Beruflich Dokumente
Kultur Dokumente
Scott Fogler
1/24/06
Chapter 3
"rA = kC A C B = Ae "E RT C A C B
We want to provide at least a qualitative understanding of why the rate law takes this
form. We will first develop the collision rate, using collision theory for hard spheres of
2
cross section Sr, "#!
AB . When all collisions occur with the same relative velocity, UR, the
AB , is
number of collisions between A and B molecules, Z
AC
B
Z AB = Sr U R C
[collisions/s/molecule]
"rA = Ae "E A
RT
C AC B
where
A=
'1 2
8k T
"# 2AB & B )
% " AB (
N Avo
E A = E oA + " P #H Rx
Where HRx is the heat of reaction and E oA and P are the Polyani Parameters. With
these equations for A and EA we can make a first approximation to the rate law
! to the lab.
parameters without going
1
CD/CollisionTheory/ProfRef.doc
HOT BUTTONS
I.
Fundamentals of Collision Theory
II. Shortcomings of Collision Theory
III. Modifications of Collision Theory
A. Distribution of Velocities
B. Collisions That Result in Reaction
1. Model 1 Pr = 0 or 1
2. Model 2 Pr = 0 or Pr = (EEA)/E
IV. Other Definitions of Activation Energy
*
A. Tolmans Theorem Ea = E
B. Fowler and Guggenheim
C. Energy Barrier
V. Estimation of Activation Energy from the Polyani Equation
A. Polyani Equation
B. Marcus Extension of the Polyani Equation
C. Blowers-Masel Relation
VI. Closure
References for Collision Theory, Transition State Theory, and Molecular Dynamics
P. Atkins, Physical Chemistry, 6th ed. (New York: Freeman, 1998)
P. Atkins, Physical Chemistry, 5th ed. (New York: Freeman, 1994).
G. D. Billing and K. V. Mikkelsen, Introduction to Molecular Dynamics and Chemical
Kinetics (New York: Wiley, 1996).
P.W. Atkins, The Elements of Physical Chemistry, 2nd ed. (Oxford: Oxford Press, 1996).
K. J. Laidler, Chemical Kinetics, 3rd ed. (New York: Harper Collins, 1987).
G. Odian, Principles of Polymerization, 3rd ed. (New York: Wiley 1991).
R. I. Masel, Chemical Kinetics and Catalysis (New York: Wiley Interscience, 2001).
As a shorthand notation, we will use the following references nomenclature:
A6p701 means Atkins, P. W., Physical Chemistry, 6th ed. (1998) page 701.
L3p208 means Laidler, K. J., Chemical Kinetics, 3rd,ed. (1987) page 208.
This nomenclature means that if you want background on the principle, topic,
postulate, or equation being discussed, go to the specified page of the referenced text.
I.
2
CD/CollisionTheory/ProfRef.doc
A. Rigid Spheres
Species A and B are modeled as rigid spheres of radius A and B, respectively.
A
B
2!A
2!B
We shall define our coordinate system such that molecule B is stationary wrt
molecule A so that molecule A moves towards molecule B with a relative
velocity, UR. Molecule A moves through space to sweep out a collision volume
with a collision cross section, !" 2AB , illustrated by the cylinder shown in Figure
R3.A-2.
!AB
!AB
UR
Figure R3.A-2 Schematic of collision cross-section.
! AB = ! A + ! B
If the center of a B molecule comes within a distance of ! AB of the center of
the A molecule they will collide. The collision cross section of rigid spheres is
Sr = !" 2AB . As a first approximation, we shall consider Sr constant. This
constraint will be relaxed when we consider a distribution of relative velocities.
The relative velocity between gas molecules A and B is UR.
# 8k B T &1 2
UR = %
(
$ " AB '
where
kB = Boltzmanns constant = 1.381 10
= 1.381 kg m2/s2/K/molecule
23
(R3.A-1)
J/K/molecule
This equation is given in most physical chemistry books, e.g., see Moore, W. J. Physical Chemistry, 2nd Ed.,
Englewood Cliffs, NJ: Prentice Hall, p.187.
3
CD/CollisionTheory/ProfRef.doc
kB
AB
"
$
R
=$
$ M AM B
$
# MA + MB
%
'
'
'
'
&
(R3.A-2)
Average Velocity,
(meters/second)
Molecular Diameter ()
H2
CO
Xe
He
N2
O2
H2 O
C2H6
1687
453
209
1200
450
420
560
437
2.74
3.12
4.85
2.2
3.5
3.1
3.7
5.3
C6H6
CH4
NH3
H2S
CO2
N2 O
NO
270
593
518
412
361
361
437
3.5
4.1
4.4
4.7
4.6
4.7
3.7
Courtesy of J. F. OHanlon, A Users Guide to Vacuum Technology (New York: Wiley, 1980).
4
CD/CollisionTheory/ProfRef.doc
!l4
6
47
8
!V = (U R !t )"#2AB
!V
A
The bends in the volume represent that even though molecule A may change
directions upon collision the volume sweep out is the same. The number of
collisions that will take place will be equal to the number of B molecules,
B , that are in the volume swept out by the A molecule:
V C
1A B = !"2AB C
BU R
Z
(R3.A-3)
!
A,
However,
we have many A molecules present at a concentration, C
3
(molecule/dm ). Adding up the collisions of all the A molecules per unit
AB of all the A molecules with all
A , then the number of collisions Z
volume, C
B molecules per time per unit volume is
Sr
67
8
2
C
= Sr U R C
AC
B
Z AB = "# AB U R C
! A B
(R3.A-4)
$
'1 2
!
Z AB = "# 2AB & 8k B T ) C
AC
B [molecules/time/volume]
% " (
(R3.A-5)
AC
B [molecules/time/volume] (R3.A-6)
"rA = Z AB = #$ AB '
* C
& # )
12
A C
B
# "rA &
C
2 # 8k B T &
N 2Avo
%
( N Avo = )* AB %
(
N Avo '
N Avo N Avo
$ ) '
$1
12
3 123
23
CA
CB
"rA
5
CD/CollisionTheory/ProfRef.doc
(R3.A-7)
"rA =
% 8#k B T (
#$ 2AB '
*
12
(R3.A-8)
N Avo C A C B [moles/time/volume]
# )
&
1444
424444
3
A
'1 2
8#k B T
A = " 2AB &
)
% AB (
(R3.A-9)
N Avo
(R3.A-10)
"rA = AC A C B
!
Example
H + O 2 " OH + O
at 273K.
Additional information:
Using the values in!Table R3.A-1
Collision Radii
Hydrogen H
Oxygen O2
"O 2 =
3.1
1.55 = 1.5 x 1010m
2
Solution
(R3.A-E-1)
A = Sr U R N Avo
A=
$ 8k T '
"# 2AB & B )
% " (
12
N Avo
# 8k B T &1 2
UR = %
(
$ " '
kB
R
8.314 kg " m 2 s 2 K mol 8.314kg m 2 s 2 K mol
=
=!
=
# (1g mol)(32 g mol)&
M AM B
1kg
0.97 g mol )
%
(
1000g
MA + MB
$ 1g mol + 32 g mol '
!CD/CollisionTheory/ProfRef.doc
(R3.A-9)
(R3.A-1)
kB
= 8571m 2 s 2 K
Sr = "# 2AB = "[# A + # B ] = " 0.68 $10 %10 m +1.55 $10 %10 m
(R3.A-E-2)
! A=
(R3.A-E-3)
3
m3
11 dm
A = 2.29 "10
= 2.29 "10
mol# s
mol # s
(R3.A-E-4)
$10 10 ' 3
m3
1mol
A = 2.29 "10
"
&
)
mol# s 6.02 "10 23 molecule % m (
6
A = 3.81"10 14 ()
molecule s
(R3.A-E-5)
The value
! reported in Masel from Wesley is
A =1.5 "10 14 ()
molecule s
10 8
dm 3
dm 3
< A calc <10 11
mols
mol s
Terms of cubic angstroms per molecule per second the frequency factor is
There are a couple of things that are troubling about the rate of reaction given by
Equation (R3.A-10), i.e.
M1p367.
7
CD/CollisionTheory/ProfRef.doc
(R3.A-10)
"rA = AC A C B
"rA ~ A ~ T
!
or
"rA = Ae "E RT C A C B
(R3.A-11)
k = Ae "E RT
(R3.A-12)
A
b
b = impact parameter
B
B. Collision theory does not explain activation barriers. Activation barriers occur
because bonds need to be stretched or distorted in order to react and these
processes require energy. Molecules must overcome electron-electron repulsion
in order to come close together
C. The collision theory does not explain the observed temperature dependence
given by Arrhenius equation
k = Ae E RT
D. Collision theory assumes all A molecules have the same relative velocity, the
average one.
# 8k B T &1 2
UR = %
(
$ " AB '
(R3.A-1)
Masel, 1p
!
8
CD/CollisionTheory/ProfRef.doc
k = Ae "E A
RT
A. Distribution of Velocities
We will use the Maxwell-Boltzmann Distribution of Molecular Velocities
(A6p.26). For a species of mass m, the Maxwell distribution of velocities
!
(relative velocities) is
# m & 3 2 )mU 2
f (U,T)dU = 4" %
e
(
$ 2"k B T '
2k B T
U 2 dU
(R3.A-13)
U
Figure R3.A-5 Maxwell-Boltzmann distribution of velocities.
# & 3 2 )U 2
f (U,T)dU = 4" %
e
(
$ 2"k B T '
2k B T
U 2 dU
The term on the left side of Equation (R3.A-13), [f(U,T)dU], is the fraction of
molecules with velocities between U and (U + dU). Recall from Equation (R3.A4) that the number of AB collisions for a reaction cross section Sr is
Z AB = Sr (U)U C
123 A B
(R3.A-14)
k ( U )
We now let k (U) be the specific reaction rate for a collision and reaction
of A-B molecules with a velocity U.
(R3.A-15)
Equation (R3.A-15) will give the specific reaction rate and hence the reaction
rate for only those collisions with velocity U. We need to sum up the collisions
of all velocities. We will use the Maxwell-Boltzmann distribution for f(U,T) and
!all relative velocities.
integrate over
k (T) =
"
"
# 0 k (U)f(U,T)dU = # 0 f (U,T)
Sr (U) UdU
(R3.A-16)
Maxwell distribution function of velocities for the A/B pair of reduced mass
AB is
U 2
# & 3 2 2 ) 2k T
f (U,T) = 4"%
( U e B
2"k
T
$
B '
(R3.A-17)
! k (T) =
"
#0
% ( 3 2 2 + 2k T
Sr U 4$'
* U e B dU
& 2$k B T )
(R3.A-18)
For brevity, we let Sr=Sr(U), we will now express the distribution function in
terms of the translational energy T.
!We are now going to express the equation for k (T) in terms of kinetic
energy rather than velocity. Relating the differential translational kinetic
energy, , to the velocity U:
U 2
!t =
!
2
2
Multiplying and dividing by
and , we obtain
d" t = UdU
and hence, the reaction rate
# &3 2
k (T) = 4"% !
(
$ 2"k B T '
* 0 Sr
2 U
e
2
U 2 # 1 &
%
(
2 $ k BT '
#1&
% ( UdU
$ ' 123
2
dU
23
12
d, t
Simplifying
# &3 2 2
= 4"%
(
$ 2"k B T ' 2
2p185, A5p36
CD/CollisionTheory/ProfRef.doc
10
* 0 Sr
+t e
+t
k BT
d+ t
#
&1 2
8
(
k (T) = %
%$ " (k B T) 3 ('
* 0 Sr
+t e
#
&1 2
8
(
k (T) = %
%$ " (k B T) 3 ('
+t
k BT
d+ t m 3 s molecule
+ 0 Sr () t )) t
e ,) t
k BT
(R3.A-19)
d) t
Again, recall the tilde, e.g., k (T) , denotes that the specific reaction rate is per
molecule (dm /molecule/s). The only thing left to do is to specify the reaction
cross-section,
Sr(E), as a function of kinetic energy E for the A/B pair of
!
molecules.
Pr = 0"
Sr [E, T] = 0
for E < E A
(R3.A-21)
Pr =1
Sr [E, T] = #$ 2AB
for E % E A
(R3.A-22)
11
CD/CollisionTheory/ProfRef.doc
#
&1 2
k = % 8 k B T (
$ " '
) E A , /E A
+*1+ RT .- e
$ E '
= U R "# 2AB &1+ A ) e *E A
% RT (
RT
"0 2AB
(R3.A-23)
Derive
RT
(Click Back 1)
!
(Click Back 1)
#
&1 2
!
8
(
k (T) = %
%$ " (k B T) 3 ('
* o Sr (+ T )+ T
Sr = 0
Sr = #$ 2AB
" % "*
#
&1 2
8
( ") 2AB
k (T) = %
3
! %$ " (k B T) ('
$
'1 2
8
) ( k B T) 2
= "# 2AB &
&% "( k B T) 3 )(
=
!
X=
'1 2
8k T
"# 2AB & B )
% " (
e -* T
,* * t
*
, E* k TT
k BT
k BT
e -*T
d+ T
d* T
k BT
d* T
k BT
E ,E RT dE
e
RT
RT
"T
d"
"
E
E
, dX = T , X =
, T =
k BT
k BT
RT k B T RT
+E
e ,+ T
CD/CollisionTheory/ProfRef.doc
12
"
k (T) =
$ 8k T '
"# 2AB & B )
12
+E
% " (
!
udv = uv #
"
vdu
RT
X e12dX
{
3 = ,Xe
u
'1 2 + E A *E
e A
"
RT
,
%
(
$
,X /
dv
8k T
"# 2AB & B )
-*
,X
RT
+ e *E A
'1 2 * E A - 0E
+ 1/e A
,
% " ( + RT .
$
8k T
"# 2AB & B )
/.
EA
+E
RT
e ,X dX
RT
RT .
0
/
RT
EA
>1
RT
$ 8k T '
"# 2AB & B )
N Avo
% " (
=A
12
EA
RT
EA
RT
Sr = Pr "# 2AB
E
Generally, A >>1, so
RT
!
!
2
U "# E
k = R AB A e %E A
14
4RT
244
3
RT
A$
Converting k to a per mole basis rather than a per molecular basis we have
12
#
&
#
&
E
*8k
T
EA
2
B
! A" = % A () %
A
( N Avo =
AB
$ RT '
AB '
RT
$
144424443
A
k = A"e #E A
RT
EA
Ae #E A
RT
RT
We have !
good news and bad news. This model gives the correct temperature
dependence but predicted frequency factor A is even greater than A given by
Equation (R3.A-9) (which itself is often too large) by a factor (EA/RT). So we
!
have solved one problem, the correct temperature dependence, but created
another problem, too large a frequency factor. Lets try Model 2.
13
CD/CollisionTheory/ProfRef.doc
B.2 Model 2
In this model, we again assume that the colliding molecules must have an
energy EA or greater to react. However, we now assume that only the kinetic
energy directed along the line of centers E<< is important. So below EA the
reaction cross section is zero, Sr=0. The kinetic energy of approach of A toward
( )
and
#E " E A &
Pr = %
for E > E A
$ E ('
(R3.A-24)
(R3.A-25)
Sr = #$ 2AB
(E % E A )
for E > E A
(R3.A-26)
(Click Back 2)
UR
ULC
The impact parameter, b, is the off-set distance of the centers as they approach
one another. The velocity component along the lines of centers, ULC, can be
obtained by resolving the approach velocity into components.
At the point of collision, the center of B is within the distance AB.
UR
"
b
!AB
14
CD/CollisionTheory/ProfRef.doc
sin " =
(1)
# AB
(2)
U 2LC U 2R
E LC =
=
cos 2 " = E cos 2 "
AB AB
%
b2 (
E LC = E 1" sin 2 # = E'1" 2 *
& $ AB )
(3)
(4)
The minimum
! energy along the line of centers necessary for a reaction to take
place, EA, corresponds to a critical value of the impact parameter, bcrit. In fact,
this is a way of defining the impact parameter and corresponding reaction
cross section !
(5)
Sr = "b 2crit
Substituting for EA and bcrit in Equation (4)
$ b2 '
E A = E &1" crit
)
2
% # AB (
(6)
$ E '
b 2cr = " 2AB &1# A )
%
E (
(7)
% E (
Sr = "b 2crit = "# 2AB '1$ A *
&
E )
(8)
Sr = 0
E " EA
(9)
& E )
Sr = #$ 2AB (1% A +
'
E *
E > EA
(10)
U 2R
E = AB
2
15
CD/CollisionTheory/ProfRef.doc
"# 2AB
Model 2
Sr
Model 1
EA
#
&1 2
k (T) = % 8k B T (
$ " '
ESr (E )e )E RT dE
+0
(RT)
(R3.A-20)
#
&1 2
k (T) = % 8k B T (
$ " '
") 2AB (E * E A )e *E RT dE
,E
(RT)
(R3.A-27)
Integrating gives
k (T) =
$ 8k T '
"# 2AB & B )
% " (
12
e *E A
Derive
RT
(Click Back 3)
(Click Back 3)
E " EA
Pr = 0
Sr = 0
E > EA
Pr =1#
#
&2
8
( ") 2AB
k (T) = %
3
%$ " (k B T) ('
$
'1 2
8
) (kT) 3
= "# 2AB &
&% " (k B T) 3 )(
!
!
CD/CollisionTheory/ProfRef.doc
' E *
Sr = %& 2AB )1# A ,
(
E +
$*
$
,** kT
16
, +* /
*+ kT
d+
.1* 1 + e
A+ 0
3E
e -* RT d* - **
,** e -* kT
d*
kT
"
k BT
=
E
RT
'1 2 $ E A
E '
+ 1* A ) e *E RT
&
RT (
% " ( % RT
$
8k T
"# 2AB & B )
$ 8k B T '1 2 *E
2
RT
k ( T) = Ae "E A
RT
RT
C AC B
(R3.A-28)
This is similar to the equation for hard sphere collisions except for the term
e "E A
Bingo!
RT
k (T)
$ 8#k B T '
= " 2AB &
)
%
12
N Avo e *E A
RT
(R3.A-29)
This equation gives the correct Arrhenius dependence and the correct order of
magnitude for A.
(R3.A-11)
"rA = Ae "E RT C A C B
!
Effect of Temperature on Fraction of Molecules Having Sufficient Energy to React
Now we will manipulate and plot the distribution function to obtain a
!
qualitative understanding
of how temperature increases the number of reacting
molecules. Figure R3.A-8 shows a plot of the distribution function given by
Equation (R3.A-17) after it has been converted to an energy distribution.
We can write the Maxwell-Boltzmann distribution of velocities
U 2
# &3 2 2 ) k T
f (U,T)dU = 4"%
( U e B dU
$ 2"k B T '
U 2
in terms of energy by letting " =
to obtain
2
!
!
17
CD/CollisionTheory/ProfRef.doc
# & 3 2 2 ) 2k T
f (U,T)dU = 4"%
( U e B dU
2"k
T
$
B '
f (" t ,T)d" =
2
#
12
(k B T)
32
"1 2 e
"
k BT
d" t
where f(,T) d is the fraction of molecules with kinetic energies between and (+d).
We could further multiply and divide by kBT.
12
2 $ " '
*E RT d"
f (",T)dE = 1 2 &
) e
k BT
# % k BT(
!
Recalling
"
k BT
E
RT
12
2 # E &
dE
f (E, T)dE = 1 2 % ( e )E RT
RT
" $ RT '
12
2 # E & e )E RT
f (E, T) = 1 2 % (
RT
" $ RT '
!
f(!, #)
Fraction of molecules
with energy ! " or greater
E
, we could have put the distribution in dimensionless form
RT
2
f (X,T)dX = 1 2 X 1 2 e #X dX
"
E
E + dE
f(X,T)
dX is the fraction of molecules that have energy ratios between
and
!
RT
RT
By letting X =
12
2 # E &
dE
f (E, T)dE = 1 2 % ( e )E RT
" $ RT '
!RT
# 4 &1 2 1 2 +E RT
= *E %
e
dE
( E
A $ "(RT) 3 '
)
18
CD/CollisionTheory/ProfRef.doc
Derive
CH 2
|
O " CH 3 " CH 3 C H CH 3 + !
OH
|
CH 2
H CH 3 will not
Otherwise, if it hits anywhere else (say the end carbon) CH 3 C
be formed
!
!
IV. OTHER DEFINITIONS OF ACTIVATION ENERGY
M1p.36.
19
CD/CollisionTheory/ProfRef.doc
*
E !e
A. Tolmans Theorem Ea = E
"Average Energy % "Average Energy %
of Molecules
1
! a = $ Undergoing ' ( $ of Colloiding ' + kT
$
' # Molecules & 2
Reaction
#
&
3
The average transitional energy of a reactant molecule is kT .
2
A + BC " AB + C
#
ABC
E
!
EA
AB, C
A, BC
Products
Figure R3.A-9 Reaction coordinate diagram.
For simple reactions, the energy, EA, can be estimated from computational
chemistry programs such as Cerius2 or Spartan, as the heat of reaction between
reactants and the transition state
R + HR" # RH + R"
!
where R = OH, H, CH3, the relationship is shown in Figure R3.A-10.
!
CD/CollisionTheory/ProfRef.doc
20
E a = 7 cal mol
!
A + BC " AB + C
!
We consider the superposition of two attraction/repulsion potentials, VBC and
VAB, similar to the Lennard-Jones 6-12 potential. For the molecules BC, the
Lennard-Jones potential
! is
VBC
12
6*#
&
#
&
r
r
= 4" LJ ,% 0 ( ) % 0 ( /
,+$ rBC '
$ rBC ' /.
(R3.A-35)
VBC = D e
!2" (rBC ! r0 )
! 2e
(R3.A-36)
When the molecules are far apart the potential V (i.e., Energy) is zero. As
they move closer together, they become attracted to one another and the potential
energy reaches a minimum. As they are brought closer together, the BC molecules
21
CD/CollisionTheory/ProfRef.doc
begin to repel each other and the potential increases. Recall that the attractive force
between the B and C molecules is
FBC = "
dVBC
dx
(R3.A-37)
The attractive forces between the BC molecules are shown in Figure R3.A-11.
A potential similar to atoms B and C can be drawn for the atoms A and B.
The F shown in figures a and b represents the attractive force between the
! in the distances shown by the arrows. That is the attractive
molecules as they move
force increase as we move toward the well (ro) from both directions, rAB>ro and
rAB<ro.
BC
AB
VBC
VAB
kJ
F
molecule BC
kJ
molecule
FBC
!LJ
FAB
rBC
rAB
r0
rBC
rAB
(a)
r0
(b)
One can also view the reaction coordinate as a variation of the BC distance for a
fixed AC distance, l
l 444
644
47
8
|A
" B# C|
rAB rBC
l 444
644
47
8
|A
BC |
l 444
644
47
8
| AB
C|
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Reference
S2
BC
AB
S1
Energy
Ea
E1R
!HRx =E2P E1P
E2P
rBC
r1
r*BC = r*AB
r2
r*
rAB
Reaction Coordinate
Let S1 be the slope of the BC line between r1 and rBC=rAB. Starting at E1R at r1, the
energy E1 at a separation distance of rBC from r1 can be calculated from the product
of the slope S1 and the distance from E1R. The energy, E1, of the BC molecule at any
position rBC relative to r1 is
E 1 = E 1R + S1 (rBC " r1 )
(R3.A-38)
$
'
10kJ
&%e.g., E 1 = "50kJ + nm # [5 " 2] nm = "20kJ)(
!
Let S2 be the slope of the AB line between r2 and rBC=rAB. Similarly for AB, starting
on the product side at E2P, the energy E2 at any position rAB relative to r2 is
E 2 = E 2P + S2 (rAB " r2 )
(R3.A-39)
*
# 20kJ &
( ) (7 "10)nm = "20kJ/
,e.g., E 2 = "80kJ + % "
$ nm '
+
.
!
"
"
E "1 = E "2 at rBC
= rAB
(R3.A-40)
(R3.A-41)
(R3.A-42)
"
"
! E 1R + S1 rBC # r1 = E 2P + S2 rAB # r2
Rearranging
!
!
"
"
S1 rBC
# r1 = (E 2P # E 1R ) + S2 rAB
# r2
14243
$H Rx
23
CD/CollisionTheory/ProfRef.doc
"
"
rBC
= rAB
= r"
S1 r " # r1 = $H Rx + S2 r " # r2
E a = E "1 # E 1R = S1 r " # r1
yields
E a = E!a + " P #H Rx
(R3.A-43)
Derive
!
Equation (8) gives the Polyani correlation relating activation energy and heat of
reaction. Values of E oa and P for different reactions can be found in Table 5.4 on
!
page 254 of Masel. One of the more common correlations
for exothermic and
endothermic reactions is given on page 73 of Laidler.
(1)
Exothermic Reactions
!
E a = 48.1+ 0.25("H Rx ) kJ mol
If "H Rx = #100kJ mol ,
then
(R3.A-45)
E a = 23.1kJ mol
(2)
Endothermic Reactions
E a = 48.1+ 0.75("H Rx ) kJ mol
(R3.A-46)
E!
a = 48.1+ (0.75)(100 kJ mol) = 129 kJ mol = 29 kcal mol
Also see R. Masel Chemical Kinetics and catalysis, p603 to calculate the
! from the heat of reaction.
activation energy
! Szabo proposed an extension of Polyani equation
(R3.A-47)
D i = Dissociation Energies
!back)
Derive (Click
!
S1 r " # r1 = $H Rx + S2 r " # r2
(A)
(B)
Rearranging
Solving for r*
r" =
#H Rx
S r $S r
+ 11 2 2
(S1 $ S2 ) S1 $ S2
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CD/CollisionTheory/ProfRef.doc
(C)
E a = E "1 # E 1R = S1 r " # r1
(R3.A-43)
$ "H Rx S1 r1 # S2 r2 '
E a = S1 &
+
) # S1 r1
S1 # S2 (
%S1 # S2
(E)
Rearranging
# S1 &
*S1 r1 " S2 r2
Ea =%
" r1 /
()H Rx + S1 ,
+ S1 " S2
.
$ S1 " S2 '
# S1 &
*S1 r1 " S2 r2 " S1 r1 + S2 r1 =%
()H Rx + S1 ,
/
S1 " S2
+
.
$ S1 " S2 '
(F)
(G)
# S1 &
# S1S2 &
Ea =%
(*H Rx + %
([ r1 " r2 ]
S1 " S2 '
S1 " S2 '
$1
$
424
3
1442443
(H)
E +a
)P
# "H Rx & 2
E A = %1+
( E A0
$ 4E A0 '
C. Blowers-Masel Relation
The Polyani Equation will predict negative activation energies for highly
exothermic reactions. Blowers and Masel developed a relationship that
!
compares quite well with experiments throughout the entire range of heat of
reaction for the family of reactions
R + HR" # RH + R"
as shown in Figure R3.A-13.
25
CD/CollisionTheory/ProfRef.doc
We see the greatest agreement between theory and experiment is found with
the Blowers-Masel model.
VI. CLOSURE
We have now developed a quantitative and qualitative understanding of the
concentration and temperature dependence of the rate law for reactions such as
A+BC+D
with
rA = k CACB
We have also developed first estimates for the frequency factor, A, from collision
theory
A = Sr U R N Avo =
'1 2
8k T
"# 2AB & B )
% " AB (
N Avo
E A = E oA + " P #H Rx
These calculated values for A and EA can be substituted in the rate law to
determine rates of reaction.
"rA = kC A C B = Ae "E A
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CD/CollisionTheory/ProfRef.doc
RT
D = dissociation energy
ro = equilibrium internuclear distance
= constant
Model B3 Stored Energy
This third method considers vibrational and translation energy in addition to
translational energy. Even though this approach is oversimplified, it is
satisfying because it gives a qualitative feel for the Arrhenius temperature
dependence. In this approach, we say the fraction of molecules that will react
are those that have acquired an energy EA.
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CD/CollisionTheory/ProfRef.doc
$ " ' 2 #1 1
(R3.A-30)
f (",T) =
e#" kT
$1
' &% k B T )(
k BT
& n #1)!
%2
(
dF = f (",T)d" = fraction of molecules with energy between and ( + d)
For methane, there are 3 transitional, 3 rotational, and 9 vibrational degrees of
freedom, n = 15. Because Equation (31) is awkward, the two dimension
!
equation is often used, with n = 2 and the distribution function is
1
e#" k BT
f (",T) =
k BT
(R3.A-31)
Activation Energy
From the Maxwell-Boltzmann distribution of velocities we obtain the
! of the molecules as shown below. Here, fd is the
distribution of energies
fraction, dF, of molecules between and + d.
dF = f (",T)d"
We now say only those molecules that have an energy, EA or greater, will react.
Integrating between the limits E* (i.e., EA) and infinity, we find the fraction of
! energy EA or greater
molecules colliding with
F=
1
kB
% e"# k
T #*
BT
d#
dF =
#$
%E
Integrating
"E RT
"
k BT
E
RT
dE
F = e "E A!RT
(R3.A-32)
"rA = Ae "E A
RT
C AC B
k = A e "E A
!
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CD/CollisionTheory/ProfRef.doc
RT
= A e "#*
kT