CHAPTER 1

1.1. For the thermal cracking of ethane in a tubular reactor, the following data were
obtained for the rate coefficient at different reference temperatures:

T(°C) 702 725 734 754 773 789 803 810 827 837
-1
k(s ) 0.15 0.273 0.333 0.595 0.923 1.492 2.138 2.718 4.137 4.665

Solution

The Arrhenius expression

 E 
k  A exp  
 RT 

is transformed logarithmically into:

E
ln k  ln A 
RT

For each data point ln k and 1/T is calculated:

x = 1/T∙10³ y = ln k

1.025 –1.897
1.002 –1.298
0.993 –1.100
0.974 –0.519
0.956 –0.080
0.941 0.400
0.929 0.760
0.923 1.000
0.909 1.420
0.901 1.540

The slope and the intercept (ln A) are calculated by linear regression:

 x y
E  xy  N
 
R  x 2
x 2

N

ln A 
 y  m x
N

with x = 1/T and y = ln k.

 So:

E
  28497. or E  56623 kcal/kmol or 2.37  10 5 kJ/kmol.
R

ln A = 27.245 or A = 6.800∙1011 s-1

1.2. Derive the result given in Table 1.2.4.2-1 for the reaction
.
A
B

Q
S

  

Solution
A
B

Q
S

  

The continuity equation for species A reads:

dC A
 k C A C B (1)
dt

To integrate (1), CB has to be expressed as a function of CA:

C B  C B0  (C A 0  C A )

Hence,

CA t
dC A

C A0
C A (C B 0  C A 0  C A )
 k  dt
0

or
1 CB  CA
kt  ln 0
CB0  CA 0 CA 0  CB

Expressing the concentrations CA and CB as a function of the conversion of the reactant,

xA:

C A  C A 0 1  x A 

 
C B  C B 0  C A 0  C A  C B 0  C A 0  C A 0 1  x A 

 CB0  CA 0 x A

Hence

1 C B 0  C A 0 1  x A 
kt  ln
C B 0  C A 0 C A 0 (C B 0  C A 0 x A )
 or
1 M 1  x A 
C A 0 kt   ln
M 1 M  xA
with
C B0
M
C A0

1.3. Derive the solutions to the rate equation for the first order reversible reaction given
in Section 1.2.3.

Solution

1
For A  Q
2

dC A
rA    k1 C A  k 2CQ
dt

 k 1C A  k 2 C A 0  C Q 0  C A 
or
dC A
dt
 k 1  k 2 C A  k 2 C A 0  C Q 0  
This is a standard form, with integrating factor

exp [  (k1  k 2 ) dt ]  exp (k1  k 2 ) t 

Thus


d  k1  k 2 t
dt
e  
C A  e   k1  k 2 t k 2 C A 0  C Q 0 
and

C A  e  k 1  k 2 t \ b  k 2 (C A 0  CQ 0 ek 1  k 2 t dt  K ) 


k2
k1  k 2
 
C A 0  CQ 0  Ke  k 1  k 2 t

Now, at t = 0, CA = CA0, leading to

k1C A 0  k 2CQ 0

C A  C A 0  CQ 0  k k k2

k1  k 2
e   k 1  k 2 t
1 2

which is the solution given in Section 1.2.3.

The alternate approach in terms of conversions is somewhat simpler:

 
rA  k1  k 2 C A 0 x A eq  x A 
dC A dx
  CA 0 A
dt dt

 CA 0
d
dt

x A  x A eq 
Then

d
dt
 
x A  x A eq  k1  k 2  x A  x A eq  
and direct integration gives:

x A  x A eq
ln  k1  k 2 t  0 
0  x A eq
or
 x 
ln1  A   k  k t
 xA  1 2
 eq 

1.4. A convenient laboratory technique for measuring the kinetics of ideal gas phase
single reactions is to follow the change in total pressure in a constant volume and
temperature container. The concentration of the various species can be calculated
from the total pressure change.

Consider the reaction

aA  bB  ...  qQ  sS  ...

(a) Show that the extent can be found from:


V p t  p t0 
ξ
RTΔα 

where Δα  q  ... - a - b - ...

(Note that the method can only be used for Δα  0 .)

(b) Next show that partial pressure for the jth species can be found from

p j  p j0 
aj
Δα
p t  p t0 
(c) Use the method to determine the rate coefficient for the first-order decomposition of
di-t-butyl peroxide
 CH3 3 COOCCH3 3  2CH3 2 CO  C2H 6
The data given below are provided by J.H. Raley, R.E. Rust, and W.E. Vaughn
[J.A.C.S., 70, 98 (1948)]. They were obtained at 154.6°C under a 4.2-mm Hg partial
pressure of nitrogen which was used to feed the peroxide to the reactor. Determine the
rate coefficient by means of the differential and integral method of kinetic analysis.

t (min) pt (mm Hg)

0 173.5
2 187.3
3 193.4
5 205.3
6 211.3
8 222.9
9 228.6
11 239.8
12 244.4
14 254.5
15 259.2
17 268.7
18 273.9
20 282.0
21 286.8
∞ 491.8

Solution

a) For 0   α jA j
j

N j  N j0  α j ξ
Also,
RT RT
pj  N j, pt   p j   Nj
V j V j

Thus,

ξ  α j   N j  N j0  
j j


V
RT

p t  p t0 
with Δα   α j
j
 
V p t  p t0 
ξ 
RT Δα

b) Use

pj 
RT
V
Nj 
RT
V

N j0  α j ξ 
RT V p t  p t0
 p j0  αj
V RT Δα

 p j0 
αj
Δα
p t  p t0  
c) CH 3 3 COOCCH 3 3  2CH 3 2 CO  C 2 H 6

rA 
1 dξ 1 V 1 d
 
V dt V RT Δα dt
pt  pt 0  

 kC A  k
pA

k 
RT RT  pA 0 
(1) 
pt  pt 0   
2 
or
d
   1 
p t  p t 0  2k p A 0  p t  p t 0   
dt  2 

Integrating yields:

 1

 p A0  2 p t  p t 0 
ln    kt
 p A0 
 

The integral method uses a plot of ln [ ] vs. t, and the slope gives the value of k.
Alternatively, a linear or nonlinear regression method could be used: k = 0.0193 min-1.


The differential method utilizes slopes from the p t  p t 0 data plotted vs. 
 1
 

p A 0  2 p t  p A 0  , the slope of which, or regression techniques, gives the rate
 
coefficient: k = 0.0196 min-1.
 0.5

0.4

 1

 p A0  2 p t  p t0 
- ln   0.3
 p A0 
 

0.2 Slope = 0.0193 min-1

0.1

0
0 5 10 15 20 25
time(min)

1.5. The results of Problem 1.4 can be generalized for the measurement of any property
of the reaction mixture that is linear in the concentration of each species:

λ j  K jC j

The λ j could be partial pressures (as in Problem 1.4) various spectral properties, ionic
conductivity in dilute solutions, and so on. Then the total observed measurement for the
mixture would be:

λ   λ j   K jC j
j j

a) For the general single reaction,

α A
j
j j 0

show that the relation between the extent of reaction and λ is

 ξ
λ  λ 0    α j K j 
 j V

where

λ 0   K jC j0
j
b) After a long (“infinite”) time, the extent ξ  can be evaluated for irreversible reactions
from the limiting reagent, and for reversible reactions from thermodynamics. Use this
to formulate the desired relation containing only measured or determined variables
(see Frost and Pearson [41]):

λ  λ0 ξ

λ  λ ξ

The total observed property for the mixture is given as

λ   K jC j
j

a) For the general reaction

α A
j
j j 0

the concentration at reaction extent ξ is

Nj N j0 ξ
Cj    αj
V V V

Thus,

N j0 ξ
λ  Kj   K j j
j V j V

 ξ
  K jC j0    K jα j  , constant volume
j  j V

b) For infinite time, either ξ  can be found from the thermodynamic equilibrium
constant

αj
 ξ 
K C    C j0  α j  
j  V

or from the limiting reactants:

ξ
0  C 0,LR  α LR
V

In either case from part a):

 ξ
λ   λ 0   α jK j
V

Solving for the extents,

ξ λ  λ0

V  α jK j
and
ξ λ  λ0

V  α jK j

Dividing the two gives the desired result:

ξ λ  λ0

 λ  λ0

1.6. Show that the general expression for the concentration at which the autocatalytic
reaction of Section 1.2.3.3 has a maximum rate is
C CQ

12

CC
1

 
Q

0
A

   
0

0
Q
a
x
m

 

Note that this agrees with the specific results in the example.

Solution

From Section 1.2.3.3, the rate written in terms of only CQ is:

r  k 1 C 0  C Q C Q  k 2 C Q2

The maximum rate will be at r C Q  0 :

r
 0  k 1C 0  2k 1C Q  2k 2 C Q
C Q
or
C  
1
C0
k1 1
 C0
K
k1  k 2 2 1  K
Q max
2

where K is the equilibrium constant.

This can be written as

  CQ   C 
   1 K 1  A0 
C   
 Q0  max 2 1  K  C Q0 

1  C A0 
 1
2  C Q0 

for the irreversible case with K   , as in the numerical calculations.

1.7. Derive the concentration as a function of time for the general three species first
order reactions:
1
A Q
2

4 3 5 6

These should reduce to all the various results for first order reactions given in
Sections 1.2 and 1.3. Also determine the equilibrium concentrations CAeq, CQeq, CSeq
in terms of the equilibrium constants for the three reactions.

Solution

The general solution method is best explained in terms of the complex reaction network
notation where the rate for the jth species is given by:

dy j  N 
 k j1y1  k j2 y 2  ...     ' k lj  y j  ... (1)
dt  l 1 

A solution is assumed of the form:

y j  Yj0 e  λt (2)

where Yj and λ are constants to be determined. Substituting (2) into (1) gives

Yj  λ e  λt  k jl Y1e  λt  ...    ' k lj Yje  λt  ...

or
 
k j1Y1  k j2 Y2  ...    ' k lj   λ Yj  ...  0 (3)

If equations (3) are written out for each of the j = 1, 2, … N species, they form a set of N
equations for the N unknown, Yj. Note that they are homogeneous algebraic equations
(RHS ≡ 0), and so they only possess solutions if the determinant of the coefficients is
zero.
 λ   ' k  l1 k12 k13  k1N
k 21 λ   ' k  l2 k 23  k 2N
   0 (4)
  
k N1 k N2 k N3  λ   ' k lN 
When multiplied out; (14) will be an Nth order equation, with N-roots. For each of these
roots, a set of the constants Yj can be found from (3): Yjr. Then the general solution will
be

N
y j   C r Yjr e  λ rt (5)
r 1

where Cr are constants of integration to be found from the initial conditions. For our
specific problem, the determinant, (4), is:

λ  k1  k 3  k1 k3
k2 λ  k 2  k 6  k6 0 (6)
k4 k5 λ  k 4  k 5 

which when expanded gives:

λ 2  λk1  k 2  k 3  k 4  k 5  k 6   k1 k 4  k 5  k 6 
λ 0
 k 2 k 3  k 4  k 5   k 3 k 5  k 6   k 4 k 6 
or

λ λ 2  αλ  β  0  (7)

Thus, the roots (eigenvalues) are

λ1  0
α  α 2  4β
λ 2,3  (8)
2

(Note, Wei-Prater would number these λ 0 , λ1 , λ 2 .)

Then the solutions will have the form

C A  C1 YA1  C 2 YA2 e  λ 2 t  C 3 YA3 e  λ 3t (9)

C Q  C1 YQ1  C 2 YQ2 e  λ 2 t  C 3 YQ3 e  λ 3t (10)
C S  C1 YS1  C 2 YS2 e  λ 2 t  C 3 YS3 e  λ 3t (11)

where the Yjr are found from

 λ r  k 1  k 3 Y1r  k 1Y2r  k 3 Y3r  0
k 2 Y1r  λ r  k 2  k 6 Y2r  k 6 Y3r  0 (12)

k 4 Y1r  k 5 Y2r  λ r  k 4  k 5 Y3r  0

for each of the λr (actually, only two of the equations will be independent, and so two of
the Yjr can be found in terms of the third).

Finally, the integration constants, Cr, are found from the initial conditions:

C A0  C1 YA1  C 2 YA2  C 3 YA3

C Q0  C1 YQ1  C 2 YQ2  C 3 YQ3 (13)

C S0  C1 YS1  C 2 YS2  C 3 YS3

Clearly, these manipulations are most easily done utilizing matrices.

The equilibrium concentrations will be found from (9)-(11) for t   :

C A,eq  C1 YA1 (14)

where YA1 and C1 are known in terms of the kji and initial concentrations. From the
principle of microscopic reversibility, it is also time that each reaction is individually at
equilibrium, leading to:

 CQ  k
   1  K I
 CA  eq k 2

 CA  k
   4  K II (15)
 CS  eq k 3

 CS  k
   6  K III
C 
 Q  eq k 5

with

K I K II K III  1 (16)

The total mass balance is

C A  C Q  C S  C A0  C Q0  C S0  C 0 (17)

Then, using (17) and (15):

 1
C Ae  K I C Ae  C Ae  C 0
K II
or
C0
C Ae   C1 YA1
1  K I  K II

Similarly

C0
C Qe   C1 YQ1 (18)
K II  1  K III
C0
C Se   C1 YS1
1
K II  1
K III

1.8. For the complex reactions

aA  bB 

1
qQ

q' Q  b' B 

2
sS

(a) Use (1.1.2-15) and (1.1.2-17) to express the time rates of change of NA, NB, NQ,
and NS in terms of the two extents of reactions and stoichiometric coefficients a, b,
b’, q, q’, and s; for example,

dN A dξ dξ
 a 1  (0) 2
dt dt dt

(b) In practical situations, it is often useful to express the changes in all the mole
numbers in terms of the proper number of independent product mole number
changes—in this case, two. Show that the extents in part (a) can be eliminated in
terms of dNQ/dt and dNS/dt to give

dN A a dN Q a q' dN S
 
dt q dt s q dt

dN B b dN Q  b q' b'  dN S
    
dt q dt  s q s  dt

This alternate formulation will be often used in the practical problems to be

considered later in the book

(c) For the general reaction

α A
j 1
ij j i  1, 2, ..., M
 The mole number changes in terms of the extents are

dN j N
dξ i
  α ij
dt j1 dt
or
dN dξ
 αT
dt dt

where N is the N-vector of numbers of moles, ξ is the M-vector of extents, and αT is

the transpose of the M x N stoichiometric coefficient matrix. Show that if an
alternate basis of mole number change is defined as an M-vector

dN b
dt

that the equivalent expressions for all the mole number changes are

dN
dt
 αT αb    T 1 dN b
dt

where αb is the M x M matrix of the basis species stoichiometric coefficients.

Finally, show that these matrix manipulations lead to the same result as in part (b) if
the basis species are chosen to be Q and S.

Solution

aA  bB  qQ ξ1

(a) q' Q  b' B  sS ξ2

 
N j   α ij ξ i , N j  N j0   α ijξ i
i i

Thus,

 
N A   a ξ1 (1)
  
N B   b ξ1  b' ξ 2 (2)
  
N Q  q ξ1  q' ξ 2 (3)
 
NS  s ξ 2 (4)

 
(b) Rearrange for ξ1 and ξ2 in terms of N Q , N S :
  1
ξ 2  NS (5)
s
 1  q'  1  q' 1 
ξ1  N Q  ξ 2  N Q  NS (6)
q q q qs

Thus,

 a  a q' 
NA   NQ  NS (7)
q sq
 b  b r'  b' 
NB   NR  NS  NS (8)
r s r s

(c) For the general reaction

N
0   α ijA j , i  1, 2, ..., M (9)
j 1

The change in mole numbers is:

 
N
~
 [α~ ]T ξ (10)
~

If the new M-vector basis species are


N
~
(11)

the M x M matrix of basis species stoichiometric coefficients is part of the total

stoichiometric matrix:


α~  [α~ ]α1,1,MM 11
β α
 (12)

(The stoichiometric coefficient matrix can always be arranged to have the new basis
species coefficients first.)

Now the subset of the mole number change equations for the new basis species are:

 b

N~  [α~ ]T ξ
b


~
(13)

which is equivalent to (3)-(4) above. Then solving for the extents gives

 N
 b
1 
ξ  [α~ ]T
b
~
(14)
~

which is equivalent to (5)-(6) above.

Finally substitute (14) into (10) to give the desired results:



N~  [α~ ] [α ]
T
~
N
b T 1
 b

~
(15)

This general result can be used to define any conversion basis in a complex reacting
system.

It is instructive to use (15) for the simple example of part (b).

aA  bB  qQ
ξ 
q' Q  b' B  sS ξ   1 (M = 2)
~
ξ 2 

 a 0 
 b  b'
  a  b q 0
α~   α~   
T
,  q  q'
 0  b'  q' s 
 
0 s 

Then checking the rate vector:

  
 a 0    a ξ1 0 
 b  b'      

 
ξ  b ξ  b' ξ
N  [α~ ] ξ  
T   1   1
 
2
~  q  q' ξ   q ξ  
   2  1 q'

ξ 2

0 s 
 0 s ξ 2 

as in part (a).

Now choose the alternate basis vector:

 b 
N
N    Q
~
 NS 
 
and
 q 0
α~  
b

 q' s 

Then, working out the intermediate matrix steps:

q  q'
[α~ ]T  
b

0 s 
  s  q'
0 q 
{[α~ ]T }1   
b

qs
and
  a 0   s  q'
 b  b' 
b T 1    0 q 
α~ {[α~ ] } 
T

 q  q' qs
 
0 s 

  as  aq' 
 bs  bq' b' q 
1
  
qs  qs qq'q' q 
 
 0 qs 

  a/q  aq' /qs 

 b/q  (bq' /qs)  b' /s 
 
 1 0 
 
 0 1 

Finally,

 a  aq'  
  q N Q  qs NS 
 

   
  NS 
b bq' b'
 
  b
 T 1
  N Q  
N
~
α N
~  q  qs s  
  
 NQ 
  
 NS 

or

 a  a q' 
NA   NQ  NS
q sq

 b   b q' b'  
N B   N Q     NS
q s q s 

 
NQ  NQ

 
NS  NS
1.9. Show that the overall orders for a free radical reaction mechanism with a first
order initiation step are 3 2 and 1 2 for a ββ, respectively μμ termination.

Solution

(a) ββ termination

A 1 
k1
2R 1

R 1  A 1 
k2
R 1 H  R 2

R 2 
k3
R 1  A 2

R 1  R 1 
k4
A1

Disappearance rate of reactant A1:

 dC A1
 k1C A1  k 2C R 1 C A1  k 4C 2R 1 (1)
dt

Steady state for the intermediate radicals R 1 and R 2 :

dC R 1
 2k1C A1  k 2C R 1 C A1  k 3C R 2  2k 4C 2R 1  0 (2)
dt
dC R 2
 k 2 C R 1 C A 1  k 3C R 2  0 (3)
dt

From (3): k 3C R 2  k 2C R 1 C A1

Elimination of C R 2 from (2) yields:

2k1C A1  k 2C A1 C R 1  k 2C R 1 C A1  2k 4C 2R 1  0

k1
CR 1  CA (4)
k4 1

Substitution of (4) into (1):

dC A1 k1 3 2
  k2 CA (5)
dt k4 1

since k1 is negligibly small.

(b) μμ termination

A1 
k1
2R 1

R 1  A1 
k2
R 1 H  R 2

R 2 
k3
A 2  R 1

R 2  R 2 
k5
A3

Disappearance rate of reactant A1:

 dC A1
 k1C A1  k 2C R 1 C A1 (6)
dt

Steady state for the intermediate radicals R 1 and R 2 :

dC R 1
 2k1C A1  k 2C R 1 C A1  k 3C R 2  0 (7)
dt

dC R 2
 k 2C R 1 C A1  k 3C R 2  2k 5C 2R 2  0 (8)
dt

Solution of (7)-(8) for C R 1 and C R 2 yields:

k1 1 2 k1 k 3 k1 1 2
CR 2  CA and CR 1  2  CA (9)
k5 1 k2 k2 k5 1

Substitution of (9) into (6) :

dC A1  k k k1 1 2 
  k1C A1  k 2C A1 2 1  3 CA 
dt  k2 k2 k5 1 

k1 1 2
 3k1C A1  k 3 CA (10)
k5 1

k1 1 2
 k3 CA
k5 1
1.10. The thermal decomposition of dimethyl ether

CH 3 OCH 3  CH 4  CO  H 2
or
CH 3 OCH 3  CH 4  HCHO

is postulated to occur by the following free radical chain mechanism:

CH 3 OCH 3 
k1
CH 3  OCH 3

CH 3  CH 3 OCH 3 
k2
CH 4  CH 2 OCH 3

CH 2 OCH 3 
k3
CH 3  HCHO

CH 3  CH 2 OCH 3 
k4
C 2 H 5 OCH 3

(a) For a first order initiation step, use the Goldfinger, Letort and Niclause
table [1948] to predict the overall order of reaction.

(b) With the help of the steady state assumption and the usual approximation
of small initiation and termination coefficients, derive the detailed kinetic
expression for the overall rate:

dCH 3OCH 3 
  k o CH 3OCH 3 
n

dt

and verify that the overall order, n, is as predicted in part (a). Also find ko in
terms of k1, k2, k3, k4.

(c) If the activation energies of the individual steps are E1 = 80, E2 = 15, E3 =
38, E4 = 8 Kcal/mol, show that the overall activation energy is Eo = 62.5 Kcal/mol.

Solution

(a) The termination is of the type βμ. Hence, for a first order initiation, the overall order of
reaction is 1.

(b) Disappearance rate of CH3OCH3:

dCH 3OCH 3 
dt
 
  k1 CH 3OCH 3   k 2 CH 3 CH 3OCH 3  (1)

Steady state for the intermediate radicals CH 3 OCH 2 and CH 3 :


d CH 3   
 k 1 CH 3 OCH 3   k 2 CH 3 CH 3 OCH 3 
dt
(2)
 

 k 3 CH 3 OCH  k 4 CH
2  
3 CH OCH   0
3

2
 
d CH 3 OCH 2  
 k 2 CH 3 CH 3 OCH 3   k 3 CH 3 OCH 2  
dt
(3)
 
 k 4 CH 3 CH 3 OCH 2  0 
Solving (3) for CH 3OCH 2  yields:

CH OCH   k CH CH OCH  

 2

k  k CH 
2 3 3
3 2 
(4)
3 4 3

Substituting (4) into (2):

k1 CH 3OCH 3   k 2 CH 3 CH 3OCH 3   

 k3
 
k 2 CH 3 CH 3OCH 3  k 4 CH 3 k 2 CH 3 CH 3OCH 3 
 0
   
k 3  k 4 CH 3  
k 3  k 4 CH 3  
or


2k 2 k 4 CH 3  2
 
 k 1 k 4 CH 3  k 1 k 3  0

The terms k1k 4 CH 3  may be dropped because k1 and k4 are small compared to the
other k’s. Hence

CH   2kk kk

3
1 3
(5)
2 4

Substitution of (5) into (1):

dCH 3OCH 3 
 k1 CH 3OCH 3   k 2 CH 3OCH3 
k1k 3

dt 2k 2 k 4

dCH 3 OCH 3  k 1k 2 k 3
  CH 3 OCH 3  (6)
dt 2k 4

This corresponds to n = 1.

The apparent rate coefficient reads:

k1k 2 k 3
ko 
2k 4

(c) The overall activation energy is determined by means of (7):

 E
1
80  15  38  8  62.5 kcal/mol .
2

1.11. K. Laidler and B. Wojciechowski [Proc. Roy. Soc., A260, 91 (1961)] provide the
following table of individual rate constants for ethane pyrolysis:

Reaction A 0 E (Kcal/mol)
1 1.0 1017 85.0 1st order initiation
1a 2 (6.5) 1017 70.2 2nd order initiation
2 2.0 1011 10.4 hydrogen abstraction
3 3.0 1014 39.5 radical decomposition
4 3.4 1012 6.8 H   C 2 H 6  H 2  C 2 H 5
5 1.6 1013 0 H   C 2 H 5  termination
6 1.6 1013 0 C2 H 5  C2 H 5  termination

• in s-1 or cm³ mol-1 s-1

(a) Derive the overall kinetic expressions for the four combinations of the two
possible initiation steps (1 or 1a) and the termination steps (5 or 6).

(b) Compare the overall rate constants at T = 837°K with the experimental
value of 8.4 10-4 s-1.

(c) Show that the ratio of the rates of reaction 5 and 6 is given by:

r5 k 3 k 5 1

r6 k 4 k 6 C 2 H 6

(d) Calculate the “transition pressure level” where terminations (5) and (6)
are equivalent (r5 = r6) at T = 640°C, and compare with the measured value of 60
mm Hg. At this point, the overall reaction is changing from 1 to 3/2 order.

Solution

(a) Reaction scheme:

1. C 2 H 6 
k1
2CH 3

1a. Χ  C 2 H 6 
k1a
2CH 3  Χ

2. C 2 H 6  CH 3 
k2
CH 4  C 2 H 5

3. C 2 H 5 
k3
C2H 4  H