Chemical Equilibrium

• Concepts Activity
Fugacity
Equilibrium constant
Solid vapor equilibrium
Ellingham diagrams
Sievert’s law
Control of oxygen partial pressure

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 Activity/Fugacity
• For ideal gases and mixtures of condensed phases, the “activity” of a
species is equal to its mole fraction. That means that its influence on
the properties of the system is its mole fraction (X) multiplied by the
total system property. For a gas mixture, the partial pressure of A is:
PA = XA P
• In real systems, the influence of one component on the properties of
the system may be different than its mole fraction would suggest.
Activity is given by the ratio of the fugacity of a substance to its
fugacity in a standard state (usually pure substance at 1 atm, same T)
f
a A = Ao
fA
• You may also see this expressed in terms of an activity coefficient an
mole fraction, but the idea is the same. The proportional effect of the
amount of substance A on the whole system property in question is
not simply given by its mole fraction
a A = γ A XA
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 Activity/Fugacity
• For real gases, the fugacity is the effective pressure corrected for
non-ideality

• For solids and liquids, fugacity is equal to the vapor pressure of in

equilibrium with the condensed phase since, at equilibrium, the
partial molar free energy of the solid and gas must be equal

• For gases, the ratio of fugacity to partial pressure must approach

one (ideal behavior) as total pressure approaches zero.

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 Activity
• For any substance dG A = −SA dT + V A dP
At constant temperature dG A = V A dP
• The difference between the Gibbs’ free energy of a material under any
conditions can be determined by integrating that equation.

• First V is replaced by RT/P since the fucacity RT

of any phase is related to the vapor pressure dG A = dP
P
• Integrating gives the difference in free GA fA

energy between the state of interest and ∫ dG = RT ∫ d ln f

the standard state o
GA f Ao

o f 
∆G = G A − G A = RT ln Ao  = RT ln a A
fA XA fA , pure  fA 
• For a real solution aA = =
fAo fAo
• For an ideal solution aA = XA
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 Chemical Equilibrium
• A chemical reaction can be written bB + cC ⇔ dD + eE
• The free energy change can be
δWrev = ∆G = dG D + eG D − bG B − cGC
expressed in terms of the partial
molar free energy for each component
o
• For each component, the partial molar G B = G B + RT ln( a B )
free energy is given in terms of activity

• Substituting
for each term

 ad ae 
∆G = 0 = ∆G o + RT ln Db cE 
• In the case of ∆G = O (equilibrium)  a BaC 
the ratio of acitivities is the equilibrium
 ad ae 
constant Ka
WS2002 ∆G o = −RT ln Db cE  = −RT ln5K a
 a BaC 

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 Gaseous Equilibrium Example
1
• Consider the equilibrium 2
O2 ⇔ O

• If heat is added, equilibrium will shift the reaction in the direction that
absorbs heat (this reaction is endothermic)

• Equilibrium constant

• Free energy of reaction ∆G o = ∆G of ,O − 12 ∆G of ,O 2

at 1000 K
∆G o1000 = −187 , 000 J
• Free energy is related to equilibrium constant by

• If the total pressure is 1 atm, the equilibrium composition at 1000 K is

XO = 1.5 x 10-10 atm
XO2 = ~1 atm

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 Solid-Vapor Equilibrium
• Consider the reaction 4 Cu(s) + O2(g) ⇔ 2 Cu2O(s)

• We can write and expression of Ka

• The activity of pure, condensed phases is unite
The activity of an ideal gas is its partial pressure

• ∆G° vs. T is known

• The partial pressure of oxygen for the equilibrium can be

calculated at any temperature. At 1000 K

• Below the equilibrium PO2, the metal is stable. Above, the oxide is
stable

• Plot at all temperatures

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 Variation in ∆G° with T
• For a chemical reaction at any temperature T ∆G oT = ∆H oT − T∆SoT
T
• For each component of the reaction
H oT = H o298 + ∫ CpdT
298
T
CP
SoT = S298 ∫
o
+ dT
298
T
• For the reaction T

where ∆CP is the difference in heat ∆H oT = ∆H o298 + ∫ ∆C dT

p
capacity between products and reactants 298
T
∆CP
∆SoT = ∆S298 ∫
o
+ dT
298
T

• So, combining ∆G oT = ∆H o298 + ∆CP ( T − 298 ) − T∆SoT − T∆Cp (ln T − ln 298 )

∆G = A + BT + CT ln T
∆G oT ≈ ∆H o − T∆So
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 Ellingham Diagrams
• Specific for reactions of the form
(2x)M + O2 = 2MxO

• Plot previous page on ∆Go vs. T axes, slope =-∆S°, intercept = ∆ H

°

• Lines of equal pO2 can be plotted since: ∆G o = −RT ln K a

(a ) = (1) = 1
2 2
MxO
Ka =
(a ) (a ) (1) (P ) (P )
2x 2x
M O2 O2 O2
 1 
• So: ∆G o = −RT ln
( )
 PO 2 
( )
 = RT ln PO 2

• Known for many metals

Below line, metal stable
Above line

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 Sievert’s Law
• When a diatomic gas dissolves in a metal, it dissociates
H2(g) ⇒ 2H (dissolved in copper)

• We know that a 2H
Ka =
aH2

• At low concentrations of H if it behaves ideally, the activity of

monatomic hydrogen in the metal is equal to its concentration
[ ]
2
H
Ka =
PH 2

[H ] = K P
2
a H2

[H ] = K P
1/ 2 1/ 2
a H2

• Sievert’s law states that the amount of a diatomic gas dissolved in

metal is proportional to the square root of its pressure
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