3 Chemical l(inetics

( Fastracl« Revision )
► Chemical kJnetlcs Is the branch of chemistry which deals ► Molecularity of a RHctlon
with the study of reaction rates and their mechanisms. ► It is the number of reacting species (atoms, Ions or
► Rlite of a Chemical Reaction: Rate of a reaction Is the molecules) t.akJng part In an elementary reaction
change In concentratlon of a reactant. or product in unit which must colUde simultaneously In order to bri ng
time. about a chemical reaction.
► For the reaction, R -➔ P ► For a complex reaction, moiecuiarity of the slowest
step Is same as the order of the overall reaction.
Rate of reaction ~ - A (R) "' + A (PJ
Al AI ► The slowest step In a reaction mechanism Is called the
rate determining step.
where, Rate of disappearance of reactant R = - A (RI , ► Integrated Rlite Equations
At
► These are different for the reactions of different
and Rate of forma'tlon of product P ... + A (Pl reaction orders.
M ► Half.Ufe of a reaction Is the time In which the
►· Unit of rate of a reaction Is mol L- 1 s- 1 or mol L- 1 m1n- 1 concentration of a reactant Is reduced to one half (Y1)
On liquid form) and atm s-1 or atm min-• On gaseous form). of Its Initial concentration and ils represented as t,12•
►· Instantaneous Rate: For the reactlon, ► Ufe time is the time in which 98% of the reaction is
completed.
n1 A + n2 B - m1C + ~ D, the Instantaneous rotes can be
represented In the followlng manner: ► FGr I Zero Order RHctlon
1 d (Al l d (8) 1 d (CJ 1 d [DI ► Rate ., k (AJO
-- - - =- - - - =+- - - +- - -
n, dt n2 dt m1 dt m2 dt ► Integrated rate law, (A)1 ° - kl + (A) 0
► Factors Affecting the Rate of Reaction or k "' (AJo-(AJr
► Concentration of reawnts
t
► Temperature of reaction where, [A] 0 w lnltlal concentration,
► Pressure of reaction (A) 1 w Rnal concentration after time 't ',
► Presence of catalyst ► Unit of the rate constant 'k' Is mol L- 1 s-1•
► Nature of reactants
► Surfoce area of react.1nts ► Half-Ufe period, t, 12 "' ~ (t,12 ex (Al0 )
► Effect of rad la tlons
► FGr a First Order Reaction
► Rlite Law
► Rate m /c(A)I
► It is the representation of rate of reaction In terms of ► Integrated rate law,
concentration of the reactants. It Is also called as rate In (AJ 1 = - kt + In IAJ 0,
expression or rate oquatlon.
or J,. .. 2.30310 ~
► For a general reaction, aA + b8--> cc + dO t 910 [(Ale
Rate :, k(AJ 0 [B)ll
Z.303 o
-d[RI ., k(A)o(B)ll or k o - - log10 - -
dt t (o -x)

where, k .. proportionality constant or rate constant, ,vhere, a = inltlal concentration,

o and bare exponents. (o-~ = concentration after time 't'.
► Unltof'k 'iss- 1 ormln-1•
► Order of• Raactlon 0.693
► It Is the sum of powers of the concentration of the ► Half-life period, t,12 =-k-
reactants In the rate !Aw expression.
(Thus, half-life Is independent of (R) 0.)
► Order of a reaction can be 0, 1, 2, 3 and even a fraction.
► FGr • Sacond Ordor RHctlon
► Reactions taking place in one step are called
► Rate c k (A]Z
elementary reactions.
► When a sequence of@lementary reactions gives us the ► Integrated rate law, ....!... m let +- ...!....
products, the reactions are called complex reactions. (Ale (Alo
 k .. _1 . _ _
X _ It is the energy needed to form the Intermediate e.tlled
or activated complex or it is the extra energy contained by
t o(o-x)
the reactant molecules that results into effective collisions
► Unit of 'k' lsmo1-1 Ls- 1 or M-1 s- 1 where, M Is molarity. between them to form the products.
► Half-Ufe period, t,12 ,,, _1_ _ _ 1 ► If kz
and le, are rate constants at temperature 2 and T1 r
k[A]o ha respectively, then ·
► For nth Order Reaction
► ~te = k[A]n
109~= ....!R- [T2 -T1]
", 2.303R r,.r2
► lntegrated rate law, (n - 1) kt .. -
1
[Ar-•- _
- ,_
[A)g - 1 ► Catalyst: A catalyst Is a substance lllhlch Increases the
rate of reaction without itself undergoing any permanent
2<11 -1J 1 chemical change.
► Half-life period, t,12 .. -
k(n-1)(A)8- 1 ► Characteristics of Catalyst:
► It does alter Gibbs energy (AG) of a reaction.
► Pseudo First Order Reaction: This reactlon Is not truly
of the first order but under certain conditlons become ► It catalyses the spontaneous reactions but does not
reaction -o f first order. catalyse non-spontaneous reactions,
► It does not change the equilibrium constant.
For example, addle hydrolysis of ester (ethyl acetate).
► It catalyse forward as well as backward reactions.
► Arrhenius Equation: The temperature dependence of rate
of a chemical reaction Is expressed by Arrhenius eq_uatlon. ► Collision Theory: According to this theory, rate of reaction
depends on the collislon frequency and effective collisions.
k =A, ,rE;,lffr
The number of colUslons per second per unit volume of
wh·ere, A .. Arrhenius factor or frequency factor, the reaction mixture Is known as collision frequency (z).
E0 = activation energy (in J mot- 1), R., gas constant and Thus, In collision theory activation energy and proper
T••temperature. orientation of the molecules together determine the
► ActJvatJon Energy: It Is given by the energy difference criteria for an effective collision and hence the rate of a
between activated complex and the reactant molecules. chemical reaction.

',,
-f Multiple Choice Questions ~
~ Practice Exerci.se
Q6. A first order reaction takes 30 minutes for SO"
Ql The unit of rate constant for a first order reaction completion.The value of rate constant kwould be:
(C0Sf2023)
Is: a. 2.5 x 10-3 mIn-1 b. 2.75 x 10· 0 m1n-1
a. mot L-1 s· 1 b. L mol1 s-1
c. 1.25 x 10-3 m ln·1 d. 2.31 x 10- 2 mln-1
c. s-1 d. mol L"1
Q 2. The velocity (rate) for a zero order reaction: Q7. The slope In the plot of log ~
[R)
vs time for a flri
A + B-➔ C
a. r ate = k (AJ0 (BJ 0 b. rate = k (A)1(BJD order reaction Is: 1casr 2023)
c. rate = k (A)O(B) 1 d. None of these +k
a. b. -,. k
2.303
Q3. For a zero order reaction of the type
A -➔ products, the rate equation may be
-k d. -k
C. - -
2.303
expressed as: (COSE2023J
Q8. lh • niactlon, the Initial concentration of the
a k " (A~ -(A) b. k .. (A)-(A~
reactants lncreaMs fo.ur fold and the rate becomes
t t
sixteen times Its initial value. The order of the
c. k "' (A~ -(A) d. k _ (Alg -[A) . t reaction Is: (CBSE 2023)
2t 2 a. 2.0 b, 3.5 c. 1.5 d. 2.5
Q4. The rate constant for the reaction, Q9. Which of the following statement Is tn.187
A 1- 28 ~ product Is expressed by R = [A) (8] 2•
(CIJSE sq}' 202 J ·24 J
The order of reaction will be:
a. Molecularity of reaction can be zero or a fraction.
a. 2 b. 3
c.5 d. 6 b. Molecularity h.ns no meaning for complex
reactions.
Q 6. The order of the reaction
c. Molecul.Drity of a reacUon Is an experimental
hv
H2(g) + Cl2 (g)->2HCl(g) Is: (COSE2023} quantl!y
a. 2 b. l d. Reactions with the molecularity three are verv
C. 0 d. 3 rare but are fast
Q10. The time required for the half-completion (tvz) of Q 19. If the initial concentration of substance A Is
a first order reaction Is: 1.5 M and after 120 seconds the concentration of
a. dependent on Its initial concentratJon substance A Is 0.75 M, the rate constant for the
b. Inversely proportional to Its Initial concentration reactlon if it follows ttro order kJnetlcs Is:
c. inde·pendent of its initial concentration (C8SESQf2023·2 4)
·cl. dependent on square root of Its Initial concentrat!On a. 0 .00625-mol L-'s-1
Q11. The half-life period of a first order reaction Is 400s. b. 0.00625 s-1
Its rate constant will be: c. 0.00578 mol L-'s- 1
a. 1.73 x 10-3 s-1 b. l44 ~ 10-3 s-1 d. 0.00578 s-1
c. 2.72 x 10· 3 s· 1 d. 2.88 x ,o-3 s·I Q 20. Which radioactive Isotope would have the longer
Q12. If a reaction obeys the following equation: half Ufe 150 or 190 ? (Given rate constants for 1 s0
k = 2.303l _ _,!_ and 190 are 5.63 >< 10-3 .- 1 and k .. 2.38 x 10-2s- 1
t 0910 (o-x) respectively): (CBS£ SQf 2022-23)
a. 1so
The order of reaction will be:
b. l9Q
a. zero b. first c. second d. third
c Both will have the same half life
Q13. The half-life of a reaction Is doubled when the
d. None of the above Information given ts Insufficient
initial concentration is doubled. The order of the
reaction Is: (CBSE 2023) Q2L Arrhenius equation can be represented graphically
a. 1 b. 2 c. 4 d. 0 as follows:
Q14. For the reaction, A+ 28 ➔ AB2 , the order w.r.t.
reactant A is 2 and w.r.t. reactant 8. What will be
change In rate of reaction If the concentration of A
Ink (s- ~
is doubled and 8 is halved? (CBS£ SQ}> 2022·23}
a. increases four times
b. decreases tour times 1/T (s-1)
c. Increases two times The (I) Intercept and (II) slope of the graptt are :
d. no change
(COSE SQf 2022·23)
Q18. For the reaction 3A ➔2.8, rate of reaction - d(A) a. (I) In A (II) E/R
dt
b. (I) A (II) ..£0
Is equal to: (CSSE:2023/
+2 d(BJ
c. (i) In A (ii) -£0 / R
+3 d (BJ
a. 2 dr b. 3 dt d. (I) A (II) -Eo
+-I d(B) Q22. Actlvatlon energy of a chemical reaction can be
d. +l d(B)
c. 3 de 2 de calculated by: (NCERT EXEAIPUIR}

Q 16. The number of molecules that react with each a. determining the rate constant at standard
temperature
other In an elementary reaction Is a ~sure of
the: (CBSE:2023} b. determining the rate constant at two
a. actlvatlon enersv of the reactlon temperatures
b. order of the reaction c. determlnlng the probJl'llUty of collision
c. stoichiometry of the reaction d. using catalyst
d. molecularity of the reaction Q23. Which of the following graphs represents
Q17. The value of rate constant for a tint order reaction exothermic reaction? (NCEllTEXEt.fPIAR)
Is 2.303 x 10-2s- 1. What will be the time required Adivetod oomplex
to reduce the concent,:atlon to 1/ 1Oth or Its Initial
concentration? l
a. 100 s b. 10 s c. 2303 s d. 23.03 s
Q 18. The half•lffe for a first order reaction Is 4 minutes.
The time after which 99.9% reaction gets
(I) f
completed Is:
a. 16 mlnutos
c. 32 minutes
b. 8 minutes
d. 40 mlnutos
I Roocllon ooordlnokl -
Produc:ta
 Acl.Nated complex c. Activatlon energv of both forward and backward
reaction Is E, + E1 and reactant Is more stable
l than producl

(Ji)
r cl Activation energy of backward reactlon Is E,.a.nd
product Is more stable than reactant
Q26. The role of a catalyst.lsto change: (NCERTEXEMPLA/1)
J Raactants

R&ecllon eootdlnate -
a. Gibbs' energy of reactlon
b. enthalpy of reaction
c. activation energy of reaction
Adivaled complex d. equilibrium constant
Qrt. Which of the following Is affected by catalyst?
l a. .AH b. 6G c. f 0
(C85E202J)
d. ~S
(iii)
f ·f Assertion & Reason
' I ,

Type Questions ~

i R&aclants

Raactlon coordinate -
Products
Directions (Q. Nos. 28-34): Each of the following questions
consists of 1wo statements, one is Assertion {A) and the other is
Reason (R). Give answer:
a. {I) only b. (ii) only a. Both Assertion (A) and Reason (R} are true and
c. (iii) only d. (i) and (ti) Rea$on (R) Is the correct expkinatlon of Assertion
(A).
Q24. According to Anhenlus equation rate constant
b. 8oth Assertion (A) and Reason (R) are true but
k Is oqua, to A,-t.lRT' . Which of the following
Reason (R) Is not the correct explanation of
1 Assertion (A).
options represents the graph of Ink vsT?
c. Assertion (A) is true but Reason (R) is false.
(HCERT £XEMPLAR.J cl. Assertion (A) Is false but Reason (R) Is true.
Q28. Assertion (A): Order of the reaction can be zero or
fractional
a. .,.
t t
b. .,. Reason (R): We cannot determine order from
.E £: balanced chem:ical equation. {HCERTEXEMPLAR)
Q29. Assertion (A): Order and molecularity of a reaction
are always same.
1,r - Reason (R): Complex reactions Involve a sequence

t
of elementary reactions and the slowest step is
rate determining. (CBSE2023\
C. .,.
.E
d. l
....
Q 30. Assertion (A): Order and molecularity are· same.
Reason (R): Order Is determined experlmentall
.6 and molecularity is the sum of the stoichiometric
coefficient of rate determining elementary step.
1,r - 1,r- (HCERT EXEMPLAR)
Q25. Consider the given figure and mark the correct Q-31. Assertion (A): The molecularity of the reaction
option. /HC.EIIT£XEMPLARJ H2 + Br2 ➔ 2H8r appears to be 2.
ActJveted oomplex Reason (R): Two molecules of the reactants are
Involved in the given elementary reaction.
{C85E2023)

l
~
Q 32. Assertion (A): The enthalpy ,of reaction remains
constant in the presence of a catalyst.
Reason (R): A catalyst participating In the reaction,
I forms different activated complex and lowers

I A&actanta
down the actfvation energy but the difference
in ~nergy of reactants and products remains the
same. (HCEIITEXt'MPLAR)
Q33. Assertion (A): All colUslons of reactant molecules
Reaction ooordlna1e- lead to product formation.
a. Activation energy of forward reaction Is E, + E2 Reason (R): Only those collisions in which
and product Is less stable than reactant molecules have correct orientation and sufficient
b. ActJvatlon energy of forward reaction Is E1;, E2 kinetic energy lead to compound formation.
and product Is more stable than reactant. (HCEAT EXEMPI.AA)
Q34. Assertion (A): Rate constant determined from Arrhenius equation are fa irly acc.urate for si mple as well as
complex molecules.
Reason (R): Reactant molecules undergo chemical 1change Irrespective of their orientation during colUslon.
(NC!llT EXUIPI.AII}

mol l 4 1 _, For n., 0. tv:z "' (A)

1 (c) Unlt = - -x - - - 1 1
=s
· s (moll- ) If Cv2 Is doubled. (A) Is also doubled. ·so the reaction Is

2. (a) rate = k (AJO (BJO of zero order.

14-. (a) Increases four times
3. (a) k ... IA)q-(A) Given: order w.r.t. reactant A .. 2
r
So. for the given reaction. Rate .. (AF
4. (b) 3
If (A] Is doubled. then Rate = (2A) 2 "' 4 (A)2 = 4 Rate
5. (c) Given reaction is a photochemical reaction and 15. (a) Given reaction Is 3A - > 28
the order of all such reactions is zero as it does not
For this reaction.
depend upon the concentration of reactants.
6. (d) For a first order reaction. the relation between t,n rate of reaction: -l d(A) ,. .l d(BJ
0.693
3 de 2 dt
ilnd rate constant Is t112 ., --;;--
-d[A) 3d(8)
= cit =2dt
=> k o- - = - - a 2,31 M 10_zmn
0.693 0.693 I -1
tv2 30 16. (d) molecularity of the reaction
17. (a) let Initial concentration be o
7. (a) +k
2303 Then. final concentration (o - x) = 1 of o = o
10 10
a. (a) According to the rate law.
For first order reaction.
r = k[Ar - (l) 2.303 l o
where k .. rate constant ro.- og - -
k o-x
Now. on Increasing the con.centration four fold and
rate sixteen times Its Initial value. ., 2.303 . lo _ o_
16r ffl k (4A)n •.(2) 2.303 X lQ...2 g O / IQ
Combining eqs. (1) and (2). we get •• 100 log 10
16 ., 4n

) or. 41 .. 411
or. n:: 20
Hence, the order of the reaction is 20.
9. (b) Molecularity has no meaning for compl~
r .. 100s.
18. (d) For a first order reaction.

t Vl -_ 0.693
k
- .
-
_ 0.693
4- k
reactions.
k = 0.693 ...(1)
10. (c) Independent of Its lnltlill concentration 4
11. (a) Given. tvi ., 400s 2.303 o
Also. t ., - -log10 -
k 0-X
0.693
For first order reaction. t112 = - k- 2.303x4 100
I "' 0 .693 log (100 - 99.9) (from eq. (1))
.., _ _
0.693 /( c:, 0.693
k
⇒

400 ., 2303x4 l lO00

0
Cv2
0.0017325
0.693 8 °
2303 4 3
.. l.73 >( lQ-3 !!-1 = x x .. 39.9 .. 40 minutes
0.693
12. (b) flr!it
13. (d) We know thot half life Is related to co_n tentrntlon 19. (a) For zero order klneucs. the rate constilnt.
as: k (RoJ-(R)
O
rV2 .. (A)1~ where n .. order oft.he reaction C

Here. n ., 2 1.5-0.75
or. k=
1 120
t112 ., (A) .. 0.00625 mot L• 1s· 1
 20. {a) 15a The in1egrn1ed nue equation nre different for lhe
The rate constant for the decay of 150 is less than reactions of different reaction orders. We shall
so
that for 1'9Q. therefore. the rate of decay of 1 will be deLcm1ine these equal.ions onJy for zero and first
slower and wlU have a longer half-life as compared order chemical reactions.
to 190. Zero order reaction me~s that the rale of lhe
21. (c) (I) ln A. (II) -E0 / R renction is proponional 10 1.ero power of the
In Arrhenius equation. a plot of ln k with l / T g)ves a concentration of reactnnts. Consider Lhe reaction.
straight' Line with slope .. - E0 / Rand Inter cept ., ln A R ~ P, Rate= d[RJ/dt = k(R]O
22. (b) determining the rate constant at two temperatures
First order reaction means !hat, the rnte of lhe
23. (a) (I) only
reaction is proportional 10 the first power of lhe
concenirotion of reactants, R. For the reaction,

24. (~) ~
t R-... P, Rate = d1~) = A1RI and the iniegraling

rate equation is k = ( lit) In [R)J[RJ where, [RI is

finnl concentration and [R )0 ii. Initial concentration
1/T- of reactanl, respectively.
2!>. (a) Activation energy of forward reaction Is £ 1 -+- £1
RNd tfte glllffl P!JSSOge car.fully arid give the
and prod'uct Is less stable than reactant
answer of the (ollowihg questions:
26. (c) actlvaitlon energy of reaction
27. (c) £0 Q l For .a hypothetical reaction,
28. (b) Both Assertion (A) and Reason (R) .are true but R --+ products; rate = - "(RJ. The negative
Reason {R) Is not the correct explanation of sign used In the rate expression Indicates:
Assertion (A). a. decrease in the concentration of react.ants
29. (d) Order and molecularity are same for an with time
elementary reaction because such reactions b. decrease In the rate wltli time
proceed in a single step but they are mot same for c. reacUon Is reversible .
all reactions.. so. assertion Is false. r:t. None of the above
30. (d) Order and molecularity may or may not be same Q2. For .a reaction, P + Q - > R + S
as order can be zero and even a fraction but The curve which depicts the variation of the
molecularity cannot be zero or a non-Integer.
concentration of products Is:
31. (a) In the given reaction. two moles of reactants
le .. H and Br are In the element.in,, step of the - - - P
reactfon and ~ence. the molecularity appears to ,,.a
be 2. It Is clear that both assertion and reasons ,,,'
,
are true and reason Is the correct explanation of ,, .. ""·, , ,,'
assertlon.
,,' , ' ',
"
32. (a) Both Assertion (A) and Reason (R) are true and ,. '\
Reason (R) Is the correct explanatlon of Assertion ''
(A). ' ',,.R
s
33. (d) Only effective collisions lead to the formation of Tlm9 -
product so assertion Is false but reason Is true a, P b. Q c. R d. S
as It defines the correct. meaning or effective
colUsion, Qa. For the reaction,
34. (c) Assertion (A) Is true but Reason (R) Is false. Hg(I) -1- Cl2(g) - t Hg('1(s)
The rate of reaction Is given as:
-f Case Study Based Questions ~
' I ,

a. 6(HgClz) b. _ A(Hg)
Case Studyl At At

The instwllnneous rule can be measured by C. - A(Clz) d. All of these

At
determination of slope of the tnngen1at point 'r' In
concentrmion vs lime plo1. This makes it difficult Q4. Cont.act process Is used In the formation of
lo determine the rute luw und hence the order of sulphur trloxlde,W
the renc1ion. In order 10 avoid lhis difficulty, we 2S02 (g) + 0 2(g) ~ 2S~(g)
can integrate lhe differential rn1e equal.ion 10 give
u relation between directly mensured experimental The rate of reaction ciJn be expressed as
darn, i.e.., concentrations 01 different times und rnte -6C02J ... 2.5 x 10-4 mol L- 1 s- 1
com1tnn1. M
 Then rate of disappearance of (SO 2) will be: 3. For first order reaction.
a. 50.0 x lQ-5 mol L- 1 s-1
0.693
b. 3.75 x 10.... mot L-1 s- 1 CsCNc. = t 111 =- - k-
c. 2.5 x 10-4 mol L•1 s· 1
d. 4.12 x 10.... mol L• 1s· 1 n .7B = 0.693
••-------ll Answers I1-------• k

1. (a) decrease In the concentration of reactants with time 0 693

k= · ~ 0.009
2. (a) P 77.7B
3. (d) All of these 2.303 o
4. (a) 50.0 " 10-5 mol L•1 s· 1 and t30'1b =--;;-log(o-x)
Case Study 2 2.303 100
c o]'oglog(l00 - 30)
The ra1e law for a chemical reaction relates the
reaction rate with the concentrations or partial = 255.B9 (log 10 - log 7)
pressures of the reocUlJlts. For a general reaction "' 255.B9 (1- 0.8450)
aA + bB ~ C with no intermediate steps in
= 39.66 minutes
its react.loo mechanism, meaning that it is an
elementary reaction, the rrue law is given by
OR
r mk[A ~, [B)Y, where [A] and (BJ express the Given (A)i0 = Sg. [A) = 3g
concentrations of A and B in mole-,; per litre. and I< "' 1 x 10-3 p.e r sec
Exponents .Tandy vary for each reaction and are Using.
determined experimentally. The value of k varies
with conditions that affect reaction rote, such M c.. ~k 1og ~ (Al
temperatµre, pressure, surface area. etc. The sum
of these exponents is known as overall reaction
order. A zero order reaction has a consumt rate =~ lo ~
l xlO~ g3
that is independent of the concentration of the
reaclants. A nrsl .order reaction depends on the = 2.303 K 103 (log 5- log 3)
concen.trntion of only one reactant. A reaction is = 2.303 (0.6990 - 0A771)
said 10 be second order when the overall order is °' 511 sec.
two. Once we have detcrmi_ned lhe order of the
reaction, we can go back and plug in one set of our Case Study3
initial vaJues and solve fork. (CBSE 2 022 Tarm-2) The rn1e of reaction is concerned with decrease
RHd the giv.n passage carefully and give the in concencrotion of reac1ants or increase in the
answer of the following qwstions: concentn:icion of products per uni1 time. It can (
QL Calculate the overall order of • reaction which be expressed as instantaneous rate a1 :a particular
has the following rate expression: instant of time and average role over n large
Rate ., k (A)t/2(8) 312 interval of Lime. Mathematical repres·enta1jon of
Q2. What Is the effect of temperature on rate of rate of reaction is given by rate law. Rate constant
reactlon7 nnd order of a reuction can be ,detem1ined from
Q 3. A first order reaction takes 77.78 minutes for
rn1e low or its integro1ed rate equation. (CBS£ 2023}
50" completion. Calculate the time required RHd the glv.n passage care(uUy and give th•
for 30" completion of this reaction (log 10 = answer of the following questions:
1, log 7 .. 0.8450). Q1. What Is average rate of reaction?
OR Q2. Write two factors that affect the rate of
A first order reaction has a rate constant reaction.
1 "10-J per sec. How long wm 59 of this QS. (i) What happens to rate of reaction for zero
reactant take to reduce to 3 g7 order reaction?
(log 3 = 0.4771; log 5 "' 0.6990) (II) What Is the unit of k for zero order reaction?
OR
• I Answers l • (I) For• reaction P + 2Q ➔ Products.
1. Overnll order of reaction m l + ! ., ~ ., 2 Rate " k ['PJt/2((2) 1. What ls the ordorof tho
2 2 2 reaction?
2. The ra le of reactlon Increases on Increasing the (II) Define pseudo first order reaction with an
temperature. example.
••--------1 Answers 1 - !- - - - - - •
Ans. For the reaction. n1A + n 2 8 --4 m 1C + m 2p

Average velocity ., 1 d(A) - - 1 d[B)

1. Average rate of reaction Is defined as the ratio· of
change in concentration of reactants or products to n1 dt fli dt
the change ln time interval of a chemical reaction.
It Is denoted bv 'r' and Is represented as:
= 1
1 djcj ,. + _1_ dIO I
m1 dt m 2 dt
Average rate of rea.ction = change In concentration
time Q4. For which type of reactions, order and molecularity
have the same value? (HCERfEXEMPLAR)
Rate(R) = ~ Ans. React ions completing in only one step le. the first
6t
order reactions have same value of order 'anci
2. The two factors that affect the rate of reaction are:
molecularity.
(I) concentration of the reactants.
Q5. State a condition under which a bimolecular
(ii) temperature of the reactants.
reaction is kinetically first order reaction.
3. (i) For zero order reaction. the rate of reaction is {HC£ATEXEMPLAR)
Independent of the reactant concentration. Hence,
Ans. The given condition Is possible only when one ·of the
Increasing or decreasing the concentration of the
reactant is in excess and there occurs a very small
reacting species has no effect on the reaction rate.
change In Its concentrat.lon during the course of the
(II) For zero order reaction, the unit of 'J< is
reaction. This happens in pseudo first order reaction
mol L-'s-1•
(klnetlcallv bimolecular reaction) e.g.. hydrolysis of
OR ester In acidic medium.
(I) Order of the reaction =½+1=I=1.5 Q6. The specific rate of a reaction Is
6.2 >< 10· 3 mol L· 1r 1. What ls the order of the
(11) Pseudo first order reaction Is defined as the reac- reaction?
tion which Is bimolecular but order Is one. Ans. The reaction Is of zero order.
For example: acidic hydrolysis of ester (ethvt
Q 7. Give one example of a fractional order reaction.
acetate).
I
Ans. H7. + Brl __. 2MBr : Rate ,. k [HJ(Br J112 : Order •• 1,½.
-~ Very Short Answer Type Questions ~
Q 8. Rate of reaction Is given by the equation :
Ql What do you mean by velocity of a reaction 7 Rate = k (A] 2(8]. What are the units for the rate and
Explain. rate constant for the reaction?
Ans. The ra~e at which concentration of reactants·changes Ana. Unit of rate = MolL"1!>· 1: Unit of rate constDnt
In unit time Is called velocity of the reaction. (k) = L2 mo1· 2 s-1•
If the change In mole product (concentration) of Q9. What Is the rate detennlnlng step In a multi-step(
reactant during lnf1nlteslmaUy small time dt Is dx. reaction?
then Ana. The slowest step In the reaction Is the rate
determining step.
Velocity of reaction = dx Q10. State one condltlo1:1 In which a bimolecular reaction
dt
If during the period dt. the remaining mole of
may be kinetic.ally of the first order.
reactant are dC. then Ans. By taking one of the reac tants In wrge excess so that
It may not contribute towards the order.
Velocity of reaction 111 - ~. Q ll. Give an example of pseudo first order reaction.

Q2. What Is Instantaneous velodty? How could you Ana. CH3COOCfi5 + H20-> CH3COOH+ C/f90 H
(Excess)
predict It?
Ana. Tha actual velocity of a reaction at a particular Rate = k(CH3COOC2HsJ (H 20)0
moment Is called Its Instantaneous velocity. It can Q12. For a reaction R --+ P, half•Ufe (t,n>Is obsetVed
be determined by plotting a graph between time and to be Independent of the Initial concentration of
concentration. The slope of tangent drawn a.t a point
reactants. What Is the order of reaction? (C8SE20 17J
of time vs concentration plot at some specific time Ana. For the reaction. R __. P. half-Ufe (tin) Is ob5erved
to be inde.pendent of the Initial concentration of
and specific concentration show the Instantaneous
reactants. thus it follows ftrst order reaction.
velodtv of the reaction.
Q13. What Is an elementary reaction?
Q3. For the following reaction, write the average
An,, The reaction taking place in a single step Is an
velocity of the reaction.
elementary reaction. For example.
n1 A + n2B - ->m1C + m20 N2(g) + 02(9) --; 2NO(g)
 Q JA. In some chemical reactions, It Is found that a large Q 22.. Will the me constant of the ruction depend upon
number of coWdlng mole(:ules have energy more r If the E<K.1 (activation energy) of the reaction is
than threshold energy value, yet the reactions a,:e zero? ('CBS£ 20201
quite slow. Explain. Ans. No. when Eoc, -= 0. k = Ae-OtRT = A. Thus. I< becomes
Ans. The reactant molecules may not be properly Independent of T.
oriented at the tlme of collisions. Q23. If the concentration is expressed In mol L• 1 units
Q15. Express the relation between the half.lit. period and time In seconds, what would be the units of k:
of a reaction and initial concentration for the (I) for a zero order reaction, (II) for a first order
reaction of the nth order. reaction?
1 Ans. (i) For zero order reaction : k has unit : mol L•1s·1•
Ans. For nth order reactlon. C112 ... - 1-
(A)0 (Ii) For ftrst order reaction: k has unit : s·1.
Q24. Why does the rate of a reaction not remain constant
Q16. For a reaction, A + B - - > Prod_ uct, the rate law
throughout the reaction?
is glve-n by (r) "' k (A]112(8] 2 • What Is the order of
Ana. The rate of reaction represents Ule change In molar
reaction?
concentration of reacting species taking part in the
Ans. Order o.f reaction = 1/2 + 2 = 2.5 reaction per unit time. 'Since the change in molar
Q17. Fon reaction A-> B, the rate of reaction becomes concentration Is not uniform. the rate of reaction
twenty seven times when the concentration of A does not remain constant
is Increased three times. What Is the order of the Q 25. C.Onsider the decomposition of hydrogen peroxide
reaction? in alkaUne medium which is catalysed by iodide
Ans. For the reaction. let r = k (A)n Ions.
According to the data. 27 r = k (3A)" o+r
n 2H202 ---t 2H20 + 02
21r. k (3A) or (3)3 = 3"
This reaction takes place in two steps. as given
r k(Ar
below:
:. Order of reaction (n) = 3. Step-I: H20 2 + 1· - H10 + I0"(slow)
Q 18. A reaction Is 50" complete In 2 hours and 75" Step-II: H20 2 +to· -.... H20 + 1· + 0 2 (fast)
complete In 4 hours. What Is the order of reaction? (I) Write the rate law expression and determine
Ans. Since the amount left after one-half period the order of reaction w.r.t. H20 r
(2 hrs) Is one-half (50%) of the original amount (II) What Is the molecularity of each !Individual
and the amount left after two-half periods (4 hrs) Is step?
one-fourth (2 5%). this suggests that the reaction Is Ana. (I) For a complex reaction. the rate of overall reaction
of first order. depends upon the rate of reaction slowest step.
Q19. What Is meant by elementary step In a reaction? Hence. R.lte law expression: Rate ., k [H 20 2) [t-]

I
~
Ana. A complex reactlon occurs through a sequence of Order of reaction w.r:t. H10 2 ,. 1
steps known crs elementarv steps. Each elementarv (II) Molecularity of both Step-I and Step-II ls ~
step has Its own molecularity. Q26. A first order reaction Is found to have rate
Q20. Derive an expression to calculate time required for constant k w 5.5 x 10-14s-1. Find the half-life of
completion of zero or~er reaction. (HCERT EXD.I PLAAJ the reaction.
Ans. For a zero order reaction. (A] = (A]0 - kr Ana. For a first order reaction.
When the reaction 1$ completed, (A) .. 0
t 0.693 Cl 0.693 <o l.26 x10'3s;
t ■~
Cl

k v2 k (5.5 x10"14 s·1)

Q 21. Write the order and units of velocity constant for Q 27. Give an example or second order reaction.
the following reaction: Ans. CH3COOc,H, + NaOH - ) cH,COONa + C2H,;DH
H2 + Cl2 - 4 2HCl Q 28. What Is :activation ene,oy? How Is rate constant
sunugt,1 1 .,HCL related to activation energy?
Ans. For the reaction, H2 •· CI2 •e- -• L Ans. Activation energy Is given b'{ the energy difference
The order of reaction = 0. between activated complex and the reactant
[ihls Is bec.iuse concentration of none of the molecules or it Is the extra energv contolned by the
reactant changes with tlme.] reactant molecules that results into effective collision
)( between them to form the products.
For
. a zero order reaction, k = -t Rate constant (k) for a reattlo"n Is related to actlViltlon
On substituting the units. energv as:
E
Unit of k c moVL = mo\ L"1 G" 1' ln k mln A - ..:Jl.
s RT'
 Q29. On Increasing temperature, activation energy for a Ana. For the reaction.
reaction dKrease.s. Why? 2N 20s(g)-► 4N02 (g) + 0 2(g)
Ana. Activation energy and temperature are Inversely Overall rate of reaction can be given as under:
proportional to each other.
Q30. What is the effect of adding a catalyst on:
_.!., d(N205] = .....!. d(N0 2l., + d[0 2l
2 dr 4 dr dt
(i) Activation energy (EJ, and
(ii) Gibbs energy (AG) ofa reaction? (COSE2017) Given. d(N02) = 2.Bx 10-3 M s- 1
Ans. (I) Activation energy (EJ of the reaction decreases dt
on adding catalyst - d(N205) =?
(II} Addition of catalyst does not change the 11c1we of dt

' I ,
Gibbs ene,::gy (~G) of a reaction.
TiP- - - - - - _ ,
-ID... Short Answer Type-I Questions ~ Do not forger co put correa sign ogolnsc products and
reactants while writing rare low for a reaction .
Q L What do you mean by rate of a reaction? For the
reaction N01 (g) + CO(g) - C02(g) + NO(g), the 1 d(N2O5) = + 1 d{NC¾)
proposed mechanism is as follows: 2 dt 4 dt
(I) N01 + N02 --+ NO + N0 1 (slow)
(II) NOs + co - > col +NOz (fast) or - d(N20 5) = .!.x2x2..Bx10-3 M s-1
dt 4
What Is the velocity (rab!) of reaction?
Ans. The rate of chan e in concentration of reactant with
.. 1.4 " 10-3 M s-1
time is called velocity rate of reaction. Q 5. What are pseudo unlmolecular reactJons? Explain
For reaction: N0 2(g) + CO(g) - • NO(g). witJI an example.
The rate of the reaction is decided by slow reaction Ana. Pseudo Unlmolecutar Reactions: The reactlons for
[step (I)) of the proposed mechanism, Thus. which the values of order and molecularity are not
Velocity (rate) of reaction .. I< [NOJ [N02) ,. l<[N01)2 sam·e are called pseudo unfmolecular reactions.
e.9_(I) Hydrolysis of sugar:
Q 2. Explain how and why wlU the rate or reaction for a
H'
given reaction be affected when: Ctf122O11 t H2O -> Cr,HL'2O£. t- ~H12Or,
(I) a catalyst Is .added
(II) Hydroly1l1 of ethyl acetate:
(II) the temperature at which the reaction was
H'
taking place Is decreased. CHl OOCi\(I} + H20(I) --. CH 3COOH(I) + C2HsOH(I)
Ana. (I) When a cat:ilyst Is added. the rate of reaction will
Increase. The ca_talyst decreases the activation For both the above reactions. order ls one because
ene.rgy of the reaction therefore. the reaction concentration of H20 remains unchanged but
becomes faster. molecularity Is two. So these reactions are pseud(
(Ii) When the temperature at which the reaction was unlmolecular or pseudo molecular reactions.
taking plc'lce Is decreased. the rate of reaction For these reactions. rates can be given a11:
will decrease. At lower temperatures. the kinetic Rate "' k [C12H22 O1 J.
energy of molecules decreasl?!i theteby. the Rate = k (CH3COOCzHJ [H2QJO
colllslons decrease resulting In a lowering of rate Q 6. (l) The convenlon of molecule A to B foU.owod
of reaction, second otder kinetics. If concentration A or
Q 3. Write the order of following reactions with reason: increased to three times, how will it affect the
(I) N2 + :SH 1 : 2NHj rate of fonnatlon of 87
(II) CH1COOC 1H5 + NaOf-h==• CH 5COONa +C1H5OH (II) Define Pseudo first order reaction with an
fo
e,cample.
Ana. (I) N2 + 3H2 ~ 2NH3 Ana. (I) The given reaction Is A-->8
The velocity of this reaction does not depend Since. it follows second order kinetics so.
upon the concentration of N2 and Hi- So It Is a !!!:!! Rate, .. l<[A)2 ...(1)
order reaction. where k .. rate constant
(II) CH3COOC2H5 .., NaOH . - CH 3COONa + CzH50H (A) ., concentration of A
Since concentration of one mole of each react.ml If the concentration or (A] Is made to increase 3
Is ch.1nglng. s.o It Is a second order reaction. times. then rate will Increase by 9 times as:
Q4. For the reaction 2N 20 5(g)->4N0 2(g) + 0 2(g), Rate2 "' I< [3A]2 =- 9k{A)2 ...(2)
the rate of formation of N02 (g) Is 2.8 x 10-s M s· 1. From eqs.. (1) and (2.). we have (R.'lte)i ., 9 x (Rate)1
Cakulate- the rate of disappearance of N20 5(g). Hence. the rate of formation of B will Increase by
(C8SE 201 BJ 9 times.
 (ii) Pseudo first order reaction Is defined as the Q 9. In a first order reaction, the concentration
reaction which Is bimolecular but order Is one. For af substinct reduces to half of the initial
example: acidic hydrolysis of ester (ethyl acetate). concentration In 40 seconds. Calculate velocity
Q7. Analyse the given gr.aph dr.awn between constant for the reaction.
concentration of reactant vs time Sol Concentration of the substance reduces to half of
its initial value in 40 seconds. so this is the half-lie
J!l
~ 1.6 period (t 112) of the substance.
For a Arst order reaction.
~
·o o.a Velodtyconstant (k) =~ = 0·693
j I
I
I
I = 1.73
tl/2
10-2 5- l
><
40s

80.4 ------•------
C
I
Q10. A first order reaction Is completed 50" In
8 02 • I
100 seconds. Find out the rate «mstant of the
reaction.
0 10 20 30 Ans. Time required for 50% (half) completion of a
llme - reaction is called Its half-life period (tin).
(1) Predict the order of re.action. So here tv2 "' 100 s.
(ii) Theoretically, can the concentration of the For a Arst order reaction.
reactant reduce to zero after Infinite tlme7
Explain. (CBSE 2020/ Rate constant. I<=~ - ~ s-1
Ans. (I) It can be seen that. the concentration of the
reactant decreases exponentially with time which
-------
t112 100
6.93 >< 10·3 s•I
=

Is a characteristic of the 'first order reaction' and Q11. A first·'order reaction takes 69.3 min for SO"
the ra te of the reaction here Is proportional to the completion. What Is the time needed for 80" of
f1rst power of the concentration of the reactants. the reaction to get completed?
(ii) The first order rate equation. A "' Ag fth 1 (Given: log 5 = 0.6990, log 8 = 0.9030, log 2 =0.3010)
(C8SE SQP 2022 ·23}
where. A Is the concentration of the reactant at
time t and A0 is the initial concentration of the
Sol Given: t112 ., 693 min
reactant. We know that. Half-life trn = 0.693/k
Putting the value A o 0. we get or. k., 0.693 / tvi
k "' 0.693/69.3 = 1/100 ., 0 .01mln-1
A0 e--111 ., 0, therefore e-1•1 .. O
Hence. r ... oo. since k cannot tie zero. So. theoretically. 2.303 ~
For first order reaction, k .,, - - log (RI
the concentration of the reactant will become zero 1
at infinite time. whore. [RoJ ., 100. [R] .. 100 - 80 "' 20
Q8. In a reaction 2N 2O5(g) -> -4NO 2(g) + 0 2(9), the 23031 100
or. t "' Q.01 og
concentration of N20 5 decreases from 0.Smol L- 1 20
to 0.4mol L-1 In 10 minutes. Calculate the average or. t ., 230.3 log S
rate of this reaction and rate of production of N01 or. t ., 160.9 min (·: log 5 '° 0.6990)
during this period. (C85E2022 Tann•2) So. the time needed for 80% of the reaction to get
' completed Is 160.9 min.
Sol Average rate o.f this reaction ., _1_ &(N:iOsl
2 M Q12. Time required to decompose S02Cl~ to half of its
Initial amount Is 60 minutes. If the decon,posltlon
a _J..,.,.,,,......._...,mol L-1 Is a first order reaction, calculate the rate constant
2( of the reaction. /NCEJtT INTEXTJ

.. O.l mol L- 1 m1n· ·1 .. 0.005 mol L-1 mln·1

SOL nme required to decompose half of a substance Is
20 CDlled its half-Ufe (tin). So here tv2 .. 60 minutes.
For the given equation. For a Ar9t order reaction.

1" x Rate of disappearance,of N2D5 Rate constant. k .. 0 ·693 "' 0·693

rv2 60 minutes
= 2.4 x Rate or formation of NO2
----------
• 1.15 10-z mlnute·
>< 1

Q13. The half-Ufe of a first order reaction Is 60 minutes.

How long will It take to consume 9096 of the
"" !Qro of rormauon of N02 c 4 x[-½A{;~G]] reacunt?
[Given: log 2 = 0 .3010, log 3 = 0.4771, log 10 = 1)
,. 4 >< 0.005 .. 0.02 )( mol L- 1m1n-1• (COSE 202S)
Ans. For a first order reaction (ii) When concentration is reduced to half. the rate
, . of reaction mav be expressed as:
Ve.oatv constan t . k "' -0.693
- .. -0.693 mIn-1 Reaction rate (r") .. 1<(1/2 A)2
t1,2 60
Let the flrst order reaction takes t, minutes to 2
consume 90% of the reactant then. · r • = k(Al 21 .. 114 or r•"' 1/4
r k{A)2
Initial amount of the reactant (o) = 100 _and remaining
amount of the reactant (o-x) Hence. reaction rate will be reduced to 1/4.
= (100 - 90) = 10 Q16. Velocity (rate) conmnt for a first order reaction Is
For a first order reaction.
7 " 10-4 s 4 . Cal.cul.ate the time taken by the
2.30] O
Rate constant k ., - - log10 - reactant to re.duce to 1/4 of Its Initial concentration.
r o-x Sol. Given. k w7 " 10·4 s-1•
or, 0.693 230.3 l 100 Suppose Initial concentration of the reactant = o
60 = - t- og,o 10
0
Remaining amount of reactant (o - ,c) =
Of,
60
r .. ~~~;3 minutes 4
For a first order reaction.
= 199.39 min.
He.nee. the time required will be 19939 minutes. 2.3031
Velocity (rate) constant. - r - os,oH
QIA. Show that for a first order reaction, time required
for completion of 99" of reaction Is twlc.e the time On substituting the .values. we have
required for completion of 90" of reaction.
(COSE 2019) 2.303 o
Sol For flrst order reaction.
k ., ~log10 o / 4

k=2303l ~ 2.303 lo 4
_ 2.303 x 2 x 0.3010
t og (R) = 7X 10-4 glO - 7 X 10-4
Given: (R]Q"' 100 (suppose) = 0.198 " 104 = 1.9B x 103 seconds
then (RJ .. 100 - 99
Q 17. The rate constant for the first order reaction Is
(for '99% completion of reaction)
60 s-1 , How much tlme will It take to reduce the
r .. fq9%
Initial concentration of the reactant to its 1/16th
Putting the values. we get
value? (HCCRT EXERCIS£)
2.3031 100
r9')1!& "' - k - og-1- Sol. For the first order reactJon.

2 03 t ., 2303log~
or r99'll, = ·~ tog 100 I< (o - x)

(
2.303 >< 2 Let the Initial concentration be o.
or r99% ., I< ...(1) Final concentrstlon (o - x) ., o/16: k = 60 s- 1
For 90% completion of reaction. 0
t =~ l o - -
(6Ds-1) go/ 16
tCJ()IJ!,"' _2.303 l 100
k_o810

2.303 w-2.303 log 16 .,, _ _x_

2..303 _ = 0 .0462 s
1.2041
1 1
or tg()I)!, Ill - k - -(2) (60s- ) (GOs- )
On comparing eqs. (I) and (2), we find ~ 4.62 • 10-2 s
t 9!>% "" 2" t'JC11!, QlB. The half-life for radioactive decay of UC is
Q15. A reaction is second order with respect to a 5730 years. An archaeological artifact contained
reactant. How Is the rate of reaction affected If wood had only 80" of the 14C found In a living
the concentration of the reactant is (I) doubted tree. Estimate age of the sample. (HCEllrl~XERCISEJ
(II) reduced to half?
o~::
(HCEIIT f:XfRCISE)
Ans. Let the reaction be: A - ·> Products 3 1
Re.action rate (r) = k{A)2 (for second order reaction) Sot. Decay congtont (k) .. = ~vr·
(I) When concent.ratlon I{; doubled. the rate of
reaction may be expressed as: Radioactive decays follow first order kinetics
Reaction rate (r) = k(2A)2
r .. ~k1og~
(A) .
~ a k(iAf ., 4 or r' ., 4r
r k(A]2 k 0.693 -1
- 5730 vr
Hence. reaction rate become.s four times-
 (AcJ "' 100% : (A) '" 80% Ans. Av.rage Velocity: The change In concenirratton of
reactant or prQ(f uct present in a reaction per unit
r =(2303x5730I r } l 100 time Is called the average velocity of the reaction.
0 .693 y og 80
Average velocity
., ( 2.30 3 X 5 7.30 X0 .0969 \,,. .,, change In concentration of reactant
o .693 r time taken for the change
"' 1845 years. = change In concentration of produa
1
Q19. The rate constant for the first order decomposition time taken for ~he change
of N20s is given by the following equation:
4
Instantaneous Velodty: The actual velocity of
log k = 23 _6 _ 2 x10 k a reaction at a particular moment ls called Its
T Instantaneous velocity. If change In concentration
Calculate E0 for the reaction. of reactant or product of a reaction Is repr esented
[R = 8.314 J K-.1 mol- 1] bv 6C and time taken ls represented by 6t.
(COSE 2023}
then instantaneous velocity of the reaction = i oC •
Sol Given. log k = 23.6 - 2 x 10" k 6t
T
Effect of Temperature on Velocltv of Reaction.:
According to Arrhenius equatlon.
On Increasing the temperature of a reaction.
~ the number of activated molecules of r eactants
logk =logA - A
2.303RT increases. Consequently. the number of effective
collisions betwe,en them In·ueases. The number
Equating similar terms In the equations. we get
of effective colUslon between reactant molecules
-E0 - 2xlcfk In unit time Is called velocity of reaction. Thus. on
Rf = T increasing temperature of a reaction. its veloclty
or. £0 = 2 x 10" "R Increases. The value of rate constaRI als.o Increases
= 2 x 104 I< )< 8.314 Ji<-1 mot-• on Increasing temperature. J0°t rise In temperature
=16.628 ,c 1011 J mol-1 makes the value of rate constant double or triple,
Hence, E0 for the reactl.on will be 166 .28 KJ,!!!,ol- 1, This Is also the reason for Increasing the velocity of
reaction On Increasing temperature.
Q 20. (I) Radioactive decay follows first-order kinetics.
The Initial amount of two radioactive elements Q 2. Define molecularity and order of reaction .
X and Y Is 1 gm each. What will be the ratio Ans. Molecularity of Reaction: The number of reactant
of X and Y after two days If their half•Uves are molecules taking part in a chemical reaction is
12 hours and 16 hou,s respectively? called the molecularity of the reaction. If the
(ii) The hypothetical reaction P + Q -► R Is half number of reactant molecules taking part In a
order w.r.t. 'P' and zero order w.r.t. 'Q'. What Is chemical reaction. is 1. 2. 3. etc.. then the reaction is
the unit of rate constant for this reaction? called unlmolecl.lllar. bimolecular. trlmolecular. e!C. {
(CBS£ SQ} 2023-24) respectively.
(1) For first order reaction. h.alf-Ufe of X"' 12 hours Example: When ammonium nitrite Is heated. Its one
Two days .. 48 hours which means 4 half lives molecule take.s part In the r eaction, so mol ecularity
of this reaction Is one.
Amount of X left .. i6l of Initial value
NH4N02 ~ 2H20 + N2 t
Now. half-{lfe of Y .. 16 hours
Two days .. 48 hours which mea'n& 3 hal f Uves Molecularity of reaction Is always a whole number
I.e.. it is not In fraction.
Amount of X left ., .!. of Initial value Order of Reaction: The numb<!r of the reactant
8
molecules taking part In a chemlu1l reaction.
Ratio of X: Y = ..!. : .!. = 1 : 2 concentration of whlc.h changes during the course
16 8 - of the reaction Is called order of the reaction.
(II) Rate for the given reaction .. I< (P}V2 Example-: ·
So. the unit of rate constant for this reaction ts CH 3COOC2H6 + NaOH --+ CHaCOONa + C2H60H
mo1-V2 L- v2 s-1• In this reaction. concentration of one molecule of
' I ,
each reactant changes during the course of the
-~ Short Answer Type-II Questions ~ reaction. So it Is a second order react.Ion.
Q L What do you mean by average velocity and Q3. Answer the following questions:
Instantaneous velocity of I chemical reaction? (1) Identify the order of roactlon from the following
Describe briefly the eff11ct of temperature on unit for Its rate constant:
velocity of reaction. [mol-1 s-1]
 (II) The conversion of molecules from A to B follow Q6. A reaction Is first order In A and second order In B:
semnd order kinetics. If concentration of A is (i) Write differential rate equ.ation.
Increased to three times, how will it affect the (II) How Is rate affected when the concentration
r•te of formation of B? of B Is tripled7
(Ui) Write the expression of Integrated rate equation (Ill) How Is rate affected when the concentration
of both A and B are doubled?
for zero order reaction.
(HCERT EXE.llCISE; CBSE 2022 Tonn 2)
Ana. (I) The order of the reaction Is 2. Ana. (I) Differentia l rate equation fo r the reaction Is:
(ii) The given reaction Is A__.B
rate (r) .. k (A) 1 (Bj2•
Thus. Rate (r) ,. l<{A) 2 _,(I) (II) Ol:fferentlal rate equation for the reaction Is:
(It follows second order kinetics) rate (r') "' k [A) 1 (38)2
If concentrat ion of A Is Increased three times.
New rate (r) = k{3A)2 = 9 k(A]2 = 9r (from eq. (1))
r = k(A}' (3B)2 = 9 or,.,. 9r
r k(A)1[8)2 -
Hence. rate of fom,atlon of B will Increase by
9 tJmes. The reaction rate will Increase 9 times.
(Hi) Integrated rate equation for zero order (Ill) Differentia l rate equation for the reaction Is:
reaction: kt .. (Rig - [R}. wher e k .. rate constant. 2
Rate (r") ,. k (2A)1 (28)2 : !::_ = k (lA)' [.29) =8
(R) 0 .. initial concentrat ion of reactant and [R} is r k (A)1 [8)2
the concentrat ion of reactant at time t or r' .. er
Q4. The decompos.ition of NH on p&.tlnum surface The reaction rate will increase B times.
5
Is a zero order rHctlon. What are the rates of Q 7. Observe the graph shown in figure and answer the
pn,ductlon of N1 and H2, If It .. 2.5 >< to-A mot-1 L s- 17 following questions.
(NCEnT £XERCISE)
SOI. 0ecompos ftlon of NH 3 on platinum surface can be
represente d as l
ir
Pt
2N~(g) -->N2(g) + 3H;z{g)
Here rate of decomposltlon of NH and rates of
3
formation of N 2 and H are related In the following
2
manner.
1 d(NH3l • d(N2) = 1 d(H2) Tlme -
Rate of the reaction =-
1 dt dt (J) What Is the order of the reaction?
3 dt
(ii) What Is the slope of the curve?
Since. the reaction Is of zero order.
(iii) Write the relationship between It and ~
_ 1 l{NHo) ., f l .. 1 (H ) ,. k (half-life period).
2 dt dr 3 dt Ana. (I) The reaction Is of t1rst order.
=2.5 " JQ--4 mot L-1 9- t (ii) For first order reaction.
k- 2.303 1 ~
Rate of format ion of N 2) .. k
2 a d[N
dt
- t og (R}

.. 2.5 >< 1~ mol L- 1 s-1 ~ kt

an(j rote of formation of or log (RJ .. 2.303
H "'d(H2) a 3k k
Thus. slope ..
2 dt 2303
.. 3 " 2.5 " 10- 4 mol V 1 s·' (ill) For first order reaction .
= 7.5 x 10 ◄ mol L- 1 s- 1 _ 0 .693
Q5. How the rate of the reaction will be affected when: t v2 - - -
k
(I) surface area of th• reacunt ls lncreased7 Q8. The reaction bebwen A and 8 Is first order with
(II) temperature of the reaction Is decreased? respect to A and zero order with respect to 8. For
(Ill) catalyst Is added In a rwerslble reaction? this reaction, ftU In the blanks In the following table.
(COSE2020)
ElCptrlment (A) moVL (B)moVl Initial Rate
Ant. (I) The rate ot tho reaction Increases when surface mol/Llmln
area of the reactant Is Increased. I 0.1 0.1 2.0 )( 10-2
(11) The rate of tho reaction docroases when
temJ)(!roture of the reaction Is decreased.
II - 0.2 4.0 ..10-2

(Ill) The rate of the reaction lncreaooG whon catalyst

Ill 0.4 OA -
Is added In a reversible reaction.
IV - 0.2 2.0>110- 2
(COSE20 J9)
 Sol ·. The reaction takes 10 minutes for 20% completion.

TiP- - - - - - - - - , :. After 10 minutes. (o - x) = (100 -20) = 80

Do not forger to check unlrs as they must be In some k = 2303 1 _!QQ= 2303 ><0.097
sysrern of units. 10 °
810 80 10
= 0.022 minutes
According to the given data.
Suppose the reaction takes t1 minutes for 75%
Rate law expression can be given as below:
completion.
Rate ., k (A) (8]0
le.. t "' r, and (o-x) ., 100 - 75 a 25
or Rate ., k(A)
Now. f rom experiment I. 2.303 100 2303
k=-log 10 -=-><logl04
20" 10-2 mol L· 1 min·• .. k(0.1) mol L· 1 r1 25 c1
k = 20 x 10"2 mol L- 1 min- '
or 0.022 = ~x2x03010
0.1 mol L-1 t,
.. 0.2 mln-1
t ., 2303)( 0.6020
Again. from experiment II 1 0.022
4.0 " 10" 2
=0.2(A) (:. r = k(A))
"' 63.02 minutes
(A) = 0.2 mol L- 1
QU A fl~ order reaction takes 30 minutes for 75%
From experiment Ill.
decomposition. Calculate t vi·
Rate = 02 " 0.4
Given:
= 8.0 x 10-2 mol L- 1mln-1
(log 2 = 0.3, log 3 = 0.48, log 4 " 0.6, log S = 0.7)
From experiment IV.
2.0 x 10- 2 "' 0.2 (A) (:. r = k(A)) Sol Let initial concentration be (A]0•
1 Then. concentration after 30 minutes
(A) " 0.1mol L-
Q9. The Initial concentration of N20 5 at 318 K was (A] =l?.. x(A)0 =~
0.60 " 10-2 mol L-1 In the first order reaction 100 4

N20 5(g) __. 2N02(g) + j0 2, which became

For flrst order reaction.
k 2..303 r
=-r- c og,o (A)
!&_!
0.20 i< 10-2 mol L-1 after 60 minutes. Calculate the
rate constant at 318 K. (log 3 = 0.4771)
Sol Given. Initial concentration. 2 303
· 1og(Aa)/
-~
ko 36""'" 4 = 007·
. 71og 4
o .. 0:60 x 10-2 mot L-1
Remaining concentration (o - x) ., 0.20 x 10-2 mol L"1 ., a.on x o.G
Time taken. t ., 60 minutes. = 0.046 x m-1
For a Rrst order reaction. For first order reaction.
2.303 o
Rate constant. k = - l o g10 ~ t v2 = - - = -0.693 = lS0J
0 .693 I Utes
. mn
f ~ k 0.046
On substltutlng the values. we have Q12. In a first order reaction, a substance remalM half
k 2..303 I
1
(0.60x10" mol L- ) 2 of Its Initial amount In 100 minutes, then predict,
0810 In how much time, It will remain one-fourth of Its
.. 60 minutes (0.20x10·2 mol L-1)
Initial amount?
2.303 l 2303x OA771 I t -I Sol For a first order reaction.
30
60 m inutes 0810
0
60 m nu !Hi 2.303 o
Velocity constant. k '" ~ log,oE }
= 1.83 x 10-2 m lnute- 1
Q 10. A first order reaction Is 20" completed In when r "' 100 mlnute9, (o - x) = s/2
10 minutes. How much time It t.akes for 75"
2.303 0
completion? (log 10 2 = 0.3010) k=7oo"logl00/2 '
Sol. For a first order reaction.
2.303 o
valoclty con61ant k m- log10 =~l 2 = ~ x 0.3010
r
'i':""'"'.'.t(

~
100 0810 100
where o .. Initial concentration of reactilnt ., 100 .. 6.93 x 10"3 minute-•
(o - x) ., amount (concentration) of reactant after Suppose. the !lubstQnce remnlns one fourth of Its
time t. initial amount (o) in t1 minutes. then (o - .x) •· o/4,
 2.303 o 2.303 · For 75% completion of reaction.
6.93 x 10-1 ° - -log10- ., - log 10 4
r1 o/4 r1 o =100. o - "=-
100 - 75 =25, k =0.0143 mln· 1
2.303 X 2 X 0.3010 r = 2.303 lo _o_
I< 8 o-x
or 6.93 x 10- 3 0
t,
2.303 100
2.303x2x0.3010 = 0.0143 log 25
or C1 "' _ xl0-3 = 200 minutes
6 93 2.303
Q13. Rate constant for the trrst order reaction has been = _ Log 4 =96.968 min
0 0143
found to be k = 2.54 x 10-3 s-1. Calculate Its .!th
life. (log2 • 0.3010). 4 COMMON ERR(DR - - -- - - -
Sol For a first order reaction. Students often inoke mistakes in doing calculotions or
2.303 o forget to wrice unitt.
Rate constant k 0 - t- log,o (<i":x)
Q15. Prove that half·Ufe of a first order reaction does
where. le • 2.54 x 10· 3 s· 1 (given) not depend upon the Initial concentration of the
a = lnlt.lal concentrntlon of the reactant
reactant
Sol. For a first order reaction.
(o - x) = concentrallon after completion of 314th
part of the reaction. 2.303 o
k .. - - log 1O- -
3 4o-3o o t o-x
=0 - - 0 = - - - When half of the reactant Is used.
4 4 4
changed concentratlon (x) '" O.So and t •• Cvi
On substituting the values In above equallon of
(h.ilf-Ufe)
rate constant we have
2303 o
2.303 o k r:, - - log10 - - -
I< .. - , -log .. 2.54 x J0-3 s·1 r112 o- 0.So
10014
2..303 o
t= 2.303 lo 4 =- log,10 -
tv 2 0.5o
254 x 10·3s-1 810
2303
= 2.303x2xlogm2 :s - - logl 0 2
tv 2
2.54 x 10· 3s-l
2.303
2.303 x 2 x 0.3010 or t V2 = ---r-tog 10 2
a 5
2.54 .x l(j3 2303 X 0.3010
=
1.386 s m545.67S
o
2.54 x 10-3 k I ·: log102 ° 0.3010\(
0.693
QIA. A first order reaction takes 20 minutes for 25" or r112 =- k -
decompOiSltlon. Calculate the time when 75" of'
the reaction will be completed. ,cos£ 2017) There ls no concentration rerm In the a.bove equation,
(Given: log 2 .. 0.3010, log 3 = 0.4771, so time required for the half-completion of a first
log4 0.6021)
12
order reaction (le.. half-life) does not depend upon
2.303 o the concentration of the reactant. Proved
Sol. For a first order reaction. k "' , 1 o g H Q16. FoUowlng data are obtained for the reaction:
where, k "' rate constant o ., Initial concentration
1
Nz0s _.... 2NO2 + 202
(o - x) "' concentration after tlme 'r'
Lt Is given that the first orde( reaction Is 25% t/1 0 300 600
completed In 20 min.
o ,. 100. o- x .. 100 - 25 c 75, t = 20 min. (N 20J/mbl L•1 t6 x 10"2 o.e x 10-Z 0.4 >< 10~

(I) Show that It follows first order reaction.

k a 2303 tog~
20 75 (II) Calculate the half·llfe.
(Given: log 2 = 0.3010, log 4 ., 0.6021) (COS£20l7/
= ~~ (log 4 - log 3}
3
Sol. (I) Given data.
2 3 tis o 300 600
C •; ~ (2 X 0,3010 - 0,4nt)
(N 20J/mol L-1 1.6 )( 10- 2 0.8 X 10· 2 OA x 10·2
., 0.0143 mln- 1
 Using hit and trial method. Ql8. Prove that time required for the completion of
, 2303 [RL
three-fourth of a first order reaction Is twice the
For first order reaction, k = ~ ogw time required for the completion of half reaction.
Sol For a ftrst order reaction.
Fr om the above data. r =300 s. (R) 0 =tG x 10-2 moll-1 2303 0
and [R) = 0,8 x 10-2. Velocity constant k= t .tog-(o-x ) ...(I)
Puttil'lg the values in the expres.slon, we get
When half of the reactJon Is completed.
k =- - og·_.___........_ __
2.3031 (1.6 x 10- 2 ) mol l -l
0
(0.8x10- 2) mol l - 1 t = tvi and x=
300 2
2 303 tog2 = 2 303 x 03010 On substit\!tlng the values In eq. (1), we have
= ·
300 30 0 2.3031 o 2.3031
k ... - - og[ci) .. - - og-
o
k m2.31 x lQ-3 s-1 Cv2 lo-~J
rv2 o/2
Thus. it Is proved that reaction proceed through ftrst
order kinetics as the ra te constMt remains same. 2.3031og
k c, - 2
(II) Half-Ute (tv 2) =~ Cv2
k
3
0.693 When th part of the reaction Is completed.
t1,2., _ _ _ _ - 300 s 4
2.3lx10-3 s- 1 - __
3
r .. t~ and x = o><
Q17. Prove that the time required Is 10 times of the 4
half-life period for the completion of 99.9" of a 2303l o 2.303
ftrst order reaction. k =- - ogF-¥)=- -1og-o
Sol Suppose for th!:! given Rrst order reaction. half-life
t314 o- 3o C31i. .£.
4 4
period Is r\12 then:
0.693 2.3031
k o- 2303
- og 4 = - - >< 2log2
tV2 "' - ; ; -
t 314 t314
(where. I< = velocity or rate constant) 2.303
or r91,. = - k - x2log2 ...(3)
or ...(1)
On substltuUng the value of k from eq. (2) in eq. (3},
w e have
Suppose the reaction takes time t for 99.9%
completion, then: _ 2><2303xlog2xt
112 _
t314- 2.303><1og2 -2xt112
Initially

After time
100
A

t (100 - 99.9)
--> B
0
99.9
t~: 2 X fV2
Thus. the time required for the completion of three-
I
"' 0.1 fourth of a first order reaction Is twice the time
For a Rrst order reaction. required tor the completion of half re-action.
Velocity constant.
Ql9. Write short note on the following:
2303 o (I) specific velocity constant
ko - -log 10 -(
r o-x) (II) activation energy
where. o .. 100 and (o - x) .. 0.1 Ane. (I) Specific Velocltv Constant: Suppose In a chemical
reaction. the molar roncentratlon-of the reactant
2.303 100 2-303
k=r log,om = ~ x lo810 1000 at any moment ls C. then at that moment. velodl',I
of the reactJon ( dxlde) is directly ~roportlonal to
2.303 3 2.303 the concentration of the reactanl .e~
k ., ~ log10 10 ., ~ x 31og10 ID
dx dx
- oc C or - mk.C
2303x3 dr dt
= ...(2)
t where k Is a constant called velocity constant
From eqs. (I) and (2).
dx
If C'" I moVL then dt = k.
0.69 3 2.30 3 x 3 r O 2.303 x 3 r .,, lOr
- rv2 = t or --=·=._____1/2
0 693 1/2 Thus. at constant temperature and unit
concentration of the reactant. the ~loclty
Thus. the time required tor the completion of 99.9% of a reaction Is called the specific velocll',I
of a f1rst order reaction Is 10 Umos of Its half-life constant of tho reaction. Its value Is different for
period (tia). Provad. different reactions and Its units depend upon the
 nature of the reaction. Its value raises with rise On the basis of this equation. when log10 k l.s plotted
in temperat'ure. with 1/ T. slope of the plot is equal to -E,,12.303.
(II) Activation Energy: The extra amount of e.nergy From It value of E0 Is calculated.
obtained from the collision of reactant mole-
cules. which Is enough to GJrry out a reaction and
form products ls called activation enersv. Thus.
the minimum energy other than the average
iI \
j~
~,r-- _ - Eu
Z 303R
potential energy of the reactions. which Is
obtained by the colUslons of reactant molecules 1/T~
and converts reactant molecules Into products Is Plot of log " k vs 1 / T
called activation energy. Q2l The following data were obtained during the
Activation energy .. Threshold energy - Average first order thermal decomposition of CzH 5Cl at a
potential energy of reactant molecules. constant volume: C2H5Cl (g) ➔ CzH 4(g) + HCl (g)
Arrhenius proposed an equation to explain the
Experiment Time (s-1) Total pnssure (atm)
effect of temperature. on velocity of reaction.
called the Arrhenius equation. 1 0 0.4
According to this equation k = Ae• ErJRT ...(I)
2 100 0.6
where. A ,., pre-exponential coefficient or Calculate the rate constanL
frequency factor
(Given: log 2 .. 0.3010, log 3 .. 0.4771,
E0 ° activation energy
I< .. velocity rnnstant of the reaction log -4 • 0.6021) (C8SE2023)
R .. gas constant Sol. The given reaction Is:
and T = absolute temperature C2H5Cl(g)--+ C2 H0 {s- 1) + HCl (g)
Q20. Give Arrhenius equation. How would you calculate At r = o P0 o o
the actlvatJon energy of a reaction by graphical
method? At r"' 100 P0 - P P P
Ans. Arrhenius Equation: After time t total pressure ., (P0 - P) + P + P
...(1) or. P1 = P0 .,. P
or. P0 - P = 2P - P1
For a first order reaction. we have

k =~ l o8
r · P0 - P
(..!sL...)
"2.303log( P0 )
r 2Pa - Pr
1/T
Plot oflog 1 k vs 1 / T At t "' 100. P, = 0.6. Pa "' OA
where. k = velocity constant of a reaction. 0
2.303 ( 0.4 )
E0 ., activation energy of a reaction. R"'gas constllnt. I< 100 log 2 x0.4-0.6
T = absolute temperature. and A = pre-exponential
°' 2.303 ~ 0.3010 X 1(}-2 st?C-I
con9tant or frequency factor.
On taking logarithm eq. (1). we have ., 6.932 " 10-3 sec-1
lo&, k "' log. A - EJRT ... (2) Hence. the rote constant Is 6.932 x 10-3 St!c-1.
Q22. The rate constant for the decomposition of
On the basis of eq. (2). following graph Is obtained.
when lo&ek Is plotted with 1/T.
hydrocarbons is 2.-418 x 10- 5 s-1 at 5-46 K. If the
energy of actlvatJon Is 179.9 kJ/ mol, what will be
From the slope or this plot. value or E0 can be
the value of pre-exponential factor?
calculated. Unit of E0 depends upon the units of R.
This Is bec.iuse slope Is - E0 /R. Bv substituting the (NC£ATfXfAC/SfJ
value of R. we get the value of EIY Sol. Given I< .. 2418 x 10·9 9· 1• E0 ,. 179.9 kJ mo1·1. T"' S46 K
Above eq. (2) can also be written as According to Arrhenius equation. k., Ae· Ea IRT
E E
2.303log 10 k c 2.3031og10 A-jft: or lnk •• lnA - 'f;t

or
Ea ...(3)
loglO I< m log,o A- 2303RT or log k .. log A - 2.30 3 RT
 or log A = log I< .., Eq ~ log (2418 x 10-5) or. log 8 . E ( 20 )
2.303RT . 19.147 JK-1 mot- 1 96000K
179.9 or. E0 19.l47 x 9600 0
+-------,---- 20x3log2
2303 X 8.314 X 1~ :>< 546 K

"' (- 5 + 038-34) -1- T7.208l ai 12.5915 s- 1 .. 19.147 " 1600

03010
or A = Antllog (125915) s-1 = 3.9 >< 1012 s-1
Q23. In general, it Is observed that the rate of a = 101778.0 73 J mo1- 1
chemical reaction doubles with every 10• rise Hence. activation energy (E0 ) for the reaction Is
in temperature. If the generalisation holds for a 101.778 kJ mol- 1•
reaction in the temf)Hature range 295 K to 305 K, Q 25. The rate of a reaction doubles when temperature
what would be the value of activation energy for changes from 21•c to 37•c. Calculate energy of
the reaction? (NC.EAT IHTOOJ activation for the reaction. (CBS£ 2023)

Sol According to Arrhenlu~ equatJon. Sol We know that

log! i=
k1
Ea [1--.. !. )
2.3 03 R T1 T2
lo (~)=
g k1
Ea
2.303R
T2 - T1 ]
Tifi _
k2'k, "' 2 ; r, w 295 K: T2 ., 305 K: R., 8,314 J 1(-1mo1- 1 E0 = 2.3 03 R log ( ~)
k1 T2 -T1
(.!IL]
: . log 2 = Eo
2.303 x (8.314 JK-1 m ol- ') 295K
[_!_ __ l_ ]
30 51<
T, "' 2r c .. 213 + 21 .,, 3□o K
T2 •., 37• C • 273 + 37 ., 3IOK
R '" 8.314 JK- 1 mot-1
or 0 .3010 = E
2303 x(B.314 J m ol-1)
x (l0)
295x30 5 f
:. €0 = 2303 x 8.314 JK'"' mol- 1x log ( )[30~~ 310 ]

f = 030l0x23 03 x8314 x295x30 5 ( I-I) ., 2.303 x 8.314 x 0 .3010 x 9300 J mol- 1

o ID Jm o
-= 53. 598.595 Jmot·l
= 51855 J m ot-1= 51.855 kJ mo1•i Hence. energy of acUvation for the reaction is
Q24. Afirst order reaction Is 50" complete In 80 minutes 53.599 kJ mol' 1.
at 300 K and in 10 minutes at 320 K. Calculate Q 26. The rate con.stants of a reaction at 200K and SOOK
a,ctlvatlon energy (£0 ) for the reaction. are 0.02 s- 1 and 0.20 s-1 respectively. Calculate
(R "' 8.314 JK-1 mol-1) the value of £0 • (Given 2.3'03R = 19.15 JK- 1 mot~1).
(Glvon: log2 = 0.3010,log 3= 0.4771,'°94= 0.6021) (C8S£ SQP 2 02 3·24)
Sol We know that

~
(COS£ 2023)

Sol
Given. t V2 ., 80 m in at 300 K
: . For first order. log( * )~ 2.3~3 R [ *-*J
I< 0 .693 0.693 where. k2 -= 0.20 s-1• 1<1 .. 0.02 s-1
, .. (tvi)1 ° 80 m ln Tn= 200K. T2 "' SOOK and 2.303R ., 19.15 JK- 1 mot-1

0.69 3 I -I
a --m n log(~~~) = 23~3R[ 2~0 - 5~0]
BO
Slm llar\V, at Ta ., 320K log 10 = ~ ( 300 )
19.15 200 x 500
k = 0.693 = 0.6 93 m in-I
2 (t,12>2 10 Ea., 19.15" 200>e 500 .. 6383 J mol-1
or.
300
For calculation of activa tion energy. we know
Hence. the value of E0 Is 6383 kJ mol-'.

log( ~ )= 23~3~(1XJ -f
' l ,

Long Answer Ty pe Questions ~

Pu tting the values In above aquatlon. we get Q1. What Is the dtfl'erenc• between molecularity and
order of a reaction? E,cplaln by giving an ex.ample.
l ( 0 .693 80 ) E Ant. Difft,.nce betwun molecularity and order of a
og 7o x 0.693 • 2.303 x 8.314 JK- 1mo1- 1 reaction:
(I) Molecularity of a reaction Is always a whole
320 - 300 ) number w hile ordC!•r of a reaction Ciln be In
( 300x320
fractions.
 (ii) Molecularity of a reaction can never be zero O 1 0
whereas order of reaction c.an be zero. kt mloge- or /c m- lo~ - -
o-,x r Oa )(
(Ill) Molecularity and order of a reaction can be same
or different. 2.303 a
k o- -log 10 - - ...(3)
(Iv) Molecularity shows the number of molecules t o-x
taking part In a step of a reaction whereas
Eq. (3) Is called kinetic equation of first order
orderr of reaction shows a relationship between reaction.
the velocity of reaction and concentration of
With the help of this equation. value of k can be
reactants.
calculated. Value of k remains constant at constant
(v) The number of molecules takln art in the
temperature.
velod rate determinln Ste of a reaction.
Is c.aUed the molecularity of the reaction. Order Q3. The following data were obtained for the reaction:
of a reaction shows the number of molecules. 2 NO + 0 2--+ 2NOl'
concentration of which determines the velocity
of the reaction. Initial rate of
(vi) Molecularity of a reaction Is obtained from Experiment [NO)/M (OJ/M formation
its mechanism whereas order of reaction Is of NO, ' M mln-1
obtained from experiments. I 0.3 0.2 7.2 >< 10-2
Example: Following examples clearly show
difference between molecularity and order of the
2 0.1 OJ 6.0 )( 10-3
reactions. 3 0.3 DA 2.88 >< 10·1
(I) CHlCOOC 2H6 + NaOH - > CH3C00Na + C2H50H 4 0.4 0.1 2.40 X 10-2
H"
(ii) CH3COOC 21-ls + H20 --> CH3COOH + Ci\OH (I) Find the order of re1ctJon with respect to NO
and 0 1.
Reactions (I) and (ii) both are bimolecular. Reaction
(ii) Write the rate law and overall order of reaction.
(I) l.s of second order because velocity of the reaction
depends upon the concentrations of CH 3COOC 2H5 (iii) calculate the rate c.onstant (k).
and NaOH both. However reaction (ii) is of first order. Sol. (i) For the given reaction:
2NO + 0 2 -> 2N02
This is because velocity of this reaction depends
The rate law can be expressed as:
.only upon the concentration of CH1COOC2H,.
Q2. What do you mean by order of a reaction? Find Rate law co k [NO)• (Oz}Y
the expression of velocity constant of a first order Now. with the given data. we can determine the
reaction. values of x and y as:
Ans. Order of a reaction: The number of the reactant
molecules takln rt in a chemical reaction. 7.2 X lQ-2 ., /( [0.3)• [0.2)Y ... (1)
concentrat on o c anges ur ng t e course
of the reaction Is called order of the reaction.
3
6.0 x 10· ca I< [0,1)" (OJ)v ...(2!/
288 x 10"1 = k [0.3)• (0.4)V
Expresiion of Velodtv Constant of First Order
Reaction: Suppose a first order reaction Is as follows:

Initial concentration
A -,Product
o moVL O moVL
2.40 x 10-2 .. k (0.4)• [O.l)V
Dlvldlng eq. (4) by eq. (2). we get
...(3y

(4\
Concentration after time r (o - x) mol/L x moVL 2.40x 10-2 .. k{0.4JX (0.l)Y
For a first order reaction. 6.0 )( 1crl k(0.1)# (O.l)Y
Velocity of the reaction. !!!.. .. (Al° 4-0 (4)• or x 1
dt IU QI

dx NeX't. dividing eq. (3) by eq. (1). we get

Velocity of the reaction after time r.dt = k(o - x)
2.e ex ur' _k{o.3r (o.4)Y
d><
or -( - 7.2 X 10- 2
o- x} =k.dt ... (1) l<{Q.3}" (0.2)Y

Here. k Is a constant called the velocity constant of 4 ., (2)Y or (2)2 .. (2)v or. y .. 2
first order reaction. So. order w.r.t NO Is ! and order w.r.t. 0 2 Is ~
dx
On lntesratlng both side&. J~ • Ik. dt (II) Rare law= k (NO)I (Oz}2
\ 0 - XJ
Overa.11 order of reaction Is 3.
or - log 0 ,(o - x) m kt + I ... (2)
where I = Integration conswnt.
When t .. o. >< .. O then - lo&o o .. /
(Ill) Rate constant. I< =
.
R.11e
1
(NO) (0 ) 2
..
7:lx l0-2
(0.3}1(0.2)2
2
On substituting the value of / In eq. (2). we have
- log 0 (o - x) .. kt - lo&o o 7.2 x 10· 2
= .. 6 moL-2 L-2 mln-1
l<t "' loga o - lo~ (o - x) 1.2x10- 2
 Q4. (I) A first order reaction Is 75" completed in
40 minutes. Calculate Its t 112• Sol (i) for a first order reaction. k .. 2303 1og-
0
-
r 0-X
(ii) Predict the order of the reaction In the given
where. k = rate constant. o = Initial concentration
plots:
(o - ,x) = concentration after time 't'
It Is given that the first order reaction is 75%
completed In 40 min.

(a)
l
1112
o = 100. o - x = 100 - 75 = 25. r = 40 min
k 0 2.303 100
40 1ogTs
2303
IRli - m~log4

2 303
= · X 0.6021
40
(b) l
1112
k = 0.0347 mln-1

Now. half4lfe (tvz) = 0 ·693

k
{R)o,- r 0.693
Vl a 0.0347
where (R] 0 Is the Initial concentration of
reactant. ., 19.98 i: 20 min.
[Given : log 2 • 0.3010, log-4 • 0.6021) (ii) (a) First order reaction
(C85E 2017) (b) Zero order re.action

~ _C_h_a_p_t_e_r_~_e_s_t_
Multiple Choice Questions change In concentration of reactants a.nd products
with time?
Q l. The activation energy for a reaction at a given
temperature Is found to be 2.303 RT J mot-1• The
ratio of rate constant to the Arrhenius factor Is:
a. 0.01 b. 0.1 c. 0.02 d. 0.001

r·
Which of the following expression Is correct for
rate of reaction given below?
SBr(aq) + 8,0- ,(oq) + 6H'(oqJ ➔ 3Br2 (oq) + 3H 20(1)

t
IOI
(
a. A(Br-1 = 5A(W)
At 6t

d. ~ = 6 A(H")
b. i
g
M M
Q 3. The decomposition of a substance follows first
VL-======
Time-•►
191
order kinetics. If Its conamtratlon ls reduced to 1/8
of Its Initial value In 12 minutes, th• rate constant
of tho deco111poslt1on system Is:
2 303
a. (~togl)min-
12 8
1 b. ( ·
12
1osa)m1n-1
Tlmo -

d. ( ~ loge
1
)min-1

Q4. Consider the reaction, A ~ 8. The

concentration of both the reactants and the
products varies exponentially with time. Which
of the following figures correctly describes the
Directions (Q, Nos. 5-6): Each of the following questions (Ill) A first order reaction has a rate constant
consists of Mo statements, one is Assertion (A) and the other is 2 " 10-s s-1• How long will 69 of this reactant
Reason (RJ. Give onswer: take to reduce to 2g7
a. Both Assertlon (A) and Reason (R) are true and OR
Reason (R) Is the correct exptanatlon of Assertlon The half-life for radioactive decay of 14 C is
(A). 6930 years. An archaeological artifact
b. Beith Assertion (A) and Reason (R) are true but containing wood had only 75" of the 14 C
Reason (R) Is not the correct explanation of' ,found In a living tree. Find the age of the
Assertion (A).
sample.
c. Assertlon (A) Is true but Reason (R) Is false. (tog 4 .. 0.6021 log 3 "' 0.4771 log 2 = 0.3010
d. Assertion (A) Is false but Reason (R) Is true. log 10 = 1)
Q5. Assertion (A): For the reaction Very Short Answer Type Questions
CHCl 5 • Cl 2 _ . CCL~ +- HCl Q 8. For a chemical reaction R - P, the variation in
Rate =k(CHClJ(Cl2JV2 the concentration (R) vs time (t) plot Is given as:
Reason (R): Rate of reaction Is always equal to
the sum of the stoichiometric coefficient of the
reaction species in a balanced chemical equation.
Q6, Assertion (A): 5096 of zero order reaction is
completed in 100 sec, therefore, 75'¼ reactlon w ill
be complete in 150 sec . ,_
Reason (R): The rate constant of a zero order (l) Predict the order of the reaction.
reaction depends upon tlme. (ii)' What Is the slope Wof the curve?
Case Study Based Question Q 9. In some cases, it Is found that a large number
of colliding molecules have energy more than
Q7. The ra1e of reac1ion is concerned with decrease threshold energy yet the reaction Is slow, why7
in concentration of reuctunts or increase in
the concen~ration of products per unit time. Short Answer Type-I Questions
It eun be expressed as lnstnntaneous rate at a Q10. With the help of a diagram, explain the role of
particular in~tnnt of time and ~verage rate over activated complex In a reaction.
a large intervnl of time. A number of foc1ors
such os temperature, coocenLrotion of reactants, Q lL For a reaction: Hz +Cl2 ~ 2HCl
couiJyst affe.ct Lhe rote of reaction. MnthemnticaJ (i) Write the order and molecularity of this reaction
representntion of nue of o reaction is given by (ii) Write the unit of k.
rote law: Q 12. The rate of most reactions become double wheJ
Rule "' k(Af[BJ>" their tempeRture is raised from 298K to 308K.\
x and y indico1e how sensitive the ro1e is 10 1he Calculate their activation energy, '
change in concemrntion of A and 8 . Sum of x + y (Given, R 8.314 OJ mol-lK- 1)
gives the overall ord:er of u reuction. Short Answer Type-D Questions
When a sequence of elementary reactions gives
us the products, the re-0clions ore cnlled complex Q 13. The rite co·nstant for the first order decomposition
reactions. Molcculurily and order of an elementary of H20 2 Is given by the following equation:
reaction are same. Zero order renctions ure 4
log le • l4.l _ 1.0 X 10
relatively uncommon but they occur under special T
condilions. All nnturol and nJ'cificial radioactive
Calculate E0 for thls r•actlon and rate constant k If
decay of unsrnble nuclei 1ake pince by first order
Its half•Ufe period be 200 minutes,
kinetics.
(Gl11en R = 8.31◄ JK- mot- )
1 1
Read dte glwn passage ca#T(ully and give tit• Q14. ~ first order gas phase reaction:
answer of the following questions: A282(g)- 2A(g) + 28(g)
(I) What Is the effect of temperature on the rate at the temperature 400•c has. the rate constant
constant of a reaction? k "' 2.0 l( 10_. s· 1. What percentage of A282 Is
01) How order and molecularity are different for decomposed on heating for 900 seconds?
complex rea.ctlons7 (Antilog 0.0781 .. 1.197)
 Q 15. For the reaction,
2NO(g) +- Cl1{g) ----t 2NOCl(g)
logk - logA
-
Eo
- 2.303R
(1)T
The following data were collected. AU the
where E0 ls the activation energy. When a graph
measurements were taken at 2631<.
1
Is plotted for log k vs T , a straight Une with a
Initial Initial Initial rate of
Exp. No. [NO) (C~ disappearance of C'2.
(M) slope of -42S0K Is obtained. Calculate 'E0 ' for
(M (M/mln)
the reaction. (Given R .. 8.314 JK-1 mol--1)
1 0.15 0.15 0 .60
(II) Draw the plot of ln k vs 1/T for a chemical
2 0.15 030 t 20 reaction. What does the Intercept represent?
3 030 0.15 2.40 What Is the relation between slope and Ei
4 0.25 0.25 ? Q Ji. (I) Expla.ln the following tenns:
(a) Order of reaction
(I) Write the expression for rate law.
(II) Calculat.e the value of rate const.ant and specify (b) Rate determining step of a reaction
Its unit (c) Molecularity of a reaction
(Ill) What Is the Initial irate of disappearance of Ch (II) A reactant has a half-life of 10 min.
In experiment 47 (a) Cakulate the rate constant for the first
long Answer Type Questions order reaction.
Q16. (I) Rate constant 'k' of a reaction varies with (b) What fraction of the reactant will be left
•r·
temperature according to the equation after an hour of the reaction has occurred?