Kinetics

Jerry

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Contents

• 18.1 The rate of chemical reactions

• 18.2 The rate expression and order of reaction

• 18.3 Determining the rate equation

• 18.4 The Arrhenius equation

• 18.5 The rate-determining step Practice questions

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The rate of chemical reactions
Rate of the reaction
• Definition: The change in concentration of reactants or products with unit
time.

Rate of the reaction at any instant A  2B  C

• Calculation formula:
a change in concentration
rate  
b time

• Unit: mol/(dm3·s)

Initial rate
• Definition: The rate at t=0 3
The rate of chemical reactions
Questions ：
1 ls the concentration being plotted that of a reactant
or a product? Explain your answer.

2 The tangent to the curve at the time 300 seconds is

drawn on the graph. Find the gradient of the tangent.
Remember to include units.

3 What does this gradient represent? Without drawing

tangents what can be said about the gradients of the
tangents at time 0 seconds and time 600 seconds?

5 Explain your answer to question 4.

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The rate expression and order of reaction
Rate of the reaction
• The rate expression X Y  Z
rate  k[ X ] [Y ]
m n

Rate constant k
• Properties 1: Different for every reaction
• Properties 2: Varied with temperature Not the same to
stoichiometric coefficient !!
Order of reaction m n (From experiments)
• The order to reactant: the order to X/Y is m/n, the reaction is m/n-th order
to X/Y, m/n is the order to X/Y
• The overall order: the reaction is (m+n)-th order overall, the overall order
of the reaction is m+n
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The rate expression and order of reaction
Units of the rate constant
• Zero order reaction rate  k[ A]0 [ B ]0  k ABC
• Unit: mol/(dm3·s)
rate  k[ A]1[ B ]0  k[ A]
• First order reaction rate
• Unit: s-1 k
[ A]

• Second order reaction rate  k[ A]1[ B ]1  k[ A][ B ]

• Unit: mol-1 dm3 s-1 rate
k
[ A][ B]
• Third order reaction
rate  k[ A]1[ B ]2  k[ A][ B ]2
• Unit: mol-2 dm6 s-1
rate
k
[ A][ B]2
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The rate expression and order of reaction
Questions ：

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Determining the rate equation
Finding the order of a reaction by using rate-concentration graphs

• Experiments results analysis

1 Measuring the reaction rate for different values of A
2 Plot the reaction rate-concentration graph
3 Determining the order by graph

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Determining the rate equation
The initial rate method

• Definition: the gradient of the tangent at t=0 is the initial rate

• Importance: we know the initial concentration through the initial rate

Q1: Determining the order to each reactant.

Can we tell the order directly by stoichiometric coefficient ?
Q2: Determine the rate constant 9
Determining the rate equation
The effect of temperature on k

• T increases k increases (Always)

Reason of the rate depends on temperature

Activation energy Ea

The collisions of particles have enough energy

to break bond energy.

T is greater, there are more particles have

higher energy.

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Determining the rate equation
Questions ：

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The Arrhenius equation
The Arrhenius equation
 Ea / RT
N%  e x  0, e  1
x The fraction of molecules with energy greater
than the activation energy

742684
 Ea / RT
k  Ae
k, rate constant
A, pre-exponential factor

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The Arrhenius equation
Logarithmic form of the Arrhenius equation
Ea

ln(a b)  ln a  ln b
 Ea / RT
ln k  ln( Ae )  ln A  ln e RT

Ea E 1
ln k  
RT
 ln A   a   ln A
R T
ln a  x ln a
x

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The Arrhenius equation
Using the Arrhenius equation

Calculate Ea from the gradient

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The Arrhenius equation
Question

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The rate-determining step
Reaction mechanism
BrO3 (aq )  6 H  (aq )  5 Br  (aq )  3Br2 (aq)  3H 2O(l )
The reaction is the collision of particles.

It is unlikely that all reactants collide at the same time

There is a very-short intermediates

The rate-determining step/rate-limiting step

A B C Y  Z The slowest step may govern the rate of the
whole process
A  B 
fast
D (first intermidiate)
D 
slow
 E (second intermidiate) Reactant before the rate-determining step could
affect the overall rate and appear in the rate
E  C 
fast
Y Z expression.

rate  [ A][ B ][ D ] 16
The rate-determining step
Using the order of the reaction to find the rate-determining step
C4 H 9 Br  OH   C4 H 9OH  Br 

关键理解：化学键的断裂是不是同时的

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The rate-determining step
Question:

Catalyst appears firstly at left and

then at right.

Catalyst is firstly consumed and

then produced.

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Small summary

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Thank you

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