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(a) Temperature of reaction.
(b) Concentration of reactants.
(c) Concentration of products
e.c
(d) None of these
(ii) If the rate equation of a reaction 2A + B product is , rate
2 fre
=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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(iii) For a fast reaction the rate constant is relatively _______and
half-life is ________.
(iv) The second order reaction becomes ________if one of the
e.c
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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(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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(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.
e.c
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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Rate =- . =- . =+ . =+ .
Remember that in order to have a unique value of the reaction rate
e.c
(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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Ans.
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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
e.c
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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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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Enthalpy change of reaction Energy of activation of
reaction
1. “The heat change when the 1. “ The minimum amount of
e.c
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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Ans. Calculation of k:
For a first order reaction
e.c
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
w.a
[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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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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(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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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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Is reached much sooner but the percentage yield remains
uncharged.
e.c
(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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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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Formula used:
e.c
n =1 + fre
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n =1 + =1 + 1.89=2.89
n =3
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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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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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Temperature(K) Rate constant(
3 -1 -1
cm mol s )(K)
500 6.814 x 10-4
e.c
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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(ii) Measure the slope of this straight line and calculate the
energy for actives this reaction.
Ans. 8326.32: 160.6 Jmol-1.
w.a
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