LJ r r.u\dv,.-3
ig,flX#.
h exa|/l
Topic5: ReactionKinetics
-JIAI
E
Cowntrattbn
dforoduc0
dt
Rate = -
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#
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=-Ei'.
l/,1.,,^_.
:4x(O*nol alla-\g-t
.nstarfuansralz
at
t--o .
_ /_
&_+?g_:_
lnrt;nporlorrgS
(ii) instantaneous
rate
= chanqein I I
time taken
(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 $r
Ttre
lo:rar
no
racton {o o&ur
c claisioxr,.rth.e
errergefic
or5r,
suffrcient
J--
66rflisis11
errergterH.c
:gffii.L.*;-ffid;*
reacfi.orr
*,*h cornect
onentqtor
chaga "t
AH= e^ttv^lpl
o. re(d'bn'
>
t\
el
g
GD
g
a,
F*
G'
s.
tu
<t
I.L
1e
at
^o/Ao"lltg
(}
&
h5\.er^erej*
releosed
6^lerff
f,lei:ction
FGactsnts
ale
not stqtle.
Prtegness
:,P
tTm
(ii)corfcentration
or pressure
I size
or
'smaller
particle
sZe,
-total
surfacr
area
exposed
to collision
increases
)reases
-frequenry
equency
of collision
increases
-fiequency
of
effective
collision
increases
-r dtE
Increases
ofsas
tlt
Progre=s
ra\ax)
x utl'/l t?,rnP;rczeset7'C
LJVr%\
ic
(+aH).
e J,t^5*^'
(iv) * Catalyst
(iii) Temperature
EoC
+vacatatXs-f
Trf'flf
R4 Po.El
For higherconcentration,
totalno. of particlesper unit
volumeincreases
f requencyof collisions
increases
frequencyof effective
collisions
increases
rate increases
R.erection
Endorlrerrn
neo.ction
H}a'"--(-AH)
rticle
.tvc.Ac r l'A
"l
= Fo - Al-l
I
n r
I
I
\
lEa*/ocaarrsr
,,",n,|_-y'^\Ilo'gn"
lReirrLe;rs
\\
lo.,t"r*ocatalys:\
urrm{el7st
lFelh#rl
ffi;?rRssctioo
Coordinate
= FewccEision:
Lowconcentration
I
|At
'
AH fu notcneT
E
1&
, rth
>F.'
ov\
tOtc
-'rrcret*
MT
Yata {}'
(rH)
neclwnism
at,la*'on
ll.'le
MAnequationthatshowsthedependenc$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.^
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.
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
re r r=\<
zetDnAer
2. By using
graph [A] vs. t
LUt
finear
equation
tl
t\
"zr' FJk
L\
t;\
t&i i\---_
Lutc'
4{
fy,=mstc,rt
t:i\
{-i
3. By using
.*kfef'
5lda*
J (tstr,; = I'd+
.t A_(
\+
.=kIA-l
r6t Jer
,-^{* l$ry,-fi=..,
-4
tet'ft'fe
,o^st(nF
= ls+ 6rde.r
l.\-'
t,li;j["$#f**r.ra1 +ffi,
&.Ac ctr.
t>O.
'u-'L<'
TE " P1
$+
[n]r-.-kttrnl"
inlnlr.-tt*hfd
t^Ial:
4. By using
initial rate
->t
Compare
2 experiments:
Initialrateremainsconstant
whenconcentration
of
reactant
is doubled
Compare
2 experiments:
initialrate
is doubled
when
concentration
of reactant
is
doubled
lAl;:M Rate;M/s
lA1,M
Compare2 experiments:
initialrateis x4 when
concentration
of reactant
is
doubled
Rate,M/s
lN, M
11
22
33
11
21
31
Rate,M/s
t1
24
39
or
ratet= k[AlrmfBrrq , ":1,':
.",:i3.lt:
-1
.rqjrrt
rate2=k[A]2m[B]2n i ' - r.
.By
"#; . 'g- D
e.g:
A+B
JnoA molecules
in slowstep rnolecularity
in - reactionis zeroorderwith
'
respectto A
the ratedetermining
stepgivesthe
numberof
molecules
involvedin the
raledetermining
step in
mechanism.
r-laa{1
mJ*e
Je\cr tu'{t4n\ rca't(,n
dP
6. By using
unlts of raie
constant, k
-> Prod.tn1-5'
AtR ->
AtB
i*"n
J*'+
slow
twoA moleculesandoneB
molecule
in slowstep
reactionis 2noorderwith
respectto A and1'torder
withresoectto B.
s-r
lr,.-3
nno\
?- .r.+"=ffnlftJ
2A+B
"na*e
A -.-...--+prodrrcts
A + A -""---.*prt>dr,rcts
A + B_+p$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:
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$ltcl
ffi
k=ffi"
t,^nrt4 k.
6ol-'rft3
5-l
eg1.
Exoeriment
1
lAl/moldm"
0.100
0.100
0.300
lBl/ moldm-'
0.100
0.200
0.100
Initialrate
/ moldmos-'
4.0x 10-5
4 . 0x 1 0 1.
ro*s=P[n1^[e]^
E"pO 4.ovro-5= hfo.,oo)q(
oroo)^
expO
+',
4.oxto-=
Sk ( o . r o o ) q ( o . r o o ) "
'(oim)/' 9n=o
Difftrential
ratelaw
3.6x 10"7
constanl
\ O,too
"', k
nn =)
ZerothOrder
FirstOrder
Rate=-43-=*tft
SecondOrder
4Bl--{nlz
Concentration
vs.time
c
.e
F
p
:(lJ
:IJ
E
c
ol
U
Straight-line
plot
to determine
rate
constant
rO
-9
f
c,
a)
I
.o
(,
.t,
o
g
'o
U
M
[AJi,,
Rate,M/s
lA),M
1
2
3
2
3
n'=#
#=rfr**
lAl=[A]0.-k
or
lnlAl= ln[]e- kt
[A]=ffis- kt
iv
:c
Relativerate
vs.concentration
:c,
(J
Integrated
ratelaw
.g
(u
Rate,
M/s
I
2
0.693
. -ntn=
M/s
[A1,M Rate,
I
2
3
1
4
9
f,,r=
6fu0
M-1is-r
ontql" rJJ
Zero order
Rate constant /
unit
needn
morrioisa
Firstorder
k=r4Al.
ay,
Second order
k =dtal.
k = Q',b13
T',/r_
uArt"tK= *o\Jr"3S-'
i,m**
k=
-f
Examples:
l.
Orgl + NOze)
at a certain
,= l"=kf.J*
lOl (atoms/cm"
5.O x 1O'
0
1-Ox lO-"
2 , Ax l A '
3.Ox 1O-'
1.9 x lO'
6.8 x 1O-
2.5 x 1O"
(,i\ /
-,( . r .
!il/'o-':4ol
fol nolcmS
8.31xroa5;:r$
3,15xr o- ' s N
l,l3 xto-i5
,*,,i^',o*b \- ,
io {tu
[*d
-?
.,"-3
\,
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?
@) How-long
glcrn'?
concentration
ln(hq$i1)
=-(l'r+b)t+
;Iza*t)
"+= o.jeJeo,
n*r,
fe#rJ/o
* bnrortt'attort '
(r fcUt3l'61'
-1a;+
= QfCl{l),OJt
r+24')+1"(r:5)
*- a - 1[.$tto*a)(
i
:'f
L i/ --.1
i^l
/'Pt
{-
c.l
lrtilnti rrre
c,j
11
rq.{a.
'1.
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
' 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
\r
l-, t'!
a
ior-J"
rn=l
ll:o
- , .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
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.
*
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'
$,,## =xil","'ttti:*[:;*
| = )c
_.r..-
ll}'htrd1
t*.^t5, = i"-,.01(1'rxro
rqte.tc*
t , or
(^uto*-s
-,
;3 ,
-t
,^,iJr1^9
^
eSlattn R red'rct;on'
awrAo4ox
Exercise:
1.Aqueouschlorine
dioxidedisproportionates
in an alkalinesolutionaccording
to the
+3
following
+b
equation.
-r
,.29loz(aq)+ zoH-(aq)
9lo3-(aq)+ cloi(aq) + Hzo(l)
(af+ Basedontheaboveequatiorfexplainwhatdo youunderstand
by thetermdrcproportionation.l2l
is a reacton *6efu
Disproporttonctton
"I """
""""3'
"""I"
iit
-xperiment
number
1
0.0575
tOH-l/moldm-3
0.0216
0.0713
0.0216
[ClO2/moldm-3
Initialrate/moldm-3s-1
1.26x 1O-2
8.21x 10-3
3
0.0575
0.0333
1.26x 1O-2
(i)DeterminetheorderofreactionfoitheoiEroportonationotJ,..'s.t
, u . q -3/ , , , , - 1
rate=kfcttl"l1 [orf'I'
/,fl yto3" k ( 0"0qfi)"( 0,0>lb)
;.ri=
ril,q(i rif^,,rri),t,ri
(ii)Calculate
rateconstant,
k, for thedisproportionation
of aqueouschlorinedioxide.
ll
r9 : htqrq:l:
t_ot
k: 1/ktyt-'ol,n!
S'
s.xIl:" : tr\!:q+jlll.qryl)
.rqoiJ
(iii)Calculate
thepH of theaqueouschlorinedioxideif itsconcentration
is 0.100moldm-3andthe initialrateof
-['5,0 foHl*
x 10-2motdm-3s-1.
Grrvg11
l*disproportio-nationis3.56
plt=
IOH , f oH =
rata
: ktsqJ[oH:J,
: {{l(9:19?)l[9t'],'p{!/: l:nrr(o-1911?)
' ?:??t!q-]
: 11
=
z
ior,rf;:0,0i,0
,iil,n-poH
"' r" '" /)rfq rj,F
;ih; ;;;;;;itif'
iiiil;ffi
"i
ru,o,
i;i; No;;;;o;;i 3ili i;;;;
;Jffi.
/rlN.ry
nr$
o.def
=l.bllto{ s-t
mt1 con:tonlc,
k :-ffiA tttL =
(iii)calculatethe half-life,
*y
t_-o$+i=h\bs
- lnL
t>
Kt
sJ
rcra=l,ii *touI N"o
3a) ln acid solution,bromideions are slowlyoxidisedto brominey'by bromate(V)ions as representedby the following
ionicequation.
BrOs- + 6H'+
sBi
)
3Br2 + 3HzO
ExperimentNumber
[BrOj ]/ moldm
[Bf ]/moldm
[H- ]/moldm
0.400
0.280
0.031
0.031
0.600
0.280
0.600
0.031
0.560
4
0.400
0.062
0.280
The followingdatagivesthe.regiglt
temperature.
the
of fourexperiments
at constant
i)
Writetheivo naft-Stt"atonsfor theabovereaction.
1 . 2 9x 1 0
1 . 9 4x 1 0
2
3
I B'
- -+
B"r * )e-
3 . 8 7x 1 0
5 . 1 6x 1 0"
toxtAatron)/
--r !*:9 * 9: I Z
rlllrl9:9r-:!9:
kr&0s-1":!:::l:H:]:
nn\e=
ffi#: ffi :ltst)(Bffi)ll;3*):
't',q+xt0*":'f'D:6uo'\iif
"""""""*
ezt4t$f",
/'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
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)
Deterriinegraphically
of PAN atZSoC.111
the orderof the decomposition
s
l\r Q.stI'atT-L-t. 3o"D
-30,0=30"&.
T; i,;J il( f,Qts 5,9"9
(ii)
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)
: 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.
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)
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
: k\,, l1ddtron
:L..q^..fl6t91 $ra| dlgd: *hg t1lar@
t1 ^155f1
'
"t .eqd\rrqctqrrt'
^
i
o
s\
Oder
reactrm i$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
0.200
0.152
0 . 11 5
0.088
0.067
0.051
75
+(^+
I CH3CO?H + C?H'OH
0
25
50
+ ;;;.+;i[f
r-o\*'!
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
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."$.',nde...*Az=#*l.:?:t!.r.I.?".3&.rc!g'
j
c\
r
o
**
**
jf:,}
^[fffi;'J","*':;:.:^*;?iffiiflHffi'ffiti
ric,li-*,r,
(d)Thestudent
wishesto modifytheexperiment
bychanging
theconcentration
of theethanol.
(i)Explain,
withtheaidof an equation,
whywatershouldnotbe usedto dilutetheethanol.
"'"'.'u
t+
*o\er
"t$
6qqettorr
dotentined b5
StoithiolrnrG*a
;*fi$,*,8.r1
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
reaction,
1
- reaction
occuronlyin onestep
- eg.rate= k [RCH2Br][OHl
e.g:rate=k[(CH3[CBr]
--+
RCll>B.t ol.t RCilzOH
r B.-
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;'$qfi
It
3) write
the ratedetermining
step ( it
mustbe
the same
as crder
of
reactionl
rate law)
S{*p ? i
rafe determining
@
Frop<rse l,rlt*c|lc,nissn :
. TCI + HZ* HCT + HI
Expt Datawni'sdRare,Ls,o
SteSa
{Hzll
*r.eiac.atesrry
S{aw iRD$"!
balamce
Ctf
1.
Z.
3.
F$.r< l{ afte
! r r y rFroposed
vFees
.nrecf*r*isrn
rrser.r4+rt,
ecorrect?
4,
I gga
r
{
iLla
equatr.osril{*.fl _
lacJhcteps adds up to overellbalanced
E*ch step ls ti kely { i nvolva u ai& i nto,lecu lar corri.sionl lV j
SJow sfep fFOS.f is lfi same as exparimantatg. Rate i-.*
fA
G
Rt te Law fdr stow step BOS) = Expr Rrac Lgw
kftcqtfH2]: = k[tci]t [H2f
,Jl
f]:
, ,,-'
l-)
steps by
existing
an
intermedi
ate I
transition
state
making
sure that
the sum
of all the
individual
steps
must give
the
overall
balanced
equation
tS
Sr.n f : )N01
NO + COz
r )il101-+ N0 t NOs
+ co-> N O r + f o r
N03
I NO -rcoe
co+Qff> tor'to
"{rir o*ND:E No:
sr?ar
0
f
-;m'",tb"jT''He'
s*?fl'6\ ' t o r
:
+
Stq)
4r0l
+P1r6
1O- B'1-
E g . . F o r t h e r e a c t i o n : l N O+ - B r 2 )
The ratelaw is : rate = k[NO]'
Suggesta mechanism
for the reaction.
2NOBr
s*t,
'txercise:
r*te=tfAB]"[sJ^;.1t
+ B z in the presence
The initialratesdeterminedfor the reaction: A B + B
)A
of a catalystC, at varying
concentrationof reactantsand
are
rn the tablebelow
l A B l /m o l d m - '
l B l/ m o l d m
lCl / moldm
lnitialrate/ moldm-" min-'
2.0
2.0
4.0
2.0
2.0
2.4
2.0
1.0
2.0
1.0
1.0
2.0
''(he
2.0
1.0
1.0
4.0
rq'fe= k[rl[c]
ral*r:.5!Pt :
S{ep}
't"" :
B{c -r BC
ABtBc+ C+B"+A
to be indeper{dent
of [2], but directlydroportionalto [H. ] and diregtly-glryrtional to [propanone].
(i) Constructthe balancedstoicTr-6mEtric
eduetionfor the overa!ireaction.
f. * uthl{s .t 1r -?
CilsC0Cil:T
+ )H* +J-
(ii)Vvritethe ral.eequationfor this reection,and statethe cverallorderand the unitsof the rate.consiant
ta{a
: ktH:ltgl:*^il
+1..
X
CF.-CI3Ct-i-Y
(*low)
+ F:"
Cli.CCCFt.
a l-
i l-t'
pro'cucls
(tasii
(s lcv;rl
Fr(:.ii:la
(fasti
I
a
t
;
v-4+<et
t:
iY.
one H4 qnd
cvfBcoctU
ii; + ir+>'
arodrct,
't"""""'
hVp)yq
.b,nilg-,
.J:.n .?eto.
*7*r *.fh *p ec*
to brom,'ng.$
concerrtcaton
"(
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
-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
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,
+\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
-^*__*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
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
: #*: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
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
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;
"+
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
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$cnly
flecreares.
Fe'*-escgielyg!
:
medn4n,:d1
mrEentahl
oliea&{
\r,.orho\reacF,on
Hence,actirrationenergy
)8"++ S"0r"-i93)Fe3l
i
I
Reaction: H
F,f---f-l
+..."."-^:_
,t/
afi fienspsecis
up
::
Nicket 7 /
3. Deadsorpiion.
^q
e.g 2:
ZSOa{g).C}2(g,t)2SO3(g)
- the productmcleculesbreakawa,,'
from ihe surfaceof catalyst
- this sunace is now free for further
adsorptionof reactantrnolecules
Ir'
nzchan,Srn:
50r*M,i
thpEafoofishlsqrdilt
t\
5t} * ttO
t\
N 0 + 5 . 0 2+ N O z
. ai-rttiisilr',t
dlvriart*lrtqila!i'
I
i
I
I
I
--l_
r'-' 1
;1. I
^,
4rt+X!
t\rrarullg*-l
fli.
-*t*"
It9"-"*ir/,
.o.idr1s'c'
i-
1cc,d,1n.
r.'<'('d4
4 2t*-
,. ) rearJ,ov ( o'dtnnt
[--_*
Exercise:
1(b) (i) Niirogen tnonoxide ls used l,rsa catali'st in the Conlact process. The niechalnisn,suggesierJis as folloivs
+ 9^ -__B' zNC2(9)
3NO(g)
+ So3(s)
or(g) + So2 ----+
ir{o(g7
Descr;be
hownitrogen
monoxide
actsas e cataivst.
qrts
JSort 0o --
ccFal,4stin
' .N*wqar
; ' . . . 9 . ' . ; . .rnonoxicl
' ' ' . . . . . . : i . . . . . ' . . . . ' ' . . as
. . . . ' . t J . .[oriloeene-alS
.';9.'.,....
J* catalqses
fla
) S0: .
tle reachbn,
"ffiffin|,l
Kadr,o bq .lnnq,4qiB ox'/ctron s-qf
....'...'.'....*|.'J....''.''.t}'.C'}........''.."..:....,.:.'.j."..;..'.....:.*..'Y.'
fo + 4 *
..nNp'-..;J..ii:,in'I.j'.j4-',l.Nq,
yAan"tle qrcatql@reactrfil
..11k..9..S.ftp.6_.
i^1ldyp"l
_hsue
!?l%..g.f:V*.g.I.Q{W!t
(i;) Platinun,
idalsousedas a caialystin theContactprocess.
platinumactsas iiatalyst in this
DescTide-how
(a8b/2CC3)
F'rocess. t01
sorand0r
. .9:Ft].911....i.L..t'kn1.9....$*.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;
^*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:Q?..
: r'4'Qt Q:
f4 crc4 Qrt
t r c**allsed'
.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"
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"
);,