Prepared by : Niloy Mondal

ID: 18.01.04.135

Rate of Reactions:
Reaction rate, the speed at which a chemical reaction proceeds. It is often expressed in terms of either
the concentration (amount per unit volume) of a product that is formed in a unit of time or the
concentration of a reactant that is consumed in a unit of time.
The speed of a chemical reaction may be defined as the change in concentration of a substance divided by
the time interval during which this change is observed:
rate=Δconcentration/Δtime
For a reaction of the form A+B→CA+B→C, the rate can be expressed in terms of the change in
concentration of any of its components

rate=−Δ[A]/Δt rate=−Δ[B]/Δt rate=Δ[C]/Δt

in which Δ[A] is the difference between the concentration of A over the time interval t2 – t1:
Δ[A]=[A]2–[A]1
Notice the minus signs in the first two examples above. The concentration of a reactant always decreases
with time, so Δ[A]&[A] are both negative. Since negative rates do not make much sense, rates expressed in
terms of a reactant concentration are always preceded by a minus sign to make the rate come out positive.

Consider now a reaction in which the coefficients are different:

A+3B→2D
It is clear that [B] decreases three times as rapidly as [A], so in order to avoid ambiguity when expressing
the rate in terms of different components, it is customary to divide each change in concentration by the
appropriate coefficient:
rate=−Δ[A]/Δt=−Δ[B]/3Δt=Δ[D]/2Δt

Rate Laws:
At a fixed temperature the rate of a given reaction depends on concentration of reactants.
The exact relation between concentration and rate is determined by measuring the reaction
rate with different initial reactant concentrations. By a study of numerous reactions it is
shown that : the rate of a reaction is directly proportional to the reactant concentrations, each
concentration being raised to some power.
Thus for a substance A undergoing reaction,
 rate ∝ [A]^n
or, rate = k [A]^n ...(1)
For a reaction
2A + B ⎯⎯→ products
the reaction rate with respect to A or B is determined by varying the concentration of one reactant,
keeping that of the other constant. Thus the rate of reaction may be expressed as
rate = k [A]^m [B]^n ...(2)
Expressions such as (1) and (2) tell the relation between the rate of a reaction and reactant
concentrations.
An expression which shows how the reaction rate is related to concentrations is called the rate
law or rate equation.
The power (exponent) of concentration n or m in the rate law is usually a small whole number
integer (1, 2, 3) or fractional. The proportionality constant k is called the rate constant for the reaction.
Examples of rate law :
REACTIONS RATE LAW
(1) 2N2O5 ⎯⎯→ 4 NO2 + O2 ; rate = k [N2O5]
(2) H2 + I2 ⎯⎯→ 2HI ; rate = k [H2] [I2]
(3) 2NO2 ⎯⎯→ 2NO + O2 ; rate = k [NO2]2
(4) 2NO + 2H2 ⎯⎯→ N2 + 2H2O ; rate = k [H2] [NO]2
In these rate laws where the quotient or concentration is not shown, it is understood to be 1. That
is [H2]^1 = [H2].
It is apparent that the rate law for a reaction must be determined by experiment. It cannot be
written by merely looking at the equation with a background of our knowledge of Law of Mass Action.
However, for some elementary reactions the powers in the rate law may correspond to coefficients in
the chemical equation. But usually the powers of concentration in the rate law are different from
coefficients. Thus for the reaction (4) above, the rate is found to be proportional to [H2] although the
quotient of H2 in the equation is 2. For NO the rate is proportional to [NO]2 and power ‘2’ corresponds
to the coefficient.

Order of Reactions:

The order of a reaction is defined as the sum of the powers of concentrations in the rate law.
Let us consider the example of a reaction which has the rate law
rate = k [A]^m [B]^n ...(1)
The order of such a reaction is (m + n).
The order of a reaction can also be defined with respect to a single reactant. Thus the reaction
order with respect to A is m and with respect to B it is n. The overall order of reaction (m + n) may range
from 1 to 3 and can be fractional.

Examples of reaction order :

RATE LAW REACTION ORDER
rate = k [N2O5] 1
rate = k [H2] [I2] 1+1=2
rate = k [NO2]2 2
rate = k [[H2] [NO]2 1+2=3
rate = k [CHCl3] [Cl2]^1/2 1+1/2=3/2

Reactions may be classified according to the order. If in the rate law (1) above
m + n = 1, it is first order reaction
m + n = 2, it is second order reaction
m + n = 3, it is third order reaction
MOLECULARITY OF REACTIONS:

Chemical reactions may be classed into two types :

(a) Elementary reactions
(b) Complex reactions
An elementary reaction is a simple reaction which occurs in a single step.
A complex reaction is that which occurs in two or more steps.
Molecularity of an Elementary Reaction
The molecularity of an elementary reaction is defined as : the number of reactant molecules
involved in a reaction.

Thus the molecularity of an elementary reaction is 1, 2, 3, etc., according as one, two or three
reactant molecules are participating in the reaction. The elementary reactions having molecularity 1, 2
and 3 are called unimolecular, bimolecular and termolecular respectively. Thus we have :
(a) Unimolecular reactions : (molecularity = 1)
A ⎯⎯→ product
Examples are : (i) Br2 ⎯⎯→ 2Br
(ii) H C COOH-H C COOH ⎯⎯→ COOH C H- H C COOH
maleic acid fumaric acid

(b) Bimolecular reactions : (molecularity = 2)

A + B ⎯⎯→ products
A + A ⎯⎯→ products
Examples are :
(i) CH3COOC2H5 + H2O ⎯⎯→ CH3COOH + C2H5OH
Ethyl acetate acetic acid ethyl alcohol
(ii) 2HI ⎯⎯→ H2 + I2
(c) Termolecular reactions : (molecularity = 3)
A + B + C ⎯⎯→ products
Examples are :
2NO + O2 ⎯⎯→ 2NO2
2NO + Cl2 ⎯⎯→ 2NOCl

Half Life of Reaction:

The half-life of a reaction, t1/2, is the amount of time needed for a reactant concentration to decrease
by half compared to its initial concentration.

Zero Order
the zero order kinetic rate law is as followed, where [A] is the current concentration, [A]0 is the initial
concentration, and k is the reaction constant and t is time:
[A]=[A]0−kt
In order to find the half life we need to isolate t on its own, and divide it by 2. We would end up with a
formula as such depict how long it takes for the initial concentration to dwindle by half:
t1/2=[A]0/2k
The t1/2 formula for a zero order reaction suggests the half-life depends on the amount of initial
concentration and rate constant.

First Order
 In order to solve the half life of first order reactions, we recall that the rate law of a first order reaction
was:
[A]=[A]0e−kt
To find the half life we need to isolate t and substitute [A] with [A]0/2, we end up with an equation looking
like this:
t1/2=ln2/k≈0.693k
The formula for t1/2 shows that for first order reactions, the half-life depends solely on the reaction rate
constant, k. We can visually see this on the graph for first order reactions when we note that the amount
of time between one half life and the next are the same. Another way to see it is that the half life of a first
order reaction is independent of its initial concentration.

Second Order
In order to solve for half life of second order reactions we need to remember that the rate law of a second
order reaction is:
1/[A]=kt+1/[A]0
As in zero and first order reactions, we need to isolate T on its own:
t1/2=1/k[A]0
This replacement represents half the initial concentration at time, t (depicted as t1/2). We then insert the
variables into the formula and solve for t1/2. The formula for t1/2 shows that for second order reactions, the
half-life only depends on the initial concentration and the rate constant.

Determination of Order of Reactions:

Zeroth-Order Reactions
A zeroth-order reaction is one whose rate is independent of concentration; its differential rate law is rate
= k. We refer to these reactions as zeroth order because we could also write their rate in a form such that
the exponent of the reactant in the rate law is 0:
rate=−Δ[A]/Δt=k[reactant]0=k(1)=k
Because rate is independent of reactant concentration, a graph of the concentration of any reactant as a
function of time is a straight line with a slope of −k. The value of k is negative because the concentration of
the reactant decreases with time. Conversely, a graph of the concentration of any product as a function of
time is a straight line with a slope of k, a positive value.
The graph of a zeroth-order reaction. The change in concentration of reactant and product with time
produces a straight line.
The integrated rate law for a zeroth-order reaction also produces a straight line and has the general form
[A]=[A]0−kt
where [A]0 is the initial concentration of reactant A. (Equation 14.16 has the form of the algebraic equation
for a straight line, y = mx + b, with y = [A], mx = −kt, and b = [A]0.) In a zeroth-order reaction, the rate
constant must have the same units as the reaction rate, typically moles per liter per second

First-Order Reactions
In a first-order reaction, the reaction rate is directly proportional to the concentration of one of the
reactants. First-order reactions often have the general form A → products. The differential rate for a first-
order reaction is as follows:
rate=−Δ[A]/Δt=k[A]
If the concentration of A is doubled, the reaction rate doubles; if the concentration of A is increased by a
factor of 10, the reaction rate increases by a factor of 10, and so forth. Because the units of the reaction
rate are always moles per liter per second, the units of a first-order rate constant are reciprocal seconds
(s−1).
The integrated rate law for a first-order reaction can be written in two different ways: one using exponents
and one using logarithms. The exponential form is as follows:
[A]= [A]0e−kt
where [A]0 is the initial concentration of reactant A at t = 0; k is the rate constant; and e is the base of the
natural logarithms, which has the value 2.718 to three decimal places. Recall that an integrated rate law
gives the relationship between reactant concentration and time. By taking the natural logarithm of each
side of Equation 14.20 and rearranging, we obtain an alternative logarithmic expression of the relationship
between the concentration of A and t:
ln[A]=ln[A]0 −kt
Because Equation 14.21 has the form of the algebraic equation for a straight line, y = mx + b, with y = ln[A]
and b = ln[A]0, a plot of ln[A] versus t for a first-order reaction should give a straight line with a slope of
−k and an intercept of ln[A]0. Either the differential rate law or the integrated rate law (Equation 14.21) can
be used to determine whether a particular reaction is first order.
Graphs of a first-order reaction. The expected shapes of the curves for plots of reactant concentration
versus time (top) and the natural logarithm of reactant concentration versus time (bottom) for a first-order
reaction

Second-Order Reactions
The simplest kind of second-order reaction is one whose rate is proportional to the square of the
concentration of one reactant. These generally have the form 2A → products. A second kind of second-
order reaction has a reaction rate that is proportional to the product of the concentrations of two
reactants. Such reactions generally have the form A + B → products. An example of the former is a
dimerization reaction, in which two smaller molecules, each called a monomer, combine to form a larger
molecule (a dimer).
The differential rate law for the simplest second-order reaction in which 2A → products is as follows:
rate=−Δ[A]/2Δt=k[A]^2
Consequently, doubling the concentration of A quadruples the reaction rate. For the units of the reaction
rate to be moles per liter per second (M/s), the units of a second-order rate constant must be the inverse
(M−1·s−1). Because the units of molarity are expressed as mol/L, the unit of the rate constant can also be
written as L(mol·s).
For the reaction 2A → products, the following integrated rate law describes the concentration of the
reactant at a given time:
1/[A]=1/[A]0+kt
Because Equation 14.23 has the form of an algebraic equation for a straight line, y = mx + b, with y = 1/[A]
and b = 1/[A]0, a plot of 1/[A] versus t for a simple second-order reaction is a straight line with a slope
of k and an intercept of 1/[A]0.

Key Equations
zeroth-order reaction
Equation 14.15: rate=−Δ[A]/Δt=k
Equation 14.16: [A] = [A]0 − kt
first-order reaction
Equation 14.19: rate=−Δ[A]/Δt=k[A]
Equation 14.20: [A] = [A]0e−kt
Equation 14.21: ln[A] = ln[A]0 − kt
second-order reaction
Equation 14.22: rate=−Δ[A]/Δt=k[A]^2
Equation 14.23: 1/[A]=1/[A]0+kt

Temparature Dependence of Reaction rate:

The Arrhenius Equation
For an A + B elementary reaction, all the factors that affect the reaction rate can be summarized in a single
series of relationships:
rate = (collision frequency)(steric factor)(fraction of collisions with E > Ea)
where rate=k[A][B]
Arrhenius used these relationships to arrive at an equation that relates the magnitude of the rate constant
for a reaction to the temperature, the activation energy, and the constant, A, called the frequency factor:
k=Ae−Ea/RT
The frequency factor is used to convert concentrations to collisions per second. Because the frequency of
collisions depends on the temperature, A is actually not constant. Instead, Aincreases slightly with
temperature as the increased kinetic energy of molecules at higher temperatures causes them to move
slightly faster and thus undergo more collisions per unit time. T is the absolute temperature (in K) and R is
the ideal gas constant [8.314 J/(K·mol)]. Ea indicates the sensitivity of the reaction to changes in
temperature. The reaction rate with a large Ea increases rapidly with increasing temperature, whereas the
reaction rate with a smaller EaEa increases much more slowly with increasing temperature.
If we know the reaction rate at various temperatures, we can use the Arrhenius equation to calculate the
activation energy.
lnk=lnA+(−Ea/RT)=lnA+[(−Ea/R)(1/T)]

Theories of Reaction Rate:

Transition state theory are as follows:
1. Rates of reaction can be studied by examining activated complexes near the saddle point of
a potential energy surface. The details of how these complexes are formed are not important. The
saddle point itself is called the transition state.
 2. The activated complexes are in a special equilibrium (quasi-equilibrium) with the reactant
molecules.
3. The activated complexes can convert into products, and kinetic theory can be used to calculate the
rate of this conversion.

Collision Theory
If two molecules need to collide in order for a reaction to take place, then factors that influence the ease of
collisions will be important. The more energy there is available to the molecules, the faster they will move
around, and the more likely they are to bump into each other. Higher temperatures ought to lead to more
collisions and a greater frequency of reactions between molecules. In the drawing below, the cold, sluggish
molecules on the left are not likely to collide, but the energetic molecules on the right are due to collide at
any time. The concepts of collision frequency can be applied in the laboratory:
(1) The temperature of the environment affects the average speed of molecules. Thus, reactions are
heated to increase the reaction rate.
(2) The initial concentration of reactants is directly proportional to the collision frequency; increasing the
initial concentration will speed up the reaction.
For a successful collision to occur, the reactant molecules must collide with enough kinetic energy to break
original bonds and form new bonds to become the product molecules. This energy is called the activation
energy for the reaction; it is also often referred to as the energy barrier.