Slow

H20, +H* +Br HOBr +

H,O
HOBr+H* + Br. Fast H,0+ Br2
Gi) Reduction of nitric oxide with hydrogen. Tho reaction 1s
2 NO +2 H N2+ 2 H,0
The rate law equation is found to be
dx
Rate d k|NOJ# [H,|
hs suggests thatthe reaction is of the third order and the rate dotcrmining step (slow step) should
nvolve two molecules of NO and onc molccule of H,. Thus the following mechanism has bccn proposed

Slow
2 NO+H N + H02
H,0 +H Fast2 H,O
8.21. DISTINCTION BETWEEN ORDER AND MOLECULARITY OF AREACTION
The main points of difference betwcen the ordcr and thc
molecularity of a rcaction may be summarized
as follows
Order of reaction Molccularityy of reaction
I. It is the sum of the concentration terms on which1. In simple reactions, it is cqual to the number
the rate of reaction
actually depends or it is the of molecules of the reactants as
sum of the
exponents of thc concentrations in
represcnted in
the balanced equation. In
the rate law equation. complex reactions,
it is the number of molecules involved in the
slowest step.
2. It need not be a whole number i.e., it can be 2. It is always a whole number.
fractional as well as zero.
3. It can be determined experimentally only and 3. It can be calculated by simply adding the
cannot be calculated. molecules of the slowest step.
4. It is for the overall reaction and no separate steps 4. The overall
molecularity of complex rcaction
a
are written to obtain it. has no
significance. It is only the slowest step
whose molecularity has
overall reaction. significance for the

5. Even the order ofa simple reaction may not be 5. For simple
reactions, the
be obtained from the molecularity
can usually
equal to the number ofmolecules of the reactants
as seen from the balanced equation. stoichiometry of the
equation.

8.22. METHODs FOR THE DETERMINATION OF THE ORDER OFA REACTiON

The methods commonly employed for the determination of the ordcr of a reaction arc
bricfly described
below
1. By using integrated rate equations. n this method, the initial concentrations of the reactants
and the concentration of any one of the rcactants or products at
different instants of time are determined
experimentally. Then either ofthe following two methods may be employed

Pradeep's PHYSICALcHEMTSTRYiVOLi
398 A****
 The following rate data were obtained
Experiment Initial pressure (torr) Initial rate of increase in total pressure (tor)
1. 300 0-61 ()
2. 200 0-27 (r
Predict the order of reaction. [Ans. 2]
4. Consider the following data for the reaction
A +B> Products
Run Initial concentration of A Initial concentration ofB Initial rate (mol L' s)
1. 0-10 M 1-00 M 21x 10-3
2 0-20 M 1-00 M 8-4x 10-3
3. 0-20 M 2-00 M 8-4x 10
Determine the orders of the reaction with respect to A and with respect to B, and the overall order of the
reaction. [Ans. w.r.t. A = 2, w.r.t. B = 0, overall order = 2]

5. The following data were obtained for the reaction

2 NO, g)+F, (8)2 NO,F (8)
Expt. Initial concentration Initial rate (mol L min)
NO] F2
I 0-20 0-05 6-0x 104
II 0-40 0-05 1-2 x 10-3
III 0-80 0 10 4:8x 10-3
Determine the order of reaction and write the rate law equation for the reaction.
[Ans. Rate =k [NO,] [F2]]

8.23. COMPLICATIONS IN THE DETERMINATION OF

THE ORDER OF A REACTION (SIMULTANEOUS REACTIONS)
The various ratc equations derivod and the methods discussed for the determination of the order of a
reaction are based upon the assumption that there is no disturbing factor to the reaction under consideration.
However, in actual practice, complications arise quite often because of the following reactions that take
placc at the same time (callcdsimultaneous reactions) alongwith the main reaction;
) Opposing or Reversible reactions
(i) Consccutive reactions
(ii) Parallel or side reactions
We shall now discuss cach of thesc simultaneous reactions one by one.
(1) Opposing or Reversible Reactions. fin a reaction, the reactants react to form the products
and the products also react to give back the original substances under the same conditions, it is called
a reversible reaction. In other words, the rcaction takes
place not only in the forward direction but also in
the backward dirction (i.e., the forvard reactionis opposcdby the reverse reaction).
Depending upon the order of the forvard reaction and that of the backward reaction, different cases
may be considered as follows
Case I. When both frward and backward reactions are offirst order*, This is the
and may be represented as follows: simplest case

A B

Generally, for first order reactions, rate constant for forward reaction is represented by k, and that
reaction by k . Similarly, for second order reactions, they are represented by and of backward
k, k_,
CHEMICAL KINETICs
407
 If the compared to that
small as
that ofhe
fo velocity constant for the backward reaction (ki) istovery However, ifthe
a

forward
the
reaction (k), the formere
backward
be neglected in comparison
can
the latter.

take place at comparable rates, the rate equation

has to be modified asfoll
forward a
Suppose a is the initial concentrationA and x is the decrease in the concentration ofAA in
in time
this
time t. At
instant, the concentration of B would be x. Then
Rate offorward reaction =k(a-x)
Rate of backward reaction = k, X

Net rate of the reaction in the forward direction would be

a-x)-k, x
When the equilibrium is attained,
Rate of forward reaction = Rate of backward reaction

i.e., ky(a-x)=k, *
where x is the decrease in the concentration of A or increase in the concentration of B when equilibrium
is attained.
Substituting the value of k, from eqn. (i) in eqn. (), we get
d a-)-a.)x
e

(a-x)x,-(a-x,)x= k,
- 1 ) * = k adt
or

Integrating this equation, we get

-x In (r-x)=kat +I
where I is the constant of integration.
When t=0, x = 0
-x, In x
=
I
Substituting this value of I in eqn. (v), we get
-x, In (*-X) =k,at-x, Inx
which on rearranging gives
kat x Inx,-x, In (r, -:)

or "x-x
Thus knowing the values of a and X the rate constant k,for the forward reaction can be evaluate

be calculated as follows:
Alternatively, both k,and k, can
From eqn. (viin)

Pradeep's PHYSICAT CHEMISTRYv o L

 From cqn. ()
k (a-x)=k,* or
ka-k, x, =k,*,
or k ax(k +k,) on k +k
Putting this valuc in eqn. (ix), we got

.ri)

and
From this k, can be evaluated cither by directly substituting
eqn. the value k,+ of x the values
k, from the
x at any time t or by plotting -In (x,-x) vs. time / which will be lincar and calculating k+
slope of the line.
determined and we know that
Also the cquilibrium constant K for the given reaction can be

k
k .ci)

be calculated.
Using eqns. (xi) and (xii), the values of k,and k,
can

into propance.
Examples: (i) Isomerisation of cyclopropanc chloroform solution at 14°C.
Muta-rotation of n-bromonitro camphor in
(i)
second order reaction, i.e.,
When first order reaction is opposed by
a
Case II.

B + C
A
kb (assuming no B or C is present initially)
0
Initial conc. a

Conc. after time t (a-) reaction will be given by

net rate of the forward
At any instant of time, the
.
.civ)
dx k (ax)-k,*2
reaction.
reaction
= Rate of backward
Rate of forward
At equilibrium,

Hence
a- ..xvi)
k
or
(xiv), we get
value in eqn.
Substituting this
.vi)
k(a*)-k, (a-x,
dt usual and then integrating,
the
fractions as
nto partial
then splitting
variables and
Separating the
result obtained is
.xvi)
a(x
2a
409
 ample. Decomposition of certain alkyl ammonium halides into a tertiary amine and an alkyl hala
in aqueous solution. alkyl halide
Case 1 . When a second order reaction is opposed by afirst order reaclion, i.e.,

A + B C
Initial conc. 0 (assuming no C is present initiall)
Conc. after time t a X a-x

The simplest case has been considered where initial concentrations of A and B have been taken as
equal.
. Net rate of forward reaction will be
given by
dt k a-x)2 -k,x
and at equilibrium,

k (a-x,)2 =k, *, (a-x)2

or
,=k
Substituting this value in eqn. (xix), separating the variables and then
integrating, we get
KX
k t(a2
a a()
Example. Isomerisation of an alkyl ammonium cyanate to the
aqueous soBlution corresponding substituted urea in
i.e., NH,R +CNO H,N CO NH.R
Some More Examples. Some more
examples of the reversible reactions whose kinetics have been
studied are as follows
2 HI H2tl2 (Both forward and backward
are of second order)
reactions
(ti) 2 NO +0, 2 NO
(Forward reaction is of third order, backward
reaction is of second
Cit CH,CoOH +C,H,OH order)
CH,COOC,Hs +H,O (Both forward and backward
are of second
reactions
(2) Consecutive Reactions. It has alrcady been discussed that in case order)
order of the reaction is usually not of complex reactions, the
equal to the
molecularity of
stoichiometry of the equation. Such reactions are, theretore, Supposedtheto reaction as observed from the
take place in a number of
The slowest step is the rate determining step. 1he variouS
step reactions thus written steps.
reaction are called consecutive reactions. ror example, let us consider for the overal
the general complex reaction.
2A +B>C
Suppose, by experiment the rate ot reaction 4JIBJ ie., the rate
molecule of A and one molecule of B. The slow step should, therefore, of reaction depends upon one
involve only one molecule of A
and
one molecule of B. The step reactions (or tne conseeuve reactions)
may, therefore, be written as

A40 Pradeep's pHM