RATES OF REACTION

Increasing the rates of chemical reactions is important in industry because it helps to

reduce costs.
The rate of reaction is the speed at which a chemical change takes place. It is followed
by measuring the rate at which reactants are used up or the rate at which products are
formed. This allows a comparison to be made of the changing rate of a chemical
reaction under different conditions.
Rate = amount of reactant used or Rate = amount of product formed
time time
Chemical reactions can occur only when reacting particles collide with each other with
sufficient energy. The minimum amount of energy which particles must have to react is
called the activation energy.
Various factors alter the rate of a reaction:
the state of division of the reactants i.e. the particle si!e of a solid": the smaller
the particle si!e# the faster the reaction is.
the concentration of dissolved reactants or the pressure of gases: the higher the
concentration or the pressure# the faster the reaction is.
the temperature of the reaction mi$ture: the higher the temperature# the faster the
reaction is.
the addition of a catalyst speeds up the reaction
1. The Particle Size of Solid Reactants
The reaction used to study the effect of particle si!e is the reaction of calcium
carbonate# in the form of marble# with dilute hydrochloric acid.
CaC%&s" ' ()Cla*" CaCl(a*" ' )(%l" ' C%(g"
The reaction is followed by the change in mass of the reaction flask with time as carbon
dio$ide is given off. It would also be possible to measure the change in the volume of
carbon dio$ide given off with time by collecting the gas in# for e$ample# a gas syringe.
Method:
+ constant mass of marble chips was weighed out and placed into a (,-cm
&
conical
flask. .--cm
&
of ./ hydrochloric acid was added from a measuring cylinder. The flask
was loosely stoppered with cotton wool to allow the gas to escape but to prevent the
loss of li*uid splashes" then placed onto an electronic balance. The mass of the conical
flask was recorded every .,s for the first minute# then every &-s for a total of ten
minutes. It is assumed that the temperature of the reaction mi$ture stayed constant.
The e$periment was repeated with three different si!es of marble chips# keeping all
other variables the same. The results were tabulated and a graph of mass of carbon
dio$ide y0a$is" against time $0a$is" was plotted.
TOPIC 11.2.: RATES AN! ENER"# 1
Res$lts:
1arge 2articles /edium 2articles 3mall 2articles
TOPIC 11.2.: RATES AN! ENER"# 2
Time 4s
/ass of
flask4g
/ass of
C%( 4g
/ass of
flask 4g
/ass of
C%( 4g
/ass of
flask 4g
/ass of
C%( 4g
-
.,
&-
5-
6-
.(-
.,-
.7-
(.-
(8-
(9-
&--
&&-
&5-
&6-
8(-
8,-
87-
,.-
,8-
,9-
5--
Inter%retation of Res$lts:
The reaction occurs only on the surface of the calcium carbonate. :or a given mass of
calcium carbonate# the smaller the si!e of the particles# the greater is the surface area
and the faster the reaction. This is shown on the graph by the gradient becoming
steeper as the particle si!e decreases.
3ince the same *uantities of reactants are involved in all three reactions# the same
mass of carbon dio$ide is given off in all of them# if the reaction is allowed to go to
completion. This is shown by all three curves levelling off at the same total mass of
carbon dio$ide.
The calcium carbonate is in e$cess# so the hydrochloric acid is used up completely as
the reaction takes place. 3ince its concentration decreases with time# the reaction
becomes slower and slower. This shown on the graph by a curve of steadily decreasing
gradient.
The e$pected mass of carbon dio$ide can be calculated. 3ince the calcium carbonate is
in e$cess# the mass of carbon dio$ide depends on the amount of hydrochloric acid
used. .--cm
&
of ./ )Cl contains -..mole of )Cl.
CaC%&s" ' ()Cla*" CaCl(a*" ' )(%l" ' C%(g"
( moles . mole
-.. mole -.-, mole
-.. mole -.-, $ 88 g
-.. mole (.(g
TOPIC 11.2.: RATES AN! ENER"# &
The smaller the particle size (the bigger the surface area) , the
faster the reaction
2. The Te'%erat$re
The reaction used to study the effect of temperature is the reaction of sodium
thiosulphate solution with dilute hydrochloric acid.
;a(3(%&a*" ' ()Cla*" (;aCla*" ' 3s" ' )(%l" ' 3%(g"
The reaction is followed by the appearance of colloidal sulphur as the reaction
proceeds. The formation of sulphur begins as soon as the reactants are mi$ed# but it
takes time for observable amounts to be produced. The time taken to reach a particular
point in the reaction can be determined by standing the reaction flask on a piece of
paper marked with a feint cross and timing how long it takes for the cross to be
obscured when looked at from above.
Method:
.-cm
&
of sodium thiosulphate stock solution concentration 8-g per litre" were
measured out into a measuring cylinder and poured into a (,-cm
&
conical flask. 8-cm
&
of water were measured out in a similar way and added to the flask. The flask was
heated gently over a <unsen burner to a temperature slightly above the desired
temperature. The flask was placed on a piece of paper marked with a feint cross. ,cm
&
of (/ hydrochloric acid were measured out into a second measuring cylinder. +s the
acid was poured into the conical flask# a stopwatch was started and the mi$ture gently
swirled. The initial temperature was recorded. The stopwatch was stopped when the
cross# viewed from above# became obscured. The time and the final temperature were
recorded. The mean of the initial and final temperatures was taken as the temperature
of the reaction.
The e$periment was repeated for five different temperatures# keeping all other variables
constant.
The results were tabulated and from the results a graph of .---4 time y0a$is" against
temperature $0a$is" was plotted. .---4 time is a measure of the rate"
Res$lts:
Initial
temp. /
o
C
Final temp.
/
o
C
Mean
temp. /
o
C
Time /s !!!/time /s
"
Inter%retation of Res$lts:
The graph is an e$ponential curve: the rate of reaction increases rapidly with
temperature# a rise in temperature of .-
o
C appro$imately doubling the rate.
TOPIC 11.2.: RATES AN! ENER"#
The higher the temperature, the faster the reaction
+n increase in temperature increases the rate of reaction in two ways:
The %articles collide 'ore ener(eticall)
The particles of a substance have a range of different energies# the average energy
being proportional to the temperature in =elvins. +s the temperature increases# the
particles move faster i.e. they have more kinetic energy"# and the proportion of particles
with higher energies increases. Therefore# the number of collisions with energy greater
than or e*ual to the activation energy rises rapidly as the temperature increases# and so
the rate rises rapidly. This is the ma#or effect.
The %articles collide 'ore fre*$entl)
The particles move around faster and therefore there is a greater chance that they will
be involved in a collision. This is a minor effect.
TOPIC 11.2.: RATES AN! ENER"# +
reactants
bonds
forming
bonds
breaking
Reaction path
Chemical
>nergy
products
>
a
)
In the reaction between thiosulphate
ions and hydrogen ions# as the ions
collide covalent bonds are broken and
new bonds are formed. 3ince energy is
needed to break bonds# the colliding
particles must have a minimum energy
on collision sufficient to break the
bonds. This energy is known as the
activation energy ($a).
%nly those collisions with energy
greater than or e*ual to the activation
energy will result in a reaction.
&. The Concentration of Reactants
The reaction used to study the effect of concentration is the reaction of sodium
thiosulphate solution with dilute hydrochloric acid.
;a(3(%&a*" ' ()Cla*" (;aCla*" ' 3s" ' )(%l" ' 3%(g"
The reaction is followed by the appearance of colloidal sulphur as the reaction
proceeds. The formation of sulphur begins as soon as the reactants are mi$ed# but it
takes time for observable amounts to be produced. The time taken to reach a particular
point in the reaction can be determined by standing the reaction flask on a piece of
paper marked with a feint cross and timing how long it takes for the cross to be
obscured when looked at from above.
Method:
,-cm
&
of sodium thiosulphate stock solution concentration 8-g per litre" were
measured out into a measuring cylinder and poured into a (,-cm
&
conical flask. The
flask was placed on a piece of paper marked with a feint cross. ,cm
&
of (/ hydrochloric
acid were measured out into a second measuring cylinder. +s the acid was poured into
the conical flask# a stopwatch was started and the mi$ture gently swirled. The stopwatch
was stopped when the cross# viewed from above# became obscured. The time was
recorded.
The e$periment was repeated for five different concentrations# keeping all other
variables constant.
+ graph of .--- 4time y0a$is" against volume of ;a(3(%& $0a$is" was plotted.
3ince the total volume of the reaction mi$ture is constant at ,,cm
&
" the concentration of
;a(3(%& is proportional to its volume.
Res$lts:
Constants: total volume of ;a(3(%& solution ,-cm
&
(/ hydrochloric acid ,cm
&
temperature .7
o
C
conical flask ? cross
%olume of &a'(')*
(+!g/l) /cm
*
%olume of
,') /cm
*
Time /s !!!/ time /s
"
,- - &( &..&
8- .- 8- (,.-
&- (- ,( .6.(
(- &- 96 .(.9
.- 8- .9( ,.7
TOPIC 11.2.: RATES AN! ENER"# ,
Inter%retation of Res$lts:
The graph is a straight line through the origin# therefore the rate of the reaction is
directly proportional to the concentration of sodium thiosulphate.
To react# the reacting particles must collide@ therefore the rate will be faster the greater
the number of collisions there are in a given volume in a given time. The more
concentrated the solution is# the greater the number of particles there are in a given
volume and therefore the greater the fre-uency of collisions. It is important to note
that only a very small proportion of the total number of collisions is successful and leads
to a reaction.
Effect of Press$re
2ressure is important only in reactions involving gases. 2ressure affects gaseous
reactions in the same way that the concentration affects reactions in solution. +s the
pressure is increased# the greater the number of particles there are in a given volume
and therefore the greater the number off collisions in a given time. Therefore# as the
pressure increases# the rate increases.
TOPIC 11.2.: RATES AN! ENER"# -
&-
(-
.-
-
.---4 time 4s
0.
Volume of ;a
(
3
(
%
&
4cm
&
.- (- &- 8- ,-
$
$
$
$
$
The more concentrate. the solution, the faster the reaction
. Addition of a Catal)st
The reaction used to study the effect of a catalyst is the decomposition of hydrogen
pero$ide:
()(%( ()(% ' %(
The reaction is catalysed by several metal o$ides@ the compound used here is
manganeseIV" o$ide. The reaction is followed by collecting the o$ygen given off and
measuring its volume at regular intervals of time. The gas may be collected either in a
gas syringe or over water in a burette.
Method:
9cm
&
of (- volume hydrogen pero$ide were measured out using a measuring cylinder
and poured into a .--cm
&
conical flask. 8&cm
&
of water were measured out in a similar
way and added to the conical flask. -.,g of powdered manganeseIV" o$ide was
weighed out and added to the flask. The flask was connected by a delivery tube to a
.--cm
&
gas syringe. + stopwatch was started. The volume of o$ygen# which had
collected in the gas syringe# was recorded at &- second intervals for ten minutes.
=eeping all other variables constant# the e$periment was repeated using -.9,g and ..-g
of the same manganeseIV" o$ide.
Res$lts: Constants: (- volume )(%( 9cm
&
water 8&cm
&
temperature .7
o
C
%olume of )' /cm
*
Time /s !./g of Mn)' !.0/g of Mn)' .!g of Mn)'
- - - -
&- ..7 (.6 &.(
5- 8.. 5.- ,.9
6- 5.( 9.6 6.8
.(- 7.& .-.& .(.-
.,- 6.6 .(.. .8.5
.7- ..., .&.7 .9..
(.- .(.7 .,.8 .6.-
(8- .8.8 .5.7 (...
(9- .5.( .7.( (&.&
&-- .9., .6.9 (,..
&&- .7.7 (-.7 (5.7
&5- .6.6 ((.. (7.,
&6- (..9 (&.. &-.-
8(- ((.7 (8.( &..5
8,- (&., (,.( &(.6
87- (,.- (5.& &8.(
,.- (5.- (9.8 &,.,
,8- (9.- (7.& &5.5
,9- (9.9 (6.- &9.9
5-- (7.7 &-.. &6.-
TOPIC 11.2.: RATES AN! ENER"# .
+ll three reactions are being observed only in the early stages and are far from
complete. 3ince all three reactions use e$actly the same *uantity of hydrogen pero$ide#
they should# when complete# give the same total volume of o$ygen.
+ graph of volume of o$ygen y0a$is" against time $0a$is" was plotted.
Inter%retation of Res$lts:
The reaction is faster the more catalyst there is present@ this is shown by the increasing
steepness of the curves.
The reaction takes place on the surface of the catalyst. Increasing the mass of catalyst
increases the surface area and therefore speeds up the rate.
+ catalyst can be used over and over again to speed up the conversion of reactants to
products. Aifferent reactions need different catalysts.
TOPIC 11.2.: RATES AN! ENER"# /
reactants
Reaction path
Chemical
>nergy
products
>
a
)
>
a cat
+ catalyst does not affect the outcome of
a reaction@ the same product is formed but
in a shorter time. + catalyst works by
weakening bonds# which lo1ers the
activation energy for the reaction. If the
activation energy is lowered# more
particles have enough energy to react and
therefore the reaction goes faster.
+ catalyst is not used up in the reaction
but is recovered unchanged at the end.
2 catalyst is a substance 1hich increases the rate of a chemical reaction but is
not use. up in the reaction.
ENER"# 0 C1EMICA2 C1AN"E
Auring a chemical reaction# e$isting chemical bonds are broken and new bonds are
formed.
energy must be supplied to break e$isting bonds
energy is released when new bonds are formed
The overall change in energy# which takes place during the reaction# is called the heat
of reaction and is given the symbol ) pronounced Bdelta )C".
If the energy needed to break e$isting bonds is less than the energy released when new
bonds are formed# the reaction will give out energy usually as heat" to its surroundings.
The temperature of the reaction mi$ture will rise. This is called an e3othermic reaction.
:or an e$othermic reaction# the sign of the heat change )" is negative. >a is called the
activation energy and is the minimum energy needed for a reaction to take place.
Dhen a catalyst is added to a reaction# it provides an alternative reaction path with a
lower activation energy. If the activation energy is lowered# the reaction goes faster.
+ll reactions involving burning# e.g. the burning of magnesium# are e$othermic.
>a
Chemical
>nergy
)

Reaction path

De can make use of e$othermic reactions is devices such as hand warmers and self
heating cans where heat may be needed in a remote environment.
TOPIC 11.2.: RATES AN! ENER"# 13
reactants
products
bonds
forming
bonds
breaking
If the energy needed to break e$isting bonds is greater than the energy released when
new bonds are formed# the reaction will absorb energy usually as heat" from its
surroundings. The temperature of the reaction mi$ture will fall. This is called an
en.othermic reaction. :or an endothermic reaction# the sign of the heat change )" is
positive.
>a
Chemical
>nergy

Reaction path
The reaction of sodium hydrogencarbonate with hydrochloric acid is endothermic.
;a)C%& ' )Cl ;aCl ' )(% ' C%(
De can make use of endothermic reactions is devices such as chemical cold packs to
put on an inEury to reduce swelling and numb pain.
If a reversible reaction is e$othermic in one direction it will be e*ually endothermic in the
other. >g

Cu3%8.,)(- Cu3%8. ' ,)(-
Fou need to heat blue hydrated copper sulphate to produce white anhydrous copper
sulphate so this process re*uires energy and is therefore endothermic.
)owever# when water is added to white anhydrous copper sulphate a lot of heat is given
out as it turns blue and so is e$othermic.
TOPIC 11.2.: RATES AN! ENER"# 11
reactants
products
)