TOPIC 6: KINETICS

6. 1 Rates of reaction
6.1.1 Define the term rate of reaction.
rate of reaction =
a decrease (or increase) in the concentration of a reactant (or product)
over a unit of time
There are different types of rates of reactions.
Instantaneous rate (= rate at any given instant during the reaction)
initial rate = the instantaneous rate at the start of the reaction (t = 0) when an infinitesimally small amount
of reactant is used up; gradient of tangent in the graph !elow;
any instantaneous rate can !e calculated !y wor"ing out the gradient of the tangent drawn at the point of
the instant in time on the concentration#time graph; e.g. t = $s .
%dd units to the graph a!ove&&&
Average rate
The average (or overall) rate of a reaction over a certain interval of time is e'ual to the change in the
concentration of a reactant or product that occurs during that period of time divided !y the time over which
the average is measured.
During any reaction the concentration of the reactants decreases whilst the concentration of the products
increases as shown !y the graph !elow.
%s a result of the decrease in reactant concentration( the rate usually is the highest at the start of the
reaction (= initial rate) and always decreases as the reaction goes on and !ecomes )ero at the end. The
rate is always e*pressed in terms of one su!stance involved in the reaction.
+*ample of data collected during the measurement of the rate of a reaction e*periment
The data was used to calculate the average rate for each ,0 second period.
time (s) concentration of reactant % (mol dm
#-
) average rate (mol dm
#-
s
#1
)
0.0 0.01.00
,0.0 0.01010 -./0 * 10
0,
100.0 0.00/16 -../ * 10
0,
1,0.0 0.00$10 ..$. * 10
0,
.00.0 0.00,26 .../ * 10
0,
.,0.0 0.00,00 1.2. * 10
#,
-00.0 0.00,00
Topic 6 , hours 3age 1
(a) Draw a graph. (!) 4hat happened after -00s5 (c) 6alculate the average rate of the entire reaction.
(d) Draw a tangent at 100 s( calculate the rate and see if it corresponds with the value in the ta!le.
Individual rate (= for any reagent or product in a particular reaction)7
The rate of any reaction is usually measured or calculated with respect to a particular species in that
reaction. The rate of the reaction is the individual rate of reaction for that specie. The individual rate of
appearance or disappearance of any other species or su!stance needs to !e calculated using the coefficient
of the su!stance in the !alanced e'uation.
+*ample7 8tudy the e'uation7 , 9r
#
(a') : 9r;-
#
(a') : 6<
:
(a') - 9r. (a') : -<.; (l)
n this e'uation( the !romide ion( 9r
#
( disappears at a rate , times higher than the !romate ion( 9r;-
#
( as it
has a coefficient of , in the e'uation; the rate of disappearance of the !romide ion is , times greater than
the rate at which the !romate ion disappears. ;r the rate at which the 9r. evolved appears is half the rate at
which the <
:
is used up.
E!eri"ental !rocedures for "easuring rates
6.1... Descri!e suita!le e*perimental procedures for measuring rates of reactions.
6.1.-. %nalyse data from rate e*periments
%ll e*perimental procedures can !e divided into . groups7
continuous procedures: measure a property during the reaction at given time intervals (e.g. every
minute); usually used when the investigator wants to follow the change in reaction rate during a reaction.
Techni'ues used to follow rate of reaction during one reaction7
ta"e a sample from the system( stop the reaction in the sample and measure the concentration of
one of the reactants or products !y titration (=titrimetric analysis);
as the reaction proceeds( measure the change in intensity of colour of one of the reactants using
a colorimeter (needs cali!ration) (=colorimetric analysis);
measure the change in the a!sorption spectrum with a spectrophotometer;
measure the change in gas volume;
measure change in electrical conductance during reactions in ions are either used up or created
(needs cali!ration) (=conductimetric analysis);
discontinuous procedures: the same reaction is carried out many times each time with different
starting conditions e.g. different concentrations or different temperatures; usually one reading or
measurement per e*periment; rate is the reciprocal of the time the reaction too" ; alternatively( the initial
rate of each reaction is compared. =sed to esta!lish the rate law of a reaction (see <>);
+*amples of discontinuous methods7
?iodine#cloc" reaction@;
the ?disappearing of the cross reaction@.
Anal#sis of data: inter!retation of gra!$s
;!taining rates from graph7 to !e as accurate as possi!le the rate should !e determined for an as small a
time interval as possi!le (instantaneous rates of reactions) which is difficult; it is made easier !y drawing
tangents to a graph line as shown a!ove.
Topic 6 , hours 3age .
6. %. Collision T$eor#
6...1 Descri!e the "inetic theory in terms of the movement of particles whose average energy is proportional to
temperature in Aelvins.
6..... Define the term activation energy( Ea.
6...- Descri!e the collision theory.
6...1 3redict and e*plain( using the collision theory( the 'ualitative effects of particle si)e( temperature(
concentration and pressure on the rate of a reaction.
6..., 8"etch and e*plain 'ualitatively the Ba*well09olt)mann energy distri!ution curve for a fi*ed amount of gas at
different temperatures and its conse'uences for changes in reaction rate.
6...6 Descri!e the effect of a catalyst on a chemical reaction.
6...$ 8"etch and e*plain Ba*well09olt)mann curves for reactions with and without catalysts
I"!ortant ideas of t$is t$eor#7
%ll particles move and the average amount of "inetic energy of all the particles in a su!stance is
proportional to the temperature in Aelvin.
The central idea of this theory or model is that "olecules "ust collide to react;
Cot every collision will lead to a reaction.
Dor a collision to result in a reaction it must !e successful which means it must7
occur with enough energy this minimum amount of energy is called the activation energy, Ea ; so
reacting species must have E Ea ; the particles must collide with enough energy so that bonds can
be broken and the reactant can be changed into product;
during the collision, the particles must approach each other in the correct way (correct collision
geometry); the particles must be moving in the right direction, glancing collisions will not result in a
successful collision

rate of reaction =
num!er of successful collisions
during a unit of time
t is important to appreciate that only a small fraction of collisions lead to a reaction (a!out 1 in every 10
1-

collisions).
Su""ar#
The three characteristic properties of reactant particles that afect the rate of reaction
are:
frequency of collisions
kinetic energy
correct collision orientation or geometry
&ualitative effects of !article si'e( te"!erature( concentration and catal#sis
Concentration: (or pressure for a gas)7 if the concentration increases this increases the num!er of
particles in a unit of volume and hence the num!er of collisions per unit of time; if the rate of collisions
increases so does the rate of reaction.
4e can also use concentration to e*plain why during most reactions7
The initial rate is the highest rate during the reaction (steepest slope) as at the start of the reaction(
the concentration of reactants is the greatest and therefore there are the greatest num!er of
successful collisions
The curve !ecomes less steepErate decreases as the concentration of reactant decreases
The curve flattensErate slows down to )ero when all reactants are used up
Topic 6 , hours 3age -
Te"!erature: the higher the temperature( the more "inetic energy the reactant particles have. This
increases the rate of reaction or result in more successful collisions per unit of time !ecause7
ncrease in fre'uency of collisions
The num!er of particles that have the same or more energy than the activation energy has also
increased; when these particles with + +a collide( the collision will !e successful.
4e can use a Ba*well# 9olt)man energy distri!ution curve show why temperature has such a great
effect on the rate of a reaction. These curves show the changes to the distri!ution of "inetic energy
when the temperature is increased; it also shows how an increase of 10A dou!les the reaction rate as it
dou!les the amount of particles of which + +a.

B%F4+>># 9;>TGB%C energy distri!ution curve (see diagram !elow)7
shows the distri!ution (or spread) of "inetic energy( at a given time( of particles in a sample of a
gas at a given temperature (it is a purely statistical analysis).
highest point represents( the most pro!a!le energy; the greatest fraction of molecules have this
energy at a given instant.
the curve is asymmetrical around the ma*imum value
the area underneath is proportional to the total num!er of particles in the sample of gas.
the shape should !e the same for any gas at a given temperature as at the same temperature
the average "inetic energy should !e the same.
The curve does not cross or touch the *#a*is.
Ba*well#9olt)man curve (from http7EEneon.chem.uidaho.eduEHhonorsE111I.0CotesE!olt).html)
Ba*well#9olt)man curves at three different temperatures
Topic 6 , hours 3age 1
Bain points7 %t higher temperatures7
the curve is more to the right
lower pea"
same area
end of the curve is a!ove the curve of a lower temperature
curve does not meet the *#a*is&&
Surface area: changes to the surface area in heterogenous reactions changes the num!er of collisions
!etween the fluid phase and the solid surface (gas or li'uid)( hence more collisions per unit of time.
Catal#st: a catalyst increases the rate without !eing used up; it does this !y lowering the activation
energy of the reaction so that more collisions !ecome successful as more collisions happen with energy
more than he activation energy. 9y lowering the activation energy( a catalyst increases the rate of !oth
forward and reverse reaction.
This lowering of the activation energy can !e done !y providing an alternative reaction pathway
(homogenous catalyst). f the catalyst is a solid its effect can !e increased !y using the catalyst in a
powder form when its surface area is increased.
(from http7EEwww.chemguide.co.u"EphysicalE!asicratesEcatalyst.htmlJtop)
Examples of catalysts
reaction catalyst type of catalyst
2H
2
O
2
(aq) 2H
2
O (l) + O
2
(g) MnO
2
(s) heterogenous
2SO
2
(g) + O
2
(g) 2SO
3
(g) V
2
O
5
(s) heterogenous
2H
2
(g) + N
2
(g) 2NH
3
(g) Fe (s) heterogenous
hydrogenation of a C=C double bond
Ni (s) heterogenous
Topic 6 , hours 3age ,
+nthalpy level diagram to show effect of catalyst
Topic 6 , hours 3age 6