1-

s = k f o ti n U

md lo m
s md lo m = k

3-

1- 3-

lecnac
d n a sti n u t r e s nI . 2

Copyright N Goalby Bancroft's School

] A[
et a R = k
t c ej b u s s a k e vi g ot
n oit a u q e et a r e g n a r r a e R . 1
Calculating units of k

] A[ k = et a R : n etti r w yll a u s u 1 = 0 + 1 = r e d r o ll a r e v o B ni r e d r o o r e z d n a A ni r e d r o t s rif si n oit c a e r 0 = n d n a 1 = m 0 ] B[] A[ k = et a R

noitauqe noitcaer decnalab eht ta gnikool yb dnuof

eb tonnac yeht ;tnemirepxe morf denimreted eb
tsum sredro noitcaer eht fo seulav eht :rebmemeR

)llarevo redro tsrif( elpmaxE

dro tsrif( elpmaxE

s md lo m
s md lo m
s md2-lom

1- 6
1- 6

22-

si k fo tinu eht noitcaer llarevo redro dr3 a roF

s md1-lom

1- 3

1-

si k fo tinu eht noitcaer llarevo redro dn2 a roF

s
s
s

11-

si k fo tinu eht noitcaer llarevo redro ts1 a roF

erutarepmet esaercni ew fi sesaercni ti

d n a e r ut a r e p m et cifi c e p s a ot s r ef e r k f o e ul a v e h T
. e r ut a r e p m et d e xif a t a t n at s n o c si tI . e mit
d n a n oit a rt n e c n o c f o t n e d n e p e d ni si k f o e ul a v e h T
n oit a u q e
et a r e ht m o rf t u o d e k r o w e b t s u m tI . n oit c a e r
f o r e d r o ll a r e v o e ht n o d n e p e d k f o sti n u e h T

.3
.2
.1

The rate constant (k)

] A[ k = r
d e r a u q s A f o n oit a rt n e c n o c
e ht ot l a n oit r o p o r p si n oit c a e r f o et a r e ht : r e d r o d n o c e s r o F
2

] A[ k = r

the rate of reaction is directly proportional

to the concentration of A
1

: r e d r o t s rif r o F

k = ] A[ k = r
n oit c a e r f o et a r
e ht n o t c eff e o n s a h A f o n oit a rt n e c n o c e ht : r e d r o o r e z r o F
0

NOTE: the orders have nothing to do with the stoichiometric

coefficients in the balanced equation. They are worked out
experimentally

) n + m( r e ht e g ot
s r e d r o l a u di vi d ni e ht ll a g ni d d a y b t u o
r e dr o at ot
r e dr o at ot
dekrow si noitcaer a rof redro lllatot ehT
tnatsnoc etar

r e dr o d n o c e s s n a e m 2
r e d r o t s rif s n a e m 1
t n at c a e r t a ht ot t c e p s e r hti w r e d r o o r e z si n oit c a e r e ht s n a e m 0

e ht d ell a c si k

) m d l o m ti n u (
A f o n oit a rt n e c n o c e ht
s n a e m ] A[ st e k c ar b er a u q s e h T

m, n are called reaction orders

Orders are usually integers 0,1,2

3-

For the following reaction, aA + bB

products, the generalised rate equation is:

The unit of r is usually mol dm-3 s-1

r = k[A]m[B]n

r is used as symbol for rate

The rate equation relates mathematically the rate of reaction to the concentration of the reactants.
Rate Equations

1. Kinetics

s md2-lom

1- 6

2
2
2
2

Copyright N Goalby Bancroft's School

The reaction is 3rd order overall and the unit of the
rate constant =

] B[ ] A[ k = r si n oit a u q e et a r ll a r e v o e h T

r e d r o o r e z si C ot t c e p s e r hti w r e d r o e ht e r of e r e h T
emas eht syats
emas eht syats
se buod
se buod
.emas eht syats etar eht )tnatsnoc gniyats B dna A( sellllbuod C fo noitartnecnoc eht sA
emas eht syats
se buod
: 4 d n a 1 st n e mi r e p x e n e e wt e b e r a p m o c B t n at c a e r r o F
r e dr o
r e dr o
2 si B
2 si B
r e dr o
2 si B ot t c e p s e r hti w r e d r o e ht e r of e r e h T
.selpurdauq etar eht )tnatsnoc gniyats C dna A( selbuod B fo noitartnecnoc eht sA
3 dna 1
3 dna 1
: 3 d n a 1 st n e mi r e p x e n e e wt e b e r a p m o c B t n at c a e r r o F
3 dna 1
dn
dn

r e d r o t s ri f si A t n at c a e r ot t c e p s e r hti w r e d r o e ht e r of e r e h T . et a r
e ht s e o d o s )t n at s n o c g ni y at s C d n a B ( s el b u o d n oit a rt n e c n o c e ht s a A t n at c a e r r o F

For reactant A compare between experiments 1 and 2

0.25

0.1

0.2

0.5

0.25

0.2

0.1

1.0

0.25

0.4

0.1

0.5

0.5

2 = r e d r o : s el p u r d a u q et a r d n a d el b u o d si c n o c fI
1 = r e d r o : s el b u o d et a r d n a d el b u o d si c n o c fI
0 = r e d r o : e m a s e ht s y at s et a r d n a d el b u o d si c n o c fI

0.5

0.1

[B]
mol dm-3

[C]
mol dm-3

Rate
mol dm-3 s-1

In order to calculate the order for a particular

reactant it is easiest to compare two
experiments where only that reactant is
being changed
C2 +B +A

0.1
[A]
mol dm-

,E2 + D

Experiment

Example: work out the rate equation for the following reaction,
data in the table

using the initial rate

Normally to work out the rate equation we do a series of

experiments where the initial concentrations of reactants are
changed (one at a time) and measure the initial rate each time.
This data is normally presented in a table.
The initial rate is the rate at the start of the reaction, where it is fastest. It is
often obtained by taking the gradient of the conc vs time graph.

Working out orders from experimental initial rate data

6-

s md2-lom = k fo tinU

1- 6

) mdlom(.3-md lom
1-s3- md lom = k

md2lom
s =k

2 3-

1-

lecnac
d n a sti n u t r e s nI . 2

n oit c a rf yfil p mi S . 3

] B[] A[
et a R = k

t c ej b u s s a k e vi g
ot n oit a u q e et a r e g n a r r a e R . 1
k fo tinu eht etaluclaC

r = k[A][B]2

overall order is 3

.redro dn2 si B dna redro ts1 si A erehw

B d n a A n e e wt e b n oit c a e r r of n oit a u q e et a r eti r W : el p m a x E

2
s md lo m
s md lo m
0 1 x 0. 3 = k
0 1 x 0. 3 = k
s md lo m
s md lo m
0 1 x 0. 3 = k
0 1 x 0. 3 = k
24-

2. 0 x 2. 0

2.40 x 106

1- 6

Copyright N Goalby Bancroft's School

Increasing the temperature increases the value of the rate constant k
Remember k is the same for all experiments done at the same temperature.

=k

] B[ ] A[
r =k

r = k [X] [Y]

: 3 t n e mi r e p x e g ni s U . k e vi g ot d e g n a r r a e r n e e b s a h
t a h t n oit a u q e et a r e ht ot ni s e ul a v e ht t u p d n a st n e mi r e p x e e ht f o e n o y n a e s o o h c , el p m a x e e v o b a e ht g ni s U
Calculating a value for k using initial rate data

s md2-lom

1- 6

The reaction is 3rd order overall and the unit of

the rate constant =
2
2
2
2

] Y[ ] X[ k = r si n oit a u q e et a r ll a r e v o e h T

r e dr o d n o c e s e b t s u m Y

.ti d el p u r d a u q e v a h ot si et a r n o , e r of e r e ht , Y f o t c eff e e h T
et a r d el b u o d e v a h lli w t a ht o s r e d r o t s rif si X w o n k e W
8 y b p u s e o g et ar

e ht d n a el b u o d Y d n a X ht o B

: 3 d n a 2 st n e mi r e p x e n e e wt e b g ni r a p m o C
r e d r o t s ri f si X t n at c a e r ot t c e p s e r hti w r e d r o e ht e r of e r e h T
. et a r e ht s e o d o s )t n at s n o c g ni y at s Y ( s el b u o d n oit a rt n e c n o c e ht s a X t n at c a e r r o F

For reactant X compare between experiments 1 and 2

Experiment

Initial concentration of
X/ mol dm3

Initial concentration
of Y/ mol dm3

Initial
rate/ mol dm3 s1

0.05

0.1

0.15 x 106

0.10

0.1

0.30 x 106

0.20

0.2

2.40 x 106

, Y d n a X n e e wt e b

Example work out the rate equation for the reaction,

using the initial rate data in the table

81 x
81 x
8 1 x = 9 x 2 x dl u o w et a r e ht n e ht e mit e m a s e ht t a d e n e p p a h s e g n a h c e s e ht fI
81 x
9x =
2 3 x dl u o w et a r t a ht 3 x si ] B[ e ht fI
2x
2x
2 x dl u o w et a r t a ht 2 x si ] A[ e ht fI
2x
] B[ ] A[ k = r si n oit a u q e et a r e ht e r e h w n oit c a e r a nI

In most questions it is possible to compare between two experiments where only one reactant has its initial
concentration changed. If, however, both reactants are changed then the effect of both individual changes are
multiplied together.
Working out orders when two reactant concentrations are changed simultaneously

Revision of AS kinetics Maxwell Boltzmann Distribution

The Activation Energy is defined as the minimum energy
which particles need to collide to start a reaction

The Maxwell-Boltzmann energy distribution shows the spread of energies that

molecules of a gas or liquid have at a particular temperature
Emp this is the most
probable energy (not the
same as mean energy)

Learn this curve

carefully

The area under the curve represents

the total number of particles present

The energy distribution

should go through the
origin because the are
no molecules with no
energy

Most molecules have energies between

the two extremes but the distribution is not
symmetrical (normal)

Only a few particles have

energy greater than the EA

Increasing Temperature

The energy distribution should never

meet the x axis, as there is no
maximum energy for molecules

s ei g r e n e r e h gi h hti w s el u c el o m e r o m g ni v a h s d r a w ot
s tfi h s n oit u bi rt si d e ht s e s a e r c ni e r ut a r e p m et e ht s A

A few have low energies

because collisions cause
some particles to slow down

The mean energy of the

particles is not at the peak
of the curve

At higher temperatures the energy of the particles increases. They collide more frequently and more often
with energy greater than the activation energy. More collisions result in a reaction

Both the Emo and mean energy shift to high energy values

. s e r ut a r e p m et r e w ol t a n a ht s ei g r e n e f o e g n a r
r e di w a e v a h s el u c el o m e ht s e r ut a r e p m et r e h gi h t A

ygrene no tav tca eht naht retaerg

ygrene no tav tca eht naht retaerg
ses aercni snoisilloc lufsseccus fo ycneuqerf eht os , ygrene noiiiitaviiiitca eht naht retaerg
ygrene no tav tca eht naht retaerg
e v a h s el cit r a p f o n oit r o p o r p r e g gi b a t a ht w o h s s h p a r g e ht , s e s a e r c ni e r ut a r e p m et e ht s A

Copyright N Goalby Bancroft's School

y gr e n e
y gr e n e
y gr e n e
y gr e n e

t n at s n o c si s el cit r a p f o r e b m u n l at ot e ht e s u a c e b
t n at s n o c ni a m e r dl u o h s e v r u c e ht r e d n u a e r a l at ot e h T

Increasing the temperature increases the value of

the rate constant k

Rate Equations and mechanisms

A mechanism is a series of steps through which the reaction
progresses, often forming intermediate compounds. If all the
steps are added together they will add up to the overall
equation for the reaction

.pets gninimreted- etar eht dellac si pets

t s e w ol s e h T . n oit c a e r f o et a r ll a r e v o e ht
l o rt n o c lli w p et s t s e w ol s e h T . n oit c a e r
f o et a r t n e r effi d a e v a h n a c p et s h c a E

The molecularity (number of moles of each substance) of the molecules in the slowest
step will be the same as the order of reaction for each substance.
e.g. 0 moles of A in slow step will mean A is zero order.

Example 1

Example 2

overall reaction
A + 2B + C
D+E
Mechanism
Step 1
A+B
X + D slow
Step 2
X+C
Y
fast
Step 3
Y+B
E
fast

r = k [A] [B] [C]

overall reaction
A + 2B + C
D+E
Mechanism
Step 1
A+B
X + D fast
Step 2
X+C
Y
slow
Step 3
Y+B
E
fast
1

D+X B+A
p et s s u oi v e r p a ni et ai d e m r et ni e ht p u
e k a m t a ht s e c n at s b u s e ht hti w d e c al p e r e b t s u m
o s st n at c a e r e ht f o e n o t o n si X et ai d e m r et ni e h T
]C[1]X[ k = r

Example 3

r = k[A] [B] [C]

n oit c a e R ll a r e v O
)g(2OC + )g(ON

)g(OC + )g(2ON
: m si n a h c e M

t s af

3
2

ON + ON

OC + 2 ON

w ol s

O N + 2 O N 1 p et S
O C + 3 O N 2 p et S

et ai d e m r et ni n oit c a e r a si 3 O N
r = k [NO ]

Example 4: SN1 or SN2? You dont need to remember the details here.
Remember the nucleophilic substitution reaction of
haloalkanes and hydroxide ions.
This is a one step mechanism

The same reaction can also occur via a

different mechanism

n oit c a e R ll a r e v O

rB + HOC3)3HC(

HO + rBC3)3HC(
: m si n a h c e M

tsaf HOC3)3HC( HO + +C3)3HC(

wols rB + +C3)3HC( rBC3)3HC(
CH3CH2OH + Br- slow step

Copyright N Goalby Bancroft's School

r = k [(CH ) CBr]
3 3

si n oit a u q e et a r e h T

r = k [CH CH Br] [OH ]

This is called SN2.

Substitution, Nucleophilic,
2 molecules in rate
determining step

si n oit a u q e et a r e h T

CH3CH2Br + OH-

This is called SN1.

Substitution, Nucleophilic,
1 molecule in rate
determining step