•

Chemical Kinetics

POINTS TO
.................. REMEMBER

1. <'hl•111knl h.lm•tk,: 11 i:-. 1hc brunch ol physicn l chemi~,ry which deals with the s1udy of the rate of chemica l
rc11rt1011 and 1lw mechanism hy which the reaction occurs.
2. l(nll' of Kearl ion: Ii muy be defined rn, the chnngc in concentrution of u reactant or product in unit time.
for u gencrol renction. /? - -• P, the ra1c of n:mc1ion muy be cxprc~sed as z
.
Rr1Ic of rcac tion =
Occrcusc in concentra tion of R
Time taken
- -I
Jncrease 111 concentration of P
l/l
=

-MRJ
Time taken
AlPJ
-I
Rate of reaction =
At
- -
6.t 0
The negative sign in ihc rate expression indicates the decrease in the concentration of the reactant and gives
a positive value of the rote.
1
Units of rate ore mol L I s- 1 or atm s· (in gaseous reactions).
The above expression of rate gives us the average rate of reaction.
3. Jo\tuntuncous Rate or Rcuc:tion: It is the rate of reaction at a particular moment of ti.me and measured as
a very small concen1ratfon change over a very small interval of Lime.
Mathcma1ically, lnstanlaneous rale = (Average rate) 61 ➔ 0
For a general reaction, R - -• P
[R]o

r
!!l

I
o c. [RJ
• z
d[P)
dt • alope

~ -d[R]
r,n,, "' di = - slope
d~ki[b
J : dl

Time - -• t,
(a)

1'18~· S,1;
--~~--~__;_;.
d[R] dlPJ
Jnstontaneous rate = dt dt
Ch
 '""' ,cm be detem1ined graphical
\n,t..'\J\\ffi)Ct)U\
,,nC l ly by drawing a tangent at time to
.
,trat1on of A or B vs um • l .
n enh
•

\(\\ conce1 e and calculatmg ils s ope.

- d(R1 er Sid
Thu,. r =- = -s lope (for R) eClf t
inst dt h~ c,.
-...
+ d[P1
r
LIi.i',
=-dt- =slope (for P)
4. Gencrnl E.'\pres.sion for Rate
of Reaction : For a general reaction,
aA + bB -~ cC + dD
- .=l_ L\[A] =.=l L\[B] =_!_ L\[C] = l ~
rav - a L\t b L\t 6.t c d f:!.t
- l d[A] - 1 d[B ] _ l d[C
] 1 d[D ]
r insl = a dt - b di C dt - d ~
5. Factors Affecting the Rate
of a Ch em ica l Re act ion :
Rate of a reactio n is influenced
by foll ow ing factors:
(a) Na tur e of reactants: It
has bee n obs erv ed tha t ion ic
sub sta nce s rea ct mo re rap idly
wit h cov ale nt bon d. This is
bec aus e ions are imm edi ate th
hen ce, rea ct rapidly but cov
alent molecules con sum e par
ly ava ilab le in aqu eou s sol uti o: the ~Ubsian
t of ene rgy in bre aki ng of 0
(b) Co nce ntr atio n of rea bond:.dtssOciat:
ctants: Rat e of a reaction
is dire ctly pro por tion al to
rea cta nts . the c
oncentrati
(c) Tem per atu re: Rate of a on of
reaction increases with the inc
rea se in tem per atu re.
(d) Pre sen ce of catalyst:
1n presence of cat aly st, the rate
equ ilib riu m stat e is attained of rea ctio n gen era lly increa
quickly in reversible reactio se
ns.
(e) Sur fac e are a of the rea s and the
ctants: The smaller the particl
rea ctio n . e size, gre ate r the sur fac e are
a and f .
(j) Radiations: The re are man aster ts the
y reactions which either do not
but tak e pla ce at a considera take pla ce at all or are quite
ble speed when exposed to sun slow in the
are cal led photochemical rea light or ultr avi ole t radiations
ctions. Examples are photosy , such rea c~
nthesis of carbohydrates, pho
6. Ra te La w: It is an exp erim
ent ally determined expression tography, e~~
of rea cta nts . which relates the rate of reactio
n with concentration
For a hyp oth etic al rea ctio n,

A + B- - - Products
Rate oc [A r [B]"
or
Rate = k[A r [B]"
wh ere k is a con sta nt cal led
specific rate of reaction or rate
If constant.
[A] = [B] = 1 mol L- l then
Ra te= k
Th us, rate con sta nt may be
defined as the rate of reaction
rea ctio n is uni ty . when the concentration of eac
h reactant in the
7. Or der of Re act ion : ll ma
y be defined as the sum of pow
law exp res sio n. ers of the concentration of the
reactants in the rate
Ord er of a rea ctio n can be
0, 1, 2, 3 and even a fraction .
Fo r a hyp oth etic al rea ctio n,
aA + bB + cC - - •
Products
Let rat e= kfA)'" [B t [C]P
wh ere , m = ord er of reactio
n with respect to A
n = ord er of reaction with resp
ect 10 B
p = ord er of reaction with
respect to C
Ov era ll ord er of rea ctio n =
m+n+p

14 xa m ide a Ch em istr
y-X II
 Units of rate constant:
For an nth order reaction. A - - • Product
Rate = k[AJ"

k = Rate = concentration x ______

or
[A]" time (concentration)"
1
= (concentration) -" time- 1
1 1
On con:,idering SJ. unit of concentration as mo! L- 1 and time as seconds. the unit of k = (mol L- ) l-11 s-

(a) Examples of zero order reactions

(1) Some enzyme catalysed reactions and reactions which occur on metal surfaces.
(11) Decomposition of gaseous ammonia on a bot platinum surface.
1130K
2NHJ.(g)---N_,(g)~JH,_(g)
Pt Cao.lys1

Irv--+
__ 2HCI (g)
(ii') 2HJ(g) ~ ~ d----tH2(g)+ l~(g)
got
Unit of k = mol L- 1s- 1
(b) Examples of 1st order reactions
(i) All radioactive disintegrations are of the first order.
(i1) Decomposition of sulphuryl chloride.

S0,,Cl, - - - SO, + Cl,

1
Unit of k = s- . Therefore. change in unit concentration does not alter the val ue of k.
(c) Examples of 2nd order reactions
(I) CH3COOC,H5 + NaOH - - - CH 3COONa + C2H50H
(ii) NO(g) + Oig) - - N01(g) + 0 2(g)
Unit of k = litre mor 1 second- 1
(d) Examples of 3rd order reactions
(i) 2NO(g) + 0 2(g) - - 2NOig)
(ii) 2NO(g) + Br2(g) - - 2NOBr(g)
Unit of k = litre 1 mor2 second- 1
s. (a) Elementary reaction: A reaction which take place in one step b called an elementary reaction.
When a sequence of elementary reactions gives the products. the reaction is called complex reactioo.
(b) Molecularity: The number of reacting species (molecules. atoms, ion-;) taking part in an elementary
reaction which must collide simultaneously in order 10 bring about a chemical reaction.
Reactions are classified as unimolecular. bimolecular and trimolecular for molecularity I. 2 and 3
res pee ti vely.
Examples:
NH4N0 2 - - • N2 + 2Hp (Unimolecular reaction)
2Hl(g) Hi(g) + I 1(g) (Bimolecular reaction)
2NO(g) + 0 2(g) 2N0 2(g) (Trimolecular reaction)
The probability of more lhan three molecules colliding simultaneously is rare.1bcrefore,
of a reaction does not extend beyond three. Molecularit) can be defined only for an eleme~
and has no meaning for a complex reaction.
(c) Intermediates: The species which are produced in one step and consumed in anolhs
intermediates.
 II , 1m tx iht ~ h.:._'i'-C \n m.;;s.. ,uc
1 ol J\ 1,111ml 1 .mt! one mn k c,,<.:.h of
In \'!ft:1.\ urt ul U ,u11I t 'Ao1II 111~.. 1~• /J and (
\ ,,11n t:u.. h
At111 ► IJ(i< ) + ('(J< )
"', • n r ,11111 0 .ilm 0 ,1l m
Al llmt " . I (/1 , I) 111111 \ .ilrn t alm
I' , (P,
(
X) ~:r ~:r
,, (I'
p
I
I 'C {) /' X p
I
,,
I
l'o1.- ~ I I
P,) 2P1 {'
I
2 303 I P, 2.303 I p
k= t og p ,
A
I og (2/> P,)
l 3. nl l• r-tninallt,n ,,r Orc h.-r of Hc,H:tion: r

I lu rt' 11rc rn,,ny inr1ho<l \ ,1\ ,11l.1hk

(c,r 1he dc\crm1nall<>n of ord
er of reac1I0n
Cu) C,1 ,,ph1cc1I mr lh<l(l ( h ) lnillal ra1c met hod
(cJ lnlc gratc<l rate la w method
la) {.r nph k·nl met hod : Thi \ mct
hod 1\ applica ble to tho<,e reactJCm
, whe;rein only one rea c, .
L'.Jfo ordf..1r F,r, t ordor I.ant,, in,.,
i i i
Second order Third oroe
i
hl\t4

a, r
a,
iii <ii
a::
a Q'.'.

Con
- - -Cl)ntrnbon~ Concenlrat,o n-+ - (Concenlrallon)2 -+ - (Concenlrallon)3- -.
Flg. 3.S
(b) J mtmJ rate me tho d: Th.., met
_ ~
hod ,., u<,cd to dete rmine the ord
tha n one rea e r o f reac tio n in .,uc h ca.<,c., wh
ctan t 1., involved It invo lve , dete
rmi nati on of order of reac tio n w
1,cp:1ra1dy For th1.,. order uf a ith re.,p cct to each~~ rTl<irc
par uc ular reactant i'> dete rmi ned
in \l. h1c.h the conc.en trat1 o n of that . A '>cri e<. of ex per ime nt are ca
C!actant
reactan t .ire ke pt w n<.ta nt. In
.
particular reac tant i-. cha nge d
each exp cnm cnt, the rate is dete
whe rea<, the concentration :~OIJt
v, tim e \ 1m,larl y concen trau.on of rmi ned fro m the plo t of conccntr°
a.no t her reac tan t,.,
.
van. dk
e ccp.ing the con centration of reM at1on
thcJ
rc..i c tJnt con <,tan t and in1t1 al rate of the
1, dete rmi ned . The data obt aine
1 niu al ra te dep end , o n d are the n com pare d to see how
the initial concentration of eac the
ior m o f rai c law ,., dete rmi ned h reac tant. Thu s, on the ba.<,is of
. the resul~ thc
Cc) lnt.e~r-.aled rate law met hod
: The re are inte grat ed rate law equ
uruJcrc.wnd the van auo n in con ati ons whi ch are very convenient
ccn trau on with time, for differen
con ccn tral ion'> at van ou-. inte t ord er of reac tion s. After stud ying 10
rval<, of time , the data are put in the
one. The ex p~'>ion whi ch give all the integrated rate law equatio
c, a conr,tant value of the rate con ns one b)
stan t decides the ord er of the reac
[R) 0 - (R) tion .
Zero ord er equ atio n; k =
1

J-1rst ord er equ atio n; k = 2-·303 [Rl o

1
- log [R]
14. Te mp cru tur t Dep end enc
e of Rat e of a Reactio n:
(a) Tem per atu re coefficient: ll
i<. defi ned a.<, the rati o of rate constanL
diff enn g by JO '. c, of the reac tion at two tempera
tu~
.
Tem per atu re coe ffi c1en Rat e constan t at (T + 10)0
t = ---- -----
Rat e con stan t at T°
For mo ,t of the rea cuo ns, tem per
atur e coe ffic ient lies betw een 2
(b> (;olli&ion frequency Cz): It and 3.
1s defi ned a-. tota l num ber of coll
(c) J•:Jfect.ivt: c.-ollisions
isio ns per unit vol ume per unit
I : Col11-.1ons whi ch lead 10 the form time. .
atio n of pro duc t mol ecu le-. are
c<>ll1\ion1,. call ed effecuve
\
l
'

I 1 18 )(a m ,de.a Ch em lstr y-X II

f
 Rate ~f react:Jon = f x z,,,,, here z IS the collis10n frequency andf is the fraction of colLisions. which are
effect:J,·e
(d) Threshold energy: The minimum energy that the reacting molecules must poss~ in order lO undergo
effectl\e collisions to form the product is called threshold energy.
(e) Ac~vated complex: The arrangement of atoms corresponding the energy maxima (threshold energy)
dunng ~e course of a reaction is called activated complex or transition state. The act:Jvated complex
has parual reactant character and panial product character.
H-H H- H H H
' \

\ _. I+ I
1-1 f I
Reactant molecules Activated comple:t Product molecules

C Fig. 3.7: FormabonolactrtatedcomplextomH,-.S~llJrpgpftlll r1J

Characteristics of an activated complex
(,) The potential energy of the activated complex is maximum.
(ii) The activated complex has a transient existence and breaks up at a definite rate to form the
products.
Exothermic Reaction Endothermic Reaction
Activated Activated

I . ror I
complex
······-----··········

Products

! 1 ··r
>-
e>
G)
C
Cl)

~
~ Reactants ······......... cg Reactants
0 0
Cl. Cl.

Products

Progress of the reaction - Progress of the reaction ---+

Flg.U:
(j) Activation energy: The energy required to form activated complex is called activation energy. It is the
difference between the threshold energy and the average energy possessed by the reacting molecules.
Activation energy (EJ = Threshold energy- Average energy possessed by reacting molecules
Acova1100 entrgy ~
Reactants Activated complex Products
For fast reactions, activation energies are low whereas for slow reactions activation energies are high.
(g) Arrhenius equation: It relates rate constant with temperature in the following way:
k = Ae-£,RT
where A is constant called frequency factor, E0 is the energy of activation.
Ea
Ink= In A- RT

log k = log A - 2303 RT

E
A plot of log k vs. 1/T is a straight line whose slope is - 2_30°
 ll ,, nm\ k~ lUo.; the mlc com t.iO
l!i Ill lWO trm pcr alu H:. • 1, and 72' then
r.o
logs.:, = log A 1 303 RT. ... (iJ
' ltJq /)

L"
•"
loi ~ = log A •,

1 ·, •
..( 11) '_.,k.lJJ<,
2.303 RI 2
'-uhtr.i.ctrng (1J lro m (1i), we
get.

•
E0 {I
log ~ - log k,= £30 3R ~
1\
l7i r1
---~-
,, •
k2 £ \Tl Ti\ -
,..,.....
0
or log "1 = 2.303 R 7i Tl r- -- ::?""""1-_,r____ ,
(h ) E ITect of tem per atu re
on rate of reactio n:
lncrea.<,Jng the temperature of
mix tur e increas.c<; the
a reaction j
fraction of ~
molecule<,, wh ich colhde
gre.ite1 tha n £ . 1t 1s cle
wit h cnergie~
ar from the ]
g
0
dia gra m alo ng. ,idc tha t wit Em:r;T/ of
h 10~ rise m i acirli.34..!(,ri
tcmJ)CTature, the are a <;howm
g the fraction ~
ot molecule<; hav ing ene
rgy equ al to or -E This area £OO HS ~
gre ate r tha n act iva tion ene frad lon of mo!eo., 1%
rgy get s alm ~t LL L- --- ---
dou ble lea dm g to alm ost "=.c.;;;;..;,c..:ca.;...lt'-----'
dou blin g of the
rat e of reaction. ----,►
15. Ca tal ) <,t. A cat aly st is a sub Fig. 3.10: ~ a n e
sta nce wh lch alt e~ __ __ ..,,.
...,~
the rat e of rea ctio n wit hou depeildlMice of rale ol a
t i~ lf und erg oin g any che ~
Fo r exa mp le, cat aly i.t Mn mical cha nge at the end of the
02 mc rea ses the r-dle of decom r~ on .
position of pot ass ium chl ora te
"1DO to a great cXSt:ot.
2K O03 2K CI + 302
Ac cor din g to mt.ermediate Hea t
complex theory, a cat aly st par
tem por ary bon d3 wit h the tietpates in a chemical rea
rea cta nts res ulti ng in an inte ctio n by formiac
and dccompo'>Cb to yie ld rme dia te com ple x. Th is has a tran
product., and the catalyst. sitory eWICaCC
A ... B .... X --- -+ A- - 8 - - + A-
Reaamru. --- B
✓
Ca wy tt

~
com pn
It bel ie" ed lha1 the catalyst
is
pro vid es an alte nut e pailiY.a
rea cta n~ and pro duc ts hen y by red uci ng the act hat ion
ce low enn g the pot ent ial ene coergy ~
rgy barrier as sho-~n in Fig..
3.1 1.

.-
Rea -;t,o n p.r.;-, Ndlo!.'" cat
; ~

-,~. ~=
.. ca- ..;~
\
_y_
£. ,.~ 1 ca"8J&l

12 0 / ~m id£ a ch em .is try 1

-Z
 It i, ckllr fnun the Arrhcniu~ e4uat10n (k = Ae E/RT) that lower the value of activation energ, faster ~ill
hl' th1• rate of reaction .
hn c1tmnplc, S02 is oxidised to S0 3 in the presence of nitric oxide as catalyst.
NO(g)
2S0 2(8) + 0 2(g) 2S0 3
Oi(g) + 2NO(g) - 2N02(g)
Rcuctunt Cata!yM Intermediate

NOi(g) + S02(g) - - . SO 3(g) + NO(g)

ln1enncd1ntc Reactant Product Catalyst
Choroctcristics of a catalyst
(i) It cnn only catalyse the spontaneou~ reaction but not the non-spontaneous reaction.
(ii) It does not change the equilibrium constant, but only helps io attaining equilibrium faster.
(iii) lt can catnJyse both forward and backward reactions to the same extent to maintain the equilibrium
state in case of reversible reaction.
(iv) It does not alter the free energy change (t.G) of a reaction.
(v) A small amount of the catalyst can catalyse a large amount of reactions.
16. Collision Theory of Chemical Reactions:
(i) Only effective collisions bring about a chemical reaction. The collisions in which molecules collide
with sufficient kinetic energy (threshold energy) and proper orientation, so as to facilitate breaking of
bonds between reacting species and formation of new bonds to form products are called as effective
collisions.
(ii) In coll ision theory, activation energy and proper orientation of the molecules together detennine the
criteria of an effective collision and hence the rate of chemical reaction.
Rate = PZ e- E.JRT
AB
where, ZAB = The collision frequency of reactants A and B
P = Probability factor or steric factor
(It take into accounts the fact that in a collision, molecules must be
properly oriented)
e- Ea/RT = Fraction of molecules with energies equal to or greater than E,r

mportant Formulae
1. Integrated Rate Equations
(i) For a zero order reaction:
[R] 0 - [R] [R]o
t=
k
and 1112 =u
(ii) For a first order reaction:

2.303 [R]o 0.693

t =- k - log [R] and t112 = - k-
Amount of the substance left after n half lives of 1st order reaction = r[R]0 .
2. Arrhenius Equation
(I) k = A e- E/ RT
where k = Rate constant, A = Arrhenius factor or frequency factor, E0 = Activation.
R = Gas constant, T = Temperature in Kelvin

.. k2 Ea [ ½- i; ]
(u) log ,;;= 2.303 R ½½
where k1 = Rate constant at T1 and ki = Rate constant at T2

(iii) Ea = - 2.303 x R x slope ( in a plot of log k vs ~)

 NCERT lntext Questions
Q 1. For lh,: n-:ld,11n R ?> I' lht 1.."\llll"\'ntnititm ol a n-ud111\I C'hun~,·, lhnu 0.0' 1\1 to 0.0l \ I 1 lCi
• 11 • 1111n
C:tl,:ulate th~ aH'rn~e rntr of t'\'m tum lL,inl! umti. vr thu1..• both III n1111uh. •, 1111d ,t1.·011ch, Ut'-',

00~ \ I 0030 1\\ O.l)I I\I :: 4 x 10 ~ M m111 1

=
25mm 25mm

or = ~,;;0 0' I'-Q:,.1 =,. 67 1041 i\l s- 1

' V, X ~ •
- - ~· !,

Q. 2. lo n re:ictioo .! \ - Produc~. ('t.m~ntnltio n or \ dl'rn•a~e., ftom 0.5 nwl I . 1

to o..i ,uol 1 1
10 minute,. Calcul3tt' the nth~ during this intl'nul. · la
.\ns. Rate of reacuoo = Rate of disappearance of \

l .l[A] 1
I (0.-l 0.5) tnol L
= 2 ~ -= - ~ 10 1nin
= 0.005 mol L- t min- 1
Q. 3. For a reuction. A+ B 4 Product, U1e rutl' hrn is giHn b) r = J. l,t] t l [Hl 2• Whut is tbr order oftht
re-:lction?
..~ns.
. O rder of reacuoo =l 2= 5
2
+
2.
Q. 4. The com ~rsion or molecule ,\ to r follows second order IJnetics. Ir concentrntio n or .l L, tntreastd to
three times. hon "ill it affect the rate of formution of l"?
Ans. Rate= k [X]~
r1 = J. [X]1 ... (i)
r~ = k [3Xf ... (ii)
1
r1 9k[X]
D1\-iding (ir) by (i). =---
rl k[,,\i
r1 = 9r1
Thus, rate of formation of Y will increase by nine times.

Q. 5. A first order reaction has a rate constant 1.15 x 10--' s-1• How lonA ,, ill 5 ~ or this reactant take IO
reduce to 3 g?
e\.ns. Gi,en [R] = 5 g. [Rl = Jg. k = l. I 5-.. 10- 3 s 1 • As the reaction is offin,t order,
0
2.303 [R] o 2.303 5g
t = -,- log [R] = _ , 1
log - - 2.00 x 103 (log 1.667) s
" ].])x JO · s 3g
= 2.0 X }03 X Q '2219 S = 443.8 !, = ~ S
Q. 6. Time required to del'Ompose SO1Cl1 to half of its initial amount b 60 minutes. If the decompo1Ultl
b a first order reaction, cakulate the rate eonstnnt of th(' reaction.

Ans. ForafiNord erreactJon. k= 0693 =

,,".! °/
6 mm
93
= l.lSSx 10-2 min- 1

(). 7. \\hat ,,ill be the effect or temperatur e on rate constant'?

An~ The rate con!>tant of a reac11on is nearly doubled with nsc m temperature by 10°. The exact dependence of
the nue constant on tt:mperature 1<; g1\en by Arrhenius equallon. k Ae £., RT where A is called frequeac:Y
factor and f~0 ,., the .icuvat1on energy of the reacuon.

122 Xam idea Chemistry- XII

 fbt "'1!.' of iht tht mot rf'.a(tion 4kil1Nes (or an lnrmN ot JO Kin of)',C1lutc Un1(lt'ntturl' from N~ " ·
l 1llru In It• I .-

E. : 2-'\03 R lot
~t
~ l r,r, Tlr. I
"'(2 lOl)(, lJ4 J K mol
-
'>(a.-
~ t
l) x I\ 30•:q,
]Q~ "- x lO~ t-. )
2°·n.
= 52S98 J mol = 52.9 kJ mor'
I he 11diutinn tncf'l) for rta(.lir,n. lHll, J - · IIJ(f) -+ Jif,t}. i~ ?O'J.5 IJ mor' ot SHI I\.. Calculate
1hr rrat't.Jon 111 rookrnlt'\ 1tf n •,R~n1, ha\-in~ l DC'IY' equal to or gn-alu than 11c1hation eoerey,
J r;iction r,I m"li:4:ulc~ having cnng) tqU21 ((1 Of pc.1er than actr.auon enerv-.
r "' n_ • e £. IT
,\'
£. £.
In t :: or log ., •
RT 2 ~03 kT
2()Q 5" 10, J mol 1
Ill Iog t =- If 8313
2 '.\01 )(X "ll4J K 'mol x581 K

A - \nt1Jog ( 18 S32lt
c ,\nt1log d9.16771 = 1.47] x w-"

ERT Exercises J
I rom 1h1· ruh· l'\p~,ion for the follo~ia~ reactions. detennior lh.eir ordtr or reaction and ~
11irn1·n,1on, or thr rnlt' l·on-.hmt,:
2
(a) \'\0(.1:) - · '\ :OL~)• '\OJ(.t:) rate-= .l(1'0f

(b) 11 1 0: (uq) + 31 (aq) + 2W - lH: 0(1) + 1;(aq) rate = iill20t1fll

(r.) Cit,( HOtgl - C.U 4 (.,l + CO(g) ra-te = A:[CH 5CHOf~l

(d) ( , H~O le:) - (\fl,(g}TJICl(g) rate = •lG,iH5Cl)

lul Rott= I.. !'\OJ'. Onier of re:ictton \\ .rt reacwnt ~O =2. Order of reacuon =2
1
R:ire moJ L s ' 1 1
lnil of k: A - --. = 1 , = L mo1 · s
~OJ- (mol L )-

(J>l Rutt = AfH:O~]{l ]. Orderofreacuonws.1.reactant HP2 = I,

Order 01 re!lCIJllD \\ r.l. reactant r = l,
Onkr oi reJcnon = I + l = 2.
Rat mol L-1s 1 1
· f' J.
l rul O ,.; =- [H~0:1fl 1 (mot -
e = - - - - - =Lmol 1s
L 1)(mol L )
J' 3 3
{d Rmt= ~ICH ,(HO] ·. Orderofrext1onw.r.t.re.k."1alll CH3 CH0= 2, Orderofreaction -= 2
-1 I
. Rate: moJ L s 1 1" 1 12 1
lnitufl: !.= - --,-= 1 =mo -Ls
(O\CHO) '2 (moll 1)1,
!tll Rste= !(C1 fl ~Cl), Orde-rofreactlon\\ .fl reaccam C1 HsCl• I.Orderofreaction= I.
Rate mol L I s 1 1
\nlt,,rt ~ *'"' (C. H ClJ - •s
mot L 1
1

Chemical KinetJa 12!

 Q.!. F th _ 00 ., -! + B ~ -LB. the rote= k HUBf '11ilh k:; .2.0 x 10-. lllof'~ l~
or 1 e :rea,..... - • L-1 d [BJ - 0 , I L-l ~ , ...,
lfiluu.i ra
• ·h - teof thereattion "hen [-l] -1
= 0.1 mol an - - mo · CaICUJat e lhts • t ~
aller µ J;. r«!uc!d 10 0.06 mol L • • , .... ,r ,
1
Imnal r.ne = .t[:\]lBf = (~.Ox 10-<i mor- L- s- ) (0.1 mol L-1) \O ~
1
= 8 x 10- 9 mol L-1 s-1 - lllolt-1}~
1
When [Al ,s reduced from 0.10 mol L- to 0.06 mnl L• 1• i,.. 0.0l mol L• 1 of ,1 has ""1cled_
l x 0.04 mol L- 1 = 0.01- moI L-t
B reacted = -:;--

No\\, (BJ = 0.1- 0.02 = 0.18 mo! L- 1

2 2 1
R::i.te = (2.0 x 10-6 mor L s- )(0.06 mol L- 1) (0.18 mo! L - 1)1
= 3.89 x 10-9 mol L-t s-1

Q. 3. The deoomposition of 1.113 on platinum surface is zero order reaction. What an, the

Ans.
or~ 2 and H1 ifk = 2.5 x 104 rnol L-1 s-1?
"''es Qf
P"
2NH3 - N:, + 3H 2

I d [NH3] d fN2] I d [H2J

Rate= - ~---:-~ =-== - -
2 dt dt 3 dt
For zero order reaction. rate = k
I d[NHJ d [N2] I d [H2]
2 dJ - -dt= - -
3 dt
= 2.5 X 10"4 mol L-I s- 1
d[N] 2
Rate of production of N,- = - d (
= 2.5 x 104 mol L -I s-•

d [H,]
Rate of production of H~ = - d -
- I

=3 x (2.5 x 10-1 mo! L- Is- 1) =7.5 x IO~ mol L-1 s-•

Q . 4. The decomposition
is ghen by of dimethyl ether leads to the fonnation of CH~. H and CO and tht mtdioam
2

Rate= k [CH30CH/12•
The rate of reaction is folio\\ ed by increase in pressure in a dosed , es.set, so the rate can ab1t •
expressed in terms of the partial pressure of dimethyl ether, i.e.,
Rate = k[PCH3ocH/12
lf the pressure is measured in bar and time in minutes, then what are U1e units of rate
constant? and nit
Ans. [n terms of pressure, unit of rate=
bar min- 1

Unit of k = - - Rate
-~ bar min
1
b -Ill . _1
[PCH OCH ]32
(bar) 3 "
- ar mm
' l
Q. 5.
Ans. '\1ention the factors that affect!; the rate of a chemical reaction.
R efeno Porn1> m remembe,5 If dll
Q.6.
A reaction is st>Cond order ,~ith respect to a reactant. Ho\\ is tile rate of reaction affected
concentration of the reactant is (i) doubled (ii) reduced to halr!
Aru..
R a1e =k IA]2 =W
Jf [Al = 2a. 2
Ra1e = k [2a] =4ka2 =4 times of the initial rate
If [A)= 2 a,
I
R.ite =
(a) I 2
k 2 "' 4 ka 2 '"'
I
4 times of the initial rate
124 Xam idea Chemistry-XII
7. \\ hut I,; tlu· d lrd ul h•111111 I 1111111• 1111 1111• 11111• 1 011~111111 ol' 1111·1wll1111f llow mu Ihl11 isl fr, I orl••111 Jll'I 111!Ill'
''" 1,111 I 011\hllll h,• l l'IH 1' '«' 1111-tl 11111111tlt11lh ,,1, 'I
I h1• 11111• , 1111\111111111 ii 11·.i, 11111111u 11•11~,•~ w ith llll 11,11,,,., 111 1r 11 ipr 111 1"''' 1111d t,n 11nu•- 11r·11rly d1111hlr f1 1r 1:vrry
111 l 11 \l' ,1l tr111pn 111t111· I ht• 1'1 11·1Irn 11 1,1• "'lll l'~r 11 1t·d q1111111111111 vl' ly hy A1d1r 1111111 t'tf11,,111111 ,
A I ,. , ,,•Ill
\\h1·11• /•,, " till' IH ll v11111111 (' lll'' f'V nl 1hr 11·1H 111111 1111d /\ I~ Ilw l1 t•q11r111yl.111111
In ,, 11wu1lo lh i-1 urrh-1· h, 1h ol) ~ljj 1111111 l'~l••r 111 w111111 , Hw roll11wl11111,•;111111 wi·r1· (lhlhluc·tl:

~~~Vnioll. 1 1- 1
o.~~ - j- o·:~, 1~ ,:.~, -1~ fl,:~, -- I
( 11lrul11h• 1111' 11, 1•rni:1• rnh• ol' 11•fli' I lo,, hl'I w,•1·11 1111• 1l11H• lnlt•• v11I .m to f,O ~"' 011d~.
,\,,•11l>(l' 1,111· ol 11' ill'l11111 ht'I\Vl'rn lh1· l11t r 1v11 I I() II() "
( 'I ( '1

f, II
(01 "/ 011) 14 1
•
(I
L
I
~
I
4.67 x HI 1 mol L ,.- •
,,o \() \() lllltl

\ n•11l'llo11 I~ llr~t onlt•r In /I 11111I "''l'0111I ,,r1h-r 111 //,

(i) Wii11• tlw dlffc·1•1·11llal rnh' ,·<p1,1tlo11 ,
(ii) I low is tlw mh• afr•·rh·d 011 i 11,· n·11i.i11~ tl11·, 1111( 1•111nati1111 of JI 1hr1·1· tlnw11?
(iii) l low i<1 tht rah' uff(·,·t<-d wlu:11 1ounnlt 11tio11 ol' 1,olh ;1 nnd /J arc• doubled ?
ell uI
q 111111 l
cit
(//) 11 lhc rom:c1111 111io11 ol ll i, 1,iplt-d. lhr 11
R11le A[A II 1/1 I' 9k IA11111 i, i.1· .• the , 11tt of 1c1,ctiM hcco,nc~ 9 lune~.
(111) 111hr ,·oncc1111 atinn ol hnlh /\ LIIHI /I fi ll' (1011hltd , thr n
Rut1· /,J 2A JJ 2/IJ 1 KA JAJJ//Jz, 1.1·.. the rtllc of ,cuction lwco111c~ 8 l1111c11.
111 o ri•urllon hdm•rn \ nnd II, lht· i111U11l r11h· ol' r1•u1•tl1111 (r0) WU"- nwa"urrd for different lnltlal

L"' : ; ..
L1
L 1t-t .
i :- =E
,·om·t•ntrntlc111, of \ 11ml /111, ~IVl'n lll'low:

= 5.07 ><
o0.20
..,o
tt, , - -$.07-)( W5
£,20
0.10
1.43 • l
OM
OM

\\ hut b lhc orckr of' rtadion \\ llh r1·~11t•tl to A 11,ul JJ'l

Lei the 1t 11c law he ,·0 /, JAi"' ll/111
(r11 ) 1 5.07 X IO ~ - k (0.20)"' (0. 10)"
(r11 )~ - 5.07 x IO ~ • /, (0.20)"' (0. 10)"
1
(r0 )i = 1.43 x 10 k (0 40)"' (0.M)"
(~,), 5 0711 1() ~ k(O Wt(0.30)"
l>ivitl,nlt (i) hy (1'1), k(0.20)"'(0 10)"
(fc,) 2 ~.07• 10 ,
I - 1" ()I 111 V' > 11 .. 0
1.41 x 111 4 A(O 40)"'(0.0~)•
(1;,) I
D1, 1thng (,,1) hy (,'i). ( , ) 5.07X l(J \ k(0.20)"'(0. IO) n
'o .,
2.821 ,. 2111 X ( l/2l'
log 2.82 1 .. 111 log 2
luij 2.!<2 1
log 2
r- 1.4% u
·1nu... 111Jc1 ol 1c11ctim1 w r.1. A 1.5 1111d 11rdr1 ol reaction w.r.t. 8 a 0.

ChefflllCM
Q l l. l h,, foll,mln,:t rr,ulb lu\\c hl'l'II obtained durin1,t the kinetic• 'lludit.•, of th,• rcuctjOh•
2, I + fl • <' ➔ I) •

Experimtnt (A)lmol L-1 [BJ/mo1 r..·1

or Dtlllol
0.1 0.1
6

--
l(
11 0.3 0.2
7.2 lot .....
Ill 0.3 0.4
2.
IV 0.4 0.1
2.
Determine the rate law and the rate constant for the reaction.
\ns.
Suppose order of reaction w.r.l. reactant Ai~ 111 and with respccLlo 13 if> n. Then the rate law w·ii
Rnte = k \A]"' \Bt
1
be
Substituting the values of experiments I to [V, we have
=
(Ratc)cxpi 1 6.0 x 10
1
=k (0.1 )"' (0. 1)"
2 .,,(ij
(Rate \xpl 11 = 7 .2 x l 0- = k (0.3)'" (0.2)"
(Ratc)CApl 111 = 2.88 X l 0- 1 = k (0.3)"' (0.4)" ...(Ji)

...(ii;)
(Rate)cxp1 ,v =2.4 x 10- 2 =k (0.4) 111
(0.1)"
.. ,(iv)
(Rate) cxp11 6.0 x 10 J k(0. \) 111 (0.l)"
(Rate\xpl IV = 2.4 x l 0- 2 = k (0.4r' (0.1)"

or l
4
(0.1)"'
= (0.4) 111 =
(I)"'
4 ' m =l

(Rate)cxpt II 7.2 x 10-2

k (0.3r (0.2)"
(Rate\xpt 111 = 2.88 X 10- 1 k (0.3)'"(0.4)"
or

or
n=2
Rate law expression is given by
Rate= k [A] [B] 2
Order of reaction w.r.t. A= 1;
Order of reac tion w .r.l. B = 2.
O verall order of reaction = I + 2 = 3

k= Rate = 6.0 x IO 3 mol L I min 1

2
(0.1 mol L 1) (0. 1 mo! L ' )2 = 6-0 mor L2 min-•
2
[A] [BJ
Q. 12. The reaction between A and Bis first order with respect to 11 and zero Ord
the blanks in tbe following table: er with respect to B. Fill II
Experiment [AJ/ mol L-•
I 0.1 0.J
II 0.2
Ill 0.4 4.0 >c 10-z
0.4
rv 0.2
2.0 >c 14,-2

126 Xam idea Chemistry-XII

 11'(> I I f\J'ft"\\1110 11,, th'1 H'il 111!11 I, 111\('0 II\
lh11t • J t,\1 l/ll!J • 1
q,q
2 11 • 10 \ mol I nun 1 ■ AflJ I '-A ) or k 0.2 mtn·
1
I lf 1 ,,\'rnnrnt I, ij J,M •
1
hv l ,,~11n Ill II l(111c • <IO~ I() 1 1n11I I I mm 1 (0 2 1111n 1) IAI or IAI -= 0.2 mol L
I 11 ,r,t'.run 111111 R1,1c ■ mi 111111 1) (0 i 11,0I I 1) _ 0.08 mol L I min· '
t ,, <'\lli."rimc 111 I\ . K,1k• 2 IJ "Y 10 'mot l I m,n 1• o 2 m111 1IAI or IAI = O.l mol V'
, ' 1I, t 1h1h th, luilf-lif, of It llr\t ordn , nu doo from their rutc (JJ11<,la11t'"> given below:
01
111 l oll !> '"' 2 1111n I U1i1 4 ~('ar, I
()693
, I liill Ille pcnod of J h~I order rcJc.llon t
' I2 k
0 '193
(I) ,, J • 0 346 "" )() 2s 3.46 X ]0 3 s
2()(1<, I

0 691
(II) ,, 2 () 146 min 3.46 , 10 1 mJn
2 flllll I

()(,93
(111) ,, '2
1
0 173 year 1.73 x 10 1ycar
4 year
I h<' half lih for radioadhe dr<'ay of 14( i<, 5730 }ear~. Ao archaeological artifact containing wood
had 1ml) 80r, of tlw 14 ( found In a thing tree. b.timate the age of the sample.
K,1d1c,.id1\C <kc.iy follow, fir -.t order krne11c~.
k = 0.693 0.693 year 1 = 1.21 x I u"-" year 1
111 5730
2.303 [Rlo
t = k log [R]

= 2.303 I 100
(1.21 x 10 4 year½ og 80
2J 03 X 0.0969 l
=
1.21 x 10 -4 year 1
= 1845 yea rs (approx.)

11uspertmcntal datn for the dccompo~ition ofN20 5

12'\0~ - 4!\02+021
11111 phase at 31H Kare ~ivcn below:
- - - - - . - - - - . - - - . . . - - - - - , - - - - , - -- , - - - - , - - - , - - - - ,
0 400 800 1200 1600 2000 2400 2800 3200
1.63 1.36 1.14 0.93 0.78 0.64 0.53 0.43 0.35

Plot (N 20 5 J again'it I.
PlDd the ha)f.Jifo period for the reaction.
Dnw a graph between log [Nl05] and t.
Wutilratelaw?
le the rate constant.
we the half-life period from k and compare it with (ii).
O 400 800 1200 1600 2000 2400
1.63 1.36 l.14 0.93 0.78 0.64 0.53
- 1.79 - 1.87 - 1.94 -2.03 - 2.11 - 2.19 -2.28

Chemical
 versus tin1e
li) Plot ofl N20s1
11.6
1.4
~
~ 1.2
~ 1.0
i0,8 .......... .
)(

<o 0.6
0.4

0.2 : 1112 = 1450 s

o 400 800 1200 1600 2000 2400 2800 3200
nme (s) ----+

till Initial concentration of (NPsl = L63 x 102M

2
Half of the concentration = 0.815 x 10 M
Tune corresponding to this concentration= 1450 s. Hence, tI/2 = 1450 s.

tm) Plot of \og [N 2OsJ versus time

-1.70

-1 .80

-1 .90
1
IQ -2.00
0N
6 -2.10
0)
.2 -2.20

-2.30

- 2.40

-2.50
400 800 1200 1600 2000 2400 2800 3200
lime(s) - - -
(fr) As plot of log [N 20 5] vs time is a straight line, hence it is a reaction of first order.
.·. Rate law is,
Rate = k [N 20 5]
.
(v) Slope of the line =- .3k
2 03
-2.46- (-1.79) 0.67
Slope = =---
3200-0 3200
From equation (i) and (ii), we get
_ _ k _ = - 0.67 k- 0.67 x2J03
2.303 3200 or - 3200
or k =4.82 x 10-4 s- 1
(ri) 0.693 0.693
I112 =- - - - - - - 1438 s
k 4.82 x J0-4s- 1
Tiie m o ,alues are aJmost same within limits of possible error.
Q. 16. The rate const.ant for a fir,;t order reaction is 60 s-1• How much time wi1J it take to
ooncentratfon of the reactant to ii.\ 1116th value?
Am. 2.303 [RJo [RJo
t = - k - log [R] as [R] =l6

128 tam idea Chemistry-XII

 ~ ~\\.'
«\ '"' 'q'
'".~,,w
-t.~ " w~ ~
\~ ~ ~-tttr ,·\.~...\~"'- ,'\Q\" "" lN- r..l'\)l.t\td, ~ ~r "ilh b.a.lf-lifr of !8.1 , tarS. lI 1 µ~ oI ~r was
~ ~ i b th<- , ~ .,..s a O\' \\ ~ b-.•t'Q hah, ut,u:td of C'Ukium. bow mum or ii will rtm:llll aflrr
,~,, ., "'~ ~ ,_..,~ ,r u '\ .,xi.~ t1 '1-c. ~b\ih~n~~
~, •~ ~ \~, '- ""~~ ,.... i,\."''' \, "~h'f\.\"r ~Dc'll~

l ~ i.~~ tt \bt ~'fil\1 'k-ft .tntl' lll ~-e,_;i_~

,•. a ~ ~- ~h~ <. .:: :- -...".' , ill .:- ~ - , (~ I ::: ~
-,~
-, --~-.., "',)~
.•
'= -
k".:., .R~
~ ~ :- 3i\.~ 1
-..'' '\. h_) ::: - - L._,. -
- ,, }ll "' ~ ,.\·

,~ !-.~ ~~• ::::-0.\\)- l

. .~ .-'l = -\"!lk·_,: l ~~=0.~I.$ pg
,~" .."U.-ul::irt ~ ~tlll_"llltt kft aft~ ti() )c:ll'S

, ~....: .: ..3-.."l-;. l
- -.., "' '\. a :::: - - ) - ""~ . ...)
.:.... _.\.

l..'11 \...,..~ ~- ::: - ...' ~.:.---

::\l::-S ~
fw a irsl ~ ~"'n.."'ll.. ~ " ~ t ~ ttqniffl:I foe 00~ COII1pk-tion is lW'K'f' tbP timr I tqui:t td (or
-.rt ~ af ~Go d N1"'00G. [CBS£ !119 t 5"'511 I J
alntOl'dcl' r!'.!:tr,:n.

( . , . SkVI. re.r.i)Q

:_;j3 ~~ ~~10
~~ = :!_~l< ~

(t::mE SC
 :\ th , t 01111 , 1 r 111 111111 1rik1-J ...
Alo 111 1n 11Jr '41~' dewmpi1'illon.. Calculate t l/2-
1,,, 11 ltr .t 1111Jr 1 11 m 111111
2 '\03 IRJo
ke t log [Ill
[UJ 11 JOO 10
Wh, t1, , i1CJ t,1111 u11•11, IRl 100 30 7
2.303 I 10
k ' 40 og 7

k 2.303 I I 428 2.43003 X 0.1547

40 og •
1
k - K,91 x trr' min
0.693 0.693
11 3
nw k IS~><I0
77.78 min
1112 -
(), l o I 111 ttw ,lrl o1t1po1;l111,n of u,ol-.opropanc to hexane and nitrogto at 543 K, the follow·
ohlnlru·d · - - - - - , .- - -----,--------. Ill& data~

( 111, uluh• llw nth• con, lunl.

'\11111. ((.'II J)i{' II N NCII(CH3 ) 2(g) - N2(g) + Cc,H,4'g)
h111111I p1 t'11._urc Po O 0
All c-1 11111c t /Ju p P P
' I UllJI J)1 c,11u1c tilter llf'TIC I(/~) (Po - p) + p + p - Po+ p or p = P, - Po
a t• r~, und (u x) cc P0 p or 1,ub11tituting the value of p,
c1 , ~ P0 (/~ J>0 ) , I.e., (a x) cc 2P0 - P,
rm II Iii HI 0 1de,· I Cllclio11
k 2.303 I _ a_ _ 2.303 I Po
- I og a - x - t og 2P. - p
0 I

2.303 35.0 2.303 35

Whc11 I .. 160 ~
k ,. 360 s log 2 x 35.0 - 54.0 = 360 s log 16
"" ;·:i! (0.3400) = 2.175 X ) 0 .J S- I

When 1 • 720 s, k 2.303 I 35.0 2.303

"' 720 s 08 2X35.0 - 63.0 = 720s log 5

"' ;;g! (0.6990) = 2.235 3

X 1().. S- I

2.175 '" 2.235 _3 _

l\vcrugc value of k "' - x 10 s 1 = 2.20 x 10 3 s..1
2
(). 2 1. ·1 hl' follc,wln~ dutu Wl'rc 1Jhl11lncd during the fin,l order thermal dccompo<,ition of SOJCli Ill 1
l'Oll',lnnt , ,,tum\•:

~ Kaperbn111t : :?!tit -
t------:------1-----1.~
: .-----+---~--__:::.;_~---~-
< 111, ulutc the rule of I c1u-tlo11 whl'n totul prc.,,urc I<, 0.65 atm.

130 Xilnl ld1°d tlwmi.,try XII

 :O:() ,l'l ,L1:) - ... SO ~l11 ) I Cl; (g)
1. ,o, 1ti
A .. -I log 2Po /~

100 s, J.. 2..303 0.5 2.303

\\ ht'II t
= l 0() s log 2 X 0.5 OJ • 100 s log ( 1.2 5)

= ~ii: (0.0%9) = 2.2316 x JO"'' s-

1

\\ hen I',= 0 65 acm. i.e.. P0 +JI = 0.65 mm

p =0.65 - P0 =0.65 - 0.50 =0.15 atm
l'n.'"111\' ot SO,Cl1 ni li1Ue r (Jlso,c,,) =P0 - p =0.50 - 0.15 ntm =0.35 aim
Rntc = J.. x Psu1C'1 2 = (2.23 l6 x 10 1 s- 1) (0.35 atm)
= 7.8 x 10-4 ntm s- 1
Tht' rote ron,tunt for lhc dl'Compositioo of NiOs nt variotLo; temperatures is gh'eo below:
0 20 4(1 60 80
0.0787 1.70 25.7 178 2140
Dnrn u gntph bt•t,leen In k and LIT and calculate the values of A and E0 • Predict the rate constant at
.,o r and soyr.
I
To dr:t\\ the grnph of In k. versus T . we can re-write !.he given data as follows:
f(KI 273 293 313 333 353
Jtr(K"I) 0.003663 0.003413 0.00319 0.003003 0.002833
Id - 14.055 - 10.982 - 8.266 - 6.331 -3.844

0
-1
-2
-3

I
--4
-5 Y2-Y1
Slope=--
-6 ,ti-x1
->(

E -7 -1 4.055 - (-10.982)
-8 = (3.663 - 3.413) X 10-J
-9
-10
-11
-12
-13
-14 (3.663, -14.055)
-15
2.8 3.0 3.2 3.4 3.6 3.8
.!x10-3 K"1 -
T
Graph of In k vs 1/T
From the graph, we find that
-Ea -(- 3.073)
Slope = R = 0.2S x 10-3

Activation enercry, E
e- a
= 0.253·073
X 10-J
x8.314 =10219S.7 J mor = 102.20 k.J/mol
1

Ea
We know that Ink= In A- RT

Chemical Kinetics t
 ..

I\\ In \ ( / ,) I I /II~
,; I
\t ' ' 7' t-.. . 111 A 1,1II~~
ll\2 JO
111 \ 1,1.M:I 1(1,1)71
K\11 1( 10 I -d/ I

l 1,•qu1' 1\1' \ hl1' h\l , \ ) K' ),. \o' I ,

F f:
1.1 1 1 1 1 1 1111 ,11 1, 111 iltl l\'n,111 l1'1111w111h11\•, 1•1111 lil' d1•fl-11111111·d 11, lo11t ,v~
It' \ ,\ II\' \l I ,I 1' n 1 \ I I •

T
'l\n

'·'' •
1/f'
1).0011\)(l

n.umn1>h
- : : - : : - - __ -:_-. -:------.-:;-~~

~
Value ofInk (from Nb)
____ \),7

c, \
, ,

-~-
____
_ __
1

~ >< 10 ~ 1
1
l'h,• rnh• ""''t""' fot11.,, th•<mnim,lllo" of h)•cl,01·11rh1uh I, 2.41 Kx IO • , 1 111 546 K. th, ,
n,'thntii\1\ I, 1,.J/nml, \\ht\l will hl1 lht• ,·nltlt' or pn'•l'\po1wntiut fnl' lor?
t 7 Q,1) 11 'lle'll),
tl\\ni, ~ . ~.-1 Ith Ill ' 1, 1J ,, I 79.9 h.J tlllll 1• 'I' = 5•16 K.
If ,,
t,,g ~ • log A " 2J03 R'r
or E,,
lo);t A = log ~ + 2.303 RT
k1gA = log (2.-1- 18 x 10 ~ s
1
) + 179.9~kJ mot
- --- 1

I
2.303 X 8.314X 10 - kJ K mot I XS461(
: (- 5 + 0J834) l:° I+ 17.208 1
= 12.5915 $ I
Qr
A = Anti log ( 12.59 I 5) s 1

12
= 3.90-t x 10 s- 1

Q, 14. C'o,.,ide, n ,-.tnio "'"'""" t - i'coduct, "ith k = 2.11 x to-',-,. C'akulate the eoncentrotion~
l.'t'mnlning u.fkr 100 s if the initial contl:'ntrntion of ;\ is 1.0 11101 L _,.

Th
\os. c unu, I
. of ,,. s,ow . fr,mt ordcc. 1-1cncc,,' = -
. "o
th"" hc n:ncnoo , Iog [RJ
2.303 [RJo

,, 0 10-2 - 1 -
-· x s -
~ I
s og
LO mol L
[A]
I I l 0 8684
or og [A = - .
100

[Al= Antilog (- 0.8684) =Antilog (l. 1316) =0.1354 mol L-1

Q. .!S. Sucrose dt'C'omposes in ucid solution into glucose nnd fructose according to the first order ra&e
"Ith t l/2 = 3.00 hours. "hut fraction of sample of sucrose remain.,; after 8 hours?
Ans. Since sucrose decomposes according to first order rnte law.
2.303 [R] o
k= ~ log [R]
As 1112 = 3.0 hours,

k= r, -; = ~
~ 3h =0.231 h-
1

0 '>3 1 1-
1 -
1 ~I [R] o
·- - 8h og [R)
[R]o
or log [R] = 0.8024

[R]o
or
[R] =Antilog (0.8024) =6.345
[R) I
or
[Rl o = 6.345 = 0.158
132 ~ :im idea Chemistry-XII
 1 28000
fhe defomposition of hydrocarbon follo ws the equation: k = (4.5 x 10 11 s- ) e-< K>tr.

Culculole £0 •
,. From Arrhenius equation, k = A e E.IRr
Ea 28000 K
- RT = T
1
or Ea= 28000 K x R = 28000 K x 8.314 J ~I mor
= 232.79 kJ mo1-1
The rate constant for the first order decomposition of H2O2 is given by the following equation:
log k = 14.34- 1.25 x 104 Kif
Calculate E0 for this reaction and at what temperature will its half-period be 256 minutes.
. 1.25 X 10 4
Given, log k = 14.34 - T
E
Comparing with the equation, log k = log A - a we get
E 2.303 RT'
a 4
30_3_R = 1. 25 x lO
-2.-

or Ea= 1.25 X 104 X 2.303 X 8.314

4 1
= 23.934 x 10 J mor
1
Ea = 239.34 kJ mor
Given, 11/2 = 256 min= 256 x 60 s
k = 0.693 = 0.693 =4.5 x 10_5 5-1
tl /2 256 X 60
Substituting the value of kin given equation, we get
25 104
log (4.51 x 10-5) = 14.34- 1. ;

5 1.25 X10 4
log 4.51 + log 10- = 14.34 - T
l 25 X 10 4
or log 4.51 - 5 log 10 = 14.34- . T
1.25 X 10 4
0.6542 -5 = 14.34- l.2S; 104 or T 18.6858

1.25 X 10 4
or T= _ = 669 K (approx.)
18 6858
3 1
The decomposition of A into product has value of k as 4.5 x 10 s- at 10°C and energy of activation
4 1
is 60 kJ mor 1• At what temperature would k be 1.5 x 10 s- ?
4 1 1
k1 =4.5 x 103 s- 1, Ti= 10 + 273 K =283 K; "1, =1.5 x 10 s- , T2 =?,Ea= 60 kJ mor
From Arrhenius equation,
k, Ea
log~ = 2.303 R
[I;-~]
½~
1
1.5 x 10 4 60000 J mol- ( T2 - 283)
1 283T2
log 4.5XJ0 3 = 2.303 X8.3 14JK-l mor

½- 283 ) 0.5228 ½- 283

log 3.333 = 3 I33.63 ( 283 ½ or 313 3. 63 283 ½
0.0472 T2 = T2 - 283
0.9528 T2 = 283
283
T2 = _
0 9528
= 291 K =297 - 213°c =24°c
 f u firit order r~Jction at 298 K i-, t<iu·
IO' t·omplt•tlon o rn - 1 a l<) tf
llw tlnu- H'•tt1h ,·d for ( K JI' llw vu luc of A I~ 4 x J0 s ' ca 1cu 1ate k at 3 I'11I< iat ,.t:
I" l ~•' , oniplrllon "1.111g . IR Io 2.303 I00 ijlltl ~%1,~ e
2303 · --=-- log - \
\th, l 1 = ·, log lR] 0 0.10lRl 0 11 90
1

0.1055 0.1055
- 2.303 (0.0458) ~ - t or ti = ~
- II I 298K

[Rl 0 2.303 100

2 303
k2 = y --::-:-:~~=--
log [RJo . 0.25 fR) 12
1og -
75
0

_ 2.303 (0.l 2S)

2879
0_:__
12
or t2 =--
0.2879
- t2 k308K

2
Butr 1 c: t 2. Hcncc,
0.10~
k lei or kk = 2.7289
"" 0.2~79
1 1

Now, from Arrhenius equation, log ~2 = 2.303a R

k E [½½-I'ij
--
~

£ (308 - 298) K
a X -:-:----:--:-:--:-
log (2.7289) = 2.3 03 xS.3 14 J K- 1 mol 1 298 K x 308 K

Ea X 10
0.4360 = 2.303 X 8.3] 4 -29--:-8-x-:-::
3078
or
Ea = 76.623 kJ mor'
Calculation of k at 318 K:

Ea
log k = log A - .3 RT
2 03

4 76.623 kJ mol - 1
10
= log( x l0 ) 2.303x8.314xl0- 3 kJK - 1mol - 1 x318K
= 10.6021 - 12.5843 = - I .9822
or
k =Anti log (- 1.9822) =Anti log (2.0178)
= 1.042 X 10-2 S-I
Q. 30. The rate of a reaction quadruples when the temperature changes from 293 K to 313 K. CalcuJate
energ} of activation of the reaction assuming that it does not change with temperature.

k2 [CBSE2019(,
Ans.
f<-i. =4k 1 ⇒ - =4
k,

k2 Ea [ ½- r; ]
log ~ = 2.303 R ½r;

⇒ 4 Ea (313 - 293)
log = 2.303X8.314 293X3J3

Ea ( 9!709
2xlog2=19J47 20 )

£ _ 2X0.3010X\9. 147 X9 J709

a - 20 = 52.85 kJ/mol

134 Xam Idea Chemistry-XII