Chemistry Notes Puspanjali PDF

Sub: Chemistry
BS 1103
1ST/ 2ND SEMESTER (Common to all Branches)
Module
CHEMICAL KINETICS
Prepared by
Dr.Puspanjali Mishra
Asst. Prof. in Chemistry
PMEC, Berhampur
Odisha
Email: puspanjali.cit@gmail.com
Mob: 9861409540
2
COURSE OUTCOME
CHEMICAL KINETICS
1. Rate of a reaction, Rate law and rate equation, Order and molecularity, Rate
constant.
2. Factors influencing the rate of a reaction.
3. Rate equations for zero, first and second order reactions, Half life period.
Calculation of rate constant of various chemical reactions from the kinetic data.
4. Methods of determination of order of a reaction.
5. Theory of reaction rates, Collision theory, Theory of absolute reaction rates.
6. Effect of temperature on the rate of reaction. Activation energy ,Calculation of
activation energy, Arrhenius equation.
7. Catalysts, Homogeneous and Heterogeneous catalysis, Theories of catalysis,
Adsorption theory, Intermediate compound formation theory.
Dr. Puspanjali Mishra. Asst. Prof in Chemistry, PMEC, Berhampur

3
SYLLBUS:
Module-II
Chapter-1 Chemical Kinetics (No. of lectures=7)
I. Rate law, Order and molecularity
II. Factors influencing the rate of a reaction
III. Kinetics of zero and first and second order reactions
IV. Methods of determination of order of a reaction
V. Collision theory,Theory of absolute reaction rates
VI. Energy of activation
VII. Homogeneous and Hetrogeneous catalysis.
BOOKS REFERRED:
 Atkines Physical Chemistry.
 Physical Chemistry by G.M. Barrow, 6th edition, Tata McGraw Hill, New Delhi,1992.
 Physical Chemistry by Puri, Sharma & pathania
 Physical Chemistry by S.Glastone
 Physical Chemistry by Bahl & Tuli
 Physical Chemistry by Gurdeep Raj

4
LESSON PLAN
CHEMISTRY
Module-II
Chapter-1 Chemical Kinetics (No. of lectures=7)
LECTURE:1 CHEMICAL KINETICS,REACTION KINETICS, RATE LAW
Key Topics Rate of a reaction, Rate law and rate equation, Order and molecularity,
Rate constant, Factors influencing the rate of a reaction, Rate equations
for zero and first order reactions, Half life period.
LECTURE:2 & 3 RATE EQUATION OF SECOND ORDER REACTIONS.
Key Topics: Calculation of first order rate constant of various chemical reactions
from the kinetic data, pseudo-first order reactions, Second order
reactions, Derivation of the rate equation for second order reactions
when (i) The reactants are same (ii) Different calculation of K2, half
life.
LECTURE:4 & 5 DETERMINATION OF ORDER OF A REACTION.
Key Topics: Methods of determination of order of a reaction. (i) Integration method,

(ii) Graphical method, (iii) Fractional –time change method, (iv)
Differential method (v) Isolation method.
LECTURE:6 THEORY OF REACTION RATES, ACTIVATION ENERGY.
Key Topics: Theory of reaction rates, Collision theory, Theory of absolute reaction
rates, Effect of temperature on the rate of reaction, Temperature
coefficient , Explanation using collision theory, Threshold energy ,
Activation energy ,Calculation of activation energy, Arrhenius
equation.
LECTURE:7 CATALYSIS
Key Topics: Catalysts, Homogeneous and Hetrogeneous catalysis, Theories of

catalysis, Adsorption theory, Intermediate compound formation theory.

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Module – II
Chemical Kinetics
Key Topics: Rate of reaction, factors affecting rates of reaction, order and molecularity, Rate
law and rate constant, Integrated rate equation and half life for different order reactions,
methods of determination of order of a reaction, Theories of reaction rates, Effect of
temperature on reaction rates and calculation of energy of activation. Catalysis and Theories of
catalysis.
Introduction:
“The branch of chemistry which deals with the study of the speeds or the rates of
chemical reactions, the factors affecting the rates of the reactions and the mechanism by which
the reactions proceed is known as chemical Kinetics.”
According to the speed or rates, the chemical reactions are classified as (i) very fast
reactions like precipitation of AgCl from AgNO3, (ii) very slow reactions like rusting of iron
and (iii) reactions of moderate speed like decomposition of H2O2.
The rates of different reactions are different due to breaking and formation of different
categories of bonds during a chemical reaction.
Rate of Reaction:
The rate of reactions is the change in the concentration of any one of the reactants or
products per unit time.
According to the law of mass action, the rate of reaction depends upon the molar
concentrations of reactants which keep on decreasing with the passage of time in a reaction.
Therefore, the rate of reaction does not remain constant throughout. One can only measure the
instantaneous rate of a reaction.
The instantaneous rate of a reaction or the rate of reaction at any instant of time is the
rate of change of concentration of ay one of the reactant s or products at that particular instant of
time.
For the reaction A→P,
[ ] [ ]
rate r= =
In general, for the reaction,

a A + bB → xX + yY,

6
[ ] [ ] [ ] [ ]
Rate = - =- = =
Factors affecting the rate of a reaction:

(i) Nature of the reactants
(ii) Concentration of the reactants
(iii) Temperature
(iv) Presence of Catalyst
(v) Surface area of the reactants
(vi) Presence of light.
Rate law and rate constant :

As the rate of a reaction at any given time will depend upon the concentration of the
reactant A at that time, for a reaction A P,
[ ] [ ]
Where concentration of the reactant A at the given instant.

n order of the reaction
k rate constant of the reaction
Thus at a given temperature, the rate constant is equal to the rate of the reaction when the
concentrations of each of the reactants is unity.
Characteristics of Rate constant:

a) Each reaction has a definite value of the rate constant at given reaction conditions.
b) The rate constant is a measure of the rate of the reaction. Greater the value of the rate
constant, faster is the reaction.
c) The unit of the rate constant depends upon the order of the reaction.
d) The value of the rate constant for the same reaction changes with temperature.

7
Order of a Reaction:-
In the study of chemical kinetics, reactions are generally classified in terms of their
„Order‟. The order of a reaction is defined as the number of molecules whose concentrations
determine the rate of the chemical reaction at a given temperature. In order words, we may
define the order of a reaction as the sum of the exponents (powers) to which the concentration
terms in the rate law equations are raised to express the observed rate of the reaction.
In a reaction of the type A P,
Rate=
Similarly, in a reaction of the type,
[ ]
,
where x, y and z are the orders with respect to the reactants A, B and C respectively and the
overall order of the reaction, n= x + y + z. The values of x, y and z may or may not be equal to
the values of a, b and c respectively. Depending upon whether „n‟ is equal to 0, 1 and 2 the
reactions are said to be of zero order, first of and second order respectively. The order of a
reaction may be zero, a whole number or a fraction.
The order of a reaction should not be confused with molecularity. The main points of
difference between the order and molecularity of a reaction may be summarized as follows;
ORDER MOLECULARITY
 It is the sum of the exponents of the  It is the number of atoms or molecules

concentration terms in the rate law in a balanced chemical equation of a
equation. simple reaction.
[ ] Molecularity= a + b + c
order of the reaction, n= x + y + z
 It is always a whole number and
 It can be zero, whole number or a
cannot be zero nor a fraction.
fraction.
 It can be calculated simply adding the
 It can be determined experimentally
molecules of a simple reaction or of
from the kinetic data.
the slowest step of a multi step
reaction.
 For simple reactions, the molecularity
 Order may or may not be equal to the
can usually be obtained from the
moleculaity.
stoichiometry of the equation.
8
Integrated Rate Reaction:-

a) Zero- order Reaction: n=0
A chemical reaction in which the rate of the reaction does not depend on the change in
concentration of the reactant is known as zero-order reaction. In other words, the rate of
reaction is independent of the concentration of reactants.
Examples:
(a) H2 (g) +Cl2 (g) → in presence of H2O.

(b) The decomposition of HI by heating over gold catalyst.
A P
At t=0 0
At t, x
On integration ∫ ∫
When t=0, x=0, I=0 , x=
→ Integrated rate equation for zero order reaction.
Unit of
The equation is used to calculate from the kinetic data. A plot of x vs t for a zero order
reaction gives a straight line passing through origin, the slope of which will be equal to
Half life period (t1/2 ):-

Half life period is the time in which half of the substance has reacted. i.e at

9
Q. A zero order reaction has half life period as 50 min. calculate the time taken for completion
of 80% and 100% of the reaction respectively.
Solution;
as x=a at 100% reaction.

⁄
b) First Order Reaction: - n=1.

For the reaction A P
at t=0 o
t x
[ ] [ ]
∫ ∫
……………………………… (1)
………………………… (2)
Putting the value of I in equation 1,
………………….. (3)
…………………………. (4)
Unit of .
Can be calculated by using the kinetic data in equations (4) at different time intervals.
The plot of vs t, gives a straight line with a negative slope= k and intercept
= .

10
Half Life Period:-

at ,x= & x=
= ln = ln 2 = 0.693
= = …………………………… (5)
=
For 1st order reaction the half life period is independent of the initial concentration of the
reactant.
Q. Calculate the time taken for 80% of a first order reaction half life period is 25 min.
Solution:
= 25 min. = min-1
At 80% of the reaction,
= = min
Q. Prove that the time taken for 99.9% completion of a first order reaction is nearly 10 times
that of for 50% completion of the same reaction at constant temperature.
Solution:
=
11
= = 1000 =
= .
Examples of 1st order reactions:

(i) Acid Catalysed hydrolysis of ethyl acetate.
CH3COOC2H5 + H20 H+ CH3COOH + C2H50H
r = k1 [ ]
(ii) Hydrolysis of cane sugar (Inversion of cane sugar).
+
Sucrose glucose fructose
r = k1 [ ]
c) 2nd order Reaction

Case – I When reactants are different or [A] [B]
Consider the reaction
A + B P
at t =0 b 0
at t ( b-x) x
rate = [ ][ ] ………………. (1)
…………………….. (2)
On integration, by using partial fraction method,
∫ *∫ ∫ + ∫ (When a>b)
[ ] …………… (3)
at t=0, x=0, I =

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when > b …………………. (4)
When …………………… (5)
The unit of k2 = conc-1 time-1 = lit mol-1 sec-1.

When a>>b, or one of the reactants is taken in excess, -b , -x .
Equation (4) becomes, k2 =
k2‟ = k2 = ……………… (6)
Equation (6) is similar to a first order rate equation and the reaction at this condition is known
as pseudo first order reaction.
Example:-
CH3COOC2H5 + H20 H+ CH3COOH + C2H50H

Excess
rate [ ], first order w.r.to the ester.
Case II, when the reactants are same or [A] = [B]:

2A P
Or A + B P, [A] = [B] = – x.
At t=0 0
At t , -x -x x
Rate = k2 ( -x)2

13
k2dt
On integration, ∫ =∫
* + = k2t + I =
At t = 0, x = 0, I =
k2t = K2 = * +
Plot of vs. t gives a straight line with intercept and slope = k2
Half-life Period of a 2nd order reaction:
At , k2 = * += [ ]=
Examples of 2nd order reaction:

Saponification of ester:
CH3COOC2H5 + NaoH CH3COONa+ C2H5OH
Rate [ CH3COOC2H5] [NaOH]
d). nth order reaction (n )
Rate = = kn ( -x)n

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= kndt
On integration, ∫ =∫
= knt + I
At t = 0, x = 0, I =
knt = * +
kn = * +
This equation is applicable to all order reaction except first order (n ≠1)
Determination of Order of reaction:
(I) Trial & Error method:

(a) The use of integrated rate expressions:
When n = 0, k=
When n = 1, k=
When n = 2, k= * +
In this method, assuming a certain order for the reaction, the rate constants at different times are
calculated from the given kinetic data. The constancy of the k values obtained suggests that the
assumed order is correct. If the k values obtained are not constant, a different order is assumed
for the reaction and again k values are calculated using the new rate expression and see if k is
constant.

15
(b)Graphical Method:-
n=0 n=1 n=2
In this method, the kinetic data is used to plot the graphs as above, and from the
shape of a particular graph the corresponding order is predicted.
(II) The Half-life Method: - (Ostwald Method)

For n=0,
n=1,
n=2,
For order,
When are the half-lives with initial concentration for a reaction,
( )
( ⁄ )
( ⁄ )
( ⁄ )
( ⁄ )

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(III) The Differential rate expression method (Vant Hoff’s Method):-
The rate of order reaction is given by
When the rates of a reaction at two different instances are measured,

&
Where C1 and C2 are the concentrations of the reactant at two different times
( )
( ⁄ )
( ⁄ )
(IV) Isolation Method:-

When more number of reactants are there, then the order with respect to a particular
reactant is determined by taking excess concentration of all other reactants (maintaining pscudo-
order conditions)expect that one, by any one of the methods discussed earlier. The order with
respect to the other reactants are separately determined in a similar manner and the overall order
is calculated,
a A +b B +c C P
If order with respect to A, B and C are respectively, then according to rate law.
[ ] [ ] [ ] Where
If B and C are in large exceeds, their concentrations remain almost constant. Hence we can
write,
[ ]
Q. The rate of a particular reaction is 0.05 mol lit-1 sec-1 when the reaction is 20% complete.
The rate of the same reaction is 0.02 mol lit-1 sec-1, when the reaction is 50% complete. Find the
order of the reaction.
Solution:
When reaction is 20% complete,
R1 =0.05 mol lit-1 sec-1
C1 = a − 0.2a =0.8 a
17
When the reaction is 50% complete,

R2 = 0.2 mol lit-1 sec-1, C2 =a a − 0.5a =0.5a
( ⁄ ) ( ⁄ )
( )
( ⁄ ) ( ⁄ )
(Ans.)
Q. The half life period of a reaction is 20 min when initial concentration was 0.5m and is 15 min when
initial concentration was 0.75m. Find the order of the reaction.
Solution:
( ⁄ )
( )
( )
( ⁄ ) ( )
(Ans.)
Theories of reactions rates:-
(I) Collision Theory

(II) Transition State Theory or Theory of absolute reaction rates.
(I) Collision Theory

This is mainly applicable to homogeneous gaseous reactions. According to this theory,
A Chemical reaction takes place due to collision of the reacting molecules.
But all collisions are not effective to result a chemical reaction. The collisions will be
effective only when,
i. The colliding molecules possess sufficient energy (equal or more than Threshold
energy) to overcome the potential energy barrier of the reaction.
ii. The molecules must be properly oriented to have direct collision.

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of reaction.
Limitations of Collision Theory

 It is purely qualitative approach.
 It is applicable only to simple gaseous reactions.
 The mechanism of a chemical reaction cannot be explained by collision theory.
 It cannot explain the steric effect of reaction.
(II) Transition State Theory
The transition state theory is also known as „theory of absolute reaction rates‟ and the „activated
complete theory‟. According to this theory the steps for the reaction :
AB+C A+ BC can be written as;
i. Formation of activated complex:

A-B+C [ ]
ii. Decomposition of the activated complex to give products:
[ ]

19
It must be remembered that the activated complex is not an intermediate. It is purely a

hypothetical concept and possesses maximum energy. The difference between the energy of the
activated complex and the reactant is the activation energy Ea.
Effect of temperature on Reaction Rates:-
Temperature has a significant effect on the rate of reaction. For most of the reactions,
Temperature co-efficient =
This effect can be explained from collision theory. For an effective collision, the colliding
molecules must have energy more then .

20
From the maxwell‟s distribution Curve (Fig.) it is evident that at 25o C a small fraction of
molecules possess energy more than and the rate of the reaction at 25o C is proportional to
the area (shaded).
When the temperature is increased by 10oC, the curve shifts as in the figure. Now at 35o C more
number if molecules are having Kinetic energy more than and is represented by the shaded
area which is almost double then the area abcd.
Now
Thus the increase in the rate of the reaction with increase in temperature is mainly due to
increased in the number of effective collisions.
Arrhenius equation
Quantitatively, the effect of temperature on the rate of a reaction and hence on the rate
constant k, was proposed by Arrhenius and is known as Arrhenius equation.
21
,
where A Pre-exponential factor or frequency factor
k rate constant
Activation energy
R Gas constant
T Temperature (Kelvin)
Using this equation, value can be calculated.
If are the rate constant values at temperatures

then,
and
Taking the difference,
[ ]
[ ]
Thus, knowing the rate constants at two different temperatures, value can be calculate by
using this equation.
The plot of will be a straight line with a ve slope.
Slope =
Thus, measuring the slope of the line, the value of can be calculated.

22
Note that the value of will be positive. Unit of is Joule mol-1.

The frequency factor A has the same unit as that of K.
As the half life of any reaction is inversely proportional to k, if and are the half-lives at two
different temperatures and .
* +.
Q. Calculate the energy of activation of a first order reaction which has half life periods 30 min
at 300 k and 10 min at 320 k respectively.
Solution:
We know that
[ ]
[ ]
(Ans.)
Q. The plot gives a straight line with a slope – Calculate of the
reaction.
Solution:
(– 1 2 104 ) 8 314 9 97 104 J mol 1 ,
1
Ea 99 7 k J mol
***************
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ASSIGNMENT QUESTIONS
1. The half life period for afirst order reactionis 50 sec. How long will it take for completion
of 60%of the reaction ?
2. If the rate of the reaction is equal to the rate constant, what is the order of the reaction ?
3. The initial concentration is 0.2 M in a second order reaction. The reaction is found to be
10% complete in 30 minutes, Calculate (i) the rate const (ii)half life period.
4. If the half –life period for a given reaction doubles when the initial concentration is
doubled, what is the order of the reaction?
5. A Zero order reaction is 50% complete in 20 minutes. What percentage would be
completed at the end of 30 minutes? Find out the time when the concentration would be
zero.
6. Distinguish between the order and molecularity of a reaction.Give examples to show where
they may be the same and where they may be different.
7. For the reaction 2A+B→ 2AB, the rate increases by 8 times when the concentrations of both are
doubled and rate doubles when only concentration of B is doubled. Write down the rate equation.
8. The half life of the reaction become 2.5 times if the concentration is made half . What is the order
of the reaction?
9. The half of the period (t1/2) of the reaction is halved as initial concentration of reactant is doubled
.What is the order of the reaction?
10. The plot of ln K vs. 1/T gave a straight line and the slope was found to be -1.2X104K.
Calculate the activation energy.
11. The value of rate constant far a reaction at 3560C and 4430C are 3X10-5 mol-1dm3s-1 and
2.5X10-3 mol-1dm3s-1 respectively. Calculate Ea forward and backward reaction if ΔH is
16.32 kJ/mol.
12. The activation energy of a first order reaction is 105KJ/mol and the pre exponential
factor has a value of 5X1013sec-1.Find out the temperature at which the half life period is
one minute.
13. The specific rate constant of a reaction increases by a factor 4 if the temperature is changed
from 270 C to 470 C. Find the activation energy for the reaction.

24
14. A bottle of milk stored at 300 sours in 36 hours and in 3 days when refrigerated at 50C.
Assuming the rate constant to be inversely proportional to souring time, Calculate the
activation energy required by souring.
15. A first order reaction is 50 % complete in 20 min at 300 K and the reaction occurs to the
same extent at 10 min .When the temperature is raised to 310 K. Calculate the activation
energy of the reaction.
16. At 3800 C the half life period for first order decomposition of H2O2 is 360 min. The energy of the
activation of reaction is 200 KJ/mol. Calculate the time required for 75% decomposition at 4500C.
17. A hydrogenation reaction is carried out a 500 K. If the same reaction is carried out in
presence of catalyst at same rate, the temperature required is 400 K .Calculate the activation energy
of the reaction if lower activation energy barrier by 20 kj/mol.
18. Write short notes on Homogeneous and Heterogeneous catalysis.
19. What is the function of catalytic promoters and inhibitors in a chemical reaction? Explain with
example.
20. Differentiate between catalytic poisoning and negative catalyst with example.
**************

Sub: Chemistry
BS 1103
1ST/ 2ND SEMESTER (Common to all Branches)
Module
ELECTROCHEMISTRY
Prepared by
Dr.Puspanjali Mishra
Asst. Prof. in Chemistry
PMEC, Berhampur
Odisha
Email: puspanjali.cit@gmail.com
Mob: 9861409540
2
Disclaimer
This document does not claim any originality and cannot be used as
substitute for prescribed textbooks. The information presented here is
merely a collection by the committee faculty members for their respective
teaching assignments as an additional tool for the teaching-learning
process. Various sources as mentioned at the reference of the document as
well as freely available material from internet were consulted of preparing
this document. The ownership of the information lies with the respective
authors or institutions. Further this document is not intended to be used for
commercial purpose and the committee faculty members are not
accountable for any issues, legal or otherwise, arising out of use of this
document. The committee faculty members make no representations or
warranties with respect to the accuracy or completeness of the contents of
this document and specifically disclaim any implied warranties of
merchantability or fitness for a particular purpose.

3
COURSE OUTCOME
i. Electrochemical cell, Concept of oxidation and reduction, Conditions for
reversibility, Cell reaction and cell representation, Relative tendencies of
electrodes to lose electrons.
ii. Cell EMF and single electrode potential covered topics EMF of a cell, Single
electrode potential, Standard reduction potentials, Determination of single
electrode potentials, Reference electrodes, Hydrogen electrode, Calomel
electrode, Electro chemical series
iii. EMF and free energy change, Nernst’s equation, Concentration dependence of
EMF of a cell, Nernst’s equation and single electrode potential, Concentration
cell. Application of EMF measurements, equilibrium constant and PH
measurement.
iv. Concentration cell, Electrode and Electrolyte concentration cell.

4
SYLLBUS:
Module-II
Chapter-2 Electrochemistry (No. of lectures=7)
i. Electrochemical cell
ii. Cell EMF and its measurement
iii. EMF and free energy change of cell reactions
iv. Electrode potential, Standard reduction potentials
v. Determination of single electrode potentials
vi. Reference electrodes: Hydrogen electrode, Calomel electrode
vii. Determination of pH
viii. dry cell, Fuel cell, Storage cell
BOOKS REFERRED:
 Atkin’s Physical Chemistry.
 Physical Chemistry by G.M. Barrow, 6th edition, Tata McGraw Hill, New
Delhi,1992.
 Physical Chemistry by Puri, Sharma & pathania
 Physical Chemistry by S.Glastone
 Physical Chemistry by Bahl & Tuli
 Physical Chemistry by Gurdeep Raj

5
LESSON PLAN
CHEMISTRY
MODULE-II
Chapter-2 ELECTROCHEMISTRY (No. of lectures=7)
LECTURE:1 ELECTROCHEMISTRY
Key Topics: ELECTROCHEMICAL CELL OR GALVANIC CELL,

REVERSIBILITY.
Electrochemical cell, Concept of oxidation and reduction, Conditions for

reversibility, Cell reaction and cell representation, Relative tendencies of
electrodes to lose electrons.
LECTURE:2 & 3 CELL EMF AND SINGLE ELECTRODE POTENTIAL
Key Topics: Cell EMF and single electrode potential, EMF of a cell, Experimental
determination of EMF , Single electrode potential, Standard reduction
potentials, Determination of single electrode potentials, Reference
electrodes, Hydrogen electrode, Calomel electrode, Electro chemical series
& its significance.
LECTURE:4 & 5 FREE ENERGY AND EMF, NERNST’S EQUATION
Key Topics: EMF and free energy change, Nernst’s equation, Concentration dependence
of EMF of a cell, Nernst’s equation and single electrode potential,
Concentration cell. Application of EMF measurements, PH measurement,
equilibrium constant..
LECTURE: 6 CONCENTRATION CELL, DRY CELL, ALKALINE DRY CELL.
Key Topics: Electrolyte concentration cell, Dry cell, Construction , reactions,

Advantages and disadvantages, Alkaline dry cell, Cell reactions.
LECTURE: 7 FUEL CELL, STORAGE CELL,
Key Topics: Fuel cell, Cell reactions and working , Applications, Storage cell, Cell
reactions during charging and discharging, Applications.

6
Electrochemistry
Introduction
Electrolytic Cell: -
A device in which electrical energy is converted in to chemical energy. i.e Chemical
reactions occur when electricity is passed through chemical reactions.
Electro-chemical cell: -
A device in which chemical energy is converted to electrical energy. i.e Electricity can be
generated out of chemical reactions (redox reaction).
Half Reaction: -
Half reactions are conceptual reactions for electron transfer reactions. The total cell reaction
can be expressed as the sum of two half reactions. One involving oxidation (Electron loss by a
species) and the other reduction (electron gain).
For example, ( ) ( ) ( ) ( )
The above reaction is the sum of an oxidation and a reduction half reactions.
( ) ( ) +2e (Oxidation)
( ) +2e ( ) (Redution)
------------------------------------------------------
Over all Reactions: ( ) ( ) ( ) ( )
The corresponding cell can be represented as:-

| ‖ |
The electrode where oxidation reaction occurs is termed as anode and the electrode with reduction
reaction is termed to be cathode.
In the cell representation, anode is written at the left and cathode at right and a // between
anode and cathode.
Electrode Potential:-
When a metal is in contact with 1M solution of its own ion, the tendency of the metallic
electrode to lose (Oxidation Potential) or gain (reduction potential) is known as standard electrode
potential.

7
Measurement of Electrode Potential:-

It is impossible to measure absolute value of single electrode potential because the oxidation
and reduction reactions do not take place independently. It is possible to measure the potential
difference between two electrodes with the help of the potentiometer by taking one reference
electrode along with the electrode whose electrode potential is to be measured.
Reference Electrodes:
I. Standard hydrogen electrode (SHE)
It consists of a platinum foil or wire coated with platinum black dipped in to an I M

solution of H+ ions and H2 gas at 1 atm. Pressure is continuously bubbled through it at 298
K. This electrode may serve as anode or cathode depending upon the other electrode to
which it is connected. The SHE is a reversible electrode. ( ) ( )
It is usually represented as Pt, ( )

(1atm)| ( )
Or ( ) ( )
( )
The standard electrode potential (E0) of a standard hydrogen electrode has been arbitrarily
fixed at zero. The E0el of other electrode can be determined by connecting it with SHE and
finding E0cell experimentally.
Let the cell be Pt, H2 (1 atm)/H+ (1M)//Mn+1(aq)/M(s)
E0cell =E0cathode – E0anode

8
E0cell = E0cathode - E0SHE = E0cathode

E0cathode =E0cell
It is common practice to express all the electrode potentials as reduction potentials. The
standard reduction potentials of all electrodes (at standard states) are determined in a
hydrogen scale (E0SHE =0.0 volt).
Due to practical difficulty in maintaing the (H+)at 1M and H2(g)pressure at 1 atm,
other reference electrodes (whose E0el values are measured in hydrogen scale ) like
saturated calomel electrode may be used.
II. Saturated Calomel Electrode :-
Calomel electrode is commonly used as a secondary reference electrode for potential
measurements.
Saturated Calomel Electrode
It consists of a glass tube in which Hg(l) is placed which is covered with a paste of
solid (Calomel). A saturated solution of KCl is then placed over the paste. A platinum
wire, dipping into the Hg(l) layer is used for electrical contact. The side tube is used for making
electrical contact with a salt bridge.

9
Calomel electrode is a reversible electrode w.r.to Cl- and can be used as cathode as well as anode.
When calomel electrode acts as an anode.
2Hg (l)
( )
-------------------------------------------------------------------------
2Hg(l) + ( )
When it acts as a cathode:-
( ) H2O
2Hg(l)
_________________________________________________
( ) ( )
The [Cl-] is automatically adjusted if saturated KCl solution is used. The Electrode potential of a
saturated calomel electrode in hydrogen scale is Ecalomel =0.2422 V. at 298 K
To obtain the E0el or Eel of any other electrode, it is combined with the saturated calomel electrode
and the emf of the resulting cell is measured. Knowing the Ecell and Ecal values, the Eel of other
electrode can be evaluated.
Ecell =Ecathode – Eanode
E0cell = E0cathode – Eanode
Electro chemical Series:-
The arrangement of the E0el (standard reduction potentials) of various electrodes in a
particular order is called ‘Electro Chemical Series’.

10
Table-1
Electrode Electrode Reaction E0el (Reduction) in volt

Li -3.045
/K -2.93
/ -2.37
/ -0.763
/ 0.00
/ 0.337
/ 0.79
/ +2.87
Significance of Electro chemical Series:

(i) Reducing/ oxidizing capacity: - The electrodes with less E0el values are better reducing
agents (as they have tendency to be oxidized)compared to the other electrodes with more E0el values
(act as better oxidizing agents as they have more tendency to be reduced).
As
Reducing agent.
Oxidizing agent.
Cu +
As
Q. Eo for Zn2+/Zn is – 0.76 V and for Fe3+/Fe2+ is +0.77 V. Which is a better reducing agent
and why?
Solution: Zn is a better reducing agent as
(ii) Displacement of metal from its solution:-

A metal with more can be displaced from its solution by another metal with less .
For example: -
As
11
can displace metallic from solution. Zn whereas the

reserve reaction cannot occur.
Q. solution cannot be kept in a container.Explain.
Ans.
Hence can reduce to give metallic .
( )+
If solution is kept in a copper container, due to the above reaction, will be

reduced and at the same time is going into solution as .
(iii) Displacement of ( ) from acid by metal:-
When Zn dust is put into an acid solution, ( ) is released.
As , ( ) can reduce H+ into H2(g).

But as , metallic Ag cannot displace H2(g) from acid.
(iv). Prediction of cathode and anode in a cell:
The values of both the electrodes in a cell are compared. The electrode with less
will act as an anode and the other electrode with more will act as a cathode.
Example: - In a cell,
As
(iv). Reactivity Series
Metal with less is more reactive in nature.
Example:- The reactivity of Mg > Zn > Cd > Cu > Ag.
Sign of electrode potential:-

According to the latest convention adopted by IUPAC, the electrode potential is given a +ve
sign, if the electrode reaction involves reduction when connected to the standard hydrogen
electrode and a negative sign, if the electrode reaction involves oxidation when connected to the
standard hydrogen electrode whose potential is taken as zero.

12
Thermodynamics of reversible cell

In an electrochemical cell,
The electrical energy=
According to Gibbs and Helmholtz, the electrical energy of a reversible cell originates from the free
energy decrease (- ) of the reaction occurring in the cell.
……………………………….. (1) Where n=No. of electrons involved.
At standard state,
………………………….. (2)
According to Gibbs-Helmholtz equation,
( )
( ) …………………………….. (3)
( )
( ) = temperature coefficient of free energy.
Substituting the value of

( )
( )
( ) ………………………………………. (4) Gibbs-Helmhalt equ of emf.
( ) Temperature coefficient of emf.
( ) at constant pressure,………………………………….. (5)
Where E1 and E2 are the emf of the cell at temp T1 and T2 respectively.
We know that
………………………………………………… (6)
Comparing eqn (4) and eqn(6)
( ) ………………………………………………….. (7)
With the help of equ (1), equ (4) and (6), it is possible to determine various thermodynamic
quantities such as accompaning the cell reaction by measuring emf of the cell and
its temperature co-efficient.
The emf and its temperature dependence help us in determining the various thermodynamic
quantities in standard state such as of a cell reaction.
………………………………… (2)

13
( ) …………………………………………. (8)
And ……………………………….. (9)
Q. In a given cell, when n=2 for the cell reaction, and the emf values are 0.345 V at 298 K and
0.330 V at 308 K, calculate values at 298 K.
Solution:-
( )
( ) ( )
At 298 K,
( )
= 135601.8 J (Ans)
Emf and equilibrium constant of a cell reaction

Let us consider a reaction occurring in a reversible cell be represented by
aA +bB cC +dD.
The decrease in free energy, , accompanying the process is given by the thermodynamic
equation.
( ) ( )
Where Q =( ) ( )
are the activities of A, B, C & D respectively.
At equilibrium, and Q = (equilibrium constant)
= at 298 K.
( )

14
Q. The standard emf of the Daniel cell involving the cell reaction is
1.10 Volts. Calculate the equilibrium constant of the cell reaction at 250C.
Solution:-
n=2, =1.10 V
(Ans).
The Nernst Equation

Effect of the electrolyte concentration on electrode potential and cell emf. :
To obtain the reduction electrode potential of an electrode, one has to consider only reduction
reaction irrespective of the nature of the electrode.
( ) ( )
( )
[ ]
[ ]
[ ]
[ ]
, As [M]=1. (T=298K)
Example:-
(i) ( ) ( ) [ ]
(ii) ( ) ( ) [ ]
(iii) ( ) [ ]
( )
[ ]
(iv) ( ) ( ) [ ]
Similarly for a cell,

15
[ ]
[ ]
[ ] [ ]
[ ] [ ]
at 298K
NB: - For solution, the activities are approximately equal to the molar concentrations and for gases;
activities are replaced by partial pressures. The pure solids, pure liquids and pure gases at 1
atmospheric pressure are assumed to have unit activities.
When then the cell is feasible and the cell reactions are spontaneous.
Q. Calculate Eocell, Keq and Ecell of the cell at 25oC.

Zn/Zn2+ (0.05M)// H+ (0.1M)/ H2(1 atm) /Pt. Given Eo(Zn2+/Zn)= - 0.76V.
Solution:
The cell Zn/Zn2+ (0.05M) // H+ (0.1M)/ H2 (1 atm) /Pt.
The cell reaction : Zn → Zn2+ + 2e
2H++ 2e → H2
______________________________
Zn + 2H+→ Zn2++H2
Eocell = Eo(H+/H2) – Eo(Zn2+/Zn) = 0 – (-0.76) = 0.76 V
( ) ( ) ( )
Keq = = =
[ ]
Ecell = Eocell [ ]
= V
Concentration Cells
The cells in which the EMF is not due to any chemical reaction but due to transfer of matter from
one half-cell to the other because of a difference in the concentration of the species involved are
known as concentration cells.
Concentration cells are of two types;
1. Electrode Concentration Cells,
2. Electrolyte Concentration Cells.

16
1. Electrode Concentration Cells: -

In these cells, two like electrodes at different concentration are dipping in the same solution. Two
hydrogen electrodes at unequal gas pressures immersed in the same solution of H+ ions constitute
an electrode concentration cell. This may be represented as: - ( ) ( ), Pt
Reaction at anode → ( )
Reaction at cathode→ ( )
____________________________
Overall Reaction ( ) ( )
This reaction is independent of the concentration of the electrolyte.

At moderate pressure, can be considered to be an ideal gas so that the ratio of the activities can
be considered to be equal to the ratio of the gas pressures. Hence, Nernst equation may be written
as;
As
When then E will be positive and the whole process is spontaneous.
2. Electrolyte Concentration Cell: -

In these cells, the two electrodes of the same metal are dipping in solutions of metal ions of
different concentration hence of different activities.
For Example,
( ) ( ) ( ) ( )
In this case both the electrodes are of the same metal and are in contact with the solutions of
ions of different concentrations.
The reaction occurring are :
At anode ( )
At cathode ( )
The overall reaction: ( ) ( )

17
The net process thus involves the transfer of ions from the solution of concentration to the
solution with concentration .
According to Nernst equation,
As for concentration cell, ,
E>0 , only when > & the cell will be feasible.
Q. Calculate the EMF of the concentration cell consisting of – electrodes, one immersed in a
solution of 0.01 M and the other in a solution of 0.1 M at 250C. The two solutions are separated by
a salt bridge.
Solution:-
The concentration cell may be represented as:-
( ) ( ) ( )
(Ans.)
Application of EMF Measurements:-
1. Determination of Solubility Products:-

The solubility product of a sparingly soluble salt is a kind of equilibrium constant in a saturated
solution.

18
At 250C,
( )
2. Determination of pH:-
a) By using hydrogen electrode:-
The potential of a hydrogen electrode in contact with a solution of H+ ions involving the
reaction. H+ +e ( )
is given by Nernst equation:
[ ]
=0 0.0591 pH
( )
Thus, the potential of hydrogen electrode depends upon the pH of the solution with which it is in
contact and hence is treated as indicator electrode. To determine the pH of the solution, the
hydrogen electrode can be combined with a reference electrode, say saturated calomel electrode.
The complete cell is represented as:
Pt, H2 (1 atm)/H+(c)//KCl(saturated)/Hg2 Cl2(s), Hg(l), Pt
The emf of the cell is determined potentiometrically. This is given by
( )
Example: The emf of the following cell is 0.445V. Calculate the pH of the solution.
Pt,H2(1atm)/H+(unknown)//KCl(sat.)/Hg2Cl2 /Hg,Pt . E0cal(sat) = 0.2415V.
Solution:-
Ecell= = ( )= )
= =3.44
pH of the solution is 3.44.

19
b) By using Glass electrode:-

The glass electrode (indicator electrode) is made of a special glass of relatively low melting
point and high electrical conductivity. It is blown in the form of a bulb which is then sealed to the
bottom of a glass tube. A solution of 0.1M HCl, which furnishes a constant [H+] concentration,
is placed inside the bulb and a Ag, AgCl electrode or simply a platinum wire is inserted to make
electrical contact. The reference electrode is usually the saturated calomel electrode.
When the glass electrode is immersed in an acid solution, a potential difference exists at the
interface between glass and the solution containing hydrogen ions. The magnitude of this difference
of potential for a given variety of glass varies with the [H+] at 250C,
[ ]
= Eg =
Where is a constant for the given glass electrode. The electrode reaction is assumed to
involve the reduction of H+ ions and is similar to a reversible hydrogen electrode.
20
When the glass electrode is combined with a saturated calomel electrode, the cell may be
represented as,
Pt, 0.1MHCl glass Experimental solution KCl(saturated) HgCl2(s), Hg Pt.
The emf of such a cell can be determined conveniently by means of a potentiometer.
( )
at 25 .
The value of is first obtained by working with solution of known pH.

The glass electrode has a number of advantages over the other electrodes and is very simple
to operate and therefore is used in chemical, industrial, agricultural and biological laboratories.
c) By using quinhydrone electrode:-

The quinone-hydroquinone system involves the following equilibrium,
C6H4O2 +2H+ +2e C6H6O2

(Quinone) (Hydroquinone)
(Q) (QH2)
For the reduction reaction given above, the potential developed on a platinum electrode immersed
in this system is given by the Nernst equation as:
( )
[ ][ ]
( )
[ ][ ]
Instead of taking quinone and hydroquinone, a small amount of quinhydrone, which is an equimolar
mixture of quinone (Q) and hydroquinone , is taken
As [ ] [ ],
The above equation is simplified as
[ ]

21
Thus the potential of quinhydrone electrode depends upon the pH of the solution with which
it is in contact and therefore can be used as an indicator electrode in pH measurement.
This electrode is preferred to the hydrogen electrode.It can be easily prepared by adding a pinch of
quinhydrone to the solution under examination and inserting a platinum electrode for electrical
connection.
The quinhydrone electrode is combined with a saturated calomel electrode to form a cell and
its Emf is measured potentiometrically.
Pt, Hg (l), Hg2Cl2(s) KCl H+ Q, , Pt

(Sat,) (Unknown)
The Emf of the above cell is given by
pH = .

22
Limitation of quinhydrone electrode:-

i. The quinhydrone electrode cannot be used in alkaline solution as hydroquinone ionizes
appreciably and quinone and hydroquinone concentration will no longer be the same which
is the basis of the measurement.In alkaline medium,
and [ ] [ ]
ii. Similarly this electrode cannot be used in presence of oxidizing medium as
Here also [ ] [ ].

23
ASSIGNMENT QUESTIONS
1. For a cell, the cell reaction is:

Mg(s)+Cu2+ (aq) ---Cu(s) +Mg2+(aq)
If the standard reduction potential of Mg and Cu are –2.37V and +0.34V,find the standard
e.m.f.of the cell.
2. What is the e.m.f of the following cell at 250C ?
Zn(s)/Zn2+ (0.01M) //Ag+(0.1M)/Ag(s) ; Given that the standard potential of Zn/Zn2+ and
Ag/Ag+ half cells are –0.76V and +0.80V respectively.
3. The e.m.f of the cell: Ag(s)/AgCl(s)//KCl(aq)/Hg2Cl2(s)/Hg(l) at 270C is 0.0525V and the
temperature coefficient of e.m.f. is +2.98 X 10-5VK-1.Find the free energy change and entropy
change at 270C.
4. The emf of the following cell is 0.445V:
Pt,H2(1atm)/H+(unknown)//KCl(stad)/Hg2Cl2 /Hg. Calculate the pH of the solution. E0KCl(stad) =
0.2415V.
5. The voltage of a cell at 250 C and 20 0C are 0.35252V and 0.35333V respectively .If the no. of
electrons involved in the overall reactions is two, calculate ΔG0 , ΔH0,ΔS0 at 25oC.
6. The eqilibrium constant for the reaction:
Ag(s) + Fe3+(aq) Ag+(aq)+ Fe2+(aq) is 0.335.Find out the standard electrode potential of
Fe3+/Fe2+,Pt ,if standard reduction potential of Ag+/Ag is 0.779V.
7. Discuss how can pH of an unknown solution is measured with glass electrode .
8. A galvanic cell is set up with Zinc and Nickel electrodes. Calculate the standard emf of the cell
(standard reduction potntial of Zinc and Nickel are –0.762V and -0.25V respevtively) .
9. Write down the overall cell reaction for Pt,Hg,Hg2Cl2 / Cl- // H+ / H2,Pt .
10. For the electrochemical cell, M /M+//X- / X, E0M+/M = 0.44 V and E0x/x- =0.33V; predict whether
the reaction,M+ + X- M +X is spontaneous ?
11. Calculate the equilibrium constant K for the following reaction at 298K
3Sn4+ + 2Cr  3Sn2+ +2Cr3+ , Given ,E0Sn/sn2+ = +0.15V, E0Cr3+/Cr = -0.74 V .
12. How is pH of a solution measured using quinhydrone electrode? Why is quinhydrone electrode
not suitable for PH measurement of alkaline solution?

24
13. At what concentration of Ag+(aq) will the e.m.f. of the given cell be zero at 250C,if
concentration of Cu2+(aq) is 0.1M?Cu(s)/Cu2+(0.1M)//Ag+(aq) /Ag(s).Given E0Ag+/Ag= +0.80 V;
E0Cu2+/Cu+=+0.34V.
14. .The e.m.f.of the cell following cell , Ag(s),AgCl(s) / KCl(aq)// Hg2Cl2 (s)/ Hg(1) at 250C is
0.0525 V and it increases by 2.98X10 –5 VK-1. Find the free energy and entropy changes at this
temperature.
15. The standard electrode potential of Pb/Pb+2 is –0.12V while that of the cell Pt/H2/H2SO4/PbSO4
is –0.35 V. Calculate the solubility product.
16. A hydrogen electrode and normal calomel electrode (0.28V) had a voltage of 0.435V When
placed in a solution at 298K.Calcul;ate the pH of the solution.
17. Differentiate between galvanic cell & an electrolytic cell.
18. Zn granules are added in excess to a 500 ml solution of 1 M nickel nitrate at 298K until
equilibrium is reached. Find out the conc. of Ni2+ in solution at equilibrium. (E0 Zn2+/Zn =
`- 0.76V, E0 Ni2+/Ni=-0.24V) .
19. From the standard reduction potentials:
Ce3+ + 3e- → Ce Eo = -2.48V
Ce4+ + e- → Ce3+ Eo = +1.61V
Calculate the reduction potential for the half cell Pt/Ce, Ce4+.
20. Will Fe reduce Fe3+ to Fe2+ ? (E0 Fe3+/Fe2+ = 0.771V , E0 Fe3+/ Fe = -0.441V) .
21. Calculate E0 and ∆ G0 for Cr3 + 2e-→ Cr2+ at 298 K.
Given Cr3+ + 3e- → Cr, E0 = 0.5V, Cr3+ + e- → Cr2+, E0 = -0.41V.
22. Out of Zn, Ni, Zn+2, Ni+ , predict the strongest oxidizing agent and strongest reducing agent?
(Eo :Zn+2 /Zn = -0.763V & Ni+2 /Ni= -0.25V).
***************

SOLID STATE
B.TECH 1st Yr
By
Dr. Puspanjali Mishra
Asst. prof. in Chemistry
PMEC, Berhampur
DEFINITION
• Matter in the solid state is characterized by
definite shape and volume, non
compressibility, very slow diffusion, high
value of rigidity and mechanical strength.
• The atoms, ions or molecules are closely
packed and are held together by strong
force of attraction. .
CRYSTAL STRUCTURE BY X-
RAYS DIFFRACTION STUDIES
Bragg’s equation
in out
n=2d.sin
n: Order of reflection
2
d: Planea spacing
= h k l
2 2 2
: Bragg Angle
CRYSTAL STRUCTURE
• Crystal-A crystal is a solid substance
having a definite geometrical shape
with flat face and sharp edge.
• Crystal lattice/Space lattice – Infinite

arrangement of points in 3D space in
which each point is identically located
with respect to the other.
SPACE LATTICE
CRYSTAL STRUCTURE
Unit cell-
• The smallest building unit in
space of crystal, which when
repeated over and over again in
3D results in a space lattice of the
crystalline substance
UNIT CELL
LATTICE PARAMETERS
• A unit cell is characterized by the Lattice
parameters:
i) Crystallographic length (a, b, c)- The
linear dimensions which the unit cell make
along the crystallographic axes.
ii) Interfacial angles (α, β, γ)-The angle
between the xy, yz, and zx axes
respectively.
LATTICE PARAMETER
β 

c
a
CRYSTAL SYSTEM
• Based on the dimension (axial
lengths a, b, c and angles α, β, γ
of the unit cell, there can be
seven types crystal system.
NAME CONDITIONS EXAMPLES
Cubic a=b=c NaCl, KCl, ZnS,
 = b =  = 90° Diamond
Tetragonal a=bc Sn, SnO2,TiO2
 = b =  = 90°
Orthorhombic a  b c KNO3,BaSO4
 = b =  = 90°
Hexagonal a=bc Zn, Cd, ZnO, Graphite
 = b = 90° , = 120°
Monoclinic abc Monoclinic Sulphur,
 = b = 90°   PbCrO2, CuSO4.2H2O
Triclinic abc CuSO4.5H2O, H2SO4
b 900
Trigonal a =b = c As, Sb, Bi, NaNO3
 = b =  < 120°  90°
UNIT CELL ARRANGEMENTS
OF A CRYSTAL SYSTEM
 Simple/primitive All corners are occupied
by atoms)
 Face centered All corners and all face
centres are occupied by
atoms)
 Body centered All corners and the body
centre are occupied by
atoms)
 End/base centered All corners and any two
opposite face centres are
SIMPLE CUBIC
FACE CENTERED CUBIC
BODY CENTERED CUBIC
END CENTERED
BRAVAIS LATTICE
There are only 14 types of space

lattices corresponding to seven
crystal system and four unit cell
arrangements.
Name Number of Conditions
Bravais lattices
Cubic 3(P,BC,FC) a=b=c
 = b =  = 90°
Tetragonal 2(P,BC) a=bc
 = b =  = 90°
Orthorhombic 4(P, BC,FC,EFC ) a  b c
 = b =  = 90°
Hexagonal 1(P) a=bc
 = b = 90°
 = 120°
Monoclinic 2(P, EFC) abc
 = b = 90°  
Triclinic 1(P) abc
b
Trigonal 1(P) a =b = c
 = b =  < 120° 
90°
UNIT CELL ARRANGEMENTS OF A
CUBIC CRYSTAL
UNIT CELL ARRANGEMENTS OF A CUBIC CRYSTAL
SIMPLE BODY FACE

CUBIC CENTERED CENTERED
CUBIC CUBIC
No.of ATOMS / UNIT CELL
Contribution of an atom to a cubic unit cell:
• Corner atom= 1/8th

• Body centre atom= 1
• Face centre atom=1/2
• Edge centre atom= 1/4th
No.of ATOMS / UNIT CELL
Simple cubic:
No.of atoms/unit cell = 8x1/8 = 1
Body centred cubic:

No.of atoms/unit cell = 8x1/8 + 1= 2
Face centred cubic:

No.of atoms/unit cell = 8x1/8 +6x ½= 4
UNIT CELL LENGTH & RADIUS OF ATOM
Simple cubic: a= cell length

Edge length = a = 2r r= radius of sphere
r = a/2.
BCC :
Body diagonal= 4r =√3a
r= √3a/4
FCC :
Face diagonal= 4r =√2a
r= a/ 2√2
ATOMIC PACKING FRACTION
ATOMIC PACKING FRACTION
For Simple cubic:
For Body centred cubic:
For Face centred cubic:

CLOSED PACKING IN CRYSTAL
• Arrangement/Packing of max no of particles in
smallest possible space (with less void) is called
close packing.
• In 3D there can be 2 types of closed packing
(a) Hexagonal close packing(3rd layer placed over
1st layer)
(b) Cubic close packing(3rd layer containing 3 atom
placed in the left out vacancies of first layer)
HCP CCP
Order of packing- Order of packing-

ABAB… ABCABC…
CN-12 CN-12
P.F.-74 P.F.-74
VOID-26 VOID-26
E.g..-MO, Mg, Be, Cd, E.g.- Fe, Ni, Ag, Au, Ca,
Co, Ti Al
Ionic Crystals
• Assume the anion is larger than the cation.
• The anions will pack together in definite
lattice positions.
• The cations will then be inserted into voids
or gaps created by larger ions.
• When the cation is larger than the hole into
which it is inserted, the anions in the
structure are pushed apart and thus are not
in physical contact.
Radius Ratio
Void type Void Coordination radius ratio

geometry No.
Tetrahedral Tetrahedral 4 r/R ≥0.225
< 0.414
Octahedral Octahedral 6 r/R ≥0.414
< 0.732
Cubic Cubic 8 r/R ≥0.732
< 1.0
NaCl
CsCl
ZnS
CaF2
THANK U

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Sub: Chemistry

1ST/ 2ND SEMESTER (Common to all Branches)

Asst. Prof. in Chemistry

2. Factors influencing the rate of a reaction.

4. Methods of determination of order of a reaction.

5. Theory of reaction rates, Collision theory, Theory of absolute reaction rates.

6. Effect of temperature on the rate of reaction. Activation energy ,Calculation of

activation energy, Arrhenius equation.

7. Catalysts, Homogeneous and Heterogeneous catalysis, Theories of catalysis,

Adsorption theory, Intermediate compound formation theory.

Dr. Puspanjali Mishra. Asst. Prof in Chemistry, PMEC, Berhampur

Chapter-1 Chemical Kinetics (No. of lectures=7)

I. Rate law, Order and molecularity

II. Factors influencing the rate of a reaction

III. Kinetics of zero and first and second order reactions

IV. Methods of determination of order of a reaction

V. Collision theory,Theory of absolute reaction rates

VI. Energy of activation

VII. Homogeneous and Hetrogeneous catalysis.

 Physical Chemistry by Puri, Sharma & pathania

 Physical Chemistry by S.Glastone

 Physical Chemistry by Bahl & Tuli

 Physical Chemistry by Gurdeep Raj

Dr. Puspanjali Mishra. Asst. Prof in Chemistry, PMEC, Berhampur

Chapter-1 Chemical Kinetics (No. of lectures=7)

LECTURE:1 CHEMICAL KINETICS,REACTION KINETICS, RATE LAW

LECTURE:2 & 3 RATE EQUATION OF SECOND ORDER REACTIONS.

LECTURE:4 & 5 DETERMINATION OF ORDER OF A REACTION.

Key Topics: Methods of determination of order of a reaction. (i) Integration method,

LECTURE:6 THEORY OF REACTION RATES, ACTIVATION ENERGY.

Key Topics: Catalysts, Homogeneous and Hetrogeneous catalysis, Theories of

Dr. Puspanjali Mishra. Asst. Prof in Chemistry, PMEC, Berhampur

In general, for the reaction,

Dr. Puspanjali Mishra. Asst. Prof in Chemistry, PMEC, Berhampur

Factors affecting the rate of a reaction:

Rate law and rate constant :

Where concentration of the reactant A at the given instant.

Characteristics of Rate constant:

Dr. Puspanjali Mishra. Asst. Prof in Chemistry, PMEC, Berhampur

 It is the sum of the exponents of the  It is the number of atoms or molecules

Integrated Rate Reaction:-

(a) H2 (g) +Cl2 (g) → in presence of H2O.

Half life period (t1/2 ):-

Dr. Puspanjali Mishra. Asst. Prof in Chemistry, PMEC, Berhampur

as x=a at 100% reaction.

b) First Order Reaction: - n=1.

Dr. Puspanjali Mishra. Asst. Prof in Chemistry, PMEC, Berhampur

Half Life Period:-

At 80% of the reaction,

Examples of 1st order reactions:

c) 2nd order Reaction

rate = [ ][ ] ………………. (1)

On integration, by using partial fraction method,

Dr. Puspanjali Mishra. Asst. Prof in Chemistry, PMEC, Berhampur

when > b …………………. (4)

When …………………… (5)

The unit of k2 = conc-1 time-1 = lit mol-1 sec-1.

Equation (4) becomes, k2 =

k2‟ = k2 = ……………… (6)

CH3COOC2H5 + H20 H+ CH3COOH + C2H50H

Case II, when the reactants are same or [A] = [B]:

Dr. Puspanjali Mishra. Asst. Prof in Chemistry, PMEC, Berhampur

Plot of vs. t gives a straight line with intercept and slope = k2