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138 THEORIES OF CHEMICAL REACTIONS

It is also possible to look at the changes in types of degrees of freedom, and


changes in internal motions on forming the activated complex. Considerable insight
into trends in A factors, and interpretations of these in terms of changes in internal
motions, can be made using rough order of magnitude calculations without having
recourse to detailed accurate values for the partition functions. The approximations
made are acceptable because contributions from the internal motions do not vary
much with mass, moment of inertia or vibrational frequency.

Typical values of these contributions:

 for each translation: 109 to 1010 dm1


 for each rotation: 10 to 102
 for each vibration: 1 to 10

Worked Problem 4.13

Question. At 298 K, and제4차 쪽지시험


assuming ¼ 1 풀이
and kT=h ¼ 6:2
1012 s1, and using
typical values (in the middle of the ranges above) for the contributions from
translation, rotation and vibration,

for each translation: 5


109 dm1
for each rotation: 50
for each vibration 5

calculate the predicted A factor for the following reaction types:

(a) atom þ atom ! activated complex;


(b) atom þ linear molecule ! non-linear activated complex;
(c) two non-linear molecules ! non-linear activated complex.

1번 문제
Answer.

(a) Each atom has three translations; the activated complex has three translations,
two rotations, one internal free translation and ;ð3
2Þ  6 vibrations i.e.
zero. The contribution from the internal translation has already been incorpo-
rated in the derivation, so that
Q6¼ 3trans; 2rots; 0vib 2rots
contributions to are ¼
QX QYZ 3trans; 3trans 3trans
TRANSITION STATE THEORY 139

kT Q6¼ 6:2
1012
50
50
value of ¼ dm3 s1
h QX QYZ 5
109
5
109
5
109
¼ 1:2
1013 dm3 s1

(b) An atom has three translations; a linear molecule has three translations, two
rotations and 3N  5 vibrations; the non-linear activated complex has three
translations, three rotations, one internal free translation and ; 3ðN þ 1Þ  7
vibrations i.e. 3N  4 vibrations.
Q6¼ 3trans; 3rots; ð3N  4Þvibs 1rot; 1vib
Contributions to are ¼
QX QYZ 3trans; 3trans; 2rots; ð3N  5Þvib 3trans
kT Q6¼ 6:2
1012
50
5
value of ¼ dm3 s1
h QX QYZ 5
109
5
109
5
109
¼ 1:2
1014 dm3 s1
(c) A non-linear molecule, A, has three translations, three rotations and 3NA  6
vibrations. Likewise non-linear molecule B has three translations, three
rotations and 3NB  6 vibrations. Total for reactants ¼ six translations, six
rotations and 3NA þ 3NB  12 vibrations.
The non-linear activated complex has three translations, three rotations, one
internal free translation and 3NA þ 3NB  7 vibrations.

Q6¼ 3trans; 3rots; ð3NA þ 3NB  7Þvibs


Contributions to are
QX QYZ 3trans; 3trans; 3rots; 3rots; ð3NA þ 3NB  12Þvibs
5vib
¼
3trans; 3rots
kT Q6¼ 6:2
1012
5
5
5
5
5
¼ dm3 s1
h QX QYZ 5
109
5
109
5
109
50
50
50
¼ 1:2
1018 dm3 s1

The results from Problem 4.13 are instructive. They are

(a) atom þ atom ! activated complex, A ¼ 1:2


1013 dm3 s1;
(b) atom þ linear molecule ! non-linear activated complex, A ¼ 1:2
1014 dm3
s1;
(c) two non-linear molecules ! non-linear activated complex, A ¼ 1:2
1018 dm3
s1.
These values of A are in molecular units, and cannot be compared directly with a
typical value of Z. This is because partition functions are molecular quantities and the
contributions to ðkT=hÞQ6¼ =QX QYZ are in molecular units. Multiplying by
2.    .   ≠          ×  ×   

  ≠    
             ×    ×    ≠  

  ≠  ⋅   

3. reduced mass는    ×   


     
   ×              ×  ×     
∴   ×  

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