08388

Rate time

Rate a 5
time

change in reactant
concentration
of
Rate A B

A more RA A
f A

A IF less DEA

Rate DA
DE

Rate D dm 3 moldmi 35
most
change in concentration
of product
DB B F B i Rate DB
Bt

Dynamic equilibrium

Rt
A Rate forward rate backward
Rn
Product
conc
moldm 3
conc of
react
and prod are
equal at equilibrium
reactant

Els

If 3

Rate of reaction is defined as the change in concentration of

reactants or products per unit time

Rate can be measured

by recording the changes in concentratio
volume collected or the increase or decreasein mass and Chang
of gas
in colour
 Types of rate measurements

Average rate

Instantaneous rate
Initial rate

Reaction B w 03 Ethene

Cann t 03
Effiffemittal
time s Oz molldm
smog
5
0 00 3.20 10

10 00 2.42 155
5
20 00 1.95 10

30 00 1 63 XIE
40.00 1 40 10
5

5
50.00 23 10

5
GO 00 1 10 10

Average rate
The rate over the whole time period
 3 Average rate
5
Average rate i 1 105 3 2 10
moldm
60 O O 00

not
very efficient nor useful
time Is as it does
not show therate

Instantaneous rate

rate at particular instant

any
3 E 10 s

1dm Rale By
gradient

p time Is
tangent

Initial rate

As a reversible ran proceeds the product

conc increases and the reverse rxn takes place more quickly
To overall net rate we would have to take both the forwardand

backward ran into account and calculate the difference b w their rates

To overcome this complication the initial rate is measured The initial rate

s the instantaneous rate at lime t 0 that is it is the rate when

 I

when the reactants mixed together

are
just
Under these conditions the product concentration are negligible so the

reverse rate is also negligible and it can be ignored

E3
tangent at t o
moldm a
for initial rate

a time Is

Rate Law and it's components

The rate law expresses rate as a function of

reactant concentration or product concentrations at
a particular temperature

AA t b B CC t dD

Rate K ATM B m and n

are orders
the
Order is the power which of reaction
and can be
concentration of a reactant is raised in found via experiment
an experimentally determined rate equation
only
 q
types of orders
1 First order 1st
2 Second order 2nd

3 Zero order o

1st order of reaction

Rate conc

Rate x A

If the conc doubles the rate doubles as rate is directly

proportional to the concentration A So it is 1st order Wr t A

of
Rate K AT B
s
rate Conc of
const reactants

Order is always determined by experiment and hot by

looking at the stoichiometry

Rate A a

moldm3 moldy

0.5
0.25

CONE I t 1122442
105 205
 the half life th is the time taken

for the initial concentration to halfit's value

t
12 is constant for 1st order
1st tyz 2nd t 42 105
1st 12 105

2nd 42 20s 10 s 10s

product
moldm 3

time
s

Zero order of reaction

Rate K A It Rate K

eg
2 NH3 N2 t 342
Rate K NH3
Rate k rate does not
 depend on NH3 conc

Rate Rate is const

moldm's
Kd
NH3
moldin
React K
gradient
Moldm 3 by

Dx

timels

Product K
malden's
gradient
g

DX
time s

2nd order
of reaction

2 NO 242 N2 2420g
eg 19 191 191

Rate K No Hz always found through

experiment
 rxn is 2nd order wit No Rate 2 NOT
if NO is doubled
rxn is 1st order writ Hz
rate is quadrupled

Rate NO
moldm35 moidm's

0.5

0.25

NOT 2 tilz 2542 time s

moldm3

t la is not constant

ie It tyz 2nd tyz

Both cone us time
graphs for 1st and 2nd
orders are curves

But tyz is constant only for 1st order runs

distinguish b w the two curves

product
moldm3

times
 Overall order
Is the sum
of individual orders
Rate K AT B
eg
Rate Wrt AT 1st order
Rati wrt B 2nd order
overall order 1st 1st 2nd order
Units k depend on the overall order
of

I Rate K A
Rate k k mold n 35

2 Rate K A
Rate K K s
A

3 Rate K A

Rate k k moi'd m3 s
2
A

Worksheet
 Q's order wrt Ht

using exp 1 and 2

D Ht 1.67
EYE
same

initial rate 2 15
I 1.67
1 2 10 5 3

when Ht by 1.67 theyrtaited changes

changes by a factor
1 67
of
o It is 1st order w r t Ht

Order Wrt Iz is zero as Iz is kept constant

at 0.002 moldm's and is not affecting rate

Order Wrt CH3COCH3

Use experiments 4 and 5

D conc 0.3 3

Yame
0 I
s
9 Rate 1.2 10
3
4 6
0
 4 6
10

Order wrt to propan 2 one is Istorder

Rate K Ht Ut3COCH3
do not write the zero order
concentrations in the rate law

Q2
02g 2140,721102 g

from exp I and 2

2
D Oz Emp 2 2.2 10
Emp I l l 0 2
same

DRate 3
Exp 2 6.40 10 2
Exp 1 3 20 10 3

older wot 02
first
from Exp 1 and 3
2
A NO Exp 3 2.6 10 2
1 3 10 2
Exp 1

A Rate 3
Exp 3 12 8 10 4
 Exp I 3 21 10 3

As NO is doubled the rate 2ndorder

quadruples
Wrt NO

Rate K Oz NOT
2 2
3 21 10 3 K l 10 10 I 3 10

K 1726

mo152dm65

311 NO z g NO 9
01g CO2
using Exp I and 2

DINO 2ndorder Wrt

g4 4
y NOT
A Rate 16
8 889
Using Exp Land 3

A Co 2

A Rate ooo s 290 Order wry

I
CO
0.00g

Rate K NO LOT To ignore

 Rate K NO

Eg 4202 Ht Rate
0.05 0.05 1 O

0.07 0.05
o.gg 0.07
1 8

order Wrt 11202

Order wot Ht
Order wrt 11202
using Enp 1 and 2
DEH2023 0 07 1 4
order wrt 4202
0.05
is Is order
D Rate 1.4
1 y
i o

Order wot Ht using exp 2 and 3

Rate 2 Ka 4202 HI
Rate 3 153 4202 Ht
0.07 0.051m
if 0.09 0.07
 m
log 1 4 X 0.09
0
1 8 0 07

5 7
log
Zero order wrt Ht

Rate K H2O 2

Reaction rate and reaction mechanism

Elementary steps

step 1 A B X slow steep

Jtep 2 X A D
fast step
step 3 D E tf
fast step
2A t B E F overall ran

Ea
fat ishigher
rate determining
step
2A B

E F
 A reaction mechanism is a sequence of single steps that
add up to the overall reaction Each step in the mechanism
is known as an
elementary step

The elementary step describes a single molecular event

ie Bond breaking Bond making or the

formation of a
transition state or intermediate
An elementary step as long it is the slow step
as
of
the reaction can be used to write the rate equation
and the orders reaction can be deduced from that
of
elementary step
A B X scow steep
A D
fast step
D E p
fast step
ZA t B E F overall
9 B
Intermediates can not be
Rate K AT B
part of the rate equation

When we have reactants in elementary stage

we can use molar quantities
 S

A B C fast step
C A D SCOW steep
D E tf
fast step
ZA t B E F

Rate KCC A
substitute as C is an intermediate

Rate K AT B A
Rate K A ZEB

Rate equation has to be from the slow step

and should be in terms of the reactants

Eg Iodination Propanone
of
CH3COCH3 Iz to ChacoCHZI HI

Rate K CH COCH Ht

Proposed Mechanism
1 Hz É cuz Ht at 3 I CH Slow step

OH
 I
2 113
É CH3 CH z CHz Ht fast

3 Cuz I CHz Iz I cha CI CH3 fast

Y I cha É CH 3 I CH z É CH 3 Htt I fast

I
Step 1 is the slow step because it has the reactants

CH3 CO City and Ht which are also present in the

equation in order Both species

rate the
first
appear as first order terms in the rate equation

Example 2

Hz C É H T HCN CHS H CN

Mechanism A
t
1 CH3 CHO Ht Hz CH OH
2 t
Hz CHCOM t CN CH3 CH COM CN
 Mechanism B
1 CH 3 CHO t CN CH z CHO CN

2 at 3 CHO CNJ Ht Hz CH H CN

Rate K CH 3 CHO CN

Qi which mechanism is consistent with the rate

equation And which step in the mechanism have you

chosen as your slow step
why

Mechanism B Step 1

Both species appear as 1st order in the

equation and Ht is in zero order

Example 3

Overall Vin 2 NO 2 Fa 2N 02 F

Rate K NOZICK

unite a two step mechanism

MMjstP Fz NO af tf

steply no for_ NO ZF

2 NO 2 t Fa 2NO2F

Example 4
Overall rxn

NO 2 CO NO CO2

Rate K NO232

suggest a 2 step mechanism

Step 1 NO z
No No NH3 Stow

V03 CO CO2 NON

NO 2 CO NO CO2

CATALYSTS
A catalyst increases the rate of vxn by providing
 t
an alternative
pathway with lower activation energy A
catalyst is not consumed in the rx n
ie it is regenerating

Catalyst increases rate of both the forward and

the reverse run

A catalyst does It increase yield of the

product but increases the rate offormation of the product
A catalyst is
required in small non stoichiometric

amounts as the catalyst is

regenerated
A area is more
catalyst with a
larger surface
effective in catalysing reactions
They can
get poisoned made ineffective usually
due to thepresenceof metals or denatured enzymes

Enzymes are biological catalysts they get

denatured at high temperatures

Enagyprofitesy
 ga uncatalysed
Energy a

KJ MOL At B
Ther Ea catalysed

CTD

vxn pathway

A pathway is a different mechanism with a lower Ear

BH remains the same 87
A B E C D

Energy
µ moil
A
AH is

a
unchanged
ga
A B
Fay
DH

Ctp

ran pathway
forward
Ea z Activation Energy for un catalysed

Ea z Activation Energy for catalysed

 Reverse
Ea z Activation Energy for un catalysed

Ea y Activation Energy for catalysed

MTpesofcatalystshy
1
omogenous
Ave in the same phase physical state as the

reactants or the rxn mixture

Generally homogenous catalysts are aqueous or in

the gas phase

Homogenous catalysts take part in the reaction and are

regenerated at the end

Exampiesy
1
Esterification catalyst
Hz CO2H t CH 30174 3602 CH 3 H2O
Hq methyl
ethanoalé
2
Hydrolysis of Esters catalysed by dilute acid
3 Gas phase Vins oxidation 502 to 503 by NOx
of
catalyst in the atmosphere acid rain H2 504

NO 2 502 NO SO 3
NO 1202 NO 2 regenerated
5 Destruction of ozone layer of stratosphere
by a CFCs G above the
no lower atmosphere
cuz Gimson
Ci t O z CLO t
0219
CLO t 03 CL t 202
203 302
a
191
6 Formation of Photochemical smog in lower

atmosphere where we live

Ozone levels
No É NO

O
ofindhower
are
atmosphere
Oz 03 harmful
NO t 4202 NO 2

catalyst
O pan smog
headaches watery burning eyes Scratchy throat
 7 Transition metal ions as catalysts

The rate of aqueous redox runs is increased by the

additionof catalysts from the d block elements

Bez transition elements can easily convert from one

onidation state to another they can be used as catalysts

For example Onidation Iodide ions by
of
peroro disulfide VI ions to Iz is catalysed by either
Fe
Fett or tag
Overall run

21dg t 52084g Iz lag t 2504Laa

Very slow rxn

Bcs btw two negatively charged ions that repel

eachother
Activation Energy is very high
Fe being a positive ion allows rate to increase

2 Heterogenous
A heterogenous
catalyst is in a different phase or physical
state than the reactants
 It is usually a solid catalyst interacting with gaseous or

liquid reactants
The reaction occurs on a solid surface which provides a

large surface area over which the reaction occurs

Step 1 Adsorption to attach loosely

Step 2 Reaction
Step 3 Desorption
Powdered
Example 1
C
CHz CH z t Hz CH 3 CH z
9 metal g
9
catalyst
H H
Hz
Hy
gadsorption
reaction
Profits
released I I H
H H
hgy desorption

The reactant molecules are

loosely attached

adsorped on the surface of the catalyst

This brings reactant particles together and facilitate
bond breaking and bond making
 2 Haber Process
Powdered Fe catalyst
Nat 342 NH3
3 Contact Process
2502 02 I 2503
Vanadium V onide catalyst V20
4 Convertor
Catalytic
Pt Pd Rb coated on the honeycombed ceramic surface
of the catalytic convertor
2 CO
less
02 2102
harmful harmful
2 NO 210 N 2 2602
gases
catty ath Oz acoztyn
The catalysts start working at a 200 C
So the car is most polluting when 1st started

in the morning

Ps notes
 quenching

At o e
r e
intervals

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Mokpo heat

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9
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is either 1st 2ndorder or
meIas if

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a
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