CHEMICAL KINETICS

Chemical Kinetics is that branch of physical chemistry which deals with the speed, or rate, at
which a chemical reaction occurs. Rate of reaction is the change in the concentration of a
reactant or product with time (M/s).
Change in conc. of reactant
𝑅𝑎𝑡𝑒 =
Time
or
Change in conc. of product
𝑅𝑎𝑡𝑒 =
Time
RATE OF REACTION
The rate of reaction is the change in concentration of reactants or products per unit time.
The instantaneous rate which is normally also referred as rate of the reaction is by drawing
the tangent at the time of interest say about (100 sec)and finding the slope of the tangent.

aA +bB → cC+ Dd

rate ∝ (a)^x (b)^y

Rate = K (a)^x (b)^y ___(1)
x + y = n (order of reaction)
K = rate constant of the reaction
 RATE LAW
The relation which express the relationship between rate with rate constant and concentration
of reactants raised to it’s power is called rate law.
OR

 The rate law expresses the relationship of the rate of a reaction to the rate constant and
concentration of the reactants raised to some power.
 The sum of the power of the reactant terms is known as order of the yxn
 For eq-1 order of yxn is n which is equal to x+y
X is the order of the yxn with respect to A
Y is the order of the yxn with respect to B
aA give rise to products
Rate =k[A]n
K=rate÷[A]n give rise to k=rate÷(1) n = k=rate÷1

RATE CONSTANT
In chemical kinetics, the rate constant (denoted by k) is a proportionality constant in the rate
law of a reaction that relates the rate of a chemical reaction to the concentration of reactants
at a given temperature. It quantifies how quickly reactants are converted to products, with a
higher k indicating a faster reaction. The rate constant is unique to a specific reaction at a
particular temperature and does not depend on reactant concentrations or the reaction time.

MOLECULARITY AND ELEMENTARY REACTION

A balanced (or stoichiometric) equation shows the reactants that are present at the beginning
of the reaction and products present at the end of the reaction. It is not common that reactants
are converted into products in one step as suggested by the stoichiometric equation. A
reaction like
NO(g) + O3(g) → NO2(g) + O2(g) ______ (1)

occurs as a result of direct collision between NO and O3. Such reactions, which occur as a
result of direct collision between reactants as indicated in the balanced equation are described
as ‘elementary reactions’; but most reactions do not occur this way. Reactants are typically
converted into products thorough several steps. For instance, consider the reaction
NO2(g) + CO(g) → NO(g) + CO2(g) ______ (2)
The impression that may be gathered from balanced equation (2) is that two molecules, one
each of NO(g) and CO2(g), are formed when one molecule of NO2(g) collides with one
molecule of CO(g); but this is not true. The experimental data suggest that the reaction occurs
in two steps. First, two molecules of NO2 collide and as a result of this an oxygen atom from
one molecule is transferred to other. The resulting NO3 then collides with CO. The two steps
are represented as:
Slow step NO2(g) + NO2(g) → NO3(g) + NO(g) ______ (3)
NO3(g) + CO(g) → NO2(g) + CO2(g) ______ (4)
It can be seen that addition of these steps (3) & (4) leads to overall balanced reaction (2).
Each of the two steps (3) and (4) is called an ‘elementary step’ of reaction (2). Thus, we can
define an “elementary step” or reaction as one which occurs as a result of the direct collision
of molecules, ions or atoms as shown by the balanced equation. All the steps of the reaction
are collectively known as the “mechanism of the reaction”.

Each step of the mechanism may involve a different number of reacting species, and this
number of reacting species is described as the “molecularity” of that step. Molecularity is
defined only for an elementary step . For instance, the molecularity of elementary step (3) is
two and the molecularity of elementary step (4) is again two. Speaking of the molecularity of
the overall reaction (2) does not make sense, since it is not an elementary reaction (But the
molecularity of slow step among (3) and (4) is taken as molecularity of the overall reaction).
It does, however, make sense to speak of the molecularity of reaction (1), because it is an
elementary reaction occurring as a direct collision between NO(g) and O3(g). Thus, the
molecularity of this reaction is two.
Additional examples of elementary reactions include:

CH 2 CH CH 3 (5)

2HI → H2 + I2______ (6)

2NO + O2 → 2NO2______ (7)
Since reactions (5), (6) and (7) are elementary reactions, their molecularities are one, two and
three, and they are termed unimolecular, bimolecular and termolecular reactions respectively.
 ORDER OF A REACTION
Conceptial Meaning Of Order Of A Reaction –
aA — products
Rate = k [A]
CASE 1:

LET [A] = IM & N=1

𝑅2 =𝐾[𝐴]1
Let[A]=2M& N=1

𝑅2 =𝐾[2]1
𝑅2 𝐾[2]1
=
𝑅1 𝐾[1]1

𝑅2
=2
𝑅1

CASE 2:
LET [A] = IM & N=2
𝑅1 =𝐾[𝐴]2
Let[A]=2M& N=2
𝑅2 𝐾[2]1
=
𝑅1 𝐾[2]2

𝑅2
=4
𝑅1

CASE 3:
LET [A] = IM & N=3
𝑅1 =𝐾[𝐴]3
Let[A]=2M& N=3
𝑅2 =𝐾[2]3
𝑅2 𝐾[2]3
=
𝑅1 𝐾[1]3
𝑅2
=8
𝑅1

CASE 3:
LET [A] = IM & N=3
𝑅1 =𝐾[𝐴]3
Let[A]=2M& N=3
𝑅2 =𝐾[2]3
𝑅2 𝐾[2]3
=
𝑅1 𝐾[1]3
𝑅2
=8
𝑅1

FACTORS INFLUENCING THE REACTION RATES

 Temperature
 Concentration of the Reactants
 Nature of Reactants
 Catalyst
 Radiation

1. Temperature:
In this Increasing temperature usually doubles or triples the rate of reaction per 10°C rise
and as the particles gain more energy and collide more effectively, hence influencing the
reaction rate.

2. Concentration of the reaction:

In this the Higher concentration increases the number of molecules per unit volume, thus
giving rise to more frequent collisions and faster reactions , influencing the reaction rate.

3. Nature of reactants:
In this the Reactions involving simple bond changes occur faster than those needing
complex bond rearrangements.

4. Catalyst:
In this the Catalysts speed up reactions in presence of catalyst which ultimately enhances
the rate of reaction hence lowering the time and influencing the reaction rate.

5. Radiation:
Some reactions speed up when exposed to light of suitable wavelength like
photochemical reactions example hydrogen and chlorine reacts explosively in light but
very slowly in the dark therefore influences the rate of reaction.

FIRST ORDER REACTION

Definition:
A reaction is said to be of first order when the rate of reaction depends on the
concentration of a single reactant raised to the power of one or we can say that the rate of
reaction is directly proportional to the first power of the concentration of the reactant.
Mathematically for a reaction
A → Products
The Rate Law is Expressed as
Rate = K[A]1
Here:
[A] = concentration of reactant A
k = rate constant of the reaction
The exponent “1” indicates it is first order.

DERIVATION OF EQUATION FOR RATE CONSTANT

First order reaction:
First order reaction is a reaction whose rate depends on the reactant concentration raised
to first power.
aA → Product
Rate= - dA/dt ___(1)
Rate=K{A}’ ____(2)
from 1 and 2
-dA/dt={A}
dA/dt=K{A}
dA/{A}=Kdt
Integrating
{A}o = initial concentration
{A}t=concentration of a at time t
integration {A}t {A}o dA/{A}=k integration t ,o dt
In {A}t -In{A}o =-Kt
:Ina-Inb= In a/b
In {A}t/{A}o= -Kt
This is known as Integrated Rate Law

Half-life of the reaction:

As a reaction proceeds, the concentration of the reactant(s) decreases. Another measure of
the rate of a reaction, relating concentration to time, is the half-life, t1/2, which is the time
required for the concentration of a reactant to decrease to half of its initial concentration.
We can obtain an expression for t1/2 for a first-order reaction as follows.
t = 1/k ln [A]o/[A]t
By the definition of half life, when t= t1/2, [A]t=[A]o/2, so
t1/2 = 1/k ln [A]o/[A]o/2
or
t1/2 = 1/k ln 2 = 0.693/k

The above equation tells us that the half-life of a first-order reaction is independent of the
initial concentration of the reactant. Thus, it takes the same time for the concentration of
the reactant to decrease from 1.0 M to 0.50 M. say, as it does for a decrease in
concentration from 0.10 M to 0.050 M. Measuring the half-life of a reaction is one way to
determine the rate constant of a first-order reaction.

CHARACTERISTICS OF FIRST- ORDER REACTION

1. Units Of First-Order Reaction:
-kt = ln([A]t / [A]₀)
-(-kt = ln([A]t / [A]₀))
kt = -ln([A]t / [A]₀)
kt = ln([A]₀ / [A]t)
k = (1 / t) × ln([A]₀ / [A]t)
k = (1 / time) × ln([A]0 / [A]t)
k = (1 / time) × ln(M / M )
k = 1 / time

∴ Units are 1 / time

i.e. s⁻¹ or min⁻¹ or hour⁻¹
 2. Reaction Of Half-Life [ T1/2]:
It is time required for the concentration of the reactants to decrease to half of its initial
concentration.
-kt = ln([A]t / [A]₀)
kt = -ln([A]t / [A]₀)
kt = ln([A]₀ / [A]t)
t = (1 / k) × ln([A]₀ / [A]t)
t₁/₂ = (1 / k) × ln([A]₀ / [A]₀ / 2)
t₁/₂ = (1 / k) × ln 2 ( [A]₀ / [A]₀)
t₁/₂ = (1 / k) × ln 2
t₁/₂ = 0.693 / k

∴ The half-life time of first order reaction is independent of the initial concentration.

3. Evaluation of first-order rate constant “k”:

-kt = ln([A]t / [A]₀)
kt = - ln([A]t / [A]₀)
kt = ln([A]₀ / [A]t)
ln[A]0 – ln[A]t = kt
- [- ln[A]t = kt - ln[A]0 ]

Alternative method:

K = ( 2.303/ t ) log (a / a-x )

log (a / a-x) = (k t )/(2.303)

where,

log (a / a-x) = (y)

t = (x)

k / 2.303 = (m)

m = k / 2.303

k = m x 2.303

UNITS FOR RATE CONSTANT

For First Order Reaction:

−𝑘𝑡 = 𝑙𝑛[𝐴]𝑡/[𝐴]0

𝑘𝑡 = − 𝑙𝑛[𝐴]𝑡/[𝐴]0

𝐾𝑡 = ln [𝐴]0/𝐴t

𝑢𝑛𝑖𝑡𝑠: − 1/time

i.e 𝑢𝑛𝑖𝑡𝑠 = 𝑠 −1 𝑚𝑖𝑛−1 ℎ𝑟 −1

For Second Order Reaction:

 HALF LIFE PERIOD

 Half life period is the time it takes for the concentration of a reactant to decrease to
half of its initial value during a chemical reactor.
 The half life period is represented by the symbol T(1/2)
 It is related to the decay constant (λ) by the formula : T(2) = 0.693/ A

GRAPH OF FIRST ORDER REACTION

The concentration v/s time graph for a first-order reaction is provided below

For first-order reactions, the equation ln[A] = -kt + ln[A]0 is similar to that of a straight line
(y = mx + c) with slope -k. This line can be graphically plotted as follows.

DECOMPOSITION OF H2O2
H2O2→H2O+ ½ O2

In presence of ferric ions (Fe+3) the decomposition is faster. The unreacted H2O2 can be
estimated by titration against KMnO4 in the presence of dil. H2SO4 (sulfuric acid). The
 volume of KMnO4 consumed at any given instant is proportional to the concentration of
H2O2 in the reaction mixture at that instant.
2KMnO4 + 3H2SO4 +5H2O2 → K2SO4 + MnSO4 +8H2O +5O2
The decomposition follows first order and the expression for rate constant is
K = 2.303/t log a/a-x

Procedure:
Take 80 ml of distilled water in a reagent bottle and add 10 ml of Fecl3 (ferric
chloride) in it. Fill the burette with KMnO4. In a conical flask take 10 ml of dil. H2SO4.
Pipette out 10 ml of H2O2 in the reagent bottle and note the time of mixing at zero time.
Quickly shake the reaction mixture and immediately pipette out 10 ml of it in conical flask
containing ice cold water and acid. Titration this against KMnO4 till the appearance of pale
pink color. Record the titer value as V0. Repeat the titer value at Vt. Take 7 such reading.
Plot a graph between log V0/Vt and time (t) and calculate K from the slope. Also plot a graph
between log Vt and time t and calculate K from the slope.
K= 2.303/t log a/a-x
Kt/2.303= log V0/Vt (or)
Log V0/Vt = Kt/2.303

Graphical representation:
Problem:

(Q). The decomposition of ethane (C2H6) to methyl radicals is a first-order reaction with a
rate constant of 5.36 × 10-4 s -1 at 700°C;

C2H6(g) →2CH3(g)

Calculate the half-life of the reaction in minutes. •Strategy: To calculate the half-life of a
first-order reaction, we use Equation. A conversion is needed to express the half-life in
minutes.

Solution:

For a first-order reaction, we only need the rate constant to calculate the half-life of the
reaction. From Equation

t ½= 0.693/k

=0.693/5.36*10-4

= 1.29 × 10 3 s x 1min/60s

= 21.5min

PSEUDO FIRST ORDER REACTION

A pseudo first order reaction is a bimolecular reaction that appears to be first order because
the concentration of one reactant is present in much a large excess that it remains practically
constant during the reaction.

In much order, the rate depends only on the concentration of the limiting, reactant and the
reaction behaves as if it were first order reaction.

HYDROLYSIS OF METHYL ACETATE

Aim:
To study the hydrolysis of methyl acetate in acidic medium and determine the rate of reaction

Introduction:

 Hydrolysis of methyl acetate is a classic experiment in chemical kinetics.

 Acetate reacts with water in the presence of an acid catalyst (HCl) to form acetic
 The reaction is usually carried out under conditions where water is in large excess,
making it a pseudo-first-order reaction Methyl acid and methanol.
Chemical reaction:

𝐶𝐻3𝐶𝑂𝑂𝐻 + 𝐻20 → CH3COOH + CH3OH

Materials Required:

 Methyl acetate
 Dilute HCl (acid catalyst)
 Distilled water
 Burette, pipette, conical flask
 Phenolphthalein indicator
 Sodium hydroxide solution (for titration)
 Water bath

Procedure:
1. Take methyl acetate in a conical flask.
2. Add water in excess.
3. Add a few drops of dilute HCl as a catalyst.
4. Heat the mixture at a constant temperature using a water bath.
5. At regular time intervals, withdraw small samples and titrate with standard NaOH using
phenolphthalein as an indicator.
6. Record the volume of NaOH required to neutralize acetic acid formed.
7. Calculate the amount of methyl acetate hydrolyzed and the rate constant “K”

Observation Table:

TIME [min] Volume of NaOH Amount of ester Log [a/x]

[mL] hydrolyzed [x]
[Link]
1. 10 2.5 0.01 2.00
2. 20 4.8 0.02 1.70
3. 30 7.0 0.03 1.52

Graphical Representation:
Result:

 The reaction follows pseudo-first-order kinetics.

 The rate constant (k) can be calculated from the slope of log [a/ {a-x}] vs time plot.

Conclusion:

 Hydrolysis of methyl acetate is a first-order reaction with respect to the ester.

 The experiment demonstrates how chemical kinetics can be used to study the rate of
reaction.

INVERSION OF CANE SUGAR

Theory:
A standard measure of the degree to which a compound is dextrorotatory or levorotatory is
the quantity called the specific rotation (denoted as [α]).
Dextrorotatory compounds have a positive specific rotation, while levorotatory compounds
have a negative specific rotation.
Two enantiomers have equal and opposite specific rotations.
The formula for specific rotation is:
[α] = α_obs / (l × c)
where:
• [α] = specific rotation
• α_obs = observed rotation
• c = concentration of the solution (in g/mL)
• l = length of the polarimeter tube (in decimetres)

For a pure substance in solution, if the color and path length are fixed and the specific
rotation is known,
the degree of rotation can be used to determine the concentration.

In the inversion of cane sugar, the rate of reaction depends on the concentrations of sucrose,
water, and hydrogen ion (H⁺), which acts as a catalyst.
When a large excess of water is used, its concentration can be considered constant, and the
concentration of H⁺ ion remains constant during the reaction.
Under these conditions, the reaction is first order in sucrose.
Let:
• A₀ = initial angular rotation
• Aₜ = angular rotation at time t
• A_∞ = final angular rotation

(A₀ - A_∞) ∝ initial concentration of sucrose

(Aₜ - A_∞) ∝ concentration of sucrose at time t

Substituting these values into the first-order rate equation gives:

k = (2.303 / t) × log₁₀[(A₀ - A_∞) / (Aₜ - A_∞)]

Summary:

 Cane sugar hydrolyzes to glucose and fructose (invert sugar)

 Reaction

𝐶12𝐻22𝑂11 + 𝐻2𝑂 → C6H12O6 + C6H12O6

Dextrorotatory and levorotatory are terms used to describe the direction in which a substance
rotates the plane of polarized light. Dextrorotatory substances rotate the plane of polarized
light to the right, while levorotatory substances rotate it to the left. This rotation is determined
by the molecular structure of the substance and its interaction with polarized light.
Dextrorotatory and levorotatory compounds are mirror images of each other and are referred
to as enantiomers.

Problem:
Q) The conversion of cyclopropane to propene in the gas phase is first order with a rate
constant of 6.7 × 10⁻⁴ s⁻¹ at 500 °C.
a) If the initial conc. of cyclopropane was 0.25 M, what is the conc. after 8.8 min?
b) How long (in min) will it take for the conc. of cyclopropane to go from 0.25 M to 0.15 M?
c) How long will it take to convert 74% of the starting material?

a) Solution:
K is given in per sec (rate constant). Convert 8.8 mins into sec:
8.8 min × 60 = 528 sec
[A]₀ = 0.25 M, k = 6.7 × 10⁻⁴ s⁻¹, t = 528 s
First order law:
ln([A]t / [A]₀) = -kt
ln [A]t = -kt + ln [A]₀
ln [A]t = -(6.7 × 10⁻⁴)(528) + ln (0.25)
[A]t = 0.25 e^(-6.7 × 10⁻⁴ × 528) = 0.18 M (≈0.176 M)

b) Solution:
[A]₀ = 0.25 M, [A]t = 0.15 M, k = 6.7 × 10⁻⁴ s⁻¹, t=?

-kt = ln([A]t / [A]₀)

t = (1/k) ln([A]₀ / [A]t)

t = (1 / 6.7 × 10⁻⁴) ln(0.25 / 0.15)

t = (1 / 6.7 × 10⁻⁴) × 0.511 = 7.6 × 10² sec
t = 7.6 × 10² / 60 = 12.7 min (≈13 min)

c) Solution:
[A]₀ = 100, 74% converted ⇒ [A]t = 26
k = 6.7 × 10⁻⁴ s⁻¹, t=?
-kt = ln([A]t / [A]₀)
t = (1/k) ln([A]₀ / [A]t)
t = (1 / 6.7 × 10⁻⁴) ln(100 / 26)

SECOND ORDER REACTION

A second order reaction is a reaction whose rate depends on the concentration of one reactant
raised to the second power or on the concentrations of two different reactants, each raised to
the first power.

General form:
For a reaction
A + B = Products
The rate law is :
Rate = k[A][B]
k =mol L^-1s^-1/(mol L^-1)(mol L^-1)
= L mol^-1s^-1(units)
If both reactants are the same (e.g.,2A gives rise to products),then:
Rate = k[A]^2
k = mol L^-1s^-1/(mol L^-1)^2
= L mol^-1s^-1 (units)
 HALF LIFE (t1/2)
For 2A gives rise to products :
t1/2 = 1/k[A]o
unlike first order reactions , the half -life depends on the initial concentration.

DERIVATION OF EXPRESSION FOR A SECOND-ORDER REACTION

Introduction:
Chemical kinetics is the study of reaction rates and the factors that influence them. For a
second-order reaction, the rate is proportional either to the square of the concentration of a
single reactant or the product of the concentrations of two reactants.
General form:
A + B → Products or 2A → Products

Theory:
Rate Law Definition: A mathematical expression that relates the rate of a chemical reaction to
the concentration of the reactants.
A second-order reaction can have two general forms.
For a second-order reaction, the rate law can be written as:
-d[A]/dt = k[A]^2 (if only one reactant is present)
-d[A]/dt = k[A][B] (if two reactants are present)
Where:
[A] = concentration of reactant A
[B] = concentration of reactant B
k = rate constant with units L mol⁻¹ s⁻¹.

Derivation of Integrated Rate Equation:

Case I: Equal Initial Concentrations
Initial concentration of A = B = a.
At time t, let x moles have reacted.
[A] = [B] = (a-x)
Rate law: dx/dt = k(a-x)²
On integration:
1/(a-x) - 1/a = kt

This confirms that a plot of 1/[A] vs. time (t) yields a straight line with a slope equal to the
rate constant k.
Case II: Unequal Initial Concentrations
Initial [A] = a, [B] = b.
At time t, [A] = (a-x), [B] = (b-x).
Rate law:
dx/dt = k(a-x)(b-x)
On integration: 1/(a-b) ln [ b(a-x) / a(b-x) ] = kt
Case III: Special Case (2A → Products)
-d[A]/dt = k[A]²
On integration:
1/[A] - 1/[A]₀ = kt

Graphical Representation:
For a second-order reaction:
- A plot of 1/[A] vs t is a straight line.
- Slope of the line = rate constant k.

This expression is fundamental as it allows for the determination of the rate constant (k) from
experimental concentration-time data and provides the necessary linear criterion (1/[A] vs.
time) to confirm that a reaction is indeed second-order.

Applications:
- Saponification of esters (hydrolysis in alkaline medium).
- Reaction between nitrogen dioxide and oxygen.
- Dimerization of ethane.

The derivation of the second-order rate law is essential to determine the rate constant from
experimental data and to confirm the order of a reaction. The linear relationship of 1/[A] vs
time is the key feature of a second-order reaction.

SAPONIFICATION OF ESTER

Definition:

Saponification is the alkaline hydrolysis of an ester in the presence of a strong base (like
NaOH or KOH), resulting in the formation of the salt of a carboxylic acid (called soap if the
ester is fat/oil) and an alcohol.

General Reaction:

 RCOOR′+ NaOH⟶RCOONa+ R′OH

 Ester + Alkali → Sodium (or potassium) carboxylate + Alcohol

Mechanism (Brief):

1. OH⁻ ion attacks the carbonyl carbon of the ester.

2. A tetrahedral intermediate forms.

3. Cleavage of the C–O bond occurs.

4. Carboxylate ion and alcohol are released.

5. Carboxylate ion combines with Na⁺/K⁺ to form the salt.

Examples:

1. Ethyl acetate
CH3COOCH2CH3+NaOH⟶CH3COONa+CH3CH2OH

(Ethyl acetate → Sodium acetate + Ethanol)

2. Methyl butanoate

CH3CH2CH2COOCH3+NaOH⟶CH3CH2CH2COONa+CH3OH

(Methyl butanoate ⟶ Sodium butanoate + Methanol)

Characteristics:

 It is an irreversible reaction (unlike simple ester hydrolysis in acid, which is

reversible).
 Produces soap (sodium/potassium salts of long-chain fatty acids).
 Widely used in soap-making industry.
 Gives a basic solution (due to excess OH⁻ ions).

Applications:

 Soap industry: Conversion of oils/fats into soaps.

 Glycerol production.
 Analytical chemistry: Used to estimate esters by back titration.

CHARACTERISTICS OF SECOND ORDER REACTION

[Link] of Second order rate constant:

A⟶ Products

Rate = K [A]2
K = Rate/ [A]2 = Ms-1 / [M]2
= M-1 s -1
[Link] of second order rate constant K:

a) If there is only one reactant, the second order rate constants can be determined by using the
equation,
1/[A]t = Kt + 1/[A]0
Kt = 1/[A]t – 1/[A]0
K = 1/t ( 1/[A]t – 1/[A]0 )
b) If there are two reactants the second order rate constants can be determined by using

3. Half-life period:

1/[A]t = Kt + 1/[A]0

1/[A]0 /2 = Kt1/2 + 1/[A]0

Kt1/2 = 1 x 2/ [A]0 - 1/[A]0

t1/2 = 1/ k [A]
 SUMMARY OF RATE LAW

 Chemical kinetics studies the speed of chemical reactions.

 Rate Law relates reaction rate with concentration of reactants.
 Rate = k[A]^m [B]^n
 k = rate constant (temperature dependent)
 m, n = order of reaction (experimentally determined)
 Overall Order = m+n

UNITS FOR RATE CONSTANTS

[k] = M^ 1^-(m+n) s^ -1

HALF LIFE PERIOD

Half life(t½) = Time required for concentration Of reactant to become half of its initial value.

Formulas:

 Zero order-t½=[A]⁰/2K(depends on [A]⁰)

 First order-t½=0.693/K(independent of [A]⁰)
 Second order-t½=1/K[A]⁰(depends on [A]⁰)

INTEGRATED RATE LAWS AND SECOND ORDER PLOTS

 Zero Order: [A] = [A]_0 - kt → straight line [A] vs. t

 First Order: ln[A] = ln[A]_0 - kt → straight line ln[A] vs. t
 Second Order: 1/[A] = kt + 1/[A]0 → straight line 1/[A] vs. t

Half-life decreases with increasing order of reaction (depends on [A]⁰)

For second order reaction:

For a reaction :

A → Products

Integrated law :

1/[A] = kt + 1[A]0

 Straight line when plotted as 1/[A] vs t

 Slope = k, Intercept = 1/[A]0

Examples:
 2NO2 → 2NO + O2
 Hydrolysis of ester in alkaline medium

Problem:

A second-order reaction has a rate constant k = 0.020 M⁻¹ min⁻¹.

If the initial concentration of reactant is [A]₀ = 0.500 M:

1. What will be the concentration after 10 minutes?

2. What is the half-life t₁/₂?
3. How long will it take for the concentration to drop to 0.100 M?

Solution:

Step 1. Integrated second-order rate law

1/[A]t = 1/[A]₀ + k t

Step 2. Concentration after 10 minutes

1/[A]t = 1/0.500 + (0.020) (10)
1/[A]t = 2.000 + 0.200 = 2.200
[A]t = 1 / 2.200 = 0.4545 M

Step 3. Half-life formula (second order)

t₁/₂ = 1 / (k [A]₀)
t₁/₂ = 1 / (0.020 × 0.500)
t₁/₂ = 1 / 0.010 = 100 min

Step 4. Time to reach 0.100 M

1/[A]t = 1/[A]₀ + k t
1/0.100 = 10.000 = 2.000 + (0.020) t
(0.020) t = 10.000 − 2.000 = 8.000
t = 8.000 / 0.020 = 400 min

Final Answers:
1. [A] after 10 min = 0.4545 M
2. Half-life = 100 min
3. Time to reach 0.100 M = 400 min

Problem:

A zero-order reaction has a rate constant k = 0.040 M min⁻¹.

If the initial concentration of reactant is [A]₀ = 0.500 M:

1. What will be the concentration after 8 minutes?

2. What is the half-life t₁/₂?
3. How long will it take for the concentration to drop to 0.100 M?

Solution:

Step 1. Integrated zero-order rate law

[A]t = [A]₀ − k t

Step 2. Concentration after 8 minutes

[A]t = 0.500 − (0.040) (8)
[A]t = 0.500 − 0.320 = 0.180 M

Step 3. Half-life formula (zero order)

t₁/₂ = [A]₀ / (2 k)
t₁/₂ = 0.500 / (2 × 0.040)
t₁/₂ = 0.500 / 0.080 = 6.25 min
Step 4. Time to reach 0.100 M
0.100 = 0.500 − (0.040) t
0.040 t = 0.400
t = 10.0 min

Final Answers:
1. [A] after 8 min = 0.180 M
2. Half-life = 6.25 min
3. Time to reach 0.100 M = 10.0 min

Problem:

A first-order reaction has [A]₀ = 0.100 M. After 5 minutes, [A] = 0.0650 M

1. Find the rate constant k.

2. Find the half-life t₁/₂.
3. Find the time required for [A] to reach 0.0100 M.

Solution:

Step 1. Find k
ln([A]t / [A]₀) = -kt
ln(0.0650 / 0.100) = -k (5)
ln(0.65) = -0.4308 = -5k
k = 0.4308 / 5 = 0.0862 min⁻¹

Step 2. Half-life
t₁/₂ = 0.693 / k
t₁/₂ = 0.693 / 0.0862 ≈ 8.0 min

Step 3. Time for [A] = 0.0100 M

ln(0.0100 / 0.100) = -kt
ln(0.10) = -2.3026 = -0.0862t
t = 2.3026 / 0.0862 ≈ 26.7 min

Final Answers:
1. k = 0.0862 min⁻¹
2. t₁/₂ ≈ 8.0 min
3. Time to reach 0.0100 M ≈ 26.7 min
 METHODS FOR DETERMINING THE ORDER OF A REACTION

1. Trial / Integral method:

This method consists in carrying out the reaction with known quantities of reactants
and determining the amount of reactants consumed after different intervals of time
and substituting the data in integrated rate law equations of first order and second
order.

First Order Equation-

Second Order Equation-

The equation which gives constant value of indicates the appropriate order of the reaction.

2. Graphical Methods:

First Order Graphs-

Second Order Graphs-

Here, experimental concentration data is fitted into different integrated rate law plots:
For first order reaction: ln[A]t = ln[A]0 - Kt
Plot: ln[A]t vs t → Straight line with slope = -K → First order reaction
For second order reaction: 1/[A]t = Kt + 1/[A]0
Plot: 1/[A]t vs t → Straight line with slope = K → Second order reaction
 3. Half-life Method:

Half-life (t1/2) is the time taken for concentration to reduce to half of its initial value.
For first order: t1/2 = 0.693 / K (independent of [A]0)
For second order: t1/2 = 1 / (K[A]0) (depends on initial concentration)
General case (nth order): t1/2 ∝ 1 / (a)^(n-1)
If experiments are carried out at two different initial concentrations a1 and a2, and their half-lives
are t1/2 and t'1/2, then:
t1/2 / t'1/2 = (a2 / a1)^(n-1)
From this relation, order (n) can be determined.

Extended Half-life Method Derivation:

From the relation: t1/2 / t'1/2 = (a2 / a1)^(n-1)
Taking logarithm on both sides:
log(t1/2 / t'1/2) = (n - 1) log(a2 / a1)
=> (n - 1) = [log(t1/2) - log(t'1/2)] / [log(a2) - log(a1)]
Thus,
n = 1 + [log(t1/2) - log(t'1/2)] / [log(a2) - log(a1)]
Hence, by knowing t1/2, t'1/2, a1, and a2, one can determine the order of the reaction (n).

4. OSTWALD’S ISOLATION METHOD:

Let us say we have 3 reactants: A, B, C.

We take B and C in excess, and the order of reaction wrt A is found out using the above 3
methods. Similarly, the order of the reaction wrt B and C is also determined.
The sum of the orders of reaction wrt A, B, C gives us the total order of the reaction.

ARRHENIUS EQUATION
The dependence of the rate constant of a reactant on temperature can be expressed by the
following equation known as Arrhenius Equation .
k = A * e^(-Ea / RT)

where:
k = rate constant
A = frequency factor
Ea = activation energy
T = temperature (in K)
R = gas constant
e = base of natural logarithms

Taking natural logarithm on both sides gives:

ln k = ln A - Ea / (RT)

This can be rearranged into the linear form:

ln k = (-Ea/R)(1/T) + ln A
A plot of ln k versus 1/T gives a straight line with slope = -Ea/R and intercept = ln A.

An equation relating the rate constants k₁ and k₂ at temperatures T₁ and T₂ can be used to
calculate Ea or the order of the reaction.

ln(k₁ / k₂) = (Ea / R) * (1/T₂ - 1/T₁)

ACTIVATION ENERGY
Activation energy (Ea) is the minimum amount of energy required to initiate a chemical reaction.

Problem:

The rate constant of the first-order reaction is 3.46 × 10⁻² sec⁻¹ at 298 K. What is the rate
constant at 350 K if the Ea for the reaction is 50.2 kJ/mol?
Solution:
Given:
k₁ = 3.46 × 10⁻² s⁻¹
T₁ = 298 K
T₂ = 350 K
Ea = 50.2 kJ/mol = 50,200 J/mol
R = 8.314 J/(mol·K)
Formula (Arrhenius equation in two-temperature form):
ln(k₂/k₁) = (Ea/R) × (1/T₁ – 1/T₂)

Step 1: Reciprocal temperatures

1/T₁ = 1/298 = 0.0033557 K⁻¹
1/T₂ = 1/350 = 0.0028571 K⁻¹
Difference = 0.0004986 K⁻¹

Step 2: Ea/R
Ea/R = 50,200 / 8.314 = 6039.82

Step 3: Multiply values

ln(k₂/k₁) = 6039.82 × 0.0004986 = 3.010

Step 4: Solve for k₂

k₂/k₁ = e^3.010 = 20.30
k₂ = 3.46 × 10⁻² × 20.30 = 0.702 s⁻¹

Final Answer:
The rate constant at 350 K is k₂ ≈ 0.702 s⁻¹
Problem:
Iodine atoms combine to form molecular iodine in the gas phase:
I(g) + I(g) → I₂(g)
The reaction follows second-order kinetics and has a rate constant of 7 × 10⁹ M⁻¹ s⁻¹ at 23°C.

a) If the initial concentration of I was 0.086 M, calculate the concentration after 2

minutes
b) Calculate the half-life of the reaction if the initial concentration of I is 0.60M
and if it is 0.42M

Solution:
Given:
rate constant k = 7.0 × 10^9 M^−1 s^−1 at 23 °C.
1/[A]_t = k t + 1/[A]_0
a) k = 7.00e+09 M^−1 s^−1
[A]_0 = 0.086 M
t = 2 minutes = 120 s
1/[A]_t = k t + 1/[A]_0 = 7.00e+09 × 120 + 1/0.086
k t = 7.00e+09 × 120 = 8.400000e+11
1/[A]_0 = 1/0.086 = 11.627907
So 1/[A]_t = 8.400000e+11 + 11.627907 = 8.400000e+11
[A]_t = 1 / 8.400000e+11 = 1.190476e-12 M

b) t₁/₂ = 1 / (k[A]₀)
Given:
[A]₀ = 0.60 M and k = 7 × 10⁹ M⁻¹ s⁻¹, then
t₁/₂ = 1 / (7 × 10⁹ × 0.60) = 2.4 × 10⁻¹⁰ s
If [A]₀ = 0.42 M, then t₁/₂ = 1 / (7 × 10⁹ × 0.42) = 3.4 × 10⁻¹⁰ s

STANDARD SOLUTIONS
There are certain substances in the lab which are never available in their pure form
(e.g.,concentrated HCl). These substances are called Secondary Standard [Link]
solution of Secondary Standard Substances are known as Secondary Standard Solution.
There are certain substances which are always available in their pure form (e.g. Na2CO3).
These substances are called Primary Standard Substances and the solution of Primary
Standard Substances are known as Primary Standard [Link] process of finding out the
exact concentration of Secondary Standard Solution using a Primary Standard Solution is
known as Standardization.
CONCLUSION:
This assignment on CHEMICAL KINETICS has been successfully completed as part of CIA
3 by the students of BMS R25. Through this work, we have gained a better understanding of
the factors influencing reaction rates and the principles governing chemical kinetics.
Submitted by,
BMS R25 Students.
Department of Bio Medical Sciences.