Unimolecular Reactions

Different considerations than bimolecular

reactions
ego Banerration Dissociation

En Ea
i fH
t
T
1
h.pe
f

1g R
St s r ncoord
S ryncoord

In the second case hard to identify the St

Need to
get Etoile right plane aka dir surface
can be on energy space
Have to think about E spree

Our 1st order perspective unimoleculurxas from Lhukmann

kinetic 8dm other Aorinert
gas
A t M K's
e At µ
K2 energetically excited molecule

A KB B or Btc
So we are putting rn vibor rot energy
This was solved by thesteady state approx

dhfi o k.CAJEM kz A 3 MJ KsCA't

CA't fkstkzCM k Ca M
 kiCMJ rftt dffy hs.ch
fat JkstkzCM
Aside
Eyring plot activation enthalpy t entropy
bet these are not actually exptly measurable

Lasttime Lindemanntheory

A t M't 1 A't t M
A b
Byk steady stateapprox
decaff o A CMJ kzCA u KsCA't

kg A't the CA't MJ R CA M

k.CN
At ekztkzCM3
Then the rate is
rctt dEEI kzcaxJ kgk.IT Em3
g J
koniCn

So Kuni kk3CM
k3 1 KzCMJ

large CM high pressures

omg Kuni kicks k rltt k.roCa indeporCM

small cm low pressures

k.ttm3
IIokun k.Cm3 JrCH k AEM 1storderin a tcm

____ This curve is often plotted as

Kuni kno versus P
Ma
 Lindemann estimated He rate constants as
k Z EolRT E E energy req'd to react
e
rateto formAtt
122 22 2
kCA df from A
ki hasunitsof contain
Rp
jp um
k EolRT
so k 3 ksE E e

Thistreatment is qualitatively correct but is off

by oom quantitatively

There are problems in both k t Ks

HinshelwoodtheostulEaetse

At M A't t M
ceasete
Energybetween etetsu
constforA ATE
Skilese se is rate e go
ff B
we need an estimateof 8k andhowitdependson E
assume classical oscillators vibrations of A n ofthem n 3N 6
assume all havethe samefrequency
TheProbability ofamoleculewi nsuchclassicaldof having EzEo

PIE Eo NII Eolrt

e
More dOrf means moreplaces to fill move w envoy
or hurt capacity is extensive

To have agiven every E from a collision is likethiswith EoSE

Shi Ea EtSE ENT SI
Ing E e RT
still assume Constant
z Z and k
Ex
Ten k she feat e Ekta Ea
Rz
Eo

T.fm X e dx where X Et
to do this have tointegratebyprts u h times H
n
 11
but only the f.rs ttem matters

one can evaluate this via repeated

but only the 1st surface term is
integral integration
by parts
others are negigbly small
important
Eo rT
kx ufdkhte f.fi EEY e

This now accounts for the of d of where emery Can exist

This stundoesn't acct for the fact that only one mode
matters is not
anI Kz actually constant

Rice Ramsperger Kassel RRK Theory

At M AYE
se
t M
we are sowing the fact
2k that only one mode needs
Attie
B the energy by wrapping it into
kaCE
If we have n modes of our molecule w total energy E the probability of
having one move w E ZEO is

Plenooezeo EMELIE I EE
EP of all E in one move
has prob Zero entropic
n1
k3 ka E A I EE
r
const

so
k.eefhakkf.nl eofAft EoY cn lEY e EkTdfE
Kate ski the
EAT
a i
En EET e DIE
if E 33 Eo or net recover hinshelwood limit
otherwise

CEI EF is a small raisedto a LARGE power

gets small
FEI
Aside Molecules have lots of vibe that washes around

Fleming Krenn gas phase expts

Nz or Oz1 in Iquid Argon or Xenon
2 VER
Vibrational
Eneroy
relaxation

Nz Nacho then
z synotgyggqaa.ua

Cf CEN in H2O I 3ofs

k

Within a molecule energywashing around is called IVR Intramolecular brationalRedistrbuton

I
So RRK theory is a statistical treatment of the moves

change of variables i

E EE Eat d I HEH EEE E.EE

EAT DET
Think off In e

Y A e Edm
A n
xn e dx

Rcn Cn l
We can also do thus w
kg MJ