CHE 156

Physical Chemistry 1
• Nelson Okpako OBI-EGBEDI
 Unit2
Topic:

• Concentration, the rate law and experimental

determination of rate expression
 Unit2
Objectives

• In this Unit, you will learn how to write the

rate law and use it to predict the speed of
reactions.

• Experimental determination of rate law.

 Expected Outcome(Unit 2)
• At the end of Unit 2, you should be able to :
• Know how concentration affects rate of
reaction;
• Determine the order of a reaction;
• Write the rate law/expression; and
• Do some calculations.
• The rate of reaction is a function of factors
such as the concentrations of the reactants,
the temperature of the reaction system, the
identity of the reactants and the catalyst
used.
• Let us consider one of the factors:
Concentration
 Concentration and the Rate Law
• The rates of most reactions change when the
concentrations of the reactants change.

• Chemical reactions are usually faster when

concs. of the reactants are increased and
slower when decreased.

• In general, the rate is proportional to the

concentration of the reactants raised to
appropriate powers/indices/exponents.
The rate is proportional to the molar concentrations
of the reactant raised to an appropriate power.

Consider the following chemical equation:

xA + yB Product(s) (6)

The above equation is like :H2 + 1/2O2 → H2O

• In Equation (7), k is the specific reaction rate
constant.
• The exponents n and m are called reaction
orders, and the sum (m + n) is the overall
reaction order.
• Equation (7) is known as the rate law.
• The rate law is an expression for the rate as a
function of concentration at a fixed
temperature.

• Equation (7) is determined experimentally.

 Experimental Determination of Rate Laws
• Most chemical changes consist of several steps
called elementary steps.

• Different reactants can affect the rate of a

particular reaction differently.

• Consequently, Equation (7) cannot be written

from the balanced chemical equation but from
experimental data.
N 2O5 
 NO2  NO3
slow

NO2  NO3  NO2  NO  O2 One Way

fast

NO  NO3  2 NO2

fast

2 N 2O5  4 NO2  O2
• To determine the order with respect to each
reactant in expression (7),

• it is necessary to study the mechanism by

which changes in the concentration of each
reactant affect the initial rate of the reaction.
• A + B → Product(s)
• Let us conduct a hypothetical experiment for
the above-named reaction in order to
determine its rate law, using the initial rates
method.
• How the initial rate depends on the starting
concs is preferable. Why? It is because ….
• as the reaction proceeds, the concs of the
reactants decrease and it may become
difficult to measure the change accurately.
• Mix the solutions of the reactants A and B
with initial concentrations [A]0 and [B]0,
respectively.

• The temperature of the mixture is fixed.

•At convenient time intervals, withdraw some
aliquots of this mixture, stop the reaction or
slow it down drastically, analyze the withdrawn
sample chemically to determine the change in
concentration of the reactant A which occurs
after reactants have been mixed.
• Instead of monitoring the change in
concentration of reactant A,
• the change in its physical property as a
function of time could be measured.
• For example, its optical absorbance,
fluorescence, optical activity or refractive
index.
• Perform other experiments with different
values of the initial concentration of A at the
same fixed temperature, keeping the initial
concentration of reactant B constant.

• Determine the initial rate, at (time = 0), for

each experiment from a plot of concentration
against time.
• Compare the initial rates obtained from these
experiments.

• If there is no change in rate, the order with

respect to A is zero.

• If the rate of reaction doubles when the initial

concentration of A is doubled, the order with
respect to A is one.
• If the rate quadruples when the initial
concentration of A is doubled, then the order
with respect to A is two.
• Similarly, varying the initial concentration of
reactant B and keeping the initial
concentration of reactant A and the
temperature of the reaction constant, the
effect of the concentration of reactant B on
the initial rate of the reaction can also be
investigated and the order with respect to B
determined.
• These experimentally determined orders with
respect to each reactant will enable us to
write Equation (7), the rate law.
• For example, consider the reaction:
A(g) + B(g) →C(g)

• The experimental rate law of the above

reaction is:
• Rate = k [A] [B]0

• What is the overall order of the reaction?

• Since the overall order is the sum of the
exponents, we obtain (1 + 0) = 1 as the
reaction order.
• For a hypothetical reaction in which B and C
react to form the product, D, the following
data were obtained from three experiments.
• B+C D
Experiments [B] [C] (Rate of formation of D)
1. 0.15M 0.075M 3.5 x 10-3mol dm-3min-1
2. 0.30M 0.15M 1.4 x 10-2mol dm-3 min-1
3. 0.15M 0.15M 7.0 x 10-3mol dm-3 min-1
BrO3 (aq)  5Br  (aq)  6 H  (aq)  3Br2 (aq)  3H 2O(l )
• Suppose we have the reaction: o
Mixture [Bro3] [Br ] Bromate
-
[H ]ions in acid
+
solution.
Relative
initial rate of
formation of
Br2
I 0.05 0.25 0.30 1
II 0.05 0.25 0.60 4
III 0.10 0.25 0.60 8
IV ? ? ? ?

R  k [ BrO3 ]l [ Br  ]m [ H  ]n
• 1  k[0.05] [0.25] [0.30]
l m n

4  k[0.05] [0.25] [0.60]

l m n

• 1 [0.30]n

4 [0.60]n
1 1
• 2
 n
2 2
• n= 2
• The exponents in the rate law appear to be
unrelated to the coefficients in the overall
chemical equation. See Equation 7

• There is, in fact, no way to know for sure what

the exponents in the rate law of an overall
reaction will be without doing experiments to
determine them.
• Sometimes, however, the coefficients and the
exponents are the same by COINCIDENCE, as
in the case of elementary reactions.

• In general, the order of a reaction must be

determined by expt; it cannot be deduced
from the overall balanced equation.
 Quiz #2

1. A + 2B D
The rate of formation of D in the above
reaction is found experimentally to be
independent of the concentration of B
and to quadruple when the
concentration of A is doubled. Write
the rate law for the reaction.
• 2. For the general rate law, Rate = K[A][B]2 ,
what will happen to the rate of reaction if the
concentration of A is tripled?
• [A] The rate will be halved
• [B] The rate will be doubled
• [C] The rate will be tripled
• [D] The rate will remain the same
3. Methanol can be produced by the following
reaction: CO(g) + 2H2(g) CH3OH(g).
•How is the rate of disappearance of hydrogen
gas related to the rate of appearance of
methanol?
4. What is the overall reaction order for the
reaction represented by the rate law:
Rate = k[H2][NO]2?
•[A] zero
•[B] first
•[C] second
•[D] third