Rate of disappearance of reactant (appearance of products)

Rate of reaction (ROR) =

Stoichiometric coefficient of reac tant (products)

For a reaction :

aA + bB cC + dD

1 d[A] 1 d[B] 1 d[C] 1 d[D]

Instantaneous rate :
a dt b dt c dt d dt

Relationship between rate of reaction and rate of disappearence of reactant (rate of appearance of product).

1 [A ] 1 [B] 1 [C] 1 [D]

Average rate :
a t b t c t d d t

Graphical method for determining rate :

[R]2 [R]1 ([P]2 [P]1 )

Avg. Rate = t2 t1 t2 t1

OA OA
Instantaneous rate = – = + = ± slope of tangent
OB OB

Important kinetic expression for reaction of type A B :

Order Zero 1st 2nd nth

Differential Rate = k Rate= k[A] Rate = k[A] 2

Rate = k[A] n
rate law

[A]0 1 1 1 1 1
Integrated [A 0 ]–[A]= kt kt = In kt = [A ] [A ]0 kt =
[A] (n 1) [A ]n [A]n0
1 1

rate law

[A ]0 ln 2 1 1 2n 1 1
Half life (t1/2) t 1/2 = t 1/2 = t 1/2 = [A ] k t 1/2 = k (n 1) [A ] n 1
2k k 0 0

(t 3/4) t 3/4 =1.5 t 1/2 t 3/4 = 2 t 1/2 t 3/4 = 3 t 1/2 t 3/4 = (2 n–1 + 1) t 1/2

1
Graphs of various order
1
Order Rate vs [A] [A] vs t log [A] vs t vs t
[A ]

Zero order

First order

Second order

Where
[A]0 initial concentration
[A] concentration at time t
t1/2 time taken for initial concentration of reactant to finish by 50%
t3/4 time taken for initial concentration of reactant to finish by 75%
Monitoring Kinetics Experimently :
The kinetics of reaction can be followed (i.e. order, rate constant etc. can be established) by measuring a
property which changes with time.
e.g. (i) Total pressure in a gaseous reaction.
(ii) Volume of a reagent (Acidic, Basic, oxidising or reducing agent)
(iii) Volume of a gaseous mixture (V)
(iv) Optical rotation (R)
For a Reaction -
An nB
t = 0 c 0 c0 conc. at t = 0
t = t c–x nx ct conc. at t = t
t= 0 nc c conc. at t =
For any measurable property X proportional to the concentration of reaction mixture at various times,
following relations can be expressed.
In terms of -
(i) X0 and x (ii) X0 and Xt (iii) X and Xt (iv) X0, Xt, and X

1 X0 1 (n 1) X 0 1 (n 1) X 1 X X0
k = t ln X x k= ln k = ln k = ln
0 t nX 0 X t t n(X X t ) t X Xt
where
x amount of reactant reacted in time 't'.
X0 measured property at t = 0
Xt measured property at t = t
X measured property at t =

2
Examples : (For Monitoring Kinetics Experimently)
(i) Inversion of cane sugar :
C12H22O11 (aq) + H2O C6H12O6(aq) + C6H12O6(aq)
H

Sucrose Glucose Fructose

dextro-rotatory dextro-rotatory laevo-rotatory
(+66.5°) (+52.5°) (–92°)

(Laevo-rotatory)

2.303 r r0
k log
t r rt
r0 = rotation at time, t = 0
rt = rotation at time, t = t
r = rotation at time, t =
(ii) Acidic hydrolysis of ethyl acetate :

CH3COOC2H5 + H2O CH3COOH + C2H5OH

H

2.303 V V0
k log
t V Vt

V0 = Volume of NaOH solution used at time, t = 0

Vt = Volume of NaOH solution used at time, t = t
V = Volume of NaOH solution used at time, t =
Note : Here NaOH acts as a reagent. Acetic acid is one of the product the amount of which can be found by
titration against standard NaOH solution. But being an acid-catalysed reaction, the acid present originally
as catalyst, also reacts with NaOH solution.

Important characteristics of first order reaction :

t1/2 is independent of initial concentration.
In equal time interval, reactions finishes by equal fraction.
t = 0 t = t t = 2t t = 3t ....
Reactant conc. a0 a 0x a 0x a 0 x ........
2 3

x = fraction by which reaction complete in time 't'.

k
Graph of ln[A] vs t is straight line with slope =
2.303
Graph of [A] vs t is exponentially decreasing.
Zero order :
• t1/2 of zero order is directly proportional to initial concentration.
• In equal time interval, reaction finishes by equal amount.
t = 0 t = t t = 2t t = 3t .....
C0 C0 – x C0 – 2x C0 – 3x ....
• Graph of [A] vs t is straight line.
[A ]0
A zero order reaction finishes in t
k
Temperature dependence :
– Arrhenious equation : k = A.e–Ea/RT
– E a = minimum energy over and above the avg. energy of reactant which must be possesed by reacting
molecule for collision to be succesful.
– A = frequency factor - proportional to number of collisions per unit volume per second.
3
– e = Fraction of collision in which energy is greater than Ea.
–Ea/RT

– A and Ea are constant i.e. do not vary with temperature

Ea
ln k = ln A –
RT
Graph : Graphical determination of Ea.

k T 10
Temperature coefficient =
kT

By default T = 298 K

k2 Ea 1 1
Variation of rate constant with temparture ln
k1 R T1 T2

Endothermic and exothermic reactions :

H = E af – E ab

Parallel reaction :

(i) Rate = (k1 + k2 ) [A] - (differential rate law)

k1 [B ]
(ii) k2 [C ]
0 .6 9 3
(iii) t1/2 =
k1 k2
k1 k2
(iv) % of B = 100 ; % of C = 100
k1 k2 k1 k2
(v) [A] = [A]0 e –(k 1 k2 )t

Pseudo-order reaction :
Rate law rate = k [A]m [B]n
Pseudo rate law :
rate = k1 [A]m
[B] assumed constant in two cases :
(i) B in large excess (ii) B CATALYST