Course Code: CH-380

Course Title: Physical Chemistry-I

BS-Chemistry ( Semester V)

Dr. Khadija Munawar

Assistant Professor
Department of Chemistry, School of Natural Sciences,
National University of Sciences and Technology(NUST), Islamabad
Course Contents
 Assessments
Mid Term Exam
(after 8 weeks of semester)
Assignments: 2-3
Quizzes:3-4 (announced/unannounced
Final Term Exam
(after 16 weeks of semester)
Chemical Kinetics
Lecture # 1
15th September 2023
 Chemical Kinetics/Reaction Kinetics
Kinetics mean motion/movement

Branch of Chemistry which deals with

Rate of chemical reaction
Factors affecting rate of reaction
o Temperature (Arrhenius equation)
o Concentration (Order of reaction)
Mechanism of reaction
 Types of Reactions
On the basis of rate, three types of reactions:
Very fast reactions: nano/pico sec.
(Ionic reactions)
Very slow reactions: years
(rusting of iron)
Moderate reactions: hours/mints/sec.
(molecular reactions)
Require finite time to break and form bonds
So chemical kinetics deals with moderate reactions
 Rate of Reaction
Rate mean speed, so rate/speed is defined as:

Change in concentration of reactant/product w.r.t. time

Rate: Change in concentration/Time taken
: Cf-Ci/tf-ti
EXAMPLES: A→B
The change in con. used ,the same time interval is used
respect to that con.
Rate of any reaction can not be determined
Rate of reaction of some particular reactions are calculated
 Individual Rate
(Rate of Reactant/Rate of product)

Example: 2A+3B→5C
Rate of A or rate of disappearance of A or rA
-dA/dT
Rate of B or rate of disappearance of B or rB
-dB/dT
Rate of C or rate of appearance of C or rC
dC/dT
All rates equal or not?
If No then what is the sequence of increasing order?
 Rate of Reaction
Example: 2A+3B→5C
rA≠rB≠rC
Rate of reaction and individual rate of
reaction are not equal and there is no
role of stoichiometric coefficients in
individual rates
what is the rate of reaction then?
 Rate of Reaction
Example: 2A+3B→5C
rA≠rB≠rC
Rate of one mole or one con. change per
unit time is known as rate of reaction

Rate= 1/2.rA=1/3.rB =1/5.rC

Rate of Reaction
 Rate of Reaction
Example:

4NH3+5O2→4NO+6H2O

Write rate of reaction, rate of

appearance of NO, rate of
disappearance of O2
 Individual Rate
(Rate of Reactant/Rate of product)
Ratio of rate and ratio of moles
are same in a balanced chemical equation
Examples: A+2B→3C
(Ans: If we have a rate of A then we can get the values of rate
of B and C by multiplying the no of moles of respective specie)
2A→B
(Ans: The no. of moles of A are double the no. of moles of B
so the rate of A will be the double of rate of B)
 Individual Rate
(Rate of Reactant/Rate of product)

Example:

N2+3H2→2NH3
rNH3= 0.001, rH2 = ?
 Types of Rate
Two types of rate:

Instantaneous rate (very small interval of time)

Rate: dc/dt = Slope of tangent
Example: A+3B→4C
Average rate (large interval of time)
Rate: Cf-Ci/tf-ti
Example: A+3B→4C
Graphical representation of
rate of reaction

Examples: 2A→B
A→B
A→2B
A→B+2C+3D
 Molecularity of Reaction
Total number of reactant molecules collide
simultaneously in an elementary chemical reaction

Can not be zero, fractional, negative

Only Positive value (1,2,3)
Max. molecularity is 3 (more than 3 molecules
can collide but product will not form)
For complex reactions, it is not defined or
meaningless
 Order of reaction
The rate of chemical reaction is represented
by equation know as Rate Law Equation or
Rate expression equation

Sum of the powers of the concentrations of

the reactant in the rate law expression
equation is known as order of reaction

Order of reaction is not affected with

stoichiometric coefficients
 Order of reaction
Example: 2A+3B→5C
Rate = k [A] .[B] m n

m+n= order of reaction

It may be equal to or may not be equal to

stoichiometric
Experimental quantity coefficients
May be zero, fractional, negative, positive
Max. order is 3
 Order of reaction
Example:
A→B
Rate = k[A] n

Rate = k[A] ,Rate = k

0

Rate = k[A]1 ,Rate α [Con]

Rate = k[A] ,Rate α [Con]
2 2

Rate = k[A] ,Rate α [Con]

3 3
Order of reaction
 Units of Rate and Rate Constant
Rate = d[C]/dt = Molarity/Sec = Mol.dm-3/Sec

The unit of rate always remain same but

the unit of rate constant changes by
changing the rate of reaction

Q: What are the units of rate constant for zero,

first, second and third order reactions?
Units of Rate and Rate Constant