MODERN'S ab¢ + OF CHEMISTRY-XII

PROBLEMS Accelerate Your Potential

(for JEE Advance)

[Probien@6Ammonia decomposes as: Rate = 1[N] _IN] _1[,]

2NH,(g) »N,(g) + 3H,(g) 2 dt dt 3 dt
The rate of reaction can be expressed as ; Substituting the given values,
[NH,J
df
_ ~ [N,,
a
IN]
dt
_e, [NH,J and
3
1
5h[NH,] = ,[NH,J= ,[NH,]
1

-,
1 1
dIH,I] ,[NH, or 5=k=gt
dt 3 3
if k, = 1,thenk,=2andk,= 3
Derive relationship between k,, k_and k,
kkk,=2:1:3
Solution I The rate of the reaction is given by

.1. 7see....Garon. n
Is there any reaction for which reaction rate does not decrease with time ?
Ans, For a zero order reaction, the reaction rate does not decrease with time because it is independent of concentration
of the reactants.
Q.2. How will rate of a reaction change when [A], is doubled and tripled for
Gi) zero order reaction
Gii) second order reaction
Ans, When [Al is doubled
(i) the rate ol zero order reaction remains unchanged.
(ii) the rate of second order reaction becomes four times.
When [Al,, is tripled.
(i) the rate of zero order reaction remains unchanged
(ii) the rate of second order reaction becomes 9 times.
• 3. Why is the use of instantaneous rate of reaction preferred over average rate of reaction ?
Ans, The rate of reaction continuously decreases with time (except for zero order reaction) and therefore, average rate
has no significance for the reaction.
Q.4. What is the order of a reaction whose rate constant has same units as the rate of the reaction T
Ans, Zero order reaction. (H.P.S.B. 2010)
C • 5. State the order with respect to ench reactant and overall order for the following reaction;
2N0Br(g) -» 2NO (g) + Br, (g)
0 Rate = k [NOBr]
N Wat are the units of rate constant? (Pb.S.B. 2016)
C Ans, Order w.r.t. NOBr = 2
Overall order = 2
E Units of rate constant = mo]Ls
p Q. 6. A reaction is found to be zero order. Will its molecularity be zero ? (H.P.S.B. 2010)
T Ans, No, molecularity of a reaction cannot be zero.

u Q.7. The rate of a reaction is equal to rate constant of the reaction. Mention the order of the reaction.
(Assam S.B. 2016)
A Ans, Zero order reaction.
Q.8. How is rate constant related to concentration of the reactants
L Ans, Rate constant does not depend upon the concentration of the reactants.
Q. 9. For a reaction : 2NH,(g) »
Et N,(g) + 3H,(g)
Rate = k
(i) Write the order and molecularity of this reaction.
(ii) Write the unit of k. (A.1.S.B. 2016, D.S.B 2016)
»
Ans. 2NH,(g) -T N,(g) + 3H,(g
Rate= k
(i) Order of reaction : Zero order
Molecularity = 2(bimolecular)
(ii) Unit of k = mo]Ls'or atms'
CHEMICAL KINETICS

Q. 10. Identify the order of a reaction from each of the following rate constants; (H.P.S.B. 2010)
(i) k=2.3x105L mole (ii)k=3.1x104s! (iii) k=9.310'molLs
Ans, Order can be predicted by the inspection of units of rate constant
(i) second order reaction (ii) first order reaction (iii) zero order reaction
Q.11. For the reaction : Ester + Ht » Acid + Alcohol, rate = k [Ester] [HJ, Find the order of reaction.
(Pb. S.B. 2005)
Ans, Order = 1
Q.12. For the assumed reaction :X + 2Y, 2XY_, write the rate equation in terms of the rate of
disappearance of Y,.
Ans, 1Iyl IX,JAY,, TY,I _tx.(Y.
2 dt dt 2 2

Q.13. For the reaction: CL,(g) + 2N0 (g » 2NOC(g)

The rate law is expressed as rate = k[NO] [CL]
What is the overall order of the reaction ? (D.S.B. 2007)
Ans, Overall order = 1 +2= 3.
Q. 14. Express the rate of the following reaction in terms of disappearance of hydrogen in the following
reaction: 3H,(g) +N,(g) » 2NH,(g) (A.1.$.B. 2007)
1 dIH,I
Ans, Rate=g al
Q. 15. The decomposition reaction of ammonia gas on platinum surface has a rate constant,
k=2.5x104molLs, Wat is the order of the reaction ? (C.B.S.E. Sample Paper 2007)
C Ans, Acording to units of rate constant; it is a zero order reaction.
Q. 16. What is the molecularity of the reaction
0
N c ,' ca? (C.B.S.E. Sample Paper 2007)
Ans, Unimolecular. 2
C Q.17. The decomposition of NH_, on platinum surface, 2NH, (g) "
, N,(g)+3H,(g) is a zero order reaction
E with k = 2.5 104Me'. What are the rates of production of N, and H? (D.S.B. 2007; 2008)
p
Ans, Rate = _1 d[NH,I IN,I _1 H, =k=2.5x10'Ms
T 2 dt dt 3 dt
u Rate of production of N,
IN,T =2.510Ms
A dt
1ad1H,J
L 3 dt = 2.510'Ms
dIH,I
Rate of production of H, =3x2.5x10'=7.5x10'Ms'
dt
Q. 18, If the concentration be expressed in mo] L units and time in seconds, what would be units for rate
constant, k (i) for a zero order reaction (ii) for a first order reaction (DS.B. 2008)
Ans. (i) For a zero order reaction,Rate = k[A]
mol L'
=kxl or k=moll-ls
s
(ii) For a first order reaction, Rate = k[A]
mol L' mol L or k=sl
s
Q.19. Identify the order of a reaction if the units of its rate constant are ;
(i) L'mols' (ii)Lmolls (A.1.$.B.2011
Ans, (i) Zero order (ii) Second order
Q. 20. A reaction is of second order with respect to a reactant. How is the rate of reaction affected if the
concentration of the reactant is reduced to half? What is the unit of rate constant for such a reaction ?
(Al.S.B. 2011)
Ans. For a second order reaction, Rate = k[A]?
If the concentration of A is reduced to half, rate will become 1/4 of the original value.
Units of k
molL' _ uolL
s
9°
k =
 MODERN'S ab¢ + OF CHEMISTRY-XII

Q. 21. In the reaction ; aA + bB » products; if concentration of A is doubled (keeping B constant), the

initial rate becomes four times and if B is doubled (keeping A constant), the rate becomes double,
What is the rate law equation and order of the reaction? (ManipurS.B. 2012
Ans, Rate = k[A] [B], Order = 1 +2= 3.
Q. 22. The rate constant of a reaction is 3 x 10? min. What is the order of reaction ? (Assam. S.B. 2012)
Ans, Order = 1 (from units of rate constant).
Q. 23. For a reaction:A +B » P, the rate law is given by,r = k[A]' [B].
C What is the order of reaction ? (A4.1.$.B.2013)
1 1
0 Ans, Order =
2
+2=2 -or2.5.
2
N Q.24.For a reaction, rate law is give as rate = k[A] [B],
C Can the reaction be an elementary reaction ? Explain. (Pb.SB 2009)
Ans, For an elementary reaction, order of a reaction should be equal to molecularity of the reaction and molecularity
E
p should be integral. For the given reaction, order of reaction is %(
1 +½).Since molecularity cannot be fractional,

T therefore, for the given reaction, order is not equal to molecularity. Hence, given reaction cannot be elementary
u reaction.
A Q.25.The rate of formation of a dimer in a second order reaction is 9.5 x 10-5 mo Ls at 0.01 mol L
monomer concentration. Calculate the rate constant.
L Ans, If the monomer is represented by X. Then,
2X 0X,
Since the reaction is of second order, the rate of reaction will be given by:
Rate = k[X]?
Rate = _1AX] _IX,l _o.s10°mo1L,1
2 dt dt
9.5x 10molLs = k(0.0l molL2
9.5x10°
k = =095Lmols
(0.01
INTEGRATED RATE EXPRESSION
We have learnt that for a general reaction:
aA +bB »cC +dD
rate may be expressed as :
Rate = k[A]P [B]
This form of equation is called differential rate equation. It is not always
convenient to measure the instantaneous rate because it is measured by
determination of slope of the tangent at point 't' in the concentration versus
time graph. Therefore, it is difficult to determine the rate law and hence
order of the reaction. In order to solve this problem, we can integrate the rate
equation and obtain integrated rate equation which gives a relation between
directly measured experimental quantities i.e., concentrations at different times
and rate constant. The integrated rate equations are different for reactions
of different orders.
The integrated rate equations for different order reactions can be derived
as given below :
Zero order reaction
A reaction is said to be of zero order, if its rate does not depend on the
concentration of any of the reactants. Consider the general zero order reaction :
R » Product
Let [R] be the concentration of the reactant R and k is the rate constant
for the zero order reaction. For the zero order reaction, the rate of the reaction
is proportional to zero power of the concentration of R. Thus,
Rate _ dIR] _ [RI"=kx1 €: [R"=1
dt
or d[RJ = -kdt ...(4)
CHEMICAL KINETICS

],gmpielb, S.No. Time (s) Total pressure (atm)

The decomposition of NO, at 318 K according to the 1. 0 0.5
following equation follows first order reaction : 2. 100 0.512
1
N,0,4g »2NO,g+ 5 0,4g Calculate the rate constant. N.CE.R.TN
Solution : Let the pressure of N,O, decreases by 2x atm
The initial concentration of NO, was 1.24 x 10? mol
Since 2 moles of N,O, decompose to give 2 moles of N,O, and
Land that after 00 minutes was 0.20 x 10 molL•
1 mole of 0,, then the pressure of N,O,(g) increases by 2x atm
Calculate the rate constant of the reaction at 318 K. and that of 0.(g) increases by x atm.
N.C.E.R.T (Meghalya 8.B. 2015) 2N,0,g) »2N,0,(g) + 0,g)
Solution : For a first order reaction At time,t =0 0.5 atm 0 0
%.2303,IR At time t (100 s) (0.5 -2x) atm 2x atm ax atm
k g [RJ Total pressure, p, = (0.5--2) +2x +=0.5 +
or x=p,-0.5
t = 60 min. [R], = 1.24 10 mol L-
t = 100s,p, =0.512 atm
[R] = 0.20 10 ? mol L- or x=p,-0.5=0.512-0.5 =0.012 atm
2.303,_log 1.2410 mo1 L' Now, pN,O, = 0.5-2=0.5-2x0.012=0.476 atm
0.2010 mo L'
s

- 60 For a first order reaction,

_23091%6.2.2.303 x 0.7924 pN,0,%, _2.303,, 0.5 atm
k = 2.303,,10g 0
60 60 t pUN,0,,
=
100 0.476 atm
= 0,0304 min'
2.303 2.303
lit,gmpiel} = lOO log 1.0504 = x 0.0214
100
The decomposition of a compound is found to follow = 4.93 104s'
first order rate law. If it takes 15 minutes for 20 per ]l,9mp4el
cent of original material to react, calculate The following data were obtained during the first order
(i) the specific rate constant thermal decomposition of SO.Cl, at constant volume.
(ii) the time at which 10 percent ofthe original material
so,Cl(g » SO,(g+Cl,g
remains unreacted
(iii) the time it takes for the next 20 per cent of the Experiment Times/s Total pressure /atm
reactant left to react after first 15 minutes. 1 0 0.5
(D.S.B. 2002)
Solution : (i) For the first order reaction: 2 100 0.6

.2308IA Calculate the rate of reaction when total pressure is

t [Al 0.05 atm. (CBSE Sample Paper 2011)
Let [Al, = 100, [A] = 100 --20 = 80 Solution; For the decomposition of SO,CL,
k = 2.303 lo 100 s0,CL,(g) -» SO,(g) + CL,(g)
15 g 80
Att=0 Patm 0 0
2.303 . 1 At time t x x
£x00969=0.0149 min (p -v)atm
P, = p-x+x+x =p+
(ii) If [A],, = 100, and [A] = 10, then
or x = p,Po
• 2303,, [A, =P% -'P, D=2p%-P
"a
Now at time t, p(SOCL,)=p%
k = 2.303 log Po
_ ~""1su.s %n
2308 t 2p%-p
0.0149 10
when t = 100s
(ii) If [Al, = 80, [A] = 80_ 80x20 _ e4
o '

2.303,
100
80
= %"5,osos
2.303 0.5 2.303
10o ls125
t = 0.0149 og 64 = 2.2316 10°-
2.303 When p, = 0.65atmi.e.p +p =0.65 atm
=
x0.0969 = 15.0 min.
0.0149 p =065-p=0.65 --0.50 =0.15 atm
]ls,gmpie( Pressure of SO,CL, at time t = 0.50--0.15
The following data were obtained during the first order = 0.35 atrn
thermal decomposition of NO,(g) at constant volume, Rate = 2.2316 10-33 0.35
2N,0,(g) »2N,0,4g + 0,g = 7.8x 105atms'