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Rpida
2.
(g) 2O O(g) (g) O
2
k
k
3
2 , f
2 , r
+
Lenta
2O
3
(g) 3O
2
.
NOTA: el paso 2 es quien lmita la velocidad de la reaccin
- Ecuacin de velocidad:
(Reaccin lenta)
- Remover el intermediario, O:
- Sustituir la ecuacin 2 en la 1:
] O ][ O [
] O [
k
k
] O [ k ] O ][ O [ k
3
2
2
2 , r
2 , f
2
2 2 , r 3 2 , f
=
=
] O [
] O [
k
k
] O [
] O ][ O [ k ] O [ k
2
3
1 , r
1 , f
2 1 , r 3 1 , f
=
=
2
3
3
2
2 , r
2 , f
1 , r
1 , f
c
] O [
] O [
k
k
k
k
K
=
=
- La contante de equilibrio de una reaccin reversa:
aA + bB cC + dD
cC + dD aA + bB
Ejemplo 1 Determine la constante de equilibrio para la siguiente
reaccin:
N
2
(g) + 3/2 H
2
(g) NH
3
(g)
dados N
2
(g) + 3H
2
(g) 2NH
3
(g) K
c
= 1.7x10
2
Ejemplo 2 Determine la contante de equilibrio para la formacin de
HI(g) si la concentracin en el equilibrio H
2
, I
2
y HI son 0.0060 M,
0.106 M, y 0.189 M, respectivamente.
H
2
(g) + I
2
(g) 2HI(g) K
c
= ?
Ejemplo 3 Determine la constante de equilibrio de la siguiente
reaccin.
H
2
(g) + I
2
(g) HI(g) K
c
= ?
La constante de equilibrio K
c
f , c
r , c
K
1
K =
b a
c d
f , c
] B [ ] A [
] C [ ] D [
K =
c d
b a
r , c
] C [ ] D [
] B [ ] A [
K =
- Para gases se pueden usar K
c
y K
p
.
Ejemplo 1. Escriba le expresin de quilibrio en funcin de
las presiones parciales de los gases en la reaccin.
N
2
(g) + 3H
2
(g) 2NH
3
(g) K
P
= ?
Ejemplo 2. Cual es la expresin de equilibrio de la
siguiente reaccin?
N
2
(g) + 3/2 H
2
(g) NH
3
(g) K
P
= ?
Ejemplo 3. Determine la constante de equilibrio (K
P
)
para la formacin de un mol de amoniaco, si la reaccin
se lleva a cabo a 500K, y donde P
NH3
= 0.15 atm, P
N2
= 1.2
atm y P
H2
= 0.81 atm en el equilibrio.
Constante de equilibrio K
c
, K
p
- La relacin entre la constante de equilibrio de concentraciones y la presin, se
obtiene de la ley del gas ideal.
PV = nRT
- Sustituyendo la P en la ecuacin de equilibrio (considerando la reaccin):
aA + bB cC + dD
Ejemplo 1. Determine K
p
para la sntesis de NH
3
a 25C;
N
2
(g) + 3H
2
(g) 2NH
3
(g) K
c
= 4.1x10
8
Ejemplo 2. Determine K
p
para la sntesis de HI a 458C;
H
2
(g) + I
2
(g) HI(g) K
c
= 0.142
Relacin de K
c
y K
p
RT ] A [
RT
V
n
P
A
A
=
=
( ) ( )
( ) ( )
( )
( )
( ) ( )
n
c
) b a ( ) d c (
c P
b a b a
d c d c
b a
d c
b
B
a
A
d
D
c
C
P
RT K RT K K
RT ] B [ ] A [
RT ] D [ ] C [
RT ] B [ RT ] A [
RT ] D [ RT ] C [
P P
P P
K
A + +
+
+
= =
=
= =
- En la expresin de equilibrio no se incluye a los
solventes o a los slidos.
- Su composicin es constante.
- Concentracin de agua 55.5 M; muy alta comparada con
los reactivos y los productos.
- La concentracin de un slido tal como el CaCO
3
se
mantiene constante.
Ejemplo: Determine la expresin de la constante
de equilibrio
CaCO
3
(s) + C(gr) CaO(s) + 2CO(g)
Equilibrio heterogneo
Aplicacin de la constante de
equilibrio
- La magnitud de la constante de equilibrio predice la direccin de la
reaccin.
- Muy grande K (ejemplo 10
10
) principalmente
productos.
- Muy pequea K (ejemplo 10
10
) principalmente
reactivos.
- Cuando la K=1; la mezcla esta en equilibrio .
Ejemplo: para cada una de las siguientes reacciones mencione cul
especie predomina en el equilibrio.
AgCl(s)
Ag
+
(aq) + Cl
(aq) K
=
1.8x10
10
Ag
+
(aq) + 2NH
3
(aq)
+
2
3
) Ag(NH
7
10 7 . 1 x K =
H
2
CrO
4
(aq) + H
2
O(l)
4
HCrO (aq) +
H
3
O
+
(aq)
K = 0.15
- Direccin de Reaccin: El cociente de reaccin puede ser usado
para determinar direccin de la reaccin con las
concentraciones iniciales..
- Cociente de reaccin: Para la reaccin general,
aA + bB cC + dD,.
donde t se refiere al tiempo en el que se miden las
concentraciones de la mezcla de reaccin., pero no han
alcanzado el equilibrio necesariamente.
- La Comparacin de Q
c
con K
c
revela la direccin de la reaccin:
Si Q
c
< K
c
, tendencia a formarse productos
Si Q
c
> K
c
, tendencia a formarse reactivos
Q
c
= K
c
, equilibrio.
Ejemplo: Determine la direccin de la reaccin
H
2
(g) + I
2
(g) 2HI(g). Asuma que [H
2
]
o
= [I
2
]
o
= [HI]
o
=
0.0020M a 490
o
C por lo cual K
c
= 46.
Uso de la constante de equilibrio
b a
c
t
d
t
c
[B] [A]
[C] [D]
Q
t t
=
Calculando las concentraciones
en el equilibrio
- Usando una concentracin inicial, estequiometra y el valor de la
K
c
, las concentraciones en el equilibrio de todos los componentes
de la reaccin pueden ser calculados.
[H
2
]
o
= [I
2
]
o
= 24 mM, fueron mezclados y calentados a 490
o
C en un
contenedor . Calcule la composicin en el equilibrio de los
compuestos reaccionantes., si el valor de K
c
= 46.
Solucin: Elaborar una tabla de equilibrio, sustituir con la ecuacin
de equilibrio y resolver matemticamente.
H
2
(g) +I
2
(g)2HI(g)
H
2
(g) +
I
2
2HI(g)
Init. Conc. 0.024 M 0.024 M 0
A to Equil. x
x
+2x
Equil.
0.024 M x
0.024 M x
+2x
Using the Equilibrium Constant
(cont)
- E.g.2 For the reaction: PCl
5
(g) PCl
3
(g) + Cl
2
(g), K
c
= 0.800 M at 340
o
C.
Find the equilibrium amounts of these compounds if they all start out at
0.120 M.
- Solution: Determine Q
c
so that you know which direction the reaction will
proceed. Q
c
= 0.120 < K
c
reaction proceeds to products.
PCl
5
(g)
Cl
2
+
PCl
3
(g)
Init. Conc. 0.120M 0.120M 0.120M
A to Equil. x
+x +x
Equil.
0.120 M x
0.120 M + x 0.120 M + x
Equilibrium concentrations of each component are in last row.
Substitute into equilibrium expression and solve for x.
It may be necessary to rearrange so that quadratic equation can be
used.
.
Rearrange to ax
2
+ bx + c = 0; determine a, b, c and substitute into
quadratic equation:
( )
x M 0.120
x M 0.120
K
2
c
+
=
a 2
ac 4 b b
x
2
=
- A change to the system, which is initially at equilibrium,
can cause a change in the equilibrium composition.
- Le Chteliers Principle: If a stress is applied to a
reaction mixture at equilibrium, reaction occurs in the
direction that relieves the stress.
- Types of stress on equilibrium:
- Concentration of reactants or products. You can add or
remove one or more components in a reaction mixture.
- With gases changing the pressure or volume is a way of
changing the concentrations of all components in the
mixture.
- Change temperature.
John A. Schreifels
Chemistry 212
Chapter 15-
19
Factors that Alter the Composition of an Equilibrium Mixture
Changes in Concentrations
- Addition or removal of either reactant or product shifts the
equilibrium to reduce the excess compound.
- Removal of product or addition of reactant has the same effect; they
shift the equilibrium to the right.
E.g. Consider the formation of NH
3
(g); the equilibrium conditions are
listed in the first row; then half of the NH
3
(g) is removed. We
calculate Q
c
and compare it with K
c
. Q
c
< K
c
reaction goes to right
to form more NH
3
(g).
E.g.2 Instead lets add N
2
so that its concentration increases 10x. This
produces a similar effect. Since hydrogen is a reactant (in
denominator), Q
c
will become much smaller than K
c
. This means that
product must form.
N
2
(g) + 3 H
2
2 NH
3
(g)
Equil. Conc. 0.50 M 3.00 M 1.98 M K
c
= 0.291
After ANH
3
(g) 0.50 M 3.00 M 0.99 M Q
c
= 0.073
N
2
(g) + 3 H
2
2 NH
3
(g)
Equil. Conc. 0.50 M 3.00 M 1.98 M K
c
= 0.291
After AN
2
(g)
5.0 M 3.00 M 1.98 M Q
c
= 0.0291
John A. Schreifels
Chemistry 212
Chapter 15-
20
Changes in Concentrations 2
- Removal of reactant or addition of product shifts the equilibrium in the
opposite direction to the left.
- E.g. Half of N
2
(g) is removed. We calculate Q
c
and compare it with K
c
.
Notice that it is greater than the equilibrium constant. Therefore the
reaction proceeds to the left to form more N
2
(g).
- E.g.2 Add NH
3
so that its concentration increases by a factor of 2. This
produces a similar effect. Since ammonia is a product (in numerator), Q
c
> K
c
. Reaction proceeds to left since there is too much product.
N
2
(g) + 3 H
2
2 NH
3
(g)
Equil. Conc. 0.50 M 3.00 M 1.98 M K
c
= 0.291
After ANH
3
0.50 M 3.00 M 3.96 M Q
c
= 1.162
N
2
(g) + 3 H
2
2 NH
3
(g)
Equil. Conc. 0.50 M 3.00 M 1.98 M K
c
= 0.291
After AN
2
0.25 M 3.00 M 1.98 M Q
c
= 0.582
John A. Schreifels
Chemistry 212
Chapter 15-
21
Changes in Pressure and Volume
- Equilibria containing gases are sensitive to changes in pressure
(volume).
- Since pressure and volume are inversely proportional, an increase in
pressure will give same result as a decrease in volume.
- A decrease in the volume increases concentration of each of the
components in the reaction mixture.
- A decrease in V shifts equilibrium to side with least number of moles of
gas.
- E.g. Determine the effect of a 2.00x increase in pressure (volume
decreases by factor of 2;V
f
= V
I
). Concentrations of reactants
and products increase by a factor of 2. Since Q
c
< K
c
, the reaction
proceeds to the right to form more NH
3
(g).
N
2
(g) + 3 H
2
2 NH
3
(g)
Equil. Conc. 0.50 M 3.00 M 1.98 M K
c
= 0.291
After AP
1.00 M 6.00 M 3.96 M Q
c
= 0.073
John A. Schreifels
Chemistry 212
Chapter 15-
22
Changes in Pressure and Volume
2
E.g.2 Determine the effect of a factor of 2.00 decrease in the
pressure (volume increases by a factor of 2;V
f
= 2 V
i
).
- We need to be vigilant so that we do not include any solids or
solvents in this, since they do not affect the equilibrium.
- E.g. Determine the ratio of Q
c
/K
c
when the pressure increases by a
factor of two and from this discuss the effect on the equilibrium:
C(s) + CO
2
(g) 2CO(g).
N
2
(g) + 3 H
2
2 NH
3
(g)
Equil. Conc. 0.50 M 3.00 M 1.98 M K
c
= 0.291
After AP
0.25 M 1.50 M 0.99 M Q
c
= 1.16
John A. Schreifels
Chemistry 212
Chapter 15-
23
- AT = AQ
c
.
- AT produces AK
c
- Whether K
c
increases or decreases depends upon two factors, AT
and AH
rxn
.
- An increase in temperature causes the equilibrium to shift towards the
endothermic side;
- A decrease in temperature causes the equilibrium to shift in the opposite
direction.
E.g. Will an increase or a decrease in temperature increase the
amount of CO produced from the following reaction
2CO
2
(g)2 CO(g) +O
2
(g) AH = 566 kJ
The Effect of a Catalyst
- It has no effect on the equilibrium.
- It speeds up attainment of equilibrium.
- K
c
related to the AH and not E
a
John A. Schreifels
Chemistry 212
Chapter 15-
24
Changes in Temperature