Kinetics

By Pharmacist Muhanad S. Al Ani

Rate and orders of reactions:

The rate, velocity, or speed of a reaction is given by the
expression
dc/dt
dc: is the increase or derease in the conc.
dt: is the time interval of this increase or derease.
so for the reaction
A
B
reactant
product
Rate of disappearance = - dA / dt
Rate of appearance = dB / dt
Also aA + bB +..
Products
a : is the no. of molecules of substance A
b: is the no. of molecules of substance B

The rate of reaction = K[A] [B]

K : is the rate constant.
If we have a reaction
A+B
product
1
1
rate = K[A] [B]
so the reaction is said to be 1 st order in
relation to substance A, and also 1 st order
in relation to substance B and the over all
reaction is 2nd order.

 Molecularity: is the no. of molecules,

atoms or ions that react to give the
product.
Ex. Br2
2Br
is unimolecular since single molecule of
Br2 is decomposes to form two bromine
atoms.
Ex. H2 + I2
2HI
this reaction is bimolecular since 2
molecules react to give the product.
Complex reaction: is the reaction that
proceed through more than one step.

Zero order kinetics

In this case the rate of the reaction is constant with time
and not depend on the conc. of the reactant.
A
B
K = - dA / dt = Ko
the initial conc. That is Ao is a rate
The conc. at time t is c
At = Ao Ko t or Ct = a - Ko t
time
so if we plot this equation in which C on the vertical axis
and t on the horizontal axis
Ao
Slop = - Ko
Ct
time

 The units of the rate constant in this case:

dA
K== Mole / liter
= LiterMole
second
second

dt

-1

-1

= mole liter second

Half life : is the time required for one half

of the material to disappear so it is the time
at which the conc. A is 0.5A
0.5 C
t1/2 = K
o

shelf life : time at 90% of the initial conc.

remain i.e. 10% of the drug disappear.
t90% = 0.1 Co / Ko

Suspensions: are apparent zero order

kinetic ??
suspension are an example on zero order
kinetic in which the conc. of the drug in
solution depends on the drug solubility, in
that as the drug decomposes in solution
more drug is released from the suspension
particles so that the conc. remains
constant .
The important point is that the conc. of the
drug in solution remains constant despite
its decomposition with time . The reservoir
of the solid drug in suspension is
responsible for this constancy.

 For any solution with no reservoir of drug to

replace that decomposed drug is 1st order
kinetic.
- d[A]
dt = K [A]

[A] : is the conc. of the drug remaining undecomposed

at time t.

k : is the 1st order rate constant.

When the conc. remain constant i.e. A is constant
Ko = K [A]

Or Ko = - d[A] / dt
this equation appear as a zero order kinetic.
so it is referred to as an apparent zero order equation
because the suspended drug reservoir that ensures
constant conc.

Example: a prescription for a liquid aspirin

preparation is called for to contain 6.5g/100
ml, the solubility of aspirin at 25C is
0.33g/100 ml therefore the preparation will
be definitely be a suspension.
The 1st order rate constant for aspirin -6
-1
degradation in this solution is 4.5 x 10 sec
Calculate the zero order rate constant and the
shelf life for this liquid preparation.

First Order Reaction

In this case the rate of the reaction is proportional to the
concentration of the substance remaining in the reaction
mixture at time t.
Kc
K : is the first order rate constant.
C: is the concentration of drug remain undecomposed at
time t.
So by integrating the equation 1:1
C0 at time t = 0 and
Ct at time t

In C In C0 = - k (t - 0)
In C = In C0 - kt
By converting to the logarithem
Log C = Log C0
k=
log

Half life in first order kinetic

t =

shelf life

log conc.

t90 %

=Slope

Time

 The unit of rate constant

K [A] = K=
K=

= se cc

Example:
A solution of a drug contained 500 unit/ml when
prepared. It was analyzed after a period of 40
days and was found to contain 300 unit/ml .
assuming the decomposition is 1st order. At
what time will the drug have decomposed to one
half its original concentration.

 second order kinetic

A + B product
so in this case we have bimolecular reaction .

if a : is initial concentration of drug A

b : is initial concentration of drug B
x : is the concentration of each drug reacting at time t

.conc.=conc
a= b

 Half life =
Unit for second order kinetic = liter mole c second c
:Example
The initial concentration of both ethylacetate and Sodium
hydroxide in the mixture were 0.01M. the change in
concentration of the alkali during 20 min. was 0.00566 mole/L .
Calculate (a) rate constant (b) t1/2

Determination of order
We have several methods:
1) Substitution Method
Data accumulated from kinetic study substituted
in the equation that describe the various order.
2) Graphic Method
We plot the data of kinetic study in the from of a graph.
a) if the concentration plotted against (t) results in
straight line, its zero order.
b) if (a x) plotted against (t) results in straight
line, its 1st order.
c) if
plotted against (t) results in straight
line, its second order if (a=b).

3) Half life Method

in zero order t1/2 is proportional to a
in 1st order t1/2 is independent on a
in second order t1/2 is proportional to
1/a if a=b

Factors that affect on the rate of reaction:

1) Temperature
The speed of many reactions increases about 2-3 times
with each 10 CCrise in temperature.
The effect of temperature on reaction rate is given by
Arrhenius equation
Ea/ RT-

K = Ae
log K = log A
A: Arrhenius factor or frequency factor
Ea: Energy of activation
R: Gas constant = 1.987 calorie/deg mole
T: Absolute temperature

or

Log A

Log
K

Slope =

So at any temperature we have a rate constant, if we have 2 temperature mean 2 rate

constant

log
Example:
The rate constant for the decomposition of 5- hydroxymethyle furfural
at 120 CC is 1.173 hr c and at 140 CC
is 4.860 hr what
c
is the activation
energy in Kcal/mole and the frequency factor in sec c for this
breakdown.

2) Specific Acid Base catalysis

Solution of a number of drugs undergo accelerated
decomposition upon the addition of acids or
bases.
When the rate law for such an accelerated
decomposition is found to contain a term
involving the concentration of hydrogen or
hydroxyl in the reaction is said to be subject to
specific acid base balance.

3) Influence of light (photodegradation)

Light is not classified as a catalyst , light
energy, like heat may provide the
activation necessary for a reaction to
occur.