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nimum Lear
ningPackage(
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y -2020-
21
Topi
c–CHEMICALKINETI
CS
Chemicalki
neti
cs-
Thebranchofchemist
ry,
whichdeal
swi t
htherat
eof
chemi
cal r
eacti
ons.t
hefactor
saff
ecti
ngtherat
eofreact
ionsandthe
mechanism oft
hereact
ion.

Rat
eofr
eact
ion-
Rat
eofachemi
cal
react
ionI
Sthechangei
ntheconcent
rat
ionof
anyoneoft hereactant
sorproductsperuni
ttime.I
tisexpr
essedinmolL-1s-1 
orMs-
1
 
oratmt i
me -
1
unit
s.
Rateofreacti
on
=(decr
ease/ i
ncreaseintheconcent
rat
ionofreact
ant/pr
oduct
/ti
metaken)

Thi
srateofreacti
onisknownasav er
agerat
eofr
eacti
on(r)
.(
r canbecal
av cul
avatedby
di
vidi
ngtheconcentrati
ondi
ff
erencebythet
imei
nter
val)
.
Forachemicalreact
ion,

Considerahy pot heticalreacti

on,assumingthatt
hev ol
umeoft hesyst em r
emains
constant
.
R P
Onemol eoft her eactantRpr oducesonemol eoftheproductP.If[R]1and[P]1ar
ethe
concentr
at i
onsofRandPr especti
velyatt
imet1and[R]
2a nd[P]2aret hei
r
concentr
at i
onsatt imet 2then,
dt=t2–t 1
d[R]=[R]2–[ R]1
d[P]=[P]2–[ P] 1
Thesquar ebr acket sintheabov eexpressi
onsareusedt oexpressmol ar
concentr
at i
on.
Rateofdi sappear anceofR
Decreasei nconcent r
ationofR =Δ[R]
/Δt (eq)1
Ti met aken

Rat
eofappearanceofP
I
ncreasei
nconcentrat
ionofP =Δ[
P]/
Δt (
eq)2
Ti
met aken

Si
nce,d[R]i
sanegativ
equantit
y(asconcent r
ati
onofreactant
sisdecreasi
ng)
,iti
s
multi
pli
edwith–1tomaket herateofthereacti
onapositi
vequanti
ty.
Equati
ons1and2gi venaboverepresentt
heav er
agerat
eof
areacti
on,r
av(av
eragerat
eofreacti
on) .
 I
nstant
aneousRateofReacti
on
Rat
eofachemi calr
eacti
onatapar
ti
cul
armomentoft
ime,
isknownas
i
nst
antaneousr
at eofr
eacti
on.

Uni
tsofr
ateofr
eact ion-(
1)i
fconcent
rat
iont
akeni
nmol
/Landt
imei
sinseconds
t
henitwi
l
lbemolL-1s-1

(2)whenreact
antsarei
ngaseousstat
esthenconcengt
rat
ionexpr
essedi
nthei
rter
m
ofpart
ial
pressur
e,thenuni
tofrat
eofreacti
onwil
lbeatm s-1

Factor
sAffect
ingRateofReacti
on
1.Natureandconcent
rati
onofreactant
2.Temper
atur
e
3.Sur
facear
eaofr
eact
ant
4.Radi
ati
onsandcat
aly
st
5.Pr
essur
eofgas
RateLawExpr
essions
Accordi
ngt
othelawofmassact
ion,

Forachemi
cal
react
ion,

aA+bB→ pr
oduct
x y x y
Rateα[A] [B] =k[A] [B]
X Y
Rate=k[A] [
B]
X Y
-
d[R]/
dt=k[A] [B]
where,[
A]and[ B]molarconcent
rat
ionsofAandBr
espect
ivel
yandki
sthev
eloci
ty
const
antorr
ateconst
ant
.Theabov
eexpr
essi
oni
sknownasr
atel
aw.

Orderofa
Reaction nt her ateequat ion
Rate=k[ A]x[B]y
xandyi ndi
catehowsensi t
ivet her at
ei st
ot hechangei nconcent r
ationofAandB.
Sum oft heseexponent s,i
.e.
, x+ygi vestheov erallorderofar eactionwher easxand
yrepresenttheor derwi threspectt othereactantsAandBr espect i
vely
.
Hence, thesum ofpower soft heconcent rati
onoft her eact
antsi nther at
elaw
expressioniscal l
edt heorderoft hatchemi calreacti
on.
Orderofar eactioncanbe0, 1, 2,3andev enaf r
action.Azer oor derreacti
onmeans
thatther at
eofr eact i
onisindependentoft heconcent rat
ionofr eactants.
Exampl e-Calcul
at et heov erallor derofareactionwhi ch
hasther ateexpr essi on
1/
2 3/
2
(a)Rate=k[ A] [
B]
3/2 –1
(b)Rate=k[ A] [
B]
x y
(a)Rate=k[ A][B]
order=x+y
Soor der=1/ 2+3/ 2=2, i.
e.,secondor der
(b)order=3/ 2+( –1)=1/ 2,i.e.,halforder
.

Unit
sofrateconst ant
Forageneralreact
ion
aA+bB cC+dD
Rate=k[A]x[B]y
Wherex+y=n=or deroft
her
eact
ion
X Y
k=Rate/[
A] [
B]
1-
n
k=(
concent
rat
ion) /t
ime

TakingSIunitofconcentr
ation, L-1andt
mol ime,
s(i
nseconds)uni
tofkf
ordi
ff
erent
reacti
onorderinfol
lowingtable

Exampl
e-I
denti
fyther
eactionorderf
rom eachofthefoll
owi
ngrateconst
ant
s.
–1 –1
()k=2.
i 3×10–5Lmol s
(i
i)k=3×10–4s–1
–1 –1
(i
)Theuni
tofsecondorderrat
econstantisLmol s, t
her
efor
e
 –1 –1
k=2.3×10–5Lmol s r epr
esentsasecondor derreact
ion.
–1
(
ii
)Theuni
tofaf
ir
storderrateconstanti
ss t heref
ore
k=3×10–4s–1r
epresentsafir
storderreacti
on.

Mol
ecul
ari
tyofr
eact
ion

Thenumberofreact
ingspeci
es(
atoms, i
onsormolecules)t
akingpar
tinan
el
ementar
yreacti
on,whi
chmustcol l
i
desimult
aneouslyinordertobr
ingabouta
chemi
calr
eacti
oniscall
edmolecular
ityofar
eacti
on.
Uni
molecul
arr
eacti
on
NH4NO2N2+2H2O

Bi
mol
ecul
arr
eact
ion:
2HI
H2+I
2

Tr
imol
ecul
arr
eact
ion:
2NO+O2
2NO2

I
ntegr
atedr
ateequat
ionf
orzer
oor
der

[ kt+[
R]=- R]0

Compar i
ngaboveequati
onofastraightl
ine,y=mx+c, i
fwepl
ot[
R]agai
nstt
,weget
astr
aightli
newi t
hslope=–kandi nter
ceptequalto[R]
0.
Fur
thersimpli
fyi
ngaboveequat
ionwegett herateconst
ant
,kas
k=[
R]0-
[R]
/t her
eR0isiniti
alconcentr
ati
on

Integrat edr ateequat ionforfir

storder
l
n[ R]=- kt+l n[R]0
k=1/ tln[ R]0/[R] eq(A)
Att met
i 1f r
om abov eequation
*ln[R]1=–kt 1+* ln[R]0 eq(1)
Att met
i 2
l
n[ R]2=–k t2+l n[R]0 eq(2)
wher e, [R]1a nd[ R]2a r
et heconcentrat
ionsoft
her
eact
ant
satt
imet
1andt
2
respect ivel y
.
Subst ract i
ngequat ion1f rom 2
l
n[ R]1–l n[ R]2=–kt 1–( –kt2)
k=1/ (t -
t
2 1) ln[R ]
1/[R]2
abov eeq( A)wr i
ttenas
k=2.303/tlog[R]0/
[R]
l
og[R]0/
[R]=kt
/2.303 eq(
B)
copmpar i
ngeq(A)wi t
hy=mx+c, i
fwepl
otln[R]agai
nst
twegetast r
aightli
newi
t ope=–kandi
hsl nter
ceptequalt
oln[
R]0

Compar
ingeq(
B)wi
thy
=mx+c,
wepl
otgr
aphbet
weenl
og[
R]0/
[R]VSt
ime(
t),
the
sl
ope= k/2.303

Whenr
eact
ant
sar
eingast
henr
ateconst
antk=2.
303/
tlogpi
/(
2pi-
pt)

Hal
fli
feofar
eact
ion

Thehalf-l
if
eofareacti
onistheti
mei nwhi
cht heconcentrat
ionofareact
anti
s
reducedtoonehalfofit
sini
ti
alconcent
rat
ion.Iti
srepr edast
esent 2.
1/
t1/
2=[
R]0/2k (forzeroor
d er
)

t2=
1/ 0.
693/
k (
forf
ir
stor
der
)

Exampl
e-Cal
culat
ethehal
fli
feofacompoundi
f90%ofagi
vensampl
eoft
hecompound
decomposedin30min

[
A]=[A]0 
e^-
kt
[
A]0 =90%
[A]=10%
t=30mi n*60s/ 1min=1800s
[10%]/
[90%] =e^-
k*1800
l
n[10%/90%]/1800=k=3. 95E-
4
t
1/2=l n(2)
/k
t1/2=.693/ 3.95E-
4=1754s
 1754s*1min/60s=29mi n
Temper at
uredependenceoftherateofreacti
on
Thetemper at
uredependenceoftherateofachemi calreacti
oncanbeaccur at
ely
expl
ainedbyAr r
heni
usequationItwasf i
rstproposedbyDut chchemist
,J.H.van’t
HoffbutSwedishchemi st
,Ar
rheni
usprovi
dedit
sphy sical
justi
fi
cat
ionandi
nter
pret
ati
on.

k=Ae- Ea/RT eq(c)

wher eAistheAr rheni
usfactororthefrequencyfact
or.Itisalsocal
ledpr
e-
exponenti
alfactor.Iti
saconst antspecif
ictoaparti
cularreacti
on.
Ri sgasconstantandEai sactivati
onener gymeasuredinjoules/mole
(Jmol –1).
Itcanbeunder stoodclear
lyusingthefollowingsi
mpler eacti
on
H2( g)+I2(g)®2HI( g)

Accordi ngtoArrhenius, thisreactioncant akepl ace

onlywhenamol ecul
eofhy drogenandamol eculeofiodinecolli
detof orm an
unstabl ei
ntermediate( Figabov e)I texi
st sf orav eryshortti
meandt henbr eaksupto
formt wo
molecul esofhy dr
ogeni odide.For mat i
onofHIt hroughtheIntermediateabov e:
Diagram showi ngplotofpot entialenergyv sr eacti
oncoor di
nate:Distri
butioncurve
showi ngener gi
es
amonggaseousmol ecul esTheener gyrequi redt oformthisintermediate,cal
led
acti
vat edcompl ex(C) ,i
sknownasact ivationener gy(Ea).i
sobt ai
nedbypl ot
ti
ng
potentialenergyvsreact ioncoor dinate.React ioncoordinaterepresentsthepr of
il
eof
energychangewhenr eactantschangei ntopr oducts.
Takingnat urall
ogarithm ofbot hsidesofequat i
on(c)Arrheniusequat i
on

l
nk=-
Ea/
RT+l
nA

Thepl nkv
otofl s1/
Tgi
vesast
rai
ghtl
i
neaccor
dingt
otheabov
eequat
ion

sl
ope=–Ea/R
andi
nter nA.Sowecancal
cept=l cul
ateEaandAusi
ngt
hesev
alues.
EFFECTOFCATALYST-I tisbeli
evedthatthecatal
ystprovi
desanal
ter
natepat
hway
orreact
ionmechani
sm byreduci
ngtheact i
vat
ionenergybetweenr
eactant
sand
product
sandhenceloweri
ngthepotential
energybarri
er.

COLLISI
ONTHEORYOFCHEMI CALREACTI ONS-iti
sbasedonkinet
ict
heor
yof
gases.I
ncol
li
siontheor
yactivati
onenergyandproperori
ent
ati
onofthemolecul
es
toget
herdet
erminethecri
ter
iaofeffect
ivecoll
i
sion.

ONECASEBASEDQUESTI
ONHAVI
NG4MCQBASEDONGI
VENPASSAGE

PASSAGE

Ther ateofachemi cal react i

oni sexpr essedei t
heri ntermsofdecr easei nt
he
concent r
ationofr eactantperuni tti
meori ncreasei nt heconcent r
ationofapr oduct
perunittime.r ateofr eact iondependsupont henat ureofreactants, concentrationof
reactants, temperature, presenceofcat al
yst ,
sur faceareaofr eactanct sand
presenceofl i
ght.Rateofr eactioni sdirectlyrelatedt otheconcent rationofreact ant .
Ratelawst atesthatther ateofr eactiondependsupont heconcent rat i
onoft ermson
whicht her ateofreactionact uallydepends, asobser vedexperiment all
y.Thesum of
power soft heconcent rat i
onoft her eactantsint her atelawexpr essioni scalledor der
ofreactionwhi lethenumberofr eact i
ngspeci estakingpar ti
nanel ement aryr eaction
whichmustcol l
i
desi mul taneousl yi
nor dert obr i
ngaboutachemi cal reacti
oni s
call
edmol eculari
tyofther eaction.

Q.1Ift
her
ateofar
eact
ioni
sexpr
essedby
,rat
e=A[
A]²[
B],
theor
derofr
eact
ionwi
l
l
be
(a)2
(b)3
(c)1
(d)0

Q.
2Theuni
tofr
ateconst
antf
ort
her
eact
ion
2H2 +2NO→ 2H2O+N2
whichhasr ate=K|
H2|
|
NO|
²,i
s
(a)mol L-1 s-1
(b)s-1
-
2
(c)mol  L²s-1
(d)mol L-1

Q.
3Forar eact
ionx+y→ z,
rat
e∝|
X|.Whati
s(i
)mol
ecul
ari
i
yand(
ii
)or
derof
r
eact
ion?
(
a)(i
)2,(
ii
)1
(
b)[i
)2,(
ii
)2
(
c)(i
)1,(i
i)1
(
d)(i
)1,(i
i)2

Q.
4Thenumberofmol eculesofthereact
ant
staki
ngpar
tinasi
ngl
est
epoft
he
r
eacti
oni si
ndicat
iveof
(
a)orderofareaction
(
b)mol ecui
ari
tyofareaction
(
c)faststepofthemechani sm ofareacti
on
(
d)half-l
i
feofthereacti
on

ANSWERS

Q1-
B,Q2-
C,Q3-
A,Q4-
B

Casebasedasser
ti
on-
reasonquest
ions

Readt
hef
oll
owi
ngpassageandanswert
hegi
venquest
ions:

Chemi calki
netics,thebr anchof  
phy si
cal chemi st
ry t
hatisconcernedwi t
h
under standi
ngt her atesof  chemi calreactions.Iti
st obecont r
asted
with t
her mody nami cs,whi chdeal swi ththedi r
ectioninwhi chaprocessoccursbutin
i
tselftellsnothingabouti t
sr ate.Ther mody namicsistime’sarrow,whilechemi
cal
kineti
csi sti
me’ sclock.Chemi calkineticsrelatestomanyaspect s
of cosmol ogy,
 geology ,
 biology ,
 
engi neeri
ng, andev en psychol
ogy andthushasfar
-
reaching impli
cat i
ons.Thepr i
nciplesofchemi calkineticsappl
ytopur el
yphysi
cal
processesaswel last ochemi calreactions.

The rat
eofar eact i
on i
sdef inedi nt
er msoftherateswithwhi chthepr oductsare
formedandt her eactant
s( ther eacti
ngsubstances)areconsumed.Forchemi cal
systemsi ti
susual todeal wi t
ht heconcentr
ati
onsofsubst ances,whichisdefinedas
theamountofsubst anceperuni tvolume.Theratecant henbedef i
nedast he
concentrati
onofasubst ancet hatisconsumedorpr oducedi nunitti
me.Somet i
mes
i
tismor econv enienttoexpr essr at
esasnumber sofmol eculesformedorconsumed
i
nuni tt
ime.
(
Ref
:Kei
thJ.Lai
dler
,For
merPr
ofessorofChemi
str
y,Uni
ver
sit
yofOt
tawa,
Ont
ari
o.Aut
horof
 The
Wor
ldofPhy
sicalChemi
str
y.)

I
nthesequesti
onsastatementofasser
ti
onf
oll
owedbyastatementofr
easoni
s
gi
ven.Choosethecor
rectansweroutoft
hef
oll
owingchoi
ces.

a)Asser
tionandreasonbot
har
ecor
rectst
atement
sandr
easoni
scor
rect
expl
anat
ionforasser
ti
on.

b)Assert
ionandreasonbot
har
ecor
rectst
atement
sbutr
easoni
snotcor
rect
expl
anat
ionforasser
ti
on.

c)Asser
ti
oni
scor
rectst
atementbutr
easoni
swr
ongst
atement

d)Asser
ti
oni
swr
ongst
atementbutr
easoni
scor
rectst
atement
.

1.
Asserti
on:
Ther
ateofar
eact
ioni
sther
ateofchangeofconcent
rat
ionofar
eact
ion
oraproduct
.

Reason:
Rat
eofr
eact
ionr
emai
nsconst
antdur
ingt
hecour
seofr
eact
ion.

2.
Asser
ti
on:
Inst
ant
aneousr
atei
susedt
opr
edi
ctt
her
ateofr
eact
ionatapar
ti
cul
ar
momentoft
ime.

Reason:
Aver
ager
atei
sconst
antf
ort
het
imei
nter
val
forwhi
chi
tiscal
cul
ated.

3.
Asser
ti
on:
All
col
l
isi
onsofr
eact
antmol
ecul
esl
eadt
opr
oductf
ormat
ion.

Reason:Onl
ythosecoll
i
sionsi
nwhi
chmolecul
eshavecor
rector
ient
ati
onand
suff
ici
entki
neti
cenergyleadt
ocompoundfor
mati
on.

4.
Asser
ti
on:
Theent
hal
pyofr
eact
ionr
emai
nsconst
anti
nthepr
esenceofacat
aly
st.

Reason:Acatal
ystlowersdowntheact
ivat
ionener
gybutt
hedi
ff
erencei
nener
gyof
react
antandproductremainssame.

Answer
s:

1.
c2.
b3.
d4.
a

MCQs

1.Whichamongt hef ol
lowingisaf alsestatement?
(a)Rateofzer
oor derreacti
oni sindependentofinit
ial
concent
rat
ionofr
eactant
.
(b)Halfl
if
eofat hir
dor derreacti
onisinverselypr
oporti
onalt
osquareofi
nit
ial
concentr
ati
onoft hereactant.
(c)Molecul
ari
tyofar eacti
onmaybezer oorfract
ion.
(d)Forafir
storderreacti
on, t2=
1/ 0.
693K
2.Forthereacti
onN2  +3H2 
→ 2NH3 
i
f Δ[
NH3]
/Δt
 =2×10-4  L-1s-1,
mol thev
alue
of −Δ[
H2]/
Δt  
woul dbe
-
4
L s1
-1-
(a)1×10   mol
(b)3×10-4 molL-1s-1
(c)4×10-4 molL-1s-1
(d)6×10-4 molL-1s-1

3.Forachemical
reacti
onA→B, iti
sfoundthatt
herateofreacti
ondoubl
eswhent
he
concentr
ati
onofAisincreasedf
ourti
mes.Theorderofreacti
onis
(a)Two
(b)One
(c)Hal
f
(d)Zero

4.Thehalfl
i
feoft
hef
ir
stor
derr
eact
ionhav
ingr
ateconst 7x10-5s-1 
antK=1. i
s
(a)12.1h
(b)9.7h
(c)11.3h
(d)1.8h

5.I
ntherat
eequat
ion,
whent
heconcent
rat
ionofr
eact
ant
sisuni
tyt
hent
her
atei
s
equal
to

a.specifi
crat
econst ant
b.averagerateconstant
c.i
nstantaneousrateconst
ant
d.Noneoft heabove

6.Theav
erager
ateandi
nst
ant
aneousr
ateofar
eact
ionar
eequal

a.att
hestar
t
b.att
heend
c.i
nthemiddle
d.whent
wor ateshav
eat
imei
nter
val
equal
tozer
o

7.Ther
ateconst
antof
 zer
o-or
derr
eact
ionshast
heuni
t

a.s-1
b.mol L-1 s-1
2 -
2 -
c.L  mol  s1
-1 -
d.Lmol  s1

8.whent
her
ateoft
her
eact
ioni
sequal
tot
her
ateconst
ant
,theor
deroft
her
eact
ion
i
s

a.zeroorder
b.fi
rstor
der
 c.secondorder
d.thi
rdorder

9.Ift
her
ateofar
eact
ioni
sexpr
essedby
,rat
e=A[
A]²[
B],
theor
derofr
eact
ionwi
l
lbe
(a)2
(b)3
(c)1
(d)0

10.Ar eacti
oninwhichreact
ants(
R)ar
econver
tedi
ntopr
oduct
s(P)fol
l
owssecond
orderkineti
cs.I
fconcentr
ati
onofRisi
ncr
easedbyt
hreet
imes,whatwi
llbet
he
i
ncreasei ntherat
eofformati
onofP?
(a)9times
(b)4times
(c)16t i
mes
(d)8times

11.Ther at
econst antofareact i
ondependsupon
(a)temperatureofthereacti
on
(b)extentofthereacti
on
(c)i
niti
alconcentrati
onofther eact
ants
(d)thetimeofcompl eti
onofr eacti
on

Answer
s:

1.
c2.
b3.
c4.
c5.
a6.
d7.
b8.
a9.
b10.
a11.
d

Asser
ti
on-
ReasonTy
peQuest
ions

I
nthesequesti
onsastatementofasser
ti
onf
oll
owedbyastatementofr
easoni
s
gi
ven.Choosethecor
rectansweroutoft
hef
oll
owingchoi
ces.

a)Asser
tionandreasonbot
har
ecor
rectst
atement
sandr
easoni
scor
rect
expl
anat
ionforasser
ti
on.

b)Assert
ionandreasonbot
har
ecor
rectst
atement
sbutr
easoni
snotcor
rect
expl
anat
ionforasser
ti
on.

c)Asser
ti
oni
scor
rectst
atementbutr
easoni
swr
ongst
atement

d)Asser
ti
oni
swr
ongst
atementbutr
easoni
scor
rectst
atement
.

1.Assser
ti
on:
Mol
ecul
ari
tyhasnomeani
ngf
oracompl
exr
eact
ion.

Reason:Theover
allmolecular
ityofacompl
exr
eact
ioni
sequalt
othe
mol
ecular
ityoft
hesloweststep.
2.
Assert
ion:Ifi
nazeroorderr
eact
ion,
theconcent
rat
ionoft
her
eact
anti
s
doubl
ed,thehal
f-l
if
eper
iodisal
sodoubled

Reason:Forazer
oor
derr
eact
ion,
ther
ateofr
eact
ioni
sindependentofi
nit
ial
concentr
ati
on.

3.Asser
tion:Half
-l
if
eper
iodofar
eact
ionoff
irstor
deri
sindependentofi
nit
ial
concentr
ation.

Reason:
Half-
li
feper
iodf
orafirstor
derreact
ion t
1/2=2.
303/
Kxl
og2
4.Asser
tion:
Therat
eofreact
ionisalwaysnegati
ve.
Reason:Minussignusedi
nexpr
essi
ngt
her
ateshowst
hatconcent
rat
ionof
react
anti
sdecr
easing.
5.Asser
tion: 
Orderoft
her
eact
ioncanbezer
oorf
ract
ional
.
Reason:
 
Wecannotdet
ermi
neor
derf
rom bal
ancedchemi
cal
equat
ion.

Answer
s:
1.
c2.
b3.
a4.
d5.
b

S.No. 2MARKSQUESTI ONS

1. ( a)Expr essther at eofr eact ionint ermsofdi sappear anceofhy drogenand
appear anceofammoni ai nt hegi venr eact ion: N2( g)+3H2( g)→ 2NH3( g)
(b)Forachemi cal react ionA→ B.Ther ateoft hereact i
onisgi venasRat e=
n
k[A] therateoft heabov er eacti
onquadr upl eswhent heconcent rat
ionofA
i
sdoubl ed.Whati st hev alueofn?
Ans: (a)Rate=- 1/3d[ H2] /dt r ate=+1/ 2d[NH3] /dt
(
b)Ans.n=2
2 (a)Theconv ersionofmol ecul esXt oYf oll
owst hesecondor derofki net
ics.
Ifconcent r
ationofXi sdecr eased3t i
mes, howwi lli
taf f
ectther ateof
format ionofY.
(b)Ifar eactonhass-1ast
i heuni tofther ateconst ant.Whatwi llbethe
orderoft her eact i
on?
2 2 2
Ans.( a)Rate=k[ A] =k[ 1/ 3A] =1/9k[ a]
Therateoff ormat i
onwi l
l become1/ 9times.
(
b)Fi r
stor derr eact ion
3 Def ine( a)rateofr eact i
on( b)speci fi
cr eact ionr at
eorr ateconst ant
Ans.( a)Thechangei nconcent r
at i
onofanyr eactantorpr oductperuni t
ti
mei scal l
edr ateofr eaction.
(b)Itisequal tot her at eofr eactionwhenmol ecularconcent r
ationof
reactantisatuni ty .

4 Wr
it
ethedi
ff
erencebet
weenor
derandmol
ecul
ari
tyofr
eact
ion.
 Sr. Or
der Mol
ecul
ari
ty
No.
1. Sum oft he coeffici
ents of No.ofreacti
ngspeciesinvol
ved
thereacti
ngspeci esinvolv
ed itssi
multaneouscoll
isi
on.
i
nt herateofreaction.
2. Determined I
tist
heoreti
calconcept
3. I
tcanbezer o I
tcannotbezer o
4. I
tmaybei nfr
action I
tcannotbeinf r
acti
on.
2
5 (
a)Rateofreact
ioni
sgi v
enbytheequat ion:-Rate=k[ A] [
B]
Whataretheuni
tsofr at
econstantf orthisreact i
on?
(
b)Achemi calr
eact
ionisofsecondor derw. r
.t
.ar eactant .Howt her
ateof
r
eacti
onaffect
edift
heconcentrat
ioni sr educedt ohal f.
2
L-1s-1 =>( L-1)
2 -1 -
22-
Ans.(a)Rate=k[A] [
B]=>K=mol mol (mol )=>K=mol Ls
1

(
b)Itisreducedt oone- f
ourth.
6 (
i)Whatistheuni tf
orKf orthef ol
lowi
ngr
eactionratelaw:
0 0 0
(
a) Rate=K[A][
B] (b) Rate=K[A] [
B]
(
ii
)Whyi stheuseofi nstantaneousrat
eofreacti
onpr efer
redov
erav
erage
r
ateofreacti
on?

Ans(i) ( a) s-1 (b) mol eL-1s-1

(i
i)Therateofreact
ionconti
nuousl
ydecr
easeswi tht i
me( exceptforzer
o
orderreact
ion)andTheref
ore,av
erager
atehasnosi gnif
icanceforthe
reacti
on.

7 (a)Achemi cal reactionisofzer oor derw. r.t

.ar eact ant .Howt herat eof
reacti
onaf fect edift heconcent r
at i
oni sreducedt ohal f?
(b)Thegasphasedecomposi ti
onofacet aldehy de
CH3CHO CH4+CO
foll
owst her atel aw, Rate=k( PCH3CHO) 3/2,uni tofPi sat m andtime
i
ssecond.Whatar et heunitsofi tsr at econst ant?
Ans.(a)Nochange
Ans.(b)At m- ½sec- 1
8 Foll
owingr eact i
ont akespl acei nonest ep:-2NO+O2→ 2NO2
Howwi l
l t
her at eoft her eactionoft heabov er eact i
onchangei fthev olume
ofreactionv essel isdi minishedt o1/ 3ofi tsor iginal volume?Wi l
lther ebe
anychangei nt heor derofr eactionwi threducedv olume?
2 1
Ans.2NO+O2 → 2NO2 =>dx/ dt=k* [NO][ O2]
[Sincei tisonest ep]
Ifthev ol umeofr eact i
onv essel isdimi nishedt o1/ 3,conc.Ofbot h
NOandO2wi l
l become3t ime, ther ateofr eactioni ncr eased27t imes.Rat e
ofthereact i
onwi l
lbecome27t i
mes, orderwi llremai nunchanged
9 Forther eactionat500K
(i
)NO2( g)+NO2( g)==>NO+NO3( sl ow)
(i
i)NO3+CO==>CO2+NO2( f
ast )
Whati sther atel awf orther eaction?Wr itetheov erall orderofther eact i
on?
 Outof( i)or(ii
),whi chonei sratedeterminingst ep.Giver eason.
Ans.Thesl owst epoft hereactionmechani sm i s:
NO2+NO2==>NO+NO3
Hence, therateofr eactionis,
Rate=k[ NO2][NO2]
2
Orrat e=k[ NO2]
Order =2
Step( i),sl
owestst epoft hemechani sm decidest her ateoft hereact
ion.
10 Thef ol l
owingdat awer eobtaineddur i
ngthef irstordert hermal
decomposi tionofSO2Cl 2ataconst antvolume:
SO2Cl 2(g)→SO2( g)+Cl 2(g)
Time/ sec Tot alpressure/ atm
0 0.40
100 0.70
Calcul atetherateconst ant(Given:log4=0. 6021, l
og2=0. 3010)
Ans:
2.
303 p
k= og i
l
t (
2pi-)
pt
2.303 0.4 2.303 0. 4 2.303 2.303
k= l
og = log = l
og4 = x
100 ( 2x0. 4-0.7) 100 0. 1 100 100
0.6021
k=1. 38x10-2s-1

11 Anal
yset
hegi
vengr
aph,
drawnbet
weenconcent
rat
ionofr
eact
antv
s.t
ime

(a)Predi cttheor derofreact ion.

(b)Theor eti
cally
,cant heconcent rationoft hereactantreducet ozeroafter
i
nfinitetime?Expl ai
n.
Ans: (a)Firstorderr eaction.
(b)Basi call
yi naf i
rstorderr eacti
ont her ateofther eacti
onisdi r
ectl
y
propor t
ional totheconcent rati
onoft her eactantleft.soast hereacti
on
proceedst heconcent rationoft her eact antgoesondecr easingandr ate
becomesmor eslowast imepasseshencei tnevercomest oend.
12 I
ft hedecomposi ti
onofni t
rogenoxi deas2N2O5→ 4NO2+O2f oll
owsaf ir
st
orderki netics.(
i).Calculatet herateconst antfora0. 05M sol ut
ionifthe
i
nst antaneousr at eis1.5x10-mol L-1s-1?ii
)Whatconcent r
ationofN2O5
45x10-5mol -1-
woul dgi vear at
eof2. l s1?
 Ans. (
a)Rat
e=K[
N2O5]
1.
5X10-6
K=Rat
e/[
N2O5]= 0X10-5
=3.
0.05

(
b)Rat
e=K[
N2O¬5]
2.45X10-
5
[
N2O5]=Rat
e/k= =0.
82
3.
0X10-5

3MARKSQUESTI ONS
1 60%ofaf ir
stor derr eact ionwascompl etedin60mi nut
es.Whenwasi thal
f
compl et ed.
Ans: k=2. 303/ 60l og[ A]0/0.4[A]0 =0 .
01527
t½ =0. 693/0. 01527 = 45.
38mi nutes
2 Ar eactioni sfirstor deri nAandsecondor derinB.
(i
) Wr itet hedi fferent ial r
ateequat i
on.
(i
i)Howi st her ateaf f
ect edoni ncreasingtheconcent r
ationofBthr
ee
ti
mes?
(i
ii
)Howi st her ateaf f
ect edwhent heconcent rationsofbothAandBar e
Doubl ed.
2
Ans.( i
)dx/ dt=k[ A] [B]
2 2
(i
i)Rat e=kab , If[B]ist r
ipled,Rat e=ka( 3b) =9kab2=9t imes.
2
(i
ii
)Ifbot h[ A]and[ B]ar edoubl ed,Rate=k(2a)(2b) =8kab2=8times.
3 Theki net icsoft her eact i
on: A+2B Pr oducts;obey sther at
eequati
on
A]X[ Y
Rate=k[ B] .Fori t, fi
nd
(
i) Or deroft her eact ion
(
ii)Appar entmol ecul arityofr eacti
on
(
iii
)Or derofr eact ionwhenBi si nlargeexcess.
Ans: i
)X+Y ii)3 i
ii
)X
4 Answert hef oll
owi ngquest i
onsont hebasi soft hegivencur v
eforaf i
rst
orderr eact ion:A——→P

(
i) Whatist
herel
ati
onbetweensl
opeofthisl
i
neandrat
econst
ant
?
(
ii
)Cal
cul
at
ethera
tec
onsta
ntofth
eabover
eac
tioni
fth
esl
opei
s3×1 0–4
–1
s .
(
i)Sl
ope=

(
ii
) Sl ope=2×10–4s–1
K =2.303×Slope =2.303×3×10–4s–1
K=6.909×10–4s–1
5 (a)Whyr ateofr eactiondoesnotr emai nconstantthroughout?
(b)Whati shalf
-lif
eper i
odofar eact i
on?
(c)Therateofdecoposi ti
onofasubst anceAbecomes8t i
meswheni ts
concentrati
oni sdoubl ed.whati st heor derofthereacti
on?
Ans( a)Ther at
eofar eactiondependsont heconcoft hereactantandt he
concof r eact antdecr easeswi t
hpassageoft ime
Ans(b)Itisthet i
mer equiredbyt her eact iontoundergo50%compl et i
onor
thetimebywhi cht heconcoft her eact antreducest ohalfofit
sinit
ialvalue
n n (
i)
Ans.(c)Rate=k[ A] =>r=k[ A]
n ( i
i
)
8r
=k[ 2A]
divi
dingiibyi
n n => n
8r/r=k[ 2A] /k[ A] 8=[ 2] =>n=3,or deris3
6 (a)Forachemi calr eaction:React ant——>Pr oduct ,t
hev ari
ationint he
concentration( R)vs.t ime( t
)pl otisgivenas:

(
i) Pr
edictt
heor
derofther
eact
ion.
(
ii
) Whatdoest
heslopeoft
hegraphrepr
esent?

(
b)Thr ee-f
our
thofareact
ioniscompl
etedi
n32mi
nut
es.Whati
sthehal
f
l
if
eper i
odofthi
sreact
ion
Ans:
(a)(i)Zer
oorder
(
ii
)Sl
ope=–k=
(b)16mi nut es
7 (a)Afterfivehal f-li
feper i
odsf oraf irstorderr eact ion,whatf ractionof
reactantremai ns?
(b)Whyar ereact i
onsofhi gheror derl essi nnumber?
(c)Whycan’ tmol eculari
tyofanyr eact ionbeequal t
ozer o?
Ans: (
a)1/ 32
(b)Ar eact i
ont akespl aceduet ocol li
deofmol ecules.Thechancesf ora
largenumberofmol eculesori onst ocol lidesi mul t
aneousl yar
eless.
Hence, ther eact i
onsofhi gheror derar el ess
(c)Mol ecul arityofar eact i
onmeanst henumberofmol eculesoft he
reactant st akingpl acei nanel ement ar yreact ion.Sinceatl eastone
mol ecul emustbepr esent, sot hatmol ecul arit
ywi llbeatleastone
8 Foracer tainchemi calreact i
on, variationint heconcent rati
on,l
n[ R]vsti
me
(s.
)plotisshownbel ow:
(i
) Whati st heor deroft hereact ion?
(i
i)Whatar et heuni tsofr ateconst ant ,
kf ort her eact i
on?
(i
ii
)Gi vether elati
onshi pbet weenkandt 1/2o ft hi
sr eact i
on.
 (
iv)I
fini
ti
alconcentr
ati
onforthi
sreacti
onbecomeshal
f,howwi
l
lt 2v
1/ ar
y?
(
v)Whatdoest hesl
opeofthi
slineindi
cat
e?
(
vi)Drawtheplotofl
og[R]
0/[
R]vstime(s).

(
i)fi
rstorder (i
i)s-1 ( i
ii
)t 2=0
1/ .
693/k
(
iv)Nochangei nt 2b
1/ ecausehalf-
li
fei
sindependentofi
nit
ial
concent
rati
on.
(
v)Sl opeofl
inei sequalto- k

(
vi)

9 (
a)Thehal
fli
feper
iodofafir
storderr
eacti
onis60mi
nut
es.What
per
cent
agewill
beleftaf
ter240minutes?
(
b)I
nthereacti
onA—>B, i
ftheconcentrat
ionofAi
splot
tedagainstt
ime,
t
henatureofthecur
veobtai
nedwillbeasshown.Whatistheorderof
t
hereacti
on ?

(
c)Wri
tet
hetwopossibl
erat
elawequat
ionsoft
hef
oll
owi
ngsecond
or
derr
eact
ions.P+Q→ Pr oduct
(
a)Ans.Noofhal
fli
ves=240/
60=4,
i.
e.n=4
Amountl
eftaf
ter4hal
fli
ves=[
A] 24=[
0/ A]0/
16=0.
0625ofA0=6.
25%
(
b)Fi
rstOr
der
(
c) Thepossi bl
er at
elaw expr
essi
onsf
ort
hef
oll
owi
ng second or
der
r
eact
ioncanbegiv
enas:(
anytwo)
 1 1 2 0 0 2
(
i)Rat
e=[
P] [
Q](i
i
)Rat
e= K[
P] [
Q](i
i
i)Rat
e=K[
P] [
Q]

10
(
a)Catal
yst shavenoeffectonequi
li
bri
um const
ant.why?
(
b)Whyequi l
i
bri
um constantofareacti
ondoesnotchangeinthepresence
ofacat aly
st?
(
c)Whati stheeffectofaddingcat
aly
stonthefreeener
gychange(ΔG)ofa
react
ion?

Ans.(a)Cataly
stcatal
ysest
hefor
wardaswellasbackwar
dreact
iontothe
sameext ent,sothattheequi
l
ibr
ium st
ater
emainssamebuti sreached
ear
li
er.
Ans.(b)Thecataly
sti
ncreasest
herat
eofforwar
dreacti
onaswellas
backwardreacti
ontothesameextant
.Henceequi
li
bri
um isnotdi
stur
bedbut
i
sat t
aint
edquickly
.

Ans.
(c)NochangeinΔGoccur
sint
hepresenceofcat
aly
st(
asf
reeener
gyof
ther
eactantandpr
oduct
sremai
nst
hesame) .

5MARKQUESTI ONS
1 (a)Foraf i
rstor
derreaction,showt hatt i
mer equi
redfor99%compl et
ionis
twicethetimerequi
redf orthecompl eti
onof90%oft her eact
ion.
(b)Consideracert
ainreact i
onA→ Pr oductswithk=2. 0×10−2s−1.Calcul
ate
theconcent r
atonofAr
i emai ni
ngaf ter100si ftheini
ti
alconcentr
ationofAi s
1.0mol L−1.
2.303 a
Ans:(a)Ans.Forthefir
stor derreaction,t= l
og
k a-
x

99
For99%compl
eti
onx= a=0.
99a
100

a
t
99%=2.
303/
klog =2x2.
303/
k
a-
0.99a

For90%compl
eti
on,
x=90%ofa=0.
90a

2.
303 a 2.
303
t
90%= log = log10=2.
303/
k
k a-
0.90a k

Hencet
99%=2xt
90%

(b)Answerk=2. 0×10−2s−1T=100s
[
A] o=1.0moL−1
Sincet tofki
heuni ss−1,t
hegivenr
eact
ioni
saf
ir
stor
derr
eact
ion
 Ther
efor
e,

=0.135molL−1(
approxi
matel
y)
Hence,t
her
emainingconcent
rat
ionofAi
s0. L−1.
135mol

2 Suppose 50 bact er i
a ar e placed i naf l
ask cont aining nutri
ent sforthe
bacteriasot hatt heycanmul t
iply
.Ast udyat35° Cgav et hef ol
l
owing
result
s
Time( minut es) 0 15 30 45 60
Numberofbact eri
a 100 200 400 800 1600
Then
(i
)Thismul ti
pli
cationofbact eriafoll
owsa
(a)zer oorderr eaction ( b) 1stor derreaction
(
c) 2ndor derr eact i
on ( d) 3rdor derreaction
(i
i
)Ther ateconst antf orther eactionis
(a)0. 0462mi n–1 ( b) 0. 462mi n–1 (c)4. 62mi n–1 (d)46.2mi n–1
(i
i
i)Ther at
eoft her eactionsi niti
all
yis
(a)4. 62bact er i
aspermi nute( b)23.1bact eriaspermi nute
(c)23. 1bact er i
aspersec (d)0. 231bact eri
aspersec
(i
v)Thet 1/2forther eactionis
(a)1. 5sec( b)1. 5mi n( c) 150mi n( d)15mi n
(v
)The expr ession used f orcal culat
ing the r ate const antv alue i
nt hi
s
experimentis

Ans:(i)b(ii
)a( i
i
i)a(iv)d( v
)
3 (a)Asampl eofaradi
o-activesubstancet akes80day stolosehal
fofit
s
radi
oact ivi
ty.Whatti
mewi l
lberequiredtol ose1/8ofitsradi
oacti
vi
ty.
(b)Entropyofactiv
ati
oni susuall
ynegat iv
e.Why ?
(c)Wr i
teorderofachemi calreact
ion, whi
chpr oceedsatauni f
ormrat
e.
(d)Whati stherati
ooft3/4:t
1/2f
oraf i
rstor derreact
ion?
(e)Stateanyonecondi ti
onunderwhi chabi molecul
arreacti
onmaybe
ki
net i
call
yoffir
storder.
Ans:(a)80+80+80=240day s
 Ans:
(b)Wit
ht hef
ormationoftransi
ti
onstatet
hereislossi
nther
andomness
oft
hereact
ingmol ecul
e.
Ans:
(c)Zero
Ans:
(d)2: 1
Ans:
(e)Whenoner eact
antispresenti
nlargeexcess

4 (
a)Forwhatt ypeofr eactionst herat
econstantshal
lhav ethesameuni tsas
therateofreaction?
(
b)Compound‘ A’withmol ecularf
ormulaC4H9Bristr
eatedwi thaq.KOH
soluti
on.Ther ateoft hisreacti
ondependsupont heconcent rationofthe
compound‘ A’ only.Whenanot heropt
ical
lyact
iveisomer‘B’ ofthis
compoundwast reatedwi thaq.KOHsol uti
on,t
her at
eofr eactionwas
foundtobedependentonconcent rat
ionofcompoundandKOHbot h.
Wr i
tedownt hest ructuralformulaofbothcompounds‘ A’and‘ B’
(
c)Af i
rstorderreactionis15%compl et
ein20mi nutes.Howl ongwi lli
ttake
tobe60%compl ete.

Ans.( a)Zer oor derr eact ion

(b)A=2- br omo- 2-met hy l
pr opane, B=2-br omobut ane
(c)k=2. 303/ 20l oga/ a-0.15a=2. 303/20l og1/ 0.85
=2. 303/ 20x0. 0706 =0.00813/ min.
K=2. 303/ tloga/ a-
0. 6a
T=2. 303/ 0.00813l oga/ 0. 4a=2. 303/0. 00813x0. 3979=112. 71min.
5 (a)Ar eactionofHy drogenandchl ori
nei nsunlightf ol
lowszer oorder
react i
ont hatmeansconcent rationdoesnotchangedur ingthereacti
on
butquant i
tydecr easescont inuousl yWhy ?
(b)Forachemi cal r eact i
onA→ B.Ther ateoft hereact i
onisgivenas
n
Rat e=k[ A] t
her ateoft heabov ereact i
onquadr upleswhent he
concent rationofAi sdoubl ed.Whati sthev alueofn?
(c)Inacer tainf irstor derr eact ion, halfther eactionwasdecomposedi n500
seconds.Howl ongwi l
l ittakef or90%compl etion?
Ans.( a)Becauseconcent rat i
oni st herat i
oofamountandv ol
ume.Dur i
ng
thi
sr eact i
onquant ityandv olumebot hdecr easessi milarl
y,t
hatmeans
concent rationdoesnotchange.
(b)n=2
(c)K=0. 693/ (t
1/2) =0. 693/ 500
=0.001386sec-1
Now, t=2. 303/ 0.001386xl og( 100) /
10
=1661sec..
6 Inar eactionbet weenAandB, thei ni
tialrateofr eacti
on( R0)wasmeasur ed
fordifferenti nitialconcent rat i
onsofAandBasgi venbel ow:
A/ L-1
mol 0.
20 0.
20 0.
40

B/ L-1
mol 0.
30 0.
10 0.
05

r
0/ L-1s-1
mol 07×10–5
5. 07×10–5
5. 43×10–4
1.
Whatist
heorderofther
eact
ionwithrespectt
oAandB?
Lett
heorderoft
hereacti
onwithr
especttoAbe‘ x’
andwi
thr
espectt
oB
 be‘ y
’.
Ther efore,Rat ecanbewr it
tenas
x y
ro=k[ A][ B]
–5 x y
5.07×10 =k[ 0.20] [0.30] ……Eq( i
)
–5 x y
5.07×10 =k[ 0.20][ 0.10] ……Eq( i
i)
–4 x y
1.43×10 =k[ 0.40][ 0.05] ……Eq( i
ii
)
Dividingequat ion( i)by( ii),weobt ain
–5 x y
5. 07×10 k[ 0. 20][ 0. 30]
= x y
5.07×10–5 k[0. 20][ 0. 10]

( )
y y
[0.30] 0. 30 y
1= y= =3
[0. 10] 0. 10
y
1= 3
y
30 = 3……. (∵30=1)
 y=0
Dividingequat i
on( i
ii)by( ii
), weobt ain
–4 x y
1.43×10 k[0.40][ 0.05]
–5 = x y
5.07×10 k[ 0.20][ 0. 10]
x
[0.40] x
2.821= x =2
[0.20]
x
2.821=2
Takingl ogonbot hsideweget
l
og2. 821=xl og2
log2. 821 0. 4504
x= = =1. 496 x=1.496≈1.5
l
og2 0.3010
 x=1. 5
Hence, theor deroft her eact ionw. r.t.Ai s1.
5andwithr
especttoBi szer
o.
Thef oll
owi ngr esul tshav ebeenobt ai
nedduringthekinet
icstudiesofthe
reaction: 2A+B→ C+D
Init
ial r ate of
-1 -
1
Exper i
ment A/ mol L B/mol
L formati
on
ofD/ molL–1min–1
I 0.
1 0.
1 0×10–3
6.
I
I 0.
3 0.
2 2×10–2
7.
I
II 0.
3 0.
4 88×10–1
2.
I
V 0.
4 0.
1 40×10–2
2.

Det
ermi
net
her
atel
awandt
her
ateconst
antf
ort
her
eact
ion.
Lett
heorderofthereact
ionw.r
.t
.Abe‘
x’and
orderoft
hereacti
onw.
r.
t.Bbe‘
y’
.
Ther
efore,
Ratecanbewr i
tt
enas
 x y
Rat
e=k[
A] [B]
0×10–3 =k[ x y
Exp.
-I6. 0.1][0.
1] ….
Eq(
i)
2×10–2 =k[ x y
Exp.
-I
I7. 0.3][0.
2] ….
Eq(
ii
)
88×10–1=k[ x y
Exp.
-I
II2. 0.3][0.
4] .
…Eq(
ii
i)
40×10–2=k[ x y
Exp.
-I
V2. 0.4][0.
1] ….
Eq(
iv)
Di
vi
dingequat
ion(
iv)by(
i)
,weobt
ain
x y
4×10–2
2. k[
0.4][0.
1]
–3 = x y
6.
0×10 k[
0.1][0.
1]
x x
4= 4 or41=4

 x=1
Di
vi
dingequat
ion(
ii
i)by(
ii
),weobt
ain
x y
2.88×10–1 k[
0.3][0.
4]
–2 = x y
7.2×10 k[
0.3][0.
2]
y
[
0.4] y
4= y =2
[
0.2]
y
22 = 2

y
=2
Theref
ore,
theratel
awi s
2
Rate=k[ A][
B]
Rateconstantcanbecal cul
atedusi
ngdat
aofanyofabov
eexper
iment
usi
ngrelat
ion:
Rate
k= 2
[A]
[B]

6.0×10–3 molL-1Mi
n-1
k= 2
[ 1molL-1]
0. [ 1molL-1]
0.

0L2mol
−2
k=6. n−1
mi