Topic 4.

1
KINETICS
Rate equations
Determining orders of reaction
Explaining orders of reaction
Effect of canging conditions on te rate constant
RATE EQUATIONS
The relationship between the rate of a chemical reaction and the concentration of the
reactants is shown by the rate equation of the reaction.
Consider the reaction A + 3B 2C + 4D
The rate of this chemical reaction is given by the e!ation
"ate # $%A&
'
%B&
y
%A& is the concentration of A( and %B& is the concentration of B.
' and y are the orders of reaction with respect to A and B respectively.
The order of reaction with respect to a given reactant is the power of that reactant)s
concentration in the rate e!ation.
The s!m of these powers( in this case ' + y( is $nown as the overall order of reaction*
The overall order of reaction is the s!m of the powers of the reactant concentrations
in the rate e!ation
$ is the rate constant of the reaction.
The rate constant is the constant of proportionality in the rate e!ation.
+. "ate of reaction
D!ring a chemical reaction( the concentration of the reactants decreases and the
concentration of the prod!cts increases.
variation of concentrations of reactants and products with time
reactants
products
concentration
t
i
m
e
The rate of a reaction is the decrease in concentration of reactants per !nit time( or
the increase in concentration of prod!cts per !nit time.
The !nits of rate of reaction are moldm
,3
s
,+
.
DETERMINING ORDERS OF REACTION
The orders of reaction with respect to each reactant in the reaction can be determined by
carrying o!t the reaction with vario!s different initial concentrations and meas!ring the
change in initial rate of reaction. The orders of reaction can be determined arithmetically
or graphically.
-f the order of reaction with respect to one reactant is being determined( the concentration
of one reactant only sho!ld change. the others sho!ld remain constant so that the change
in rate can be attrib!ted to the change in concentration of that reactant alone.
-f the overall order is being determined( the concentration of all reactants sho!ld change
by the same factor.
! T"e arit"#etic #et"od $used in Unit % e&a#inations'
/change in concentration0
order of reaction
# change in rate
-f the reaction is first order( then if the concentration do!bles the rate will also do!ble. -f
the concentration triples the rate will also triple( etc.
-f the reaction is second order( then if the concentration do!bles the rate will !adr!ple. -f
the concentration triples the rate will increase ninefold( etc.
-f the reaction is 1ero order( then the change in concentration will have no effect on the
rate of reaction.
Example 1
Consider the reaction "2 + 34
,
"34 + 2
,
The following rate data were obtained at constant temperat!re*
-nitial concentration of "25
moldm
,3
-nitial concentration of 345
moldm
,3
-nitial rate5 moldm
,3
s
,+
6.6+ 6.64 7 ' +6
,3
6.6+ 6.62 4 ' +6
,3
6.668 6.64 4 ' +6
,3
9rom e'pt 2 to e'pt +( the concentration of hydro'ide ions do!bles and the concentration
of "2 is !nchanged. The rate also do!bles( so the order of reaction with respect to 34
,
is
+.
9rom e'pt 3 to e'pt +( the concentration of "2 do!bles and the concentration of
hydro'ide ions is !nchanged. The rate also do!bles( so the order of reaction with respect
to "2 is also +.
The rate e!ation can th!s be written as follows* rate # $%"2&%34
,
&
4aving ded!ced the rate e!ation( the rate constant can be calc!lated !sing the data in
one of the e'periments.
:g in e'pt +( $ # rate5/%"2&%34
,
&0 # 7 ' +6
,3
5/6.64 ' 6.6+0 # 26 mol
,+
dm
3
s
,+
.
Example 2
Consider the reaction ;Cl
3
+ Cl
2
;Cl
8
The following rate data were obtained at constant temperat!re*
-nitial concentration of
;Cl
3
5 moldm
,3
-nitial concentration of Cl
2
5
moldm
,3
-nitial rate5 moldm
,3
s
,+
6.2 6.+ 6.6664
6.4 6.+ 6.6667
6.7 6.2 6.66<4
9rom e'pt + to e'pt 2( the concentration of ;Cl
3
do!bles and the concentration of Cl
2
is
!nchanged. The rate also do!bles( so the order of reaction with respect to ;Cl
3
is +.
9rom e'periment 2 to e'periment 3( the concentration of both reactants do!bles. The rate
increases eightfold( so the overall order of reaction is three.
The order of reaction with respect to chlorine is therefore 3 = + # 2.
The rate e!ation can th!s be written as follows* rate # $%;Cl&%Cl&
2
>o $ # rate5%;Cl
3
&%Cl
2
&
2
# 6.66645/6.2 ' 6.+
2
0 # 6.2 mol
,2
dm
<
s
,+
(! Gra)"ical #et"od $used in )racticals'
-f the concentrations in the different e'periments are not simple whole n!mber ratios of
each other( it is not easy to compare the concentrations and rates. The order of reaction
with respect to each reactant can be ded!ced by plotting a graph of concentration vs
initial rate.
a0 first,order reactions
-f "ate # $%A&( then a plot of initial rate against initial concentration will be a staight line
thro!gh the origin of gradient $*
how t he r a t e of a r e a c t i on v e r i e s wi t h
c onc e nt r a t i on - f i r st or de r r e a c t i on
c o n c e n t r a t i o n
b0 second,order reactions
-f rate # $%A&
2
( then a plot of initial rate against initial concentration will be a c!rve
thro!gh the origin.
how t he r at e of a r e ac t i on v e r i e s wi t h
c onc e nt r a t i on - se c ond or de r r e a c t i on
c o n c e n t r a t i o n
c0 1ero order reactions
-f rate # $( then a plot of initial rate against initial concentration will be a hori1ontal line*
how t he r a t e of a r e a c t i on v e r i e s wi t h
c onc e nt r a t i on - z e r o or de r r e a c t i on
c o n c e n t r a t i o n
An even better method is to plot log /rate of reaction0 against log /concentration0. This
sho!ld always give a straight line( the gradient of which is the order of reaction.
*! Measurin+ initial rates of reaction
-n some reactions( it is not easy to meas!re the rate of reaction directly( and easier to
mention the time ta$en for a partic!lar stage in the reaction to be reached.
>ince rate is the change in concentration per !nit time( it follows that the rate is inversely
proportional to time ta$en. A graph of +5t against initial concentration will give c!rves
li$e those shown above.
:'amples of s!ch meas!rements co!ld be*
- time ta$en for fi'ed amo!nt of gas to be prod!ced
- time ta$en for absorbance to change by a certain amo!nt
- !se of a cloc, reaction* the appearance of a certain colo!red prod!ct is delayed by
adding a fi'ed amo!nt of another species.
:g >
2
3
7
2,
/a0 + 2-
,
/a0 2>3
4
2,
/a0 + -
2
/a0
-odine is prod!ced in this reaction. -f starch was added to the original mi't!re( a bl!e,
blac$ colo!r wo!ld appear immediately. 4owever if a fi'ed amo!nt /ie 6.62 moles0
of sodi!m thios!lphate is also added to the mi't!re( it reacts with the iodine and a
bl!e,blac$ colo!r is only seen when all the thios!lphate has been !sed !p.
-t is possible to meas!re the time ta$en for the bl!e,blac$ colo!r to appear.
E-./AINING ORDERS OF REACTION
The orders of reaction for a chemical e!ation are not always the same as the reaction
coefficients*
:g the reaction ?3
2
+ 4
2
?3 + 4
2
3 has the following rate e!ation*
rate # $%?3
2
&
2
-t is therefore not possible to predict the rate e!ation of a reaction simply by loo$ing at
the reaction coefficients.
@any reactions consist of a series of different steps( some of which are slow and some of
which are very fast.
-t is the slowest step in a chemical reaction which determines how fast a reaction is. 9or
this reason the slowest step in a chemical reaction is called the rate0deter#inin+ ste).
Changing the rate of this step will affect the overall rate of reaction. changing the rate of
fast steps wonAt.
:g consider the reaction ?3
2
+ 4
2
?3 + 4
2
3
This reaction happens in two steps*
>tep +* ?3
2
+ ?3
2
?3
3
+ ?3 this step is slow
>tep 2* ?3
3
+ 4
2
?3
2
+ 4
2
3 this step is fast
>tep + is the slowest step and is therefore the rate,determining step. This involves two
molec!les of ?3
2
( and so do!bling the concentration of ?3
2
will ma$e collisions in this
step fo!r times more li$ely. >o the reaction is second order with respect to ?3
2
. 4
2
is not
involved in this step. it is only involved in the second( fast step. Changing the
concentration of 4
2
therefore has no effect on the rate of reaction( and the reaction is 1ero
order with respect to 4
2
.
T"e rate equation of a c"e#ical reaction is deter#ined 12 t"e nu#1er of eac"
s)ecies involved in t"e rate0deter#inin+ ste) of t"at reaction!
EFFECT OF C3ANGING CONDITIONS ON T3E RATE CONSTANT
The rate e!ation shows the relationship between the concentration of reactants and the
rate of reaction.
-f the concentration of one of the reactants increases( the rate of reaction will also
increase( the rate constant( $ will not change.
-f the press!re increases( the concentration of all the reactants will increase and so the
rate of reaction will also increases. Again the rate constant will not change.
The rate constant $ is th!s independent of concentration and press!re.
-f the temperat!re increases( however( or a catalyst is added( the rate of reaction increases
witho!t a change in concentration( and so it m!st be the rate constant( $( that is changing.
The rate constant $ th!s varies with temperat!re( and is also affected by the addition of a
catalyst.
If t"e te#)erature is increased4 t"e rate constant , also increases.
If t"e te#)erature is decreased4 t"e rate constant , 5ill decrease.
If t"e concentration or )ressure is c"an+ed at constant te#)erature4 t"e rate
constant 5ill not c"an+e.