Chaptor-4

CHEMICAL KINETIes
Chamical kinelico the onch
chamistry
which deals with thu ali e reactisr
a t which they ae 9cwung.
with the mechanim
aloo_oleals
eactuena
Kt uoake the exomplu e f Jeactian-

Kati e un chasnge in cencenluatien

unit ome
Rati of un n ms -cheng L i ncent
Jeaclant atin_f
[RI/AE
Kati of sex Lo chanpe céncantaa
paoluct

Kala o un ishghly inoivduol in ratwe

dhe olucreare / incegse ony pesduct ueact
ant do
ant net afeet the umatrone
decsmp0lisn th CAMpaundo.

Ha t C! 2HCL
LH]
dt olt dt

Na t 3H, 2NHa
dN1 H :t/
2
dTNH1
ot
olt dt

Formato SO
L S O 2G ) 0
O 4 22S0s )
So
at dt olt
 ASE 2
ormation t Ha0
H2 O2 0 2H20
d[o H20
dH
dt dt dt

Etoiliialien CHs CooH, CH; C+H

CH COOH + C2Hs OH tdlCH CooCH, CH]
-CH CooH] -dlGHsoM
dt dt
dt

ot

pe kets _ Kaactien
á l chetge in Lens
tetaltme token
(au)
dnatantinuou a l i Kun-d[R = (Ti
dt

Unib ef kat ef Keacton:

Kat of exn Mol7L mal L
the JKA _i taRuy plau in 220esw medu
meduu
e n at =
aln alm ,
 93

jactodlctig th Mati a
J.Tempralnre
Genurally thu Jato eyun jncreaso
withtump.and
with (7/0)ulu wrk an
(T+l0 Jull: fr evwylo C inceare in
Jomp. the Hati almsat JkoMLo
tusiui u p a coain extent.

uwsusse doe not olpct the ati s

i ti t akiy placin luid madium
un s aku plau in
2ae0uw muolium then prwmisu
the atu ef uwn accardiiny a k Chat
lrie'epuincape
3 Conantnalien Reactants i
hu iadanh ae cencentiialkd h e
at eL Hun io Veuy hiph and sN h e
thoe hand t h e a a of Kun.
become olowe
i n oliute
i the K U N i o
midiiuM
taki
pau
H2 No t 3H2
NL 2NH
2NH
Cpnc NH

Rat o Un
dr Kanction
Rat laueit atilio that the Kati of_an
Jun i oluette proportional Cenc kua t
A tc
Kati e un A1[&]
Kati of u n RAL6
Naw, hu wrolr of Jon. Can d dilinud a the
Aem e_pewo Dt which Conc. ase Jamd
oolortwit the Kati e xn
Ace eg U the order ef n ill be ltl:2

dype der ef Rxn

whun ho peati of un. doe ngt

olopenol en he CAnc e u adants then it a
Kno Hdor.
Decempaclion e dmmsnia
2NH N2 t 3H2
S du =k [NH3]°
ot

21 kdr Eg: Elhtrelysio wralex

H2o uctsllain> Ha2 + ó,

ol
ot
 75

3-2 olori E Formation ef Hu

H2t cl2 2HL
_d k[H1[u,]
olt

. Pactrenal axoluri E2: Deomp0itron ef adhand

CH CHO
A H 13
d k[cH;CHO] 72
ott

Unib and Katu Condant lo olloent edoe

Krno

ardor
Ko d kLx]
clt

mal k L

k mal L

2 Foet aderid =k [x]

olt
mett k mst L

k w

2. Secsnd akolve:
t
KLX
k man 2

k Lmal .
 Page No 96

aJun hae thualu paticonaa

4 . x lo- melL and th cnc
keachnt a A J = 0 . 3 mal

[L7 0. /5 mat
Clult th ordr e xn a 2A + 58-7

relr 3d
enual oxam e Odo _Reation

anc n

no
Lx me
3 mal-1
L

mal L

o n
k= S
moL S
mel
L

the_un takuipy plau un gao esus mui-

ilm then the rut o ate canalant can
b e calculatio
kaLr n
S(otm)n7
Lo n 0 k atm s
S (atm) o
 n k
atm)

alms -/
lor n 2 k=
S (atmy
Heleculasity e a Keaction
t iothu no e moleculu that a
collideiy ith each thwr n oler
changthe Juaslan in Jwe prusdutb
Aoldulasity uo odulorant sn od opun
why_the hzhmele cularib, xno aeHae
nawre
dtt io
in decauu i a l m b a t mpoible t h a t
15 o 20 0any athoe highue number omolacu
Ja callole each athere a a me t
whange the Mea cant intb psolut,

poranliali detnen COder e Kua and Melur

Nanily

oRDER of RXN MoLECULARITY

tcan be odletoxmineo Ei jai a hkesrati
enpuimenlally cal oncapt
Lt can de xeeo or a
actisnal numer peactional no.
3 t c9n _be calulatd oloeon't hate any
ko elamuntany Axn co meaning Lor complay
wel as comatu Aan.
domined by vale ef k. lJut a no. without wnib
 Date
Page No 98

ntpali Rt Euatisn
Fox xito_dor
d =k[2
olt
d -k x -k
dt
du k dt
by inlipkaing bah ude
olu Kdt O

u -kt +c
Nouw, at t=o
M -k (0 t c

-kt tMo
UUo a -Kt
Kt Xo - Ka
k Ko -u

oriat wrdor
d k[x]
olt
-d ku.dtx
du k dt

du k e
ln u k t te
 o99

a tt : o
-

n o k() +«
-Ln Lo
- Ln kt-Ln us
Kt ln Ho n k
kt An o 2-5o3 le
k 2.So3 dag

tme pokuád in which thu onc

any youbtanw becomo halo inlial canc
J denstd y
Rtlon blw k andt
Fur xuo dkolo k Mo-k

L t the tnilial concenbaliond

Ltir 2 pial cenc. /
k k
2t/ 2t2

xove that t/2 olepenole on th eonc: e Kuke

oVe
dor

For loot woder, k= 2.363Log o

tthu iñitial cenc be u
otor t/2, conc e 2
 Page No loo

k= 2-303 Jg 2 0.3o/

k o. 6 93o
t
xove that the haly e poriad f ok
J u ni wndepenolnt Conc

AL the rainoactie decay lollew shish sder q

1 order n.

Deljne peudo1 ordor nwith ekampl

Thoat un hich ake o highot oolrs
b u l Can_a as a dlor HKN . wndu
wntaunCsndiliens ake callud a Peudo1ut

kderKun
Hyduelysi o eltin
CHtoo c2Hs tH20 CH2Co0H C2 Hs OH

Rt n CHs Coo C2Hs ]LH2o

Rt k[CH; CoocaHs]Hao
Ne ardor= (+l=2
w e take H0 in excuoLH2o N |
Rt eHxn kCH3Coo C2 Hs

Fox a ljut ooler n , phsus that_tim equr

Completan, 00 un
uxa the ime yeguinud lo cemplatuen
el 11/% eacton
 fol

kE 203 Ja A
l0o

dto 2303 dog_loo

fo

divilriy by i
29
2403tKdog loo/
o 37k Loloo
/o

2 t22 2te1
AY
phos that in awa ef 1
rdr Kun
the ken
the am eguiudo 1121
thn that
t dik pla u io abeu l6 im
ug uiied or halt dho_KN
k 2 3 leg A
A

2:3o3 Jog_loo 2.303 Log looo

k O.l

Go4 2,303 lo loo

50

odubeidleng Ay
50 &rdo3/k dog loo /5o
1 9 8 lo 75oa

O 3oloA
 Page No s 2

t h hat ile piad of C i 5+30yca

dhn haw much tine wiI it_Jake to comune
CAmpltly thu yun i 1o rdee.
dhfinitd
Jempeuatunu_epndnu of thu kate e keacduen
Most el th ono awe ump enailiue and gunvally
with he ineau in timp. Jpati ef Kun, Jnlana
and ttlosule wwto lor i
awrheniu eguaton
Ae Ea/RT

ta i the acturalion envrgy Theen

A oehunius atar purpånentiad ator
Naw Jakny dog en both aids
RT

Now,at T nk AnA Ea -
RT
dn kr An Ar Ea
RT
-i
nk- Lln k = An A-Ea LnA Ea |
RT RT2
Ln k A-E
RT RT
RT RT R
 fo3

K 2303K
dheJat o u quadoupho uhun thi pmp
whang Jum 293 K 313313 K_Caluiat
Hu enuyy actireton h HUn anu-
ming thalitolot not hangtwth tump.
213K T23/3 K K=8-311 Tk me
k Ea
2.303X8131 293 313
Aeg ka a 20
0KI 2.303x 8.314 9179
20
2 30 3*8.314 999

Ea 6.60 20 X 2:303 x 8 314 x 9/7 90

2
= 52959:5538 J/mol
h ati conet. Lon thu decspaitisn y hyobrocar-
deni 2 4/8 x 1-5 at 516K Iy the envy
adiretion i 1711.1 kT/mel, what ujill e thi
value e expanentia actan
k A-TRT
dy lakr log on_beth aides
Ln A-Ea
RT
k 2.4/8 xlo
T 514K Ea 11.9 kT/msl
 pue
Page No 1S
Ea719 xlo'T/msl
n A Lk t Ea
RT

33log A 2.803 log k +Ea

RT
dos A logK +_Ea
2 303 R T

dop k + 179.9x/o
2-30 3X 546X 8 311

dog A de 2.18 *1o5 7.9.10

2 5 y 6 x 2. 303 X8 31

leg A dog 2-18 + g lo+ 329.8

2.303X8.31
Aog Adog 2.418- 5+_16474 Xlo
2363x9S }7
deg A Jog 2:918- 5+ 7:/53x1o
Jog A do 2. 18-5 +o.60/319?9 xto
A Jog 24/ 5 t 20
s o 9 A 038 3 5 + 17.20
--9 6166 19 2 2 5834
AA antilog |2 58337= 3. 832 x fo2
.

ehct Gtalyt
Gtlyat doe nat okft tu sati e Rkn becaue
thu work a/me Lor oewarol kun and backurnd xu1
acatlyss phovidi an altonelive ath_lor be
Kxh the
decxauy activalon enrgy
 lo

Atinln Eneay
eneuyby whih uactanb change
ind prsducti.

._Aake a gtaph Lor caalyd and uncatilyd

Mvin pebnial engy and kun oardina

Uncatalyaud

Keactankb catatyua
oun Coals i h o u t
odh codaly catalysto

huoducts
Rrun csordira tu

*Calicon_dheoey e Chem'val Run

demeiripolant tomo ugarourg the collisien
thuoy
Collibon eguencythe no o_melhculu uactant
whuich e aliduij uith each other 2eh ucsNad_per
wnit volume io caltd a callincènagueny (2)
Elhective collindns ut of all cellicore thou collis2
thal aee Can change eacdant mally inó the
presduct ake calud as ectue collieons
do compleb a xun 2 maoractoro were

Eregy ator upo e erepieo wek hwre

bt imc
Threhald env
Acti atisn enb
 Date
Page No 6

nly those malkcuo o_Jueailant whichhaue

hae
Cwtain minumumleelofeneg
Juactant_inh puaduct
chan
Con cha
(actinton eng)
dlation Jactor Ortentatron actor
the moleus e mactants Can e changcd indó pro
duto enly hon_prspo uentabon there
here
d pepex oientotron io ezent pAduet_uill
ngt Lorm whatere d theenerg
Ket w lake the exampe elometaky ky
hasing 2 molculo A and B whh eact
hauin with
weth
Qne anatho lorm the pkBolutt Then the
xat e thio o n will he
A+8 pAduct
Kati Z e6a/RT
whexeZAR i calliain guen e_eactant
eactant
maleulu. Kai = P z . -EoRT
whereP io t h probabilily facton ethe xn.
Max well Ditikubon negy urve

mot pushab
kunet ene

Kineie eo
 (ttl0)
er
Thio ana houso actiraiion
Zactuin f mokeulte This aua chous
Jeachuy at t praclon f moleude
Kineie enoy ueachuig at ttio)

Mot bbhable veloiby

h veloiby acguwirud by mot f thi mahculu
io calL a hu mat pusb abe velo uly