Reaction

kineticsStates
Chemical Kinetics of

MCQs = 4

Course Outline

 Rate of reaction
 Determination of the rate of a chemical reaction
 Factors affecting rate of reaction
 Specific rate constant or velocity constant
 Units of rate constant
 Order of reaction and its determination
Learning Outcomes
 Define chemical kinetics.
 Explain and use the terms rate of reaction, rate equation, order of reaction, rate constant and rate
determining step.
 Explain qualitatively factors affecting rate of reaction.
 Given the order with respect to each reactant, write the rate law for the reaction.
 Explain what is meant by the terms activation energy and activated complex.
 Relate the ideas of activation energy and the activated complex to the rate of a reaction.
 Explain effects of concentration, temperature and surface area on reaction rates.
 Describe the role of the rate constant in the theoretical determination of reaction rate.

Chemical kinetics
 Rate of reaction
 Mechanism of reaction
 Factor affecting the rate of reaction
 Order of reaction
W.O.F reaction is the fastest
 (a) Rusting of iron
(b) Burning of sulphur

(c) Transition of monoclinic sulphur into rhombic sulphur

(d) Precipitation of barium sulphate
Rate of reaction

 R = [Reactant]

 Always +ive quantity

 Rate of disappearance of reactant = Rate of appearance of product

For the reaction N2 + 3H2 2NH3 the rate of disappearance of H2 is 0.01 molL-1min-1 the rate of
appearance of NH3 would be

(a) 0.01 molL-1min-1 (b) 0.02 molL-1min-1

(c) 0.007 molL-1min-1 (d) 0.002 molL-1min-1

 For reversible reaction at dynamic equilibrium net reaction rate is zero

 Ever change

 Unit = moldm-3sec-1 , molL-1sec-1, atmsec-1

 Change in rate of reaction can be +ive or -ive

 Rf = , Rr =

Method to find out the rate of reaction

i. Volumetric
ii. Gravimetric
iii. Spectrophotometric
iv. Pressure measurement
v. Conductometric
vi. pH meteric

Factors
The rate of a reaction depends on _________
a. Collision frequency c. Collision orientation
b. Collision energy d. All of the above
Which of the following would NOT increase the rate of reaction.
a. Raising the temperature
b. Adding catalyst
c. increasing the volume of the container
d. None of thses
1. Rate of reaction Concertation (More collision)
 Concentrated > Dilute
W.O.F will react at highest rate

(a) 1 mol of A and 1 mol of B in 1L vessel

(b) 2 mol of A and 2 mol of B in 1L vessel

(c) 3 mol of A and 3 mol of B in 1L vessel

(d) 0.1 mol of A and 0.1 mol of B in 1L vessel

2. Nature of reactant:
 Gas > Liquid > Solid (Homogenous > Heterogeneous)
 IA > IIA > IIIA
 Formation of MgO > Formation of CuO
 Neutralization reaction > Rearrangement reaction
 Ionic reaction > Molecular reaction
 Double decomposition reaction > Redox reaction
3. Rate of reaction Surface area (More number of active sites)
 Burning of dust coal > Burning of piece of coal
 Al-powered + NaOH > Al-foil + NaOH
 CaCO3(powered) + Dil.H2SO4 > CaCO3(big piece) + Dil.H2SO4
4. Rate of reaction Temperature
5. Rate of reaction Intensity of light
6. Rate of reaction Pressure
7. Rate of reaction Proper orientation

8. Particle size
9. Rate of reaction No of effective collision
10. Rate of reaction Catalyst
Which of the following is true for the reaction? N2 + 3H2 2NH3

(a) (b)

(c) (d)
 PCl5 PCl3 + Cl2

(a) (b)

(c) (d)
For the reaction N2 + 3H2 2NH3 the rate of disappearance of H2 is 0.01 molL-1min-1 the rate of
appearance of NH3 would be

(a) 0.01 molL-1min-1 (b) 0.02 molL-1min-1

(c) 0.007 molL-1min-1 (d) 0.002 molL-1min-1

Change in conc of the substance is 6.4×10-3 in 10 sec rate of reaction will be

(a) 6.4×10-3 moldm-3sec-1 (b) 6.4×10-4 moldm-3sec-1

(c) 6.4×10-2 moldm-3sec-1 (d) 6.4×10 4 moldm-3sec-1

A gaseous reaction, 2A + B C shows a decrease in pressure from 120 mm to 100 mm in 10 min.
The rate of appearance of C is

(a) 2 mm/min (b) 4 mm/min

(c) 10 mm/min (d) 12 mm/min

For the reaction 2SO2 + O2 2SO3 the rate of disappearance of O2 is 2.0 × 10-4 mol L-1s-1. The
rate of appearance of SO3 is

(a) 2.0 × 10-4 mol L-1s-1 (b) 4.0 × 10-4 mol L-1s-1

(c) 1.0 × 10-4 mol L-1s-1 (d) 6.0 × 10-4 mol L-1s-1
In the formation of sulphur trioxide by the contact process 2SO2 + O2 2SO3 the rate of

reaction is expressed as . The rate of disappearance of SO2 will be

(a) 5.0 × 10-4 mol L-1s-1 (b) - 2.25 × 10-4 mol L-1s-1

(c) 3.75 × 10-4 mol L-1s-1 (d) 50.0 × 10-4 mol L-1s-1

Rate Expression
CO + NO2 CO2 + NO
 R [CO] [NO2] R = k [CO] [NO2]
 k Temperature (does not depend upon the concentration, volume, pressure, catalyst,

Rate Constant
 Unit = (moldm-3)1-n sec-1 (n = order of reaction) (Rate constant of zero order is independent of
concentration)
 R =k specific rate constant ( when [A] = [B] =1)
 The rate of first order reaction X Products, is 7.5 ×10-4 mol L-1s-1 when concentration of X is
0.5 mol L-1s-1. The rate constant of the reaction is

(a) 3.75 × 1 0-4 mol L-1s-1 (b) 2.5 × 10-5 mol L-1s-1

(c) 1.5 × 10-3 mol L-1s-1 (d) 8.0 × 10-4 mol L-1s-1
For third order reaction 3X Y + Z, the initial rate is 5 × 10-2 mol L-1s-1 when the conc of X is
0.1 molL-1. The value of rate constant for the reaction is
(a) 5 × 10-2 mol L-1s-1 (b) 3.25 × 10-2 mol L-1s-1
(c) 1.5 × 10-2 mol L-1s-1 (d) 50 mol-2 L2s-1

Rate determining steps

 Mechanism Path followed by R to form P

 Rate determining step slowest step (Determine rate)
No step is slow than this
Examples:

1. NO2 + CO NO + CO2
Rate = k[NO2]2

Step I NO2 + NO2 NO3 + NO

Step II NO3 + CO NO2 + CO2

2. 3ClO3-1 ClO3-1 + 2Cl-

Rate = k [ClO-]2

Step I ClO- + ClO- ClO2 + Cl- (Rate determining step)

Step II ClO2 + ClO- ClO- + Cl-

3. 2NO2 + F2 2NO2F
Rate = k [NO2][F2]

a) 2NO2 + F2 2NO2F

b) NO2 + F2 NO2F + F (F)

NO2 + F NO2F (S)

c) NO2 + F2 NO2F (S)

NO2 + F NO2F (F)

d) F2 2F (S)

2NO2 + 2F 2NO2F (F)

Order of reaction
 Sum of exponents
  Experimental value
 Depend upon temperature, pressure and concentration
 May be zero, negative and fraction
 Anything in excess not included in order
 Can be find by isolation method
Ways to find out the order
i. Rate equation
ii. Unit of k
iii. Data
iv. Mechanism of reaction
v. Graph

For Hypothetical reaction 2A + B product the rate constant k is equal to 5.6 × 10-6 mol L-1s-1 the
order of reaction is
(a) One (b) Three (c) Zero (d) Two
Which of the following rate laws has the overall order of the reaction equal to 0.5?
(a) r = k [x]1/2[y]1/2[z]1/2 (b) r = k [x]3/2[y]-1 [z]0
(c) r = k [x][y]0[z] -1 (d) r = k [x][y][z]
A reaction has rate law expression as r = k [A]3/2[B]-1/2 the order of reaction is

(a) 1 (b) 2 (c) 3/2 (d) -1/2

For the reaction 2A + B C + D rate of reaction increase eight times when concentration of both
A and B are double. The rate of reaction increase four times when the concentration of B is double

(a) r = k [A]2[B] (b) r = k [A] [B] 2

(c) r = k [A][B] (d) r = k [A]2[B] 2

For a reaction 3A + 2B Products, is given by the rate expression , Rate = k[A][B]2. If A is taken
in excess the order is
(a) 3 (b) 2 (c) 1 (d) 0
Example of zero order reaction
i. Photosynthesis reaction
ii. Photochemical reaction (H2 + Cl2 2HCl) (N2O N2 + 1/2O2)
iii. Reverse of Haber process
iv. Decomposition of HI
v. Enzyme catalyzed reaction(fermentation)
Example of first order reaction
 i. Decomposition of H2O2 in aqueous solution
H2O2 → H2O + 1/2O2
ii. Hydrolysis of methyl acetate in presence of mineral acids.
CH3COOCH3 + H2O → CH3COOH + CH3OH
iii. Inversion of cane sugar in presence of mineral acids.

C12H22O11 + H2O C6H12O6 + C6H12O6

iv. Decomposition of ammonium nitrite in aqueous solution.
NH4NO2 → N2 + 2H2O

v. 2N2O5 2N2O4 + O2
vi. Hydrolysis of diazo derivatives.
C5H5N = NCl + H2O → C6H5OH + N2 + HCl
vii. Radioactivity
viii. Atomization
[i.]
ix. The first order decomposition reaction of N2O5 are written as
Fractional order reaction

i. H2 + Br2 2HBr R = K[H2][Br2]1/2

ii. CHCl3 + Cl2 CCl4 + HCl R = K[CHCl3][Cl2]1/2

Second order reaction:

i. 2NO2 2NO + O2
ii. NO + O3 NO2 + O2
iii. 2NO2 + O3 N2O5 + O2

Third order reaction:

i. 2NO + O2 2NO2
ii. 2FeCl3 + 6KI 2FeI2 + 6KI + I2

Pseudo First order reaction:

i. Hydrolysis of alkyl halide in SN1

ii. Hydrolysis of methyl acetate in presence of mineral acids.

CH3COOCH3 + H2O → CH3COOH + CH3OH
iii. Inversion of cane sugar in presence of mineral acids.

C12H22O11 + H2O C6H12O6 + C6H12O6

2N2O5 NO2 + O2 Rate = k [N2O5]

N2O5 2NO2 + 1/2O2 Rate = k’[N2O5]

Which of the following fact is true

(a) k = k’ (b) k > k’ (c) k > 2k’ (d) 2k = k’

For the reaction 2A + B C + D rate of reaction increase eight times when concentration of both A and B are
double. Th rate of reaction increase four times when the concentration of B is double

(a) r = k [A]2[B] (b) r = k [A] [B] 2

(c) r = k [A][B] (d) r = k [A]2[B] 2

Consider a gaseous reaction having rate expression as rate = k[A] [B]2.if the volume of the vessel is suddenly reduced
to half the initial volume , the rate of the reaction would become …………… time the original rate.

(a) 3 (b) 2

(c) 1/2 (d) 8

Which of the following rate laws has the overall order of the reaction equal to 0.5?

(a) r = k [x]1/2[y]1/2[z]1/2 (b) r = k [x]3/2[y]-1 [z]0

(c) r = k [x][y]0[z] -1 (d) r = k [x][y][z]

A reaction has rate law expression as r = k [A]3/2[B]-1/2 the order of reaction is

(a) 1 (b) 2 (c) 3/2 (d) -1/2

For Hypothetical reaction 2A + B product the rate constant k is equal to 5.6 × 10-6 mol L-1s-1 the order of
reaction is

(a) One (b) Three (c) Zero (d) Two

For a reaction 3A + 2B Products, is given by the rate expression , Rate = k[A][B]2. If A is taken in excess the
order is

(a) 3 (b) 2 (c) 1 (d) 0

For third order reaction 3X Y + Z, the initial rate is 5 × 10-2 mol L-1s-1 when the conc of X is
0.1 molL-1. The value of rate constant for the reaction is
(a) 5 × 10-2 mol L-1s-1 (b) 3.25 × 10-2 mol L-1s-1
(c) 1.5 × 10-2 mol L-1s-1 (d) 50 mol-2 L2s-1
In the presence of acod the intial
(a) 5 × 10-2 mol L-1s-1 (b) 3.25 × 10-2 mol L-1s-1
(c) 1.5 × 10-2 mol L-1s-1 (d) 50 mol-2 L2s-1

Change in concentration of a reactant is plotted against time and the slope determined. The value

of are plotted against (a–x)2 a straight line is obtained. It may be concluded that the reaction is:
(Med-2014)
(A) First order (B) Second order
(C) Third order (D) Zero order
The rate law equation for reaction is given as the reaction is:
(Med-2015)
(A) First order (B) Second order (C) Third order (D) Pseudo first order
Consider the following reaction 2FeCl 3(aq) + 6KI(aq)→2Fe2(aq) + 6KCl(aq) +I2(s) Rate=[ FeCl3]1 [KI]2
Choose the correct molecularity and the order of reaction respectively.
(Med-2017)
A.2 and 2 B.6 and 2 C.8 and 3 D.8 and 2

2N2O5 4NO2 + O2 this reaction is an example of _________ order reaction.

(Eng-2019)

A) 1st B) 2nd C) 3rd D) Zero

The half life of decomposition of a compound is 20 min when the intial conc of compound is double,
half life reduce to 10 mins find the order of reaction t1/t2 = (A1/A2)1-n

Order Rate equation Unit of K Half life Graph

Zero R = K[A]0 moldm-3sec-1

1st R = K[A]1 sec-1

2nd R = K[A]2 mol-1dm+3sec-1

3rd R = K[A]3 mol-2dm+6sec-1


 (Moldm-3)1-nsec-1
 Molecularity
 No of atoms collide with one another and chemical reaction occur
 Theoretical value
 Whole number
 Never be zero, negative or fractional
 Not determine the rate of reaction
 Does depend upon the external factors
 Not more than three
 In multiple step reaction, every step has it own molecularity
 In complex reaction overall rate of reaction is equal to the rate determine step
For an elementary reaction, 2A + B C + D the molecularity of the reaction is
(a) 2 (b) 3 (c) 1 (d) 0
Which of the following is an acceptable value of molecularity?
(a) 5 (b) 0 (c) 3/2 (d) 2
For the reaction , [H2 + Br2 2HBr the rate equation is, rate = k[H2][Br2]1/2. The molecularity and
order of the reaction respectively
(a) 2, 3/2 (b) 3/2,3/2 (c) 1,1 (d) 1, 1/2½
 Method to find out the rate of reaction
[i.] Volumetric
[ii.] Gravimetric
[iii.] Spectrophotometric
[iv.] Pressure measurement
[v.] Conductometric
[vi.] pH meteric

Factors affecting the rate of reaction

The rate of a reaction depends on _________
a. Collision frequency c. Collision orientation
b. Collision energy d. All of the above
Which of the following would NOT increase the rate of reaction.
a. Raising the temperature
b. Adding catalyst
c. increasing the volume of the container
d. None of thses
[1.] Rate of reaction Concertation Concertation Rate of reaction (More collision)
 Concentrated > Dilute
W.O.F will react at highest rate
 (a) 1 mol of A and 1 mol of B in 1L vessel

(b) 2 mol of A and 2 mol of B in 1L vessel

(c) 3 mol of A and 3 mol of B in 1L vessel

(d) 0.1 mol of A and 0.1 mol of B in 1L vessel

[2.] Nature of reactant:

 Gas > Liquid > Solid (Homogenous > Heterogenous)
 IA > IIA > IIIA
 Formation of MgO > Formation of CuO
 Neutralization reaction > Rearrangement reaction
 Ionic reaction > Molecular reaction
 Double decomposition reaction > Redox reaction
[3.] Rate of reactionSurface area Surface area Rate of reaction (More number of active sites)
 Burning of dust coal > Burning of piece of coal
 Al-powered + NaOH > Al-foil + NaOH
 CaCO3(powered) + Dil.H2SO4 > CaCO3( big piece) + Dil.H2SO4
[4.] Rate of reactionTemperature Temperature Rate of reaction
[5.] Rate of reactionIntensity of light Intensity of light Rate of reaction
[6.] Rate of reaction Pressure
[7.] Rate of reaction Proper orientation Pressure Rate of reaction

[8.] Particle size

[9.] Rate of reactionNo of effective collision No of effective collision
[10.] Rate of reaction Catalyst Rate of reaction
Activation Energy
 Min amount of energy required convert the reactant into product
 Min amount of energy required for effective collision
 Ea(R) = Ea(F) ∆H

Exothermic Reaction
  Ea(R) > Ea(F)
 HR > H p
 ER > E p
 ∆H < 0
 Stability of product > Stability of
reactant
 ∆H = -ive

Endothermic raection

 Ea(F) > Ea(R)

 HP > H R
 EP > E R
 ∆H > 0
 Stability of product < Stability of
reactant
 ∆H = +ive

For N2 + 3H2 2NH3 + 22 kcal , Ea is 70 kcals. Ea for is ( Exothermic

reaction)
(a) 92 kcal (b) 70 kcal (c) 48 kcal (d) 22 kcal

An exothermic reaction X Y, has an activation energy 30KJmole-1 if the energy change

during the reaction is - 20KJ mole-1 then the activation energy for the reverse reaction is

(a) -30 kJ (b) 20 kJ (c) 50 kJ (d) 10 kJ

 An endothermic reaction A B has an activation energy as x kJ mol-1 of A. If energy change
of the reaction is y KJ, the activation energy of reverse reaction is

(a) -x (b) x - y (c) x + y (d) y – x

Diagram from page No 482 question 201 In the accompanied diagram, ER , EP, EX represent the
energy of the reactants, Products and activation complex respectively. Which of the following is
the activation energy for backward reaction?
(a) A (b) B (c) C (d) D
The addition of a catalyst to a chemical reaction changes? (Eng-2014)
(a) Enthalpy (b) Entropy (c) Activation energy (d) Free energy
Consider the following reaction (Eng-2015)
A+B+C M+N+O
The fact that enthalpy of M + N + O is higher than that of A + B + C indicates that:
(A) The reaction ex exothermic
(B) The reaction is endothermic
(C)Catalyst for the reaction is unnecessary
(D) The activation energy required for the reverse reaction is higher than for the forward reaction
Higher the activation energy for a reaction: (Eng-2018)
(a) Slow is the rate of reaction
(b)Fast is the rate of reaction
(c) Moderate is the rate of reaction
(d) Activation energy is not related to rate of reaction
For exothermic reversible reaction activation energy for forward direction depends upon
(Eng-2018)

a) Temperature b) nature of reactant

c) Nature of product d) both a and b

Collision theory

 Molecules Collision

Formation of product

Effective collision Proper orientation Sufficient K.E of molecules

No need for formation of H2 Ea

 K.E Ea
The number of colliding molecules of different gases calculated from kinetic molecular theory per liter
per second at standard condition is of the order of magnitude of:
(Eng-2015)
23 29 32 43
(A) 10 (B) 10 (C) 10 (D) 10
Choose the one which is not the assumption of collision theory of reaction rate: (Med-2016)
(a) For chemical reaction to occur molecule/ particles must colloids
(b) For reacting molecules/ Particles must possess a certain minimum amount of energy, the activation of
energy
(c) Every collision is not productive
(d) For hydrogen molecule formation from atoms require specific orientation

Transition state Theory

A+B AB CD

Reactant Transition state Product

(a) Unstable
(b) Cannot be separate, vibrate, rotate, structure like molecule
(c) High energy than R and P
(d) Molecular weight, intermediate distance, definite enthalpies
composition (like molecule)
According to transition state theory the reacting molecules form some kind of hypothetical structure
that loses, (Eng-2017)
(i) The structure
(ii) The ability to rotate
(iii) The ability to vibrate
Choose the correct option:
(a) i & ii (b) ii & iii (c) i & iii (d) i, ii & iii
Reactants in a transition state (Med 2018)
A) Always change to product
B) Return back to reactants
C) May return to reactants or proceeds to form products
D) Are of low energy

Catalyst

 Rate =

 Activation energy =
 Reaction path = Change
 Not consumed
 Recovered chemically
 Use in small amount
Example
 Decomposition of H2O2 = MnO2
 Cracking of crude oil = Fe
 Haber process = Fe2O3 /Mo2O3
 Hydrogenation of Ethene = Ni
 Hydrolysis of ester = HCl
 Oxidation of SO2 = NO2

Types

 Homogenous Catalysis
 Heterogeneous Catalysis
 Enzymatic Catalysis
Sr # Catalysis Enzymes
1 Increase or decrease the rate of a Increase rate of chemical reactions
chemical reaction but remain converting substrate into product
unchanged
2 Inorganic catalyst Organic catalyst or bio catalyst
3 Simple inorganic molecules Complex proteins

4 Positive and negative catalysts Activation enzymes and

Inhibitory enzymes
5 High temp, pressure Mild Temperature,Pressure
6 less sensitive to changes in pH and sensitive to changes in pH and temperature
temperature
7 Required promoter Required cofactor

Catalyst Enzyme
Function Catalysts are Enzymes are proteins that
substances that increase rate of chemical
 Catalyst Enzyme
increase or reactions converting
decrease the rate substrate into product.
of a chemical
reaction but
remain
unchanged.

Nature Catalysts are Enzymes are complex

simple inorganic proteins.
molecules.

Alternate terms Inorganic catalyst. Organic catalyst or bio

catalyst.

Reaction rates Typically slower Several times faster

Specificity They are not Enzymes are highly

specific and specific producing large
therefore end up amount of good residues
producing residues
with errors

Conditions High temp, Mild conditions,

pressure physiological pH and
temperature

C-C and C-H bonds absent Present

Example vanadium oxide amylase, lipase

Activation Energy Lowers it Lowers it

The hydrolysis of urea into ammonia and CO2 takes place in the presence of a catalyst Urease as
shown below (Eng-2013)
A) Homogenous catalysis B) Heterogeneous catalysis
C) Enzyme catalysis D) None of the above
For reversible reaction, the catalyst increases the speed of; (Eng-2019)
A) Forward reaction
B) Reversible reaction
C) Both forward and backward reactions equally
D) Forward reaction to large extent than backward reaction

Contents: Catalyst vs Enzyme

DIFFERENCE BETWEEN ENZYME AND CATALYST

Enzyme
Catalyst
1.
All enzymes are made up of proteins.
Catalysts are small inorganic molecules.
2.
They have complex three dimensional structure.
They have a simple structure.
3.
Enzymes are highly specific in their action.
They catalyze diverse reactions.
4.
They can be regulated by specific molecules which can change conformation and therefore activity.
They are not regulated by any regulator molecules.
5.
They are more sensitive to changes in pH and temperature.
They are less sensitive to changes in pH and temperature.