ECAT / FUNCAT ENTRY TEST

Chemical Kinetics
TOPIC DETAIL
(Complete)
BOOK 1
CHAPTER NO
11 (PTB)

LECTURE NO 27
REACTION KINETICS ECAT / FUNGCAT LECTURE NO 27

REACTION KINETICS

CHEMICAL KINETICS

“The study of rate of a chemical reaction, factors affecting the reaction rates and mechanism of
the reaction is called chemical kinetics or reaction kinetics.” (MCQS)
Mechanism:
“The path of reaction of steps involved in chemical reaction is called mechanism.” (MCQS)
Rate Determining Step:
“If a reaction consists of several steps, one step will be slowest than all other steps. The slowest
step is rate determining step. Other step will not affect the rate. (MCQS)

RATE OF REACTION

“The change in concentration of reactants or products per unit time is called velocity or rate of
chemical reaction.” (MCQS)
Change in concentration ∆C
Rate of reaction = = (MCQS)
Time taken for change ∆t
The unit of rate of reaction is:
–3
mol dm –3 –1
Rate of reaction = = mole dm sec (MCQS)
second

Graph:
REACTION KINETICS ECAT / FUNGCAT LECTURE NO 27

TYPE OF RATES

(i) Average rate (ii) Instantaneous rate

(i) Average Rate:
“The rate of reaction between two specific times is called average rate.”
(ii) Instantaneous Rate:
“The rate at any one instant during a specific interval of time is called instantaneous rate.”
IMPORTANT FEATURES: (MCQS)
• The average rate and instantaneous rate are equal for only one instant in any time interval.
• At first, the instantaneous rate is higher than the average rate.
• At the end of the interval the instantaneous rate becomes lower than the average rate.
• The average rate will be equal to the instantaneous rate when the time interval approaches
zero.

SPECIFIC RATE CONSTANT

Specific rate constant of a chemical reaction is the rate of reaction when the concentrations of
the reactants are unity. (MCQS)
Consider

aA + bB ––––––––→ cC + dD

a b
Rate of reaction = k [A] [B]

This expression is called rate equation. The brackets [ ] represent the concentrations and the
proportionality constant k is called rate constant or velocity constant for the reactions.
–3 –3
Let [A] = 1 mole dm and [B] = 1 mol dm
a b
Rate of reaction = k x 1 x 1 = k.
–3 –1
The unit of rate constant is “mole dm sec ”. (MCQS)
REACTION KINETICS ECAT / FUNGCAT LECTURE NO 27

ORDER OF REACTION

“The sum of exponents of the concentrations of the reacting species in the observed rate law is
called order of reaction.” (MCQS)
Order of a reaction cannot be predicted from a balance equation but must be determined form rate
law which is obtained experimentally.
aA + bB ––––––––→ cC + dD

a b
Rate of reaction = k [A] [B]

The exponent ‘a’ or ‘b’ gives the order of reaction with respect to the individual reactant. Thus
the reaction is of order ‘a’ with respect to A and order of b with respect to B. The overall
order of reaction is (a + b).

ZERO ORDER REACTIONS

“The reactions in which rate of reaction does not depends upon the concentration of any
reactant.” (MCQS)

A ……… Product
o
Rate = k [A]
Rate = k (MCQS)
Unit: mole dm-3.sec-1 (MCQS)
Examples:
(1) All photochemical reactions are of zero order. For example, photosynthesis. (MCQS)
Light
6CO2 + 6H2O ––––––––→ C6H12O6 + 6O2
Chlorophyll
(2) Decomposition of NH3.
W
2NH3 → N2 + 3H2
(3) Decomposition of PH3.
(4) Thermal decomposition of HI.
Gold surface
2HI → H2 + I2

FIRST ORDER REACTION

“The reactions in which rate of reaction depends upon the concentration of only one
substance are called first order reaction.” (MCQS)
REACTION KINETICS ECAT / FUNGCAT LECTURE NO 27
For Examples:
(1) Decomposition of nitrogen pent-oxide involves the following equation.
2N2O5(g) ––––––––→ 2N2O4(g) + O2(g) (MCQS)
The experimentally determined rate equation for this reaction is as follows:
Rate = K[N2O5]
(2) Hydrolysis of tertiary butyl bromide. (MCQS)
CH3 CH3
| |
CH3 –– C –– Br + H2O –→ CH3 –– C –– OH + HBr
| |
CH3 CH3
The rate equation determined experimentally for this reaction is
Rate = k [(CH3)3CBr] (MCQS)
The rate of reaction remains effectively independent of the concentration of water because,
being a solvent, it is present in very large excess. Such type of reactions have been named as pseudo
first order reactions.
(3) Hydrolysis of sugar. (MCQS)
H+
C12H22O11 + H2O → C6H12O6 + C6H12O6
Glucose Fructose
(4) 2H2O2 → 2H2O + O2

SECOND ORDER REACTIONS

“The reactions in which rate of reaction depends upon the concentration of three
molecules.” (MCQS)
For Example:
(1) The rate equation for this reaction is which shows that it is second order reaction.
NO(g) + O3(g) ––––––––→ NO2(g) + O2(g)

Rate = k [NO] [O3]

Third Order Reaction:
“The reactions in which rate of reaction depends upon the concentration of three
molecules.” (MCQS)
For Example:
(1) Consider the following reaction.
2FeCl3(aq) + 6KI(aq) ––––––––→ 2Fel2(aq) + 6KCI(aq) + I2
2
Rate = k [FeCl3] [KI]
REACTION KINETICS ECAT / FUNGCAT LECTURE NO 27
Fractional Orders:
The order of a reaction is usually positive integer or a zero, but it can also be in fraction
or can have a negative value. (MCQS)
Consider the formation of carbon tetrachloride from chloroform.
CHCI3(l) + Cl2(g) ––––––––→ CCl4(l) + HCl(g)

Rate = k [CHCl3] [Cl2]½ (MCQS)

The sum of exponents will be 1 + ½ = 1.5, so the order of this reaction is 1.5.

HALF LIFE PERIOD

“Half life period of a reaction is the time required to convert 50% of the reactants into products.”
(MCQS)

o
half life period for the decomposition of N2O5 at 45 C is 24 minutes
Suppose:

After 24 min After 24 min

0.10 mole.dm initial conc -----------------0.05 mole.dm --------------------0.025 mole.dm-3 etc
-3

235 8
• The disintegration of radioactive 92 U has a half–life of 7.1 x 10 years or 710 million years

• For zero order reaction half-life depends upon 1st power of initial concentration of reactant.

[t½]0 ∞ a° , Since [t½]0 = a (2k) (MCQS)

• For first order reaction half-life is independent upon initial concentration of reactants.
1 0.693
[t½]1 ∞ o , Since [t½]1 = (MCQS)
a k

• For 2nd order reaction half-life period is inversely proportional to the initial concentration of
reactants.
1 1
[t½]2 ∞ 1 , Since [t½]2 = (MCQS)
a ka

• For 3rd order reaction half-life is is inversely proportional to the square of initial concentration
of reactants.
1 1.5
[t½]3 ∞ 2 , Since [t½]3 = 2 (MCQS)
a ka
REACTION KINETICS ECAT / FUNGCAT LECTURE NO 27
Calculate the half–life period of the following 2nd order reaction when the initial
MCQS
concentrations is 0.05 M.
2HI(g) H2(g) + I2(g)

k = 1.0 dm3 mol–1 s–1

A). 20 sec C). 10 sec

B). 30 sec D). 40 sec

Solution:

RATE DETERMINING STEP

The slowest step is called the rate determining or rate limiting step. (MCQS)
The number of molecules (reacting species) taking part in the rate determining steps appear in the rate
equation of the reaction.
Let us consider the following reaction.
NO2(g) + CO(g) ––––––––→ NO(g) + CO2(g)
The rate equation of the reaction is found to be
2
Rate = k [NO2]
The proposed mechanism for this reaction is as follows.
Slow
NO2(g) + NO2(g) ––––––––→ NO3(g) + NO(g) (Rate determining step)
Fast
NO3(g) + CO(g) ––––––––→ NO2(g) + CO2(g)

DETERMINATION OF THE RATE OF A CHEMICAL REACTION

Some of the methods used for this purpose are the following: (MCQS)

1. Spectroscopy: (Reaction involves absorption of UV, Visible and IR radiation by

reactant or product)

2. Electrical Conductivity Method: (Reactions involve change in concentration by

flow of electricity)
REACTION KINETICS ECAT / FUNGCAT LECTURE NO 27
3. Dilatometric Method: (Involve small volume change)
4. Refractrometric Method: (Involve change in refractive indices of the substance)
5. Optical Rotation Method: (Involve rotation of plane polarized light by the
substance)
6 Titration (Involve all types of titrations such as redox and acid-base titrations)
7 Method of initial rates

COLLISION THEORY AND ENERGY OF ACTIVATION

• For a chemical reaction to take place molecules must collide with one another.

• Only effective collision can give rise to the products otherwise the colliding particles just
bounce back.

• The effective collisions can take place only when the colliding particles will possess certain
amount of energy and they approach each other with the proper orientation.
• “The minimum amount of energy, in addition to the average kinetic energy, which the
particles must have for effective collision is called activation energy.”
• Activated complex is an unstable combination of all the atoms involved in the reaction for
products immediately. It has a transient existence, that is why it is also called a transitions state.

ACTIVATION ENERGY FOR EXOTHERMIC

AND ENDOTHERMIC REACTIONS

Energy of activation of a reaction provided a valuable information about the way a reaction
takes place and thus helps to understand the reaction.
REACTION KINETICS ECAT / FUNGCAT LECTURE NO 27

FINDING THE ORDER OF REACTION

Order of a reaction can be determined by the following methods.

1. Method of hit and trial 2. Graphical method 3. Differential method
4. Half–life method 5. Method of large excess
1. Half – Life Method:
Let us perform a reaction twice by taking two different initial concentrations ‘a1’ and ‘a2’

and their half–life periods are found to be t1 and t2 respectively.

 t1 
log  
 t2 
n = 1+ (MCQS)
 a2 
log  
 a1 

So if we know the two initial concentrations and two half–life values we can calculate the
order of reactions (n) (MCQS)

MCQS In the thermal decomposition of N2O at 76oC the time required to decompose half
of the reactant was 255 seconds at the initial pressure of 290 mm Hg and 212
seconds at the initial pressure of 360 mm Hg. Find the order of this reaction.
A). n=3 C). n=0

B). n=2 D). n=1

Solution:
a1 = 290 mm Hg t1 = 255 seconds

a2 = 360 mm Hg t2 = 212 seconds

 t1 
log 
 t2 
n = 1+
 a2 
log  
 a1 

log 
255 
 212 
n = 1+
log 
360 
 290 
0.0802
n = 1+
0.0940

n = 1 + 0.85 = 1.85 = 2
REACTION KINETICS ECAT / FUNGCAT LECTURE NO 27

FACTORS AFFECTING RATE OF REACTION

All the factors which change the number of effective collisions per second, affect the rate of a
chemical reaction. Some of the important factors are as follows.

1. Nature of Reactants:

• Ionic compounds = Rate faster

• Covalent compounds = Rate slower

2. Concentration of Reactants:

Rate α Concentration of reactants

Combustion that occurs slowly in air (21% oxygen) will occur more rapidly in pure oxygen

3. Surface Area:

Rate α Surface area

Al foil reacts with NaOH moderately when warmed but powdered Al reacts rapidly with cold
NaOH and H2 is evolved with frothing.

4. Light:

Rate α Intensity of light (Provide energy for reaction)

The reaction of CH4 and Cl2 required light.

Sunlight
CH4 + Cl2 ––––––––→ CH3Cl + HCl

5. Effect of Temperature:

Rate α Temperature

• Rate normally doubles for every 10 K increase in temperature.

• The effect of temperature is further studied by two scientist

• Max-well Boltzmann’s curves

REACTION KINETICS ECAT / FUNGCAT LECTURE NO 27

Arrehenius Equation

–Ea/RT
K = Ae (MCQS)

CATALYST

“The substance which alters the rate of a chemical reaction is called catalyst.” (MCQS)

A catalyst is often present in very small amount.

There are two types of catalyst.

(i) Positive catalyst (ii) Negative catalyst

(i) POSITIVE CATALYST

“The substance which increase the rate of reaction is called positive catalyst.” (MCQS)

For example, the reaction between H2 and O2 in very slow at ordinary condition of
temperature but proceed more rapidly in the presume of platinum catalyst.

Pt
2H2 + O2 ––––––––→ 2H2O

Graph of Catalysis
REACTION KINETICS ECAT / FUNGCAT LECTURE NO 27

(ii) NEGATIVE CATALYST

When the rate of reaction is retarded by adding a substance, then it is said to be a

negative catalyst or inhibitor. For example, tetraethyl lead is added to petrol, because it saves
the petrol from pre–ignition. (MCQS)

AUTO CATALYSIS

“In some reactions, a product formed act as catalyst and this phenomena is called auto
catalysis.” (MCQS)

For Examples;
(i) In hydrolysis of ethyl acetate, acetic acid acts as catalyst for further reaction,
(MCQS)
H3 O+
CH3COOC2H5 + H2O CH3COOH + C2H5OH (MCQS)

(ii) When copper is allowed to react with nitric acid, the reaction is slow in the beginning. It
gains the speed gradually and finally becomes very fast. This is due to the formation of
nitrous acid (HNO2) during the reaction, which accelerates the process.

(iii) The reaction of oxalic acid and acidified KMnO4 is slow at the beginning, but after
2+
sometime Mn are produced in the reaction, which speed up the reaction.
2+
Mn
2KMnO4 + 3H2SO4 + 5H2C2O4 ––––––––→ K2SO4 + 2MnSO4 + 8H2O + 10CO2

PROMOTER OR ACTIVATOR

“Such a substance which promotes the activity of a catalyst is called a promoter or an

activator. It is also called “catalyst for a catalyst”. (MCQS)

For Examples:

(a) Hydrogenation of vegetable oils is accelerated by nickel. The catalytic activity of nickel
can be increased by using copper and tellurium.

(b) In Haber’s process for the manufacture of ammonia, iron is used as a catalyst. If small
amounts of some higher melting oxides like aluminum oxide, chromium oxide or rate
earth oxides are added, they increase the efficiency of iron.
REACTION KINETICS ECAT / FUNGCAT LECTURE NO 27
Catalysis:

“The reactions which take place in the presence of catalyst are called catalysis.”
(MCQS)

There are two types of catalysis.

(i) Homogeneous catalyst (ii) Heterogeneous catalyst

(i) Homogeneous Catalyst:

“In the process, the catalysts and reactants have same phase and the reacting system is
homogeneous throughout.” (MCQS)

For Examples:

(i) The formation of SO3 from SO2 and O2 in the lead chamber process for the manufacture of
sulphur acid, needs NO as a catalyst. Both the reactants and the catalyst are gases.

NO(g)
2SO2(g) + O2(g) 2SO3(g)

(ii) Esters are hydrolyzed in the presence of H2SO4. Both the reactants and the catalyst are in
the solution state.

H3 O+
CH3COOC2H5(aq) + H2O(l) CH3COOH(aq) + C2H5OH(aq)

(ii) Heterogeneous Catalysis:

“If the catalyst and reactants have different phases, it is called heterogeneous catalysis.”
(MCQS)

Mostly the catalyst is in the solid phase, while reactants are in the gaseous or liquid phase.

For Examples:

(i) Oxidation of ammonia to NO in the presence of platinum gauze helps us to manufacture

HNO3.

Pt
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)

(ii) Hydrogenation of unsaturated organic compounds are catalyzed by finely divided Ni.

Ni
CH2 = CH2(g) + H2(g) CH3 – CH3(g)

ZnO – Cr2O3(s)
(iii) CO(g) + 2H2(g) → CH3OH(l)
REACTION KINETICS ECAT / FUNGCAT LECTURE NO 27

CHARACTERISTIC OF CATALYST

There are many types of catalyst with varying chemical compositions, but the following
features are common to most of them.
1. A catalyst remains unchanged in mass and chemical compositions at the end of reaction.
2. It may not remain in the same physical state.
3. Sometimes we need a traces amount of a metal catalyst to affect very large amount of
reactants.
4. A catalyst is more effective when it is present in a finely divided form.
5. A catalyst cannot affect the equilibrium constant of a reaction but it helps the equilibrium
to be established earlier.
6. A catalyst cannot start a reaction, which is not thermodynamically feasible.
7. The mechanism of a catalyzed reaction is different from that of an un–catalyzed reactions.
8. A catalyst is specific in its action.
9. Temperature decrease the catalytic activity of a catalyst.
10. “Deactivation of catalyst by small amount of impurities is called poisoning of a catalyst.”
(MCQS)

ENZYME CATALYSIS

• Enzyme are complex proteins which catalyzed the chemical reactions in living systems
(MCQS). They are often called biological catalysts or biocatalysts.

• The reaction in which enzymes are used as catalyst are called enzyme catalysis.

• Many enzymes have been identified and obtained in the pure crystalline state.

• However, first enzyme was prepared in the laboratory in 1969.

For Examples:

(a) Urea undergoes hydrolysis into NH3 and CO2 in the presence of enzyme urease present
in soybean.

O
|| Urease
H2N – C – NH2 + H2O ––––––––→ 2NH3 + CO2

(b) Concentrated sugar solution undergoes hydrolysis into glucose and fructose by an enzyme
called invertase, present in the yeast.

Invertase
C12H22O11 + H2O ––––––––→ C6H12O6 + C6H12O6

(c) Glucose is converted into ethanol by the enzyme zymase present in the yeast.
REACTION KINETICS ECAT / FUNGCAT LECTURE NO 27
Zymase
C6H12O6 ––––––––→ 2C2H5OH + 2CO2

MODE OF ENZYME ACTION

In 1913, Lenore Michaels and his student M.L. Manton, studied the mechanism of enzyme catalysis.
E+S ES

ES ––––––––→ P + E

Where E = Enzyme, S = Substrate

ES = Activated complex (Reactant)
P = Product

CHARACTERISTICS OF ENZYMES CATALYSIS

The role of enzymes as catalysts is like inorganic heterogeneous catalysts. They are unique in
their efficiency and have a high degree of specificity.

For Examples:

(a) Enzymes are the most efficient catalysts known and they lower the energy of activation of
a reaction.

(b) Enzyme catalysis is highly specific, for example, urea’s catalyses the hydrolysis of urea
only and it cannot hydrolyze any other amide even methyl urea.

(c) Enzyme catalytic reactions have the maximum rates at an optimum temperature.

(d) The pH of the medium also control the rates of the enzyme catalyzed reactions and the
rate passes through a maximum at a particular pH, known as an optimum pH. The
activity of enzyme catalyst is inhibited by a poison.

(e) The catalytic activity of enzymes is greatly enhanced by the presence of a co–enzyme or
activator.

Co–enzyme:
REACTION KINETICS ECAT / FUNGCAT LECTURE NO 27
“A substance needed by enzyme in order to function is called co–enzyme.” (MCQS)
REACTION KINETICS ECAT / FUNGCAT LECTURE NO 27

Q.1 Multiple choice questions:

(i) In zero order reaction, the rate is independent of:

(a) temperature of reaction (b) concentration of reactants

(c) concentration of products (d) none of these

(ii) If the rate equation of a reaction 2A + B → products is, rate = k[A]2[B], and A is present in
large excess, then order of reaction is:

(a) 1 (b) 2

(c) 3 (d) none of these

(iii) The rate of reaction:

(a) increases as the reaction proceeds

(b) decreases as the reaction proceeds

(c) remains the same as the reaction proceeds

(d) may decrease or increase as the reaction proceeds

(iv) With increase of 10°C temperature the rate of reaction doubles. This increase in rate of
reaction is due to:

(a) decrease in activation energy of reaction.

(b) decrease in the number of collisions between reactant molecules.

(c) increase in activation energy of reactants.

(d) increase in number of effective collisions.

(v) The unit of the rate constant is the same as that of the rate of reaction in:

(a) first order reaction (b) second order reaction

(c) zero order reaction (d) third order reaction

ANSWERS

Answers Reasons
REACTION KINETICS ECAT / FUNGCAT LECTURE NO 27

(i) (b) The reaction whose rate is independent of concentration of reactants is said to
have zero order.

(ii) (a) The substance which is taken in large excess and does not affect the rate of
reaction and the order with respect to that reactant is zero. The order with
respect to “A” is zero and that with respect to “B” is one. Hence overall order
is also one.

(iii) (b) As the reaction proceeds, concentration of reactants decreases and rate of
reaction also decreases.

(iv) (d) The rate of reaction depends upon no of effective collisions between reactant
molecules. For every 10°C rise of temperature no of effective collisions are
almost doubled and so the rate of reaction.

(v) (c) For zero order reaction, rate of reaction is independent of concentration of
reactants.

Hence, Rate = K[Reactants]°

= K×1

Rate = K

For zero order reaction, units of rate and rate constant of reaction are same.