Chemical Kinetics THEORY

Chapter 12
Chemical Kinetics
Chapter Contents
z Rate of Chemical Reaction z Chemical kinetics deals with the rate of the reactions and factors
influencing the rate of a reaction.
z Rate Law or Rate Equation of
a Reaction z Gibb's free energy concerns with the spontaniety of the reaction
whereas the kinetics will deal with the speed of the reaction.
z Integrated Rate Equations z The rate of reaction are affected by light and also by electric and
z Methods to Determine the magnetic fields.
Order of Reaction
RATE OF CHEMICAL REACTION
z Factors Affecting Rate of a
Chemical Reaction [R]0
z Effect of Temperature
– [ R ] – (C2 – C1)
C1 rav = = rinst = d[ P] slope
Collision Theory of Reaction
Concentration
Concentration
z t (t2 – t1) C1 dt
Rates C2 – d[ R ] [P]
rinst = = – slope
dt C2
t rav =  [ P] = C2 – C1
t (t2 – t1)
t1 t2 t t1 t2 t
time time
[Reactant] [Product]
(a) (b)
Rate of reaction is defined as the speed with which the reactants are
converted into products at a given time. It may be expressed as the
change in concentration of any one reactant or product per unit time.
A  B
Decrease in conc. of A Increase in conc. of B
Rate = =
time taken time taken
–Δ  A  Δ B 
Rate = =+
Δt Δt
Negative sign with the reactant concentration is to nullify the minus sign
of change of concentration of the reactants and to make the rate a
positive term.
H2 + I2  2HI
Δ H2  Δ I2  1 Δ HI

Rate =  =  =+
Δt Δt 2 Δt
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158 Chemical Kinetics NEET
For a general chemical transformation,

nA + mB  pC + qD
The rates of disappearance of reactants and rates of appearance of products are equalized by dividing them
with the coefficients in the balanced chemical equation. Thus,
1 [A] 1 [B] 1 [C] 1 [D]

 
  
n t m t p t q t
Average and Instantaneous rate of reaction : By dividing the total change in concentration of reactant
or product by a time interval, we actually get the average rate of the reaction. The instantaneous rate is
obtained when a very small change in concentration (dC) is divided by very small time interval (dt). It is
assumed that in dt time, the rate of the reaction remains constant. Thus, instantaneous rate,
dC

dt
Let us consider the change,
2SO2(g) + O2(g)  2SO3(g)
the rate of the reaction can be represented by
1 d[SO2 ] d[O2 ] 1 d[SO3 ]

  
2 dt dt 2 dt
The theoretical rate of a reaction is given by law of mass action. Thus, for the general chemical change
mA + nB  Products
dx
Theoretical Rate   k[A]m  [B]n
dt
The observed rate of reaction is given by the kinetic study of the reaction.
Rate can be measured by plotting a curve between concentration of reactant and time and drawing a tangent
at a specified time. Rate at time t
dx
=– = slope of the tangent
dt
conc
dx
dt
time
Example 1 : For a reaction, 2A + B 3C , the rate of appearance of C at time t is 1.2 × 10–4 mol L–1 s–1.
Find the rate of reaction.
d[C]
Solution : = 1.2 × 10−4
dt
1 d[C] 1 −4
Rate of reaction = = × 1.2 × 10
3 dt 3
–5 –1 –1
= 4 × 10 mol L s .
NEET Chemical Kinetics 159
Example 2 : The decomposition of NH3 on platinum surface is a zero order reaction. What would be the rate
–4 –1 –1
of production of N2 and H2 if k = 2.5 × 10 mol L s ?
Solution : For zero order reaction
Rate of reaction = Rate constant (k)
2NH 3 N2 + 3H2
d[N2 ]
Rate of reaction =
dt
–4 –1 –1
Hence, rate of production of N2 = 2.5 × 10 mol L s
1 d[H2 ]
Again, Rate of reaction =
3 dt
d[H2 ]
= 3 × Rate of reaction
dt
–4
= 3 × 2.5 × 10
–4 –1 –1
= 7.5 × 10 mol L s
Law of Mass Action :

z (Guldberg and Waage Law): The rate at which a substance reacts is proportional to its active mass
(molar concentration) and the rate of a reaction is directly proportional to the product of molar concentrations
raised to the powers equal to the number of participating molecules A  B.
z For the reaction, 2A + 3B  products, theoritically.
Rate  [A]2 [B]3 or Rate = k[A]2[B]3, where k is called specific reaction rate or velocity constant. It is
defined as the rate of the reaction at a given temperature when the molar concentration of each reactant
at a given temperature is unity.
RATE LAW OR RATE EQUATION OF A REACTION

The mathematical expression which gives a relation between rate of the reaction and concentrations of reactants
is known as rate law or rate equation. The rate law is established by the kinetic study of a reaction
experimentally.
Let us consider a general reaction
mA + nB  pC + qD
dx
 [A]a  [B]b
dt
dx
or  k [A]a  [B]b
dt
The reaction is said to be of 'a' order with respect to reactant 'A' and of 'b' order with respect to
reactant 'B'.
The overall order of the reaction is (a+b).
Thus rate law is given by experimental observation. Sometimes for elementary or simple reactions rate law
can be written according to law of mass action.
Molecularity of a Reaction
It is defined as the number of reactant species which collide simultaneously to form the products. It is always
a positive integer like 1, 2, 3, ..... Higher molecularity (> 3) are rare because chances of colliding more than
three molecules at a time are very less. Molecularity is defined only for elementary (one step) reactions. There
is no meaning of molecularity for complex (reactions occurring in more than one steps) reactions.
Order of Reaction :
z The order of a reaction with respect to a reactant is the power of the concentration term of that reactant
to which the rate of the reaction is directly proportional.
z The overall order of a reaction is the sum of the powers or exponents to which the concentration terms
are raised in the rate law expression.
Let us consider a general reaction
aA + bB  pC + qD
If the rate law for this reaction comes out to be
dx
 k [A]m  [B]n ,
dt
m is the order of reaction with respect to A and n is order of the reaction with respect to B.
then, the overall order of the reaction is m + n.
z Order of a reaction is always experimentally determined quantity.
z Order of a reaction cannot be written from the balanced chemical equation.
z Order of a reaction may be zero, whole number, fractional or even negative.
Molecularity and order of a reaction may be the same for bimolecular or termolecular reactions..
z Order is defined for elementry as well as complex reactions.
2
Example 3 : The form of the rate law for a reaction is expressed as : Rate = k[Cl2] [NO] . Find out the order
of reaction with respect to Cl2 and with respect to NO and also the overall order of reaction.
Solution : Order with respect to Cl2 = 1
Order with respect to NO = 2
Overall order = 3
EXERCISE
1. For the reaction,
2N2O5  4NO2 + O2
Select the correct statement

(1) Rate of formation of O2 is same as rate of formation of NO2
(2) Rate of disappearance of N2O5 is two times the rate of formation of NO2
(3) Rate of formation of O2 is 0.5 times rate of disappearance of N2O5
(4) Rate of formation of NO2 is equal to rate of disappearance of N2O5
dx
2. = K [A]0.5 [B]0.5 [c]0.5. What will be the order of the reaction?
dt
(1) 1
(2) 1.5
(3) Zero
(4) 2
3. H2 + I2  2HI (An elementary reaction)
If the volume of the container containing the gaseous mixture is increased to two times, then final rate of the
reaction
1
(1) Become four times (2) Become th of the original rate
4
1
(3) Become 2 times (4) Become of the original rate
2
4. In a certain reaction shown below,
4A + 2B  3C
If rate of formation of C is 9.6 × 10–2 mol/L s. What will be rate of reaction?
(1) 9.6 × 10–2 mol/L s
(2) 3.2 × 10–2 mol/L s
(3) 2.4 × 10–2 mol/L s
(4) 4.8 × 10–2 mol/L s
H2O2 + 2H+ + 3I–  I3– + 2H2O
Select the correct statement
(1) Rate of disappearance of H2O2 will be three times the rate of disappearance of I–
1
(2) Rate of disappearance of H2O2 is of rate of formation of I3–
3
(3) Rate of disappearance of I– ions will be three times the rate of formation I3– ions
1
(4) Rate of formation of H2O is of rate of formation of I3–
2
6. The value of rate constant depends upon
(1) Temperature (2) Concentration
(3) Catalyst (4) Both (1) & (3)
INTEGRATED RATE EQUATIONS

1. Zero Order Reaction
The reaction whose rate does not depend upon the concentration of reactants is called a zero order reaction.
If the hypothetical chemical change.
A  B is a zero order reaction, then,
dx
 k [A]0  k , a constant
dt
Unit of Zero Order Rate Constant

dx
 k [A]0
dt
dx Change in concentration
or k 
dt Time interval
Mole / litre
=
Sec
Example of Zero Order Reaction
z Decomposition of hydrogen iodide(g) and ammonia(g) on metal surfaces.
z Combination of hydrogen and chlorine gases in the presence of sun light.
Sun light
H2 (g)  Cl2 (g)  2HCl(g)
dx
 k[H2 ]0 [Cl2 ]0
dt
2. First order reaction
If a general reaction A  B,
dx
Follows first order kinetics, then its rate law is,  k[A]
dt
where k is the rate or velocity constant.
Units of k : (rate constant) Rate = k [A]
Rate mol L1 L

k    s 1
[A] mol s
Integral rate equation for first order reactions: A  Products, dx/dt is rate of reaction; a is initial conc.
while (a – x) is the concentration after time t i.e. x is the reacted amount in time t.
dx dx
 (a  x),  k (a  x)
dt dt
on integrating –ln (a – x) = kt + I
When t = 0, x = 0
I = –ln a
–ln (a – x) = kt – ln a
a
kt = ln a – ln (a – x) = ln
ax
2.303 a
k log
t ax
z Example of first order reactions
(i) Decomposition of H2O2 in aqueous solution
1
H2O2  H2O + O2
2
(ii) Hydrolysis of Methyl acetate in presence of mineral acids.
Acid
CH3COOCH3  H2O   CH3COOH  CH3OH
(iii) Inversion of cane sugar in presence of mineral acids
Acid
C12H22O11  H2O   C6H12O6  C6H12O6
(iv) Radioactive decay
226 222 4
88 R  86 Rn  2 He
Radium Radon   particle
(v) Decomposition of nitrogen pentaoxide in CCl4 solution, N2O5  2NO2 + ½ O2

Half Life Period (t1/2) : The time in which half of the initial amount of reactants is converted to products or
the time taken for 50% completion of reaction is known as half life period.
z For zero order reaction A  Products
d(a  x) dx
  k(a  x)0
dt dt
dx
 k
dt
 x = kt
a
 t1/2  2 a
k 2k
z For first order reaction
2.303 a
k log
t ax
0.693
t1/2 
k
Pseudo-Unimolecular Reactions
Those first order reactions whose molecularity is not one are called Pseudo-unimolecular reactions.
Examples :
z Hydrolysis of an ester :

H
CH3COOC2H5 + H2O  
 CH3COOH + C2H5OH
dx
 k[CH3COOC2H5 ]
dt
So, order of the reaction is one.
Example 4 : The t1/2 of first order reaction is 60 minutes. What percentage will be left after 240 minutes?
0.693 0.693
Solution : k= =
t1/2 60
2.303 [A ]
t= log 0
k [A t ]
2.303 [A ]
240  log 0
 0.693  [A t ]
 
 60 
4  0.693 [A ]
 log 0
2.303 [A t ]
A0
At = = 0.0625 [A 0 ]
16
[At] = 6.25% of [A0]
–3 –1
Example 5 : A first order reaction has a specific reaction rate of 10 s . How much time will it takes for
10 g of the reactant to reduce to 2.5 g?
2.303 [A ]
Solution : k= log 0
t [A t ]
2.303 10
t= −3
log
10 2.5
t = 2303 × 0.301 × 2 = 1386 s.
Example 6 : Half life time for a first order reaction is 25 minutes. What time will be required for 99% completion
of reaction?
Solution : t1/2 = 25 min
0.693 0.693
k= =
t1/2 25
2.303 [A ] 2.303  100 

t = log 0 = log   = 166.16 min
k [A t ]  0.693   1 
 
 25 
EXERCISE
7. 2A + B  C + D
In this reaction, if we double the concentration of A, reaction rate become two times. And in other experiment,
we double the concentration of A and B, reaction rate again become two times. What is the order of this
reaction?
(1) 1
(2) 3
(3) 2
(4) 1.5
8. If the half-life of the first order reaction is 50 s, what will be the value of its rate constant?
(1) 1.38 × 10–2 s–1
(2) 25 s–1
(3) 34.66 s–1
(4) 1.38 × 10–4 s–1
9. In a first order reaction, on plotting a graph between t1/2 and concentration of reactant
(1) A curve is obtained
(2) A straight line is obtained having slope 45°
(3) A straight line is obtained having slope 60°
(4) A straight line parallel to the concentration axis
10. In data given below,
[A] [B] rate
mol/L mol/L mol L–1 s–1
a. 0.02 1.2 3.0 × 10–3
b. 0.04 2.4 6.0 × 10–3
The reaction may be
(1) First order (2) Second order
(3) Pseudo second order (4) Second order w.r.t. A
11. For certain first order reaction, 75% of the reaction complete in 30 min. How much time it require to complete
99.9% of the reaction?
(1) 150 min (2) 100 min
(3) 90 min (4) 300 min
12. In pseudo-order reactions
(1) The actual order of reaction is different from that expected using rate law expression
(2) The concentration of at least one reactant is taken in large excess
(3) The concentration of reactant taken in excess may be taken as constant
(4) All of these
13. The depletion of ozone involves the following steps:
K1

Step 1: O3 O2 + O (fast)
K 2
Step 2: O3 + O 
K
 2O2 (slow)
The predicted order of the reaction will be
(1) 1 (2) 1.5
(3) – 1.5 (4) Zero
METHODS TO DETERMINE THE ORDER OF REACTION
The different experimental methods used for the determination of the rate law, rate constant and order of
reaction are briefly described below :
1. Graphical Method. This method can be used when there is only one reactant. For example consider
the raction
n A  Products
If this reaction is of the first order,
Rate  [A]
or Rate = k[A] ...(i)
So that the plot of rate vs. molar concentration of the reactant would be linear and equation (i) will be
the 'rate law'
If the above reaction is of the second order,
Rate  [A]2
or Rate = k[A]2 ...(ii)
So that the plot of rate vs. [A]2 would be linear and equation (ii) would be the 'rate law' and so on.
Some Typical Linear Plots for the Reactions of Different Orders :

z Plots of rate vs concentrations [Rate = k (conc.)n]
th
Zero order Ist order 2nd order n (n  1) order
Rate
Rate
Rate
Rate
2 n
Concentration Concentration (Concentration) (Concentration)
z Plots from integrated rate equations
th
1
Conc [A]
1
Log [A]
n–1
[A] [A]
Time (t) Time (t) Time (t) Time (t)

z Plots of half-lives vs concentration (t1/2  a1 – n)
th
t1/2 t1/2 t1/2 t1/2
n–1
Concentration Concentration 1/a 1/a
2. Initial Rate Method (Ostwald's isolation method). This method can be used irrespective of the number
of reactants involved e.g., consider the reaction,
n1 A + n2B + n3C —— Products
The method consists in finding the initial rate of the reaction known concentration of the different reactants
(A, B, C,). Now the concentration of one of the reactants is changed (say that of A) taking the
concentrations of other reactants (B and C) same as before. The initial rate of the reaction is determined
again. This gives the rate expression with respect to A and hence the order w.r.t. A. The experiment is
repeated by changing the concentration of B and taking the same concentration of A and C and finally
changing the concentration of C and taking the same concentrations of A and B. These will give rate
expression w.r.t. B and C and hence the orders w.r.t. B and C respectively. Combining the different rate
expressions, the overall rate expression and hence the overall order can be obtained.
Suppose it is observed as follows :
z Keeping the concentrations of B and C constant, if concentration of A is doubled, the rate of reaction
becomes four times. This means that
Rate  [A]2 i.e., order w.r.t. A is 2
z Keeping the concentrations of A and C constant, if concentration of B is doubled, the rate of reaction
is also doubled. This means that
Rate  [B] i.e., order w.r.t B is 1
z Keeping the concentrations of A and B constant, if concentration of C is doubled, the rate of reaction
remains unaffected. This means that rate is independent of the concentration of C i.e, order w.r.t. C
is zero.
Hence the overall rate law expression will be
Rate = k[A]2[B][C]0
 Overall order of reaction = 2 + 1+ 0 = 3
3. Half-life Method : This method is based on the fact that half-change time is inversely proportional to
the initial concentration of reactant raised to the power one less than the order of reaction.
1
i.e., t1/2 
(a)n1
4. Differential Method : When the order of a reaction with respect to a particular component is 'n' and r1
and r2 are the rates of the reaction at different concentrations c1 and c2 of that reactant, then
n
r1  c1 
 
r2  c 2 
Thus, order of reaction with respect to individual reactants is determined.
5. Some reactions which seem to involve very large number of reacting particles, are in fact complex reaction
which take place through a sequence of 2 or more consective steps. The detailed study of various steps
by which reactants change into products is called mechanism of the reaction. The step which contributes
to the over all rate is the slowest step in the sequence. It is called rate controlling step.
2NO2 + F2  2NO2F
slow  fast
NO2 + F2  NO2F + F; NO2 + F  NO2F
It is confirmed by the experimental rate which is given by Rate = k [NO2][F2].

Rate Constant, Velocity Constant or Specific Reaction Rate (k) :
z The rate constant of a reaction is a measure of its rate of reaction. Fast reactions have higher value of
'k' while for slow reactions 'k' is low.
z At a given temperature, the rate constant is equal to the rate of reaction when the concentration of all
the reactants is unity.
z Rate constant, k is not affected by the concentration change of reactions, nor does it depend upon the
initial concentration of a reactant.
z 'k' remains constant throughout the progress of the reaction.
z Positive catalyst increases the value of 'k', the rate constant.
z Rate constant, 'k' is always increased when temperature rises.
z Unit of 'k' depends upon the order of the reaction.
z Unit of k for nth order reaction is (mole L–1)1–n sec–1.
z Expressions for rate constant for reaction of different orders
Reaction Order Rate law equation Rate constant
[A 0 ]  [A]
A  product 0 Rate = k k
t
2.303 [A ]
A  product 1 Rate = k[A] k log 0
t [A]
FACTORS AFFECTING RATE OF A CHEMICAL REACTION
The reaction rate is influenced by the following factors :

z Effect of Concentration : The rate of a reaction depends on the concentration of the reactants according
to rate law expression. Hence, the rate of a reaction decreases as the reaction proceeds towards the
products because the concentration of reactant (s) decreases.
z Nature of Reactants and Products : Chemical reaction which involves complex molecules as reactants
and in which complex molecules are formed as products, proceed at a slower rate. The reason is that,
greater number of bond rearrangements are involved in complex reactants and products which make the
reaction slow. Reactions involving lesser number of bond rearrangements are fast reactions. For example,
oxidation of Fe++ by MnO4– ion in acidic medium takes place faster than the oxidation of oxalate ion
(C2O42–) under the same condition.
5Fe2+ + MnO4– + 8H+  Mn2+ + 5Fe3+ + 4H2O (fast)
2MnO4– + 16H+ + 5C2O42 –  2Mn2+ + 8H2O + 10CO2 (slow)
z Presence of a Catalyst : Generally, a positive catalyst enhances the rate of a reaction by decreasing
the activation energy. But negative catalyst retards a chemical reaction.
Potential energy
Energy of
activation
without
Energy of catalyst
activation
with catalyst
Reaction coordinate
z Surface Area of Solid Reactant : This factor is important for heterogeneous reactions involving a solid
as one of the reactants. The rate of such a reaction increases with increasing surface area of solid reactant,
i.e.,
Rate of reaction  Surface area of solid reactant
For example : Wood shavings burn more rapidly than a log of wood of same mass.
Coal dust burns at a faster rate than large piece of coal.
z Exposure to Radiations : Rates of certain reactions increase by absorption of photons of a particular
radiation. Such reactions are called photochemical reactions. For example, Hydrogen and chlorine
gases do not combine with each other in dark.
EFFECT OF TEMPERATURE
Generally, the rate of a reaction increases with rise of a temperature. It has been found that in most of the
cases, a rise of 10 K in temperature doubles and in some cases triples the rate of a reaction.
Effect of Temperature on Rate Constant (Arrhenius Equation)
k = A. e–Ea/RT
Where A is a constant known as frequency factor, Ea is the energy of activation of the reaction and R is
gas constant. Both A and Ea are the characteristics of the reaction.
log k = log A – Ea/2.303 RT
Ea 1
or log k = –  + log A
2.303R T
Ea
If a plot of log k against 1/T is a straight line, the slope of this line is . Knowing the slope, Ea can
2.303R
easily be evaluated.
–Ea
slope =
2.303 R
log k
1
T
If k1 and k2 are the values of rate constants at temperature T1 and T2, then
k 2 Ea  1 1 
or ln    
k1 R  T1 T2 
k2 Ea 1 1
log    
k1 2.303 R  T1 T2 
Example 7 : The rate constant k for the first order gas phase decomposition of ethyl iodide, C2H5IC2H4 +
HI is 1.60 × 10–5 s–1 at 600 K and 6.36 × 10–3 s–1 at 700 K. Calculate the energy of activation
for this reaction.
Solution : We are given
k1 = 1.60  10–5 s–1 ; T1 = 600 K
k2 = 6.36  10–3 s–1 ; T2 = 700 K
k2 Ea 1 1
We know that log    
k1 2.303 R  T1 T2 
Substituting the values of k1, k2 and R ( = 8.314 JK–1 mol–1), we get,
6.36  10 3 Ea  1 1 

2.303  8.314  600 700 
log 5 =
1.60  10
Ea
log (3.98  102) =
(19.15)  ( 4200 )
 Ea = 2.6  19.15  4200 J mol–1 = 2.09  105 J mol–1 = 209 kJ mol–1
Example 8 : Rate constant k of a reaction varies with temperature according to the equation
Ea ⎛ 1 ⎞
log k = constant − ⎜ ⎟
2.303 R ⎝ T ⎠
where Ea is the energy of activation for the reaction. When a graph is plotted for log k versus
1
, a straight line with a slope –6670 K is obtained. Calculate the energy of activation for this
T
reaction.
−Ea
Solution : Slope of the line = = –6670 K
2.303R
Ea = 2.303 × 8.314 × 6670
= 127.7114 kJ/mol
COLLISION THEORY OF REACTION RATES
According to collision theory the reactants (atoms, ions or molecules) collide with one another to bring about
the chemical change. The number of collisions that take place per second per unit volume in the reaction
mixture is called collision frequency, z. The collisions which bring about the chemical reactions are known
as effective collisions.
The effective collisions are those which fulfill the following two conditions.
(1) Energy condition : The minimum amount of energy possessed by the colliding molecules to bring
about the chemical change is called threshold energy, ET.
(2) Proper orientation : The reacting molecules must collide in a proper orientation so that the old bonds
break and new bonds are formed. The proper orientation and improper orientation are shown below :
X Y
X Y X Y
+
X Y X Y
X Y
Proper orientation
Hence from collision theory of reaction rates it is concluded that
Rate of reaction  collision frequency (z)
or Rate of reaction = f × z
where, f represents the fraction of the total collisions which are effective.
z Activation Energy
Exothermic Endothermic
(Ea)f ETH (Ea)b (Ea)f ETH (Ea)b
Energy Energy
H H
HR
HR HP
HP
Progress of reaction Progress of reaction
ETH = Threshold Energy
HR = Enthalpy or Energy of reactants.
HP = Enthalpy or Energy of product.
(Ea)f = Activation energy for forward reaction.
(Ea)b = Activation energy for backward reaction.
Note : H = HP – HR, H = (Ea)f – (Ea)b, ETH = HR + (Ea)f or ETH = HP + (Ea)b.
The minimum amount of energy which the colliding molecules must possess as to make the chemical reaction
to occur, is known Threshold Energy.
The minimum amount of energy required by reactant molecules to participate in a reaction is called Activation
energy. (Ea)
Ea = ETH –average K.E. of reacting molecules.
EXERCISE
14. A catalyst cannot change

(1) Rate constant of the reaction
(2) Equilibrium constant of the reaction
(3) Activation energy of reaction
(4) All of these
15. Select the incorrect statement
(1) The minimum amount of energy required by reactant molecules to give product is threshold energy
(2) Activation energy is the sum of threshold energy and average kinetic energy
(3) Threshold energy is the sum of initial potential energy of reactants and activation energy
(4) Lower is the activation energy faster is the reaction
16. If the rate of reaction increases to two times with every 10° rise in temperature, then if we raise the temperature
by 40°, the new rate of the reaction will be
(1) 4 times
(2) 8 times
(3) 16 times
(4) 32 times
17. A + B  C; H = + 60 kJ/mol
Eaf is 150 kJ. What is the activation energy for the backward reaction?
(1) 210 kJ
(2) 105 kJ
(3) 90 kJ
(4) 145 kJ
18.
A
1 C
Energy 2
Reaction progress
(1) It is a 2 steps reaction, step 1 is slower than step 2
(2) It is a 2 steps reaction, step 2 is slower than step 1
(3) Single step reaction where B is a activated complex
(4) Single step reaction in which B is a reaction intermediate
19. The correct expression for Arrhenius equation is (where K is rate constant)
(1) k  eH/RT  A
E a
(2) ln k = + ln A
RT
Ea
(3) ln k = ln A +
RT
A E
(4) ln    a
 k  RT
20. The temperature coefficient of a certain reaction is found to be 3. If temperature changes from 25° to 55°, the
new rate of reaction will be
(1) 8 times (2) 9 times
(3) 16 times (4) 27 times

nt
me nment
sigAnssig
Assignment
As
Assignment
(1) Decrease to 8 times of the initial value
SECTION - A
NCERT Based MCQs (2) Increase to 8 times of the initial value
1. For a zero order reaction, the relationship between (3) Increase to 4 times of the initial value
st nd
t11 t 21 (4) Decrease to 4 times of the initial value
and is [NCERT Pg. 110]
2 2
5. Which of the following given graph represents first
st nd order reaction? [NCERT Pg. 106]
t11  t 21
(1)
2 2
(1)
st nd
t11  2 t 21
(2) t1/2
2 2
nd st
t 21  2t11 [A0]
(3)
2 2
st nd
t11  2 t 21 (2)
(4)
2 2
[At]
2. The rate constant of a reaction is 1.2  10–2 mol–2
L2 s–1. The order of the reaction is
t
[NCERT Pg. 103]
(1) 0
(3)
(2) 1 log [At ]
(3) 2
(4) 3
3. A chemical reaction can never have fractional log t
[NCERT Pg. 103]

(4)
(1) Order
(2) Half-life
[At ]
(3) Molecularity
(4) Rate constant t
4. For the reaction, 2NO(g) + O2(g) 2NO(g), the
volume is suddenly reduced to half of its value by 6. For first order reaction, t93.75% = x  t75%, the value
increasing pressure on it. If reaction is of first order of x will be [NCERT Pg. 107]
w.r.t. O2 and second order w.r.t. NO, the rate of the (1) 10 (2) 6
reaction will [NCERT Pg. 106]
(3) 3 (4) 2
7. The rate of the reaction, 2A + B products is 12. For effective collisions, the condition(s) to be fulfilled
given by the rate expression, rate = k[A]1.5 [B]0.5. is/are [NCERT Pg. 117]
If [A] is 2 molar and [B] is 100 molar, then the
(1) Energy of the colliding molecules should be
order of reaction will be [NCERT Pg. 102] less than threshold energy
(1) 2 (2) 0.5
(2) Colliding molecules must collide in a proper
(3) 1.5 (4) 1.0 orientation
8. Which of the following statement is incorrect? (3) Colliding molecules must possess energy
[NCERT Pg. 97] equal or greater than threshold energy
(1) Average rate of reaction and instantaneous (4) Both (2) & (3)
rate of reaction are always different 13. Select the incorrect statement among the following
(2) Stoichiometry of a reaction tells about the order [NCERT Pg. 117]
of the elementary reaction
(1) Acidic hydrolysis of an ester is a pseudo first
(3) Rate of chemical reactions is independent of order reaction
molecularity of reactions
1
(4) In multistep reactions, the rate determining (2) A plot of log k against has slope equal to
step is the slowest step of the reaction T
9. For the first order reaction, 2.303 R

Ea
A(g)   3B(g)  2C(g). If initial pressure of A is
p0 and after time ‘t’ from the start of reaction, the (3) Catalyst alters the rate of reaction without itself
total pressure is p, then the rate constant of undergoing any permanent chemical change
reaction is given by [NCERT Pg. 106]
(4) Fraction of molecules capable of bringing
effective collisions increases on increasing
1  p0  1  p0 
(1) ln   (2) ln  0  temperature
t  p  t  5 p  4 p 

14. If the activation energy of forward and backward
reactions in a chemical reaction, A B is 15.5
1  4p0  1  4p0  and 22.7 kJ mol–1 respectively, then select the
(3) ln (4) ln
t  p0  5p  t  5p0  p  correct option for the reaction. [NCERT Pg. 113]
(1) H of reaction is 38.2 kJ/mol.
10. A catalyst increases the rate of reaction by
(2) Reaction is always spontaneous
[NCERT Pg. 113]
(3) Reaction is exothermic
(1) Decreasing the value of Arrhenius constant
(4) Reaction is endothermic
(2) Increasing the enthalpy of the reaction
15. For the two first order reactions, rate constants in
(3) Decreasing the activation energy
terms of temperature are given below
(4) Decreasing the rate constant  1500 
 
11. If the rate constant of a reaction is 0.5  106 sec–1  P , k1  1015 e
A  T 
at 50 K and 1.5  106 sec–1 at 100 K. Then the  1000 

 T 
activation energy (Ea) for the reaction is  Q , k 2  1014 e
B  
[NCERT Pg. 115] If initially (t = 0), both reaction started with same
initial concentration of A and B, then at what
(1) 9.135 J mol–1
temperature both the reaction will have same initial
(2) 913.5 J mol–1 rate? [NCERT Pg. 112]
(3) 91.35 kJ mol–1 (1) 217 °C (2) 217 K
(4) 9.135 kJ mol–1 (3) 500 ºC (4) 500 K
6. The rate constant is numerically the same for three
SECTION - B
reaction of first, second and third order respectively.
Objective Type Questions Which one is true for rate of three reaction, if
1. For the reaction A + B  products, it is found that concentration of reactant is greater than 1M?
order of A is 2 and the order of B is 3 in the rate (1) r1 = r2 = r3
expression. When the concentrations of both A and
B are doubled the rate will increase by a factor (2) r1 > r2 > r3
(1) 10 (3) r1 < r2 < r3

(2) 16 (4) All of these
(3) 32 7. The inversion of cane sugar represented by
(4) 28 C 12 H 22 O 11 + H 2O  C 6H 12 O 6 + C 2H 12 O 6 is a
reaction
2. For the hypothetical reaction 2A  3C, the
reaction rate ‘r’ in terms of the rate of change of the (1) Zero order (2) Second order
concentration is given by (3) Bimolecular (4) Pseudo first order
d[A] 8. Consider the data below for a reaction A  B
(1) r  –
dt Time
0 10 20 30
1 d[A] (sec)
(2) r  – Rate 1.60×10
–2
1.60×10
–2
1.60×10
–2
1.59×10
–2
2 dt
1 d[A] From the above data the order of reaction is
(3) r 
3 dt (1) Zero (2) 1
d[A] (3) 2 (4) 3
(4) r 
dt 9. For the reaction N2 + 3H2  2NH3, the rate of
3. If the volume of closed vessel in which the following change of concentration for hydrogen is
simple reaction is carried out is reduced to one –0.3 × 10 –4 Ms –1 . The rate of change of
third of original volume, the rate of reaction concentration of ammonia is
becomes
(1) –0.2 × 104 Ms–1
2NO (g) + O2 (g)  2NO2 (g)
(2) 0.2 × 10–4 Ms–1
(1) One third (2) Three times
(3) 0.1 × 10–4 Ms–1
(3) Nine times (4) Twenty seven times
4. Which order reaction obeys the expression (4) 0.3 × 10–4 Ms–1
t1/2  1/[A]? 10. For the reaction H2O2 + 3I– + 2H+ – 2H2O + I3–, the
(1) First (2) Second effect on the rate of this reaction brought about by
doubling the concentration of I– without changing
(3) Third (4) Zero
the order
(1) The rate would increase by a factor of 3
1
N2O5  2NO2 + O2 . Given, (2) The rate would increase by a factor of 8
2
(3) The rate would decrease by a factor of 1/3
d[N2O5 ]
– = K1 [N2O5] (4) The rate would increase by a factor of 9
dt
d[NO2 ] 1
= K2 [N2O5] 11. The graph between the log k versus is a
dt T
straight line. The slope of the line is
d[O2 ]
and = K3 [N2O5]
dt 2.303R Ea
(1)  Ea (2) 
The relation between K1, K2 and K3 is 2.303R
(1) 2K1 = K2 = 4K3 (2) K1 = K2 = K3 2.303R Ea
(3) Ea (4)
(3) 2K1 = 4K2 = K3 (4) K1 = 2K2 = 4K3 2.303R
12. The rate law of a reaction between the substance (1) It gives rate of disappearance of reactant
A and B is given by, rate = k[A] n [B] m . On
d[C2  C1]
doubling the concentration of A and making the (2) Rate  
volume of B half the ratio of new rate to the earlier t 2  t1
rate of reaction will be (3) Both (1) & (2)
1 (4) It predicts the order of reaction
(1) nm (2) m + n
2 17. The unit of rate constant and rate of reaction are
(3) 2n + m (4) 2n – m same for
13. For a chemical process energies are plotted in graph. (1) First order (2) Zero order
(3) Second order (4) Third order
c 18. The rate of a reaction becomes 2 times for every

Energy
d 10°C rise in temperature. How many times rate of

e
reaction will be increased when temperature is
a increased from 30°C to 80°C?
b
Progress of reaction (1) 16 (2) 32
Which of the following is correct ? (3) 64 (4) 128
(1) It is the exothermic reaction, H = b – a 19. The rate constant, the activation energy and
(2) Threshold energy, e = a + c Arrhenius parameter of a chemical reaction at 25°C
are x s–1, 10x kJ/mol and 2x s–1. Value of rate
(3) (Ea)f < (Ea)b
constant as T   is
(4) All of these
(1) x s–1 (2) 2x s–1
14. Which of the following is correct?
(3)  (4) 10x s–1
k2 Ea  T  20. For a gaseous phase reaction 2A + B2  2AB, the
(1) log   
k1 2.303  T1T2  following rate data was obtained at 300K
(2) For zero order reaction, t 12 is inversely Rate of disappearance Concentration
proportional to initial concentration of B2 (mol/litre min) [A] [B2]

(3) Catalyst decreases the activation energy (i) 1.8 × 10–3 0.015 0.15
(4) All of these (ii) 1.08 × 10–2 0.09 0.15
(iii) 5.4 × 10–3 0.015 0.45
15. The given graph of t 12 vs initial concentration ‘a’ is
The rate constant for the reaction is
for
(1) 0.5 mol–1 min–1 litre (2) 0.8 mol–1 min–1 litre
t1/2 (3) 1.5 mol–1 min–1 litre (4) 2 mol–1 min–1 litre
21. For a homogeneous first order gaseous reaction
a A  B + C + D, the initial pressure was P0 while
(1) First order reaction pressure after time ‘t’ was P if (P > P 0). The
(2) Second order reaction expression for the rate constant K is
(3) Zero order reaction
2.303  2P0 
(4) Can’t predict (1) K  log  
t  3P0  P 
16. Consider the given graph plotted between
concentration Vs time 2.303  3P0 
(2) K  log  
t  2P0  P 
C1 2.303  P 
(3) K  log  0 
Conc.
C2
t  P0  P 
2.303  2P0 
Time (4) K  log  
t1 t2 t  4P0  P 
22. For a first order reaction, the time taken to reduce 29. Temperature coefficient is represented by
1 kT
the initial concentration by a factor of is 10 min.
4 (1) k (2) kT
T+10
If the reduction in concentration is carried out by a
1 k T+10
factor of , then time required (in minutes) will be (3) (4) 10 kT
16 kT
(1) 10 (2) 20 30. Which of the following can change rate constant of
(3) 40 (4) 60 the reaction?
23. With increase in temperature, rate constant (1) Temperature (2) Pressure
increase (3) Catalyst (4) Both (1) & (3)
(1) Only for endothermic reactions 31. Unit of rate constant for first order reaction is
(2) Only for exothermic reactions (1) sec–1 (2) sec
(3) Neither for exothermic nor endothermic (3) mol L–1 s–1 (4) mol–1 L s–1
reactions
32. For a first order reaction, a straight line is obtained
(4) Both for exothermic and endothermic reactions if you plot
24. For the first order reaction,
1
A(g)  2B(g) + C(g) the initial pressure (1) conc. Vs. time (2) conc. Vs.
time
PA = 90 mm Hg, the pressure after 10 minute is
(3) conc. Vs. (time)2 (4) log conc. Vs. time
found to be 180 mm Hg. The rate constant of the
reaction is 33. For an exothermic reaction (H = –60 kJ). If
activation energy for forward reaction is 130 kJ,
(1) 1.15 × 10–3 sec–1 (2) 2.3 × 10–3 sec–1
then activation energy for backward reaction will be
(3) 3.45 × 10–3 sec–1 (4) 4.6 × 10–3 sec–1
(1) 130 kJ (2) 190 kJ
25. The rate constant for the first order decomposition
(3) 70 kJ (4) 10 kJ
of a certain reaction is described by the equation
7.2  103 K 34. The half life for radioactive sample is 1386 s then
log k  9.27  . its decay constant () is
T
The activation energy of reaction is (1) 5 × 10–2 sec–1 (2) 5 × 10–3 sec–1
(1) 2 × 10–3 cal (2) 7.2 × 10–3 cal (3) 5 × 10–4 sec–1 (4) 5 × 10–5 sec–1
(3) 3.32 × 10–2 cal (4) 1.44 × 10–4 cal 35. Correct graph for first order reaction is/are
26. Hydrolysis of ester in basic medium is of

[R]
(1) Zero order (2) First order (1)
(3) Second order (4) Third order
time
27. 5 mg radioactive sample 90% disintegrate in
3 years then 99% disintegration will be in
t1
2
(1) 3 years (2) 3.1 years (2)
(3) 6 years (4) 9 years
[R0]
28. Adsorption of hydrogen gas on metal surface at
high pressure follows t1
2
(1) Zero order
(3)
(2) 1st order
(3) 2nd order [ R0]
(4) 3rd order (4) All of these
6. The correct difference between first and second

SECTION - C
order reactions is that [NEET-2018]
Previous Years Questions (1) The rate of a first-order reaction does not
1. A first order reaction has a rate constant of depend on reactant concentrations; the rate of
2.303 × 10–3 s–1. The time required for 40 g of this a second-order reaction does depend on
reactant to reduce to 10 g will be reactant concentrations
[Given that log102 = 0.3010] (2) The half-life of a first-order reaction does not
depend on [A]0; the half-life of a second-order
[NEET-2019 (Odisha)]
reaction does depend on [A]0
(1) 602 s (2) 230.3 s
(3) The rate of a first-order reaction does depend
(3) 301 s (4) 2000 s on reactant concentrations; the rate of a
2. For a reaction, activation energy Ea = 0 and the second-order reaction does not depend on
rate constant at 200 K is 1.6 × 106 s–1. The rate reactant concentrations
constant at 400 K will be (4) A first-order reaction can catalyzed; a second-
[Given that gas constant, R = 8.314 J K–1 mol–1] order reaction cannot be catalyzed
[NEET-2019 (Odisha)] 7. A first order reaction has a specific reaction rate of
(1) 3.2 × 106 s–1 10–2 s–1. How much time will it take for 20 g of the
reactant to reduce to 5 g? [NEET-2017]
(2) 3.2 × 104 s–1
(1) 238.6 second (2) 138.6 second
(3) 1.6 × 106 s–1
(3) 346.5 second (4) 693.0 second
(4) 1.6 × 103 s–1
8.* Mechanism of a hypothetical reaction
3. If the rate constant for a first order reaction
X2 + Y2  2XY is given below :
is k, the time (t) required for the completion of
99% of the reaction is given by: [NEET-2019] (i) X2 X + X
(1) t = 0.693/k (ii) X + Y2  XY + Y (slow)
(2) t = 6.909/k (iii) X + Y  XY (fast)
(3) t = 4.606/k The overall order of the reaction will be [NEET-2017]
(4) t = 2.303/k (1) 1 (2) 2
4. For the chemical reaction (3) 0 (4) 1.5
(* Modified)

N2 (g)  3H2 (g)
2NH3 (g)
9. The decomposition of phosphine (PH3) on tungsten
The correct option is: [NEET-2019] at low pressure is a first-order reaction. It is
because the [NEET-Phase-2-2016]
1 d[H 2 ] 1 d[NH 3 ]
(1)   (1) Rate is proportional to the surface coverage
3 dt 2 dt
(2) Rate is inversely proportional to the surface
d[N 2 ] d[NH 3 ] coverage
(2)  2
dt dt (3) Rate is independent of the surface coverage
d[N 2 ] 1 d[NH 3 ] (4) Rate of decomposition is very slow
(3)  
dt 2 dt 10. The addition of a catalyst during a chemical
reaction alters which of the following quantities?
d[H 2 ] d[NH 3 ]
(4) 3 2 [NEET-2016]
dt dt
(1) Activation energy (2) Entropy
5. When initial concentration of the reactant is
doubled, the half-life period of a zero order reaction (3) Internal energy (4) Enthalpy
[NEET-2018] 11. The rate of a first-order reaction is 0.04 mol l–1 s–1
at 10 seconds and 0.03 mol l–1 s–1 at 20 seconds
(1) Is halved
after initiation of the reaction. The half-life period of
(2) Is doubled the reaction is [NEET-2016]
(3) Remains unchanged (1) 54.1 s (2) 24.1 s
(4) Is tripled (3) 34.1 s (4) 44.1 s
12. The rate constant of the reaction A  B is (1) Rate = k[A] [B]
0.6 × 10 –3 mole per litre per second. If the
(2) Rate = k[A]2[B]
concentration of A is 5 M, then concentration of B
after 20 minutes is [Re-AIPMT-2015] (3) Rate = k[A] [B]2
(1) 0.36 M (2) 0.72 M (4) Rate = k[A]2[B]2
(3) 1.08 M (4) 3.60 M 19. Which one of the following statements for the order
13. The activation energy of a reaction can be of a reaction is incorrect? [AIPMT (Prelims)-2011]
determined from the slope of which of the following (1) Order of reaction is always whole number
graphs? [AIPMT-2015]
(2) Order can be determined only experimentally
T 1 (3) Order is not influenced by stoichiometric
(1) ln K vs T (2) ln K vs T
coefficient of the reactants
(4) Order of reaction is sum of power to the
ln K 1
(3) vs T (4) ln K vs concentration terms of reactants to express
T T the rate of reaction
14. When initial concentration of a reactant is doubled 20. The unit of rate constant for a zero order reaction
in a reaction, its half-life period is not affected. The is [AIPMT (Mains)-2011]
order of the reaction is [AIPMT-2015]
(1) L2 mol–2 s–1 (2) s–1
(1) More than zero but less than first
(3) mol L –1 s –1 (4) L mol–1 s–1
(2) Zero
21. The half life of a substance in a certain enzyme-
(3) First catalysed reaction is 138 s. The time required for
(4) Second the concentration of the substance to fall from
1.28 mg L–1 to 0.04 mg L–1 is
15. A reaction having equal energies of activation for
forward and reverse reactions has [NEET-2013] [AIPMT (Mains)-2011]
(1) G = 0 (1) 690 s (2) 276 s
(2) H = 0 (3) 414 s (4) 552 s
(3) H =G =S = 0 22. For the reaction, N2O5(g)  2NO2(g) + 1/2 O2(g),
(4) S = 0 the value of rate of disappearance of N2O5 is given
as 6.25×10–3 mol L–1s–1. The rate of formation of
16. What is the activation energy for a reaction if its NO2 and O2 is given respectively as
rate doubles when the temperature is raised from
20C to 35C? (R = 8.314 J mol–1K–1) [NEET-2013] [AIPMT (Prelims)-2010]
(1) 269 kJ mol–1 (2) 34.7 kJ mol–1 (1) 6.25 × 10–3 mol L–1s–1 & 6.25 × 10–3 mol L–1s–1
(3) 15.1 kJ mol–1 (4) 342 kJ mol–1 (2) 1.25 × 10–2 mol L–1s–1 & 3.125 × 10–3 mol L–1s–1
17. In a zero order reaction for every 10° rise of (3) 6.25 × 10–3 mol L–1s–1 & 3.125 × 10–3 mol L–1s–1
temperature, the rate is doubled. If the temperature
(4) 1.25 × 10–2 mol L–1s–1 & 6.25 × 10–3 mol L–1s–1
is increased from 10°C to 100°C, the rate of the
reaction will become [AIPMT (Prelims)-2012] 23. For an endothermic reaction, energy of activation is
Ea and enthalpy of reaction is H (both of these in
(1) 64 times (2) 128 times
kJ/mol). Minimum value of Ea will be
(3) 256 times (4) 512 times
[AIPMT (Prelims)-2010]
18. In a reaction, A + B  Product, rate is doubled
when the concentration of B is doubled, and rate (1) Less than H
increases by a factor of 8 when the concentrations (2) Equal to H
of both the reactants (A and B) are doubled, rate
law for the reaction can be written as (3) More than H
[AIPMT (Prelims)-2012] (4) Equal to zero
24. During the kinetic study of the reaction,

d(Br2 ) 5 d(Br  )
2A+BC+D, following results were obtained (1) 
dt 3 dt
Run [A]/mol L–1 [B]/mol L–1 Initial rate of
formation of d(Br2 ) 5 d(Br  )
D/mol L–1 min–1 (2) 
dt 3 dt
I 0.1 0.1 6.0×10–3
II 0.3 0.2 7.2×10–2 d(Br2 ) 3 d(Br  )
(3) 
dt 5 dt
III 0.3 0.4 2.88×10–1
IV 0.4 0.1 2.40×10–2 d(Br2 ) 3 d(Br  )
(4) 
Based on the above data which one of the following dt 5 dt
is correct ? [AIPMT (Prelims)-2010]
28. Half life period of a first-order reaction is 1386
(1) Rate = K[A]2 [B] seconds. The specific rate constant of the reaction
is [AIPMT (Prelims)-2009]
(2) Rate = K[A][B]
(1) 0.5 × 10–2 s–1
(3) Rate = K[A]2 [B]2
(2) 0.5 × 10–3 s–1
2
(4) Rate = K[A][B]
(3) 5.0 × 10–2 s–1
25. The rate of the reaction, 2NO + Cl2  2NOCl
(4) 5.0 × 10–3 s–1
is given by the rate equation rate = k[NO]2[Cl2]
29. For the reaction A + B  Products, it is observed
The value of the rate constant can be increased by that
[AIPMT (Mains)-2010] (a) On doubling the initial concentration of A only,
(1) Increasing the temperature the rate of reaction is also doubled and
(2) Increasing the concentration of NO (b) On doubling the initial concentrations of both A
and B, there is a change by a factor of 8 in
(3) Increasing the concentration of the Cl2 the rate of the reaction.
(4) Doing all of these The rate of this reaction is given by
26. For the reaction, N2 + 3H2  2NH3, [AIPMT (Prelims)-2009]

(1) Rate = k [A] [B]2
d[NH3 ]
if  2  104 mol L –1 s –1 , the value of (2) Rate = k [A]2[B]2
dt
(3) Rate = k [A] [B]
d[H2 ]
would be [AIPMT (Prelims)-2009] (4) Rate = k[A]2[B]
dt
30. The rate constants k1 and k2 for two different
(1) 4×10–4 mol L–1 s–1 reactions are 10 16 e –2000/T and 10 15 e –1000/T
(2) 6×10–4 mol L–1 s–1 respectively. The temperature at which k1 = k2 is
(3) 1×10–4 mol L–1 s–1 [AIPMT (Prelims)-2008]
(4) 3×10–4 mol L–1 s–1 1000

(1) K
27. In the reaction, 2.303
(2) 1000 K
BrO3 (aq)  5Br  (aq)  6H  3Br2 (l)  3H2O(l)
2000
The rate of appearance of bromine (Br2) is related (3) K
2.303
to rate of disappearance of bromide ions as
following [AIPMT (Prelims)-2009] (4) 2000 K
31. The bromination of acetone that occurs in acid Mechanism B:
solution is represented by this equation
H2(g) + ICI(g)  HCl(g) + HI(g); slow
CH3 COCH3 (aq)  Br2 (aq)  CH3 COCH2Br(aq) HI(g) + ICI(g)  HCl(g) + I2(g); fast
 H (aq)  Br  (aq) Which of the above mechanism(s) can be

consistent with the given information about the
These kinetic data were obtained for given reaction reaction? [AIPMT (Prelims)-2007]
concentrations
(1) A only
Initial concentrations, M
(2) B only
[CH3COCH3] [Br2] [H+]
(3) Both (1) and (2)
0.30 0.05 0.05
(4) Neither (1) nor (2)
0.30 0.10 0.05
34. If 60% of a first order reaction was completed in
0.30 0.10 0.10
60 minutes, 50% of the same reaction would be
0.40 0.05 0.20 completed in approximately (log 4 = 0.60,
log 5 = 0.69) [AIPMT (Prelims)-2007]
Initial rate, disappearance of Br2, M s–1
(1) 40 minutes
5.7 × 10–5
(2) 50 minutes
5.7 × 10–5
1.2 × 10– 4 (3) 45 minutes
3.1 × 10–4 (4) 60 minutes
Based on these data, the rate equation is 35. For the reaction, 2A + B  3C + D. Which of the
following does not express the reaction rate?
(1) Rate = k [CH3COCH3][Br2][H+]
(2) Rate = k [CH3COCH3][H+] d  C d B
(1) – (2) –
3 dt dt
O
(3) Rate = k [ CH 3 C CH 3 ][Br2]
dD d A 
(3) (4) –
(4) Rate = k [CH3COCH3][Br2][H+]2 dt 2dt
32. In a first-order reaction A  B, if K is rate 36. Consider the reaction, N2(g) + 3H2(g)  2NH3(g).
constant and initial concentration of the reactant A
is 0.5M then the half-life is d NH3 
The equality relationship between and
[AIPMT (Prelims)-2007] dt
d H2 
ln2 0.693 – is [AIPMT (Prelims)-2006]
(1) (2) dt
K 0.5K
d NH3  1 d H2 
log 2 (1) 
log2 dt 3 dt
(3) (4)
K K 0.5
d NH3  2 d H2 
33. The reaction of hydrogen and iodine monochloride (2)  
is given as dt 3 dt
H2(g) + 2ICI(g)  2HCl(g) + I2(g)
d NH3  3 d H2 
This reaction is of first order with respect to H2(g) (3)  
dt 2 dt
and ICI(g), following mechanisms were proposed
Mechanism A: d NH3  d H2 
(4) 
H2(g) + 2ICI(g)  2HCl(g) + I2(g) dt dt
37. For a first order reaction A  B, the reaction rate 43. The rate of the reaction, 2N2O5  4NO2 + O2
at reactant concentration of 0.01 M is found to be
can be written in three ways :
2.0 × 10–5 mol L–1 s–1. The half life period of the
reaction is [AIPMT (Prelims)-2005] d[N2 O5 ]
 k[N2O5 ]
(1) 220 s (2) 30 s dt
(3) 300 s (4) 347 s
d[NO2 ]
38. A nuclide of an alkaline earth metal undergoes  k[N2 O5 ]
dt
radioactive decay by emission of three -particles
in succession. The group of the periodic table to
d[O2 ]
which the resulting daughter element would belong  k [N2 O5 ]
is [AIPMT (Prelims)-2005] dt
(1) Group 14 (2) Group 16 The relationship between k and k and between k
and k are
(3) Group 4 (4) Group 6
(1) k = 2k; k = 2k (2) k = k; k = k
39. The rate of reaction between two reactants A and
B decreases by a factor of 4, if the concentration k
of reactant B is doubled. The order of this reaction (3) k = 2k; k = k (4) k = 2k; k =
2
with respect to reactant B is
44. For the following reaction
(1) –1 (2) –2 C6H12O6(aq) + H2(g) C6H14O6(aq)
(3) 1 (4) 2 Which one of the following is not affected by the

addition of catalyst?
Questions asked Prior to Medical Ent. Exams. 2005
(1) Rate of forward reaction
40. A reaction is 50% complete in 2 hours and 75%
complete in 4 hours. The order of reaction is (2) Rate of backward reaction
(1) 0 (2) 1 (3) Time required to reach the equilibrium
(3) 2 (4) 3 (4) Spontaneity
41. Activation energy (Ea) and rate constants (k1 and 45. A chemical reaction proceeds into the following
k 2 ) of a chemical reaction at two different steps
temperatures (T1 and T2) are related by Step I, 2A X fast
k2 Ea  1 1 Step II, X + B  Y slow

(1) ln k   R   
T T
1  1 2  Step III, Y + B Product fast
The rate law for the overall reaction is
k E  1 1
(2) ln 2   a    (1) Rate = k[A]2 (2) Rate = k[B]2
k1 R  T2 T1 
(3) Rate = k[A][B] (4) Rate = k[A]2[B]
k2 E  1 1 46. The data for the reaction A + B  C, is

(3) ln  a   
k1 R T
 2 T1 Exp. [A]0 [B]0 Initial rate
(i) 0.012 0.035 0.10
k 2 Ea  1 1
(4) ln     (ii) 0.024 0.070 0.80
k1 R  T1 T2 
(iii) 0.024 0.035 0.10
42. The half life time of 2g sample of radioactive nuclide (iv) 0.012 0.070 0.80
‘X’ is 15 min. The half life time of 1g sample of X
is The rate law corresponds to the above data is
(1) 7.5 min (2) 15 min (1) Rate = k[A][B]3 (2) Rate = k[A]2[B]2
(3) 22.5 min (4) 30 min (3) Rate = k[B]3 (4) Rate = k[B]4
47. Half-life for radioactive 14C is 5760 years. In how many 53. Activation energy of a chemical reaction can be
years 200 mg of 14C will be reduced to 25 mg? determined by
(1) 17280 years (2) 23040 years (1) Evaluating rate constants at two different
temperatures
(3) 5760 years (4) 11520 years
(2) Evaluating velocities of reaction at two different
48. A chemical reaction is catalyzed by a catalyst X.
Hence X temperatures
(1) Reduces enthalpy of the reaction (3) Evaluating rate constant at standard
temperature
(2) Does not affect equilibrium constant of reaction
(4) Changing concentration of reactants
(3) Decreases rate constant of the reaction
54. For a first-order reaction, the half-life period is
(4) Increases activation energy of the reaction independent of
49. The given reaction 2 FeCl3 + SnCl2  2 FeCl2 + (1) First power of final concentration
SnCl4 is an example of
(2) Cube root of initial concentration
(1) Third order reaction (2) First order reaction
(3) Initial concentration
(3) Second order reaction (4) None of these
(4) Square root of final concentration
50. Carbon-14 dating method is based on the fact that
55. The half-life of 6C14, if its  is 2.31 × 10–4 year –1, is
(1) Ratio of carbon-14 and carbon-12 is constant
(1) 3.5 × 104 years (2) 3 × 103 years
(2) Carbon-14 is the same in all objects
(3) 2 × 102 years (4) 4 × 103 years
(3) Carbon-14 is highly insoluble
56. A 300 gram radioactive sample has a half life
(4) All of these
3 hours. After 18 hours remaining quantity
51. For the reaction H2(g) + I2(g) 2HI(g), the rate
(1) 4.68 gram (2) 2.34 gram
of reaction is expressed as
(3) 3.34 gram (4) 9.37 gram
[H2 ] 1 [I2 ] [HI]
(1)   57. How enzymes increases the rate of reactions?
t 2 t t
(1) By lowering activation energy
[I2 ] [H2 ] 1 [HI]
(2)    (2) By increasing activation energy
t t 2 t
(3) By changing equilibrium constant
[I2 ] [H2 ] [HI] (4) By forming enzyme substrate complex
(3)   
t t 2t
58. For the reaction; 2N2O5  4NO2 + O2 rate and rate
(4) None of these constant are 1.02 × 10–4 Ms–1 and 3.4 × 10–5 s–1
respectively, then concentration of N2O5 at that time
52. The experimental data for the reaction will be (in molarity)
2A + B2  2AB is (1) 1.732 (2) 3
Experiment [A] [B2] Rate(mole s–1)
(3) 1.02 × 10–4 (4) 3.4 × 105
1 0.50 0.50 1.6 × 10–4
59. A human body required 0.01 m activity of
2 0.50 1.00 3.2 × 10–4 radioactive substance after 24 hours. Half life of
radioactive substance is 6 hours. Then injection of
3 1.00 1.00 3.2 × 10–4
maximum activity of radioactive substance that can
The rate equation for the above data is be injected
(1) rate = k [A]2 [B]2 (1) 0.08
(2) rate = k [A]2 [B] (2) 0.04
(3) rate = k [B2] (3) 0.16
(4) rate = k [B2]2 (4) 0.32
60. When a biochemical reaction is carried out in 66. The temperature dependence of rate constant (k) of
laboratory, outside the human body in absence of a chemical reaction is written in terms of Arrhenius
enzyme, then rate of reaction obtained is 10–6 times, *
equation, k  A . e E /RT . Activation energy (E*) of
the activation energy of reaction in the presence of
enzyme is the reaction can be calculated by plotting
6 1
(1) (1) k Vs T (2) k Vs logT
RT
(2) P is required 1
(3) log k Vs (4) log k Vs T
(3) Different from Ea obtained in laboratory T
(4) Can’t say anything
67. The radioisotope, tritium (13 H) has a half-life of
d(B) 12.3 years. If the initial amount of tritium is 32 mg,
61. 3A  2B, rate of reaction is equal to how many milligrams of it would remain after
dt
49.2 years?
3 d(A) 2 d(A) (1) 1 mg (2) 2 mg
(1)  (2) 
2 dt 3 dt
(3) 4 mg (4) 8 mg
1 d(A) d(A) 68. The rate of a first order reaction is 1.5 × 10–2 mol
(3)  (4)  2 L–1 min–1 at 0.5 M concentration of the reactant.
3 dt dt
The half-life of the reaction is
62. 2A  B + C
(1) 0.383 min (2) 23.1 min
It would be a zero order reaction when
(3) 8.73 min (4) 7.53 min
(1) The rate of reaction is proportional to square of
conc. of A
(2) The rate of reaction remains same at any conc. SECTION - D
of A
NEET Booster Questions
(3) The rate remains unchanged at any conc. of B
and C 1. Consider the following graph for Arrhenius equation
(4) The rate of reaction doubles if conc. of B is
Ea
increased to double log k = logA –
2.303 RT
63. The activation energy for a simple chemical
reaction A  B is Ea in forward direction. The
activation energy for reverse reaction
(1) Is negative of Ea log k 
(2) Is always less than Ea
(3) Can be less than or more than Ea
1/T
(4) Is always double of Ea
If tan  = –1 and T = 300 K, then the activation
64. The reaction A  B follows first order kinetics. The
energy is
time taken for 0.8 mole of A to produce 0.6 mole
of B is 1 hour. What is the time taken for (1) 5.74 kJ (2) 19.14 J
conversion of 0.9 mole of A to produce 0.675 mole
of B? (3) 9.57 J (4) 19.14 kJ
(1) 1 hour (2) 0.5 hour 2. Which of the following statement is incorrect for
zero order reaction?
(3) 0.25 hour (4) 2 hours
[R]0 – [R] [R]0
65. If the rate of the reaction is equal to the rate (1) k = (2) t 1 =
constant, the order of the reaction is t 2 2k
(1) 0 (2) 1
(3) t 3 = 2  t 1 (4) All are incorrect
(3) 2 (4) 3 4 2
3. The number of collisions per second per unit
volume of the reaction mixture is known as
(1) Collision number (2) [P]
(2) Collision frequency

Time
(3) Collision path
(4) Collision density
4. Consider the following equation based on collision [P]
theory Rate = PZABe–Ea/RT (3)
The term ‘P’ is known as Time
(1) Probability factor
(2) Steric factor
(3) Frequency factor (4) [R]
(4) Both (1) & (2)

Time
5. Choose the correct statement(s) among the
8. Choose the correct statement
following
(1) A catalyst changes the H of reaction
(1) Molecularity is defined only for an elementary
reaction (2) A catalyst changes the path of the reaction
(2) Molecularity of a reaction cannot be zero or (3) A catalyst initiates the chemical reaction
fraction (4) A catalyst does not change the thereshold
(3) Order of reaction can be 0, 1, 2, 3 or even a energy
fraction 9. A first order reaction is completed 50% in 50
(4) All are correct minutes, then the time required for initial
concentration to be reduced to 12.5% is
6. Consider the decomposition of hydrogen peroxide
(1) 150 minute
I(–) (2) 12.5 minute
2H2O2   2H2O + O2
OH(–)
(3) 100 minute
The rate law is given by
(4) 200 minute
d[H2O2 ] 10. The rate constant for a reaction depends on
R= – = k[H2O2] [I–]
dt (1) Temperature
The conclusion which can be drawn is (2) Concentration
(1) The order of reaction is 2 (3) Volume of container
(2) The reaction is a complex reaction (4) All of these
(3) Order of reaction with respect to H2O2 is 1

B(g), H is –40 kJ/
11. For the equilibrium, A(g)
(4) All are correct mol. If the ratio of the activation energies of the
7. Choose the correct graph for the first order 2
reaction : R  P forward (Ef) and reverse (Eb) reactions is then
3
(1) Ef = 80 kJ/mol, Eb = 120 kJ/mol
(1) [R] (3) Ef = 30 kJ/mol, Eb = 45 kJ/mol
Time
12. A2 + B2  2AB: ROR = k[A2]a[B2]b 17. A reaction rate constant is given by :
Initial ROR 2500

Initial [A 2 ] Initial [B2 ]
(Ms1) 14
k = 1.2  10 e RT sec 1 . It means
0.2 0.2 0.04 (1) log k versus log T will give a straight line with
0.1 0.4 0.04 a slope as 25000
0.2 0.4 0.08
(2) log k versus log T will give a straight line with
Order of reaction with respect to A2 and B2 are a slop as – 25000
respectively (3) log k versus T will give a straight line with a
(1) a = 1, b = 1 (2) a = 2, b = 0 slop as – 25000
(3) a = 2, b = 1 (4) a = 0, b = 2 1
(4) log k versus will give a straight line
T
13. Decomposition of N2O5 is first order reaction. t1/2 of
1 1
the reaction N2O5  2NO2 + O is 2.4 hr at 18. The reaction N2O5  2NO2 + O is of first
2 2 2 2
STP. Starting with 10.8 gm of N2O5, how much order in N2O5 with rate constant 6.2 × 10–1 s–1.
oxygen will be obtained after a period of 9.6 hr ? What is the value of rate of reaction when
mol
(1) 1.5 litre (2) 3.36 litre [N2O5]  1.25
litre
(3) 1.05 litre (4) 0.07 litre (1) 6.35 × 10–3 mol L–1S–1
14. The following mechanism has been proposed for (2) 7.75 × 10–1 mol L–1S–1
the reaction of NO with Br2 to form NOBr
(3) 5.15 × 10–5 mol L–1S–1

NO(g) + Br2(g)
NOBr2(g) ....Fast
(4) 3.38 × 10–1 mol L–1S–1
NOBr2(g) + NO(g)  2NOBr(g) ....Slow 19. In the following reaction :
Order of reaction with respect to NO(g) is A  B + C, rate constant = 0.001 Ms–1. If we
start with 1 M of A then conc. of A and B after 10
(1) 1 (2) 0
minutes respectively are
(3) 3 (4) 2
(1) 0.5 M, 0.5 M (2) 0.6 M, 0.4 M
15. Rate of formation of SO3 in the following reaction
(3) 0.4 M, 0.6 M (4) 0.1 M, 0.9 M
2SO2 + O2  2SO3 is 100 gm min–1.
20. At 300 K the half life of sample of gaseous
Hence rate of disappearance of O2 is
compound initially at 1 atm is 100 sec. When the
(1) 50 g min–1 pressure is 0.5 atm the half life is 50 sec, the order
of reaction is
(2) 40 gm min–1
(1) 1
(3) 200 g min–1
(2) 0
(4) 20 g min–1
(3) 2
16. For the reaction system : 2NO(g)+O2(g)  2NO2(g)
volume is suddenly reduced to half its value by (4) 3
increasing the pressure on it. If the reaction is of 21. Which of the following represents expression for
first order with respect to O2 and second order with
3
respect to NO, the rate of reaction will th life of first order reaction?
4
(1) Diminish to one-fourth of its initial value
k 4 2.303 3
(2) Diminish to one-eight of its initial value (1) log (2) log
2.303 3 k 4
(3) Increase to eight times of its initial value 2.303 2.303
(3) log4 (4) log3
(4) Increase to four times of its initial value k k
22. The rate of reaction is expressed in different ways (1) Unchange
as follows
(2) Increase four times
1 d[C] 1 d[D] 1 d[A] d[B] (3) Increase eight times
   
2 dt 3 dt 4 dt dt
(4) Decrease eight times
The reaction is 28. In the following reaction A  2B + C, rate constant
(1) 4A + B  2C + 3D is 0.002 Ms–1. If we start with 2 M of A then conc.
of B after completion of reaction is
(2) B + 3D  4A + 2C
(1) 0.5 M (2) 4 M
(3) A + B  C + D (3) 0.4 M (4) 0.06 M
(4) B + D  A + C 29. The decomposition of N2O5 in chloroform was
23. The unit of rate constant of elementary reaction followed by measuring the volume of O 2 gas
depends upon the evolved : 2N2O5(CCl4)  2N2O4 (CCl4) + O2(g).
The maximum volume of O2 gas obtained was
(1) Temperature of the reaction 100 cm 3. In 500 minutes, 90 cm 3 of O 2 were
evolved. The first order rate constant (in min–1) for
(2) Concentration of reactant
the disappearance of N2O5 is
(3) Activation energy of the reaction
2.303
(4) Molecularity of the reaction (1)
500
24. If 'a' is the initial concentration of the reactant, the 2.303 100
half-life period of the reaction of n th order is (2) log
500 90
proportional to
2.303 90
(1) an – 1 (3) log
500 100
(2) an
100
(3) a1 – n (4)
10  500
(4) an + 1 30. Hydrolysis of ester in acidic medium is an
example of
25. 99% of a first order reaction was completed in 32
minutes when 99.9% of the reaction will complete (1) Psuedo first order reaction
(1) 50 min (2) Zero order reaction
(2) 46 min (3) Second order reaction
(3) 48 min (4) Third order reaction

k
(4) 49 min 31. For a complex reaction A   products
26. In the reaction, A + 2B  6C + 2D, if the initial Ea  180 kJ/mol; Ea  80 kJ/mol;
1 2
d[A]
rate – at t = 0 is 2.6 × 10–2 M sec–1, what Ea  50 kJ/mol overall rate constant k is related
dt 3
d[B] to individual rate constant by the equation
will be the value of – at t = 0?
dt 2/3
k k 
(1) 8.5 × 10–2 M sec–1 k   1 2  .
 k3 
(2) 2.5 × 10–2 M sec–1
Activation energy (kJ/mol) for the overall reaction is:
(3) 5.2 × 10–2 M sec–1
(1) 100
(4) 7.5 × 10–2 M sec–1
(2) 43.44
27. For an elementary gaseous reaction 2A + B 
A2B if the volume of vessel is quickly reduced to (3) 150
half of it's original volume then rate or reaction will (4) 140
1
k 0.1 M min
32. Consider a reaction A(g)   2B(g). 1
35. The half-life for the reaction N2O5  2NO2  O
2 2
If initial concentration of A is 0.5 M then select
correct graph is 2.4 h at STP. Starting with 10.8 g of N2O5,
how much oxygen will be obtained after a period
of 9.6 h?
(1) 1.5 L (2) 3.36 L
(1) 0.5 M (3) 1.05 L (4) 0.07 L
[B] 36. For a chemical reaction at 27ºC, the activation

energy is 600R. The ratio of the rate constants at
5 10 327ºC to that of at 27ºC will be
time (in min)
(1) 2 (2) 40
(3) e (4) e2
1.0 M
[B] 37. For a reaction 2A + B  Product, if
(2) concentration of B double then half life is
0.5 M
unchanged but if only A double then rate of reaction
is also double, unit of k is
5 10 (1) mol–1 L1 s–1 (2) s–1
time (in min)
(3) mol L–1 s–1 (4) mol–2 L2 s–1
38. What will be the order of reaction for a chemical
change having log t1/2 vs log a? (where a = initial
concentration of reactant ; t1/2 = half-life)
1.0 M
(3) [B]
log t1/2 45°
5 10
time (in min)
log a
2.0 M
(1) Zero order (2) First order
(4) 1.0 M (3) Second order (4) None of these

39. Reaction A  B follows second order kinetics.
[B]
Doubling the concentration of A will increase the
5 10 rate of formation of B by a factor of
time (in min)
(1) 1/4 (2) 1/2
33. After how many seconds will the concentration of (3) 2 (4) 4
the reactants in a first-order reaction be halved, if
the decay constant is 1.155 × 10–3 sec–1 40. Two reactions proceed at 25ºC at the same rate.
The temperature coefficient of the first reaction is
(1) 100 sec (2) 200 sec 2 and that of the second is 2.5, find the ratio of
(3) 400 sec (4) 600 sec the rates of second reaction to first reaction at
95ºC
34. A first-order reaction was started with a decimolar
solution of the reactant, 8 minutes and 20 seconds (1) 0.83
later its concentration was found to be M/100. So
the rate constant is (2) 1.13
(1) 2.303 × 10–5 sec–1 (2) 2.303 × 10–4 sec–1 (3) 1.87
(3) 4.606 × 10–3 sec–1 (4) 2.603 × 10–4 sec–1 (4) 4.76
k
41. For the reaction 3A(g)  46. For the reaction A + B  products, it is found that
 B(g) + C(g), k is
–4 order of A is 2 and the order of B is 3 in the rate
10 L/mol-min.
expression. When the concentrations of both A and
d[A] B are doubled the rate will increase by a factor
if [A] = 0.5M then the value of  (in Ms –1 )
dt (1) 10 (2) 16
is
(3) 32 (4) 28
(1) 7.5 × 10–5 (2) 3 × 10–4
47. Nitric oxide (NO) reacts with oxygen to produce
(3) 2.5 × 10–5 (4) 1.25 × 10–6 nitrogen dioxide
42. Half-life (t 1/2 ) and completion time (T) of the 2NO(g) + O2(g)  2NO2(g),
–1
reaction A k = 0.001 Mmin 2B are : if initial If the mechanism of reaction is

concentration of A is 1M
K
NO + O2 NO3 (fast)
(1) 500 min, 1000 min (2) 500 sec, 750 sec
K1
(3) 500 sec, 1000 sec (4) 250 min, 500 min NO3+ NO NO2 + NO2 (slow)
43. For a first order reaction nA  B half life is then rate law is
18 minute. Then with the help of graph find value (1) Rate = K [NO][O2] (2) Rate = K [NO][O2]2
of n :
(3) Rate = K [NO]2[O2] (4) Rate = K [NO]3[O2]
B
48. If the volume of closed vessel in which the following
Concentration
A simple reaction is carried out is reduced to one

third of original volume, the rate of reaction
becomes
2NO (g) + O2 (g)  2NO2 (g)
36 t(min)
(1) One third
(1) 2 (2) 3
(2) Three times
(3) 4 (4) 1
(3) Nine times
1
44. For the reaction, N2O5  2NO2 + O2 . (4) Twenty seven times
2
d[N 2 O 5 ] 49. For a gaseous phase reaction 2A + B2  2AB, the
Given : – = K1 [N2O5] following rate data was obtained at 300K
dt
Rate of disappearance Concentration
d[NO 2 ]
= K2 [N2O5] of B2 (mole/litre min) [A] [B2]
dt
d[O 2 ] (i) 1.8 × 10–3 0.015 0.15
and = K3 [N2O5]
dt (ii) 1.08 × 10–2 0.09 0.15
The relation between K1, K2 and K3 is (iii) 5.4 × 10–3 0.015 0.45
(1) 2K1 = K2 = 4K3 (2) K1 = K2 = K3 The rate constant for the reaction is
(3) 2K1 = 4K2 = K3 (4) K1 = 2K2 = 3K3 (1) 0.5 mol–1 min–1 litre (2) 0.8 mol–1 min–1 litre
K1 (3) 1.5 mole–1 min–1 litre (4) 2 mol–1 min–1 litre

45. For the reaction, N2O4 (g) 2NO2(g), the 50. For a first order reaction, the time taken to reduce
K2
1
rate of disappearance of NO2 will be the initial concentration to a factor of is 10 minute
4
(1) K1[N2O4] – K2[NO2]2 If the reduction in concentration is carried out to a
1
(2) 2K1[N2O4] – 2K2[NO2]2 factor of , then time required will be
16
(3) K2[NO2]2 – K1[N2O4] (1) 10 minutes (2) 20 minutes
(4) 2K2[NO2]2 – 2K1[N2O4] (3) 40 minutes (4) 60 minutes
51. Consider the data below for a reaction A  B 55. Two substances A and B are present such that
[A]0 = 4[B]0 and half life of A is 5 minute and that
Time of B is 15 minute. If they start decaying at the
(sec) 0 10 20 30
same time following first order kinetics how much
-2 -2 -2 -2 time will the concentration of both of them would be
Rate 1.60×10 1.60×10 1.60×10 1.59×10
the same?
From the above data the order of reaction is (1) 15 minute (2) 10 minute
(1) Zero (2) 1 (3) 5 minute (4) 12 minute
(3) 2 (4) 3 56. The reaction A  B follows first order kinetics.
52. For a homogeneous gaseous reaction The time taken for 0.80 mole of A to produce
A  B + C + D, the initial pressure was P0 while 0.60 mole of B is 1 hour. What is the time taken
pressure after time ‘t’ was P if (P > P 0). The for conversion of 0.90 mole of A to produce
expression for the rate constant k is 0.675 mole of B?
(1) 1 hour (2) 30 minute
2.303  2P0 
(1) k  log   (3) 15 minute (4) 5 minute
t  3P0  P 
3 –1
k1 = 2 × 10 s
2.303  3P0  B
(2) k  log  
t  2P0  P  57. If, A
3 –1
k2 = 6 × 10 s
2.303  P  C
(3) k  log  0 
t  P0  P  %B in the product is
2.303  2P0  (1) 25% (2) 50%
(4) k  log  
t  4P0  P  (3) 75% (4) 80%
53. Inversion of a sugar follows first order rate equation 1
58. The graph between the log K versus is a
which can be followed by noting the change in T
rotation of the plane of polarization of light in the straight line. The slope of the line is
polarimeter. If r, rt and r0 are the rotations at
t = , t = t and t = 0 then, first order reaction can 2.303R Ea
(1)  (2) 
be written as Ea 2.303R
1 rt –r 1 r0 – r
(1) k = log10 r – r (2) k = ln r – r 2.303R Ea
t 0  t t  (3) (4)
Ea 2.303R
1 r – r0 1 r – rt
(3) k = ln r – r (4) k = ln r – r 59. The temperature coefficient for most of the reaction
t t  t  0 lies between
54. The rate constant of the production of 2B(g) by the (1) 1 & 3 (2) 2 & 3
reaction,
(3) 1 & 4 (4) 2 & 4

A(g)  2B(g) is 2.48 × 10–4 s–1 60. Which of the following is correct?
A 1 : 1 molar ratio of A to B in the reaction mixture
K2 E a  T 
is attained after (1) log   
K 1 2.303  T1T2 
(1) 26.25 minute
(2) For zero order t1/2 is inversely proportional to
(2) 27.25 minute initial concentration
(3) 28.25 minute (3) Catalyst decreases the activation energy
(4) 0 minute (4) All of these


Chemical Kinetics THEORY

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Chemical Kinetics THEORY

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Chapter 12

Δ H2  Δ I2  1 Δ HI

For a general chemical transformation,

1 [A] 1 [B] 1 [C] 1 [D]

1 d[SO2 ] d[O2 ] 1 d[SO3 ]

Law of Mass Action :

RATE LAW OR RATE EQUATION OF A REACTION

1. For the reaction,

2N2O5  4NO2 + O2

Select the correct statement

3. H2 + I2  2HI (An elementary reaction)

4. In a certain reaction shown below,

If rate of formation of C is 9.6 × 10–2 mol/L s. What will be rate of reaction?

(1) 9.6 × 10–2 mol/L s

(2) 3.2 × 10–2 mol/L s

(3) 2.4 × 10–2 mol/L s

(4) 4.8 × 10–2 mol/L s

5. For the reaction,

H2O2 + 2H+ + 3I–  I3– + 2H2O

Select the correct statement

6. The value of rate constant depends upon

(1) Temperature (2) Concentration

(3) Catalyst (4) Both (1) & (3)

INTEGRATED RATE EQUATIONS

A  B is a zero order reaction, then,

Unit of Zero Order Rate Constant

Rate mol L1 L

(v) Decomposition of nitrogen pentaoxide in CCl4 solution, N2O5  2NO2 + ½ O2

t = 2303 × 0.301 × 2 = 1386 s.

2.303 [A ] 2.303  100 

METHODS TO DETERMINE THE ORDER OF REACTION

Some Typical Linear Plots for the Reactions of Different Orders :

Time (t) Time (t) Time (t) Time (t)

t1/2 t1/2 t1/2 t1/2

It is confirmed by the experimental rate which is given by Rate = k [NO2][F2].

Reaction Order Rate law equation Rate constant

FACTORS AFFECTING RATE OF A CHEMICAL REACTION

The reaction rate is influenced by the following factors :

Substituting the values of k1, k2 and R ( = 8.314 JK–1 mol–1), we get,

 Ea = 2.6  19.15  4200 J mol–1 = 2.09  105 J mol–1 = 209 kJ mol–1

COLLISION THEORY OF REACTION RATES

(Ea)f ETH (Ea)b (Ea)f ETH (Ea)b

Progress of reaction Progress of reaction

Note : H = HP – HR, H = (Ea)f – (Ea)b, ETH = HR + (Ea)f or ETH = HP + (Ea)b.

14. A catalyst cannot change

[NCERT Pg. 103]

9. For the first order reaction, 2.303 R

at 50 K and 1.5  106 sec–1 at 100 K. Then the  1000 

(4) 9.135 kJ mol–1 (3) 500 ºC (4) 500 K

(1) 10 (3) r1 < r2 < r3

c 18. The rate of a reaction becomes 2 times for every

d 10°C rise in temperature. How many times rate of

proportional to initial concentration of B2 (mol/litre min) [A] [B2]

26. Hydrolysis of ester in basic medium is of

6. The correct difference between first and second

[AIPMT (Prelims)-2012] (4) Equal to zero

24. During the kinetic study of the reaction,

26. For the reaction, N2 + 3H2  2NH3, [AIPMT (Prelims)-2009]

(3) 1×10–4 mol L–1 s–1 [AIPMT (Prelims)-2008]

(4) 3×10–4 mol L–1 s–1 1000

 H (aq)  Br  (aq) Which of the above mechanism(s) can be

3.1 × 10–4 (4) 60 minutes

(3) 1 (4) 2 Which one of the following is not affected by the