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LU4 Reaction kinetics

4.1 rate of reaction 4.2 collision theory of chemical reaction 4.3 transition state theory 4.4 rate law 4.5 Factors affecting rate & rate constant 4.6 Homogeneous & heterogeneous catalyst
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A chemical reaction -Involve chemical reactant(s) -Will result in chemical product(s) - any relation on their rates?
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A chemical reaction 2N2O5 (g) 4NO2(g) + O2(g) As reactant is used up getting less over time Products are getting more and more over time
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Rates of Chemical Reactions


Concentration of reactant Concentration of product

Time

Time

As the reaction proceeds, the [reactant] decreases.

As the reaction proceeds, the [product] increases.

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Reaction Rates & Stoichiometry


For the general reaction
aA + bB cC + d D
where a, b, c & d are the stoichiometric coefficients

the rate expression is given by


1 [A] 1 [B] 1 [C] 1 [D] rate = = = = a t b t c t d t

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A chemical reaction 2N2O5 (g) 4NO2(g) + O2(g) [NO2] = 2 [N2O5] t t [O2] = [N2O5] t t
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A chemical reaction 2N2O5 (g) 4NO2(g) + O2(g) if [N2O5] =2.2 mol L1s1, t [NO2] = 2(2.2 mol L1s1) 1s1 t =4.4 mol L
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A chemical reaction 2N2O5 (g) 4NO2(g) + O2(g) if [N2O5] =2.2 mol L1s1, t [O2] = (2.2 mol L1s1) 1s1 t =1.1 mol L
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Consider the reaction 2H2O2(l) O2(g) + 2H2O(l) if [O2] = 0.21 mol s-1 t determine [H2O2] t
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Rate of a reaction Time involved what is the difference between Average rate instantaneous rate initial rate
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the reaction
Br2(aq)+ HCOOH(aq) 2Br(aq) +2H+(aq) + CO2(g) Time / s 0.0 50.0 100.0 150.0 200.0 300.0 400.0 [Br2]/ mol L1 0.0120 0.0101 0.00846 0.00710 0.00596 0.00420 0.00296
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What do you noticePRK 10262] ? II UNIMAS (C) NOT [Br CHEMISTRI


FOR SALE

the reaction
Br2(aq)+ HCOOH(aq) 2Br(aq) +2H+(aq) + CO2(g)

= [Br2] t For a period of 50.0 s from 0 s to 50.0 s Average rate = [Br2]final [Br2]initial tfnal tinitial = 0.0101 0.0120 mol L1
50.0 0.0 s = 3.80x105 mol L1 s1
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Average rate

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the reaction
Br2(aq)+ HCOOH(aq) 2Br(aq) +2H+(aq) + CO2(g)

Instantaneous Rate The rate of a reaction at a particular time

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the reaction
Br2(aq)+ HCOOH(aq) 2Br(aq) +2H+(aq) + CO2(g)
When t=0, a special instant Such rate known as initial rate of the reaction

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How to determine rate experimentally?

If involve gas, measure gas volume against time

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Examples of gaseous reactions


Zn(s) +H2SO4(aq) H2(g) + ZnSO4(aq) CaCO3(s) + 2HCl(aq) CO2(g) + CaCl2(aq) + H2O(l) 2H2O2(aq) O2(g) + H2O(l)

As gas has pressure, can also measure pressure changes over time
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How to determine rate experimentally?

If involve colour changes, use colourimetric method

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A chemical reaction To result in chemical products reactant molecules must collide ( The Collision Theory ) Minimum energy needed to bring about product formation ( Activation energy )
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Any chemical reaction

Collision is a necessity
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A reaction needs minimum energy

A collision may have no reaction


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Overcome activation energy

Collisions > Ea have reactions


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The Boltzman distribution of Molecules at any T


Number of molecules

Molecular energy
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Molecules with energy Ea only can react


Number of molecues

Ea

Molecular energy
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Kinetic energy of molecules


T2 > T1

T1 T2

More molecules > Ea at higher T


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Right orientation of collision

Effective collisions only can result in products


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Right orientation of collision


CH3 CH3 CHCl3 CH4 + CCl3 H-C Cl Cl CH4 + CCl3 Cl

Right orientation Wrong orientation


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CH3

H Cl-C Cl no product Cl

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Effect of increasing Temperature


Reactant molecules moving faster

Frequency of effective collisions increased Rate increased


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Transition state before product When molecules collide effectively, product immediately formed?

Effective collision

activated complex in transition state

product
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Transition state before product


Transition state is an activated complex with maximum energy to rearrange itself to the product

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Reaction kinetics
How fast a reaction can take place? Find out experimentally What relation between rate of reaction and concentration of reactants?

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Reaction kinetics
A+BC+D How fast C is produced?

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Reaction kinetics
A+BC+D Rate of C produced depends on A & B
Order wrt A

Rate = k[A]x[B]y

Order wrt B

Rate constant
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Order of a reaction
A+BC+D
Order wrt A

Rate = k[A]x[B]y If x + y = 0 If x + y = 1 If x + y = 2

Order wrt B

0th order 1st order 2nd order


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Rate constant, k A constant at a fixed Temperature If T , then k will Once order of reaction known, k can be calculated.

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The hydrolysis of CH3Br by OH- is given by the rate law Rate = k[CH3Br][OH-] Order of reaction = 2nd 1st order wrt CH3Br 1st order wrt OHThe image cannot be display ed. Your computer may not hav e enough memory to open the image, or the image may hav e been corrupted. Restart y our computer, and then open the file again. If the red x still appears, y ou may hav e to delete the image and then insert it again.

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The reaction A + B + C D + E has a rate law as below:Rate = k[A][B]2[C]0 a) What is the order wrt A? b) What is the order of the reaction?
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Consider another reaction CH3COOCH3 + OH CH3COO + CH3OH

Write the rate law for the reaction. Answer:


rate of reaction =k [CH

COOCH3]x [OH]y 3

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Order of a reaction
A+BC+D Order must find from experiment only Using different concentrations of A & B Get different initial rate obtained
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Expt

[X] / mol L-1

[Y] / mol L-1

Initial rate / Mol L-1s-1

1 2 3

2.20 2.20 6.60

1.50 3.00 1.50

0.00700 0.0140 0.0210

Step 1 Rate = k[X]x[Y]y


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Step 2

From expt 1 & 3 Initial rate 3 = Initial rate 1 From expt 1 & 3 0.0210 = k(6.60)x(1.50)y 0.00700 k(2.20)x(1.50)y
X=1
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From expt 1 & 2 Initial rate 2 Initial rate 1 From expt 1 & 2 0.0140 =k(2.20)x(3.00)y 0.00700 k(2.20)x(1.50)y
Y=1
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Step 3: Conclude the rate law

Rate=

1[Y]1 k[X]

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Step 4: Conclude order of chemical reaction

Rate = k[X]1[Y]1

Order of reaction = 2nd To find k, use data of expt 1 Or any other expt k=2.12x10-3 mol-1Ls-1
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More example on Order of Reaction


Consider the reaction
F2 (g) + 2ClO2 (g) 2FClO2 (g)

The rate law is expressed as


rate = k[F2 ] [ClO 2 ]
x y

To determine the values of x and y, we have to look at the experimental data for this reaction.
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Order of Reaction
Experimental data
Exp # 1 2 3 [F2] (M) 0.10 0.10 0.20 [ClO2] (M) 0.010 0.040 0.010 Initial Rate (M/s) 1.2 x 10-3 4.8 x 10-3 2.4 x 10-3

Doubling [F2] while holding [ClO2] constant will double the rate of reaction. The rate is directly proportional to [F2] The reaction is first order in F2 x=1
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Order of Reaction
Experimental data
Exp # 1 2 3 [F2] (M) 0.10 0.10 0.20 [ClO2] (M) 0.010 0.040 0.010 Initial Rate (M/s) 1.2 x 10-3 4.8 x 10-3 2.4 x 10-3

Quadrupling [ClO2] while holding [F2] constant will quadruple the rate of reaction. The rate is directly proportional to [ClO2] The reaction is first order in ClO2 PRK 1026 CHEMISTRI II UNIMAS (C) NOT y=1 FOR SALE
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Order of Reaction
Exp # 1 2 3 [F2] (M) 0.10 0.10 0.20 [ClO2] (M) 0.010 0.040 0.010 Initial Rate (M/s) 1.2 x 10-3 4.8 x 10-3 2.4 x 10-3

Since the reaction is first order for both [F2] and [ClO2], the rate law is written as

rate = k[F2 ][ClO 2 ]


The reaction is (1+1) or second order overall.
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QUESTION Consider the reaction at 25 C A + 2B C

Expt 1 2 3 4

[A] / mol L1 0.100 0.200 0.400 0.100

[B] / mol L1 0.100 0.100 0.100 0.300

Initial rate / mol L1s1 5.50x106 2.20x105 8.80x105 1.65x105

a) Determine the rate law for the reaction. b) What is the rate constant for the reaction?
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Try 2
In the reaction A B , the initial rate is 1.7x104 mol L1s1 when the concentration of A is 0.25 mol L1 a) What will be the initial rate of reaction if [A] is 0.75 mol L1 with zero order of reaction? b) What will be the initial rate of reaction if [A] is 0.75 mol L1 with 1st order of reaction?

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Rate constant A constant at a particular temperature Always bigger at a higher temperature K and Ea related as in Arrhenius equation

k=Ae
Where A Ea R T

Ea RT

is the frequency factor is the activation energy is the universal gas constant is the reaction temperature.
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Rate constant If many k s are done at different temperature Can determine Ea of a reaction

k=Ae

Ea RT

Plot graph of ln k against 1/T and Ea can be determined from gradient of the linear graph

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Arrhenius Equation

k = Ae

Ea RT

Ea 1 ln k = + ln A R T
ln A

ln k

Ea slope = R

1 /T
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1st order reaction


A product Rate of reaction = k[A] Rate of product = d[A]
dt

So, k[A] =
d [ A] A

d[A] dt

= k[A]
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1st order reaction


By integration of d [ A] = k[A] A Obtained
ln( [ A] ) = kt
0

or

[ A]

ln [A]0 ln[A] = kt
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ln[A]

Gradient of the linear graph equals k

[A] t
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The reaction 2A B is a first order reaction with a rate constant of 2.8x102 s1 at 80 C. How long (in seconds) will it take to decrease from 0.88 mol L1 to 0.14 mol L1 ?
answer ln [A] ln[A] = kt 0 t = ( ln [A] - ln[A] ) /k 0 = ln0.88

ln0.14 2.8x102 s1
= 66 s
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Try 1

The reaction 2N2O5 4NO2 + O2 is a first order reaction with a rate constant of 5.1x104 s1 at 45 C.
If the initial concentration of N O 2 5

is 0.25 mol L1 , what is the concentration after 3.2 minutes?


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Half-life of a reaction Time required for the initial amount of reactant to decrease to half its initial amount 10 g t 8g t 5g 4g
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Half-life of a reaction For a 1st order reaction kt1/2 = ln2

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example the decomposition of cyclopropane to propene is a first order reaction with a rate constant of 6.7x104 s1 at 500 C.
Calculate the half-life of the reaction. ln2 = kt 1/2 hence, t = ln2/k 1/2 = ln2/6.7x104 s1 = 1.0x103 s

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Try

The half-life of first order reaction is 84.1 minute. Calculate the rate constant of the reaction

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Half-life of 1st order reaction is independent of amount of active substance

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PRK 1026 CHEMISTRI II UNIMAS (C) NOT FOR SALE

Half-life what fraction of active material is left after 4 half-lives? answer

PRK 1026 CHEMISTRI II UNIMAS (C) NOT FOR SALE

1/8 1/16
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Reaction mechanism a) Most reaction goes to product through a number of steps b)always has a slowest step c)rate determining step
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Reaction mechanism
A reacts with B to form products X and Y Step 1 Step 2 Step 1 + Step 2 A+B X +M M+A Y 2A + B X + Y slow fast

So, rate = k[A][B]


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Reaction mechanism
NO reacts with O2 in 2 elementary steps Step 1 Step 2 NO + O2 NO3 NO3 + NO 2NO2

Given that, rate = k[NO]2[O2]

Which step is rate determining? Why?


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A catalyst Helps to increase rate of a reaction , but it is not used up How a catalyst works?
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PRK 1026 CHEMISTRI II UNIMAS (C) NOT FOR SALE

How catalyst increases rate

Ea reduced in presence of a catalyst H not changed


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Effect of Catalyst on Ea

Uncatalysed reaction Catalysed reaction

Potential energy

Normal reaction mechanism

Ea uncatalysed A+B
Alternate reaction mechanism

Ea catalysed

C+D Progress of reaction


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Catalyst reduces Ea

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How catalyst increases rate Catalyst provides alternative route with a lower Ea Catalyst takes part in reaction Catalyst not used up Note: catalyst does not change the products nor its quantity
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How a catalyst works


Keep in mind that:
The normal uncatalysed reaction mechanism still exists with Ea = Ea uncatalysed. Catalyst provides an alternative reaction with Ea = Ea catalysed. Because Ea catalysed < Ea uncatalysed, most reactants would follow the alternative reaction mechanism as it is easier.
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Types of catalysts Homogeneous catalyst Heterogeneous catalyst

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Homogeneous catalyst
Catalyst and reactants of same phases

S2O82-(aq) and I- (aq) react to give 2-(aq) using I2 (aq) and SO4 3+(aq) as catalyst Fe
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Homogeneous catalyst

S2O82-(aq) + I- (aq) I2 (aq) +SO4


2-(aq)

Fe3+(aq)

Reaction takes place in 2 steps


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Homogeneous catalyst
2Fe3+(aq) + 2I-(aq)2Fe2+(aq) + I2 (aq)
S2O82-(aq) +2Fe2+(aq)2Fe3+(aq)+ 2SO42-(aq)

More reasonable for reaction to occur with opposite charges


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Homogeneous catalyst
In the reaction , Fe3+(aq) is a catalyst, and Fe2+(aq) is an intermediate

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Intermediates
X and Y reacts to produce Z in the presence of a catalyst, C. The reaction steps are as:

X + C XC .........(1) Y + XC XYC ........(2) XYC CZ .........(3) CZ C + Z .........(4)

State the intermediates.


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Intermediates
answer

XC XYC CZ

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Heterogeneous catalyst
Catalyst and reactants of different phases

The Haber Process of making NH3(g) from H2(g) and N2(g) using Fe as catalyst
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Heterogeneous catalyst
3H2(g) +N2(g) Fe as catalyst 2NH3(g)

Use surface adsorption theory to explain the role of Fe in increasing the rate of reaction

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Surface adsorption theory

H2 and N2 molecules adsorbed on surface Dissociation happens to give H and N atoms H and N atoms form bonds to become NH3
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The hydrogenation of ethene to ethane is catalysed by nickel:

E.g.: Hydrogenation of C2H4

CH 2 = CH 2 ( g ) + H 2 ( g ) CH 3 CH 3 ( g )
H H

C
H

C
H

H H2

Ethene

Nickel (catalyst)
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Adsorption
H H

C
H

C
H

Both ethene & hydrogen bonds to nickel.


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Formation of CH2-CH3 radical


CH 2-CH3 radical

C
H

C
H

The radical uses the unpaired electron to bond to the surface.


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Reaction with another H atom

C
H

C
H

The radical reacts with another H atom.


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Desorption

H H H

Ethane H

C
H

Desorption of ethane from the surface of nickel occurs.


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Summary on reaction kinetics Rate of reaction can change Collision theory to explain reaction A reaction needs activation energy Reaction has a mechanism Catalyst changes route of reaction but not H nor quantity of products Catalyst is specific in action
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PRK 1026 CHEMISTRI II UNIMAS (C) NOT FOR SALE