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Chemical Kinetics

The document provides a comprehensive overview of chemical kinetics, detailing the rate of reaction, stoichiometric relationships, and various rate laws for different orders of reactions. It also discusses methods for monitoring reaction kinetics experimentally and the effects of temperature on reaction rates, including the Arrhenius equation. Key characteristics of zero, first, and second-order reactions are highlighted, along with graphical representations and important equations related to reaction rates.

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3 views5 pages

Chemical Kinetics

The document provides a comprehensive overview of chemical kinetics, detailing the rate of reaction, stoichiometric relationships, and various rate laws for different orders of reactions. It also discusses methods for monitoring reaction kinetics experimentally and the effects of temperature on reaction rates, including the Arrhenius equation. Key characteristics of zero, first, and second-order reactions are highlighted, along with graphical representations and important equations related to reaction rates.

Uploaded by

sayankundu5121
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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CHEMICAL KINETICS

Rate of disappearance of reactant (appearance of products)


Rate of Reaction (ROR) =
Stoichiometric coefficient of reactant (products)
n1 A + n2 B → n3 C + n4 D
1 d[A] 1 d[B] 1 d[C]
Instantaneous or Average Rate of Reaction = − 𝑛 ( dt ) = − n ( dt ) = n ( dt ) =
1 2 3
1 d[D]
( )
n4 dt
Relationship between rate of reaction and rate of disappearance of reactant (rate of
appearance of product).
1 Δ[A] 1 Δ[B] 1 Δ[C] 1 Δ[D]
Average rate: − ( ) = − ( ) = ( ) = ( )
a Δt b Δt c Δt d dΔt
d[A]
Rate of Disappearance of A = −
dt
d[B]
Rate of Disappearance of B = −
dt
[C]
Rate of Disappearance of C = +d
dt
[𝐷]
Rate of Disappearance of 𝐷 = +𝑑 𝑑𝑡
Unit of ROR = molL−1 time −1 "ROR is always positive.
Rate Law (Experimental Expression)

[R]2 − [R]1 ([P]2 − [P1 ])


Avg. Rate = − ( )=
t 2 − t1 t 2 − 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 = Rate = Rate = k[A]n
rate law k[A] k[A]2
Integrated [A0 ] − [A] kt kt 1 1
rate law = kt [A]0 1 kt = [
= ln = (n − 1) [ A]n−1
[ A] [ A] 1
1 − ]
− [ A]n−1
0
[ A]0
Halflife [A]0 t1/2 t1/2 1 2n−1 − 1
t1/2 = 1 t1/2 = [ ]
(𝐭 𝟏/𝟐 ) 2k ln 2 k(n − 1) [ A0 ]n−1
= =
k [ A]0 k
𝐭 𝟑/𝟒 t 3/4 t 3/4 t 3/4 = 3t1/2 t 3/4 = (2n−1 + 1)t1/2
= 1.5t1/2 = 2t1/2

Graphs of Various Order

Order 𝑅𝑎𝑡𝑒 𝑣𝑠 [𝐴] [𝐴] 𝑣𝑠 𝑡 𝑙𝑜𝑔 [𝐴] 𝑣𝑠 𝑡 𝟏


𝒗𝒔 𝒕
[𝑨]

Zero
order

First
order

Secon
d
order

Where
[A]0 ⇒ initial concentration
⌈A⌉ ⇒ concentration at time t

𝑡1/2 ⇒ time taken for initial concentration of reactant to finish by 50%


t 3/4 ⇒ time taken for initial concentration of reactant to finish by 75%
Monitoring Kinetics Experimentally
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.
1 P0
k = ln ( )
t P0 − x
Example: (For Monitoring Kinetics Experimentally
(i) Inversion of cane sugar:
CH3 COOC2 H5 (𝑎𝑞) + H2 O → CH3 COOH + C2 H5 OH
Sucrose Glucose Fructose
𝑑𝑒𝑥𝑡𝑟𝑜 − 𝑟𝑜𝑡𝑎𝑡𝑜𝑟𝑦 𝑑𝑒𝑥𝑡𝑟𝑜 − 𝑟𝑜𝑡𝑎𝑡𝑜𝑟𝑦 𝑙𝑎𝑒𝑣𝑜 − 𝑟𝑜𝑡𝑎𝑡𝑜𝑟𝑦
(+66.5°) (+52.5°) (– 92°)

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:
𝐻+
CH3 COOC2 H5 + H2 O → CH3 COOH + C2 H5 OH
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 be 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 𝑎0 𝑥 𝑎0 𝑥 2 𝑎0 𝑥 3 …. x = fraction by which reaction complete in time ' t '.


𝑘
• Graph of In [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−E2 /RT


• Ea = minimum energy over and above the average energy of reactant which must be
possessed by reacting molecule for collision to be successful.
• 𝐴 = frequency factor - proportional to number of collisions per unit volume per second.
• e−Ea /RT = Fraction of collision in which energy is greater then Ea .
E
• A and Ea are constant i.e. do not vary with temperature In k = In A − RTa
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 temperature ⇒ In = [ − ]
k1 R T1 T2
Endothermic and exothermic reactions:

Δ𝐇 = 𝐄af − 𝐄ab
Parallel reaction:
(i) Rate = (k1 + k 2 )[A] - (differential rate law)
k [B]
(ii) 1 =
k2 [C]
0.693
(iii) t1/2 =
k1+k2
k1 k2
(iv) % of B = × 100; % of C = × 100
k1+k2 k1 +k2
−(k+k1 +k)t
(v) [A] = [A]0 e

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

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