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5.62 Physical Chemistry II

Spring 2008

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5.62 Spring 2007

Lecture #33

Page 1

Transition State Theory. I.

Transition State Theory = Activated Complex Theory = Absolute Rate Theory

! " H2 + F " [H2F] !k! HF + H

Assume equilibrium between reactants H2 + F and the transition state.

[H 2 F] [H 2 ][F] Treat the transition state as a molecule with structure that decays unimolecularly with rate constant k. d[HF] = k [ H 2 F ] = kK [ H 2 ] [ F ] dt K =
k has units of sec1 (unimolecular decay). The motion along the reaction coordinate looks like an antisymmetric vibration of H2F, one-half cycle of this vibration. Therefore k can be approximated by the frequency of the antisymmetric vibration [sec1] k frequency of antisymmetric vibration (bond formation and cleavage looks like antisymmetric vibration)
d[HF] = K [H2] [F] dt d[HF] = dt

! $ (q* / N) # *H & e'E /kT [ H 2 ] [ F ] F 2 # (q N ) (q / N) & " %

* ' g * , ) H 0 F , e-E kT , g 2g +( 0 0 +

! (q / N) $' q * ' q * rot vib &) H , ) *H K = # trans H2 ) # q trans N &( q rot2 + ( q vib2 " %

Reaction coordinate is antisymmetric vibrational mode of H2F. This vibration is fully excited (high T limit) because it leads to the cleavage of the HH bond and the formation of the HF bond. For a fully excited vibration h kT The vibrational partition function for the antisymmetric mode is

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q*asym = vib

1 ' 1 ! e!h" kT

kT h!

since eh/kT 1 h/kT

Note that this is an incredibly important simplification. The unknown simply disappears! We do not need to estimate it!

K =
where

%( q + ( q*. + ( g + kT " q N rot vib $ H trans F '* H2 - * *H2 - * H20 F - e /E kT 2 h! # ( q trans N ) ( q trans N ) &) q rot , ) q vib , ) g 0 g 0 , $ '

q
or

*! vib

3n"5"1

#
i=1

1 1 " e"h$i /kT

if transition state is linear

q*! = vib

3n"6"1

#
i=1

1 1 " e"h$i /kT

if transition state is nonlinear n is # of atoms in transition state

q*! partition function from which the antisymmetric vibrational mode is vib excluded; it has become the reaction coordinate
So
kT " K = K = K h! K " = special modification of K

that excludes the partition function for the antisymmetric vibrational mode What is E?

(ZPE)TS Potential Energy V0 E (ZPE)R H2 + F HF + H

Reaction Coordinate

Reaction Coordinate

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Since a molecule cannot have a vibrational energy lower than its zero point energy, the effective barrier along the reaction coordinate is E = V0 + (ZPE)TS (ZPE)R V0 is the potential energy difference between the bare barrier (saddle point) and the reactant bare minimum. For linear H2F, n = 3, so 3n51 = 3 regular vibrational modes, thus
1 E = V0 + h #! $ sym.st. + 2!bend " !H2 % & 2 !### "#### # $
Difference in ZPE

FORMULATION of kTST
d[HF] kT kT " = ! K " [ H 2 ] [ F ] = K [ H 2 ] [ F ] = k TST [ H 2 ] [ F ] dt h! h

so kTST =
kT K h

but not all reactant molecules make it all the way to products some are reflected back to separated reactants. Thus,
k TST = ! kT " K h

where transmission coefficient (a fudge factor)

EVALUATION OF kTST POTENTIAL ENERGY SURFACE KNOWN:

E directly from potential energy surface
I (moment of inertia of transition state)
calculate from geometric structure of transition state analyze shape of potential in saddle point region trajectory calculations consider = 1 for now.

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H2 + F HF + H

T = 300K

m H2 = 2

m F = 19

Translational part
! (qtrans N ) $ = Nh 3 # H & # ( q trans N ) ( q F N ) & (2'kT)3/2 " 2 % trans ( m + * *m m ) H2 F ,
3/2

=
3/2

6 !10

23

mol

-1

$ 6 !10 23 ! 0.021 ' (6.63!10"34 Js)3 & ) (2# !1.38 !10"23 J/K !300K)3/2 & 0.002 ! 0.019kg ) % (

= 2.52 107 m3 mol1 Rotational part

! H2 = 2 ! = 1

q rot =

IH2 = 4.56 !10 "48 m 2 kg

8! 2 IkT "h 2 I = 1.24 !10 "46 m 2 kg

q I ! H2 rot = = 54.4 q H 2 IH 2 ! rot

(assume linear transition state)

Vibrational Part H2F is a linear transition state (assumed) 3n51 = 3 vibrational degrees of freedom (one vibration is reaction coordinate)
h! h! s b = 5771K stretch = 573K (doubly degenerate) bend k k

h!H2 k = 6323K q*! (1 " e"h#s kT ) (1 " e"h#b /kT ) vib = "1 *H 2 (1 " e"h#H2 /kT ) q vib

"1

"2

= 1.38

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Electronic part

g = 2 (S = 1 / 2 ) g F = 6 ( L = 1,S = 1 / 2 ) g H2 = 1 0 0 0 2 2 (spin orbit splitting of F P1/2 P3/2 is 404 cm1) g 1 0 = F H2 g 0 g0 3

Calculate E

V0 = 3.8kJmol!1

" = 1.20 #1014 s!1 " = 1.19 #1013 s!1 (reasonable guesses) s b (How do we guess values for ! and ! ?) s b 14 1 !H2 = 1.32 " 10 s
1 E = V0 + hN #! + 2! " !H2 % = 6.1 kJ mol"1 b $ s & 2

Calculate kT/h kT/h = Putting it all together:

k TST = ! kT " K h

1.38 !10"23 J/K ! 300K = 6.24 1012 s1 "34 6.63!10 Js

1 = 1 6.24 #1012 s$1 2.52 #10 $7 m 3mol$1 ( 54.4 ) (1.38 ) e$6.1 RT 3 7 $6.1 RT = 3.93 #10 e

)(

kTST = 3.40 106m3mol1s1 at 300K

kEXP = 2.70 x 106 m3 mol1 s1

acceptable agreement

Experimental value is smaller because is probably not 1. Sometimes kTST will be smaller than kEXP because of tunneling. This model for kTST does not take the quantum mechanical phenomenon of tunneling into account. Tunneling can make the reaction rate become faster than the kTST prediction. If kTST < kEXP, it may mean that there is some tunneling contribution.

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