Chemical Kinetics Dr. Dina A.

Ali

Physical Chemistry

Chemical Kinetics

This chapter introduces the principles of chemical kinetics, the study of reaction rates,by
showing how the rates of reactions may be measured and interpreted.

The rate of a chemical reaction might depend on variables under our control, such as the
pressure, the temperature,and the presence of a catalyst, and we may be able to optimize the
rate by the appropriate choice of conditions. The study of reaction rates also leads to an
understanding of the mechanisms of reactions, their analysis into a sequence of elementary
steps

1- Empirical chemical kinetics

The first steps in the kinetic analysis of reactions are to establish the stoichiometry of the reaction and
identify any side reactions. The basic data of chemical kinetics are then the concentrations of the
reactants and products at different times after a reaction has been initiated. The rates of most chemical
reactions are sensitive to the temperature, so in conventional experiments the temperature of the
reaction mixture must be held constant throughout the course of the reaction. This requirement puts
severe demands on the design of an experiment. Gas-phase reactions, for instance, are often carried out
in a vessel held in contact with a substantial block of metal.

Liquid-phase reactions, including flow reactions, must be carried out in an efficient thermostat. Special
efforts have to be made to study reactions at low temperatures, as in the study of the kinds of reactions
that take place in interstellar clouds

1-1 Experimental techniques

The method used to monitor concentrations depends on the species involved and the rapidity with
which their concentrations change. Many reactions reach equilibrium over periods of minutes or hours,
and several techniques may then be used to follow the changing concentrations
Chemical Kinetics Dr. Dina A. Ali

1-1-1-Monitoring the progress of a reaction

A reaction in which at least one component is a gas might result in an overall change in pressure in a
system of constant volume, so its progress may be followed by recording the variation of pressure with
time.

Spectrophotometry, the measurement of absorption of radiation in a particular spectral region, is widely

applicable, and is especially useful when one substance in the reaction mixture has a strong
characteristic absorption in a conveniently accessible region of the electromagnetic spectrum .Other
methods of determining composition include emission spectroscopy, mass spectrometry, gas
chromatography, nuclear magnetic resonance, and electron paramagnetic resonance

1-1-2-Flow method
In a real-time analysis the composition of the system is analysed while the reaction is in progress. Either
a small sample is withdrawn or the bulk solution is monitored. In the flow method the reactants are
mixed as they flow together in a chamber (Fig. 1).

The reaction continues as the thoroughly mixed solutions flow through the outlet tube, and observation
of the composition at different positions along the tube is equivalent to the observation of the reaction
mixture at different times after mixing. The disadvantage of conventional flow techniques is that a large
volume of reactant solution is necessary. This makes the study of fast reactions particularly difficult
because tospread the reaction over a length of tube the flow must be rapid. This disadvantage is
avoided by the stopped-flow technique, in which the reagents are mixed very quickly in a small chamber
fitted with a syringe instead of an outlet tube (Fig. 2).
Chemical Kinetics Dr. Dina A. Ali

The flow ceases when the plunger of the syringe reaches a stop, and the reaction continues in the mixed
solutions. Observations, commonly using spectroscopic techniques such as ultraviolet–visible
absorption, circular dichroism, and fluorescence emission, are made on the sample as a function of time.
The technique allows for the study of reactions that occur on the millisecond to second timescale. The
suitability of the stopped flow method to the study of small samples means that it is appropriate for
many biochemical reactions.

1-1-3-Flash photolysis
Very fast reactions can be studied by flash photolysis, in which the sample is exposed to a brief flash of
light that initiates the reaction and then the contents of the reaction chamber are monitored. Most
work is now done with lasers with photolysis pulse widths that range from femtoseconds to
nanoseconds . The apparatus used for flash photolysis studies is based on the experimental design for
time-resolved spectroscopy . Reactions occurring on a picosecond or femtosecond timescale may be
monitored by using electronic absorption or emission, infrared absorption, or Raman scattering. The
spectra are recorded at a series of times following laser excitation. The laser pulse can initiate the
reaction by forming a reactive species, such as an excited electronic state of a molecule, a radical, or an
ion

2-Rates of reactions
The rate of a reaction tells as to what speed the reaction occurs. Let us consider a simple reaction

A ⎯⎯→ B
The concentration of the reactant A decreases and that of B increases as time passes. The rate of
reactions is defined as the change in concentration of any of reactant or products per unit time. For
the given reaction the rate of reaction may be equal to the rate of disappearance of A which is equal
to the rate of appearance of B.

Thus
Chemical Kinetics Dr. Dina A. Ali

rate of reaction = rate of disappearance of A

= rate of appearance of B

Or:

Reaction rates depend on the composition and the temperature of the reaction mixture. Consider a
reaction of the form

A + 2 B →3 C + D
in which at some instant the molar concentration of a participant J is [J] and the volume of the system is
constant. The instantaneous rate of consumption of one of the reactants at a given time is −d[R]/dt,
where R is A or B. The rate of formation of one of the products (C or D, which we denote P) is d[P]/dt
(note the difference in sign). This rate is also positive. It follows from the stoichiometry for the reaction

A + 2 B →3 C + D
That

reaction rates of homogeneous reactions are reported in moles per cubic decimetre per second
(mol dm−3 s−1) or related units
Chemical Kinetics Dr. Dina A. Ali

Example/Determining the Reaction Rate of Hydrolysis of Aspirin

Data for the hydrolysis of a sample of aspirin are in the Table below

The graph shows the concentrations of aspirin and salicylic acid as a function of time, based on the
hydrolysis data In the Table

Example/ If the rate of formation of NO in the reaction 2 NOBr(g) → 2 NO(g) + Br2(g) is

reported as 0.16 mmol dm−3 s−1, we use νNO = +2 to report that The rate of the reaction:

v = 0.080 mmol dm−3 s−1.

Chemical Kinetics Dr. Dina A. Ali

Because νNOBr = −2 it follows that

d[NOBr]/dt = −0.16 mmol dm−3 s−1.

The rate of consumption of NOBr is therefore 0.16 mmol dm −3 s−1

3-Rate laws and rate constants

The rate of reaction is often found to be proportional to the concentrations of the reactants raised to a
power. For example, the rate of a reaction may be proportional to the molar concentrations of two
reactants A and B, so we write

v = k[A][B]
with each concentration raised to the first power. The coefficient k is called the rate constant for the
reaction. An experimentally determined equation of this kind is called the rate law of the reaction

A rate law is an equation that expresses the rate of reaction as a function of the concentrations of all
the species present in the overall chemical equation for the reaction.

4-Order of a Reaction
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
Chemical Kinetics Dr. Dina A. Ali

5- Molecularity of a Reaction
Chemical reactions may be classed into two types :

(a) Elementary reactions and (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.

5-1 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

(b) Bimolecular reactions : (molecularity = 2)

A + B ⎯⎯→ products

2 A ⎯⎯→ products
Examples are :

(i) CH3COOC2H5 + H2O ⎯⎯→ CH3COOH + C2H5OH

(ii) 2HI ⎯⎯→ H2 + I2

(c) Termolecular reactions : (molecularity = 3)

A + B + C ⎯⎯→ products
Examples are :
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2NO + O2 ⎯⎯→ 2NO2

2NO + Cl2 ⎯⎯→ 2NOCl

5-2 Molecularity of a Complex Reaction

Most chemical reactions are complex reactions. These occur in a series of steps. Each step is an

elementary reaction. The stepwise sequence of elementary reactions that convert reactions to products

is called the mechanism of the reaction. In any mechanism, some of the steps will be fast, others will

be slow. A reaction can proceed no faster than its slowest step. Thus the slowest step is the
ratedetermining

step of the reaction.

The decomposition of N2O5,

2N2O5 ⎯⎯→ 4NO2 + O2

is an example of a complex reaction. It occurs by the following steps :

Step 1 2N2O5 ⎯⎯→ 2NO2 + 2NO3 (slow)

Step 2 NO2 + NO3 ⎯⎯→ NO + NO2 + O2 (slow)

Step 3 O + NO3 ⎯⎯→ 2NO2 (fast)

Overall reaction 2N2O5 ⎯⎯→ 4NO2 + O2

Each elementary reaction has its own molecularity equal to the number of molecules or atoms

participating in it. It is meaningless to give the molecularity of the overall reaction because it is made

of several elementary reactions, each, perhaps with a different molecularity. At best could be thought

of as : the number of molecules or atoms taking part in the rate-determining step.

Thus step 2 in the above mechanism is rate-determining and has molecularity ‘2’ which could be

considered as the molecularity of the decomposition reaction of N2O5.

Chemical Kinetics Dr. Dina A. Ali

6-PSEUDO–ORDER REACTIONS
A reaction in which one of the reactants is present in a large excess shows an order different from

the actual order. The experimental order which is not the actual one is referred to as the pseudo

order. Since for elementary reactions molecularity and order are identical, pseudo-order reactions may

also be called pseudo molecular reactions.

Let us consider a reaction

A + B ⎯⎯→ products

in which the reactant B is present in a large excess. Since it is an elementary reaction, its rate law can

be written as

rate = k [A] [B]

As B is present in large excess, its concentration remains practically constant in the course of

reaction. Thus the rate law can be written as

rate = k′ [A]

where the new rate constant k′ = k [B]. Thus the actual order of the reaction is second-order but in

practice it will be first-order. Therefore, the reaction is said to have a pseudo-first order.
Chemical Kinetics Dr. Dina A. Ali

Example of Pseudo-order Reactions:

Hydrolysis of an ester. For example, ethyl acetate upon hydrolysis in aqueous solution

using a mineral acid as catalyst forms acetic acid and ethyl alcohol.

CH3COOC2H5 + H2O ⎯⎯→ CH3COOH + C2H5OH

ethyl acetate (excess) acetic acid ethyl alcohol

Here a large excess of water is used and the rate law can be written as

rate = k [CH3COOH] [H2O]

= k′ [CH3COOH]

The reaction is actually second-order but in practice it is found to be first-order. Thus it is a

pseudo-first order reaction.