Chapter 10

Chemical Kinetics:
The Rates of Reactions

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Chemical Kinetics

Chemcal kinetics is concerned with the rate of chemical reactions.

Chemical kinetics deals with
- how rapidly reactants are consumed wnd products formed;
- how reaction rates respond to changes in the conditions or the
presence of a catalyst;
- the identification of the step by which a reaction takes place
(reaction mechanism).

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Chemical Kinetics

Two reasons for studying the rates of reactions

- One is that the practical importance of being able to predict how
quickly a reaction mixture approaches equilibrium.
The rate might depend on variable under our control (T, p,
catalyst), and we might be able to optimize it by the appropriate
choice of conditions.
- Another is that the study of reaction rates leads to an understanding of the mechanism of a reaction, its analysis into a sequence of
elementary step.

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Chemical Kinetics

Enzyme kinetics, the study of the effect of enzymes on the rates of

reactions, is also an important window on how these
macromolecules works.
We need to cope with a wide variety of different rates and a process
that appears to be slow may be the outcome of many faster steps.

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Empirical Chemical Kinetics

The first step in the investigation of the rate and mechanism of a
reaction is the determination of the overall stoichiometry of the
reaction and the identification of any side reactions.
The next step is to determine how the concentrations of the
reactants and products change with time after the reaction has been
initiated.
- The temperature of reaction mixture must be held constant
throughout the course of the reaction, for otherwise the observed
rate would be a meaning average of the rate for different
temperatures.
The method used to monitor the concentrations of reactants and
products and their variation with time depends on the substances
involved and the acidity.
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Empirical Chemical Kinetics

- Spectrophotometry
- The conductivity of the solution
- pH meter
- Polarimetry
- The detection of light emission,
titration, mass spectrometer, gas
chromatography, magnetic
resonance.

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10.1 Spectrophotometry
The key result for using the intensity of absorption of radiation at a
particular wavelength to determine the concentration [J] of the
absorbing species is the empirical Beer-Lambert law.

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10.1 Spectropjotometry

A = log (I0/I) = [J] L = - log T%

T% = I/I0 x 100%

- : the absorbance
- I0 : the incident intensity
- I : the transmitted intensity
- L : the length of the sample
- : the molar absorption coefficient ()
(extinction coefficient, )
- depends on the wavelength of the incident reaction and is greatest
where the absorption is most intense.
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10.1 Spectropjotometry

In a typical spectrophotometer, the absorbance is plotted as a

function of wavelength, so A may be determined directly from the
data at a given wavelength.

= [J] L

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10.2 Experimental Techniques

In a real-time analysis, the concentration of a system is analyzed
while the reaction is in progress by direct spectroscopic observation
of the reaction mixture.
In the flow method, the reactants are mixed as they flow together in
a chamber.

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10.2 Experimental Techniques

- The reaction continues as the thoroughly mixed solutions flow

through a capillary outlet tube at about 10 ms-1, and different
points along the tube corresponds to different times after the start
of the reaction.
- Spectrophotometric determination of the composition at different
positions along the tube is equivalent to the determination of the
composition of the reaction mixture at different times after mixing.
- Disadvantage : a large volume of reactant
- Particularly important for reactions take place very quickly.

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10.2 Experimental Techniques

The stopped-flow techniques avoids this disadvantage

- The two solutions are mixed very rapidly (< 1 ms) by injecting
them into a mixing chamber designed to ensure that the flow is
turbulent and that complete mixing occurs very quickly.
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10.2 Experimental Techniques

Very fast reactions can be studied by flash photolysis.

- The sample is exposed to a brief flash of light that initiates the
reaction, and then the contents of the reaction chamber are
monitored spectrophotometrically.
- Laser : 10-9 s (ns), 10-12s (picosecond), 10-15s (femtosecond),
10-18s (attosecond)
Fast reactions are also studied by pulse radiolysis in which the
flash of electromagnetic radiation is replaced by a short burst of
high velocity electrons.

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10.2 Experimental Techniques

In contrast to real-time analysis, quenching methods are based on

stopping, or quenching, the reaction after it has been allowed to
proceed for a certain time and the composition is analysis at leisure.
- Cooling suddenly; adding the mixture to a large volume solvent;
rapid neutralization of an acid reagent
- This method is suitable only for reactions that are slow enough for
there to be little reaction during the time it takes to quench the
mixtures.

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Reaction Rates
The raw data from experiments to measure reaction rates are
quantities that are proportional to the concentrations or partial
pressures of reactants and products at a series of times after the
reaction is initiated.
Intermediates can not be studied because their existence is fleeting
or their concentration is so low.
More information about the reaction can be extracted if data are
obtained at a series of different temperatures.

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10.3 The Definition of Rates

The rate of a reaction taking place in a container of fixed volume is
defined in terms of the rate of change of the concentration of a
designated species.
Rate = |[J]| / t = |d[J]| / dt
- [J] is the change in the molar concentration of the specied J that
occurs during the time interval t.
- All rates are positive.

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10.3 The Definition of Rates

The instantaneous rate of the reaction its rate at a specific instant.

- The instantaneous rate of consumption of a reactant is the slope of
its molar concentration plotted against the time, with the slope
evaluated as the tangent to the graph at the instant of interest and
reported as a positive quantity.

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10.3 The Definition of Rates

- The instantaneous rate of formation of a product is also the slope

of the tangent to the graph of its molar concentration plotted, and
also reported as a positive quantity.
- The steeper the slope in either case, the greater the rate of the
reaction.
[J] : moles / dm3 ; t : second ; rate : moles dm-3 s-1 (Ms-1)
- The instantaneous rate :
The various reactants in a given reaction are consumed at different
rates, and the various products are also formed at different rates.
- These rates are related by the stoichiometry of the reaction.

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10.3 The Definition of Rates

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10.3 The Definition of Rates

We have to be careful to specify exactly what species we mean when

we report a reaction rate.
The most sophisticated definition of a unique rate of a reaction is in
terms of the stoichiometric numbers, J , that appear in the
chemical equation.
- Stoichiometric numbers are the stoichiometric coefficients but
written as positive for products and as negative for reactants.

= (1/J) d[J]/dt
- The rate is always positive because whenever [J] / t is negative,
so is the stoichiometric number.
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10.3 The Definition of Rates

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10.3 The Definition of Rates

A complication : if the reactants form a slowly decaying

intermediate, the products do not form at the same rate as the
reactants turn into the intermediates.
- Complication advantage : the observation that the consumption
and formation rates are not related by the reaction stoichiometry is
a good sign that a long-lived intermediate is involved in the reaction.

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10.4 Rate Laws and Rate Constants

The rate of reaction is often found to be proportional to the molar
concentration of the reactants raised to a simple power.
- It may be found that the rate is directly proportional to the
concentrations of the reactants A and B.
= kr [A] [B]
- The coefficient kr is called the rate constant (rate coefficient).
- The rate constant is independent of the concentrations of the
species taking part in the reaction but depends on the temperature.
An empirically determined equation is called the rate law of the
reaction.
- A rate law is an equation that expresses the rate of reaction in
terms of the molar concentrations of reactants and/or products.23
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10.4 Rate Laws and Rate Constants

The units of kr are always to convert the product of concentrations

into a rate expressed as a change in concentration divided by time.
- Ex.

= kr [A] [B]
[A] , [B] : mol dm-3 (M)
kr : dm3 mol-1 s-1 (M-1s-1)

- In gas-phase studies concentrations are commonly expressed in

molecules cm-3, so the rate constant for reaction above would be
expressed in cm3 molecule-1 s-1.
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10.4 Rate Laws and Rate Constants

(Self-test 10.1)
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10.4 Rate Laws and Rate Constants

Once we know the rate law and the rate constant of the reaction,
- we can predict the rate of the reaction for an given composition of
the reaction mixture;
- we can use a rate law to predict the concentration of the reactants
and products at any time after the start of the reaction.
- An observed rate law is also an important guide to the mechanism
of the reaction, for any proposed mechanism must be consistent
with it.

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10.5 Reaction Order

- A rate law provides a basis for the classification of reactions
according to their kinetics.
- Reactions belonging to the same class have similar kinetic behavior
- their rates and the concentrations of the reactants and products
vary with composition in a similar way.
This classification is based on their order, the power to which the
concentration of a species is raised in the rate law.
- First order () in A : = kr [A]
- First order in A and first order in B : = kr [A] [B]
- Second order () in A : = kr [A]2
The overall order of a reaction with a rate law of the form
= kr [A]a [B]b [C]c is the sum, a+b+c, of the orders of all the
components.
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10.5 Reaction Order

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10.5 Reaction Order

A reaction need not have an integral order, and many gas-phase

reactions do not.
- Ex.
= kr [A]1/2 [B]
half-order (1/2) in A; first-order in B;
three-halfs (3/2) order overall
If a rate law is not of the form = kr [A]a [B]b [C]c , the
reaction does not have an overall order.
- Ex.

H2(g) + Br2(g) 2 HBr(g)

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10.5 Reaction Order

- A typical rate law for the action of an enzyme E on a substrate.

KM ; a constant
Under certain circumstances a complicated rate law without an
overall order may simplify into a law with a definite order.
- [S] << KM

= kr /KM [E] [S]

first-order in S
first-order in E
second-order overall
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10.5 Reaction Order

A rate law is established experimentally, and cannot in general be

inferred from the chemical equation for the reaction.
- Ex.

H2(g) + Br2(g) 2 HBr(g)

- The rate law does happen to reflect the reaction stoichiometry.

H2(g) + I2(g) 2 HI(g)
= kr [H2] [I2]

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2nd Exam

Date : 12/9/2014 ()
Time : 19:00 ~ 22:00 PM
Place : C01-202

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