PROBLEMA 1

Considere la siguiente secuencia de reacciones para la descomposicin de un perxido

orgnico ROOR en disolvente SH.
ROOR K 1 2 R O

RO +SH K 2 ROH + S

S + ROOR K 3 SOR + RO

2 S K4 S2

Demuestre que la velocidad de desaparicin del perxido es:

r ROOR =K 1 [ ROOR ] + K 3
K1.
K4.
[ ROOR]3 /2

Solucin
Teniendo en cuenta que la velocidad de desaparicin del perxido ser:
ROOR=K 1 [ ROOR ] K 3 [ ROOR ] [ S ]
r

ROOR= K 1 [ ROOR ] + K 3 [ ROOR ] [ S ]

r (1)

Aplicando la aproximacin de estado seudo estacionario a los productos intermedios

radicalarios
S y RO , se deduce que

S


r s =K 2 [ SH ] [ RO ] K 3 [ S ] [ ROOR ] 2 K 4

r RO =K 1 [ ROOR ] K 2 [ RO ] [ SH ]K 3 [S ][ ROOR]

Sumando algebraicamente ambas expresiones se obtiene

S
[ ]2 =0
2 K 1 [ ROOR ] 2 K 4

S
[ ]2
2 K 1 [ ROOR ] =2 K 4

[ S] =
K1
K4
[ ROOR ]

Sustituyendo el valor obtenido [ S ] en la ecuacin cinetica de desaparicin del perxido (1)
se llega a :
 ROOR= K 1 [ ROOR ] + K 3 [ ROOR ] [ S ]
r

ROOR= K 1 [ R OOR ] + K 3 [ ROOR ] (

r
K1
K4
[ ROOR ] )

Agrupando trminos comunes , la velocidad de desaparicin de perxido tiene como

ecuacin:

r ROOR =K 1 [ ROOR ] + K 3
K1 .
K4 .
[ROOR]3 / 2

PROBLEMA 2
PARA LA REACCIN EN FASE GASEOSA
H 2+ NO2 K 1 H 2 O+ NO

SE A PROPUESTO EL SIGUIENTE MECANISMO EN CADENA

H 2+ NO2 K 1 H + HONO

H + NO 2 K 2 OH + NO

OH + H 2 K 3 H 2 O+ H

OH + NO2 K 4 HNO3

DETERMINE LA EC. DE LA VELOCIDAD DE FORMACION DEL AGUA

Solucin:
Formacion del agua
r H O =k 3 [ H 2 ] [ O H ]
2

Para el radical O H :
r O H =k 2 [ H ] [ N O2 ]

r O H =k 3 [ O H ] [ H 2 ]

r O H =k 4 [ O H ] [ N O2 ]

r O H =k 2 [ H ] [ N O2 ] k 3 [ O H ] [ H 2 ]k 4 [ O H ] [ N O 2 ] ..(

Para el radical H:
r H =k 1 [ H 2 ][ N O2 ]

r H =k 2 [ H ] [ N O2 ]

 r H =k 3 [ O H ] [ H 2 ]

r H =k 1 [ H 2 ][ N O2 ] k 2 [ H ] [ N O2 ] + k 3 [ O H ] [ H 2 ] (

IGUALANDO ( ) Y ( )

k 2 [ H ] [ N O2 ] k 3 [ O H ] [ H 2 ]k 4 [ O H ] [ N O 2 ] =k 1 [ H 2 ] [ N O 2 ] k 2 [ H ] [ N O 2 ] + k 3 [ O H ] [ H 2 ]

k 1 [ H 2 ][ N O2 ]
= k 4 [ O H ] [ N O2 ]

K 1 [ H 2 ][ NO 2 ]
[ OH ] =
K 4 [ NO 2 ]

K 1[ H 2]
[ OH ] = ()
K4

REMPLAZANDO [ OH ] EN ( )

r H O=k 3 [ O H ] [ H 2 ]
2

REMPLAZANDO EN ( )
k 3 [ H 2 ] K 1 [ H 2 ]
r H O= 2
K4

Se obtiene finalmente:
k1 2
r H O= k3 [ H 2 ]
2
k4

PROBLEMA 3
La cintica de formacin del HBr fue estudiada por bodenstein y linid en 1906. el mecanismo
propuesto es
Br 2 K 1 Br +Br

Br + H 2 K 2 HBr + H

H + Br 2 K 3 HBr +Br

HBr + H K 4 Br + H 2

Br + Br K 5 Br 2

Si la ecuacion cinetica obtenida tiene la forma

 1 /2
[ HBr ] P [ H 2 ][ Br 2 ]
=
t [ HBr ]
1+q
[ Br 2 ]
CUAL SERAN LOS VALORES DE LOS COEFICIENTES P Y Q EN TERMINOS DE
K1,K2,K3, K4 Y K5
DEL MECANISMO DE REACCION O SE TIENE QUE

Br 2 K 1 Br +Br
1
Br + H 2 K 2 HBr + H
2
H + Br 2 K 3 HBr +Br
3
HBr + H K 4 Br + H 2
4
Br + Br K 5 Br 2
5
HALLANDO rHBr

DE (2) rHBr=K 2 [ Br ] [ H 2 ]

DE (3) rHBr=K 3 [ H ] [ Br 2 ]

DE (4) - rHBr=K 4 [ H ] [ HBr ]

- rHBr=K 2 [ Br ] [ H 2 ] + K 3 [ H ] [ Br 2 ]K 4 [ H ] [ HBr ] ( )

PARA [ Br ]

r Br =K 1 [ BR 2 ]
DE (1)

DE (2) - r Br =K 2 [ Br ] [ H 2 ]

DE (3) r Br =K 3 [ H ] [ Br 2 ]

DE (4) r Br =K 4 [ H ] [ HBr ]

2
DE (5) - r Br =K 5 [ Br 2 ]

2
r Br =K 1 [ BR 2 ]
- K 2 [ Br ] [ H 2 ] + K 3 [ H ] [ Br 2 ] + K 4 [ H ] [ HBr ] - K 5 [ Br ] ( )

PARA [ H ]

DE (2) r H =K 2 [ Br ] [ H 2 ]

DE (3) - r H =K 3 [ H ] [ Br 2 ]

DE (4) r H =K 4 [ H ] [ HBr ]

 r H =K 2 [ Br ] [ H 2 ]K 3 [ H ] [ Br 2 ] - K 4 [ H ] [ HBr ] ( )

SUMANDO ( ) Y ( )
2
0=K 1 [ BR 2 ]K 5 [ Br ]
2
K 1 [ BR 2 ]=K 5 [ Br ]

1 /2
K
( )
[ Br ] = 1
K5 [ Br 2 ]
1/ 2
I)

REMPLAZANDO EN )

0=K 2 [ Br ] [ H 2 ]K 3 [ H ] [ Br 2 ] - K 4 [ H ] [ HBr ]
1/ 2
K1
0=K 2
K5 ( ) 1 /2
[ Br2 ] [ H 2 ]K 3 [ H ] [ Br 2 ]
- K 4 [ H ] [ HBr ]

1/ 2
K1
K2
( )[
K5
Br 2 ]
1 /2
[ H 2 ]=K 3 [ H ] [ Br 2 ]+ K 4 [ H ] [ HBr ]
1/ 2
K1

[ H ]=
K2
( )

K5
1 /2
[ Br2 ] [ H 2 ]

(II)
K 3 [ H ] [ Br 2 ]+ K 4 [ H ] [ HBr ]

D E ( I ) Y ( II ) EN ( )

- rHBr=K 2 [ Br ] [ H 2 ]+ K 3 [ H ] [ Br 2 ] K 4 [ H ] [ HBr ]
REMPLAZANDO
-
1 /2 1 /2

( ) ( )
K1 K1
K1 1/ 2
K2 ( )
K5
[ Br 2 ]
1/ 2
[ H2] K2 ( ) K5
1/ 2
[ Br 2 ] [ H 2 ]
rHBr=K 2 ( )
K5
1 /2
[ Br 2 ] [ H 2 ]+ K 3 K 3 [ H ] [ Br 2 ] + K 4 [ H ] [ HBr ]
[ Br 2 ]K 4 K 3 [ H ] [ Br 2 ] + K 4 [ H ] [ HBr ]
[ HBr

1 /2

( )
K1

- rHBr=K 2 K 1
1/ 2
K2 ( ) K5
1/ 2
[ Br 2 ] [ H 2 ]
K5 ( ) 1 /2
[ Br 2 ] [ H 2 ]+ ( K 3 [ Br 2 ]K 4 [ HBr ] )
K 3 [ H ] [ Br 2 ] + K 4 [ H ] [ HBr ]

1/ 2
K 3 [ Br 2 ] K 4 [ HBr ]
-
rHBr=K 2
K1
( )
K5
1 /2
[ Br 2 ] [ H 2 ] ( 1+
K 3 [ Br 2 ] K 4 [ HBr ] )
 1/ 2
K 3 [ Br 2 ] + K 4 [ HBr ] + K 3 [ Br 2 ] K 4 [ HBr ]
rHBr=K 2
K1
( )
K5
1 /2
[ Br 2 ] [ H 2 ] ( K 3 [ Br 2 ]K 4 [ HBr ] )
1/ 2
2 K 3 [ Br 2 ]
] ( )
K1
rHBr=K 2
( )
K5
1 /2
[ Br 2 ] [ H 2 K 3 [ Br 2 ] K 4 [ HBr ]

1 /2
K1

rHBr=
2 K2
( )
K5
1/ 2
[ Br 2 ] [ H 2 ]
K 4 [ HBr ]
1+
K 3 [ Br 2 ]

DONDE
1/ 2
K1
p=2 K 2
( )
K5

K4
q=
K3

PROBLEMA 4
Hinshelwood indica que la descomposicin trmica del acetaldehdo transcurre segn el
siguiente mecanismo en cadena:
C H 3 CHO K 1 CH 3 +CHO
..(1)

C H 3 CHO+ CH 3 K 2 CH 4 +CO+CH 3
.(2)

CH 3 K 3 C 2 H 6
(3)

Teniendo en cuenta que la velocidad de la primera reaccin es pequea en comparacin

con la segunda cuando las cadenas son largas, demuestre que:
k
r C H CHO =k 2 1 [ C H 3 CHO ]
3
k3
1.5

Solucin:
La (1) es pequea en comparacin a la ec. (2)
r C H CHO
Para hallar entonces solo hacemos uso de la ecuacin (2) y no de la (1) debido
3

a que esta es pequea en comparacin a la ec. (2):

r C H CHO =k 2 [ CH 3 ] [ C H 3 CHO ]
De (2): 3

Para el radical CH 3 tenemos lo siguiente :

r CH =k 1 [ C H 3 CHO ]
3


r CH =k 2 [ C H 3 CHO ] [ CH 3
3

]
r CH =k 2 [ C H 3 CHO ] [CH 3 ]
3

r CH =k 3 [ CH 3
3

]
r CH =k 1 [ C H 3 CHO ] k 3 [ CH 3 ]
3

Por ser radical libre igualamos a cero:

k 1 [ C H 3 CHO ] k 3 [ CH 3 ]=0

[ CH 3 ]=
k1
k3
[ C H 3 CHO ]

Reemplazando en la ecuacin (2) , se demuestra que:

k
r C H CHO =k 2 1 [ C H 3 CHO ]
k3 3
1.5

PROBLEMA 5
El cloruro de etilo experimenta una descomposicin trmica en fase gaseosa.
C2 H 5 Cl C 2 H 4 + HCl

Un posible mecanismo en cadena para esta reaccin es:

C2 H 5 Cl K 1 C 2 H 5 +Cl

C2 H 5 +C2 H 5 Cl K 2 C 2 H 4 Cl +C 2 H 6

Cl +C2 H 5 Cl K 3 C 2 H 4 Cl + HCl

C2 H 4 Cl K 4 C2 H 4 +Cl

C2 H 4 Cl +Cl K 5 C 2 H 4 Cl 2

Demuestre que para esta reaccin la constante de velocidad est dada por:

K=
K5
K1. K3 . K 4

Solucin:
r C H Cl=K [ C 2 H 5 Cl ]
Del enunciado asumimos que: 2 5

C2 H 5 Cl K 1 C 2 H 5 +Cl
(1)

C2 H 5 +C2 H 5 Cl K 2 C 2 H 4 Cl +C 2 H 6
(2)
 Cl +C2 H 5 Cl K 3 C 2 H 4 Cl + HCl
(3)

C2 H 4 Cl K 4 C2 H 4 +Cl
(4)

C2 H 4 Cl +Cl K 5 C 2 H 4 Cl 2
(5)

Ecuacin cintica del reactante:

r C H Cl=K 1 [ C 2 H 5 Cl ]
de (1): 2 5

r C H Cl=K 2 [ C 2 H 5 Cl ] [ C2 H 5 ]
de (2): 2 5

de (3): r C H Cl=K 3 [ C 2 H 5 Cl ] [ Cl ]
2 5

r C H Cl=K 1 [ C 2 H 5 Cl ] + K 2 [C 2 H 5 Cl ] [ C 2 H 5 ] + K 3 [ C2 H 5 Cl ] [ Cl ] ( )
2 5

Ecuacin cintica del radical [ C2 H 5 ] :

r C H =K 1 [ C 2 H 5 Cl ]
de (1) :

2 5

r C H =K 2 [ C2 H 5 Cl ] [ C 2 H 5 ]
de (2) :

2 5

r C H =K 1 [ C 2 H 5 Cl ] K 2 [ C 2 H 5 Cl ] [ C2 H 5 ]
2

5

Se aproxima al estado estacionario del radical libre:

[ C 2 H 5 ]
=r C H =0

t 2 5

K
[ C2 H 5 ]= K 1 ( )
2

Ecuacin cintica del radical [ Cl ] :

r Cl =K 1 [ C 2 H 5 Cl ]
de (1) :

de (3) : r Cl =K 3 [ C2 H 5 Cl ] [ Cl ]

de (4) : r Cl =K 4 [ C2 H 4 Cl ]

de (5) :
r Cl =K 5 [ Cl ] [ C 2 H 4 Cl ] r Cl =K 1 [ C2 H 5 Cl ]K 3 [ C2 H 5 Cl ] [ Cl ] + K 4 [ C 2 H 4 Cl ] K 5 [ Cl ] [C 2 H 4 Cl ]

Se aproxima al estado estacionario del radical libre:

[ Cl ]
=r Cl =0
t

0=K 1 [ C 2 H 5 Cl ] K 3 [ C 2 H 5 Cl ] [ Cl ] + K 4 [ C2 H 4 Cl ]K 5 [ Cl ] [ C 2 H 4 Cl ] ()
Ecuacin cintica del radical [ Cl ] :
r Cl =K 1 [ C 2 H 5 Cl ]
de (1) :

de (3) : r Cl =K 3 [ C2 H 5 Cl ] [ Cl ]

r Cl =K 4 [ C2 H 4 Cl ]
de (4) :

de (5) :
r Cl =K 5 [ Cl ] [ C 2 H 4 Cl ] r Cl =K 1 [ C2 H 5 Cl ]K 3 [ C2 H 5 Cl ] [ Cl ] + K 4 [ C 2 H 4 Cl ] K 5 [ Cl ] [C 2 H 4 Cl ]

Se aproxima al estado estacionario del radical libre:

[ Cl ]
=r Cl =0
t

0=K 1 [ C 2 H 5 Cl ] K 3 [ C 2 H 5 Cl ] [ Cl ] + K 4 [ C2 H 4 Cl ]K 5 [ Cl ] [ C 2 H 4 Cl ] ()

Ecuacin cintica del radical [ C2 H 4 Cl ] :

rC H =K 2 [ C 2 H 5 Cl ] [ C 2 H 5 ]
de (2) :

2 4
Cl

rC H =K 3 [ C 2 H 5 Cl ] [ Cl ]
de (3) :

2 4 Cl

r C H =K 4 [C 2 H 4 Cl ]
de (4) :

2 4
Cl

r C H =K 5 [ Cl ] [ C 2 H 4 Cl ]
de (5) :

2 4
Cl

C2 H 4 Cl = K 2 [ C2 H 5 Cl ] [ C 2 H 5 ]+ K 3 [ C 2 H 5 Cl ] [ Cl ] K 4 [ C2 H 4 Cl ]K 5 [ Cl ] [ C 2 H 4 Cl ]
r

Se aproxima al estado estacionario del radical libre:

[ C 2 H 4 Cl ]
=r C H Cl =0

t 2 4

0 K 2 [ C2 H 5 Cl ] [ C 2 H 5 ]+ K 3 [ C 2 H 5 Cl ] [ Cl ] K 4 [ C 2 H 4 Cl ]K 5 [ Cl ] [ C 2 H 4 Cl ] ( )

Ahora sumando () + () y reemplazando ():

K 1 [ C 2 H 5 Cl ]
[ C2 H 4 Cl ]= K [ Cl ] ( )
5

Reemplazando () en ():
K 1 [C 2 H 5 Cl ] K 1 [ C2 H 5 Cl ]
0=K 1 [ C 2 H 5 Cl ] K 3 [ C 2 H 5 Cl ] [ Cl ] + K 4
( K 5 [ Cl ]

)
K 5 [ Cl ]
(
K 5 [ Cl ] )
[ Cl ] =
K1 . K 4
K 3. K5
()
Ahora con la ecuacin (3):

Cl +C2 H 5 Cl K 3 C 2 H 4 Cl + HCl

r C H Cl=K 3 [ C 2 H 5 Cl ] [ Cl ]
2 5

[ Cl ] =
K1 . K 4
K 3. K5

r C H Cl=K 3 [ C 2 H 5 Cl ]
2 5

r C H Cl =K 3 [ C 2 H 5 Cl ]
2 5 ( K1 . K 4
K3 . K5 )
r C H Cl=
2 5 ( K1 . K4 . K 3
K5 )
[ C 2 H 5 Cl ]

Se compara con la ecuacin descrita en el problema y se obtiene que es similar:

K=

K1. K3 . K 4
K5