as follows;
referred as Upper Critical Solution Temperature (UCST). 33% Phenol and 67% Water, Temperature: 341.3 K.

⚫ Here, area outside of “ABC” is indicative of completely miscible mixture of 𝑫 Examples: System Critical Solution 𝐷
Phenol-Water system (one phase). °Y °W °Y °W
a b Temperature (K) a b
- hence, F = C-P + 2 ; F = 2-1 + 1 = 2 (Bivariant) °x °x
Aniline-Hexane 332.6
⚫ Hence, out of Temperature, Pressure and Concentration, any of the two
variants need to be fixed to describe the system Phenol-Isopentane 336.5
⚫ Area inside of “ABC” is indicative of 1. Phenol in Water and 2. Water in Phenol
equilibrium systems (two phase). 𝐴 𝐶 CS2-CH3OH 313.5 𝐴 𝐶
- hence, F = C-P + 2 ; F = 2-2 + 1 = 1 (Univariant)
Water 33% Phenol Aniline-Water 440.0 Water 33% Phenol
⚫ Hence, determining either Temperature or Concentration is sufficient.
100% 100% 100% 100%
165 Mass % Phenol 166 Aniline-Benzene 332.5 Mass % Phenol

Two Component Systems (Liquid-Liquid) Distribution Law/ Nernst’s Distribution Law

Distribution of Solute X between Solvent A and B

While mixing the two different liquids together:-
Solute X
(i) One liquid is mixed with another liquid at all different concentrations.
Ex: Methanol-Water mixture ❑ If we take two immiscible solvents A and B in a beaker, they form separate
layers.
❑ When a solute X which is soluble in both solvents is added, it gets distributed Solvent A
(ii) One liquid can mix with another partially. or partitioned between them.
Ex: Phenol-Water mixture ❑ Molecules of X pass from solvent A to B and from solvent B to A.
❑ Finally, a dynamic equilibrium is set up.
❑ At equilibrium, the rate, at which molecules of X pass from one solvent to the Solvent B
(iii) Completely immiscible with each other other is Balanced.
Ex: Benzene-Water mixture
Distribution of solute X between solvent A and B.

𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑋 𝑖𝑛 𝐴 Table: Illustration of constancy of concentration ratio of a solute between layers of Two
= 𝑎 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝐶𝑜𝑛𝑐𝑛𝑒𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑋 𝑖𝑛 𝐵 immiscible solvents.
Concentration of Acid in Concentration of Acid in 𝑪𝟏
-For example, the following results from the distribution of succinic acid between
ether and water illustrate the constancy of the ratio of the concentrations in Ether (C1) Water (C2) 𝑪𝟐
each layer.
0.0046 0.024 0.191
0.013 0.069 0.188
0.022 0.119 0.185
0.031 0.164 0.189
167 168
 Statement of Nernst’s Distribution Law Solved Problem

Distribution of Solute X between Solvent A and B

❑ Nernst (1891) studied the distribution of several solutes between different

appropriate pairs of solvents.
❑ He gave a generalization which governs the distribution of a solute between Solute X
two non-miscible solvents.
❑ This is called Nernst’s Distribution law (or Nernst’s Partition law) or simply
Distribution law or Partition law.
Solvent A
If a solute X distributes itself between two immiscible solvents A and B at
constant temperature and X is in the same molecular condition in both solvents,

𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑋 𝑖𝑛 𝐴 Solvent B
= 𝐾𝐷
𝐶𝑜𝑛𝑐𝑛𝑒𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑋 𝑖𝑛 𝐵
-If C1 denotes the concentration of the solute in solvent A and C2 the
concentration in solvent B, Nernst’s Distribution law can be expressed as

𝐶1
= 𝐾𝐷
𝐶2
The constant KD (or simply K) is called the Distribution coefficient or
Partition coefficient or Distribution ratio.

169 170

Solved Problem Solved Problem

171 172
 Solubilities and Distribution Law Solved Problem

Distribution of Solute X between Solvent A and B

-When a solute is shaken with two non-miscible solvents, at equilibrium both the Solute X
solvents are saturated with the solute.

-Since the solubility also represents concentration, we can write the

distribution law as,
Solvent A

𝐶1 𝑆1
= = 𝐾𝐷
𝐶2 𝑆2 Solvent B
-where S1 and S2 are the solubilities of the solute in the solvents.

Hence knowing the value of the Distribution coefficient (KD) and the solubility of
solute in one of the solvents, the solubility of solute in the second solvent can be
calculated.

173 174

Explanation of Distribution Law Limitations of Distribution Law

❑ This is an equilibrium law.

❑ When the distribution of the solute X has reached dynamic equilibrium,
the rate (R1) at which molecules of X pass from solvent A to B is proportional ❑ The conditions to be satisfied for the application of the Nernst’s Distribution law are:
to its concentration (C1) in A.
❑ The rate (R2) at which molecules of X pass from solvent B to A is proportional
to its concentration (C2) in B. 1. Constant temperature
❑ Also, at equilibrium, the rate of migration of solute from one solvent to the -The temperature is kept constant throughout the experiment.
other is equal.
2. Same molecular state
Thus, we have, -The molecular state of the solute is the same in the two solvents.
𝑅1 ∝ 𝐶1 ; Solvent A C1 C1 C1 -The law does not hold if there is association or dissociation of the solute in one of the solvents.
Or 𝑅1 = 𝑘1 × 𝐶1 where 𝑘1 is a constant
3. Equilibrium concentrations
Again 𝑅2 ∝ 𝐶2 ; Solvent B C2 -The concentrations of the solute are noted after the equilibrium has been established.
C2 C2
Or 𝑅2 = 𝑘2 × 𝐶2 where 𝑘2 is a constant
4. Dilute solutions
Since at equilibrium 𝑅1 = 𝑅2 -The concentration of the solute in the two solvents is low.
-The law does not hold when the concentrations are high.
At equilibrium, the number of molecules of “X” passing from solvent “A” into “B” is
𝑘1 × 𝐶1 = 𝑘2 × 𝐶2
proportional to its concentration in “A” and vice versa. Also, the rate of migration of 5. Non-miscibility of solvents
𝐶1 𝑘1 solute molecules from A to B and B to A is equal (Illustration). -The two solvents are non-miscible or only slightly soluble in each other.
Or = = 𝐾𝐷
𝐶2 𝑘2 -The extent of mutual solubility of the solvents remains unaltered by the addition of solute to them.
𝐶1
Or = 𝐾𝐷
𝐶2
This is the Nernst’s Distribution law equation. Since k1 and k2 are constants at
the same temperature, the distribution coefficient KD is also constant if
temperature is fixed.
175 176
 How is Distribution Law Modified by Change in Molecular State Solved Problem

⚫ It was pointed out by Nernst that C1/C2 is constant only if the solute exists as Distribution diagram when the solute is
simple molecules in the two solvents. Taking nth root on both sides in eqn associated in one solvent
⚫ If the solute undergoes association or dissociation in one of the solvents, it is (2) we get,
found that C1/C2 is not constant.
⚫ In these cases, distribution law applies only to that part of the solute which is 𝐶3 No Change
present as simple molecules. 𝑛 = 𝑛
𝐾𝐶 ……………(3)
𝐶2

(1) When Solute undergoes Association Dividing equation (1) by (3) we get, Solvent
A
⚫ Suppose the solute is present as simple molecules X in solvent A. 𝐶1 𝐾𝐷
⚫ In solvent B, n molecules of X associate to form Xn molecules. 𝑛
= 𝑛
= 𝐾 (𝑎 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡)
⚫ If a few single molecules X are also present in solvent B the equilibria that 𝐶2 𝐾𝐶
exist in the two solvents are shown in Figure.
Thus, when association occurs in one
-Let C1 be concentration of X in solvent A.
solvent, the distribution equation is
Solvent
modified as B
-C3 be concentration of X in solvent B. And C2 be concentration of Xn in solvent B.
Association
Applying distribution law to the equilibrium 𝐶1
𝑛 = 𝐾𝐷
X in solvent A ⇌ X in solvent B, we have, 𝐶2
𝐶1
= 𝐾𝐷 ……………(1)
𝐶2
Note: Since the solute exists largely as associated molecules, the total
-Applying the mass law to the chemical equilibrium, concentration of X determined experimentally in solvent B is taken as the
nX ⇌ Xn concentration of the associated molecules Xn.
[𝑋]𝑛 𝐶3𝑛
177 = 𝐾𝑐 or = 𝐾𝑐 ……………(2) 178
[𝑋𝑛 ] 𝐶2

How is Distribution Law Modified by Change in Molecular State

Henry’s Law – A Form of Distribution Law
(Cont.)
(2) When Solute undergoes Dissociation Henry’s law states: at a constant temperature the solubility of a gas in a liquid is Distribution diagram illustrating Henry’s law
proportional to the pressure of the gas above it.
⚫ Suppose the solute is present as normal molecules X in solvent A and it Distribution diagram when dissociation occurs in one solvent
Henry’s law may be mathematically expressed as C = kP
dissociates into A + B in solvent B. -where C is the solubility (or concentration), k is a constant, and P is the pressure of the Gas in Space
⚫ The equilibria set up in the two solvents are shown in Figure. gas, k is called Henry’s constant. Phase B
⚫ Let C1 be the concentration of X in solvent A and C2 the total concentration of
X (dissociated and undissociated) in solvent B. Explanation:
⚫ If the degree of dissociation in solvent B is x, No Change ⚫ Henry’s law is, in fact, a form of Distribution law.
⚫ If a vessel containing a liquid and a gas is shaken, at equilibrium the gas can be Phase A
X⇌A+B regarded as distributed between the liquid (Phase A) and the space above (Phase B).
Gas Dissolved in (Liquid)
1-x x x Solvent A ⚫ The influence of partial pressure on solubility is utilized in making carbonated
beverages like beer, champagne, and many soft drinks. Liquid
⚫ So called ‘soda water’ is bottled under a carbon dioxide pressure of about 4 atm. When
-Hence the concentration of the undissociated (or normal) molecules in solvent B
the bottle is opened to the air, the partial pressure of CO2 above the solution is
is C2 (1 – x). decreased (about 0.001 atm), and CO2 bubbles out. CO2 gas
Atmospheric
Pressure CO2 partial
-Applying distribution law to normal molecules in the two solvents, -Let C1 be the concentration of the gas in phase B 4 atm
released to pressure
-C be the concentration of the gas in phase A 1 atm 0.001 atm
𝐶1 Applying the Distribution law
= 𝐾𝐷 𝐶
= 𝐾𝐷 (a constant)
𝐶2 (1 − 𝑥) Solvent B 𝐶1
We know that molar concentration of gas is proportional to its pressure, P. CO2
⚫ This is the modified distribution law equation when there is dissociation in one 𝐶 dissolved
Hence, = 𝑘 (a constant) or 𝐶 = 𝑘 × 𝑃 in Water
𝑃
of the solvents.
⚫ A case of this type arises in the distribution of a weak acid (e.g., succinic acid Dissociation
This is Henry’s Law equation. Like distribution law, Henry’s law holds good for dilute
or oxalic acid) between ether and water. solutions of gases which do not react with the solvent. (a) (b) (c)
⚫ C1 and C2 can be determined by direct titration of the two layers against
standard alkali solution. -If a mixture of gases is in contact with a liquid, the partial pressure of an individual gas, (a) CO2 gas at 4 atm in equilibrium with dissolved CO2 resulting in high solubility of CO2 ;
⚫ The value of x can be found by measuring electrical conductance of solution in not their total pressure, determines the mass of each gas dissolving. (b) In opened bottle pressure is released to 1 atm and hence equilibrium shifted upward, gas
solvent B. -In such a case, the solubility of each gas is proportional to its partial pressure. bubbles evolved causing brisk effervescence;
(c) Partial pressure of CO2 in air being 0.001 atm, practically the whole of CO2 is removed from
179 180
solution, leaving the soft drink flat as the equilibrium is established.
 Solved Problem Solved Problem

181 182

Determination of Equilibrium Constant (Kc) from

Study of Complex Ions
Distribution Co-efficient
Determination of Equilibrium Constant
Equilibrium Constant (Kc) : In a reaction at equilibrium, the equilibrium concentrations of all
reactants and products can be measured. The equilibrium constant (K) is a mathematical
relationship that shows how the concentrations of the products vary with the concentration of
the reactants. Water
◆ Distribution law helps in determining the equilibrium constant of a reaction when one of the I2 + KI ⇌ KI3 Layer If the value of Kc comes out to be constant by taking different concentrations of KI and I2 to
reactants is soluble in two non-miscible solvents. start with, it proves the existence of KI3 or the complex ion 𝐼3− .
◆ Let us illustrate by taking example of the reaction when potassium iodide reacts with iodine to
form potassium triiodide. KI + I2 ⇌ KI3
I2 𝐼2 + 𝐼 − ⇌ 𝐼3−
This reaction can be carried in water, while iodine is soluble in both water and benzene. Benzene
Layer
Thus, The distribution law is, therefore, helpful in the study of complex ions.
Procedure: (1)To find the distribution coefficient of I2.
-Iodine is shaken with water and benzene in a bottle. Other examples of complex formation are:
𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐼2 𝑖𝑛 𝑊𝑎𝑡𝑒𝑟
-The concentration of iodine in the two layers is then determined by titration against standard = 𝐾 (Distribution Co − efficient)
𝐶𝑜𝑛𝑐𝑛𝑒𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝐼2 𝑖𝑛 𝐵𝑒𝑛𝑧𝑒𝑛𝑒
thiosulphate solution. Thus, CuSO4 + 4NH3 ⇌ CuSO4 .4NH3 or [Cu(NH3)4]2+ 𝑆𝑂42−
𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐼2 𝑖𝑛 𝑊𝑎𝑡𝑒𝑟 ∴ Conc of I2 (free) in water layer (a) = K × b
= 𝐾 (Distribution Co − efficient) Hence conc of KI3 in water layer = c – Kb C6H5NH2 + HCl ⇌ C6H5N𝐻3+ 𝐶𝑙 −
𝐶𝑜𝑛𝑐𝑛𝑒𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝐼2 𝑖𝑛 𝐵𝑒𝑛𝑧𝑒𝑛𝑒
∴ Conc of KI in water layer = a – (c – Kb) = a – c + Kb
(2) To find the equilibrium constant (Kc) using the value of K.
-A solution of KI of concentration a is shaken with iodine in a bottle. We can now say that the equilibrium constant (Kc) of the reaction
-To this is added some benzene and shaken.
-On standing, the mixture separates into two layers. I2 + KI ⇌ KI3
-The equilibria that are set up are shown in Figure.
-The concentration of iodine is determined in the two layers by titration against standard
[𝐾𝐼3 ] 𝑐 − 𝐾𝑏
𝐾𝑐 = =
thiosulphate solution. 𝐾𝐼 [𝐼2 ] 𝑎 − 𝑐 + 𝐾𝑏 𝐾𝑏
-Let ‘b’ be the concentration of I2 in benzene layer, ‘c’ be the concentration of I2 in water layer Note:
which is really the total of the concentration of free I2 and KI3. -The square brackets denote concentrations in water layer.
-K is the value of distribution coefficient of iodine between water and iodine as determined
183 -Since all the quantities on the right-hand side are known, the 184
earlier. equilibrium constant (Kc) can be calculated.
 Extraction Applications of Distribution Law

Extraction in a Separatory Funnel Stationary

Details of a chromatography column liquid film Mobile liquid There are numerous applications of distribution law in the laboratory as well
EXTRACTION WITH A SOLVENT:
Ether as in industry. Here we will discuss some more important ones by way of
⚫ The extraction (removal by a solvent) of an organic substance from an aqueous solution is recapitulation.
probably the most important application of Distribution law. Solvent
⚫ The process is carried by shaking the aqueous solution with a immiscible organic solvent, say ether + (1) Solvent Extraction
(ethoxyethane), in a separatory funnel. Mixture
Ether Solid
⚫ The distribution ratio being in favour of ether, most of the organic substance passes into ether Coloured ⚫ This is the process used for the separation of organic substances from
layer. layer support
bands aqueous solutions.
⚫ On standing, the aqueous and ether layers separate in the funnel. The lower aqueous layer is run ⚫ The aqueous solution is shaken with an immiscible organic solvent such as
out, leaving the ether layer behind. Aq. Solution Ether Silica
Water ether (or benzene) in a separatory funnel.
⚫ This is then transferred to a distillation flask. Ether is distilled over while the organic substance of A layer ⚫ The distribution ratio being in favour of ether, most of the organic
is left as residue in the flask. layer
Band of substance passes into the ethereal layer.
⚫ If desired, the process may be repeated with aqueous layer left after the first extraction with a
fresh quantity of the solvent. Solute 1 ⚫ The ethereal layer is separated and ether distilled off. Organic
Glass
⚫ The other common solvents used for extraction are hexane, benzene, chloroform, acetone, carbon substanceis left behind.
wool
disulphide, etc. ⚫ The process of extraction is more efficient if the solvent is used in a
⚫ The greater the distribution ratio is in favour of the organic solvent, the greater will be the Band of number of small portions than in one whole lot.
amount extracted in any one operation. Step 1 Step 2 Solute 2 ⚫ Thus multiple extraction is preferred to simple extraction.
Ether is added to Aq. On Shaking, A distributes ⚫ The multiple extraction is also the basis of the industrial counterflow
Solution of A between Ether and Water solvent extraction.
layer ⚫ A dilute solution of the substance enters at the top of a column or tower.
In partition chromatography, the liquid
Step 3 ⚫ At the same time the extracting solvent enters at the bottom.
film on the solid support is the stationary
⚫ As the aqueous solution and the solvent pass each other, the solute
Ether layer is separated (a) (b) (c) phase. The second phase is an immiscible
distributes itself in favour of the solvent.
by running out the water solvent flowing down. Each solute (S and
⚫ Since the process of extraction is repeated many times at different
layer S ) is distributed between the stationary
levels in the tower, maximum quantity of substance is removed in the
liquid film and the mobile liquid phase. The
solvent.
185 186 solute (say S ) with higher distribution ratio
comes down first.

(2) Partition Chromatography (3) Desilverization of Lead (Parke’s Process)

⚫ This is a modern technique of separating a mixture of small amounts of organic materials.

⚫ A paste of the mixture is applied at the top of a column of silica soaked in water.
⚫ When molten zinc is added to molten lead containing silver (argentiferous lead), zinc and lead form
⚫ Another immiscible solvent, say hexane, is allowed to flow down the column.
immiscible layers and silver is distributed between them.
⚫ Each component of the mixture is partitioned between the stationary liquid phase (water) and the
⚫ Since the distribution ratio is about 300 in favour of zinc at 800º C, most of silver passes into the zinc
mobile liquid phase (hexane).
layer.
⚫ The various components of the mixture are extracted by hexane in order of their distribution
⚫ On cooling the zinc layer, an alloy of silver and zinc separates.
coefficients.
⚫ The Ag-Zn alloy is distilled in a retort when zinc passes over leaving silver behind.
⚫ Thus the component with the highest distribution coefficient is first to move down in the flowing
⚫ The lead layer still contains unextracted silver.
hexane which is collected separately.
⚫ This is treated with fresh quantities of molten zinc to recover most of the silver.
⚫ Similarly, a component with a lower distribution ratio comes down later and is received in another
vessel.

187 188
 (4) Confirmatory Test for Bromide and Iodide (5) Determination of Association

⚫ When a substance is associated (or polymerized) in solvent ‘A’ and exists as

simple molecules in solvent B, the Distribution law is modified as
⚫ The salt solution is treated with chlorine water.
⚫ Small quantity of bromine or iodine is thus liberated. 𝑛 𝐶𝐴
⚫ The solution is then shaken with trichloromethane (chloroform). =𝐾 ...(1)
𝐶𝐵
⚫ On standing chloroform forms the lower layer.
⚫ The free bromine or iodine being more soluble in chloroform concentrates into
the lower layer, making it red for bromine and violet for iodine. -when ‘n’ is the number of molecules which combine to form an associated molecule.

-Suppose benzoic acid is associated to bimolecules, (C6H5COOH)2, in benzene and is

present as simple molecules in aqueous layer.

Then equation (1) can be written as follows where n = 2.

−2 𝐶𝐵𝑒𝑛𝑧𝑒𝑛𝑒
=𝐾 ...(2)
𝐶𝐴𝑞𝑢𝑒𝑜𝑢𝑠

-The concentrations in benzene and aqueous layer are determined experimentally.

-If the under root of the concentration in benzene divided by the concentration in
aqueous layer gives a constant value benzoic acid exists as bimolecules (dimer) in
benzene.

189 190

(6) Determination of Dissociation (7) Determination of Solubility

⚫ Suppose a substance ‘X’ is dissociated in aqueous layer and exists as single ⚫ Suppose the solubility of iodine in benzene is to be determined.
molecules in ether. ⚫ Iodine is shaken with water and benzene.
⚫ At equilibrium concentrations of iodine in benzene (Cb) and water (Cw) are found
⚫ If ‘x’ is the degree of dissociation (or ionisation), the distribution law is experimentally and the value of distribution coefficient calculated.
modified as
𝐶𝑏
𝑪𝟏 = 𝐾𝐷
=𝑲 𝐶𝑤
𝑪𝟐 (𝟏 − 𝒙)
𝑆𝑏
Where, But, = 𝐾𝐷
𝑆𝑤
C1 = concentration of X in benzene
C2 = concentration of X in aqueous layer
where Sb = solubility in benzene; and Sw = solubility in water.
⚫ The value of ‘x’ can be determined from conductivity measurements, while C1 and
C2 are found experimentally. If the solubility of iodine in water (Sw) is known, the solubility in benzene can be
calculated.
⚫ Thus the value of ‘K’ can be calculated. Using this value of K, the value of ‘x’ for
any other concentrations of ‘X’ can be determined.

191 192
 (8) Deducing the Formula of a Complex Ion (𝑰𝟑− ) (9) Distribution Indicators

⚫ Some iodine is added to a solution of KI and the reaction mixture shaken with benzene.

(a) The [I2] in water layer can be found knowing the value of KD (determined separately) and
concentration of iodine in benzene (determined by titration against thiosulphate).

(b) The total concentration of iodine, [I2] + [𝐼3− ] in water layer is found by titration against
thiosulphate. Knowing [I2] from (a), [𝐼3− ] can be calculated. Benzene ⚫ In iodine titrations, the end point is indicated by adding starch suspension which turns blue.
layer
(c) The initial concentration of KI taken is represented by the equilibrium concentrations ⚫ A greater sensitivity can be obtained by using what we may call ‘Distribution Indicator’.
[I–] + [𝐼3− ].
Water ⚫ A few drops of an immiscible organic solvent such as chloroform (or carbons tetrachloride) is
-Knowing [𝐼3− ] from (b), [I–] can be found. layer added to the solution.

Substituting the above values of concentrations in the law of Mass Action equation of the ⚫ The bulk of any iodine present passes into the organic layer and imparts intense violet colour
reaction in water layer, to it.

𝐼3−
=𝐾
𝐼2 [𝐼− ]

the value of equilibrium constant K can be calculated.

-If it comes out to be constant for different concentrations of iodine, it stands confirmed that the
formula of the complex 𝐼3− , which we assumed is correct.

193 194

2
Unit 3. Solid State

195 196
 Solid State: Introduction Crystalline and Amorphous Solids

Crystallography: “Crystallography is the experimental science of determining the arrangement of atoms in crystalline solids”
A crystal or crystalline solid: is a solid material whose constituents (such as atoms,
Solid State: the state of matter in which materials are not fluid but retain their boundaries without support, the atoms or molecules molecules, or ions) are arranged in a highly ordered microscopic structure,
occupying fixed positions with respect to each other and unable to move freely. forming a crystal lattice that extends in all directions.

ADD ENERGY ❑ In addition, macroscopic single crystals are usually identifiable by their
geometrical shape, consisting of flat faces with specific, characteristic
S. Properties Solid Liquid Gas
orientations.
No
❑ The scientific study of crystals and crystal formation is known as
1 Volume Determined Determined No crystallography.
❑ The process of crystal formation via mechanisms of crystal growth is called
2 Shape Clear Shape Clear Shape No crystallization or solidification.
Example Example
Solid Liquid Gas 3 Binding Force Strong Less Too Low

REMOVE ENERGY 4 Compression Possibility No Less Too High

5 Density Too High High Less

⚫ Objects do exist in Solid, Liquid and Gaseous states. 6 Diffusion Behaviour Too Less Slow Speed
7 Mobility No Controlled Un-
⚫ In which, we have studied the Gaseous state and Liquid State in CHB-201. controlled In condensed matter physics and materials science, an amorphous or
8 Structure of Molecules Closely Weak Weak non-crystalline solid is a solid that lacks the long-range order that is
⚫ In order to understand the Solid state well, it is essential to recall the
Packed characteristic of a crystal.
Gaseous and Liquid state and compare with the Solid state.
9 Mixing Behaviour Too Less Less Mix with all
⚫ It can be understood from the following Table. ratios

197 10 Collision Distance Too Less Less High 198

Symmetry & Group Theory Symmetry Vocabulary

1
Configuration:
The symmetry properties of molecules and how they can be used to predict vibrational spectra, hybridization, optical “the exact position or orientation in three dimensional space of an object”
activity, etc.
3 2
1
Identical Configuration:
“results from an operation returning an object to its original position”

3 2
3
Equivalent Configuration:
“an orientation that is indistinguishable from the initial orientation”

2 1
Symmetry Operation:
“a (real or abstract) operation, whose application to a geometrical structure, yields an
orientation that is indistinguishable from the initial orientation”

Symmetry Elements:
“the geometrical elements that are used to perform the symmetry operation”
199 200
 Symmetry Elements Crystal or Space Lattice and Unit Cell

Crystal Lattice:
“a regular three dimensional arrangement of points in space is Actual
Symmetry Element Symbol Symmetry Operation arrangement
called a CRYSTAL LATTICE”
of atoms
Identity, “Whole of Space” E Do Nothing in a crystal
⚫ In a solid crystalline material, the atoms or molecules are arranged regularly
Mirror Plane Σ Reflection and periodically in three dimensions.

Proper Rotation Axis (this is a line) 𝐶𝑛𝑚 Proper Rotation ⚫ To explain crystal symmetries easily, it is convenient to represent an atom or
a group of atoms that repeats in three dimensions in the crystal as a unit. Crystal
Improper Rotation Axis (this is a line) 𝑆𝑛𝑚 Improper Rotation Lattice
⚫ If each such unit of atoms or atom in a crystal is replaced by a point in space, Unit
then the resultant points in space are called space lattice. Cell
Inversion Center (this is a point) I Inversion (this is a 𝑆2 )
⚫ Each point in space is called a lattice point and each unit of atoms or atom is
called basis or pattern.
n = tells you what fraction of a circle to rotate
⚫ A space lattice represents the geometrical pattern of crystal in which the Lattice Points
𝐶2 rotate halfway around or 360° /2 = 180 surroundings of each lattice point is the same.
Unit Cell
m = how many time to repeat the operation. ⚫ If the surroundings of each lattice point is same or if the atom or all.

If no m value given, assume one.

⚫ A unit cell is the smallest portion of a crystal lattice that shows the three-
dimensional pattern of the entire crystal.
⚫ A crystal can be thought of as the same unit cell repeated over and over in
three dimensions.
⚫ Unit cell will be having symmetry elements same as crystal.
201 202

Crystal or Space Lattice and Unit Cell Typical Crystal Systems

⚫ There are 230 types of crystals.

⚫ Based on symmetry those can be classified into 32 types.
⚫ These 32 types can be reduced into 14 Bravais lattices and 7 crystal systems.
Lattice Point Locations
⚫ Inner structure of the crystal can be explained based on Bravais or crystal lattices.

⚫ Features of 7 crystal systems can be learned from the table in the next slide.

Cubic System
➢ The cubic system is a crystal system with a cube as unit cell of the lattice.
➢ The three crystallographic axes (a, b, c) have equal lengths and the angles formed are Cubic Unit Cells
all 90 degrees.

Regular arrangement: Space Lattice Irregular arrangement: Not a Space Lattice

Simple Cubic (SC) Body-centered Face-centered

Cubic Unit Cell (BCC) Cubic Unit Cell (FCC)

203 204
 Seven Crystal Systems Simple Cubic (SC)

S. Crystal Axis Angles No. Examples ⚫ Simple cubic (SC) is a crystal lattice structure and unit cells with the most
No Systems Bravai straightforward structure and the most basic unit cell.
⚫ To visualize this, imagine taking a large number of identical spheres, such as tennis
s balls, and arranging them uniformly in a container.
Figure.1 When metal atoms are arranged with spheres in one layer
Lattice directly above or below spheres in another layer, the lattice structure is
⚫ The simplest way to do this would be to make layers in which the spheres in one layer
s called simple cubic. Note that the spheres are in contact.
are directly above those in the layer below, as illustrated in Figure 1.
⚫ This arrangement is called simple cubic structure, and the unit cell is called the simple
1 Cubic a=b=c α=β=γ 3 NaCl, KCl, CsCl,
cubic unit cell or primitive cubic unit cell.
= 90° ZnS ⚫ In a simple cubic structure, the spheres are not packed as closely as they could be,
and they only “fill” about 52% of the volume of the container.
⚫ This is a relatively inefficient arrangement, and only one metal (polonium, Po)
2 Tetragonal a=b≠c α≠β=γ 2 SnO2, TiO2, Sn
crystallizes in a simple cubic structure.
= 90° ⚫ As shown in Figure 2, a solid with this type of arrangement consists of planes (or
3 Monoclinic a≠b≠c α = γ = 90°; 2 CaSO4.2H2O, layers) in which each atom contacts only the four nearest neighbors in its layer; one Figure.2 An atom in a simple cubic lattice structure contacts
atom directly above it in the layer above; and one atom directly below it in the layer six other atoms, so it has a coordination number of six.
β ≠ 90° NaSO4.10H2O
below.
⚫ The number of other particles that each particle in a crystalline solid contacts is
known as its coordination number. Lattice Points Lattice Points
4 Orthorhombic a≠b≠c α=β=γ 4 KnO3, BaSO4
⚫ For a polonium atom in a simple cubic array, the coordination number is, therefore, six.
= 90°
⚫ In a simple cubic lattice, the unit cell that repeats in all directions is a cube defined
5 Triclinic a≠b≠c α≠β≠γ 1 CuSO4. 5H2O, by the centers of eight atoms, as shown in Figure 3.
≠ 90° H3BO3 ⚫ Atoms at adjacent corners of this unit cell contact each other, so the edge length of
this cell is equal to two atomic radii, or one atomic diameter.
⚫ A cubic unit cell contains only the parts of these atoms that are within it.
8 Corners
6 Rhombohedral a=b=c α=β=γ 1 CaCO3, NaNO3 ⚫ Since an atom at a corner of a simple cubic unit cell is contained by a total of Simple Cubic Lattice Cell
≠ 90° eight-unit cells, only one-eighth of that atom is within a specific unit cell.
And since each simple cubic unit cell has one atom at each of its eight “corners,” Figure.3 A simple cubic lattice unit cell contains one-eighth of an atom
7 Hexagonal a=b≠c α=β= 1 ZnO, CdS, there is 8×1/8=1 atom within one simple cubic unit cell. at each of its eight corners, so it contains one atom total.
205 206
90°; γ = 120° Graphite

Body-centered Cubic (BCC) Face-centered Cubic (FCC)

⚫ Most metal crystals are one of the four major types of unit cells.
⚫ For now, we will focus on the three cubic unit cells: simple cubic (which we have already seen), body-centered cubic unit cell, and face-centered cubic unit cell.
⚫ Many other metals, such as aluminum, copper, and lead, crystallize in an arrangement that has a cubic unit cell with atoms at all of the corners and at the centers
⚫ (Note that there are actually seven different lattice systems, some of which have more than one type of lattice, for a total of 14 different types of unit cells.
of each face, as illustrated in Figure.
We leave the more complicated geometries for later in this module.)
⚫ This arrangement is called a face-centered cubic (FCC) solid.
⚫ A FCC unit cell contains four atoms: one-eighth of an atom at each of the eight corners (8 × 1/8 = 1 atom from the corners) and one-half of an atom on each of
⚫ Some metals crystallize in an arrangement that has a cubic unit cell with atoms at all the corners and an atom in the center, as shown in Figure.
the six faces (6 × 1/2 = 3 atoms from the faces).
⚫ This is called a body-centered cubic (BCC) solid.
⚫ Atoms in the corners of a BCC unit cell do not contact each other but contact the atom in the center.
⚫ The atoms at the corners touch the atoms in the centers of the adjacent faces along the face diagonals of the cube.
⚫ A BCC unit cell contains two atoms: one-eighth of an atom at each of the eight corners (8 × 1/8 = 1 atom from the corners) plus one atom from the center.
⚫ Because the atoms are on identical lattice points, they have identical environments.
⚫ Any atom in this structure touches four atoms in the layer above it and four atoms in the layer below it.
⚫ Atoms in an FCC arrangement are packed as closely together as possible, with atoms occupying 74% of the volume.
⚫ Thus, an atom in a BCC structure has a coordination number of eight.
⚫ This structure is also called cubic closest packing (CCP).
⚫ Atoms in BCC arrangements are much more efficiently packed than in a simple cubic structure, occupying about 68% of the total volume.
⚫ Isomorphous metals with a BCC structure include K, Ba, Cr, Mo, W, and Fe at room temperature. (Elements or compounds that crystallize with the same structure
are said to be isomorphous.)

Body-centered cubic structure Face-centered cubic structure

Figure. In a body-centered cubic structure, atoms in a specific layer do not touch each other. Each atom touches four atoms in the layer above it and four Figure. A face-centered cubic solid has atoms at the corners and, as the name implies, at the centers of the faces of its unit cells.
207 atoms in the layer below it. 208
 Cubic Closest Packing (CCP) Hexagonal-closest Packed (HCP)

⚫ In CCP, there are three repeating layers of hexagonally arranged atoms.
⚫ Each atom contacts six atoms in its own layer, three in the layer above, and three in the layer below.
⚫ In this arrangement, each atom touches 12 near neighbors, and therefore has a coordination number of 12.
⚫ The fact that FCC and CCP arrangements are equivalent may not be immediately obvious, but why they are actually the same structure is illustrated in Figure.
⚫ Because closer packing maximizes the overall attractions between atoms and minimizes the total intermolecular energy, the atoms in most metals pack in this
manner.
⚫ We find two types of closest packing in simple metallic crystalline structures: CCP, which we have already encountered, and hexagonal closest packing (HCP)
shown in Figure.
⚫ Both consist of repeating layers of hexagonally arranged atoms.
⚫ In both types, a second layer (B) is placed on the first layer (A) so that each atom in the second layer is in contact with three atoms in the first layer.
⚫ The third layer is positioned in one of two ways. In HCP, atoms in the third layer are directly above atoms in the first layer (i.e., the third layer is also type A),
and the stacking consists of alternating type A and type B close-packed layers (i.e., ABABAB⋯).
⚫ In CCP, atoms in the third layer are not above atoms in either of the first two layers (i.e., the third layer is type C), and the stacking consists of alternating type
A, type B, and type C close-packed layers (i.e., ABCABCABC⋯).
⚫ About two–thirds of all metals crystallize in closest-packed arrays with coordination numbers of 12.
⚫ Metals that crystallize in an HCP structure include Cd, Co, Li, Mg, Na, and Zn, and metals that crystallize in a CCP structure include Ag, Al, Ca, Cu, Ni, Pb, and Pt.

Cubic-closest packed structure

Figure. A CCP arrangement consists of three repeating layers (ABCABC…) of hexagonally arranged atoms. Atoms in a CCP structure have a coordination
number of 12 because they contact six atoms in their layer, plus three atoms in the layer above and three atoms in the layer below. By rotating our perspec
tive, we can see that a CCP structure has a unit cell with a face containing an atom from layer A at one corner, atoms from layer B across a diagonal (at two Cubic-closest
Hexagonal-closest
corners and in the middle of the face), and an atom from layer C at the remaining corner. This is the same as a face-centered cubic arrangement. packed structure packed structure

Figure. In both types of closest packing, atoms are packed as compactly as possible. Hexagonal closest packing consists of two alternating layers (ABABAB
209 210 …). Cubic closest packing consists of three alternating layers (ABCABCABC…).

Law of Rational Indices Law of Rational Indices

Weiss Indices: Miller Indices:

Z Z
⚫ The Weiss parameters, introduced by Christian Samuel Weiss in 1817, are the ancestors ⚫ Miller indices are referred as a “reciprocal of distance of the plane which intersect
of the Miller indices. fundamental axes such as X,Y,Z from the origin (O).

⚫ They give an approximate indication of a face orientation with respect to the ⚫ They are defined with the (hkl) notations.
crystallographic axes and were used as a symbol for the face.
⚫ For example, lets consider a plane which intersect the X,Y,Z axes by 1,1,1 units,
⚫ Weiss parameters are the reciprocal of Miller indices, each followed by the corresponding 1 1 1
respectively then its Miller indices are : : (1:1:1). Hence, this plane is defined as (111).
1 1 1
axis symbols.
c c ⚫ If a plane intersect the X-axis by 1 unit distance and parallel to Y,Z-axes as well means
⚫ Weiss indices are referred as a “plane which intersect fundamental axes such as X,Y,Z (intersects at ∞ distance)
b O from the origin (O). b O 1 1 1
Miller indices are 1: ∞: ∞ ; 1 : ∞ : ∞ = 1: 0: 0 hence, it is (100) plane.
X ⚫ For example, lets consider a plane which intersect the X,Y,Z axes by 3,2,1 units,
X
a respectively then its Weiss indices are (3:2:1). a ⚫ If a plane intersect the X,Y,Z-axis by 4:3: ∞ unit distance
1 1 1
Miller indices are 4 : 3 : ∞ = 3: 4: 0 hence, it is (340) plane.
⚫ Sometimes, intersecting plane might be parallel to the any one of the axes, for example, a
plane intersect the X,Y axes by 2,1-unit distance and it is parallel to the Z-axis then Weiss
indices are (2:1:∞). ⚫ If a plane intersect the X,Y,Z-axis by 3:2: 5 unit distance
Y Y 1 1 1
Miller indices are 3 : 2 : = 10: 15: 6 hence, it is (10,15,6) plane.
5

Few planes of the cubes are given in the next slide……

211 212
 Few Planes of Cubes Examples for Better understanding

213 214

Interplanar Distances X-Ray Crystallography/Bragg’s Equation

⚫ The size of the unit cell and the arrangement of atoms in a crystal may be determined
from measurements of the diffraction of X-rays by the crystal, termed X-ray
crystallography.
⚫ Diffraction is the change in the direction of travel experienced by an electromagnetic
wave when it encounters a physical barrier whose dimensions are comparable to those of
the wavelength of the light. Maxima and minima cancel
⚫ X-rays are electromagnetic radiation with wavelengths about as long as the distance
Maxima and minima reinforce
❑ Among the seven crystal systems, cube is a simplest one. between neighboring atoms in crystals (on the order of a few Å).
⚫ When a beam of monochromatic X-rays strikes a crystal, its rays are scattered in all (a) Constructive (b) Destructive
❑ For instance, lets consider a unit cell with a edge distance of a = b = c; corresponding angles α = β = γ = 90° on analysis, directions by the atoms within the crystal. Interface Interface
⚫ When scattered waves traveling in the same direction encounter one another, they
it will be having 100, 110 and 111 planes. Figure. Light waves occupying the same space experience interference, combining to
undergo interference, a process by which the waves combine to yield either an increase or
a decrease in amplitude (intensity) depending upon the extent to which the combining yield waves of greater (a) or lesser (b) intensity, depending upon the separation of their
❑ And distance between the two planes, dhkl can be obtained from the following equation; waves’ maxima are separated (see Figure). maxima and minima.
Incident Diffracted
𝑎 beam beam
❑ When X-rays of a certain wavelength, λ, are scattered by atoms in adjacent crystal planes
𝑑ℎ𝑘𝑙 = 1
𝑙2 ) ൗ2
separated by a distance, d,
(ℎ2 + 𝑘2 + ❑ they may undergo constructive interference when the difference between the distances
traveled by the two waves prior to their combination is an integer factor, n, of the
Here, a = edge distance of the unit cell Figure. The diffraction of X-rays wavelength.
scattered by the atoms within a ❑ This condition is satisfied when the angle of the diffracted beam, θ, is related to the
hkl = Miller indices of the plane crystal permits the determination wavelength and interatomic distance by the equation:
of the distance between the
Constructive Interference
atoms. The top image depicts nλ=2dsinθ
Incident constructive interference
Diffracted
beam between two scattered waves and ❑ This relation is known as the Bragg equation in honor of W. H. Bragg, the English physicist
beam
a resultant diffracted wave of who first explained this phenomenon.
high intensity. The bottom image ❑ Figures illustrates two examples of diffracted waves from the same two crystal planes.
depicts destructive interference The figure on the left depicts waves diffracted at the Bragg angle, resulting in
and a low intensity diffracted constructive interference, while that on the right shows diffraction and a different angle
wave. that does not satisfy the Bragg condition, resulting in destructive interference.
215 216
Destructive Interference
 X-ray diffractometer The Structures of Ionic Crystals

❑ Ionic crystals consist of two or more different kinds of ions that usually have different
❑ An X-ray diffractometer, such as the one illustrated in Figure, may be used to measure the angles at which X-rays are sizes.
diffracted when interacting with a crystal as described earlier. ❑ The packing of these ions into a crystal structure is more complex than the packing of Octahedral holes Tetrahedral holes
❑ From such measurements, the Bragg equation may be used to compute distances between atoms as demonstrated in the metal atoms that are the same size.
following example exercise. ❑ Most monatomic ions behave as charged spheres, and their attraction for ions of opposite
Diffracted X-rays charge is the same in every direction.

X-ray beam ❑ Consequently, stable structures for ionic compounds result

(1) when ions of one charge are surrounded by as many ions as possible of the opposite
Crystalline charge and
material (2) when the cations and anions are in contact with each other.

❑ Structures are determined by two principal factors:

-the relative sizes of the ions and the ratio of the numbers of positive and negative ions in
the compound.
❑ In simple ionic structures, we usually find the anions, which are normally larger than the
Collimator to
cations, arranged in a closest-packed array. (additional electrons attracted to the same
X-ray source focus beam
nucleus make anions larger and fewer electrons attracted to the same nucleus make cations
X-ray diffraction Imaging Surface smaller when compared to the atoms from which they are formed.)
X-ray diffraction pattern
❑ The smaller cations commonly occupy one of two types of holes (or interstices) remaining
between the anions.
❑ The smaller of the holes is found between three anions in one plane and one anion in an
(a) (b) adjacent plane. Figure. Cations may occupy two types of holes between anions:
❑ The four anions surrounding this hole are arranged at the corners of a tetrahedron, so the octahedral holes or tetrahedral holes.
hole is called a tetrahedral hole.
Figure. (a) In a diffractometer, a beam of X-rays strikes a crystalline material, producing (b) an X-ray diffraction pattern that can ❑ The larger type of hole is found at the center of six anions (three in one layer and three in
be analyzed to determine the crystal structure. an adjacent layer) located at the corners of an octahedron; this is called an octahedral
217 218 hole.

The Structures of Ionic Crystals Unit Cells of Ionic Compounds

❑ Depending on the relative sizes of the cations and anions, the cations of an ionic compound
may occupy tetrahedral or octahedral holes, as illustrated in previous slide.
❑ Relatively small cations occupy tetrahedral holes, and larger cations occupy octahedral
holes.
❑ If the cations are too large to fit into the octahedral holes, the anions may adopt a more
open structure, such as a simple cubic array.
❑ The larger cations can then occupy the larger cubic holes made possible by the more open
spacing.
❑ There are two tetrahedral holes for each anion in either an HCP or CCP array of anions.
❑ A compound that crystallizes in a closest-packed array of anions with cations in the
tetrahedral holes can have a maximum cation: anion ratio of 2:1; all of the tetrahedral holes
are filled at this ratio.
❑ Examples include Li2O, Na2O, Li2S, and Na2S.
❑ Compounds with a ratio of less than 2:1 may also crystallize in a closest-packed array of
anions with cations in the tetrahedral holes, if the ionic sizes fit.
❑ In these compounds, however, some of the tetrahedral holes remain vacant.
❑ The ratio of octahedral holes to anions in either an HCP or CCP structure is 1:1.
❑ Thus, compounds with cations in octahedral holes in a closest-packed array of anions can
have a maximum cation: anion ratio of 1:1.
❑ In NiO, MnS, NaCl, and KH, for example, all of the octahedral holes are filled.
❑ Ratios of less than 1:1 are observed when some of the octahedral holes remain empty.
219
❑ Many ionic compounds crystallize with cubic unit cells, and we will use these
compounds to describe the general features of ionic structures.
❑ When an ionic compound is composed of cations and anions of similar size in a
1:1 ratio, it typically forms a simple cubic structure.
Tetrahedral hole Octahedral hole Cubic hole
Cation radius is about Cation radius is about Cation radius is about ❑ Cesium chloride, CsCl, (illustrated in Figure) is an example of this, with Cs+ and
22.5 to 41.4% of the 41.4 to 73.2% of the 73.2 to 100% of the Cl− having radii of 174 pm and 181 pm, respectively.
anion radius anion radius anion radius
❑ We can think of this as chloride ions forming a simple cubic unit cell, with a
Figure. A cation’s size and the shape of the hole occupied by cesium ion in the center; or as cesium ions forming a unit cell with a chloride
the compound are directly related. ion in the center; or as simple cubic unit cells formed by Cs+ ions overlapping Body-centered simple cubic structure
unit cells formed by Cl− ions.
Figure. Ionic compounds with similar-sized cations and anions, such as CsCl,
❑ In a simple cubic array of anions, there is one cubic hole that can be ❑ Cesium ions and chloride ions touch along the body diagonals of the unit cells.
usually form a simple cubic structure. They can be described by unit cells
occupied by a cation for each anion in the array. with either cations at the corners or anions at the corners.
❑ In CsCl, and in other compounds with the same structure, all of the ❑ One cesium ion and one chloride ion are present per unit cell, giving the l:l
cubic holes are occupied. stoichiometry required by the formula for cesium chloride.
❑ Half of the cubic holes are occupied in SrH2, UO2, SrCl2, and CaF2.
❑ Note that there is no lattice point in the center of the cell, and CsCl is not a
❑ Different types of ionic compounds often crystallize in the same BCC structure because a cesium ion is not identical to a chloride ion.
structure when the relative sizes of their ions and their
stoichiometries (the two principal features that determine
structure) are similar.
220
 Crystal Structure of NaCl Crystal Structure of ZnS

❑ When an ionic compound is composed of a 1:1 ratio of cations and anions that
differ significantly in size, it typically crystallizes with an FCC unit cell, like
that shown in Figure.

❑ Sodium chloride, NaCl, is an example of this, with Na+ and Cl− having radii of
102 pm and 181 pm, respectively.
❑ We can think of this as chloride ions forming an FCC cell, with sodium ions
located in the octahedral holes in the middle of the cell edges and in the
center of the cell.
❑ The sodium and chloride ions touch each other along the cell edges.
❑ The unit cell contains four sodium ions and four chloride ions, giving the 1:1
stoichiometry required by the formula, NaCl.
⚫ Co-ordination number for NaCl crystal is 6 (each ion is surrounded by six
adjacent ions).
⚫ Each unit cell consist of four Na+ and four Cl- ions.
⚫ A FCC unit cell contains four NaCl molecules: one-eighth of Na+ ion at each of
the eight corners (8 × 1/8 = 1 atom from the corners) and one-half of Na+ ion
on each of the six faces (6 × 1/2 = 3 Na+ ion from the faces).
⚫ Cl- ion present in the edge (total 12 edges in a cube) of the unit cell is shared
by 4 adjacent/neighbor cubes/unit cells hence, in a cube there are 12 × 1/4 =
3.
⚫ In addition, there is one more Cl- ion in the center of the cube. Total 4 Cl-
ions.
⚫ Hence, there are four NaCl molecules present in a single FCC unit cell.
221
Face-centered simple cubic structure
Figure. Ionic compounds with anions that are much larger than cations, such
as NaCl, usually form an FCC structure. They can be described by FCC unit
cells with cations in the octahedral holes.
Face-centered cubic structure
❑ The cubic form of zinc sulfide, zinc blende, also crystallizes in an FCC unit
cell, as illustrated in Figure.
❑ This structure contains sulfide ions on the lattice points of an FCC lattice.
(The arrangement of sulfide ions is identical to the arrangement of chloride
ions in sodium chloride.)
❑ The radius of a zinc ion is only about 40% of the radius of a sulfide ion, so
these small Zn2+ ions are located in alternating tetrahedral holes, that is, in ZnS face-centered unit cell
one half of the tetrahedral holes.
❑ There are four zinc ions and four sulfide ions in the unit cell, giving the
Figure. ZnS, zinc sulfide (or zinc blende) forms an FCC unit cell with sulfide
empirical formula ZnS.
ions at the lattice points and much smaller zinc ions occupying half of the
tetrahedral holes in the structure.
222

Crystal Structure of CaF2 Calculation of Ionic Radii

❑ A calcium fluoride unit cell, like that shown in Figure, is also an FCC unit
cell, but in this case, the cations are located on the lattice points;
equivalent calcium ions are located on the lattice points of an FCC lattice.
❑ All of the tetrahedral sites in the FCC array of calcium ions are occupied
by fluoride ions.
❑ There are four calcium ions and eight fluoride ions in a unit cell, giving a
calcium: fluorine ratio of 1:2, as required by the chemical formula, CaF2.
❑ Close examination of Figure will reveal a simple cubic array of fluoride
ions with calcium ions in one half of the cubic holes.
❑ The structure cannot be described in terms of a space lattice of points
on the fluoride ions because the fluoride ions do not all have identical
environments.
❑ The orientation of the four calcium ions about the fluoride ions differs.
CaF2 face-centered unit cell
Figure. Calcium fluoride, CaF2, forms an FCC unit cell with calcium ions
(green) at the lattice points and fluoride ions (red) occupying all of the
tetrahedral sites between them.
If we know the edge length of a unit cell of an ionic compound and the position
of the ions in the cell, we can calculate ionic radii for the ions in the compound if
we make assumptions about individual ionic shapes and contacts.
Calculation of Ionic Radii
➢ The edge length of the unit cell of LiCl (NaCl-like structure, FCC) is 0.514 nm
or 5.14 Å.
➢ Assuming that the lithium ion is small enough so that the chloride ions are in
contact, as in Figure, calculate the ionic radius for the chloride ion.
Note: The length unit angstrom, Å, is often used to represent atomic-scale
dimensions and is equivalent to 10−10 m.
Solution
✓ On the face of a LiCl unit cell, chloride ions contact each other across the
diagonal of the face:
✓ Drawing a right triangle on the face of the unit cell, we see that the length of the diagonal is equal to four chloride radii (one radius from each
corner chloride and one diameter—which equals two radii—from the chloride ion in the center of the face), so d = 4r.
✓ From the Pythagorean theorem, we have:
a2 + a2 =d2
which yields:
(0.514 nm) + (0.514 nm)2 = (4r)2 = 16r2
2

Solving this gives:

r = √(0.514 nm)2 + (0.514 nm)2 /16 = 0.182 nm (1.82˚A) for\;a\;Cl− radius.
223 224
 Graphite and Diamond Graphite and Diamond

⚫ The blue circles symbolize two things

-The lattice points of a face-centered cubic (fcc) lattice.
-Carbon atoms sitting on the lattice points.
⚫ The green circles symbolize carbon atoms too - but not lattice points.
⚫ The red lines symbolize the very strong bonds between carbon atoms.

⚫ All atoms are strongly bonded to 4 neighbors and that's why it is difficult to rip them apart.
⚫ In other words: Diamond is very hard!
⚫ The black lines are only there to guide the eye in seeing the cubic lattice.
⚫ They have no meaning. A diamond emerges if one puts a dumbbell formed by two carbon
⚫ Blue and green spheres are carbon atoms, the full red lines are strong carbon - carbon
atoms on any lattice point of the fcc lattice; just look at the picture to see this.
bonds.
⚫ The word "diamond" goes back to the ancient Greek "adámas=unbreakable.
⚫ The dashes red lines are very weak bonds and that's why it is easy to move one atomic
⚫ It may surprise you that diamond has not only the highest hardness of all (natural) materials,
layer relative to another one.
but also the highest thermal conductivity of any bulk material.
Carbon ⚫ It is clear that we have a hexagonal lattice here. It is not so clear how the atoms are
⚫ The diamond structure – i.e. a FCC lattice and two atoms as base – is a much loved structure Covalent bond Carbon atom
atoms distributed.
among atoms.
Weak
⚫ Take the blue and green spheres to be silicon (Si) or germanium (Ge) atoms and you have the Binding
structure of those semiconductors. forces

⚫ Take the blue spheres to be gallium (Ga) or indium (In), and the green spheres to be arsenic
(As), phosphorous (P) or antimonide (Sb) atoms, and you have compound semiconductors like
GaAs or InP that are indispensable to optoelectronics.
⚫ The atoms are strongly bonded to each other but not quite as strong as carbon atoms.
Silicon is quite hard but not as hard as diamond.
Covalent
bond
Structure of Diamond Structure of Graphite
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Schottky and Frenkel Defects Key Concepts and Summary

Schottky Defect: Frenkel Defect:

⚫ Forms when oppositely charged ions leave their lattice sites, creating ⚫ Smaller ion (usually the cation) is displaced from its lattice position to
vacancies. interstitial site.

⚫ These vacancies are formed in stochiometric units, to maintain an overall ⚫ Creates a vacancy defect at its original site and an interstitial defect at ❑ The structures of crystalline metals and simple ionic compounds can be described in terms of packing of spheres.
neutral charge in the ionic solid. its new location.
❑ Metal atoms can pack in hexagonal closest-packed structures, cubic closest-packed structures, body-centered structures, and
⚫ Density of the solid crystal is less than normal. ⚫ Does not change the density of the solid. simple cubic structures.

⚫ Occurs only when there is small difference in size between cations and ⚫ Shown in ionic solids with large size difference between the anion and ❑ The anions in simple ionic structures commonly adopt one of these structures, and the cations occupy the spaces remaining
𝑟+ 𝑟+ between the anions.
anions. ( ≅ 1) cation. (𝑟 − < 1, like 0.6/0.4)
𝑟−
❑ Small cations usually occupy tetrahedral holes in a closest-packed array of anions. Larger cations usually occupy octahedral
holes.
❑ Still larger cations can occupy cubic holes in a simple cubic array of anions.

❑ The structure of a solid can be described by indicating the size and shape of a unit cell and the contents of the cell.

❑ The type of structure and dimensions of the unit cell can be determined by X-ray diffraction measurements.

Perfect Crystal Schottky Defect Frenkel Defect

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 Thanks for Your
Kind Attention
• For Queries Contact at

3 • Dr. S. Manivannan,
• Chamber: 42A, Department of Chemistry,
Institute of Science, BHU.
• Phone: 7708806985,
• email: smanivannan@bhu.ac.in

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