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Chemical Equilibrium
Chemical Equilibrium
Equilibrium
Dr. Amir HABIB
Study of Chemical
Equilibrium
Means
dG = RT dP/P = RT d ln P
For a real gas we define fugacity (f)
dG = RT d ln f
Lim f/P = 1 as P 0
dĜi = RT d ln fi
where dĜi is partial molar Gibbs free energy
∆Ĝ = Ĝ2 – Ĝ1 = RT ∫f1 f2 d ln f = RT ln f2/f1
OR
μ 2 – μ1 = RT ln f2/f1
STANDARD STATE
Is defined in terms of Pressure and physical Form
Temp is constant as activity is an isothermal
concept
As ai = f i / f 0 at same temp
i
The Diff in sp Gibbs free energy b/w a material
under arbitrary set of conditions and a standard
state ( at same temp )
A ctivity o f B ,
fB0
fB
aB
0
Pu re xB Pu re
A Mole fraction B, B
The fugacity of a material B is the mole
fraction of B multiplied by fugacity of Pure B.
If pure material B is taken as standard state,
then the activity of B is simply the mole
fraction of B in this solution.
For example A-B ideal solution consisting of 80
mol % B, the activity of B is 0.8, if pure B is
taken as the standard state. The activity of A
is 0.2 if pure A is taken as the standard state
fB= xBfBP
aB = fB / fB0 = xBfBP / fB
If fBP= fB0 then aB = xB
Ideal solution
Chemical Equilibrium
Considering a chemical reaction
bB + cC = dD + eE
We are already familiar
0Wrev = ∆G = dĜD + eĜE –bĜB –cĜC
From ĜB = GB0 + RT ln aB
Same holds for Reactant C and products D and E
∆G = d(GD0 + RT ln aD ) + e (GE0 + RT ln aE )
– b(GB0 + RT ln aB) – c(GC0 + RT ln aC)
∆G = dGD0 + eGE0 bGB0 cGC0
+ RT ln (aDdaEe/ aBb aCc)
∆G = ∆G0 + RT ln Ja
Ja = aDd aEe/ aBb aCc
Equilibrium can be achieved when no reversible work can be done b/w two
states that is
∆G = 0
Therefore, ∆G = ∆G0 + RT ln Ja
0 = ∆G0 + RT ln Ja(Equilibrium)
∆G0 = RT ln Ka
Ka is special value of Ja when the system is at chemical equilibrium –
equilibrium constant for reaction in terms of activities
Applications of ∆G0 = RT ln Ja
Example 1
A tank of
O2 is more stable Pure Oxygen
at 1 atm
Lets calculate concentration
of O in the tank at 1000K
(Given: Standard Gibbs Free energy of
formation of O is 187,800J per mole of O at
1000K)
½ O2 O
As
∆G = (np)molar Gibbs free energy of products –
(nr)molar Gibbs free energy of reactants
Assuming O & O2 both are ideal gases
ln PO/P1/2 O2 = ∆G0/ RT
= 22.58
PO/P1/2 O2 = 1.5 E1010
PO + PO2 = 1 atm
PO = 1.5 E1010
Example 2
= 190,360 at T 1000 K
‘a’ for Cu2O is 1 as it exists in pure form during
reaction
‘a’ for Cu is as well 1,
as we are calculating PO2 at which pure Cu will
coexist with O2
‘a’ for O2 = PO2
as the standard state for gases is the pure gas at 1
atm
∆G0 = RT ln 1/ PO2
-190360 = 8.314 * 1000 ln PO2
ln P = -22.90
P = 1.14 * 10-10 atm
∆G0 Versus T,
∆G0 = RT ln Ka
CuO stable 0 u0
Showing regions of + O2
0
Cu2O
O
2Cu2
stability of Cu2O and stable
O2
Cu. 4 C u +
0
0 0 u 0 Cu stable
Line represents the
equilibrium b/w 2 0 200 400 600
phases Temperature (K)
The graph can be
made more complete
by adding another
oxide of Cu, i.e., CuO
Sources of Info on ∆G0
For a chemical reaction,
∆G0T is sum of the Gibbs free energies of formation
of products, less the sum of the Gibbs free energies of
formation of the reactants at the same temperature
In addition actual values of the standard Gibbs free
energy of formation for chemical compundsare
available in many references.
In some cases values of ∆G0T are tab at 100K
intervals from zero to the highest
temperature for which they are known, and at
298 K
Others works report data as algebraic
equations
∆G0T = A + BT + CTlnT
This form arises because the ∆C0p terms in equ
∆ H0T = ∆H0298, T + ∫T298 ∆Cp0 dT
T∆Cp0 (ln T – ln 298)
= (∆H0298 298∆Cp0)
∆Cp0 Tln T
∆G0T= A + B T + C T ln T