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Reactions
Chemical equilibrium studies the extent of reactions
and the ways it can be altered
Kinetics and equilibrium are two different aspects of
chemical reactions (fast reactions may proceed to a
great, lesser or a limited extent; same is true for slow
reactions)
Equilibrium
forward
[A]
Rate
Concentration
Equilibrium
[B]
reverse
Time
Time
[A] = constant
[B] = constant
Ratefwd = Raterev
k
[NO 2 ]2 on T (K = 0.211 at 100C)
1 =K=
k 1
[N 2O 4 ] K determines the proportion of
aA + bB cC + dD
[C]ec [D]ed
Kc =
[A]ea [B]eb
aA + bB cC + dD
Qc =
[C]c [D]d
[A]a [B]b
At equilibrium Q = K
[H 2O]2
[H 2 ]2 [O 2 ]
At equilibrium Qc = K c
or
BA
[B]
[A]
1
Qc =
=
[A]
[B] Qc
Q (or K) of the reverse reaction is the
reciprocal of Q (or K) of the forward reaction
Qc =
AB
or
nA nB
[B]
[B]n
Qc =
Qc' =
= (Qc ) n
[A]
[A]n
Multiplying a reaction by a factor, n, raises Q
(or K) to nth power
1. A + B C
2.
CD
A+BD
Q1 = [C]/[A][B]
Q2 = [D]/[C]
Qc = [D]/[A][B]
[C] [D]
[D]
Q1 Q2 =
=
= Qc
[A][B] [C] [A][B]
Q (or K) of the sum of two or more reactions
is the product of their Qs (or Ks)
k fwd
k rev
kfwd[A]a[B]b = krev[C]c[D]d
[C]c [D]d
= Qc = K c
[A]a [B]b
Kc =
k fwd
k rev
K c = K c K c ... =
k fwd k fwd
...
k rev
k rev
[H 2(g)] [O 2(g)]
[H 2O(l)]2
Qc = [H 2 ]2 [O 2 ]
Qc =
P
( PC / RT )c
1
= aC b
a
b
c (a + b )
( PA / RT ) ( PB / RT )
PA PB ( RT )
Qc = [Ag + ][Cl - ]
Qc = [SO 2 ]/[O 2 ]
Qc =
PC
1
n
a
b
PA PB ( RT )
Qc = Q p
1
( RT ) n
Q p = Qc ( RT ) n
n = c ( a + b )
c
Qp =
PC
a
b
PA PB
K p = K c ( RT ) n
Example:
H2S(g) + H2O(l) H3O+(aq) + HS-(aq)
K = [H 3O + ][HS - ] / PH 2 S
Example: Calculate Kc and Kp for the reaction
2BrCl(g) Br2(g) + Cl2(g)
if at 500 K, the equilibrium concentrations of BrCl,
Br2 and Cl2 are 0.131, 3.51 and 0.156 M,
respectively.
[Br2 ][Cl 2 ] 3.51 0.156
Kc =
=
= 31.9
0.1312
[BrCl]2
PNO 2
PN 2O 4
1.2 2
= 0.60
2.4
K p = 0.98
A + 2B C
[C] = +x
[A] = -[C](1 mol A/1 mol C) = -[C] = -x
[B] = -[C](2 mol B/1 mol C) = -2[C] = -2x
i+c=e
[]
i
c
e
Kc =
A + 2B C
[C]i
[A]i
[B]i
-x
-2x
+x
[A]i - x [B]i - 2x [C]i + x
[C]
([C]i + x )
=
2
[A][B]
([A]i x )([B]i 2 x ) 2
Q<K
Q>K
Q
Forward
Reverse
i+c=e
[N2]e = x = 0.21 M
[H2]e = 3x = 0.63 M
i+c=e
i
c
e
[]
0.25
-2x
0.25 - 2x
0
+x
x
x x
= 0.022
(0 .25 - 2 x ) 2
[H 2 ][I 2 ]
[HI]2
= 0.022
Kc =
0
+x
x
x2
= 0.022
(0 .25 - 2 x ) 2
(0.15 + x ) x
0.15 x + x 2
= 0.022
= 0.022
2
2
(0 .25 - 2 x )
0 .25 2 0.25 2 x + 4 x 2
x1 ,2 =
x=
b b 2 4ac
2a
0.15
+x
0.15 + x
0
+x
x
[H 2 ][I 2 ]
[HI]2
= 0.022
Kc =
i+c=e
[I2]e = x = 0.0077 M
[H2]e = 0.15 + x = 0.15 + 0.00768 = 0.16 M
[HI]e = 0.25 - 2x = 0.25 - 20.00768 = 0.23 M
i+c=e
x
= 0.022 x = 0.022 0.25 0.022 2 x
0 .25 - 2 x
0.0371
x + 0.297 x = 0.0371
x=
= 0.029
1 + 0.297
Kc =
i
c
e
0
+2x
2x
Kc =
[NH 3 ]2
[N 2 ][H 2 ]3
= 0.0010
(2 x )2
= 0.0010
(0 .060 - x )(0 .040 - 3 x ) 3
x = 3.1 10 5
4x2
10. 0 .060 0 .040 3
=
=
10
.
x
(0 .060)(0 .040) 3
4
x = 0.0031
The assumption is not justified since x and 3x are
more than 5% of 0.060 and 0.040
x2 =
[HI]2
0.50 2
=
= 1 > Kc
[H 2 ][I 2 ] 0.50 0.50
x3 =
x4 =
i+c=e
Qc =
x n+1 =
x1 =
i
c
e
H2(g) +
0.50
+x
0.50 + x
I2(g) 2HI(g)
0.50
+x
0.50 + x
( 0 .50 2 x ) 2
= 0.45
(0 .5 + x )(0 .5 + x )
0.50
-2x
0.50 - 2x
Kc =
[HI]2
[H 2 ][I 2 ]
= 0.45
(0 .50 2 x ) 2
= 0.45
(0 .5 + x ) 2
(0 .50 2 x )
= 0.45 (0 .50 2 x ) = 0.45 (0 .5 + x )
(0 .5 + x )
0.165
0.50 0.67 0.50 = 2 x + 0.67 x x =
= 0.062
2 + 0.67
Changing Concentration
If the concentration increases, the system reacts to
consume some of it; If the concentration decreases,
the system reacts to produce some of it
Expansion (P by V)
The equilibrium shifts in a direction that produces
more gases and increases the pressure
The equilibrium shifts toward the side with
more moles of gas
2 mol gas
1 mol gas
PC
( nC RT / V )
n
V
=
= C
PA PB ( nA RT / V )( nB RT / V ) nA nB RT
As V is reduced, Q decreases (Q<K) and the
reaction shifts forward
Qp =
Changing Temperature
Affects the value of K
Example: A + B C + D + heat
H < 0
The forward reaction is exothermic, while the
reverse reaction is endothermic
Increasing T favors the endothermic reaction so
the reaction shifts in reverse
T1 = 298 K
T2 = 3000 K
Kp1 = 4.310-31
Kp2 = ?
ln
K p2
4.3 10 31
181 10 3 J/mol 1
1
181 10 3 1
1
exp
=
31
4.3 10
8.314 3000 298
181 10 3 1
1
K p 2 = 4.3 10 31 exp
K p2
K p 2 = 1.6 10 2
Kp is much larger at 3000 K because the forward
reaction is endothermic and therefore is favored
by T