§9.6 rate theories of elementary reaction extensive reading: levine, pp. 879-881
TRANSCRIPT
Two important empirical rules:
Rate equation (law of mass action)
Arrhenius equation
RT
EAk aexp
Type of reaction
Unimolecular reaction
Bimolecular
reaction
Termolecular
reaction
A 1013 s
1011 mol-1dm3s-1
109 mol-2dm6s-1
A seems related to collision frequency.
RT
EaexpBoltzmann distribution term
[A][B]r k
It is obvious that a molecule of A cannot react with a molecule of B unless the two reactant molecules can somehow interact. This interaction can only take place if they come within a certain distance of each other, i.e., collides with each other.
A reaction can take place only if the molecules of the reactants
collide. Therefore, the rate constant of the reaction may be predicted
by calculation of the collision frequency of the reactants.
Collision theory is proposed independently by Max Trautz in 1916
and William Lewis in 1918. Thereafter, C. Hinshelwood made
modification on its.
Basic consideration and brief history
http://en.wikipedia.org/wiki/Collision_theory
6.1 Fundamental assumptions of SCT
for gaseous bimolecular reaction
1) The reaction rate of reaction is proportional to the collision
frequency (Z), which can be solved by kinetic theory of molecule;
ABr Z q
where ZAB is the collision frequency of A with B per unit cubic meter
per second, q is the portion of effective collision.
reaction rate can be expressed as:
2) The collision can be either non-reactive (elastic) collision or reactive collision. Only the molecules posses energy excess to a critical value (Ec) can lead to reactive collision. The reaction rate
should be in proportion to the fraction of reactive collision (q).
6.2 Calculation of ZAB
SCT assumes that molecules can be taken as rigid ball without inner structure.
dA dB
dA and dB are the diameter of A and B molecule, respectively.
Definition: mean collision diameter: dAB
ABBA d
dd
2
The way to collide: 撞个满怀、擦肩而过,失之交臂
When the concentration of A is NA/V (molecm-3):
2ABAB dZ V
N
V
N BAA
When both A and B moves, the relative velocity VAB should be used.
22BAAB
ii M
RT
8
according to the kinetic theory of gases
A BAB
A B A B
8 8 8 M MRT RT RT
M M M M
AB
8RT
A B
A B
M M
M M
(reduced mass)
2 2A B A BB AB
2 2
8 8
8[A][B]
AB A
AB
N N Ln LnRT RTZ d d
V V V V
RTL d
Decomposition of HI: 2HI = H2 + I2
2 2 2AA AA
A
2 8[A]
2
RTZ L d
M
2 2AB AB
8[A][B]
RTZ L d
?
For example
At 1.0 105 Pa and 700 K, d = 3.50 10-10 m, Z HI-HI = ?5
31 1
1.0 10 Pa[HI] 17.41mol m
8.314J K mol 700K
p
RT
23 2 10 2 2AA 3
34 3 1
2 8 8.314 7003.1416(6.02 10 ) (3.50 10 ) (17.41)
2 3.1416 128 10
1.017 10 m s
Z
Generally, ZAB of gaseous reactions at ambient temperature and
pressure is of the magnitude of 1035 m-3s-1.
If reaction takes place whenever the molecules collides:
2 2AB AB
8[A][B]
RTZ L d
A
AB
[A]N
ddV
r L Zdt dt
2ABAB
[A] 8[A][B]
Zd RTd L
dt L
[A][A][B]
dk
dt 2
AB
8RTk d L
because
k = 7.88 104 mol-1dm3s-1
When c0 = 1.00 mol dm-3, the half-life of HI is 1.27 10-5 s.
This result differs greatly from the experimental fact. In 1909, Max
Trantz introduced fraction of reactive collision (q) to solve this great
discrepancy.
6.3 Calculation of q
Only the molecules posses energy excess to a critical value (Ec) can
lead to reactive collision.
It is apparent that E of translational energy of motion is related to
the relative motion of two molecules. And Ec is thus the minimum
translational energy of motion (critical / threshold energy) along the
connecting line between the mass-point of the two molecules which
are to collide.
If the energy exchange between colliding molecules is much rapid than reaction, the energy distribution of molecules may still obey the Maxwell-Boltzmann distribution equation.
RT
E
n
nq cexp
*
Boltzmann factor
If Ec = 120 kJmol-1, T = 300 K, then
q = 1.27 10-21
This suggest than among 7.8 1020 collision only one collision is effective.
The fraction of the collision with the energy equal to or greater than Ec is:
6.4 Calculation of k
ABr Z q
2 2 A BAB AB
A B
8[A][B]
M MRTZ L d
M M
2AB
8exp [A][B]cERT
r d LRT
[A][B]r k
2SCT AB
8exp cERT
k d LRT
RT
EBTk c
SCT exp2
1
B is a constant independent of T.
RT
E
n
nq cexp
*
RT
EAk aexp
ca ERTE 2
1
RT
EBTk c
SCT exp2
1
The experimental activation energy (Ea) depends on
temperature.Using Ea for substitution of Ec,
2AB
8exp c
SCT
ERTk d L
RT
2AB
8exp a
SCT
ERTek d L
RT
The pre-exponential factor corresponds to the collision frequency. This is the reason why A is also named as frequency factor.
6.5 Comment on SCT
1) The expression for the rate coefficient given by SCT conforms
qualitatively to the Arrhenius equation observed experimentally. This
suggests that SCT reveal the principal features of the reaction, i.e., in
order to react, molecules have to collide (the pre-exponential term) and
the collision should be sufficiently energetic (the exponential term)
(1) Successfulness
SCT gives a vivid physical image of the reaction process:
2) As pointed out by SCT, the pre-exponential factor, dependent
only on the masses of the species involved in the collision, can be
calculated easily.
ca ERTE 2
1
SCT reveals the physical meaning of the pre-exponential factor, i.e., the collision frequency.
3) SCT demonstrated theoretically that experimental activation energy depends on temperature.
(2) Shortcomings
1) For calculating k, Ec is needed. However, SCT can not give Ec.
Calculation of k depends on the experimental determination of Ea.
Therefore, SCT can not predict the kinetic features of the reaction
theoretically.
2) The quantitative agreement between SCT and experiments is poor.
Reaction Ea Acal Aexp Acal./Aexp.
2NOCl2NO+Cl2 107.8 2.95109 3.23109 0.91
H+Br2 HBr+Br 3.76 4.61010 6.76109 6.76
NO+O3NO2+O2 9.61 7.94109 6.31107 1.25102
CH3+CHCl3 CH4+CCl3 24.2 1.51010 1.26106 1.19104
2-cyclopentadiene dimer 60.6 8.13109 2.45103 3.32106
In some cases, the agreement between experimental and calculated A values can be quite good. However, in many cases, the observed rate is definitely too small. It was found that the more complex of the reactant molecules, the greater the discrepancy between Acal and Aexp.
In fact, the reactant is of complex molecular structure. To take reactant molecules as rigid balls without inner structure will spontaneously result in systematic error.
?
2 ONBr Br2 + 2 NO
CH3+CHCl3 CH4+CCl3
The colliding molecules must be suitably oriented.
Substitution
OH¯ + CH3Br CH3OH + Br¯
The great discrepancies between experimental and calculated A were recognized around 1925. The equation
RT
EAk a
SCT exp
was then modified by introduction of an empirical factor P called the steric factor / probability factor.
RT
EPAk a
SCT exp.
.exp
calA
AP
Steric factor (P), ranging between 1~10-9, represents the fraction of energetically suitable collisions for which the orientation is also favorable, can be only determined experimentally.
SCT can not give any clue to calculate P.