Chapter 2 CHM476 (Part 1)

2.
0 KINETICS
Learning Outcomes
At the end of this topic, you should be able to:
1. Define rates of reaction and rate law

2. Determine the order of reaction using initial rate, integration and half-life
method.
3. State and explain the factors affecting rates of reaction based on collision
theory
4. Relate between rate of reaction with temperature using Arrhenius equation
5. Describe reaction mechanism in terms of molecularity, rate determining step
and approximation method
6. Explain catalytic kinetics using homogeneous and heterogenous catalysis, acid
base catalysis and enzyme catalysis.
2.1 Rates of reaction Contents
2.1.1 Definition and units
2.1.2 Determination of rates of reaction
2.2 Factors affecting rates of reaction
2.2.1 Collision Theory
2.2.2 Transition State
2.3 Rate Law and Order of Reaction
2.3.1 Rate law for Zero, First and Second order
2.3.2 Rate law for reactions higher than second order
2.3.3 Rate law for fractional order
2.4 Methods to determine order of reactions
2.4.1 Initial rate
2.4.2 Integration
2.4.3 Half life
Contents
2.5 Relation between rate and temperature
2.5.1 Arrhenius Equation
2.5.2 Determination of activation energy by graphical method or
calculation using Arrhenius Equation
2.6 Reaction mechanism
2.6.1 Basic processes - molecularity
2.6.2 Reversible, series and parallel reactions
2.6.3 Relationship between rate law and reaction mechanism
2.7 Catalytic kinetics
2.7.1 Homogeneous and heterogeneous catalysis
2.7.2 Acid-base catalysis
2.7.3 Enzyme catalysis
Introduction
• Chemical kinetics: study and discussion of chemical reactions with respect to
reaction rates, effect of various variables
• The study of motion is called kinetics, from Greek kinesis, meaning movement.
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2.1 Rates of reaction
2.1.1 Definition and units
Definition: the amounts of a reactant reacted or the amount of a product formed per
unit time, (moles per second).
amount reacted or produced

Rate of reaction = ----------------------------------
time interval
Units: g /s, mol/s, or %/s
6
concentration change of a reactant or product
Rate = ---------------------------------------------------
time interval
= d[reactant] OR d[product]
dt
Units:
Ms-1 @ moldm-3s-1 @ molL-1s-1
7
rate given by the average change in
concentration of a reactant or product per
Average Rate unit time over a certain time interval
rate at a particular time and is given by

RATES OF REACTION Instantaneous Rate the tangent to the curve at that time in
the concentration-time graph
rate at the start of the reaction when an infinitesimally

Initial Rate small amount of the reactant has been used up and is
given by the gradient to the curve at time t = 0
Consider this reaction:
Br2(aq) + HCOOH(aq) → 2Br-(aq) +2H+(aq) + CO2(aq)
Rate(M/s) K (s-1)
Time(s) [Br2] (M)
x 10-5 x 10-3
0.0 0.0120 4.20 3.50
50.0 0.0101 3.52 3.49
100.0 0.00846 2.96 3.50
150.0 0.00710 2.49 3.51
200.0 0.00596 2.09 3.51
250.0 0.00500 1.75 3.50
300.0 0.00420 1.48 3.52
350.0 0.00353 1.23 3.48
400.0 0.00296 1.04 3.51 9
To calculate average rate Rate(M/s) K (s-1)
Time(s) [Br2] (M)
x 10-5 x 10-3
Average rate = - d[Br2] 0.0 0.0120 4.20 3.50
50.0 0.0101 3.52 3.49
dt
100.0 0.00846 2.96 3.50
= -[Br2]final – [Br2]initial 150.0 0.00710 2.49 3.51
tfinal – tinitial 200.0 0.00596 2.09 3.51
250.0 0.00500 1.75 3.50
300.0 0.00420 1.48 3.52
= -(0.0101 – 0.0120)M 350.0 0.00353 1.23 3.48
50 - 0 400.0 0.00296 1.04 3.51
= 3.80 x 10-5 Ms-1
10
To calculate instantaneous rate
Rate(M/s) K (s-1)
Examples ; rate at t = 100s , Time(s) [Br2] (M)
x 10-5 x 10-3
200s 0.0 0.0120 4.20 3.50
Plot graph [Br2](M) vs t(s) 50.0 0.0101 3.52 3.49
Draw the tangent to the curve 100.0 0.00846 2.96 3.50
at the particular time. 150.0 0.00710 2.49 3.51
200.0 0.00596 2.09 3.51
250.0 0.00500 1.75 3.50
300.0 0.00420 1.48 3.52
350.0 0.00353 1.23 3.48
Concentration
400.0 0.00296 1.04 3.51
•
Time
11
2.1.2 Determination of rates of reaction
To measure a reaction rate, we usually monitor either a product or a reactant for
its change.
❑Some of the characteristics to be monitored are:
-changes in pressure
-changes in colour (use spectrophotometer )
-temperature for exothermic or endothermic reaction, and
-presence of certain key substance
12
Reaction Rates and Stoichiometry
• To generalize let the chemical reaction be represented by,

a A + b B -> c C + d D
then the rate is represented by any one of the following
d[A] 1 d[B] 1 d[C] 1 d[D]

rate = - --- ---- = - --- ---- = --- ---- = --- ----
a dt b dt c dt d dt
13
In acidic solutions, hydrogen peroxide and iodide ion react according to the equation:
H2O2 + 2H+ + 3I- → 2H2O + I3-.
In this reaction, the reaction Rate can be expressed as :
decreasing Rate of H2O2, - d[H2O2]/dt

decreasing Rate of H+, - d[H+]/2 dt
decreasing Rate of I-, - d[I-]/3 dt
increasing Rate of H2O, + d[H2O] /2 dt
increasing Rate of I3-, +d[I3-]/dt
d[H2O2] 1 d[H+] 1 d[I-] 1 d[H2O] d[I3-]

RATE = _ ------- = _ ------ = _ ------- = + ---------- = + --------
dt 2 dt 3 dt 2 dt dt
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Graph concentration vs time
Concentration
product
reactant
time
t
15
Examples
Consider the reaction for the combustion of methane, CH4 ,
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)
If the methane is burning at a rate of 0.16 molL-1s-1 , at what rates are CO2 and H2O being formed?
16

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2.

1. Define rates of reaction and rate law

amount reacted or produced

Units: g /s, mol/s, or %/s

rate at a particular time and is given by

rate at the start of the reaction when an infinitesimally

= 3.80 x 10-5 Ms-1

• To generalize let the chemical reaction be represented by,

d[A] 1 d[B] 1 d[C] 1 d[D]

In this reaction, the reaction Rate can be expressed as :

decreasing Rate of H2O2, - d[H2O2]/dt

d[H2O2] 1 d[H+] 1 d[I-] 1 d[H2O] d[I3-]

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