Chemical

Equilibrium
Dr. Amir HABIB
Study of Chemical
Equilibrium
Means


Considering the equilibria among different

chemical species

Calculating values of the partial molar Gibbs
Free energy for materials

These calculations are made using the concept
of thermodynamic activity
Gibbs Free Energy
(G) energy that is available to do work is
related to enthalpy, H and entropy S and
temp, T.

G=H–TS
Enthalpy and Entropy
(H) – energy of inter- and intra- molecular
bonds that binds atoms and molecules
together
Entropy (s) – “disorder of the system”
“More disorder”~ larger S value and less
energy is available to do work based on the
equation.
Any chemical reaction that results in a conversion
of a liquid or solid to a gas will result in a large
increase in entropy.
Increase in entropy equivalent to a decrease in the
free energy of the system.
2nd Law of Thermodynamics states that a system
tends to lose “useful” energy and approach a
state of minimum free energy, or an equilibrium
state
Thermodynamic Activity
‘a’
 Of a component varies with
Physical Form of that Comp.
Concentration of that Comp.


It is evaluated relative to a STANDARD STATE at

same temp.


‘a’ = 1 at the standard state



‘a’ is defined in terms of a quantity called

FUGACITY

Fugacity
‘a’ is a ratio of fugacity of material to its
fugacity in the standard state
Fugacity as a property of gas, taking it to be
the pressure of the gas corrected for its non
ideality.

For illustration , let the change of molar Gibbs
free energy of a single gas with pressure at
constant temperature
 dG = V dP (dG =-S dT + V dP , with dT =
0)

If the gas is ideal (V = RT /P), then


 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


 μ stands for chemical potentials

ai = f i / f 0
i

The STANDARD STATE of a gas/solid/liq is pure
gas/solid/liq at 1 atm. Other STANDARD STATEs
used in special cases.

Difference b/w Standard and
Ref. States
REFERENCE STATE
 Define condition of material in terms of Temp,
Pressure and Physical Form
 Ref. State = A pure element in its equilibrium
condition at 298 K, ∆H0298 = 0,
 Enthalpy at temp other than 298 K is not Zero
and can be calculated from Heat Capacity.


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 )


 ∫ dGi =Ĝi – Gio = RT ln fi/foi = RT ln ai


 Gio is molar Gibbs free energy in standard state
 and fo is fugacity in standard state

If material is ideal gas
 Ĝi – Gio = RT ln Pi/Poi = RT ln ai
‘a’ of ideal gas at 2 atm = 2, as fo = 1 atm
If the pressure of pure gas is less than 1 atm,
and if one atm is chosen as the standard
state, the a of the pure gas will be less than
one
Pure Nitrogen at 0.1 atmhas an activity of 1/10
th, if pure Nitrogen at 1 atm is the standard
state

The fugacity of a condensed Phase a liq/solid is
equal to the fugacity of the vapor in
Equilibrium with it.
E.g., if eq vapor pressure of a liq is 0.01 atm at
a sp temp than its fugacity is 0.01 atm
( Vapor is ideal)
The value of thermodynamic activity changes
not only with pressure but also with
composition
The fugacity of material in an ideal solution
varies linearly with mole fraction of that
substance over the entire composition range.
Fu g a city o f B ,

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


 ∆G0  = ∆G0f,O  – ½ ∆G0f,O2

 = 187800 – 0

∆G0 = ­ RT ln aO/a1/2  O2  = ­ RT ln PO/P1/2  O2


 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


Equilibrium in water-hydrogen-oxygen system.

At 2000k a system is to be operated so that
the partial pressure of O2 will be 1 E 10-
10 atm.

What should be the ratio of hydrogen to water

vapor to achieve this condition?

 H2+ ½ O2 H2O
From Table
∆G0= ­246,000 + 54.84 T                  at 2000k
lnKa  = ­∆G0/ RT  = 8.20
Ka =     ?         =    aH2O  / aH2  a1/2 O2
Assuming H, O and H2O(g) are ideal 
Ka = PH2O  / PH2  P1/2 O2
As PO2 = 10 -10 atm
As well
 PH2O  + PH2  +P1/2 O2 = 1 atm
PH2O = x  , PH2  =1­x
x =0.0352



Solid Vapor Equilibria
Example 3: Calculation of equilibria b/w solids
and gases
4Cu(s) + (g)O2 2Cu2O(s)


If we know ∆G0, we can calculate the pressure of 

Oxygen in equilibrium with Cu(s) and Cu2O(s) 


If PO2 > PO2 at Eq. , rxn proceed to right

If PO2 < PO2 at Eq. , rxn proceed to left

Calculate the PO2 below which rxnproceed left
ward at 1000 K ( Cu2O decompose to Cu and
O2) i.e., PO2 at Eq.

~?1 whether Cuprous oxide can be reduced to
metallic copper at 1000K by lowering
pressure.

~?1 What level of vacuum is required to
prevent the oxidation of copper upon heating
to 1000K in pure O2.
∆G0 = ­ RT ln Ka = ­ RT ln a2Cu2O  / a4Cu  PO2


∆G0 = ­ 339000 – 14.24 T ln T +247 T 


  = ­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


 ∆G0T = Σproducts  np ∆G0f,T  – Σreactants  nr 

∆G0f,T  
∆G0T can also be calculated from values of ∆H0T 
and ∆S0T 
 ∆G0T = ∆H0T ­ T ∆S0T 
 where    ∆H0T = ∆H0298, T  + ∫T298  ∆Cp0 dT 

 And ∆S0T = ∆S0298, T  + ∫T298  (∆Cp0 / T)dT 



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 

 And ∆S0T = ∆S0298, T  + ∫T298  (∆Cp0 / T)dT 

Treated as independant of temperature.

If Cp0 is const.
 ∆ H0T = ∆H0298  + ∆Cp0 (T­298) 

 And ∆S0T = ∆S0298  + ∆Cp0  ln (T/298)

Then ∆G0T = ∆H0298  + ∆Cp0 (T­298)­ T∆S0298             


 ­T∆Cp0  (ln T – ln 298)


 = ∆H0298  + ∆Cp0T­ 298∆Cp0 ­ T∆S0298       

  
 ­T∆Cp0  ln T


                  = (∆H0298  ­ 298∆Cp0) 


 + T(­∆S0298  + ∆Cp0  ln 298) 



 ­∆Cp0  Tln T

∆G0T=  A + B T + C T ln T


 Where  A = (∆H0298  ­ 298∆Cp0) 

 B= ­∆S0298  + ∆Cp0  ln 298
 C= ­∆Cp0