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equilibria
9.1 Chemical equilibrium
• Kc – equilibrium constant
• Kc dependent on temperature, always specify
temperature when Kc reported
9.2 The equilibrium constant, K, and
the reaction quotient, Q
aA + bB cC + dD
• The following holds when equilibrium is
established:
C c D d
Kc
A a B b
• Equilibrium constant expression
• Kc – equilibrium constant
• Kc dependent on temperature, always specify
temperature when Kc reported
9.2 The equilibrium constant, K, and
the reaction quotient, Q
aA + bB cC + dD
C c D d
Qc
A a B b
• Qc – reaction quotient
• Expression for systems not necessarily at
equilibrium
• Kc can have only one positive value at a
specific temperature
• Qc can have any positive value
9.2 The equilibrium constant, K, and
the reaction quotient, Q
• Qc = Kc at equilibrium
• Qc > Kc system reacts to use up
products and generate more reactants
• Qc < Kc system reacts to use up
reactants and generate more products
c d
pC p D
p p
Kp a b
p A pB
p p
9.2 The equilibrium constant, K, and
the reaction quotient, Q
• The relationship between Kp and Kc
n
RT g
K p K c
p
Δng = (number of moles of gaseous products) –
(number of moles of gaseous reactants)
– Important to use correct units in this
equation
• Equilibrium concentrations in mol m-3
• Equilibrium pressures in Pa
K c mol m 3 1000 n K c mol L1
g
9.2 The equilibrium constant, K, and
the reaction quotient, Q
• Manipulating equilibrium constant
expressions
– When the direction of an equation is
reversed, the new equilibrium constant is
the reciprocal of the original
Kc
PCl 5
PCl3 + Cl2 PCl5 PCl 3 Cl2
Kc '
P Cl3 Cl2
PCl5 PCl3 + Cl2
P Cl5
' 1
Kc
Kc
9.2 The equilibrium constant, K, and
the reaction quotient, Q
• Manipulating equilibrium constant
expressions
– When the coefficients in an equation are
multiplied by a factor, the equilibrium
constant is raised to a power equal to
that factor.
K
PCl 5
PCl3 + Cl2 PCl5 c
PCl 3 Cl2
2
Kc "
P Cl5
2PCl3 + 2Cl2 2PCl5
P Cl3 2 Cl2 2
K c '' K c 2
9.2 The equilibrium constant, K, and
the reaction quotient, Q
• Manipulating equilibrium constant
expressions
– When chemical equilibria are added,
their equilibrium constants are multiplied.
Kc1
N2 O 2
2N2 + O2 2N2O
N2 2 O 2
NO 2 4
2N2O + 3O2 4NO2 Kc 2
N2 O 2 O 2 3
NO 2 4
2N2 + 4O2 4NO2 Kc 3
N2 2 O 2 4
N2 O 2 NO 2 4
NO 2 4
Kc1 Kc 2 Kc 3
N2 2 O 2 N2 O 2 O 2 3 N2 2 O 2 4
9.2 The equilibrium constant, K, and
the reaction quotient, Q
• The magnitude of the equilibrium
constant
– Product concentrations are in the
numerator of Kc
– The size of Kc gives a measure of how
far the reaction proceeds towards
completion when equilibrium is reached
9.2 The equilibrium constant, K,
and the reaction quotient, Q
• The magnitude of the equilibrium
constant
reactant product
9.2 The equilibrium constant, K, and
the reaction quotient, Q
• Equilibrium constant expressions for
heterogeneous systems
– Homogeneous reaction, all reactants and
products are in the same phase
– Heterogeneous reaction, more than one
phase exists in reaction mixture
2NaHCO3(s) Na2CO3(s) + H2O(g) + CO2(g)
Kc = [H2O(g)][CO2(g)]
– Do not include the concentrations of pure
solids or pure liquids
9.2 The equilibrium constant, K,
and the reaction quotient, Q
• Equilibrium constant
expressions for
heterogeneous systems
– For any pure liquid or solid at
constant temperature, the
ratio of amount of substance
to volume of substance is
constant
9.3 Equilibrium and Gibbs
free energy
• Free energy diagrams
– Phase changes
9.3 Equilibrium and Gibbs
free energy
• Free energy diagrams
– Chemical reactions
3
4
4
1
2
9.3 Equilibrium and Gibbs free
energy
• The relationship between ΔGθ and K
G G RT lnQ
– R is the gas constant, 8.3141 J K–1 mol–1
– T is the temperature in kelvin
– lnQ is the natural logarithm of the reaction
quotient
• Gaseous reactions: Q is calculated using partial
pressures expressed in Pa
• Reactions in solution: Q is calculated from
molar concentrations
9.3 Equilibrium and Gibbs free
energy
• The relationship between ΔGθ and K
G G RT lnQ
The reaction 2NO2(g) N2O4(g) has ΔGθ = –5.40 kJ
mol-1 at 298 K. In a reaction mixture, the partial
pressures of NO2 and N2O4 are 0.25 × 105 Pa and
0.60 x 105 Pa, respectively. In which direction must
this reaction proceed to reach equilibrium?
pN O p
2 4
N O
2 4
p
Qp p
2 G G R T ln 2
p NO
p NO
p
2
p
2
9.3 Equilibrium and Gibbs free
energy
G 5 . 40 kJ mol 1 5 .40 10 3 J mol 1 T 298 K
1
R 8 . 314 J K mol 1 p 1 10 5 Pa
p N O 0 . 60 10 5 Pa
2 4
p NO 0 . 25 10 5 Pa
2
5
0.60 10
5
3 -1 1 -1
G 5.40 10 J mol 8.314 J K mol 298 K ln 1 10
5 2
0.25 10
5
1 10
G 2 . 0 10 2 J mol 1
CuCl4 2
Q
4
Cu OH2 2 Cl
4
9.4 How systems at equilibrium
respond to change
• Changing the pressure in gaseous
reactions
– Two ways of changing the total pressure
• Changing the volume of the system
• Adding an inert gas
– Consider the equilibrium
N2(g) + 3H2(g) 2NH3(g)
2
p NH
p
3
Qp
3
p N p H
p p
2 2
9.4 How systems at equilibrium
respond to change
• Changing the pressure in gaseous
reactions
– Changing the volume of the system
n NH
2 2
p NH
p
3
3
Qp Qc V2 c
n
nH
3 3 V
p N p H nN
p p
2 2
2 2
V V3
2 2
Qc
NH3
Qc
n NH 3
V 2
N2 H2 3
3
nN nH 2 2
9.4 How systems at equilibrium
respond to change
• Changing the pressure in gaseous
reactions
– Adding an inert gas
• Increases total pressure of system
• Does not alter the position of equilibrium
• Add helium to N2/H2/NH3 equilibrium mixture
• Does not react with products or reactants
2
• Qp is not changed p
NH
p
3
Qp
3
p N p H
p p
2 2
9.4 How systems at equilibrium
respond to change
• Changing the temperature of a reaction
mixture
– Value of the equilibrium constant, K, can
only be changed by altering the temperature
– The van’t Hoff equation states:
d ln K H
– The slope of thedTplotof lnK
2 versus T has the
RT
same sign as ΔH θ
9.4 How systems at equilibrium
respond to change
• Changing the temperature of a reaction
mixture
HI 2
Kc
H2 I2
equilibrium initial change in
= +
concentration concentration concentration
Kc
CO 2 H2 4 .06
CO H2 O
CO(g) + H2O(g) CO2(g) + H2(g)
Initial concentration (mol L-1) 0.100 0.100 0.0 0.0
Change in concentration (mol L-1) -x -x +x +x
Equilibrium concentration (mol L-1) 0.100-x 0.100-x x x
x x x 2 .01 0 .100 x
Kc 4 . 06
0 .100 x 0 .100 x x 0 .201 2 .01x
x2
4 . 06
0 .100 x 2
x 2 . 01x 0 .201
x 3 . 01x 0 .201
4 .06 2 .01 x 0 . 0668
0 .100 x
9.5 Equilibrium calculations
Qc
CO 2 H2
CO H2 O
0.0668 2
Qc 2
4.1
0.033