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Chemical Kinetics (Complete Unit)
Chemical Kinetics (Complete Unit)
Chemical Kinetics (Complete Unit)
Thermodynamics
feasibility
Equilibrium
extent
Kinetics
Rate of the
reaction
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Types of reactions
Precipitation reaction,Neutralisation
fast reaction
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Content of the chapter
Concentration as a function
of time
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Definitions
Chemical Kinetics:-
Study of reaction rates and their mechanisms
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Rate of a chemical reaction:
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Rate of a reaction
A→B
• Rate of disappearance of A = -d[A] /dt
• Rate of formation of B = +d[B] /dt
• d[A] = change in concentration of A over time period dt
• Because [A] decreases with time, d[A] is negative.
• d[B] = change in concentration of B over time period dt
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Graphical representation of rate of a reaction
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AVERAGE RATE • INSTANTANEOUS
Instantaneous rate
RATE
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?
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A
-Δ[ R]/ Δt
= -( 0.02-0.03)/25 M min‾¹
=4X10‾⁴ M min‾¹
=4X10‾⁴/ 60M sec‾¹
=6.67x10 ‾⁶M sec‾¹
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For a reaction
aA+bB→cC+dD
Rate of a reaction=
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Examples
N2 +3 H2 → 2NH3
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Factors affecting rate of reaction
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Effect of concentration
Rate Law
Rate of a reaction is directly proportional to
concentration of reactants raised to some power
Which may or may not be same as
stoichiometric coefficient of reactants in a
balanced chemical equation.
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Differrential rate equation
For a reaction:
aA + bB → Product
Rate = k[A]x[B]y
k is called rate constant
x and y may or may not be equal to stoichiometric
coefficient a and b
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Example
2NO+O2→ 2NO2
2
rate=k [NO ] [ O2 ]
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Order of a reaction
Sum of the powers of the concentration of the
reactant terms in experimentally determined rate
equation.
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?
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Examples of zero order reaction
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Examples of First Order reaction
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Order of reactions…
A
X→ Y follows second order kinetics
r =k [X] 2
X is increase 3 times ,rate will become 9 times
r =k [3X] 2 i.e., r= 9x k X2
Unit of rate constant
Depending on the order of the reaction unit of
rate constant changes
For a general reaction aA+bB → cC+dD
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Units of rate constant
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?
Identify order of the reaction if the units of its rate
constant are i)L‾¹ mol sec‾¹ ii)L mol‾¹ sec‾¹
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?
.
The decomposition reaction of NH3
on platinum surface is given
N2 +3 H2 → 2NH3
What are the rates of production of N2 and H 2
if K= 2.5 X10-4mol l-1 s-1
A der
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Elementary Reaction
in one step
NH4NO2 → N2 + 2H2O
N2O4(g) → 2NO2(g)
Molecularity
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Molecularity….
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Complex reactions
Definition:
Multistep reactions where products are
obtained after completion of a sequence of
elementary reactions
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Slow
fast
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Difference between order and molecularity
order molecularity
Experimental quantity theoretical
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Integrated rate equations
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Integrating both sides
[R] = – k t + I
where, I is the constant of integration.
At t = 0, the concentration of the reactant [R]=[R]o
where [R]o is initial concentration of the reactant.
Substituting in equation )
[R] = –k × 0 + I ]
[R]o=1
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Concentration vs Time plot for zero order
reaction
[R0]
Concentration of R
Time
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First Order Reactions
Consider the reaction,
R→P
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Concentration vs Time plot for first order reaction
y=mx+c
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Half Life of a reaction
The half-life of a reaction is the time in which the
concentration of a reactant is reduced to one half of its
initial concentration. It is represented as t1/2
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Half life for a first order reaction
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A
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Temperature dependence of the rate of reaction:
T –temperature
k-rate constant
R-universal gas constant
Ea-activation energy
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Temperature dependence of the rate of reaction:
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Transition State Theory
According to Arrhenius, reaction takes place
through formation of unstable Intermediate
called activated complex which exist for short
time and then breaks up to form product.
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Activation energy (Ea)
• Ea is always positive.
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Increasing the temperature of the substance
increases the fraction of molecules, which collide
with energies greater than Ea.
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It is clear from the diagram that in the curve at (t + 10),
the area showing the fraction of molecules having energy
equal to or greater than activation energy gets doubled
leading to doubling the rate of a reaction.
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For a chemical reaction with rise in
temperature by 10°, the rate constant is nearly
doubled
k(T+10)
The ratio kT is called the temperature
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Arrhenius Equation
k = A e-Ea /RT
e-Ea /RT = Fraction of molecule having K.E. > Ea
Natural logarithm of Arrhenius equation gives
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Arrhenius Equation
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Arrhenius Equation
Equation - 2
Equation - 1
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Effect of catalyst on rate of reaction
A catalyst is a substance which alters the rate of a
reaction without itself undergoing any permanent
chemical change.
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Effect of Catalyst on Rate of reaction
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Collision theory
Rate = ZABe-Ea/RT
Z AB the number of collisions per second per
unit volume of the reaction mixture.
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Collision theory continued…..
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Collision theory…
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