NATIONAL POLYTECHNIC SCHOOL
Department of Preparatory Classes
2023/2024
Chapter 5
Free enthalpy (Gibbs function)
Introduction
To determine whether a process is spontaneous or not, it is necessary
determine two variations of entropies, that of the system and that of the
external environment, then examine the sign of the sum of these two
variations. J. W. Gibbs, who laid the foundations of the thermodynamics at the
end of the 19th century demonstrated that these two calculations could be
combined into one.
The entropy function makes it possible to predict the direction of the
transformation but its use is not obvious for chemical reactions.
Indeed the entropy to consider is that of the universe (system + external
environment) while it is preferable to define conditions linked directly to the
system studied without worrying about the exterior.
Thus, we define two new state functions
Free Enthalpy « G »
Free energy « F »
Free Enthalpy « G »
The variation in the enthalpy of the environment is given by the amount of heat
transmitted to it during a process.
At constant pressure , we have: Qrev = ΔH
The transformation is carried out at a T =Cste
Sext = – ΔH / T .
By substituting Sext in the expression of the 2nd principle, we obtain:
Stot = ΔS – ΔH / T
– T⋅Stot = ΔH – T⋅ΔS
The free enthalpy ΔG, or Gibbs (free) energy, is then defined by:
ΔG = ΔH – T⋅ΔS Or ΔG = – T⋅Stot
ΔG = ΔH – T⋅ΔS Or ΔG = – T⋅Stot
At constant temperature and pressure, the variation in the free enthalpy of a
system is proportional to the overall variation in entropy of the system and its
environment outside.
A transformation is spontaneous (irreversible) if :
According to the 2nd law of thermodynamics
Stot > 0
ΔG = – T⋅Stot < 0
Thus we conclude that:
If : ΔG<0 A transformation is spontaneous (irreversible)(G decreasese)
If : ΔG>0 The transformation cannot take place spontaneously(G increases)
If : ΔG=0 The system is in equilibrium
For a chemical reaction:
Sens 2
aA + bB cC + dD
Sens 1
If : ΔG<0 The reaction takes place in the direct direction (direction1): it
is spontaneous
If : ΔG>0 The reaction takes place in the opposite direction (direction 2)
the system is in equilibrium: the reaction takes place in both
If : ΔG=0
directions
Free energy « F »
At constant volume , we have: Qrev = ΔU
The transformation is carried out at a T =Cste
Sext = – ΔU / T .
By substituting ΔSext in the expression of the 2nd principle, we obtain:
Stot = ΔS – ΔU / T
– T⋅Stot = ΔU – T⋅ΔS
The free energy ΔF, is then defined by:
ΔF = ΔU – T⋅ΔS Or ΔF = – T⋅Stot
A transformation is spontaneous (irreversible) if :
According to the 2nd law of thermodynamics
Stot > 0
ΔF = – T⋅Stot < 0
Thus we conclude that:
If : ΔF<0 A transformation is spontaneous (irreversible)(F decreasese)
If : ΔF>0 The transformation cannot take place spontaneously(F increases)
If : ΔF=0 The system is in equilibrium
For a chemical reaction:
Sens 2
aA + bB cC + dD
Sens 1
If : ΔF<0 The reaction takes place in the direct direction (direction1): it
is spontaneous
If : ΔF>0 The reaction takes place in the opposite direction (direction 2)
the system is in equilibrium: the reaction takes place in both
If : ΔF=0
directions
Relationship between G and F
F=U-TS
G = H – TS G = U+PV – TS=F+PV
H=U+PV
G =F+PV
Calculation of the change in free enthalpy during
chemical reactions
The standard free enthalpy of formation (ΔG°f)
We call the standard free enthalpy of formation of a compound (ΔG°f), the
variation in free enthalpy accompanying the formation of a mole of this compound
from its constituents taken in their standard reference states.
The standard free enthalpy of the reaction (ΔG°r)
We have chemical reaction takes place at P=Cste and T=Cste:
ΔG°R
aA + bB cC + dD
ΔGR° = 𝜟𝑮𝒇° Produits - 𝜟𝑮𝒇° réactifs
Example: Calculate the standard free enthalpy of this reaction
Data
The reaction takes place in the direct direction
(direction1): it is spontaneous
• A second method for calculating ΔGr Using the
equation:
ΔGR° = ΔHR° – T⋅ ΔSR°
The molar free enthalpy of a gaseous compound:
To calculate the free enthalpy of a gas, you must start from the definition of
free enthalpy:
G = H – TS
G = H – TS=U+PV-TS G =U+PV-TS
H=U+PV dG=dU+PdV+VdP-TdS-SdT
G =U+PV-TS dU=TdS-PdV
dG=VdP-SdT
T=Cste dG=VdP
ΔG = 𝑉𝑑𝑃
𝑅𝑇
ΔG = 𝑑𝑃
𝑃
To determine the constant, we place ourselves in reference conditions, namely Pref = P° =
1atm
ΔG = nRTlnP/P°
𝑷
GP T = G° T + nRTln
𝑷°
L’enthalpie libre GP T= G° T + nRTlnP
molaire du gaz
à T et à P
L’enthalpie libre
molaire standard à T
In the case of a perfect gas mixture: the molar free enthalpy of each
constituent i under its partial pressure Pi at the temperature T is given by
GP T(i)= G° T(i)+ nRTlnPi
The total free enthalpy of the mixture
GP T(tot)=∑n(i) GP T(i)
General case: concept of activity:
In the general case, chemical reactions can involve compounds in different
physical states (sol, liq, vap) thus constituting several phases, each of which
can be a body or a mixture.
We should therefore consider the generalization of the ideal gas equation which
only concerns gaseous homogeneous systems.
Free enthalpy and activity:
Each chemical species X is associated with a dimensionless quantity whose
value is 1 when the chemical species is in the standard state.
This quantity is called activity and is denoted aX for the chemical species X.
the formula for free enthalpy is then written:
In general case we have:
GP T (X)= G° T (X) + nRTlnaX
𝑪
In the case of a solution : aX= (C : concentration and C° : concentration
𝑪°
of reference =1mol/L )
𝑷
In the case of a gas : aX= (P : pressure and P° : reference pressure = 1atm)
𝑷°
Pure solid : a=1
Chemical equilibrium
Some reactions can be considered complete. This means that if
stoichiometry is respected, the reactants disappear entirely,
replaced by the products. We then speak of a yield, a reaction
rate, or a degree of completion of the reaction of 100%.
Example : is a total reaction
However, physical transformations and many chemical reactions are
not complete.
Example :
In this case, the system does not evolve beyond a certain level of
progress, corresponding to a state of equilibrium.
A chemical equilibrium is the result of two opposing
phenomena occurring at the same time and at the
same rate. A reaction is said to be in a state of
equilibrium if the reactants and products of the reaction
are present and their quantities of matter remain
constant. It is symbolized by a double arrow.
Homogeneous and heterogeneous equilibrium
Example 1 :Homogeneous equilibrium in liquid phase (totally miscible: only one
phase)
CH3COOH(l) + CH3OH(l) CH3COOCH3(l) +H2O(l)
Example 2: Heterogeneous Equilibrium (consisting of several phases)
CaCO3(s) CaO(s) + CO2(g)
Thermodynamic equilibrium conditions
Sens 2
aA + bB cC + dD
Sens 1
The conditions for the evolution of a system are linked to the sign of the free
enthalpy ΔG (for isobaric transformations)
If : ΔG<0 The reaction takes place in the direct direction (direction1): it
is spontaneous
If : ΔG>0 The reaction takes place in the opposite direction (direction 2)
the system is in equilibrium: the reaction takes place in both
If : ΔG=0
directions
Equilibrium law, equilibrium constant
Sens 2
aA + bB cC + dD
Sens 1
ΔG =Gproduits – Gréactifs = [cG(C) +dG(D)]- [aG(A) +bG(B)]
the molar enthalpy of each constituent is given by
GP T (X)= G° T (X) + RTlnaX
ΔG= [c(G° T (C) + RTlnaC) + d(G° T (d) + RTlnaD )]-[ a(G° T (A)+ RTlnaA)+ b(G° T (B)+ RTlnaB)]
ΔG= [c(G° T (C) )+ d(G° T (D) )] - [a(G° T (A) )+ b(G° T (B) )]+RT [(lnac (C) + lnad (D))-( lnaa (A)+ lnab (B) )]
ac (C). ad (D)
ΔG= ΔG° +RT ln
aa (A). ab (B)
Equilibrium is reached when ΔG =0 therefore:
ac (C). ad (D)
ΔG° +RT ln =0
aa (A). ab (B)
ac (C). ad (D)
K= equilibrium constant
aa (A). ab (B)
Equilibrium law
The law of mass action = law of Guldberge et Waage
ΔG° +RT lnK=0 ΔG°= - RTlnK
−∆𝑮°
K= e
Remark
𝑹𝑻
The constant K depends on the temperature and the sociometric coefficients,
it has neither dimension nor unit.
