11/$o\m-3

L '.i\ ' i'''l-'

LJ r r.u\dv,.-3
ig,flX#.
h exa|/l

Topic5: ReactionKinetics

-JIAI
E

Cowntrattbn

Rate of a reactionis the changeof the

dforoduc0
dt

Rate = -

molJrrd S-l : .rrut"i.qk .

perunittime.
of a reactant
or a product

no\ Arvi3

ln
For reaction : aA +

bB

rr\,re arb,tor,.dA.s
''^
Rate of disappearanceof reactants=
(Ytd.latts -ve).

cC +

';"$rt ,t Nr:{nollm3s-l
lCo,uorl

"\D

slo]c\toyrre*rtcCoe,0ftc]ertL
.

=
4[o]
A
a ,.- Gl
4il

=
Rateof appearance
/ formation
of products

".

= A#

JtA] -= --+ atBI=-rZ at4-+

--w'T
Ear^U
R a t e =- :q
b
;T-

E
cEtt, *t*t
A[il*.q\*,*ro6

N1t34t ) lNH3,

E
n) '*,*n
4 oh.^yp.oante
"t-

f *Nl.\3._
lF^"\';+
-

a-rnr:=-38
- l, n}1il
=-l {rHrJ='-;;I o"- = A|
-df^'lJ-+ 4ENr43'1
-dE.
lt",t- . -{=z
|

4 Nl43=qfo^F"*n {ormckton

l*t( + .fo.rnahon Nq=1'1too\ drnf s-f .

"$
't
-S C ) ,
"Pp-tarue
l. fn the reaction: HzOz+ 2l- + 2H'
)
2H2O * lz
''t-i;d;;rorm-"ti*
oi f, i"zr iot roiort s-i,oetermin-e'fne
rateofformation
ofwater
a 'L
l [ tn4>v
r o) 1 n ,l
,tr Jo[
f iLl l' 4
0 rl o j ra
)l L 1
, . d
, ^l tOd)
-..nr3)
dLtl
L ") 1 .,:-dtW
ol,tl't"o]

L'T=-Ei'.

l/,1.,,^_.
:4x(O*nol alla-\g-t

.nstarfuansralz
at
t--o .
_ /_
&_+?g_:_

lnrt;nporlorrgS
(ii) instantaneous
rate

(i) average rate

= chanqein I I
time taken

= gradientof tangentat a particular

time

(iii) initial
initialrate
rate

= rateat timezero
= gradientof tangentat t = 0
0.016

M
| /': il*

W'W

0.0t{
0.0t?

t':ojl.

03t0

nr/rjri

0.06

(rHiw17c

0.006
0.001
0.@
0

Time

) pudtcl5

oaacbrrts :

dun'ra'j

r<a.ctaftS

rrsvt sl)}ryn

rich

fouuqtc( r*n

gud.^cts.

e-

fe"('rArSle
rX n'

"eue/G;
reAeorr.

+ E7rEo
) wrtct,uner(atron

-t
.a{a = ri\o\ dttt3 S

- reactantparticlesmustcollide.

- onlythosecollisions
withenergyequalto or greaterthan ACt,Va-tronencrflq
andwith
orientation(effectiveco||isions)wi||resu|tiriflroductsformation.
(Activation
energy= theminimumenergythatmustbe overcome
by reactantmolecules
beforea reaction
cantake

place.)

il mtniil,Lm onenVl $r
Ttre

lo:rar
no

racton {o o&ur

c claisioxr,.rth.e

errergefic

or5r,

suffrcient

J--

66rflisis11

errergterH.c

:gffii.L.*;-ffid;*

reacfi.orr

*,*h cornect
onentqtor

chaga "t
AH= e^ttv^lpl
o. re(d'bn'

>

t\
el
g

GD
g
a,

F*

G'

s.
tu

<t

I.L

1e
at

^o/Ao"lltg

(}

&

h5\.er^erej*

releosed

6^lerff
f,lei:ction

FGactsnts

ale

not stqtle.

Prtegness

:,P

tTm

(ii)corfcentration
or pressure

I size
or

'smaller
particle
sZe,
-total
surfacr
area
exposed
to collision
increases
)reases
-frequenry
equency
of collision
increases
-fiequency
of
effective
collision
increases
-r dtE

Increases

ofsas
tlt

Progre=s

ra\ax)
x utl'/l t?,rnP;rczeset7'C

LJVr%\

ic

(+aH).

e J,t^5*^'

(iv) * Catalyst

(iii) Temperature

EoC
+vacatatXs-f

Trf'flf

R4 Po.El

For higherconcentration,
totalno. of particlesper unit
volumeincreases
f requencyof collisions
increases
frequencyof effective
collisions
increases
rate increases

R.erection

Endorlrerrn
neo.ction

H}a'"--(-AH)
rticle

.tvc.Ac r l'A
"l
= Fo - Al-l

For an increasein temperature, Catalysts

- particlesmovewith higher
- alterthe mechanism
speedand energy
by loweringthe activation
energy
- averagekineticenergyof
- morecollidingparticleswill have
particlesincreases
K.E ; loweredE.
x &c,
- frequencyof effective
- frequencyof effectivecollisions
collisionsincreases
increases
- rate increases
- rate increase
I

Effectof T on reactionrate can

alsobe explainedby
(1) Maxwell-Boltzmann
distributioncurve

I
n r
I
I
\
lEa*/ocaarrsr
,,",n,|_-y'^\Ilo'gn"
lReirrLe;rs

\\

lo.,t"r*ocatalys:\
urrm{el7st
lFelh#rl
ffi;?rRssctioo
Coordinate

= FewccEision:
Lowconcentration

I
|At

'
AH fu notcneT

E
1&

, rth

>F.'

ov\

tOtc

-'rrcret*

MT

Yata {}'

(rH)
neclwnism

l amwrL ,(. y,t,,riJ

( n o .f rr"U I

at,la*'on
ll.'le
MAnequationthatshowsthedependenc$orthereactionrateonthe,gngn@trmofeachreactant.
- Usedto predicthowreactionratedependson theconcentration
of reactant.
Forreaction:aA + bB )
products

tr*r'l?'#ffitrL

rq{an[ol'[eJ"

rarz=[to]at*1"
- o*r "t::lgn
rr\r.^

r,rrrrl --- h- rate ors{s*_;

K
rabrr -'-*u'

rsfe

'ffi%?ffiHb
,ru'

*ga=i*Ja1or
t

,s
*= *#*o

mg*trrs-Sa-I

t'
H*nnotion"
h mr* dm-$

(i) order of reaction with respect to a reactant is the powerto which concentrationof the reactantis raisedin the
rateequation.

(ii) Determinationof order of reaction

Method

Zero order

1. By using
Rate = k [A]"
rateequation Rate = k

Zse

6r-e,.er o'4t

r<rpat to A

Firstorder
Rate = k [A] \t*o.Je" oah reTtt
'

y =mx

rate

A+ pad.tts

toA

f.

Secondorder
Rate -- k
{=nX

'f,',:df gt.

6tad.errt

IAJ U

l"t'[-l'te

4M^2

-fakn {e" o't6'la\

re r r=\<
zetDnAer

2. By using
graph [A] vs. t

LUt

finear

equation

tl

t\

"zr' FJk

L\
t;\

t&i i\---_

[A]U= -ft + [A]o t

V:^^{+C.

Lutc'

4{
fy,=mstc,rt

t:i\
{-i

3. By using

.*kfef'
5lda*
J (tstr,; = I'd+
.t A_(
\+

.=kIA-l

r6t Jer

,-^{* l$ry,-fi=..,

-4

tet'ft'fe
,o^st(nF
= ls+ 6rde.r

coflcn{rqtr0^ trr beomr h"t'tf

l.\-'
t,li;j["$#f**r.ra1 +ffi,

&.Ac ctr.
t>O.

'u-'L<'

,u ,,/, = )(tu' t,/r)

tt',i,
1/[A],=t<t+1/[AL
rl

TE " P1

$+

[n]r-.-kttrnl"
inlnlr.-tt*hfd

t^Ial:

-:. r ' +[nJ,

fe]r tct

4. By using
initial rate

->t
Compare
2 experiments:
Initialrateremainsconstant
whenconcentration
of
reactant
is doubled

Compare
2 experiments:
initialrate
is doubled
when
concentration
of reactant
is
doubled

lAl;:M Rate;M/s

lA1,M

Compare2 experiments:
initialrateis x4 when
concentration
of reactant
is
doubled

Rate,M/s

lN, M

11
22
33

11
21
31

Rate,M/s

t1
24
39

or
ratet= k[AlrmfBrrq , ":1,':

.",:i3.lt:

-1

.rqjrrt
rate2=k[A]2m[B]2n i ' - r.

- then solvefor m and n

.By

"#; . 'g- D

e.g:
A+B

JnoA molecules
in slowstep rnolecularity
in - reactionis zeroorderwith
'
respectto A
the ratedetermining
stepgivesthe
numberof
molecules
involvedin the
raledetermining
step in
mechanism.
r-laa{1
mJ*e
Je\cr tu'{t4n\ rca't(,n
dP

6. By using
unlts of raie
constant, k

-> Prod.tn1-5'
AtR ->
AtB

i*"n

J*'+

rnr\= \'!t =2 '

slow

twoA moleculesandoneB
molecule
in slowstep
reactionis 2noorderwith
respectto A and1'torder
withresoectto B.

one A.moleculeand one B

moleculein slow step
reactionis 1ttorder
with respectto A and B
respectively

s-r
lr,.-3
nno\

?- .r.+"=ffnlftJ

2A+B

"na*e

A -.-...--+prodrrcts
A + A -""---.*prt>dr,rcts
A + B_+p$rtucts
A + A * A -"----+Fr+<tucts
A+A*E*.-+products
A + B -tsC-----+products

Unt'molecular
Firnolecrrlar
Eirnolecular
Tsrrnolecr.d*r
f?rmolecular
?lrmotecrrlar

ett'.r

e.g:

Eternenttr stp f SloogE)

iolecula{r

hffi

slow
)
C

' -1

:l-*w ' ,

Bafe :
Fste :
F.at:
RAt :

f[AJ'
ft[A]=
ft[A][S]
T:IAF

Rat:.*tAl1sl
Rat: l''tAlt$ltcl
ffi

k=ffi"

t,^nrt4 k.

6ol-'rft3

5-l

eg1.

Exoeriment
1

lAl/moldm"
0.100
0.100
0.300

lBl/ moldm-'
0.100
0.200
0.100

Initialrate
/ moldmos-'
4.0x 10-5

4 . 0x 1 0 1.

Determinethe orderof reaction,write tfre rate

tg sguationand determinethe rate

ro*s=P[n1^[e]^
E"pO 4.ovro-5= hfo.,oo)q(
oroo)^
expO

+',

rq*e=ktAf " [tlo

. 3,bxro:
E"pO
=lfl-S!o.,T)^
.,.,:r=
lili"
."pd = 4,gxto-s= 1c1o,too)il(o.roo)n
;;'-;r:{,}j"f
q
=(3j#)^
-'J
ft . :
-l
: !ll,*il:it,'1,"
= lt,gy I'c
mol-'c-l*3

4.oxto-=
Sk ( o . r o o ) q ( o . r o o ) "

'(oim)/' 9n=o

Difftrential
ratelaw

3.6x 10"7
constanl

\ O,too

"', k

nn =)

ZerothOrder

FirstOrder

qate=- 4B] =/<

Rate=-43-=*tft

SecondOrder

4Bl--{nlz

Concentration
vs.time
c

.e

F
p

:(lJ
:IJ
E

c
ol
U

Straight-line
plot
to determine
rate
constant

rO

-9
f

c,
a)
I

.o
(,

.t,

o
g

'o
U

M
[AJi,,

Rate,M/s

lA),M

1
2
3

2
3

n'=#

#=rfr**

lAl=[A]0.-k
or
lnlAl= ln[]e- kt

[A]=ffis- kt

iv
:c

Relativerate
vs.concentration

:c,

(J

Integrated
ratelaw

.g

(u

Rate,
M/s
I
2

0.693
. -ntn=

M/s
[A1,M Rate,
I

2
3

1
4
9

f,,r=
6fu0
M-1is-r

ontql" rJJ

Zero order
Rate constant /
unit

needn

morrioisa

Firstorder

k=r4Al.
ay,

Second order

k =dtal.

k = Q',b13
T',/r_

uArt"tK= *o\Jr"3S-'

i,m**

k=

-f

\4,^* "+k * rvol-'clrr.98-l

Examples:
l.

The rate of the reaction

teml)fiature.

Orgl + NOze)

NO1s1 + Oael was studied

at a certain

,= l"=kf.J*

(a)in *refirsts1toj"Tp"lT:r,*: Io=*o, irr(.rg"h"$"#:L1:*":T#

lol3 molegules/cm3-with the followinsn datlcJllected:
Time (s)

lOl (atoms/cm"
5.O x 1O'

0
1-Ox lO-"
2 , Ax l A '
3.Ox 1O-'

1.9 x lO'
6.8 x 1O-

2.5 x 1O"

(,i\ /

-,( . r .

!il/'o-':4ol
fol nolcmS
8.31xroa5;:r$
3,15xr o- ' s N
l,l3 xto-i5

,*,,i^',o*b \- ,
io {tu

[*d

-?

.,"-3

\,

Wh+t ir, tlrg order of the reactiolllvith

respect to oxygen atoms?
lhe rea.ctton \4S consfaryt t\d.tt lTta .

=) Tt rs Srs+ ondcr a*h rztgect to D a{orn'

(b) The r:ea,ctionif known to be firsi ordcr with respect to NO:. Deter:mine the overall
rate law and the value of the rate constant.

Fct= k[oJIr.rO']
k'' = l e i s foJ,ENoJ,

-o)xro-'s+ (t,ro-o)xt6-t=
k= (8:BI
b,4JXtoo
ffi

2- The decornposition of a certain insecticide in water follows first-order kinetics with a rate
k constant of 1.45 yt-'. a quantity of this insecticide is washed into a lake on June l,
leading to a concentr:ation of 5.O x lO-? g/cm3. fA"l
(a) What is the concentration of the insecticide on June I of the following

year?

tiiJn*'rt ?lffis"' t=/'rl*'ii 3dz

til#'=='i:-;tli
lnLff'Jlf ro,,o'\
M'
=hlff-l
/,4b
-J

@) How-long
glcrn'?

will it take forthe

concentration

of the insecticide to decrease to 3.O x lO-?

ln(hq$i1)
=-(l'r+b)t+

;Iza*t)

"+= o.jeJeo,

3 " The decomposition

of dimethyl- ether, (CH3hO at 510P C is a first-order process with a

rate constant of 6.8 x loa s-l(CH3)sOqd .} CHa6+ Hz(e)+COGy
If the initial pressure of (cH:)zo is 135 torr, wh:rt ii its pressure after I42o s?

n*r,

fe#rJ/o

* bnrortt'attort '

lnfrw\rolt =-kt t h[rorq)ro]

"
-d

(r fcUt3l'61'
-1a;+

= QfCl{l),OJt

r+24')+1"(r:5)
*- a - 1[.$tto*a)(

?ru*,..4 COb)rD" ,1,4+q(

&+"r /4>0s,

i
:'f
L i/ --.1

i^l

/'Pt

{-

c.l

lrtilnti rrre

c,j

11

rq.{a.

'1.

' k Inl^ fg]"

I l0,l-\nr,.;;1n

rt
vnI
w,
Y"

-ox\3 ,
, tt t

,ttl

(j, t:j

.f "t-rL l , i. Jl,

^ ,1,.(/\rl

iJ
l.|,{,

, ,.rc l,;,r],
r,'ii -'kf Al

/i

t,?

fl ( ( 1"{l'^'tff /

S'.1|
i,trf

r:

; t

lrl

---

( rxo

i.t

delurvtirti
nlsE

ta{6 = k-f AJ* tgJ "

' k[AJ'[sJ'

-i

- I

"!

m:l'n-. I
d.rt to tto\et*\o;15

(t

rn ratr d*ov*^*1frf
I

-.

lh

t cr vUt j^l :\ / ^
(.!7r
'{f,
j

oil - _:,

.l

lC\,"'icl

'

,'1.
t,';,; - f:r f

i.,l

' I

r ( .r t i

ri,

':r

.,

t,f

t-

-:rh i

ra{e: k llurt ."i. CB,l t

= k I t( d 3 t r . g g r J t

\r

l-, t'!
a

ior-J"
rn=l
ll:o

.t," y'- 1 r-,

5

, ,; t:: l. Cttlr,t f,'

"t
t

- , .r

\-

.;

-.

':!-

. , ( : . i t . ) 1O L I
')

'

/ r., zym(6,4)n

:k

i:; !1';1
,

i:::tt

A8
1. Thefollowfng
reaction
occursat ?FoC.?j.W+2W 1

g=

C
2tlaofl +

WD

"Bteojj@
4 . 0x 1 0

Et

3.2x 10
1 . 6x 1 0

'jotJ =o[,ro)"(

?e,=
9?'

8 . 0x 1 0

\--I
a)

1 . 2 8x 1 0

Describe
theorderfor-rp#n
*fu.
r"nO
,a+e=
kffhl'[ il"o]'

to
fi}st Jn" '6nfra
"erPct A
x setod, "'de,v u"*h reApct{o B .
\

b) calculatethe
raleconslanr.ry-The-reac(;ton
. , .i , . , ,
4 , 0 x t o - + =k ( o , r 0 f i o , i ; 1 t
;.= o,tF..rra
{
o l->
c) Writetheraleequarron. ) ^6rvrirt

.ate-_o,+ t N"-jI Hrolt

d) Cafculate
the ratefor Trial5
.lJxto-3aa
6!pla'3,y1s;t
m{p = O,t;-(0,30)(O,th)a=
e) Cafcutate
rheconcen-*:il4fven

thedaratromTriat6.

/,28xro-).-o,*LlU.I[o,y)-

A;.3
[N"J = p,).mo\

lL,ld^s

k = 62.1M'1s-1fora reaction
which
issecond
order
::1il,:r;"jt:,Tsfant reaction
forreactant
A,
(M/sec)
wr,"n
in"
iniii"r
.on.il;ff;
A
is0.0050
M.
ra{e. k r;lr!"
= s),1fi,ooSo;>
--

o.

/.55''o; I )rr,'3 s-l

2 Mnoa'+s Hzczo4+ 6 H*-+ z rilnz*+
10co2 + g Hzo

*
c,o,-PI,
ouP51" J:P
:""=u.rrr,H$=ffi

10
:Lt Lq:-il*l*r i-1-0**-IL--1,0
exlo
il
..3I1*0:_""."i1
-rxro
"1,.{+_
li*" jL__=9J-19:

#wlffir=ffi
1 . 2x 1 0

letftr {''

af,*,'

.t =)A
A=).

"_".,

((,o)'
? .: t,bxtoB k(rxrar)A1t*to9)o

3 . 5x 1 0

(1rrtrry( otL
Txto+T(I x{.-r)-A

reaoaq! .,, _
?^"^t',P?t!ilg"t"g7,.h
=ze'rc'fficrA =)B 9 B=r

,,^'tiiih;,H;K _un
rqfs.=kf u"o*]"lurtrd /
c) calcutate
therarelor Trial5.
rxto-l )
k(rxro-3)'(
7ru\ \, f,6xr0-3=
k = ) X(OS
*ot-'A*''r-, t'

$,,## =xil","'ttti:*[:;*
| = )c

_.r..-

ll}'htrd1
t*.^t5, = i"-,.01(1'rxro
rqte.tc*
t , or

(^uto*-s
-,
;3 ,
-t
,^,iJr1^9
^

eSlattn R red'rct;on'
awrAo4ox

Exercise:

1.Aqueouschlorine
dioxidedisproportionates
in an alkalinesolutionaccording
to the
+3
following
+b
equation.
-r
,.29loz(aq)+ zoH-(aq)
9lo3-(aq)+ cloi(aq) + Hzo(l)
(af+ Basedontheaboveequatiorfexplainwhatdo youunderstand
by thetermdrcproportionation.l2l

is a reacton *6efu
Disproporttonctton
"I """
""""3'

"""I"

iit

6artz ubstaltcz w&"qool o).tJdtm ud

(b) Theresultsof thekineticstudyof thedisproportionation

of aqueouschloridedioxideareshownin thetable
below.

-xperiment
number
1

0.0575

tOH-l/moldm-3
0.0216

0.0713

0.0216

[ClO2/moldm-3

Initialrate/moldm-3s-1
1.26x 1O-2

8.21x 10-3

3
0.0575
0.0333
1.26x 1O-2
(i)DeterminetheorderofreactionfoitheoiEroportonationotJ,..'s.t

, j D I l , r t x t o - )k=( 0 , 0 1 1 3 ) " { 0 o t ' 6 1 n

*Df 8.I x(o*=k (g,ohi)il(o,orb)^

- F izp :ig;ff), *=i:fi;i:

, u . q -3/ , , , , - 1
rate=kfcttl"l1 [orf'I'
/,fl yto3" k ( 0"0qfi)"( 0,0>lb)

;.ri=
ril,q(i rif^,,rri),t,ri

(ii)Calculate
rateconstant,
k, for thedisproportionation
of aqueouschlorinedioxide.

ll
r9 : htqrq:l:
t_ot
k: 1/ktyt-'ol,n!
S'
s.xIl:" : tr\!:q+jlll.qryl)
.rqoiJ

(iii)Calculate
thepH of theaqueouschlorinedioxideif itsconcentration
is 0.100moldm-3andthe initialrateof
-['5,0 foHl*
x 10-2motdm-3s-1.
Grrvg11
l*disproportio-nationis3.56
plt=
IOH , f oH =

rata
: ktsqJ[oH:J,
: {{l(9:19?)l[9t'],'p{!/: l:nrr(o-1911?)
' ?:??t!q-]
: 11
=
z
ior,rf;:0,0i,0
,iil,n-poH
"' r" '" /)rfq rj,F
;ih; ;;;;;;itif'

iiiil;ffi

"i

ru,o,
i;i; No;;;;o;;i 3ili i;;;;

;Jffi.

l^[Aft =-kt +ln[Al"

/rlN.ry

Fromthe graph , for the O""o.porition of N2O5,

(i) determinethe order of reaction,
F

nr$

o.def

(ii) calculatethe rate constant,

=l.bllto{ s-t

mt1 con:tonlc,
k :-ffiA tttL =
(iii)calculatethe half-life,

*y

t_-o$+i=h\bs

- lnL

t>

Kt

(iv) writethe rate equation

sJ
rcra=l,ii *touI N"o

3a) ln acid solution,bromideions are slowlyoxidisedto brominey'by bromate(V)ions as representedby the following
ionicequation.
BrOs- + 6H'+
sBi
)
3Br2 + 3HzO
ExperimentNumber

[BrOj ]/ moldm

[Bf ]/moldm

lnitialrateof reaction/mol dm-"s-'

[H- ]/moldm

0.400
0.280
0.031
0.031
0.600
0.280
0.600
0.031
0.560
4
0.400
0.062
0.280
The followingdatagivesthe.regiglt
temperature.
the
of fourexperiments
at constant
i)
Writetheivo naft-Stt"atonsfor theabovereaction.

1 . 2 9x 1 0
1 . 9 4x 1 0

2
3

I B'

- -+

B"r * )e-

3 . 8 7x 1 0
5 . 1 6x 1 0"

toxtAatron)/

--r !*:9 * 9: I Z
rlllrl9:9r-:!9:
kr&0s-1":!:::l:H:]:
nn\e=
ffi#: ffi :ltst)(Bffi)ll;3*):
't',q+xt0*":'f'D:6uo'\iif
"""""""*
ezt4t$f",

ii) Calculatethe orderof reactionwith respectto BrO3-. , Bf. and. H* , f5ns.

/'r4:!......!:)1
I19.1
...1
"....9.?!f

l:bgtI 15'
M\",I'

ffiffi'j:ffi:(ffi1
ns I

.. . ^

p =).

:: 1::::1T:: J*d/,wr
Tb'*;-

to-eOs

;tV d/;J-n;

&:

Thi;;;F
Nr!;*'";;1
:.,Y

4(b) Peroxyacetylnitrate(PAN) is an air pollutantformedin the photochemicalsmog"The concentrationof PAN in a

pollutedair
a sampleis
fs analysed
anafvsedat
25oC The resultsare olven In lhetable below
atZ5-CJ.

Time/min

Concentration
of PAN/10-10moldm-3

8.4

1 0 . 0 20.0
6.6

5.3

30.0

40.0

50.0 60.0

4.2

3.5

2.8

2,'l

(i)

't PA}d/l'o't r"{ }tn-3

1,x616p{vAtron

Deterriinegraphically
of PAN atZSoC.111
the orderof the decomposition

'0.0 3'0o 4b,o V'0,0 bb,O

s
l\r Q.stI'atT-L-t. 3o"D

-30,0=30"&.
T; i,;J il( f,Qts 5,9"9
(ii)

Eo'* ;s Cot ."der reaeheq,

Calculatethe-1ateconstantfor the decomposition

of PAN atZSoC. IZI
l, -- Q$41
lv
+'t^
.t.7.....

k:'S:qoF\!h:l
(iii)
Predictthe concentrationof PAN in air at 25oC after 90 minutes. [2]
rh
rI r
, ^\
":
3
1rto"o)=/o
;t.M;;ii fftp+^f"" rd,]; ; ll_{:'iJ_ll
rytd*: \ . . . .ll. . 1tt'. I . : . . . . . . . . . . . . . . . . . m o
5(b) (i) The mechanismof the decompositionof ozonein the stratosphereis proposedto occurvia two stepsas
follows:
t03#oz+o
step 1 ( fast)

o *

oj

k',

2oz

steP2(slow)

wherek1,k -1andk2 arethe rateconstants

for thereactions.
Writetheequation
for theoverallreaction,
andderivethe rateequation
for thedecomposition
of ozone.[6]

: ti*filg,fillffn*::i

4 o?oila
::dj "$**--+.:1f*@osrftc'1

r0

^ /'t$

Y\

A-t

$* . Pt-Y{
O.(c) Cycnlhpanedecomposes
intoprc'pene
throughtheringopeningof cyclopropane
according
to theequation
CsHo )
CH2=611611.
The rateconstant
forthedecomposition
is 15.12s-l at 400oc.
(i) Write the rateequationfor the decompositionof cyclopropane.

= tb,nt CrUrJ*
/
rc,.{a
(ii) Calculatethe half-lifeof cyclpropane.

t'' *r,'

t11

"/
o.o+bgs
ffi= e+O,q$

*.

(iii) lf 1.0 mol of cyclopropaneis introducedinto a 1 dm3container,what is the concentrationof cyclopropaneat 4OOoC

lr[gruJ
+h(l:9)
q,oulglt)
: _!lb:t])(

(iv)Whatis therelationship
betweencyclopropane
andpropene? t1l
thal qrQ t5ofne,1,5
......d.

(v) Namea chemical

compound,
otherthancyclopropane,
thatmaybe usedto producepropene t1l

ri*s*:t

ilo?af0\
"'

""1""1""

o{- a\cohor)

-"1. Propanone,CHaCOCH3,
re?ctSwith brominein acidicsolutionaccordingto the equation
H'
CH3COCH3a Brz
+ HBr
---)
CH3COCH2BT
A seriesof experimentswere carriedout to studythe rate of reactionbetweenCH3COCH3and Br2at room
temperatureTheresuIts of the experimentsare shown in the tablebelow.
Expeiment
/
Initialrate/
lcH3cocH3l
[BrzJl ^
lHcrl/^
number
mol dm"
moldm'
mol dm"
mol dm{ s-l
1
0.80
0.0010
0.20
3.4 x 10-"
2
0.80
0.0020
o.2a
3.4 x 10-3
?
1.60
0.0010
0.20
6.8 x 10-3
4
0.80
0.0010
0.40
6.8 x 10-3
(a)
Determinethe rate law for the reactionbetwepnCH3COCH3and Brr.
t8l

c( _ klusnupl^[+,1^[uufP4
ffi

, #XlS:GHft,

rcNs * rvLw\3ruLvr-3j
L->J L".-".:J..:...t.....e...w.!.r.r.|.....?FJE=:..;.\@.1..v,
"irFdi;tm3'-' 'U;8
;
lF= )n
r : ti!+tF ( *Sf;
slq-4me,.t
-1*l
tL=J

/
A > D. t / 1

./

ffiffiiIffiff.:tffi):ttsH):z
i .'o.'E(f)
;""'

"""'r

4;i _; ??)4
I2l
=-h[q111ao
a,tr1
rc!uEael7 ::k : p,q
il n:!-i4r1l- i
'1.........'...

(b)
tD)

Calculate
ualcurate
therate
tne
rateconstant,
constant,
k, lor
K,
for the
the reaction.
reaction.

3,4xro*.
k [o.so)(
o.>o)
(c)

Explainthe roleof HCI in the reaction.

.

t3I

)114.q
L|L[prcv,.J^i|+,,^^|;/i:A*tJ(,;;+,o.a$i+1;;;;,'!:1t5,/;
. . { . .... .. . .

i;i {:r"{trffi,k#:^4,t,Sh*in/rzt

(a,ioit,,l
tl

(iii)writetherateequation
for thereaction[1]

r - . . -1 )-

-h

r*z =,F#

117t20141

lCaHrl

11. (a) Explainthe termsrateequation,orderof reactionand rateconstant.

: k\,, l1ddtron
:L..q^..fl6t91 $ra| dlgd: *hg t1lar@
t1 ^155f1
'
"t .eqd\rrqctqrrt'
^
i
o
s\
Oder

,-+ '\\e reacttm ca+?on

reactrm i$S\
to a ;saetanrf ;; . .*\;
' . " " rerpac{. . ' . .p;";
..t..
""1'..'

;"

-*1..go,"^

"fJ

.*;^i; i*;tTH.;T:',.*,.';*;t-::#:*
o"; ;;
:q.^r.

(b)Ethylethanoate
undergoes
a stowacio-catarvluotnvoroivrir
i."*"i". dl!#ft
:^ -thz
CH3CO?C2H' + HrO

HCt

100
125

"?:y

a l td the followino results were obtainecl

0.200
0.152
0 . 11 5
0.088
0.067
0.051

75

+(^+

I CH3CO?H + C?H'OH

The reactionwas followedtwicewith differentconcentrations

S of HC
Time/ min.
With[HCl]=0.1 moldm-'
lethylethanoatel/ mol dm-3

0
25
50

+ ;;;.+;i[f

r-o\*'!

With IHC|]= 0.2 moldm-"

lethylethanoatel/ mol dm-3

0.200
0.115

0.067
0.038
0.022
0.013

L*fl,{gf0. b IlbJ166t}i3

*,rJJ
glil\-l

(ii)Useyourgraphs
1.
to showthatthereactionis firstorderwithrespectto theesrer,

Jr l"$ qet;g,dfo
lgtf !fu, lf s {,* q4<1M,thraee&
" t' ""

'
s*r
exot
\

5xr# -^\/ o . r t n
6.ri
0.1
71=
Ir-1.

r.61xro'>

rAtar

(iii)Deducethe rateequationand calculatethe rateconstant,givingits units.

natg
: hf cUsCr)*c"H
t) t+tct]

= k(0,>oo)(0 , ! )
bgO"'o-3
k = 0,1)b,ntol-'alms
mirfl
(c) Why is it not possibleto determinethe orderwith respectio waterin thisexperiment?

'fo

rema)n

for

r-tctetion,

Plottheexperimental
resultson the

-.ii) Explain,as fully as you can, why the experimentalresultsindicatethat the overallkineticsare first crd.er..

t\q+q..Jc'ta\
vdqrg OQ
,4t..*rlg.
srnrs
c'nl ut ,4".*!.b rbr.*jrd,H.r,.Jtlfiinph
"t

*M+:#ws*Fsd#"[,!=rfi{iiTl,#f
i;i,,wl#lffi,*r,I*reffi
-+e...qre1!3,'I;tpn
F+hqnpl
.'S..
used.inle.,q?,..q.(eal
fhsit:

.nT.e$e.lgl
.rgn{$...3p?ID.!:M?t

(c)(i)Calculate
howmanymoleYofgaswereproduced
in theexperiment,
conducted
at roomiemperature
and
3*3ff*pressure.

q:o0pc^l.,Ng."$.',nde...*Az=#*l.:?:t!.r.I.?".3&.rc!g'

j
c\
r
o
**
**
jf:,}
^[fffi;'J","*':;:.:^*;?iffiiflHffi'ffiti
ric,li-*,r,
(d)Thestudent
wishesto modifytheexperiment
bychanging
theconcentration
of theethanol.
(i)Explain,
withtheaidof an equation,
whywatershouldnotbe usedto dilutetheethanol.

"'"'.'u

-'NJ MrQ+ .Neol J fl*

i l:{t*g oat*lggf+.tt_^th u,atl o 8.n h*"-"St5^

(ii)Suggesta suitablesolventthe studentcoulduseto dilutethe ethanol.
\enzsro

t+

*o\er

"t$

6qqettorr

dotentined b5
StoithiolrnrG*a

;*fi$,*,8.r1

Forn stJctF sdqgaat McJ^a{srn

'-..,0rli'1'rqt)
(i) reaction
mecnGnism
is thesequernce
cf .#UlUTi
rilrEril,cily lreps
steps
tW

to
re ueUUilOe
describe
ihelgfmallon
ine
formation
pJ
OI fifeoUCIS.
andis pi.oposed
An(
Rrqducts,
step)

basedon rcte equation( vrhichconteinsonly the speciesihat are involvedin the r*te:- detera^tn;a
(ii) the rate- determiningstep is the siep with the highestactivationenergyor tne stoweststep
stepsmustgivethe overallbalancedstoiChiometric
equation
{iii)the surnof ali the individual
(i) by
order of
reaction
Orderof
reaction

Molecularity
( the no. of
species
involvedin
rate
deiermining
step)

I
Rate
determining
step

!f order o

lf orderof the reactionr. stoichiomelry;t

reaction,
.t <
- reaction
occursin morethan1 step

reaction,
1
- reaction
occuronlyin onestep
- eg.rate= k [RCH2Br][OHl

e.g:rate=k[(CH3[CBr]

--+
RCll>B.t ol.t RCilzOH
r B.-

-* (tLl)aLB, * 0H-+(tHr)rco tB."

elucrrton

Mechanism:

Mechanism:

B''
I fcrr.\t+
i;
aiHr)S&
+
:
oH'+
BrR(,,lrOH
RLI{&+
$?t
"t
'
sT", [M)t.noH'S'(cu.1rcoH

Mechanism

Stepsto
write
mechanism:

S#f*mfroffssd
nmsfr
rnlsrrs

1) check
whether
order cf
reaction

' iilethnltm
rocornf
HUsf
lwovenff
sfolcfiltrfdry
afnid,ofiffderyerfnonhflf
#hmrlrpd
ftate
lru
, fttfl?thry
fltl$Iadd
stfpJ
rplorrenflfshnmd
ryr#on

-|JlF

stoichio-

co#mrg
lsrnttrdy
due
hgchtrtysdortwhfan
CIgssr#
tarroruJ

metry

1P*9
.{ryryr,il{*jfhn,
ldeclnnlsm
fftlSlco#etafe
rfltrfiahkry

l write
the
overall
balanced
equation

f*te,ltiv;'$qfi

It

3) write
the ratedetermining
step ( it

mustbe
the same
as crder
of
reactionl
rate law)

S{*p ? i

rafe determining

@
Frop<rse l,rlt*c|lc,nissn :
. TCI + HZ* HCT + HI

siep fstow s6epj

= k{tclf

Expt Datawni'sdRare,Ls,o
SteSa

{Hzll

*r.eiac.atesrry

S{aw iRD$"!

balamce

Ctf
1.
Z.
3.

F$.r< l{ afte
! r r y rFroposed
vFees
.nrecf*r*isrn
rrser.r4+rt,
ecorrect?
4,
I gga
r
{
iLla
equatr.osril{*.fl _
lacJhcteps adds up to overellbalanced
E*ch step ls ti kely { i nvolva u ai& i nto,lecu lar corri.sionl lV j
SJow sfep fFOS.f is lfi same as exparimantatg. Rate i-.*
fA
G
Rt te Law fdr stow step BOS) = Expr Rrac Lgw
kftcqtfH2]: = k[tci]t [H2f

,Jl
f]:

, ,,-'

l-)

steps by
existing
an
intermedi
ate I
transition
state
making
sure that
the sum
of all the
individual
steps
must give
the
overall
balanced
equation

Eg. For the reaction: NOz + ^ CO )

The ratelaw is : rate = k[NCz]'
Suggesta mechanig6n
for the reaction.

tS
Sr.n f : )N01

NO + COz

r )il101-+ N0 t NOs

+ co-> N O r + f o r
N03

I NO -rcoe

co+Qff> tor'to
"{rir o*ND:E No:
sr?ar

Eg. For the reaction: 2HzOz)

2HzO * Oz whichis catalysedby iodideion.
The rate law is : rate = k[HzOz][l-]

0
f
-;m'",tb"jT''He'
s*?fl'6\ ' t o r
:
+

Stq)

4r0l

+P1r6

1O- B'1-

E g . . F o r t h e r e a c t i o n : l N O+ - B r 2 )
The ratelaw is : rate = k[NO]'
Suggesta mechanism
for the reaction.

co*d!.st chelY ttta P"S%'

2NOBr

Stepl: }NO &5. AUO,

s*t,

MOrt 8,,1 )NOtr

'txercise:

r*te=tfAB]"[sJ^;.1t

+ B z in the presence
The initialratesdeterminedfor the reaction: A B + B
)A
of a catalystC, at varying
concentrationof reactantsand
are
rn the tablebelow
l A B l /m o l d m - '
l B l/ m o l d m
lCl / moldm
lnitialrate/ moldm-" min-'

2.0
2.0
4.0
2.0

2.0
2.4
2.0
1.0

2.0
1.0
1.0
2.0
''(he

2.0
1.0
1.0
4.0

rtaetron rS {.'st 'rdar

urrth rer Fc+-b c

t""""'

1\e.q.*.:T: {.,"1ad1 ^nh..-lc+

{oB.
: ffr =(g)m ) rvr= 0 . llro-.eaeto615 Tero aier ^*f
:3f."t. u: R:
e l:l

rq'fe= k[rl[c]

'n"";;.i;;i;;il;;;;;;, ;";iyil;i;"; i;; i"i;;;;;;;i;present.

ioii,es.=iiz-"Gp

ral*r:.5!Pt :

S{ep}
't"" :

B{c -r BC

ABtBc+ C+B"+A

. . . a . ' tW.v:fd ....... .....1 $

ralerd{reaction
between3rgy6one,
Cft999H3 andicding.dgive
iodopropanone,
CH3COCH2I
, isfouncj
f. !a)fne

to be indeper{dent
of [2], but directlydroportionalto [H. ] and diregtly-glryrtional to [propanone].
(i) Constructthe balancedstoicTr-6mEtric
eduetionfor the overa!ireaction.

f. * uthl{s .t 1r -?

CilsC0Cil:T

+ )H* +J-

(ii)Vvritethe ral.eequationfor this reection,and statethe cverallorderand the unitsof the rate.consiant

ta{a
: ktH:ltgl:*^il

Ur{tS ,+ $V a^{rat* = mol''c)m3 Sa

we-^ll *da( = l+l :) '

(iiii Suggesivrithreasonsvyhichof the fu.llowu',g

t-.;opossiblemechanisme,
A or B, fits tl-reobserveokineticdaia (X and
Y ere inlermediates):
1
I

+1..

X
CF.-CI3Ct-i-Y

(*low)

+ F:"

Cli.CCCFt.

a l-

i l-t'

pro'cucls

(tasii

(s lcv;rl

Fr(:.ii:la

(fasti

I
a

t
;

v-4+<et

t:

iY.

n is-Atttf' A r ' ppprterst

1" ' ''l "' .''
tp F]l ond[cilaoof'J
, :lly

one H4 qnd

,n. *.]3: d:terl:liXXs+gXlthgslo,,r$ry),

g? 11r19\rgl
't{:,;ioali;T";"s'H+'+'I."'

cvfBcoctU
ii; + ir+>'

arodrct,

't"""""'

hVp)yq
.b,nilg-,
.J:.n .?eto.
*7*r *.fh *p ec*

to brom,'ng.$

concerrtcaton

"(

B.. do.s ^ot

....tl't s.t.+lt...-t*. d .q"*91:..

-- -SOs.
_;b)Oxidesof nitrogenin the atmospherecontributeto the formationof acid rain by catalysingthe olidationof SO2to
Write equationsto show how this occurs,and describethe type of catalysisobservedhere. 250' t Or -> :S03.

re
a.stiYation

enerlgy

raE csnstant
\Y

\*
:

racbr

fiequsrcy
pre-exp(]nenjal

t*k:rs-rA-Ea

Agl\/
I

lC*

t\

fa:br

Mn ErnPeratrre

grrqcr:nsa'rt s3\ Jrnol-' K-\

.

-tf

/nK=-F(7)+lnf\
""'.
Kt',

Ff-r-

* : rosrA - =:===*--

V
N

-==-*e

\
mathEmaticaj
quantity. e
F
rr

(or

-Ea
RT -kel

'^t
.1
t--qo'*:
>*/r-'
|
t-1. ,

fa

'}l.^
l n, kat

Uses of Arrhenius
Effect of T & catalyst on rate constant, k
1. Whentemperature
increases,
2 Catalystlowersthe activaiionenergy.
k incfdSes
rate imr?ases
So, k lncreaEeS -, rate ----$g!ggsl

23O

21O

Rcte -nsf-ard-,k , on\ @

25C

qr T a.,.J ."t-!s*
tt

.\,\

(b) Determination
of activationenergy
(i) Formulamethod

[nk2

[nk1

__t

\tN

1l
Tr)

kr

,,4,'

.l^
---{ ,

{
R = 8.31J mol-1Kr

L,

Eg. In a reaction,rateconstantsare 2.3 x 10-3s-l and 4.3 x 10'2s-l at 2OoCand 90oCrespectively.

What is the
activationenergyof the reaction?

+\l
hY. - Br+
fi\Tr-T,

"'kr

r-\
t - l t g r d , 3 ) =-- F o t r
a(-ffiffi
/' frl f r*+r,3) ,t*tt6/
F o = 3 6 q 1 3 , bl

=36.q14kf x 31tJ.^"\-\
To determinethe rateconstantat certaintemperature

7'

Ea

k"

eg. In a reaction,the activationenergyis 275 kJ mofl. The rate constantat 400oCis 1.16x 10{ s-1.What is the rate
constantat 450oC?
hIt
Eqr r
.It
, kt

1"4 =- R-(T, - T,)

-^*__*rr)
/h(,qS ), - #= (o*-*r,
rr{z oons*ar* *f 4b0'C, kr = 3,48 tlo*

a-r

(ii) GraphicalMethod:

-Ea. 1
RT

lnk-lnA+
Y=

|TIX

Make a plot of In k vs, 1/T

Slope = -EalR
Ea=-slopexR
R - 8-314 J/K-mcl

Ea= -{-12247)x8_314
= 1 A 2 , O O OJ
= 1O2 kJ

tQ
tL)

txerctSe:
1 { b ) T h e a c t i v a t ieonne r g yE, , , o f a r e a c t i o n c abne c a l c u l a t e d f r otrhne A r r h e n i u s e q u a t iko=n A e - E d : l r , w h e r e r < =
rateconstant,R = gasconstant,T =temperatura,
A = frequencyfactor,
ln an investigation,
the rateconstantsfor the gas-phasedecomposition
of dinitrogenoxideintoits elamentsare
(Q5b/2005)
measuredat fivedifferenttemoeratures.The resultsare shournin the table
ln
kls-'
T/K
-3
838
1.10x10-'*h
/' lq'rlo-5
-' -C
?ql xto
1001
3 . 8 0x 1 0
-' -0
*ro-+
Q'11
I UJU
E . 7 ' xl 1 0
r3, 8
{.bo rto
1053
1 . 6 7 0 . st3
-+
8.S1xro
9.+.1
1125
11.5
graphically
Determine
the activation
energyof the decomposition
of dinitrogen
oxide. Writean equationfor the
and statathe orderof thisreaction. t8l

+ lk'.

6s

tnh"
tnA- F(+).

-7

-q

-b

-?
ll.lr0 -+ lNz * 0'
ae"rl

on unrt.rPK | '+v. rta&on

: #*:dr

^fft h N,0.

2. At 45'C and 70oC, the first order rate constantsof a reactionare 1.79x
is the enthalpyof activation?
[ R = 8.31J mol-lKl1

rot6
,.0 +.15;io;;ti ;;;p".ii""rv.
ffi"l

t\

ro{r13/

Ea = tll l t+15
= ll1k5 ^ol''
3.il; ffi;;i;.';q;"ii"' i" gi";; [ :o;'e;'ii.A;"il;; n"pJ""'i7til;; i;;l;; ;l s;"cil;; ;irt;b
"'
Calculatethe activation
enerjy, in kJ.mol-l,
for thisreaction. [GasconstantR = 8.31J Kt mol-1] l16t2}O4l

{r(=t: - Fft("im-r-"1)
Eq

: 818>1
J

= 81,5
k5 . ^ot-t
tQ

!l

4 Variationof ihe rateconstanlwithtemperature

fcrthe reactionA )

Temoerature
iK
x
298
3,35 )-r
308
3.!ts ro
318
3,r+x D : 3
3,oB to-3
32A

a R b b-3

28 + c it 5

Rateconstant/s-'
1 . 7 4x 1 0 b
6.61x 10-'
2 . 5 1x 1 0 7 . 5 9x 1 0 *

2 . 4 0x 1 0 "

338

(a)(i)Whatis meantby rateconstant? [1]

tabre
berow
T"?;Un"
-t0,qs
-q.L)

-s.>1
-'1,E

- 6 ,o 3 .

qqnp*qntgS .qry_pqdlflqlrtV
&trlgen+hereqcf,sr rctta otd fiiz
..tgi(..ctrs91l{..1)....^.

(ii)What
istheorderof thisreaction?
Justify;lr.';.;;;

i;fhnae^*J+i;

"+

.eqetonts 'tl.c^+qr lii alk'e$stron'

fLe.....ea..{,qn..:1...$$..
Si"s*gder g.7.r.o,r....!...g:'
.
.gde{..1aifh
..31?g1t..to..A1.
.R1te..cD.^.*4.^r.
"t
(b) (DBy plottinga graphof ln k against1/T, determinethe activationenergyfor the reactionabove.
.,
!
r
hbt__,/l -..,
,

f/x'o-rK

kJ *u\-'

(ii) Basedon the graphwhich you have plofted,calculatethe half-lifeof the abovereactionat 300 K.
-l

T= 3ook'
=r;;;.;..;;-i

,{= g.?5xro-S
+.; -a6q3 ;:;^;

[4]

[19/2015]

.tfi
{21- \./

PqctioA'

a*a\tc

p{p,rat s'$e
sarne

qenefiL\
'
honlo
heterp
artto

,t4{rfit.
^
'd$et+
catktgst
pvnd..rce

i-occursvrherir:6[|ystandi-occr.lr"sv,,.irgpcat3iystancireecrantl-@uctsof|
reactants
arein_gd\g--arein-M.
phl,sicalstatej
I
*'"
iuu"tion
is
a
catatysiforih;|
Physii:alstate.
re"ction.
i
|
i
transitionelementsare
- Transitio.metalsi ccmpouncis
(because j zrrrnoor Sceor2_t-16H*
I Elg{gggrouscatarvst

il."ffi;ffi,

lt@sin

\irc**i1'

e ' g,ffi.::l^,.i
1: 2l-'+szoaz-i

l z + z s , a t i I e .-g :i ' { 3 *'r1l

t.^-.--Il
tci)
,ir
r r^X)
tfe3 |
t=-.=---Jf.i.-{al
I ..it6

trodilct:catalvst

|r = , . a t e i n c r e a s e _s a s c a t a l y s t i s p r o d u c e
Ratedecreases'
|
because

l*dsorption:
I'

Fe3*ascaiai*!

-;zco,1-i{r,i-ibH,o

zni

H-tt
i-r
".csorpi:on:
i:I
__ia

the

I rate

,^..*Jtt+

|tnt".
*
Tlwexa
,]
rJ'+,[q,r+a" +)F.ot i
f
inxfu^tr_*
*lNtn:"H;:"T[T:i::JffJfiT
\={
aFe'*
2s0+1t \0i-+ rF.e*'I cataivel'This
i
i

- t^to"ken
thebonds
in i
(rq,cta
themotecutes t)
I
- -i1g""6e-- theconcentration
- - of
- I
I|
i

T
I
i|

|
I

time
|\
rni<ti"rrot"
istow,
producucatalvst
i""*use
rsnotproducedl,sl

the reactants

InBrea:icn
sBF$cnly

flecreares.
Fe'*-escgielyg!
:
medn4n,:d1

mrEentahl
oliea&{

eI-+ x Ee"g )Eon+"t-i

I" I

\r,.orho\reacF,on

Hence,actirrationenergy

)8"++ S"0r"-i93)Fe3l

i
I

Reaction: H

F,f---f-l

+..."."-^:_

,t/

afi fienspsecis
up

::

Nicket 7 /

3. Deadsorpiion.

^q

e.g 2:

ZSOa{g).C}2(g,t)2SO3(g)

- the productmcleculesbreakawa,,'
from ihe surfaceof catalyst
- this sunace is now free for further
adsorptionof reactantrnolecules

Fcr other reactions,

ilmtalan |
rf*echqfi
I

Ir'

nzchan,Srn:

50r*M,i

thpEafoofishlsqrdilt

t\

5t} * ttO

t\

N 0 + 5 . 0 2+ N O z

. ai-rttiisilr',t
dlvriart*lrtqila!i'

I
i
I
I
I

--l_

r'-' 1
;1. I

^,

4rt+X!

t\rrarullg*-l

fli.

-*t*"

It9"-"*ir/,

.o.idr1s'c'

i-

1cc,d,1n.
r.'<'('d4

4 2t*-

,. ) rearJ,ov ( o'dtnnt
[--_*
Exercise:
1(b) (i) Niirogen tnonoxide ls used l,rsa catali'st in the Conlact process. The niechalnisn,suggesierJis as folloivs

+ 9^ -__B' zNC2(9)
3NO(g)
+ So3(s)
or(g) + So2 ----+
ir{o(g7
Descr;be
hownitrogen
monoxide
actsas e cataivst.

qrts

JSort 0o --

ccFal,4stin
' .N*wqar
; ' . . . 9 . ' . ; . .rnonoxicl
' ' ' . . . . . . : i . . . . . ' . . . . ' ' . . as
. . . . ' . t J . .[oriloeene-alS
.';9.'.,....

J* catalqses
fla

) S0: .

tle reachbn,

"ffiffin|,l
Kadr,o bq .lnnq,4qiB ox'/ctron s-qf

....'...'.'....*|.'J....''.''.t}'.C'}........''.."..:....,.:.'.j."..;..'.....:.*..'Y.'

fo + 4 *

..nNp'-..;J..ii:,in'I.j'.j4-',l.Nq,
yAan"tle qrcatql@reactrfil
..11k..9..S.ftp.6_.
i^1ldyp"l
_hsue
!?l%..g.f:V*.g.I.Q{W!t

(i;) Platinun,
idalsousedas a caialystin theContactprocess.
platinumactsas iiatalyst in this
DescTide-how
(a8b/2CC3)
F'rocess. t01

I*rvr-3* s t lggpseri::d** lSy: T 3 I-l:fT gT* \:: nfy

sorand0r
. .9:Ft].911....i.L..t'kn1.9....$*.1..
J.t..*Xl...S:..s'Etrt.
er-brtqlr.
1l l&q.b +he
'rts
N\o\eule cn
sretace \
\

""'l'):t.-""'

;"
{ H(' H*",i"''; i;,-;Jl;

lorrninq fumpocarq b"tds. Msorptr66 t^rcql.enthe lon,ls

^*filril;il;
...,,'+i -,',r,**,
....+l' . .. .. .'. .

.....I*:tt*'.te.{3.,...*dsr$:v.1..
*he...i.s".*x:...Ss...naq9t.tss.,.o.s...?i.I!g...
...Jk r.l*t}-t-..
n:klde..:1..
...y*.*.......qi.4d:et;.!.:..t!*..t*..
hytd.k...t*..hr.N
2. (b) The decomposition
of aqueoushvdrogenperoxidecan be acceieratedby the additionof a smallamountof acidic.

ofsodium
solution
brcmicle
ThlptatrsissteRsfr'eas
fo"itlto
Brz +

HzQz

zBi +

2H:' .-

horaogmzna catn$lrs

(tul zooe)

Or

(i) Writean overallequationforthe aboveexothermicreaction. tl j

. .*I:Q?..
: r'4'Qt Q:

(ii) Sketchand labelthe energyprofiiesfcr the catalysedand uncatalysecj

reactionscn the axes hrelow.
energy

f4 crc4 Qrt
t r c**allsed'

{.,-ro t.abS " {.roS-}cp5

.l

Ca{ntpo6 tcac+.oA

fieactioncoordinate
(iii)Statetlo crbsen,si;or)s
{ot itr+calalysedrear:ticn. tz

. : ..Ff|gyr3;r%r.4qyf
l A .qr x rdsqvd.
-

"'

tolowLaas to\rrtrqn

""'u.'..""r'|!,.r'r1""'|-'.!'

tqr,r/
"'-7"

bo,ayt a,vl 'lqrns

colov.rle*;s

'Sain,

(il')Otherthancaial-r.si
aricrc.llcertiraiion,staiehov,yoi;v,,ou1o
inc;rease
iire ratecf iec:o,riposition
cf hyo'roge
r,
F e l c x r d eI i l
|

-t
.
Increa.Y+he +o$Def,d\\lP
't

""

)t"

);,