CHE 156

Physical Chemistry 1
• Nelson Okpako OBI-EGBEDI
 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:
N 2O5 
slow
 NO2  NO3

NO2  NO3  NO2  NO  O2 One Way

fast

NO  NO3 
fast
2 NO2

2 N 2O5  4 NO2  O2
 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

 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 = (Units of initial concentration) x (9)
• 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  log e 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
• k 2t   (19)
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.