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Dr.S.Alexandar,M.Pharm,Ph.D,
Associate Professor
Vinayaka Missions College of Pharmacy,
Yercaud main road,
Kondappanaickanpatty,
Salem,Tamilnadu,
Pin:636008
Chemical Kinetics
A study of
(1) reaction rates
(2) the factors affecting reaction rates
(3) reaction mechanisms
(the detailed steps involved in
reactions)
Outline: Kinetics
Reaction Rates How we measure rates.
Rates of Reaction
An important part of studying
chemical reactions is to monitor the
speed at which they occur. Chemists
look at how quickly, or slowly,
reactions take place and how these
rates of reaction are affected by
different factors.
k = rate constant
m and n = reaction orders (not related to a, b,...)
α β
Rate law : R = k [A] [B] ...
Rate Constant
Then, the overall order of the reaction is (m+n). The order with respect to A is m.
The order with respect to B is n. If m=1; n=0 and vice versa, the order of the
reaction is 1, and the reaction is called first order. If m=1, n=1, the order of the
reaction is 2 and the reaction is called second order and so on. A zero order
reaction is one where the reaction rate does not depend upon the concentration of
the reactant. In this type of reaction, the rate constant is equal to the rate of the
reaction.
Determining order of reaction
∆[ A ]
Rate = − = k[ A ]
∆t
Concentration-Time Equations
First-Order Integrated Rate Law
– Using calculus, you get the following equation.
[ A]t
ln = - kt
[ A]o
– Here [A]t is the concentration of reactant A at time t, and [A]o is the
initial concentration.
– The ratio [A]t/[A]o is the fraction of A remaining at time t.
Concentration-Time Equations
Second-Order Integrated Rate Law
– You could write the rate law in the form
∆[ A ] 2
Rate = − = k[ A ]
∆t
Concentration-Time Equations
Second-Order Integrated Rate Law
1 1
= kt +
[ A]t [A]o
– Here [A]t is the concentration of reactant A
at time t, and [A]o is the initial concentration.
Concentration-Time Equations
Zero-Order Integrated Rate Law
– The Zero-Order Integrated Rate Law equation
is:.
[ A] = −kt +[ A]o
Half-life
The half-life of a reaction is the time required
for the reactant concentration to decrease to
one-half of its initial value.
0.693
t =
1
2
k
Half-Life (1st order)
Half-life: the time
that it takes for the
reactant
concentration to drop
to half of its original
value.
Half-Life
The decomposition of ethane (C2H6) to methyl radicals
(⋅CH3) is a first order reaction with a rate constant of
5.36 x 10−4 s−1 at 700 0C.
C2H6 → 2CH3
1 min
1293 s × =21.5 min
60 s
Half-life
The half-life of a reaction is the time required
for the reactant concentration to decrease to
one-half of its initial value.
ln( 12 ) = −kt 1
2
Half-life
For a second-order reaction, half-life
depends on the initial concentration and
becomes larger as time goes on.
– Again, assuming that [A]t = ½[A]o after one half-life, it can be shown that:
1
t =
1
2
k[ A]o
Half-life
For Zero-Order reactions, the half-lite is
dependent upon the initial concentration
of the reactant and becomes shorter as
the reaction proceeds.
[ A ]o
t1 =
2
2k
Summary of Orders
Graphing Kinetic Data
In addition to the method of initial rates, rate laws can
be deduced by graphical methods.
This means if you plot ln[A] versus time, you will get a straight line for a
first-order reaction.
Graphing Kinetic Data
– If we rewrite the second-order concentration-time equation in a slightly
different form, it can be identified as the equation of a straight line.
1 1
= kt +
[ A]t [ A]o
y = mx + b
This means if you plot 1/[A] versus time, you will get a straight line
for a second-order reaction.
Graphical Methods
Given concentration and time data,
graphing can determine order
Collision Theory
Rate constants vary with temperature.
Consequently, the actual rate of a
reaction is very temperature dependent.
Otto Cycle
Diesel Cycle
Carnot Cycle
Isothermal Process: the temperature of the system and the surroundings remain
constant at all times. (q=-w)
The most efficient heat engine cycle is the Carnot cycle, consisting of two
isothermal processes and two adiabatic processes. The Carnot cycle can be thought of
as the most efficient heat engine cycle allowed by physical laws. When the
second law of thermodynamics states that not all the supplied heat in a heat engine can
be used to do work, the Carnot efficiency sets the limiting value on the fraction of the
heat which can be so used.
Phase Rule
The phase rule is an important generalization dealing with the
behavior of heterogenous systems. In general it may be studied with
the application of phase rule is it is possible to predict qualitatively
by means of diagram the effect of changing pressure, temperature
and concentration on a heterogenous system in equilibrium. For a
closed, homogeneous system of constant composition (e.g., an ideal
gas), we require two parameters of state (for example, T and p) in
order to describe it. For a heterogeneous system in equilibrium,
consisting of one component (e.g., water substance) and two phases
(e.g., liquid and vapour), we require only one parameter of state
(for example, T). The phase rule allows one to determine the
number of degrees of freedom (F) or variance of a chemical system.
This is useful for interpreting phase diagrams
The least number required to define the state of the system.
Degrees of Freedom
Intensive variables that must be known to describe the system
completely. Ex. temperature, concentration, pressure, density, etc.
F = C− P+ 2
This example may be expressed more generally in terms of Gibb’s phase rule:
F=C–P+2
Where
c is number of components
The number two is specified because this formulation assumes that both T and P can be
varied.
F = C – P + 2 = 1 – P + 2 = 3-P
F=3–1=2
F=3–2=1
Phase Diagram for H2O