Problem 1 203 →

302

We have a self collision reaction : Oz 1- Oz → 302

which can be modelled as A + A →

products .

00

Now we know ; 2- =

f Targ ITJAAZ .

( 1- E-
F)
TE
P(Er ) der

EF

Assuming the reaction as an

Eavg =

(RPmˢa / %
elementary
h ✗ NAZ .
reaction so that

TAA TA hard sphere Colliding

JA-{ Assuming 03 as
= =

Assuming Elastic Collision .

[ ( %÷ )
112

( ¥
) .hn?PCEr)dEr
l
Toni
-

here
-

z =

, Er
't
Er

.fi?n-rn-2.exp(-E;-,)n -2r- p(4.+kBmT-.n)&n-oA2exp(-,Ea

÷
(4¥
Z =

) nnt '

where p is the steric factor ; or is the rate

of reaction .

h = Ate) -

exp ( _ EHR ,zT ) -

na
≥

A- (T ) =
p ( RBm÷)% .

ITJAZ
(a) Now k A- (T )
(-_) NAZ ②
-

exp
= - -

IKBT

By definition the SI -

units of r are
(mm÷ ] ,

hens from Equation ① i

AG ) (A) expffzj-1.mn?(moml-.2 ]
[mI ]
r = -

m3 Sec
J
.

-
A
dimension
of dimensionless

Equating dimensions ; [A ]
[mm◦=(m;]
-

la ]
=/ mm÷
%
( KBT
)
4
Now we have; P + Tnt must have dimension
of [A ] .

IT MA
↳ [me]
dimension
of
P be (P ) .

[m/s]
"
dimension
(4¥32 / dim of speed
→
of
2

( ( my
[ ] =/ ]
P ) -

.
m3
Mol -
see

here ,
[P ] =
[ moe ] -1
 "2
(b) ACT ) =

p(4RBˢ
Ktm / ? ; p=1 d- on 7=298

TAA = 4-2×10-6 m KB = 1.38×10-23 Jk

-1

4kBT_ == 256.32 m/s Moz ⇐ 488m /m◦e

tm

Moz 7- 97×10--26 kg/

particle
•
=

heng ,

A- (7) = 1.42×10-8 m3_

Mol -
Sec

(e) TAA = 1-2×10-9 m 7=298 K

(256.32 ) (1-2×10-9)
≥
ACT ) = t

ACT ) = 1-16×10-15 m3_

Mol -
see

(d) kobs = 1541 Koos = 1-04×10-3 m3-

Mol min 60 Mol -
Sec

Robs = 1-667×10-9 m3_

Mol -
Sec
 r
'
=

(ˢ)% trait exp

/ %-) not

for smallest value

of reactive cross-section ;

IT TAFT
(B % = 1-667×159 at 7- 298K

TATA = 1-44×10-6 m

the
% smallest value of the collision reactive cross-section at kobs =

'
0.0001 Lmot min
'
is 1-44×10-6 m .

The reactive cross-section in part (b) is 4-2×15 Gm and in

part (C) is 1-2×10-9 m

.

When the reactive cross-section is 4.2×10-6 m the reaction will

,

happen as this is
larger than the smallest value of reactive

cross-section of 1- 44 ✗ 156m at kobs = 0.0001 Lmot ' mint .

However , when Jan = 1-2×10-9 m < the smallest reactive -

Cross -
section ( 0¥a = 1-44×10-6 m
) at kobs = 0-0001 Lmotmiñl
the reaction will not happen .
 Problem 2 Dz -1 Br → DBS + D

Kt
≠
D- D + Br ← ( D- -- -

D - - -

Br / → D- Br + D

A linear transition state is postulated .

(a) h = Vict = Vi k≠CDzCBr

*

Ej
[ ]
function
K± = QE where ; &} =
Partition

Per volume
ÑF Ñ°Br
,
✓

Redefining Energies
Kᵗ
e×p(-Eq )
=
QE -
① to
, lowest state ( Non superscript)
Q°Dz
.

Br

QE , Q¥
÷iy<
< 1 because there
Q¥ =
-

,
exist asymmetric
vibration in the linear transition

state .

Q" "
QE
%÷ QI -20
÷-nuy↳,=k¥~
=
=

k÷:¥q "Pt÷)
E- =

a =

ÉQ¥e×p(_¥ ) Q :zQ°Br
c☐zCBr

Q-iE.QI.IQ#.+QEec)Qgzogg
(
AH
k☐⇐ Q¥
)=ᵗʰ¥(QEQI.IQ?EQ:i?)(Q+:Q:+Q?i.QI:)
""
=

,
 Q =
Qtrans Qrot Qvib Qeiec
.
- -

For Dz : linear molecule (D- D)

312
Qtr ==
(2ñmDzAzT ) ; Assuming 3D translation .

43

Qrot =
8t2kTI→z (for linear Mol .

) here 0=2

h④z
linear molecule with N=2
Qvib =
I
3N -5=1 vibrational mode
1-
expEÉi )
.

Qelec = I # unpaired e- in Dz = 0

For Br

3/2

Qtr =(2ñmBrk☐T )
43

Qrot = 1 ( monoatomic )

Qelec
Qvib = 1 ( monoatomic ) =
2s -11

" S = # unpaired e- / = I
1 I
Qelec =
z
Br
For (1) - - -

D - - -

Br )≠
Qtr = 2*%
43

[linear ]
±
I
Qrot = 8^-2 RT .
transition 8=-1
site
h2o

Qelec I # unpaired e-
= = 1 S =
1£
Qele = 25+1 = 1 .

We have N =3 linear molecule .

hence we have 3N -
5 vibrational modes 4
4

Qvib =
IT 1-
I
ftp.vi-J
i=i -

exp
heng ,
 Q°É QF 0T¥
"

of
(b)
Estimating
and the translation portion
partition function ;

Q¥ = ( 2itk☐T)% . m3k m :
IG/ particle .

43

In general for mass .cm ) at room temperature 7=298 K .

QF =
(1.43×1070) m3 / 2

here ,

specie m ( Ks / particle ) QI

Dz 6-68×10-27 7.81×1030

Br 1.33×10-25 6.93×1032

( D- . -

D . -
-
Br )ᵗ 1.39×10-25 7.41 ✗ 1032

◦
±
QT = Quan == 1-37×10-31
Q¥?ns .
Q°Br
trans
(C)
Evaluating Rotational part It = 28 amu -

Ang?

IDZ
◦ 2
= 0-553 amu A-

(7.4×1047) (
of
Qrot = 811-2-127 • It =
28 amu -

Ang )
h2

Ipz=( ) ( 0-553
Q°D2 811-2127
7.4*87 Ang )
'
= amu -

rot

2h2

Lamu -

Ang = (1.66×1527) (10-20) = 1-66×1547

kgmz

¢0Bn
tot
=L

Q¥t =
343.91

Q°D2
rot
= 3.40

Qiot = Q°Ét = 101.28

Q%EQ%E
(d)

☒± = { 1É=%fEÉÉIÉÉ%y } h2
I

{ ff2itmpzkp.TT?).f8T2kT.Ip#n-yH)(fTmBrkf}
¥2 Br

h3

°÷ É IF o
given only vibration mode that is not cancelled is the weakest

vibration mode rest all

gets cancelled .

hence the simplification of the above expression leads to : -

{( 2.) [ ✗ hvi }
"
8 # KT
(2ñm±kBT / . It
Q°± h2 1 ⇐
e-

ffktmp.IT/%ff81T2kT.Ip+mBkTfJh3
=

% QBs
h2 h3

HI hence
<< 1
following
we
got the relation .

Kat

a
:-p
Q°DzQ°Br :Y, !¥¥;%¥÷;±¥i h3
h3

h2
h2

h3
.
 from the parts (b) and (c) we can write above functional
form as
,
'

Q°Trans Qrot
0

QI
k¥
'

= -

Q°DzQ°Br

Q°trans = 1-37×10-31

rot = 101.28

here Q°±_ = 8.6×10-17

,

Q°pz QBs

hence the pre -

exponential factor = 8.6×15-17 m%mo1 -

)
see
 ( 2.) [ )
" 811-2127
(2ñm±k☐T / [
±

(e) A- ( T )
=/ ᵗᵈÉ?)f(2iTmpzkj)ʰ8ñ2kT%÷tmkÉ
h3 2h2 his

2h3 (m±)% It
k%--
.

(mDz)% Ipz @ itmprkp / 3/2 .

73/2

ACT ) = 2h21m ± )% It

(MDz)% Ipz
'

☒ Mor)% ; kjf

)%2I±
herd , Mt
42
A- (e) = .
.

Mpzm Be \ IDZ '

KBT

hence functional form Pre exponential factor

the
of is;

((
.2I±
]
AKI = h2 •
Mt

21T
MDZMBR Ipgz
KBT -
 Problem 3 NO + 2X NX + OX

(a) ks
Consider; No + 2X
¥ NX + OX ; where k , is the

forward reaction male constant and k -

z is the backward reaction
hate constant .

each step to be
Assuming elementary step .

kg = Ks (No )( ✗ 12 and 96 = k# ( NX ) ( ox )

At Equilibrium the forward and backward rate must be equal ;

Mf =
96

k , ( No / ( x ) ( NX ) COX )
'
=
K .
,

AI ,
K -
KI i where k is the Equilibrium Constant .

K -
I

K = ( NXKOX )
( No ) ( ✗ 12

Also , ( No ) = Pno K = (NX ) Cox ) RT

Pno .
(✗ 12

( NX ) ( ox ) =
two .
#
( ✗ 12 RT

(x ) =

( K
RT
-

Pno
.
( NX )
(0×7)%2
 from site balance ; (x ! = (x ) + ( NX ) + ( ox )

(x) .
=

( RIINX /
KPNO (0×1)%-1 ( Nx ) + COX ) site balance

Since there is no preferential adsorbtion ; we can consider;

( NX ) __
( ox ) =

(A¥
K =
RI ( NX ) ( ox )
PNO ( ✗ 12

K = RI .
CAX )2 hence ;
f- PN 4)
2

(
%
(X ) =
(AX) -
RT

4PNiK
/
÷ (X) ◦
=
(x ) + ( AX ) ( As ( Nx ) -_ Cox )= LAX )k ]

(
"
4.) CAN
( Ypg ) ]
= -
1 +

I "2
(AK ) = = 2 ( Priok )
to ( RT ) % Zlpnok /
"
I
(¥p÷)%
+ 2
+

here (A =
2 ( Panik )
,

( ✗ to 2
RT 1- Povo k -
Defining ; fractional coverage of specie /× )o
(¥g=⊖j
J over =

( Nx ) CAI
l↑¥;Iz
Now; = Qnx =

to 2( ✗ to

÷ ② Nx == Pno .
K

2
RT +
Pnjk

① Nx =
( Pno ) %
I + 2
@ ¥5142
No
-

NI.CN#--lzAYf-.,--s0-No--0-nx--4Aj,?--l-z
( to ✗

D- No = Pno k -

2
RT 1- Pno - k

① No =
( PN◦¥)%
I + 2
@ ¥] "z
No
-
(b) We know ; K =
exp
/ %-)-

where sG°= Sti -

Tss

skids < O

K =

expf-s.lt#s5)=exP(-ffI).exp(spI)
ˢH°<

e×pÉ /
" 0

hence ,
K =
•

e×P )
this quantity decreases

as the temperature
increases .

% As Temperature increases i SG increases which makes

* small thence the process becomes unfavourable .

Which in turn results in low surface coverage .

higher temperature ; surface coverage decreases

•

: At .

.
(c) Given ; Shads =
-75 KJ /moe

Qiu Qi
K± =

QÑO
-

exp
/÷ / ,
Considering Qj=Qᵗa
j
"

on# 1!
.

( it when Qnx and Qox are immobile ;

Q°Nx =L Q%× = I MNO = 4.98×1526 kg/ particle

Mx = 9.76×10-26 kg / particle
Kᵗ 1- exp
.(_÷ )
-
=

0in .
-

Qfvo = ( 21T mnokrst )% =

Kitty > )%Mw% = 2.95×1032
h3 h3

k± =
1-
2. 95
✗ 1532 -

exp
/ _n÷ )
tore ,
Adsosbtioni E = 75 KJ / mol

K = Kt = 1-
2- 95
✗ 1532 .

expf -1-75001 )
8-314×450

hence; K = 1-72×1524 at 7=450 K

Now ; AG = -
RT link

where; D8 = SHO -

TSS
°

Sti -

Tss =
-

RT Ink

hence ; S5 = SHO -1 RT lnk

65° =
-

75000 + (8-314) (450 ) -

lmk
450

when
15° =
-
621-55 % Case NX and OX

are immobile .

④ NX and OX are mobile on

Surface

K = QÑxQ8x exp
/ ¥)
-

Einslmoe .

Qiu

NI Q°Nx ≠ 1 and Q%x -1-1 as

they are mobile on surface .

( 21T mivxkrst )%
Q°N× =

h3
=

¥3k .mn?k-- 1.12×1033

( 21T moxkot )%
Q°ox
(2iTkg;ʰm*3k 1-27×1033
= = =

h3
 No = 2-95×1032

K
:
Q%xQexp(_¥ )
•
=

Q°No

(1.12×1033) (1-17×1033)
K
/ -175000
)
-

exp
=

(2-95×10-32) (8.314 )(950 )

K =
(4-44×1033)<(5.08×108)
hence ; K = 2.25×1042 at T= 450K

Now ; AG = -
RT link

where; 18=1110 -

TSS
°

Sti -

Tss =
-

RT Ink

hence ; S5 = SHO -1 RT lnk

65 = -75000 + (8-31471450) -

lmk
450

when
15° =
644.11 % Case NX and OX

are mobile .