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1st year chemistry n0tes new

CHAPTER11 REACTION KINETICS

TEXT BOOK EXERCISE


Q1. Multiple choice questions
(i) In a zero order reaction, the rate is independent of

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(a) Temperature of reaction.
(b) Concentration of reactants.
(c) Concentration of products

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(d) None of these
(ii) If the rate equation of a reaction 2A + B product is , rate
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=k[A] [B]. and A is present in large excess, then order of reaction
is
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(a) 1 (b) 2
(c) 3 (d) none of these
(iii) The rate of reaction
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(a) Increases as the reaction proceeds.


(b) Decreases as the reaction proceeds.
(c) Remains the same as the reaction proceeds.
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(d) May decrease or increase as the reaction proceeds.


(iv) With increase of 10oC temperature, the rate of reaction doubles.
This increase in rate of reaction is due to:
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(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
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(d) Third order reaction


Ans. (i) b (ii) a (iii) b (iv) d
(v) c
Q2. Fill in the blanks with suitable words.
(i) The rate of an endothermic reaction_______wiht the
increase in temperature.
(ii) All radioactive disintegration nuclear is of ________order.

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(iii) For a fast reaction the rate constant is relatively _______and
half-life is ________.
(iv) The second order reaction becomes ________if one of the

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reactants is in large excess.
(v) Arrhenius equation can be used to find out_________of a
reaction. fre
An. (i) increases (ii) first (iii) large : small
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(iv) First order (v) energy of activation
Q3. Indicate TRUE or FALSE as the case may be.
(i) The half-life order reaction increases with temperature.
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(ii) The reactions having zero activation energies are


instantaneous.
(iii) A catalyst makes a reaction more exothermic.
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(iv) There is difference between rate law and the law of mass
action.
(v) The order of reaction is strictly determined by the
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Stoichiometry of the balanced equation.


Ans. (i) False (ii) True (iii) False (iv) True
(v) False
Q4. What is chemical kinetics? How do you compare chemical
kinetics with chemical equilibrium and thermodynamics?
Ans. Chemical thermodynamics can be used:
(i) To predict whether or not a reaction will proceed to the
right, as written.
(ii) To predict the extent to which a reaction will proceed before
reaching a condition of equilibrium.
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(iii) To enable the amount of energy theoretically required by or


released during reactions to be calculated,
Thermodynamics cab tells us where the position of equilibrium lies
between the reactants and the products. It enables us to calculate the
equilibrium constants. It has the following limitations.
(i) It can only predict the us where possibility of a reaction but not
its success.

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(ii) It cannot tell us about the rate at which a reaction will occur. It is
because time is not a thermodynamic variable.
(iii) It provides no information about the mechanism of the reaction.

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This is because the change in any state function is path
independent.
Chemical kinetics can be used: fre
(i) To determinc the rate of reaction, that is the rate at which
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products are formed or the rate at which reactions are used up in
the reaction.
(ii) To understand the factors that affects the rate of a reaction.
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(iii) To find the mechanism of a reaction.


Example: When gaseous H2 and O2 are mixed, thermodynamics tell
us that H2O should be formed, since H2O is more energetically stable
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than H2 and O2. It is a well known fact that at room temperature, a


mixture of H2 and O2 will not produce H2O. However, if the mixture is
sparked, water is produced with explosive violence, thereby proving the
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prediction of thermodynamics. However, it does not give any indication


of how fast the reaction will proceed.
Q5. The fast of a chemical reaction with respect to products is written
with positive sing, but with respect to reactants is written with a
negative sing. Explain it with reference to the following
hypothetical reaction.
aA + bB cC + dD
Ans. The concentration of reactants decrease with time whereas the
concentration of products increases with time.

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The rate of disappearance of reactant is always negative. A


negative sign in the rate expression indicates that the
concentration of the reactant decreases with time.
For the general reaction:
aA + bB cC + dD
The rate of reaction is given by

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Rate =- . =- . =+ . =+ .
Remember that in order to have a unique value of the reaction rate

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(independent of the concentration term chosen), it is necessary to divide
each concentration change by its coefficient in the balanced equation for
the reaction.
Q6.
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What are instantaneous and average rates? Is it true that the
instantaneous rate of a reaction at the beginning of the reaction is
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greater than average rate and becomes far less than the average rate
near the completion of reaction?
Q7. Differentiate between
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(i) Rate and rate constant of a reaction


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Ans.
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Rate of reaction Rate constant of


reaction
1. “The change 1. “The proportionality
in concentration of constant in rate law
a reactant or equation which relates
product per unit concentration to the rate
time is called the of reaction is called rate
rate of reaction.” constant of reaction.”
2. The reaction 2. It is independent of
takes place in one the concentration of the
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phase. reactant.
3. The 3. Its units depend
mechanism upon the order of reaction
involves the and differs according to
formation of an order of reaction.
intermediate
substance.

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(ii) Homogeneous and heterogeneous catalyses
Ans.
Homogeneous catalyses Heterogeneous catalysis

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1. “The process in which the 1. “The process in which the
catalyst and catalyst and the reaction are in
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the reactants are in the same different phases is called
phase is called homogeneous heterogeneous catalysis.”
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catalysis.” 2. The reaction takes place at
2. The reaction takes place in a phase boundary. The gaseous
one phase. The catalyst is molecules react at the surface of
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uniformly distributed and is the solid catalyst.


itself in the same phase. 3. The mechanism involves
3. The mechanism involves adsorption. Molecules are bound
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the formation of an intermediate to „active sites‟ on a solid


substance. surface.
(iii) Fast step and the rate determining step
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Ans.
Fast step Rate determining step
1. “A relatively rapid step of 1. “The slowest step of the
the reaction mechanism is reaction mechanism is called
called fast step.” rate determining step.”
2. The overall rate of reaction 2. The rate of this step
is independent if this step. determines the overall rate of
3. The number of molecules of reaction.
each reactant taking part in this 3. The number of molecules of
step does not appear in the rate each reactant taking part in this
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equation. step appears in the rate equation.


Remember that except the slow step, all other steps of the reaction
mechanism are normally faster steps. The terms slow and fast are
relative. They don not necessarily imply that the reaction itself is slow or
fast.
(iv) Enthalpy change of reaction and energy of activation of reaction
Ans.

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Enthalpy change of reaction Energy of activation of
reaction
1. “The heat change when the 1. “ The minimum amount of

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reaction is carried out at energy , in addition to the
constant pressure is called average kinetic energy. Which
enthalpy change of reaction.” frethe reactant molecules must
2. It is the amount of heat have for effective collisions is
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evolved or consumed in the called activation energy of
course of reaction. reaction.”
3. It is given the symbol, H 2. It is the minimum amount
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of energy required to initiate a


reaction.
3. It is given the symbol, Ea
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Q8. Justify the following statements


(i) Rate of chemical reaction is an ever changing parameter under
the given conditions.
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Ans. The rate of chemical reaction change with time. It has a


maximum value at the beginning of the reaction, then gradually
decreases and finally becomes zero when the reactants are totally
converted into products.
(ii) The reaction rate decreases every moment but rate constant „k‟
of the reaction is constant quantity, under the given conditions.
Ans. The rate of chemical reaction is not uniform. It depends upon the
molar concentrations of reactants. The rate of reaction is directly
proportional to concentrations of reactants. Since the concentration
of reactants decreases every moment, so the rate of reaction, then
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gradually decreases with time. It has a maximum value at the start


of the reaction, then gradually decreases and finally becomes zero.
The constant, „k‟ of the reaction is independent of concentration.
So, it remains constant under the given conditions. However, it
changes with temperature.
(iii) 50% of a hypothetical first order reaction completes in one
hour. The remaining 50% needs more than one hour to complete.

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Ans. Calculation of k:
For a first order reaction

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T1/2 =

1 hour = fre
k=0693 hours-1
Calculation of time for remaining 50%
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Completion of reaction:
For first order reaction rate equation:
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K= log

t= log
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Where [A]o is initial concentration and [A] is concentration at any time t.

[A]=
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t=

t= =
t =5.6457 hours
Hence remaining 50% needs more than one hour to complete.
(iv) The radioactive decay is always a first order reaction.
Ans. Since the half-life of a first order reaction in constant and is
independent of initial concentration of the reaction, so the radio-
active decay is always a first order reaction.
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(v) The unit of rate constant of a second order reaction is dm3 mol-
1 -1
s , but the unit of rate of reaction is mol dm-3s-1.
Ans. For second order reaction: A+B Products
2
Rate =k[A]
Units of rate are: mol dm-3s-1.
Units of concentration of A: mol dm-3
Therefore, mol dm-3s-1=k(mol dm-3)2

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mol dm-3s-1=(mol2 dm-6)

k= =mol-1dm3s-1

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So, the units of rate constant of 2nd order reaction are: dm3 mol-
1 -1
s
(vi) fre
The sum of the coefficients of a balanced chemical equation is
not necessarily important to give the order of a reaction.
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Ans. The order of a chemical reaction is the sum of the exponents of
the concentration terms in the rate equation. It cannot be written by
merely looking at the balanced chemical equation. Usually, the
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powers of concentration terms in the rate equation are different


from coefficients of reactants in the balanced equation. The order
of a reaction can be determined only by experiment. For example,
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for N2O5, the rate is proportional to [N2O5] and its power is one
although the coefficient of N2O5in the balanced equation is two.
N2O5 4NO2+O2
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Rate = k [N2O5]
A reactant whose concentration does not affect the reaction rate
is not included in the rate equation. The total number of molecules
or atoms taking part in a reaction can never be zero or in fraction
while the order of reaction can be zero or in fraction.
(vii) The order of a reaction is obtained from the rate expression of a
reaction and the rate expression is obtained from the experiment.
Ans. The rate expression can be only being determined
experimentally. It expresses actual dependence of the rate on the
concentrations of the reactants. A reactant whose concentration
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does not affect the reaction rate is not included in the rate equation.
The order of reaction is the number of reacting molecules whose
concentrations alter as a result of a chemical reaction. Hence the
order of a reaction is obtained from the rate equation and the rate
expression is obtained from the experiment.
Q9. Explain that half-life method for measurement of the order of a
reaction can help us to measure the order of even those reactions

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which have a fractional order.
Q10. A cure is obtained when a graph is plotted between time on x-
axis and concentration on y-axis. The measurement of the slopes of

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various points give us the instantaneous rates of reaction. Explain
with suitable examples.
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Q11. The rate determining step of a reaction is found out from the
mechanism of that reaction. Explain it with few examples.
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Q12. Discuss the factors which influence the rates of chemical
reactions.
Q13. Explain the following facts about the reaction.
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2NO(g) + 2H2(g) 2H2O(g) +N2(g)


(i) The changing concentrations of reactants change the
rates of this reaction.
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(ii) Individual orders with respect to NO and H2 can be


measured.
(iii) The overall order can be evaluated by keeping the
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concentration of one of the substances constant.


Q14. The collision frequency and the orientation of molecules are
necessary conditions for determining the proper rate of reaction.
Justify the statement.
Q15. How does Arrhenius equation help us to calculate the energy of
activation of a reaction?
Q16. Define the following terms and give examples.
(i) Homogeneous catalysis
(ii) Heterogeneous catalysis
(iii) Activation of a catalyst
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(iv) Auto-catalysis
(v) Catalytic poisoning
(vi) Enzyme catalysis.
Q17. Briefly describe the following with examples:
(i) Change of physical state of a catalyst at the end of
reaction.
Ans. There may be change in physical state such as the particle size or

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change in the colour of the catalyst at the end of reaction. For
example, granular MnO2 used as a catalyst in the thermal
decomposition of KC1O3 is left as fine powder at the end of

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reaction.
(ii) A very small amount of a catalyst may prove sufficient
to carry out a reaction. fre
Ans. Since a catalyst is not used up in the reaction, a very small
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amount of catalyst is required. It can catalyses the reaction over
and over again. Sometimes a trace of a metal catalyst is required
to affect very large amount of reactants. For example, 1 mg of fine
platinum powder can convert 2.5 dm3 of H2 and 1.25 dm3 of O2 to
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water. Dry HC1 and NH3 combine in the presence of trace of


moisture to give dense white fume of NH4C1.
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(iii) A finely divided catalyst may prove more effective.


Ans. A catalyst is more effective when it is present in a finely divided
form than it is used in bulk. With the increase of fine subdivision,
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the free surface area is increased. As a result, the active sites on the
surface are increased. Consequently, the activity of the catalyst is
also enhanced. For example, a lump of platinum will have much
less catalytic activity than colloidal platinum. Finely divided nickel
is a better catalyst than lumps of solid nickel.
(iv) Equilibrium constant of a reversible reaction is not
changed in the presence of a catalyst.
Ans. A catalyst for the forward reaction is also a catalyst for the
reverse reaction. A catalyst speeds up the rate of both the forward

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and reverse reactions equally. So the equilibrium constant (k= )


for the reaction remains the same. A catalyst helps the equilibrium
to e established earlier. For example, the reaction of N 2 and H2 to
from NH3 is very slow. In the presence of the catalyst, the
equilibrium
N2(g) + 3H2(g) 2NH2(g)

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Is reached much sooner but the percentage yield remains
uncharged.

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(iv) A catalyst is specific in its action.
Ans. A catalyst cans catalyst only a specific reaction. When a
particular catalyst works for one reaction it may not necessarily
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work for any other reaction. It may increase the rate of one
reaction but not increase the rate of another reaction. For example,
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MnO2 can catalyse the decomposition of KC1O3 but not that of


NH3. The decomposition of NH3 is catalysed by a hot tungsten
wire.
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2KC1O3(g) 2KC1(s) + 3O2(g)


2NH3(g) N2(g) + 3H2(g)
Remember that transition metals catalyse reaction of different
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types.
For example, the decomposition of aqueous solutions of
hydrogen peroxide (H2O2) is catalysed by MnO2 or colloidal
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platinum.
2H2O2(l) 2H2O(l) + O2(g)
Q18. What are enzymes? Give examples in which they act as catalyst.
Mention the characteristics of enzyme catalysis.
Q19. In the reaction of NO and H2, it was observed that equimolecular
mixture of gases at 340.5 mm pressure was half changed in 102
seconds. In another experiment with an initial pressure of 288 mm
of Hg, the reaction was half completed in 140 seconds. Calculate
the order of reaction.
Ans. Initial pressure of reactants = Initial concentrations of reactants.
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Given: a1=340.5 mm : t1=102 seconds


A2=288 mm : t2=140 seconds
Order of reaction, n=?

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Formula used:

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n =1 + fre
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n =1 + =1 + 1.89=2.89
n =3
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Hence the reaction of third order.


Q20. A study of chemical kinetiecs of a reaction
A + B products
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Gave the following data at 25oC. Calculate the rate law

Exp. [A]
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[B] Rate
1 1.00 0.15
-6
4.2 x 10
2 2.00 0.15
-6
8.4 x 10
3 1.00 0.2
-6
5.6 x 10
Solution: Examination of the data shows that when the
concentration of B is kept constant 0.15. The concentration of A is
doubled form 1.00 to 2.00; the rate doubles from 4.2 x 10 -6 tp 8.4 x 10-6.
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Mathematically, the rate of reaction with respect to A is directly


proportional to the first power of the concentration of A. this is,
Rate [A]
Examination of the experiment 1 and 3 shows that when the
concentration of A is kept constant 1.00, the concentration of B is
increased from 0.15 to 0.2, the rate of the reaction with respect to B is
also increased form 4.1 x10-6 to 5.6 x10-6. Mathematically, the rate of

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reaction with respect to B is directly proportional to the first power of
the concentration of B. that is,
Rate [B]

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Since the rate of a reaction is proportional to the product of
concentration of the reactants, so,
Rate [A][B] fre
Rate=k[A][B]
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This equation is known as the rate law for the reaction.
Q21. Some reaction taking places around room temperature have
activation energies around 50kJ mol-1.
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(i) What is the value of the factor at 25oC.


Ans. Ea=50kJ mol-1 =50000 Jmol-1
R=8.3143 J K-1 mol-1
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At 25oC, the factor = = =1.72 x10-9


(ii) Calculate this factor at35oC, and 45oC note the increase
in this factor for every 10oC rise in temperature.
Ans. At 25oC, the factor = = =3.314 x10-9
At 25oC, the factor = = =6.12 x 10-9
(iii) prove that for every 10oCrise in temperature, the factor
doubles and so rate constant also doubles.
Ans. At 25oC, the factor =1.72 x 10-9

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At 35oC, the factor =3.314 x 10-9


At 45oC, the factor =6.12 x 10-9
Since for every 10oC rise in temperature, the factor becomes
doubles and so rate constant also doubles.
Q22. H2 and 12 react to produce HI. Following data for rate constant at
various temperatures (K) have been collected.

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Temperature(K) Rate constant(
3 -1 -1
cm mol s )(K)
500 6.814 x 10-4

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550 2.64 x 10-2
600 0.56 x 10o
650 fre 7.31 x 10o
700 66.67 x 10o
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(i) Pot a graph between on x-axis and log k on the y-


axis.
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(ii) Measure the slope of this straight line and calculate the
energy for actives this reaction.
Ans. 8326.32: 160.6 Jmol-1.
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