Chemical Kinetics - Reaction Rates

Chemical kinetics is the branch of chemistry which addresses the question: "how fast
do reactions go?”

Consider the reaction,

2 H2(g) + O2(g) → 2 H2O(l). ΔrGo = - 474.26 kJ

ΔrGo for this reaction is very large and negative, which means that the reaction is
spontaneous.

• However, we can mix hydrogen gas and oxygen gas together in a bulb or other
container, even in their correct stoichiometric proportions, and they will stay there
for centuries, perhaps even forever, without reacting. (If we drop in a catalyst - say
a tiny piece of platinum - or introduce a spark, or even illuminate the mixture with
sufficiently high frequency uv light, or compress and heat the mixture, the mixture
will explode.) The problem is not that the reactants do not react to form the
products, they do, but they cannot find a "pathway" to get from reactants to
products.
 Chemical Kinetics - Reaction Rates
Another example: consider the reaction,
C(diamond) → C(graphite) ΔrGo = - 2.900 kJ

it is negative (not very large, but still negative). This result tells us that
diamonds are thermodynamically unstable. Yet diamonds are highly
regarded as gem stones ("diamonds are forever")

On the other hand, if you were to vaporize a diamond in a furnace,

under an inert atmosphere, and then condense the vapor, the
carbon would come back as graphite and not as diamond.

How can all these things be?

The answer is that thermodynamics is not the whole story in
chemistry. Not only do we have to know whether a reaction is
thermodynamically favored, we also have to know whether the
reaction can or will proceed at a finite rate. The study of the rate of
reactions is called chemical kinetics.
 Chemical Kinetics - Reaction Rates
• What is reaction rate?
– The rate of a chemical reaction refers to the reactant consumption or the
product formation per unit time.
– It is a quantitative measure of how fast a reaction can proceed.
• some reactions proceed very fast, other reactions may proceed very
slow
• In thermodynamics where only the starting and ending states are
characterised

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 Chemical Kinetics - Reaction Rates
Why study the reaction rate?

in industry we need to know how long do we need to produce a certain

product the size and type of a reactor

we also need to know what is the best reaction conditions we should

apply using proper conditions such as T, P, concentration etc. to speed
up the desired reaction to suppress undesired side reactions when apply
a catalyst how effective it is on the desired / undesired reaction

A study of reaction rate often reveal information on the reaction

mechanism A good understanding of reaction mechanism helps us to
find a more effective way to carry out a reaction and sometimes leads to
discovery of new means of reaction

A study of reaction rate is often referred as a study of Reaction Kinetics

 Chemical Kinetics - Reaction Rates
The Rate of Reaction
-it is a quantity that tells how the concentration of a given reactants or product
changes with time

Example: A + 2B  3C + D
Rate = - rate of consumption of A
= - rate of consumption of B
= rate of formation of C
= rate of formation of D

In terms of concentration changes

d A
Average rate with respect to A Rate = 
dt

d B 
Average rate with respect to B Rate = 
2dt

d C 
Average rate with respect to C Rate =
3dt
d D 
Average rate with respect to D Rate = dt
Chemical Kinetics - Reaction Rates

Example:
The rate of formation of NO in the reaction
2NOBr(g)  2NO(g) + Br2(g)
was reported as 1.6 x 10-4 M/s . What is the rate
of the reaction and the rate of consumption of
NOBr?
 Concentration and Rate
Law of Mass Action: The rate of a chemical reaction is directly proportional to the
concentration of the reactants raised to a certain power.

Mathematically
Rate  [reactants]order

Introducing proportionality constant

Rate Law
Rate = k [reactants]order
k – the rate constant, dependent on the temperature
Consider a hypothetical reaction:
aA + bB  cC + dD

Rate Law : Rate = k[A]m[B]n

m and n = order of the reaction
m + n = overall order of the reaction
Order of reaction will indicate how the rate is affected by the concentration of
each reactant.
 Chemical Kinetics - Reaction Rates

1. Zero Order Reaction

- the rate is independent of
concentration

Consider the following reaction

A → products
Rate Law
Rate = k

Integrated rate equation

d A = k

dt
On integration with limits
[A]o - [A] = kt
 Chemical Kinetics - Reaction Order
2. First order reaction – is one whose
rate depends on the concentration of
a single reactant raised to the first
power.

Example: A  products
Rate Law:
Rate = k[A]
Integrated rate equation
d A = k[A]

dt

Integration
ln[A]t – ln[A]0 = -kt

Half life of a reaction, t1/2 – is the time

required for the concentration of a
reactant to drop one half of its initial
value . [A]1/2 =  A 0

2
 Chemical Kinetics - Reaction Order
3. Second Order Reaction – is one whose rate
depends on the reactant concentration
raised to the second power or on
concentrations of two different reactants,
each raised to the first order.

Type I Second Order in One Component

A → products
Rate Law
Rate = k[A]2

Integrated rate equation

d A
 = k[A]2
dt

Integration
1 1
  kt
[ A] t [ A] 0

Half life of a reaction, t1/2

Chemical Kinetics - Reaction Order
Case 2 [A] ≠ [B]
Type II A + B → products
Rate Law
Case 1 [A] = [B]
Rate = k[A][B]
Rate Law
Integrated rate equation
Rate = k[A]2

Integrated rate equation

d A = k[A]2

dt

Integration
1 1
  kt
[ A]t [ A]0
1 Bo  Ao  x 
ln  kt
Ao  Bo Ao Bo  x 
 Chemical Kinetics - Reaction Order

Case 3: [B]o <<< [A]o

 Chemical Kinetics - Reaction Order

4. Third Order Reactions

Consider the following reaction

A → products
Rate Law
Rate = k[A]3
Integrated rate equation
d A
 = k[A] 3
dt
Integration with limits
1 1   1 
      kt
2  [ A] 2  2 
  [ A] o 
 Techniques for finding rate laws
Three methods for determining the rate law for a reaction from
experimental data.

1. Half-lives
Run several experiments at different initial concentrations to see how the
half-life depends on [A]o
- If the half-life does not depend on the initial concentration then the
reaction is first order.

- If the half-life of the reaction is proportional to 1/[B]o then the reaction is

simple second order.

- If the half-life is proportional to 1/[B]o2 then the reaction is simple third

order.
Problem:
At 518C, the half-life for the decomposition of a sample of gaseous
acetaldehyde (ethanal) initially at 363 Torr was 410 s. When the pressure
was 169 Torr, the half-life was 880 s. Determine the order of the reaction.
 Techniques for finding rate laws
2. Initial Rate Method

The initial rate of a reaction is the reaction rate at t = 0. Designate the initial rate by Ro. One can
run several experiments and measure the rate as soon as possible after the reagents have
been mixed to determine the initial rates.
For example, assume that
Ro = k[A]x[B]y[C]z .
Run several experiments at different starting concentrations and measure Ro in each case. We
can place the data in a table as follows:
[A]o [B]o [C]o Ro
0.010 0.10 0.20 0.04 for experiment number 1,
0.020 0.10 0.20 0.08 for experiment number 2,
0.010 0.20 0.20 0.16 for experiment number 3, and
0.010 0.10 0.10 0.04 for experiment number 4.
Compare the first and second experiments. We double [A]o and the rate doubles. It looks
like x = 1. Compare the first and third experiments. We double [B]o and the rate increases
by a factor of 4. It looks like y = 2. Notice that there is no change in the rate when we cut
[C]o in half so the rate must not depend on C. This says that z = 0.
Thus we determine that the rate = k[A]1[B]2[C]0.
 Techniques for finding rate laws
We don't have to use simple whole number ratios for the concentrations, we
can do it algebraically. Take the ratio of the rates from two successive
experiments,

To find the exponent of [A] make all the concentrations in the second
experiment the same as in the first experiment except [A]. This gives,

Take the logarithm of both sides to get,

and solve for x to get,

This process can be repeated for each of the components in turn.

 Techniques for finding rate laws
3. Fit to Integrated Form
For example, to test for first order plot ln[A] vs t, and see if you get a straight line.
There may be some data scatter, but it should be random. If you see a definite
curvature in your line the reaction is probably not first order.

To test for simple second order plot 1/[A] vs t and look for a straight line.

To test for simple third order plot 1/[B]2 vs t and see if you get a straight line.

Problem:
The data below apply to the reaction, (CH3)3CBr + H2O  (CH3)3COH + HBr. Determine
the order of the reaction, the rate constant, and the molar concentration of
(CH3)3CBr after 43.8 h.
t/h 0 3.15 6.20 10.00 18.30 30.80
[(CH3)3CBr]/(10-2 mol dm-3) 10.39 8.96 7.76 6.39 3.53 2.07
Techniques for finding rate laws
Problem:
For the reaction NO2 + CO  CO2 + NO. Starting
with 0.5M of NO2 and 1M CO, after 30 minutes the
concentration of NO2 decreases to 0.325. Calculate the
concentration of NO2 after 1 hr. if the order of the
reaction is
a. zero order with respect to both NO2 and CO
b. first order with respect to both NO2 and CO
c. first order with respect to NO2 and zero with respect to
CO
d. second order with respect to NO2 and zero order with
respect to CO
Complex Reactions and Mechanism
Complex Reactions and Mechanism
Complex Reactions and Mechanism
Complex Reactions and Mechanism
 Complex Reactions and Mechanism

Limiting Case
Complex Reactions and Mechanism
Complex Reactions and Mechanism
Complex Reactions and Mechanism
d [ A]
 kr [ A]o  (kr  k f )[ A]
dt

[ A] 
[ A]o
k f  kr 

kr  k f  e
 k f  k r t

Complex Reactions and Mechanism
Temperature Dependence of Rate Constant
Temperature Dependence of Rate Constant
)

Reaction kinetics

Rate Constant & Arrhenius Equation

• The Arrhenius Equation   Ea 
k  A exp  
 RT 
– where: A pre-exponential factor
Ea is the reaction activation energy
R is the gas constant Arrhenius parameters
T is the reaction temperature in Kelvin

– Eqn.1 was initially found from fitting experimental results. After molecular kinetic
theory was established, the relation can be derived directly from the theory

• Usually A is related to the molecule collision frequency or thermodynamically to the

entropy

• Ea is an energy term which related to the

energy
Ea
reactant
energy barrier for a reaction has to overcome
product

reaction process
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)

Exp. Determination of Arrhenius

Reaction kinetics

Parameters
E 
• From the Arrhenius Equation k  A exp  a
 (1)
 RT 
To determine A and Ea

 Ea
Take log: ln k  ln A 
RT

Compare with linear equation: y=a+bx, where y=lnk, a= lnA, b=-Ea/R and x=1/T

If when can measure k at various temperature T’s

Note: As k is a function of temperature, the k value measured slope=-Ea/R

at each T as mentioned above should be different. intersect=ln A

lnk
Therefore, the above method, strictly speaking, gives
average values of Ea and A within the T’s applied.

1/T
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