hemislty nstructor, Dr.

Suha
CuLMISTRY Chemistry instructor, Dr. Suhail
Sulailehem z86@gmail,.cou M.No. : 7027820533, 9045203008
Chapter.grd (Chemical Kinetics)
Class-12th
Subject-Chemistry
Chemical kinetics is the studyof chemical processes and rates of
RATE OF CHEMICALREACTION: The ratc of a chemical reaction is thc
reactions.
changc in conccntration of any
onc of thc reactants or products per unit time.
Consider a rcaction of thc typc: C’X

Irate (r)Change in concentrati on

time interv al
*Let 'AJC]' is thec decrcase in the concentration of reactants in a
small interval of time'At' theh;
Rate = -(AC/At) (Negative sgn is used since the concent1 ation of
reactants decrefasesyith tie)
Rate =+(AX/At) (Positive sign is used since the
concentration of products increasès, uring, the reaction)
With an increase in time, the reaction rate decreases thut is wuhy
the rate of a reactiortdoes not remain constant
throughout the reaction process.
ÜNTT OFRATE OF REACTION: The rate ofa reaction is expressed in the ufits of
min (or) mol.L' sec' (or) mol.L· min'. For gases, the unit for
(conçentration) (time) like: Msec' (or) M
the rate ofeaction may be atm.si or atm minl, It is
the activities are expressed in terms ofpartial because
pressures.
INSTANTANEOUS RATE OF REACTION: Theinsntaneous rate of achemical reaction is the change in
the concentration of
any one of the reactants or products at any instant of time.

A dc
=lim Fot ahot time)

Where: dc = Change in the concentration of dreactant in an

infnitesimally Small interval of time 'dt'
dx = Change in the concentration of produciln an
irfinitesimally
concertraion
oireacdants small interval of time 'dt'
*During the reaction, the concentration of reactants concertration
ofproducts
decreases, whereas the concentration of products At
At

increases exponentially untilthey, rcach an equilibrium AX,

position. AX,

A
A
tmo
time
The concentratlon of reactants decreasos wth tlma.The concertratlon of products Inc
reases ith thme.
But both the raleg wkhrespect to
decrOaSwBh time, roaclantsaswoll as products
QUESTIOß:AFor the reàction R ’ P, the concentration of a reactant changcs from 0.03M to
0.02M in 25 minutes,
Calculae thàayaveragerate of reaction using units of time bath in minutes and seconds?
ANSWER: Rate ofteactlon = Change in concentration/time
Rate of reacion=0.03-0.02/25 = 0.0004 M/nin OR Rate of
reaction= (0.03-0.02)/25 x 60 =6.66 × 10s M/sec
QUESTION: In a reaction, 2A ’ Products, the concentration of A decreases
from 0.5 mol L-! to 0.4 mol L- in 10
minutes. Calculate the rate during this interval?
ANSWER: 0.005 mol litre min HINT: Rate of reaction = 1/2x (Change in
QUESTION: The decomposition of N,0, in CCl, at 318K has been concentration/time)
studied by monitoring the
2.33 mol/L and after 184 minutes, concentration
|N,0, in the solution. Initially the concentration of N,0, is of
it is reduced to
Written by: MR, SUHAIL YouTubeChannel: Suhail's ChemisTricks Page 1 of 19
 2.08 mol/L. The reaction takes place according to the equation: 2N,0ste) -4 NO2) +Oz(e, Calculate the average
rat of this reaction in terms of hours, minutes and seconds, What is therate of production of NO, during this
period?
ANSWER: = 6.79 x 10- mol L'/min OR = 4.07 x10*² mol L-/h OR = l.13 >x 10-5 mol L-/sec
QUESTION: For the reaction, 3A 2B the rate of reaction +d[B]/dt will be equal to
ANSWER: = -2/3 x d[A]/dt
QUESTION: Express the rate of reaction in terms of ammonia for the reaction, N, + 3H,’ 2NH3"
ANSWER: = Rate of reaction = +1/2 x d[NH,]/dt

COLLISION THEORY OF CHEMICAL REACTION

Collision theory of rates of rcactions was first proposed independently by Max Trautzb and Willianm Levis to explain ttac
råtes of bimolecular reactions occurring in a gaseous state. The main
postulates of this theory are:
1. Reactant molecules react when they collide with sufficient kinetic energy. Hence, the
Formáion ofa prodmct akes place
through collisions between reactant molecules.
2. The ninimum energy at which collision (between the
molectes) may be effective is calèd ThPshold energy.
3. The molecules of reactants having threshold
energy make the product by the collsion hetween them). These
molecules are called active molecule and the collision is
known as Effectiçe collision.
4. The molecules of reactants
having-no threshold energy,
don't make a product by the collision (between them). Thae
molecules are called pussive nolecules and the collision is NQ
natfectlvecôlmon
called a defective/inetective collision.
5. Besides threshold energy, the
active molecules must hayc aVproper
orientation before ccllision. If the reacting molecules NO
ave Effectve Goalliston NO
improper orientation, it makes the collision defectíve, and the rate of
6. An additional amount of energy
reaction becomes slow.
be
requirdto,change passive mclecules into active molecules so that thei collision may
effective is called Activation energy.
7. The activation energy depends on the nature of
chemical BTads, which are lreaking
during the reaction. Stronger the bonds,
the greater is the activation energy. IHowever, it
does notdepend on the cnthalpy of the reaction.
8. The closest distance betýcen thc centers of
t$9 molecules taling part in a collision is called
or collision diarneter (s). Tho niolecular molecular
diameter of all the gases is ncarly the same lying in the order of
10 cm.
9. The Naleculardianeter
numbeefcollisions persccond per unit volume cf the reaction mixture is known as
10. For threactioa whigh has two gaseous
reactants (A &B), collision fiequency is given by, coBlisionfrequency ().
[Where: op= Collisior
Þ dianeter, u = reduced mass, na &ns are the nur:ber cf 8kT
volume rolecules ofÀ &B in unit
11. For thÁxgaçtionhich has orly a single
Where 'n'is the nmmber cfmolecules per unit molar molecule, Acolision freqvency is given by, ZA = N2 ro'u¡y.n
volume, n =ALogadro number ehergy
Pocentiat
Activation Potential
EnergyActivation
(No)/Vm = 6.02%1023/0.0224 m-97 energy enerov

12. The fraction of effective

colli_ions increases with an increase in the total
of collisions. £Iente, the rate of a number Reactants
Produdi
reaction is directly pronoriiöral to the collision \eneray
frequency. i.e., the rate of rectjon collision frequency (Z). IeleasedProcucts Resctants absorbe
Rexcion Progress Reaction Progress
Writen by: MRSUAIL Exothormic.
Ctioy Endothermlc
YouTube Chonr react
Surasls Chernis'iCKS
Page 2or 19
 For an exothermic reaction, H, < HR whle for endothermic reaction H, > HR.

yerage
this FACTORS AIFECTING REACTIONRATE
CONCENTRATION: As a chemical reaction procceds, the concentration of the reactants keeps on decreasing while those of the
products keep on increasing. However, the rate of reaction also found to decrease. This shows that the rate of reaction is
directly related to the concentration of reacta1ts.
2. PRESSURE: It affects the rate of reaction if reacting-speçies are gaseous. For reactions involving gases, an increase iñ pressure
increases the number of collisions per unit time hence, the rate of reaction increases.
3. SURFACE AREA: The rate of reaction increases with an increase in the surface area of solid.
4. LIGHT: Light affects the rates of certain chemical reactions in which the photochemical breakdown of covalent bonds takes!
H, + Cl, 2HCI U.V.
place. Example:
5. TEMPERATURE: Most of the chemical reactions are accelerated by an increase in
eaperature. Fortxample, the
.

decomposition of NOs.
It has been found that the rate constant becomes nearly doubled if the temperature is increasedabye10Cfor a chemical reaction.
Arrhenius gave an equation to explain the effect of tenperature on the rate fof activation
reaction that is called Arrhenius equation. This equation also gives the relation, frequency energy
among the activation energy, gas constant, temperature, exponential facton pre
factor
exponential factor and rate constant.
Taking logarithms of both sides in the equation
k=Ae Rltemperature
t in Kelvin
gasconstant
In k=In A+ In eEa/RT exponential (3314JHmol k)
At temperature Ti factor

In k, =n ¢- a
RT
At temperature T2

Ink, =In A-.

Subtracting equation l* from 2nd (Since Ais constant for given reaction)
In k, -In k, =ln A-InA
RT,
E,
In k,-h: k, =
1

In k E.T-T) OR OR logBf-T)

(6 CATALYST: Ls believed that the catalyst reduces the activation énergy between
uncatalysed
reactants and products, so that at a given temperature, more molecules can react.
MnO2(s)
2 H,O2(aq)
Oz(g) 2 H,O Example: ed eaclon

ANdraclan aCslvacon.enecgy
> Lower the value of activation energy faster will be the rate of reaction.
Prodvctst

Written by: MR, SUHAIL YouTube Channel:Skhail's ChemisTricks Page 3 ot 19

 Jn

Actually, the ontalåst does not reuce activation energy. It provides an alternative route for the reaction. That
route has lower activation enerqy. î can be shown in the following diagram:
alterna KJA
=

QUESTION: The decomposition of Ainto product has value of k as 4.5 x10°s at 10°C and energy or activation
60 kJ mol'. At what temperature would kbe 1.5 x
10*s? Hen

ANSWER: From Arrhenius equation, we obtain

og
Also, k,=4.5 x 103 s, T,= 273 + 10 = 283 K. k, = l.5 x 104 s1 E, = 60 kI mol' =6.0x 10 Jmol"
Then,

581O 2303834TKmol283
05229=5I33:62-283
283T,
OS229X283
3133.627 T23
a004727,8
09528I283
L29:019 KK4PpOiMatel)
= 297 K= 24C. Hence, k would be 1.5 x 10 s at 24'C.
QUESTION: The rate of a reaction quadruples when thc temperature changes from 293 Kto 313 K.
Calculate the
energy of activation of the reaction assuming that it does not change with
temperature.
ANSWER: From Arrhenius equation, we obtain

k303RS
tis given that,kË4
I293K
33K
SI3- 293}
Therefore,log 2303*8314293X3I3
0:6021
2.303283148293313
0.6021×2303*8,314293313
52363333 mo
S286Smor
Hence, the requed eergy of activation is 52.86 kJmo:
QUESTION: The rate of the chemical reaction doubles for an inczease ot 10% in absolute temperature from 298K.
Calculate E
ANSWER: Doyourself
HINT: KFK, K* 2K , T= 298 , T= 308 ,E, =?
QUESTION: The activation energy for the reaction 2HL - H, + lois 209.5 kJ mcl' at 581K.Calculate the fraction
of molecules (K/A) of reactants having energy equal to or greater than
activation energy?
ANSWER: K=AetT K/A -eaT
 In K/A =E/RT In e (In e l)
In K/A =/RT O. log K/A =E/2,303RT
K/A = Anttlog(-/2.303RT) = Antllog (-208.5 x 1000/2.303 x 8.314 581)
= Antllog (-18.8323) - 1.47x10
Hence, the raction of molecules (K/A) of rcactants having energy cqual to or greater than
activation energy
-1,47x10"
QURSTION: Therate constant for the decompositlon of hydrocarbons is 2.418 x 10* s' at 546 K. If
the.energy of
actlvatBon is 179,9 lW/mol, what will bethe value of pre-exponentlal factor.
ANSIWERIk=2.418 x 10* s', T= 546 K, E, 179.9 kJ nnol' 179.9 %103 J mol
According to the Arrhenius equation,
log k=logA
2,303 R7
logAlbgkt2.303 RT
=log(21418%1o Z99810Jmö
2903 W831/AKma=546K
= (0.3835 - 5) + 17.2082
=12.5917
Therefore,A=antilog (12.5917) =3.9 x 10" s
(approximately)
QUESTIQN: The decomposition of hydrocarbon follov1s the
equation k=(45 × 10" s) et0 n, Calculate E,.
ANSWER: The given equation is k = (4.5 x 10" s) e0o0 K/T
Arrhenlus equation is glven by,Ae
From equation (1) and (11), we obtain
B 28000K
RI
E, FRX28000 K
8.314 J K mol x 28000 K
- 232792 J mol 232.792 kJ inol
QUESTION: The rate constant for the first
log k = 14.34 - 1.25 x orderdecmposition
of H,0, is
LOK/, Calculate E, for this reaction and at what given by the following equation:
minutes? temperature will its half-period be 256
ANSWER: Arrhenius cqu·tionigtven by,

RT

’logk=logA 2:303/RT
The given equatle is
logk =1434-12Sxl0 K/T
From equation (1) and (11), we
obtaln

Written by: MR,SOHAIL

YouTube Channel: Suhall's
 L R I M O L

Thepro

2303 RT

= 1.25 x 10 K× 2.303 x 8.314 J K- mol

-239339.3 J mol (approximately) = 239.34 k] mol
Also, when ta 256 minutes,
X= 0.693/ tz 0.693/256= 2.707 x 10 min
It is alsO given that, log k= 14.34 - 1,25 ×
10 K/T

= 668.95 K = 669K (approximately)

QUESTION: The rate constants of a reaction at 500K and 700K are 0.02s- and 0.07s' respectively. Calculate the
values of E, and A.
ANSWER: E, =18230.8 J, A= 1.61
QUESTION: The first order rate constant for the decompositionpf ethyl iodide by the reaction
CHsl ’ CH4te+ Hl) at 600K is 1.60 x 10 sts energy of activatton is 209 ki/mol. Calculate the rate
constant of the reaction at 700K.
ANSWER: 6.36 x 10- s

HALF-LIFE OF AREACTION:The half-life of a rezction.js the time in which the concentration of a reactant is reduced to half of
its initial concentrtion. It is represented as tin. tz O,693/K
QUESTION: Calculate the half-life of a first order reacion fromtheír rate constants given below: (ú) 200 s1 (di) 2
min (ii) 4 years
ANSWER: Do yourself
QUESTION: Afirst ordefeacion is found to have a rate constant, k = 5.5 x 10-14 s'. Find the half-life of the
reaction.
ANSWER: 1.26x10l5 s
QUESTION Time reguired to décompose sO,Cl, to halfof its initial amount is 60 minutes. If the decomposition
is a firsf order reacion, calculatethe rate constant of the reaction?
ANSWER: po yourself

MOLECULARITY:oal no: of rezctants taking part in an clermeatary reactin.

TYPES OF REACTIÌN BASED ON MOJECULARIIY
1. UNIMOLECH AR REACTION:The reactiou in wich onl one reacta:at takes part.
’ O2+F2 OR FCIs- ’ PCh+ Ch

2. BIMOLECULAR PEACTION: The reaction in which twc rcactants take part.

 2H1 OR NO+ F;- NO,F + F
TRIMOLECULAR REACTION: The rcaction in which threc rcactants take part. 2NO + O; ’ 2NO:
The probability ofreaction with molecilarity higher than three is very rore. It is because the collson among the molecules in
tetramolecular reactions becomes very dificult,and we know that the productformation is not passible without collision.
ORDER OF REACTION:Total no. of reactants on which the rate of 3rd ordar
Zoro.ordet [A}
Log Nist ordar2hd brdot
reaction depends. or Total no. of reactants whose concentration 1
Con
changes. oR It is defined as the sum of the powers of the inolar
concentration of reactants in the rate cxprcssion.
Example:- PCIs ’ PCl, + Cl (6) Plots:from intcgratcd rate: cquations; Rate-+
Zoro ordot 2nd order, 3rd order
On applying rate law equation, Rale Rate: 1gt order
Rate of reaction o PCs] OR dx/dt =K [PCI]
Order of above reaction is1.
RATE LAW: The representation of the rate of chemical reaction in ConcConc. (Concj? - (Conc,j
tems of the molar concentration of the reactants is called rate law.
Example:- aA +bB’Products OR Rate [A]' x (B] OR Rate k (A]" x (B]
TYPES OF REACTION BASED NORDÉR
ZERO ORDER REACTION; If the rate of reaction docs not depend on the concsentraton of reactants, the reaction is known as zero
order reaction.

2NHe)Allthe lightLNt3H)
dependent reactions are also the examble ofzero order reaction.
Rate = kNH] OR Rate = k
DERIVATION FOR ZERO ORDER REACTION: Let usconsider a general reaction, A Product
As the zero order reaction does not depend on the concentration of the reactants, rate of reaction < [A" OR dx/dt « [A]'
dx/dt = K [AJ' OR dx/dt = K x 1 OR dx/dt = K CöéentrtotoR
On integration, Jdx = K dt
1st Sope

Where: I is theintegation constafty

At, t = 0 the concentration does not change of the reactant i.e. x=0
So by equatios 1« Tima
Nkuriation nthe
=K x 0 +I
I=0
Puting the yalue of I in equation 1", x= Kt +0 OR K= x/t
FIRST ORDER REACTIOC: If the rate of reaction depends on the concentration of only one reactant, the reaction is known as first
order
Teactioi. Examples:
1)Thermal decomposition of Nitrogen pentoxide, N,Os.
N20s -’ N2O4t+ 1/2 O:, r=k[N>0s]
2) Thermal decomposition of Sulfuryl chloride, SO,Cl,.
SO:Clz SOz+Ch, r=k[S0:Clh]

Written by: MR, SOHAIL YouTube Channel: Suhail's ChemisTricks Page 7 of 19

 ebri m o l e c 1u

nr
e e a c t ii
o n
n

3) Thermal decomposition of Hydrogen peroxide, H20:. A S OI

N f:

H;01 ’ H;0 + 1/2O:, r= k[H:0:] c a st

e h
,

substances.
4) Decomposition ofall radionctive
’ Product
228
88 Ra He + Rn consider a gencral reaction:
A
Let us
DERIYATION FOR FIRST ORDER REACTION:
(a-x)
concentration of product
Concentration after 't' time, (x)=
Where, a= Initial concentration of rcactant, (a-x) = %/ t « [AJ"
concentration of onlyone reactant, rate of rcaction « [AJ' OR
on the
AS tnc st order reaction depcnds
dx/dt x (a-x) OR dx/dt = K (a-x) In(Rl (4/N
og
kmslops
dx =K (a-x) dt OR dx/(a-x) = K dt Slope k/2.308

On integration, dx/ (a-x) = K dt

-log (a-x) = Kt +-..
Where: I is the integration constant Time
A plct bot vean ln(RI anl t Potoflog [Rl/R] vs tme for a frst
At, t= 0 the concentration oes not change of the reactant i.e. x =0 for a frst wrdeT reactlon order reactlo

So by equation 1* -log (a-0)=K x 0+I

I=-log a
Putting the value ofI in equation 1#: -log (a-x) = Kt - log a QR ga- log(-x) kt
log a /(a-x) = Kt OR log (a-x) x 1/tF K
A
303,
In some books, a = Ro, a-x= RJ
reaction is known as
SECOND ORDER REACTION: If therate of reaction depends 8n theroncentration of two reactants, the
second order raction. Examples:
1) Thermal decomposition of Nitrous oxide, NOi.e. 2N20’2N2 +O:, r=k[N20]?
2) Decomposition of ClLO. i.e. 2C10 -2 h +O r=k[Cho
3) NO: + F2 ’NO,F+. dx/dt = NO:]' Fa]' Cder =1+1=2
THIRD ORDER REACTION: If the rate of reaction dependson the concentration of three reactants, the reaction is known as third
order reaction. Exampfes:
1) Reaction between NO ana tgive NO; ; 2NO +O , ’ 2NO2, r=kNO1{O]
2)Reartion between NO and Ci ivNOCI 2NO + Cl, ’2NOCI, r=k[NOJ [CI
UNIT OFRATR CONSTANT:
For 1 ordf reaction sec-!
INT OFRATE CONSTANT
For 2nd order reaction L.mole'sec!
FORYRST ORDERREACTION
For 3t ordar reaction -’ L'.molesec-! TVE SECONDORDEKNEATION Sec
FOR TAbORDERRERACTION {nmorder)
For zero order reactioi ’ nole .L'sec-! FORDA}RoRCERKRACTI N
NOTE:
1.If the molecularity of areaction is equal to its order, itis considered às elementary reactior. Otherwise, it is considered as complex
reaction.
2. The unit for the time can be expressed in minutes or hours or years also.
3. Also remember that 1 Litre =1000 mL = 1000 cm=100G ce= 1dm
 UDO ORDER REACTION OR PSEUDO FIRST ORDER
REACTION: The reaction whosc molccularity is 2 but order is1 0R First
order bimolecular reaction eg Such reactions which are not truly first order but arc bimolccular undcr certain conditions g
The reaction in which one of the two rcactants is in cxcess.

REASON: If one of the rcactants is present in excess, it may be solvent and itsconcentration willrcmain almGstconstant. In this
case, the rate of reaction will depend only on the cohcentration of the rcactant, present in a smaller amount.
CHCO0CH, + HO CH;COOH + CH,OH
Here is not any change in H:0 during the rcaction.
Rate of reaction =k[CH,CO0C:H)' H0]°
Here, order = 1+ 0 =1
In the same way, CaH:On + H;0 -’ CoH2CO% + CcHnOs Rate of reaction K[CuH1Ou
(Cane sugar) (Glucose) (Fructose)
DIFFERENCES BETWEEN ORDER AND MOLECULARITY OF AREACTION
ORDER
1. DEFINITION MOLEOULARIIY
1. DEFINITION
2. It can be fraction as wel as
zero. 2.It is always a whole no. it can neither of zero
3. It can be determined nor fraction.
experimentally not calculated. 3.It can be calculated by simply adding the
4. Order may not be equal to the no. of
molecule of lhe reactants. 4.It may be equal to he no. of
molecule.
> The overallrate of the molecole of the reactants.
reaction is controlled by the slowest step in a redetion oalled therate
ELEMENTARY REACTION:The reaction that occurs in one step is determining step.
reaction called an elementary reaction. R One
step occurring
>The reaction that occurs in more
than one step is termedas
>For elementary
reaction, the order of the reaction must complex reactions.
QUESTION: Identify the reaction order of baequato the nplecularity but molecularity should be
ANSWER: Do yourself thefollowing
equationssi) = 2.3 × 10:5L mol's (iü) k =3x 10+ st
k integral.
QUESTION: From the rate expressions, HINT: See the units of each
constants. 3NO ’ N,0 Rate = k[NOJ
i) deterimine their order of reaction and the dimensions of the reaction.
(ii) H,0, h9 + 31 e3) + 2H' ’ rate
(ii) CH;CHO ’ CHAy+ CO
ANSWER: Rate = k[CH,@HOj32 (iv) 2H,0 I,; Rate = k[H,0]I]
+
(i) Given rate = k
CH,Cl ’ C;Hu + HCl,
Rate = k [CH,C1]
[NOJ Therefore, order
(ii) Given rate =k ofthe reaction=2
[H,0} (T
Therefore, order of the reaction = 2 Dimension: L.mol's.
(iüi) Given rate =k
(iv) Given rate = k [CH, C HOThet efore, order of reaction = 3/2 Dimension:- L.mol's
[C,H,CHTherefore, order of the
QUESTION For a reacion, A+ B Dimension:- L2.mol:²g
ANSWER: Product; the ratereaction=1 Dimension: s
law is R = k[AJa
(B)'. What is the
QUESTION: Calçulatethe order of a order of the
ANSWER: a) reaction which has the rate reaction?
QUESTION: The rate constant for a first (b) expression (a) R= k [A]2 (B]2 (b) R= k
order [AJ32 (B]
concentration reactant to its 1/16th value?
of the
ANSWER: It is known th¡t,
reaction is 60 s. How much
time will it take to
reduce the initial

WPitten by: M
RSUHAIL Cho
 ( 2 9K8 ,

2.303
A3t0

2.303:
603
2.303

=4.610s(approximately)
Hence, the required time is 4.6 × 10- s.
SuESTION: The half-life for radioactive decay of "c is 5730 years. An archacological artifact containing woodhad
only 80% of the "C found in a living tree. Estimate the age of the
sample.
ANSWER: Here, ku0.693/ tiz =0.693/5730 years"
It is known that,

2308 j0y
2.303ssT00
0.693
5730
=1845 years (approximately).
Hence, the age of the sample is 1845 years.

QUESTION: the initial concentration of N,o, in the following first ayder teactiahÑ,0s0 -’ 2NOz) + 1/20z9, was
1.24 x 10² mol/L at 318 K. The concentration of N,Os aftr G minutes wa_) 0.20 x 10 mol/L. Calculate the rate
constant of the reaction at 318 K.
ANSWER: k= 0.0304 min!
QUESTION: A first order reaction takes 40 min for 301 debmposition. Calculate tu2:
ANSWER: For a firi order reaction,

According to question (a, =100,,a-X=70)

23034
40:1nin
8.91801
Therefure, tie of the decomigstign reactio is
tyz = 0.693/k
0:693
8013910 hin
7 min (aproximately)
fiist crdeeaction at 298K is cqual to that required for
QUESTIoN: Ihe time required for 10% completion of a
1.G10.s, Calculet: k at 312 K and E.
its 25% completion a303 K. If the value of A is 4 x
ANSWER: FoLa fistorder reaction,
2303
According to question at 298K (a =100, a-x =90)
According to question at 308K (a =1cc, a-x = 75)

Page 1 of 19
 2.303 N00
t 298 K,
2.303100 .2877
At 308 K,
Now according to the question,

0:tOS4. 02877

27296
From Arrhenius equation, we obtain

log 2303R7
308-298)
log(2,2303x84M
E
4296)=303384298K308
298x 308alog(2.7296)
308298
=76640:096 Tmol
=76.64k0mól
To calculate k at 318 K,

logk=iog®
2303.RT

2303x8314%318
(0.6021--10)-T25876
=985
Therefore,-*=Amtilog(-1.985S)
=1034810si
Calculate the concentration of A
QUESTION: Consider a certain reaction A ’ Products with k= 2.0x 10* s-,
remaining after 100 s if the initial concentration ofÁis 1.0 mol L-!,
ANSWER: k= 2.0 x 10 s,A100 s, a = 1.0 moL-! ,a -x =?
Since the unit of kis s the given reactioS a first order reaction.
2,303;
Therefore, k
20x102503 0
sa-x
100
2.303
20%103sloga-x
2.0%103x100,
-logax "2.303
a-x=antilog 2.0x10
%100
2303
= 0.135 mol L- (approximately)
Hence, the rermaining concentration of A is 0.135 mol L-!.
 2.30
0 . 6 9 3

2 8 . 1

QUESTION: For a first order rcaction, show that time required for 99% completion is twice the time require 2 . 3

the completion of 90% of reaction.

ANSWER: For a first order rcaction. the time required for 99% completion 1S
2.303
(a =100, a - x=1)
S03log10

For a first order reaction, the time required for 90% completion is

230o a t (a = 100, a -x =10 )

23081og10
_2303

Therefore, t, = 2t,. Hence, the time required for 99% completion of a first ordeDreaction ís tyitethe ime required for
the completiom of 90% of the reaction..
QUESTION: Show that in a first order reaction, time required for completionnf 39.9% is 1O
of the reaction.
times of half-life (t)
ANSWER: Do yourself
QUESTTON: The initial concentration of N,0, in the following irst order rcaction N,Ose ’
2 NOz) + 1/20: was
1.24x 10² mol I at 313 K. The concentration of N,0, after
60minutes was 0.20 x 10² mol L, Calculate the
rate constant of the reaction at 318K,
ANSWER: Do yourself
2.30 og
HINT: (a = 1.2£x 0* mol , a-x0.29 × 10² mol J", t=
60)
QUESTION: A first crder reaction has a rateconstant 1.15 x 10* s*. Hov long
will 5 g of thçs reactant take to
reduce to 3 g?
ANSWER: Do yourself
230
HINT: (ag5g, a-x =3,t=?)
QUESTION: During nudear exlosion, oneof the products is Sr witk hsllife of
28.1 years. If lug of Sr was
absorbed in the bones ofanewly bo:n baby instead cÉ calciuna, how much of it
will remain after 10 years and
60 yearsif it is not lostmetaboliclly.
ANSWER
693 D.693

Here, It knowp, that

30 1033
k

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 2 3 0 3

0 . 6 9 3

28.1

QUESTION: For afirst order reaction, show that time raquired for 99% completion is twice the time require? 2.30

2 3

the completion of 90% of reaction. 0.

ANSWER: For a first order reaction, the time required for 99% completion is

2303Tha (a =100, a - x =1)

0g1O0
2 }303
For a first order reaction, the time required for 90% completion is
2303
(a= 100, a - x=10)

2.3010g10
2.303

ordeDreaction is twite the pime requíred for

Therefore, t, = 2t2. Hence, the time required for 99% completion of a first
the completion of 90% of the reaction.:
for completiunnf 99.9% is 10°times of half-life (ti)
QU:STION: ^how that in a first order reaction, time required
of the reaction.
ANSWER: Do yourself
1/20:p Was
The initial concentration of N,0, in the follo wing first order rcaction ,Ost) -’ 2 NOz) +
QUESTON: Calculate the
at 313 K. The concentration of N,0, after 60minutes was0.20 × 10* mol L,
1.24 x 10² mol I,
at 318 K.
rate constant of the reaction
ANSWERi Do yourself
mol L', t= 60)
(a = 1.2 xro? mol L:, a-x,20 × 10°²
5g of this reactant take to
HINT:
has a ratesonstant 1.1S x l0* s². How long wil!
QUESTION: A first crder reaction
reduce to 3 g?
ANSWER: Do yourself
2303bg a g , a-x =3,t=?)
hallife of 28.1 years. If lpg of
Sr was
HINT: prod1cts is soSr, with 10 years and
During nuçdear exglosion, oneof the how nuch of it wil remain after
QUESTION: ci calciuna,
ofawly born baby instead
absorbedin the bonea
lost raetaholically
60years if it isnot
ANSWER

Here, It iR know)that

Page 12of19
aKremuSIi1ckS
YouTube kine:
 Written QUESTION: =3.89respectively.
Rate givenby, Concentration
0.02 When ANSWER: Rate 0.06
molL,rate
ANSWER rateQUESTION:
given =7.5 know
that,We
Rate However, ANSWER:
production molTherefore, QUESTION:Hence,
the And, Therefore, antilog(0.8024)
=k L. = of
pressure can by x mol [AJ the
10 the The mol
[AJB} Therefore, [AJ[B} Thek the
lf also,beRate'r3N25A0möls L" 0s
The rateaproductio? it The L concentration reduced fraction
For 0:158 (àpprow)
0IS76
by: pressure mol the deccmposition
is of s1 initial reaction
Now reactant of of = the
decomposition
i_ rate given decomposition N, =
k(PCH,0CH,J2
expressed.in (2.0 the (2.0
4 measured of and after A rate reaction: of 2.303
SVNATL is from
2fad:ation that I, x rate which x when sample
masured 10*) B 104)x of
the if reaction, has of 0.1
of the [AJ=
in ofHAs of k= x the reacted. Bhas mol
reaction reacted (0.1)
reaction 2A of
in bar
terms The of NH, 2.5 of (0.06)
reaction reacted sucrose
dimethyl o thc L" 0.1 +
bar. and on xNH, to x mol B
of rate N, 10* >x availableHence, with (0.2)
is platinunisurface
is on (0.18) is:
tel:bLhail
YouTube and time the
of =0.0G I, ABthat
of molLS? platinum according .0 4 (0.1
time partial reactioL ether zero =8.0
in mol
the -0.06)= mol 0Rl theremains
in concentration =
rate
minutes, leads ordea concentration L, x
0.2
minutes, pressire to L this 10
is surfaçe of0.04 mol after
followed to Therefore, is the k[A|B]
reactantA means mel"
then the repreatcd concentraton I, 8
then is mol
of L' s Calculatc hours
what formation
dimethyl zer of of tinat L'wlst,h
Unit by reactaitsA
Rate. B = L
is
are increase order availalblenrcacted) %x.04mol 0.06 k=
emislricks of by 0.15Ó.
= the 2.0
rae theeher, cf k the reaction. mol
[NH)º
units inCH, fTllowing 5rt. and)B L-is rate x
bar pressure
10:
i.e., H, L= of
of OR pactants are thc
min
Rate=k(PCH,0CH,) rate and What reaction mol²
equation. 0.06 0.02 amouht
Co Rate
and in are available ml (0.2 =mol
a and =k
rate closed the - left afteA]
the 2.5 LLVThis Calcu<ate
rates and 0.02)
Page constants? reaction x forreaction and
vessel, 10 0.18 mcl
14 of shows the is
mol" reduced the
of sorate molL L
19 Ls =that inittal
the is 0.l8
is
to e=k (PCH0c
 ate=k (PCH,0CH,)"2
Rate/(PCH,0CH,)^=k
Therefore, unit of rate constants
bar minc
()= barmin
QUESTION: A reaction, is second order with respect to a reactant. How Is the rate of reaction affected ip the
concentration of the reactant is () doubled (ii) reduced to half?
ANSWER Let the concentration of the reactant be [A]
Rateof reaction, R= k [A]
(0f the concentration of the reactant is doubled, i.e. (A] = (2A]",then the rate of the reaction would g
R' - k (2A]' =4 xk |A]
R =4R. Therefore, the rate of the reaction would increase by 4 times.
(i) If theconcentration of the reactant reduced to half, i.e. [A] =(1/2A] *,then the rate of the reactio:1 wouldbe
R =k [1/2AJ' =1/4 xk [AJ?
R' 1/4 xR - R/4 Therefore,the rate of the reaction would.be reduced to 4,
QUESUON; The conversion of molecules Xto Yfollows second order kintics. If concentratioD of Xis increased
to three times how will it affect the rate of formation of Y?
ANSWER:9 times faster
QUESTION: In a pseudo first order hydrolysis of ester in water, thefollowng results were obtained:
t/s 30 60 90

[Ester)mol L 0.55 0.31 0.17 0.085

ü) Calculatethe average rate of reaction between thetme intertal 30 to 60 seconds. (ii) Calculate the pseudo
first order rate constant for the hydrolysis of ester
ANSWER () Average rate of reaction between the time interval, 3Qto 6g seconds, =d[Ester]/dt
0:31-0.17
60-30
=0.14/30 =4.67 x10- mol L-! s-!
(ii) For a pseudo first order reaction,
2.303, 03S
For t = 30 s, 30031 1.911 x 10-² -!

For t = 60 S. 60: 1.957x 10s

0.55
For t= 90 s, 90
on08s2075 x10 S
Then, ayerage rate constant, 3

(1.911410)+(957:19*)+(207519)
3
=198x10t
QUESTION: A reaction is first order in A and second order in B. (1) Write the differential rate equation. (ii) How is
the rate affected on Increasing the concentration of B three times? (ll) How is the rate affected when the
concentrations of both A and B are doubled?
ANSWER: (i) The differential rate equation will be

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 () fthe concentration of Bis increased three times, then

Therefore, the rate of reaction will increase 9 times.

(id When the
concentrations of bothAand Bare doubled,

Therefore, the rate of reaction will increase S

times.
QUESTTON The reaction betreen A and Bis first order withresnect to A
the blanks in the and zoro ordewith respect B. Fill n
following table:
Experiment A/ molL B/ molL1 Initial ate/mofL min
0.1
0.1 2)0 x 10
0.2 40 x 10
0.4
IV
0.4
0.2 2.0 x 10-2
ANSWER: T:egiven reaction is of the first
order with
Therefore, the rate of the reaction is given by, Rate =respect to And of zero oder witlh respect to B.
From aj! (B] ’Rate = k [A
experiment I, we obtain 2.0x 10-² = k (0.1
From experiment II, we obtain R= 0.2 min-1
4.0 x 10=k[A] .2
From experiment II, we obtain A= 0.2 mol L-l
Rate = 02 X0.4=0.08 mol nain-!
From exXperiment IV, we cotain
2.0 x 10= 0.2 [A]’ [A] = 0.1
QUESTION: The following results have been mol L
obtained duringthe lkinetic studies of the reaction:
ExPERIMENT A/ mol L1 2AB’C+D
B/ mol ð
i)
0.1 Initial rate of formation of D/mol L
0.1 min-!
(ii) 0 6.0 x 10-3
0.2
(iii) 0.3 7.2 x 10
0.4
(iv) 2.88 x 10-!
0.1
Determine therate law zndï th¹ r¥te constant for the 2.40 x 10-3
reaction.
ANSWER:Let the orden of the reaction with respect to
the be' and with respect to B' be 'y'.
reaction sgiven by Therefore, rate of
According to he question,
5.0:10=&[O1 (p:1]'
2:88x10=[0.3 [o4
240×í0DA[O
Dividing equativn (iv) by (i), we obtain

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Page 16 of 19
240810 [04(o
6.0x10 [0.1] [0:1]
[o.1]"

Dividing equation (iii) by (ii), we obtain

7210

Therefore, the rate law is Rate k [A] [B]²

Rate

From experiment I, we obtain

6.0x10mol L mn
= 6.0 L mol² min
From experiment II, we obtain
: 72xI0 mol min
(0.3mol1")(o:2mol1
= 6.0 L
mol² min
From experiment III, we
obtam
}- 288xÍ0mol ttmin
{0.3mol1:')0Amöl 13)
=6.0 L? mol² min
From expefmentV we obtain
k 2.40x10 molLmin
(04molL (0.1 mol1:!)
- 6.0 L² n m
Therefore, rate constant, k = 6.0 L² mol²
QUESTION: In a reaction between A min'
and B, the initial
concentrations
A/ mol L1
of A and B as
given below: rate of
reaction (ro) was
B/ molL1 0.20 measured for different initial
0.20
0.30 0.10 0.40
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SOHAIL Youlube Channel: Suhail's
 2 . 3 0 3

1.43 x 104 7 2
s 0

r/ mol L! s-1 5.07 x 10-5 S.07 x 10-5

What is the order of the reaction with respect to A and B?

ANSWER Let the order ofthe reaction with respect to Abex and with respect to Bbe y. Thererore,

S07x10-*(O2010-10
43i0*0:40[0:05)
Based on experimental results OR equation (i) &(ii), the rate of reaction is zero order with respeci to B
Dividing equation (iii) by (ii), we obtain
143810 *[oA0 o.0s
S.07810 [o:2 [ö30}
S0710
Sineey=
2.821e2 [ö20"[ocos]-[o30r
Slog2.82121og2
log2:821
log2
= l.496 = 1.5
(approximately). The rate of reaction is 1.5 with respedt to
In this way, we can say that the order of
reaction is 1.5 because the reaction tate is .5 order with respect A
2ero order with respect toB. and
DERIVATION FOR NUMERIÇALS:
A(g)
At t 0 Pi atm
At timet (pr-x) atm
Where, piis the initial pressure attme t=0.
p:= (pi -X) + x + x=pi+ X
X= (pr-p)
Where, PA =pi-X=p1 (pr- pi)= 2pi Pt
2.303 2.303
k =
PA t log (2p,Pi- P)
QUESTION: For the ¿ecomposition ofazoisoproraue to hexane and ritrogen at 543
data are obtained. K, the following
t (sec) P(mmof Hg)
360
720
Calculate the rate constant.
ANSWER We lnov/ that
2.309 1087(2P-P)
t
P

When t= 360s

kaO8$0540- 2.175 x10s

When t =720s

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slhi:ks Page 18 of 19
 2303:;log 35.0.
T2063S.0-630 - 2.235 x 10- s-1
(2175x19 +(2235X0
=2.21 x 10 s-1
QUESTION: The following data were obtained during the first order thermal decomposition of S0,CI,
at a constant volume. SO;Cl2() SOzg) + Claig)
Experiment TÉme/s Total pressure/atm
1 0 0.5
2 100 0.6
Calculate the rate of the reaction when total pressure is 0.65 atm.
ANSWER: The rate of reaction at 0.65 atm pressure is found using the expression, Rate =%(Pso2ci2)..
For this,we have to find both `k and `Psozc12
We know that.
2.303

When t= 100 S, koE-08= 2.231 x10 3

Now, the thermal decomposition of SO,Cl, at a constant volumesrepresented by the following equation.
SO:Cl2() sO
At t=0 piatm Oatr 0atm
At time t (prx) atm X atm Xatm
We know that (Pso2c12) pi -X
After timet, total pressure, P, = (P-x) +x + X
(Where, p is the initial pressure at time t = 0).
p= (p1 - X) + X+ X= p;+ X
P: Pi =X
According to question, P, = 0.65 atm,
0.65 - P, = X
0.65 - 0.5 = X OR 0.15 =X
Therefore, when the tojalpressure is 0.65 atm, the pressure of SO.Cl, (Psozca) =P. - x
= 0.5 - 0.15 = 0.35 a f
Hence, the rate of re~ctionato,65 atmpressure =kx (Psozc2) =2.23 x 10->x 0.35 = 7.8 × 10 atm s
QUESTION: The followihg.data were öbtained during the first order thermal decomposition of N,Ose at
constantsolume, 2N,Os -2N,0ap + Ozp)
S.No. ATime/s Total Pressure/(atm)
1. 0.5
2. 100 0.512
Calculate the tate/onstant.
ANSWER: 4.98 o4 s!

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