Chemical Kinetics
Chemical Kinetics
Chemical Kinetics
Structure
Introduction
Objectives
Rate of a Reaction
Average Rate
Instantaneous Rate
Relationship between Average and Instantaneous Rate
Initial Rate
Measurement of Rate
Factors Affecting the Rate of a Reaction
Rate Laws
Differential Rate Laws: Concentration Dependence of Rate
Integrated Rate Laws: Time Dependence of Concentration
Determination of Order of a Reaction
TempeTature Dependence of Rate Constant
Kinetics and Mechanism of Reaction
Summary
Terminal Questions
9.1 INTRODUCTION
In the context of a chemical reaction three fundamental questions need to be
answered before the reaction can be put to use. These are, "Is the reaction feasible?"
i.e., whether the reaction would take place or not, secondly if it does, "How far would
it go?" which way would the equilibrium be - towards the reactants or the products
and thirdly, "How long would the reaction take?" or when would we get the
product(s)? The first two questions can be answered on the basis of thermodynamics
- the value of Gibbs free energy change of the reaction can be used to determine the
direction of the chemical reaction and the value of equilibrium constant is indicative
Chemical Kinetics concerns
of the extent of the reaction in a given direction. The answer to the third question, ,the rate of reactions and the
however, falls in the domain of Chemical Kinetics which concerns about the 'time mechanism by which they
aspect' ofthe reaction or the rate at which the reaction takes place and the mechanism occur.
by which the reactants are converted to the products. For example, the reaction
between hydrogen and oxygen gases to give water has a highly negative value of
standard free energy change ( A C (298 K) = -237 kJ mol-') i.e., it is highly feasible
reaction yet we can keep a mixture of these two gases at room temperature fo; years
without getting even a trace of water.
-
The study of reaction rates or kinetics of a reaction is of utmost importance to an
industrial chemist who intends to prepare a significant amount of a given product in a
reasonable amount of time. Further the results of a rate measurement can be
expressed in terms of a rate law which can provide clues to the mechanism of the
reaction. It goes a long way in understanding the course of the reaction and its
manipulation to achieve better yields. In this unit we begin with defining the rate of a Quantitative statements of
reaction and the different ways in which the rate can be defined. It will be followed the rate of a chemical
reaction is useful in
by the factors affecting the rate k d the techniques used to study the rates of chemical optimizing reaction
reactions. We will explain how the results of study of dependence of rate on the conditions to get meaningful
concentration of the reactants (and products) can be expressed in terms of a yields from a reaction.
differential equation called as differential rate law or rate equation. The solutions of
these differential rate equations are called as integrated rate laws and are used to
understand time dependence of concentration of reactants or products. We will
derive integrated rate laws for zero, first and second order reactions and learn about
their cha~.acteristics.Towards the end we will make an attempt to see in what way the
experimentally determined rate equation can be used to suggest a plausible
mechanism for the reaction.
Equilibrium and
Dynamics-I1 Objectives
The rate of any chemical reaction can be rapid or slow - addition of a solution of
silver nitrate to a solution of sodium chloride gives a precipitate almost
instantaneously while rusting of iron takes place in days to years depending upon thc
conditions. In studying the kinetics or the rate of a reaction different ways of
represeoting the rates like average rate, instantaneous rate etc. are used. However,
these need to be defined much more preciselp in the context of chemical kinetics. Let
us first hnderstand the meaning of average rate, then we will learn about the
instantlneous rate and the relationship between the two.
the progress of the reaction can be followed in terms of the amounts of the reactant or
the twa products. Let us say that in a given time At (delta t) the change in the
concentration of O2be A[02] (or Aco2) then the rate is represented as
Chemical Kinetics
Rate = -1
4 0 2
At
The rate of the above reaction can equally well be represented in terms of the change
in the concentration of NO. However, we see from the stoichiometry of the reaction
that NO is formed twice as fast as O2 i.e., in the time we get one mole of 0 2 we get2
- moles of NO, Therefore, when we define the rate in terms of NO we have to divide it
Rate = %- A[NOI
At
Similarly, the rate could be defined in terms of the change in the concentration of
NO2as
Where o (nu) is the symbol used for rate. Aci is the change in the concehtration of the
i th species and v, is the stoichiometric coefficient of the i th species in the balanced
chemical equation. Aci has units of mol dmd3while At has units of s therefore the rate
as defined above would have units of mol dmm3s-'or moI/dm3s.
where 4 is the ratwof conversion which is equal to dtldt , <is the extent of reaction
and. V is the volume. To understand and appreciate this definition let us first
understand the meaning of extent of a reaction.
Extent of a Reaction
The extent of a chemical reaction may be defined in t e r n of the amount of substance
(n) which has reacted in a reaction. Let us take naomoles,of a substance A and nbomoles
of the substance B and perform the following reaction.
I Equilibrium and
Dynamics41
As the reaction proceeds the number of moles of the three subst'ances (A, B and C)
change. These change in a definite fashion determined by the stoichiometric
coefficients of the reactants and the products. For every mole of A consumed twice as
many poles of B are consumed and thrice as many moles of C are produced. If the
reaction, as written, occurs once i.e., one mole of A and 2 moles of B are consumed,
Since the substances
we say that one mole of the reaction has occurred. When 5 moles of the reaction have
react in their
stoichiometric ratlos, the occurred the number of moles of different species would be:
change in the amount of a
given species is na=nao-t ; nb=nw,-2t and n,=O+35
proportional to its
stoichiometric number, v;, In general if a reaction system initially contains nomoles of a given substance, then the
in the reaction. amount of the substance at another time (ni) is given as
ni= no + v i t (9.5)
where t is called as the extent or the degree of advancement of the reaction and v,
is the stoichiometric coefficient. Since the S1 unit for amount of substance is mole,
the extents of chemical reactions are measured in terms of moles of the substances
which have reacted.
Differentiating Eq. 9.5,
Ani
for finite changes ; A< = - (9.6)
i'
According to Eq. 9.6 the change in the extent At can begiven as the change in the
number of moles of any component in the reaction divided by the stoichiometric
coefficient. Let us take an example to understand the computation of At.
Example 9.1: 6 moles of Nz and 10 moles of H2 are made to react to form ammonia
NZ+ 3Hz -
as per the following equation.
2NH3
Find the extent of reaction when the amount of H2is reduced to 4 moles. And also
find the number of moles of ammonia produced.
-
Solution:
Initial moles 6 10 0
Final moles ? 4 . ?
Change (An) 4 - 10 = - 6 ./
I
or A t = - 6 1 - 3 = 2
since At = 2, two moles of the reaction (as written ) have taken place.
i
SAQ 1
What would be A t in the above example if the formation of ammonia is represented
as
I
I
Also, calculate the number of moles of NH3 produced.
The amount of substance reacted is the most fundamental unit for the extent of a
chemical reaction but it is usually inconvenient to use because it is quiie difficult to
directly measure amount of substance in a reaction. However, if the reaction occurs The SI units of
uniformly throughout a volume, the extent of the reaction can be measured concentration is mol/m3.
However, in common use
conveniently as moles per unit volume (nlV)rather than in total moles present. Moles a more convenient unit
per unit volume for any solute are simply the concentration of that solute. In case of moll dm3 is used.
aqueous solutiofl -ince the volume is measured in the units of dm3,the extent of 1 rnol/rn3= 10-3mol/drn3
reaction can be measured in terms of mol/dm3which is nothing but the molar
concentration or the molarity, M, of the solution.
In case of reactions
Eorning back to the meaning of the rate of a chemical reaction we gave the WPAC
efinition of the rate of a chemical reaction as occurring in gas-phase,
even moles per unit
volume is not a
convenient unit. In such
cases the rearrangement
of the ideal gas law p V =
nRTto nlV=pIRTshows
where tis the extent of the reaction and ( = d t ldt, is called as the rate of conversion that at any constant
having units of mol s-' and V is the volume.
P
From Eq. 9.4 = v = instantaneous rate. Thus for homogenous reactions, the
v
instantaneous rate of the reaction can be represented as
This instantaneous rate for a given reaction can be represented (like the average rate)
in a number of equivalent ways. Let us again take the example of formation of
ammonia from nitrogen and hydrogen,
The rate of this reaction can be measured in terms of either as the rate of appearance
of NH3 or as the rates of disappearance of N2 or H2. In terms of the above definition
the instantaneous rate can be given as any of the following representations.
Having understood the meaning ofaverage and the instantaneous rates let us see the
relationghip between the two.
SAQ 2
For the dollowing reaction, write various equivalent wa); of expressing the
instantaeous rate:
2CHC13(1)+ 70H-(aq) - CO(aq) + HCOO-(aq) + 6C1-(aq) + 4H20(1)
/I
is the average rate of the
reaction during that time
interval.
[H21 ;
<;<
t1 I >I > I3
t2 ' c,
time >-
Fig. 9.1: The average and instantaneous rate: As At--+O, average rate + instantaneous rate.
We can see that the rate of formation of hydrogen does not remain constant through
out. It is quite fast to begin with and gradually becomes slow. If from time tl to tz the
concentration of Hz changes from c l to cz, the average rate within this time is given as
the slope of the cord AB (tan BAC = BC 1 AC). This may approximately be thought
of as the rate of the reaction at the middle of the time interval i.e., at (tl + t2) 12.
'r
'
As the value of At goes o decreasing (as shown in the figure) the length of the cord
becomes smaller and sma ler till at a specific time t the cord becomes tangent to the
curve at a point where A and B coincide. The slope of the tangent is called as the
instantaneous rate of the reaction at the time t. Mathematically speaking, the
instantaneous rate is the average rate in the limits of At 3 0.
Let us take an example to learn about the calculation of the rate qf reaction from a
/
kinetic data. Decomposition of Nz05in C C 4 solutions (studied by Daniels and
Jobston) at 3 18 K gave the following data (Table 9.1). \
I
tls d
The average rate say between 867 and 1877 s can be calculated'by simply computing
the change in the concentration (1.36 - 0.72 = 0.64 mol dm-3) and dividing by the
change in time (1877 - 867 = 1010 s) i.e., the
Ac - 0.64'mol dm-
Average rate = --- -
At 1010 s
The instantaneous rate at any given time can be found by drawing a tangent to the
concentration versus time curve at the specified time and finding its slope as shown
on the graph.
2.0
Instantaneous rate = -slope =- = 0.0008 = -8.0~10-~mol dm-3s-1
2500
Fig. 9.5: Defining initial rate: In the time At the average rate (slope of the chord OB)is
almost equal to the instantaneous rate at t 4 (slope of the tangent OT).
Sometimes we are concerned with chemical systems in which more than one reaction
is in progress e.g., the reaction between carbon and oxygen produce both CO as well
as CO2
2C +02 - 2CO (9.1 1)
Forworking out the rate of change of a given species in such cases the rate of all the
reactions in which the given species participates areto be taken into consideration.
For example to compute the rate of formation of CO in the above case we proceed as
follows:
Rate of reaction (i) : u, = y2) -
When more than one of Measurement of pressure or volume of a gas: In some reactions, one of the
the components are in reactants or products are a gaseous species. In such cases, the measurement of
gaseous phase, the partial pressure or the volume of the gas produced or crvlsumed provides an elegant
pressures of the species is niethod of assessing its concentration. This can be used in obtaining the rate of
to be calculated with the
help of reaction reaction. For example, the decomposition of H202.
stoichiomehy.
ii) Titrimetry: It is one of the most commonly used methods to follow the
progress of the reaction. If any of the reactants or products can be suitably
titrated without any interference from other species, then this method is useful.
For example, the progress of the reaction given above can equally well be
followed by titrating equal volumes of the reaction mixture at different time '
intervals against KMn04 solution. KMn04 reacts with H202as per the
following equation.
The formation of acetic acid can be followed by titrating with a standard alkali.
Since I? has a characteristic absorption found around 565 nm, the decrease in
the concentration of iodine, as the reaction progresses, can be followed
calorimetrically.
Besides these, a number of highly sophisticated instruments like NMR, ESR and mass NMR: Nuclear magnet~c
resonance
spectrometer are also used to study reaction kinetics. This is beyond the scope of our ESR: Electron spin
study. So up to now, we have learnt about rate of a reaction, its expression, resonance
significance and measurement. Let us now see what are the factors that affect the rate
of a reaction. Before that, attempt the following SAQ.
SAQ 3
Suggest a suitable experimental method that can be followed to monitor the reaction
rate in the following cases.
Hint: Bromine absorbs strongly in the visible region, while hydrogen and hydrogen
bromide do not.
In reactions involving solids the reaction occurs at the boundary surface of the solids.
Greater thie contact between the reactants at the solid boundary surface greater is the
rate of the1reaction. Therefore, subdividing a sdlid into smaller particles increases the
reaction rate for example, it is difficult to ignite a lump of coal whereas it is rather
easy to ignite coal dust.
Concentr~tionof Reactants
The dependence of the rate of reaction on the concentration of the reactants and
products has no unique relationship. Generally the rate of reaction increase with the
increases Cn the concentration of the reactants. The rates of some reactions increase
much more than those of the others on increasing the concentration of the reactants.
However, some reactions become slower on increasing the concentration of the
reactants and sometimes even the concentration of products also affect the rate of the
reaction. The exact relationship between concentration of reactants and products and the
reaction rates are defined by the kinetic Rate Laws which are to be determined
experimehtally for every reaction. We shall deal with these later under Rate Laws.
Temperature
The rate of a reaction generally increases with the increase in the temperature. As a rule
of the thumb the rate becomes double for every increase of 10°Cin the temperature. A
temperature dependent study of the rate of a reaction can provide useful thermodynamic
parameters about the reaction. We shall deal with the details of temperature
dependence later.
9.3 RATELAWS
The analysis of basic kinetic data i.e., the change in the concentration of a reactant or
a product as a function of time sGggests that the rates of chemical reactions are found
to be a function of the concentrations of one or more reacting species. The
proportionality between the rate and the concentration may be direct or inverse.
Further sometimes the concentrations of the products or some other external factor
also influence the rate of the reaction.
-
taw.These rate laws are empirical relationships i.e., obtained from experimental data,
these may or may no' conform to the basic stoichiometry of the reaction. The
experimentally determined rate equation for the reaction 2HI Hz + Iz; is
rate = ÿÿ HI]^
which indicates that the rate /s proportional to the second power of the concentration
-
of HI.
On the other hand for the reaction; 2N205(g) 4N02 (g) + 0 2 (g);the rate
equation has the form:
rate = &N20S]
rate = d(HBr)ldt =
/
Order of Reaction
For a general reaction,
aA + bB + ... ---t products
where a,b,..... etc are the stoichiometric coefficients in the balanced equation, we can
write the rate law as
rate = k [A]" [B]" "." (9.21)
In'this expression, [A], [B]"' etc represents the molarities of the concerned species. There is no relationship _
The exponents m, n,. ..,are generally small positive integers. However, in certain between the exponents m,
cases, these may be fractional or even negative also. The exponent of a reactant in n,. .. in the experimentally
the rate law represents the order of the reaction with respect to that reactant. The determined rate equation
and the corresponding
sum of the exponents of the concentration terms in the.rate law is called the overall . stoichiometric coefficients
order. For the rate law given in Eq. 9.21 we say that the reaction is of mth order with (a,b,...); but if it happen to
respect to A and of nth order with respect to B and so on. The overall order of the be so, it is just a matter of
reaction is chance.
m + n +..... .
Sometimes a reactant
.__/-
in the balanced chemical equation does not appear in the rate
law then the reaction is said to be of zero order with respect to that reactant. For
example, the rate equation for the reaction involving iodination of acetone
(2-propanone) in presence of acid:
i.e., the reaction is of first order both in the acid and acetone and is of zero order in 12.
P
The proportionality constant 'k' in the rate equation is called the rate constant. It is
characteristic of a given reaction and its value depends on temperature and the
1 presence of catalyst etc. The rate constant can be visualised as the rate of reaction
when all the species in rate equation are at unit concentration. For this reason, the
I rate constant is also known as the specific rate. The units of rate constant depend on
the overall order of the reaction. It has the dimensions of concentration time-'.
Equilibrium and
Dynamics-I1
The units of rate as For a rate equation expressed as: rate = k [A]"; the order for the reaction is x and the units
discussed earlier, can be for rate are rnol dm3s-I. We can discuss the units for (k) the rate constant for different
glven in different ways orders using this expression.
depending on the units
chosen for concentration
For a zero order reaction: rate = k [A]'
and time. In general the
rate should be recognized
to have the dimensions of Since [A]' = 1; rate = k
Concentration/time. .
Therefore k would have the units of rate i.e., rnol dm-3 s-'
For a first order reaction: rate = k [A]'; since [A]' = [A] with units rnol dm-3
k would have units of rate/ rnol dm-3 = rnol dm-3 s-'/ rnol dm-3 = s-I
[A]' has units (mol k would have units of rate/( rnol dm-3)2
A second order reaction involving hvo reactants ancl having the rate equation as:
rate = k [A][B]; the unit of k would again be dm3mol-'s-'.
A -
For a general reaction
products
-d[~] = kdt
*
At the start of the reaction i.e., when t = 0, the concentration of A equals the initial
concentration of reactant i.e., [A] is equal to [Ale
-[Ale = 0 + constant of integration
The form of the integrated rate law shows that a zero-order reaction will give a
straight-line plot if measured values of reactant concentration, [A], are plotted against
time. The slobe of the plot will be equal to -k, the negative of zero-order rate
constant. (Fig. 9.4)
time >-
"time >
(a> (b)
Similarly, a plot of {[Ale -[A]]lAt or A[A]lAt versus t would give a straight line
parallel to x-axis. This implies that for a zero order reaction the rate does not change
with time.
A zero-order differential rate law for a chemical reaction means that the rate of the
reaction is independent of the concentration of any reactant. A zero-order rate law can
be observed only if the actual reactant concentrations cannot change as the reaction
proceeds, which is uncommon, and so zero-order rate laws are rarely found.
An electrode reaction in which only the material adsorbed on the surface of the
electrode can react might be an example of a zero-order reaction. Let us say that the
reactant in such case is strongly adsorbed from the solution but can adsorb only to the
extent of a single layer of molecules. Then the surface of the electrode will be
completely and uniformly covered by such a layer at any realistic concentration in the
electrolyte solution. As and when these molecules react more molecules would be
adsorbed and the surface concentration of the reactant, which is the only concentration
of the reactant directly involved in the reaction, will then remain constant even though
the electrolyte concentration in the solution varies over orders of magnitude. Zero-order
rate laws can also arise as a result of several successive steps in more complex reaction
mechanisms.
Equilibrium and The first-order rate law is one of the most common forms of the rate law. For the
Dynamics-I1
-
general reaction
A products
-dhl
Rate = -= k[~]'
dt
d [ ~=-kdt
this can be rearranged to - l ,
[A1
i.e., the value of the constant of integration is simply 1n[Alo.The integrated rate law
for a first-order reaction is then:
A first-order reaction will give a straight-line plot if measured values of either ln[A]
or ln(~[A]d[A])is plotted against time. (Fig. 9.5)
time >-.
time
-
Fig. 9.6: The exponential decay of the concentration [A] as a function of time
for a first order reaction.
It can be seen that in the exponential decay there is a steep decrease in the
concentration initially. Subsequently it is followed by a gradual decrease. You can
further note that for higher values of time the curve goes almost parallel to the x-axis
which implies that it would take an infinite time for the concentration to decrease to
zero or the reaction to complete.
Thus you can see that the half life or the time taken by the original concentration to
reduce to its one half in a first order reaction is independent of the concentration. It is
constant for a given reaction. However, for any other order of reaction the half-life is
not constant but changes depending upon the extent to which the reaction has
occurred. Therefore, half-life is generally used to describe only first-order reactions
and a half-life independent of concentration establishes the order to be one.
Radioactive decay, although not a chemical process, is also found to follow first-order
kinetics.
SAQ 4
The first-order rate constant for the decomposition of N205at 340 K is 5.20 x Io-~s-'.
Calculate the time required for the concentration of N20sto fall to (a) one-half and
(b) one-fourth of its initial value.
Table 9.2: Integrated rate equations and the linearised plots for different orders
of the reaction A-+ products
The order is asicertained from the plot giving a straight line e.g., for a hypothetical set
n g are obtained (Fig. 9.7).
of data the f 0 l l ~ ~ i plots
Chemical Kinetics
1.-
-<
Y
time
-
-C
time - -.
U
-
* time
Fig. 9.7: Plots of a) [A]; b) In[A]; and c) 1/[A] versus time for a hypothetical reaction.
-
Referring to the Table 9.2, we can say that the order for this reaction is two. This
-
1
method is of hit and trial nature. However, it is applicable for simple systems like
A products. In case of reactions involving more than one reactant the analysis
becomes complex and laborious.
To understand the utility of initial rate in determining the order of the reaction let us
A + B -
consider the following reaction:
products
A given set of concentrations of A and B is taken and the rate is determined. The
experiment is repeated with a different concentration of one of the reactants while
that of the other remains the same. The comparison of the two rates gives the order of
the reaction with respect to the reactant whose concentration has been varied. It can
be shown as follows;
Rate 1 : v, = k [allm[bl]"
Rate 2 : e = k [a2Im[bl]"
Dividing *by v , we get,
-I:[ I:[
log - - mlog -
Rearranging we get,
Equilibrium and
Dynamics41 log iv''1
Dividing y by v, we get,
01 (blI
Once the value of m and n is known the overall order can be worked out by adding
them.
Clock Reaction
Clock reactions are a kind of experimental manipulation so as to measure the initial
The monitor substance is rate in terms of a time parameter. That is why such reactions are called clock
added in a very small
amount so that the
reactions. These are designed in such a way that the appearance of one of the
reaction does not go products (in [termsof which the reaction is being monitored) is slightly delayed. For
beyond just a few percent this purpose, a small amount of a substance called a monitor-substance is added. This
before the product shows by itself does not take part in the reaction but quickly consumes one of the products
UP. (in question) formed. Once whole of this monitor-substance has reacted, the products
shows up. Normally, this product is coloured or gives a distinct colour with an
'indictor' added mixture. The reaction between peroxydisulphate and
iodide ions is a of clock reactions.
In this reaction, the product monitored is free iodine (in fact I;), the monitor
substance is S,Oi- (thiosulphate) and the indicator is starch. As soon as iodine is
formed it reacts with thiosulphate ions and till all the thiosulphate ions are consumed
it does not give colour with the added indicator starch.
You would recall that we defined initial rate as Acl At for small values of At from t =
0. The amount of added monitor substance fixes the value of Ac, and the rate of the
reaction is manifested in terms of At only. If the rate is fast and the product shows up Chemical Kinetics
-~dditionsof monitor substance (2) are like winding a clock. The more you wind (i.e.
add more of 'z'), longer it would take for the product to show up. In certain reactions,
once the product has shown up, another lot of substkce 'z' is added (the clock is
rewound) and once again the time for the appearance of the product is noted. This
helps in finding rate of reaction at various Stages of reaction. The Harcourt-Esson
reaction given below can be monitored in this way:
A +B -
reactants taken in excess. Let us take the following reaction to understand it
product
if we take [B] in large excess then the effective rate law becomes
rate = k' [A]" where k ' = k [B]" (9.33)
The value of 'm' can be found with the help of graphical method or any othersuitable
method.
We can repeat the experiment this time keeping [A] in excess so that the effective rate
equation is '
Once again the order can be determined graphically (or by any other suitable
method). The sum of two orders so determined gives the overall order of the reaction.
and the reaction behaves like one following first order kinetic. Such reactions are
termed as pseudo-first order reactions.
Equilibrium and
Dynamics-I1
SAQ 5
For the reaction, C12(g)+ 2NO(g) - 2NOCl(g), the initial concentrations,
[Cl2Ioand [Noloare given along with initial rates.
-d[El2 ]
Rate = -
dt
Find out (i) the order of the reaction with respect to NO and C12;(ii) the rate law; and
(iii) thk rate constant.
If a more reliable value for E, is required, one can plot a series of values of In(k) at
different temperatures vs. t, since: ln(k) = -E,RIT + 1nA
Chemical Kinetics I$-
This is called an Arrhenius plot. Let us see how does a small change in temperature
affect the Rate? Let us assume that a reaction has an activation energy ofi50 kJimole
and the temperature changes from 27 to 37 degrees Celsius.
In other words increasing the temperature by 10 degrees nearly doubles the rate
by doubling the rate constant.
SAQ 6
The rate constantsfor the decomposition of S02C12are 1 . 0 1 ~ s-' at 552 K and
3.85 x l ~ - ~ sat- ' 600 K. Calculate the activation energy and the frequency for the
reaction, assuming them to be independent of temperature.
. .
......................................................................................................
......................................................................................................
......................................................................................................
-
birnolecular: another common type of elementary reaction inyolves two
molecules, which can either associate (A+B -AB) or give new molecules
(A+B C+D). A bimolecular reaction would have an overall second order
rate equation.
Molehlarity and order I
are same for an termolecular, etc.: there are some elementary reactions which involve the
elementary reaction association or exchange of three or more molecules at once; however, such
reactions are somewhat rare. This is because it is extremely difficult for so
many molecules to collide simultaneously to form a meta-stable intermediate
which may form the productts).
We can write a theoretical rate equation for an elementary step. In such a rate
equation the powers of concentration terms are same as stoichiometric coefficients in
the balanced equation. This characteristic of elementary steps is based on collision
model and is of fundamental importance in our approach towards suggesting a
plausible mechanism.
As said above the experimentally determined rate law is important from reaction
nlechanism point of view but there seems to be no general way of arriving at the
mechmism from the rate law. One is supposed to suggest different plausible
mechanisms and then write the theoretical rate law for each of them. The mechanism
whose theoretical rate law is closest to the experimentally obtained one is the most
likely mechanism of the reaction.
-
I mechanism with following two element@ reactions may be proposed
-
0 3 0 0 2 0 + Ok)
03k) + o k ) 202k)
64
I
r'
b The proposed mechanism should be reasonable, you may invoke the possibility .
of formation of an intermediate or of isomerisation or equilibrium between
different species.
The predicted theoretical rate law proposed mechanism should agree with the
experimentally determined rate law. We will soon take up some examples
about writing the theoretical rate laws.
Let us take a simple example where two reactant A and B react to give the product C
to learn how do we arrive at the mechanism of a reaction. We will propose different
plausible mechanisms for the reaction and evaluate the corresponding rate laws. .
Then we will analyse the result.
1) The simplest mechanism would be the one where A and B give C in just one
step like,
Since this mechanism has only one elementary step which is a bimolecular
reaction, the rate expression for such a mechanism would be
rate = kt [A][B]
2) Another possibility is that one of the reactants say A gets converted into an
intermediate, I, in a slow step. Which then reacts with B in a fast step to give
the product.
I+BC k2
slow
+C
dc k1k2
rate = - = K[A][B] where k' = -
dt k-,
B+B k'
slow
,I
Equilibrium and Since the rate determining step is ? bimolecular reaction involving two
Dynamics41 molecules of the reactant B
rate = k, [ B ] ~
5) Yet another possibility is that both A and B react $0give an intermediate which
gives the product as shown below.
rate = k, [A],[B]
Similafly we can propose a few more plausible mechanisms and evaluate their rate
expression. You can notice that of the five mechanisms proposed three (I, III and V)
conform to the same rate expression viz. rate is proportional to [A] [B]; mechanism I1
corresponds to a reaction which is first order w.r.t [A] while mechanism IV demands
These is still no way to for a second order dependence on B. Now if the experimentally observed rate law
"prove" a given shows that the rate depends on the concentration of both A and B, then mechanism I1
mechanism. and IV are out rightly rejected. We have to make a choice from mechanism I, I1 and
V or any other mechanism, which give a similar rate expression. To decipher the
most likely mechanism one has to do some more experiments to obtain information
regarding the intermediates formed, if any, or to see the effect of modifying the
reactions or changing the solvent etc.
It should not go without a mention that even if you propose a mechanism whose rate
equation matches the experimental rate equation vou cannot say that the mechanism
you have proposed is 'THE' mechanism of the reaction. It is just a plausible
mechanism. These could still be an equally compatible sequence of steps.
We have discussed a hypothetical reaction above let us take an actual example to see
how do we use kinetic data to propose mechanism for a reaction. Nitrogen (11) oxide
from jet engines reacts with ozone in the stratosphere to produce nitrogen (IV) oxide
and oxygen as per the following reaction.
Let us propose a few mechanisms for this reaction, deduce corresponding theoretical
rate laws and compare with the experimental one.
NO(@ +NO&) N202 (slow)
-
----t
-
N202 + 0 3 (g)
N203
N203 + 0 2 (g) (fast)
In this mechanism the first step is rate limiting step and as this reaction requires a
collision between two NO molecules the rate law must depend on the square of the
concentration of NO. The theoretical rate law would be rate = k FOP. Since this is
Chemical Kinetie
not the same as the rate law given above, this mechanism is not consistent with the
experimental data. Let us look into another possible mechanism:
- N + 0 (slow)
-
NO
-
0 3 +0 2 0 2 (fast)
NO2 + O2 (fast)
In this mechanism the rate limiting step requires a NO molecule to collide with an 0 3
molecule, the rate of the reaction would be rate = k[NO][03]. As this is the same as
the rate law given above, this mechanism is consistent with the experimental data.
That does not mean that this IS the mechanism. It just means that this COULD BE
the mechanism.
SAQ 7
For the reaction,
2NOW + 0 2 0 - 2N02W
Step (i) : NO + 0, 5
kl
NO3 (Both rates fast and equal)
k,
kl
Step (ii): NO3 +NO 2N02 (slow)
k2
In this unit we have defined and explained different ways of representing the rates of
reaction. ~ h k s are
e average rate- the change in concentration over a period of time,
instantaneous rate - the rate at a given instant of time and the initial rate- the
instantgneous rate at time close to zero. Different methods like, measurement of
pressu1-c or volume of a gas, titrimetry, conductometry, colorimetry etc. can be used
to follow the progress of the reaction. Reaction rates can be affected in a number of
ways and there are four factors like, nature of the reactants, concentration of
reactants, temperature and use of a catalyst that affect the rate of a reaction.
The intlegrated rate equations obtained by integrating the differential rate equations
represant change in concentration as a function of time. These equations can be used
to predict the concentration at any time and provide different ways of plotting the
experimental data which can be used to determine the order of th reaction. While
1
dealing with first-order chemical reactions, the use of a half-life 's often convenient,
it refers to the time taken by the original concentration to reduce o its one half.
Determination of the order of the reaction is crucial to establish the rate law. Of the
various methods available for the purpose, the methods of initial rates, graphical
method, half life method and isolation method have been explained. The choice of the
method depends on its suitability under given reaction conditions.
Determination of order and thence the rate equation paves the way to propose a
plausible mechanism for the reaction. There seems to be no general way of arriving at
the mechanism from the rate law. One is supposed to suggest different plausible
mechanisms and then write the theoretical rate law for each of them. The mechanism
whose theoretical rate law is closest to the experimentally obtained one is the most
likely mechanism of the reaction.
State the units of the rate constants for zeroth order, first order and second
order reactidns. The rate of reaction is measured in MS-' units.
The reaction
21-(aq) + s,o,~-
(aq)-+ I, (aq) + 2~0:- (aq)
A [s2os'-]
rate = -
In the reaction
the mechanism proposed below agrees with the experimentally observed rate
law: