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.
• 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
• Suppose we have the reaction: oxidation of Bromide ions by
Bromate ions in acid solution.

BrO3 (aq)  5Br  (aq)  6 H  (aq)  3Br2 (aq)  3H 2O(l )

Mixture [Bro3] [Br-] [H+] 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 expts to
determine them.
• Sometimes, however, the coefficients and the
expts 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
 Unit 3
Topic:

• Molecularity, Mechanism ,Predicted Rate

Law and Units of Rate Constant
 Expected Outcome:

• Obtain the units of the specific rate constant

for a given order
• An overall balanced chemical equation does
not tell us much about how a reaction takes
place.
• 2H  O  2H O
2 2 2

• The chemical equation represents the sum of

a series of simple reactions called the
elementary steps/elementary reactions.
• They represent the progress of the overall
reaction at the molecular level.

• The sequence of elementary steps that leads

to product formation is called the reaction
mechanism.
What is Mechanism of a reaction?
• The mode by which a reactant is transformed
into a product is the mechanism of the
reaction.

• Collection of individual kinetic processes/

elementary steps involved in the
transformation of reactants into products
• Explanation of how a reaction takes
place/occurs.
• The molecular EVENTS which occur during a
reaction.
• The SERIES of individual steps leading to the
overall observed reaction.
• For example: consider the thermal
decomposition of dinitrogen pentoxide. The
STOICIOMETRIC equation for the reaction is:
2 N 2O5  4 NO2  O2
• The reaction can take place in stages, probably
as follows:
 Molecularity, Mechanism and Predicted Rate
Law

• Most chemical reactions consist of elementary

reactions or steps.

• One of these steps, which is much slower than

the others, determines the rate of the reaction
and it is referred to as the rate-determining or
rate-limiting step.
• An elementary reaction can be characterized
by the number of reactant molecules involved
in it.

• This number of molecules or species on the

reactant(s) side / in an elementary reaction
/step is known as the molecularity of the
reaction.
• For the elementary process, the order(s) in its
rate law are the same as the stoichiometric
factors, or equal to the coefficients of the
reactants in the chemical equation for the
process.
• An elementary step in which only one reacting
molecule participates is UNIMOLECULAR

• Two molecules is BIMOLECULAR .

• TERMOLECULAR reaction involves the

participation of three molecules in one
elementary step.
• The rate of an elementary reaction is
proportional to the product of the
concentrations of the reactants that are in
that step.

• Therefore, the rate law for an elementary

process can be predicted from the chemical
equation for the process.
• Consider the reaction:

• PCl5 →PCl3 + Cl2

• The above reaction can be explained by a two-step
mechanism:
• Step (1) is the slow (rate limiting) step.
• PCl5 →PCl4 + Cl. slow
• Step 2 PCl4 →PCl3 + Cl. fast

Net: PCl5 →PCl3 + Cl2

• The experimentally determined rate law is:

• Rate = k [PCl5]
• and, from the rate-limiting step, the predicted rate law is
• Rate k [PCl5]
• The elementary steps must satisfy two
requirements:

• The sum of the elementary steps must give

the overall balanced equation for the reaction.

• The rate-determining step, which is the

slowest step in the sequence of steps leading
to product formation, should predict the same
rate law as is determined experimentally.
• The order of multistep reaction must be
obtain experimentally.

• For example, the conversion of A + C D

• A B slow, RDS
• B+ C D very fast
• A+C D

• The rate at which D is formed depends on how

quickly A gives B, not how quickly B reacts
with C. The rate equation would be:

• Rate = k[A]x
 Consider a hypothetical reaction:
2C  D  E  F

• What is the rate law of the rate determining

step in terms of the concentrations of the
reactants in the overall balanced equation?
• Fast step: rate1 (forward reaction)
• Rate2 (backward reaction)

• (i)

• (ii)

• The rate of the slow step:

• Rate (iii)
• Sub. (ii) into (iii) yields the overall rate as

• Rate (iv)
 UNITS OF RATE CONSTANTS
• The units of the specific rate constant depend
on the overall order of the reaction.

• The units are worked out from the units of the

individual terms in the rate equation.

Units of initial rate

• Units of rate constants = (9)
(Units of initial concentration) x
•
• The units of rate are mol dm-3 time-1 and the
units of [B] are mol dm-3

• Substituting these units into Equations (9)/

(10), and assuming that time is in seconds and
x = 1, gives the units of k as s-1 or time-1.

• [ ] = mol dm-3
• M = mol dm-3
 Quiz # 3

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
• Reference:
• Fundamental Physical Chemistry(Revised
Edition). Edited by Iweibo I., Okonjo K. & Obi-
Egbedi N.
 Unit 4
Topic:

• ORDER, KINETICS EQUATIONS/CONCS-TIME

EQUATIONS
 Expected Outcome:
• At the end of this Unit 4, you should be able
to:
• 1. Derive kinetic equations for first and second
orders reactions
• 2. Explain the meaning of half-life of a
reaction
• 3. Do calculations using the kinetic equations
 ORDER OF REACTION
• Reaction can be classified by its order/ we can
classify reactions into:
• Zeroth/Zero order
• First order
• Second order
• Third order(rarely)
• Fractional order
• Negative order
 KINETICS EQUATIONS/CONCS-TIME
EQUATIONS

• The rate law tells us how the speed/rate of a

reaction varies with concentrations of the
reactants at a particular moments.

• The relationship between the concentration of

a reactant and TIME can be obtained from the
rate law of a reaction.
• This can be done by integration of the rate
expression/ transform a rate law into a
mathematical relationship between conc. and
time.
•
•
•
•

x x t t
dx

x 0
  kdt
b  x t 0
• Separating the variables and integrating
Equation (13) between the limits x = 0 at t = 0
and x = x at some time t, we have

x x t t
• [ ln(b  x)] x 0  k[t ]
t 0 (14)

b
• ln  kt (15)
bx

• 1
 xdx  ln x  loge x
•
• We can have the equation as:

b
• ln  kt
bx

• b
 exp  kt 
bx
• (b  x)  b exp  kt 
•
[ B]t  [ B]0 exp(kt )
log(b-x) Slope = - k/2.303

Mol dm-3

Time/s

Linear plot for a first order reaction

•
 Second-order Reactions
• let us consider a situation in which the
reactants are present with initial equimolar
concentrations.

Consider a reaction :

• C+D → Products
• [C] = [D] i.e., the initial conc. of
[C]=[B]
•
 d [C ]
  k[C ][ D]
• OR dt
d [C ] d [ D] dx
   k 2 [c  x ]2
• OR dt dt dt

x t
dx
• 
0
(c  x ) 2
 k
0
2 dt (17)
 x
 1 
• k 2t   (18)
c  x 
0

• 1 1 (19)
k2t  
cx c
• Equation (19) is the second-order kinetic
equation. k2 can be evaluated graphically.

• Or by substitution of the initial concentration

and the concentration of a reactant at time t
into Equation (19).
1/c-x

Slope = k2

Time/s

Linear plot for a second order reaction

•
•
•
•
• Half- life of zero order:
• Second-order Half life:
•
 METHODS FOR ORDER
• The order of a reaction can be determined by:
• Graphical method
• Substitution method- constant ks
• Half-life method.
 Half-Life Method
•
•
• Example
• The rate constant for the first-order
decomposition of N2O5 at temperature t0C is
2.2 x 10-1s-1.
• If the initial concentration of N2O5 is 3.6 x 10-3
mol dm-3, what will the concentration be after
four half-lives?
• For a first-order reaction, the half-life is
independent of the initial concentration of the
reactant.
• After the first half-life, the initial concentration
would have decreased by half.

• Therefore, after the fourth half-life, the

concentration will be 2.25 x 10-4 mol dm-3.