CHEMICAL KINETICS Chemical Thermodynamics vs Chemical Kinetics

- deals with the study of rates of chemical reaction

and with the elucidation of the mechanism by which Spontaneity of Rate/speed of
the reaction proceed reaction reaction
- supplies information about the rate and mechanism
responsible for the conversion of reactants to
products
SPONTANEOUS does not mean FAST
FAST does not mean SPONTANEOUS

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Factors affecting rate of reaction:

For a reaction to 1. Concentration of species
occur: concentration, frequency of collision, rate
Thermodynamically 2. Temperature
favorable temperature, frequency of collision, rate
G = (-) 3. Pressure
pressure, frequency of collision, rate
Kinetically
favorable 4. Catalyst

substance that hastens the rate of reaction but is not
activation energy consumed in the reaction
(Ea) must be
Lowers Ea
surmounted
No effect on the spontaneity of reaction, only affects
the kinetics
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Reaction Rate (v) Example:
- change in concentration of species per unit time

Consider the reaction:

The rate of disappearance (consumption) of
reactants can be expressed as:

The rate of appearance (production) of products

can be expressed as:

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Sample Problem 4.1. Types of Reactions

The rate of formation of NO in the reaction
(According to number of reaction substrates)
2NOBr (g) 2NO(g) + Br2(g)
was reported as 1.6x10-4 mol/L-s. What is the rate of
1. Single substrate reactions
reaction and the rate of consumption of NOBr(g)?
Example: A products
2A products
Sample Problem 4.2.
The instantaneous disappearance of NO2 in the
reaction 2. Bisubstrate reactions
2NO2 + F2 2NO2F Example: A + B products
is reported as 1.22x10-4 mol/L-s. What is the rate of 2A + B products
appearance of NO2F?
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Types of Reactions RATE LAW/RATE EQUATION
an equation that expresses the rate of reaction as a
(According to number of reacting molecules or molecularity) function of concentration or pressures of all the
species present in the overall chemical equation for
the reaction at some time
1. Unimolecular reactions
The rate of reaction is often found to be proportional
Example: A products to the concentrations of the reactants raised to a
power.

2. Bimolecular reactions
REACTION ORDER
Example: 2A products the power to which the concentration of a species is
A + B products raised in a rate law
3. Termolecular reactions
OVERALL ORDER of a reaction
Example: 3A products
the sum of the order of all the components
2A + B products
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Consider the reaction: Examples of Rate Laws:

A + B products 1.
Rate Law:
1st order (unimolecular)
2.
where: m = order of reaction wrt A
n = order of reaction wrt B 2nd order (bimolecular)
k = rate constant 3.
m+n = overall order of reaction
1st order wrt CH3COOH, 1st order wrt ethanol
Rate constant, k 2nd order overall
- independent of concentration but depends on 4.
temperature 2nd order wrt NO, 1st order wrt O2,3rd order overall
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 Rate law is determined experimentally and is Methods of Determining the Rate law
not equal to the stoichiometry (coefficients of
reactants and products) of the chemical of a Reaction
reaction.
1. Method of Initial Rates
ex: H2(g) + Br2(g) 2 HBr(g)
2. Integrated Rate Law
In certain cases the rate law does reflect the 3. Method of Half-lives
stoichiometry of the reaction, but that is either a
coincidence or reflects a feature of the underlying
reaction mechanism.

Rate order can be whole number, fraction, zero or

negative
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Sample Problem 4.3.

METHOD OF INITIAL RATES
For the reaction:
Initial Rate
A products
instantaneous rate determined just after the reaction
begins (after t = 0) in which the initial concentration of The initial rate of the decomposition of substance A
the reactants have not yet changed significantly depends on the concentration of A as follows:

Example:

Determine the order of the reaction wrt A and

plot lnv vs ln[A] calculate the rate constant.
slope = n
y-int = ln k 15 16
Sample Problem 4.4. Sample Problem 4.5.
The recombination of iodine atoms in the gas phase in
the presence of argon was investigated and the order of Given the following data, determine the rate law
the reaction was determined by the method of initial expression and rate constant (k) for the reaction by
rates. The initial rate of the reaction Method of Initial Rates.
2I(g) + Ar(g) I2(g) + Ar(g)
were as follows: A + 2B AB2

Experiment Initial [A], Initial [B], Initial rate of formation of

M M AB2 (M/s)
1 1x10-2 1x10-2 1.5x10-4
2 1x10-2 2x10-2 1.5x10-4
Determine the order of the reaction wrt I and Ar and
calculate the rate constant. 3 2x10-2 3x10-2 6.0x10-4
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INTEGRATED RATE LAW First Order Reactions

First Order Reactions
1. Rate depends on the
A products concentration of only
one reactant ln[A]0
(n=1) (unimolecular). Other
reactants may also be
present but each will be ln[A]
zero order. Slope =-
=-k
2. Reactant concentration
decreases exponentially
with time with a rate
determined by k
y x t
slope = -k
y-int = ln[A]0 19 20
 METHOD OF HALF-
HALF-LIVES First Order Reactions
At t1/2: [A] = [A]0

Half-life, t1/2
- time it takes for a substance to fall to half of its initial
concentration.

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Examples of 1st order reactions: Sample Problem 4.7.

2H2O2(l) 2H2O(l) + O2(g) The variation in the partial pressure of azomethane
2SO2Cl2(l) 2SO2(g) + Cl2(g) with time was followed at 600 K with the results
2N2O5(g) 4NO2(g) + O2(g) given below. Confirm that the decomposition
CH3N2CH3(g) CH3CH3(g) + N2(g)
is 1st order in azomethane, and find the rate constant
Sample Problem 4.6. at 600 K.
A certain 1st order reaction has a half-life of 20.0
mins.
1. Calculate the rate constant for this reaction.
2. How much time is required for this reaction to be Note: Partial pressure of a gas is proportional to
75% complete? concentration

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 Second Order Reactions Second Order Reactions
A products
Rate depends on the
(n=2) concentration of one
2nd order reactant or
two 1st order reactants Slope = k

x
y slope = k
t
y-int = 1/[A]0
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Second Order Reactions Examples of 1st order reactions:

2NO2(g) 2NO(g) + O2(g)
Half-life, t1/2
At t1/2: [A] = [A]0
Second Order Reactions
A + B products

Rate Law:

Half-life is directly Cannot be integrated until

proportional to 1/[A]0 the relationship between
[B] and [A] is known
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 A + B products
Initial [A]0 [B]0
Change -x -x
At time t [A]0 x [B]0 - x

Evaluating using method of partial fractions by using [A] = [A]0 and [B] = [B]0 at t=0

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Zero Order Reactions Zero Order Reactions

A products
Rate is independent on
the concentration of
(n=0)
the reactant
Increasing the
concentration of [A
[A]]
reactant will not speed Slope =-
=-k
up the rate of reaction
y x
slope = -k
y-int = [A]0
t
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 Zero Order Reactions Pseudo-First Order Reactions
Half-life, t1/2 When either [A] or [B] remains constant as the
At t1/2: [A] = [A]0 reaction proceeds, the reaction.
If for example [B] remains constant then:
A + B products

Half-life is directly
proportional to [A]0 An equation identical to a 1st order expression

Example of zero order reactions: One way to obtain a pseudo-first order reaction is to use
2NH3(g) 3H2(g) + N2(g) (reversed Haber process) large excess of one of the reactants (e.g. [A]>>>[B]
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Higher Order Reactions

For the reaction: A products

(n1)

Half-life, t1/2

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 Sample Problem 4.8.
For the reaction: A products
The reacon A C + D is carried out at a parcular
temperature. As the reaction proceeds the
concentration of the reactants [A] are measured at
various time observing the following results:
a. What is the order of reaction?
b. Write the rate-law expression for the reaction.
c. What is the value of k at this temperature?

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Sample Problem 4.9. Modified Integrated Rate Law

The gas-phase decomposition of NOBr is second
order in [NOBr], with k = 0.810 M-1s-1 at 10C. How For the reaction: aA products
many seconds does it take to use up 1.50x10-3 M of
this NOBr?

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