Beruflich Dokumente
Kultur Dokumente
Chapter 14
the rates of the forward and reverse reactions are equal and
H2O (g)
Chemical equilibrium
N2O4 (g)
2NO2 (g)
14.1
N2O4 (g)
2NO2 (g)
equilibrium
equilibrium
equilibrium
14.1
constant
14.1
N2O4 (g)
K=
[NO2]2
[N2O4]
aA + bB
K=
[C]c[D]d
[A]a[B]b
2NO2 (g)
= 4.63 x 10-3
cC + dD
Law of Mass Action
14.1
K=
[C]c[D]d
aA + bB
[A]a[B]b
cC + dD
Equilibrium Will
K >> 1
Favor products
K << 1
Favor reactants
14.1
[NO2]
2NO2 (g)
Kp =
[N2O4]
2
PNO
PN O
2
In most cases
Kc Kp
aA (g) + bB (g)
cC (g) + dD (g)
Kp = Kc(RT)n
n = moles of gaseous products moles of gaseous reactants
= (c + d) (a + b)
14.2
Homogeneous Equilibrium
CH3COOH (aq) + H2O (l)
[CH3COO-][H3O+]
Kc =
[CH3COOH][H2O]
[CH3COO-][H3O+]
= Kc [H2O]
Kc =
[CH3COOH]
General practice not to include units for the
equilibrium constant.
14.2
COCl2 (g)
[COCl2]
0.14
=
= 220
Kc =
[CO][Cl2]
0.012 x 0.054
Kp = Kc(RT)n
n = 1 2 = -1
R = 0.0821
T = 273 + 74 = 347 K
2
PNO
PO 2
2
PNO
2
PO 2 = Kp
2
PNO
2
2
PNO
14.2
[CaCO3]
[CaO]
14.2
CaCO3 (s)
PCO 2 = Kp
PCO 2 does not depend on the amount of CaCO3 or CaO
14.2
Kp = Kc(RT)n
Kc = Kp(RT)-n
n = 2 0 = 2
T = 295 K
A+B
C+D
Kc
C+D
E+F
Kc
A+B
E+F
Kc
[C][D]
Kc =
[A][B]
[E][F]
Kc =
[C][D]
[E][F]
Kc =
[A][B]
Kc = Kc x Kc
14.2
N2O4 (g)
K=
[NO2]2
[N2O4]
2NO2 (g)
= 4.63 x 10
-3
2NO2 (g)
N2O4 (g)
[N2O4]
1
= 216
K =
=
2
K
[NO2]
14.2
kf
kr
AB2
ratef = kf [A][B]2
rater = kr [AB2]
Equilibrium
ratef = rater
kf [A][B]2 = kr [AB2]
kf
[AB2]
= Kc =
kr
[A][B]2
14.3
14.4
14.4
2Br (g)
Br2 (g)
2Br (g)
0.063
0.012
-x
+2x
0.063 - x
0.012 + 2x
(0.012 + 2x)2
= 1.1 x 10-3
Kc =
0.063 - x
Solve for x
14.4
(0.012 + 2x)2
= 1.1 x 10-3
Kc =
0.063 - x
4x2 + 0.048x + 0.000144 = 0.0000693 0.0011x
4x2 + 0.0491x + 0.0000747 = 0
2
-b
b
4ac
x=
ax2 + bx + c =0
2a
x = -0.0105 x = -0.00178
Initial (M)
Change (M)
Equilibrium (M)
Br2 (g)
2Br (g)
0.063
0.012
-x
+2x
0.063 - x
0.012 + 2x
Le Chteliers Principle
If an external stress is applied to a system at equilibrium, the
system adjusts in such a way that the stress is partially offset
as the system reaches a new equilibrium position.
Changes in Concentration
N2 (g) + 3H2 (g)
Equilibrium
shifts left to
offset stress
2NH3 (g)
Add
NH3
14.5
Le Chteliers Principle
Changes in Concentration continued
Remove
Add
Remove
Add
aA + bB
cC + dD
Change
left
right
right
left
14.5
Le Chteliers Principle
Changes in Volume and Pressure
A (g) + B (g)
C (g)
Change
Increase pressure
Decrease pressure
Increase volume
Decrease volume
14.5
Le Chteliers Principle
Changes in Temperature
Change
Increase temperature
Decrease temperature
Exothermic Rx
Endothermic Rx
K decreases
K increases
K increases
K decreases
colder
hotter
14.5
Le Chteliers Principle
Adding a Catalyst
does not change K
does not shift the position of an equilibrium system
system will reach equilibrium sooner
uncatalyzed
catalyzed
Chemistry In Action
Life at High Altitudes and Hemoglobin Production
Hb (aq) + O2 (aq)
Kc =
HbO2 (aq)
[HbO2]
[Hb][O2]
Le Chteliers Principle
Change
Shift Equilibrium
Change Equilibrium
Constant
Concentration
yes
no
Pressure
yes
no
Volume
yes
no
Temperature
yes
yes
Catalyst
no
no
14.5