Chapter Two

Thermodynamic Relations and

Equilibrium Conditions
 Content
✓ Thermodynamic Potential and Maxwell relations

✓ Measurement of Properties ( partial molar

properties)

✓ Equilibrium conditions

✓ Phase equilibrium

✓ Chemical potential

✓ Ideal mixtures and Gibbs phase rule

 Thermodynamic Potential

• Thermodynamic potential or fundamental

function is a quantity used to describe or
analyze the state of a system. We have four
fundamental functions: Internal energy (U),
Enthalpy (H), Helmholtz free energy (F), and
Gibbs free energy (G). They are “potential
energy” defined as capacity to do work.
• Internal Energy (U): The total energy contained within a
system, including kinetic, potential, and molecular energies.
• Enthalpy (H): The total heat content of a system at constant
pressure.
• The Gibbs' free energy (G): The energy available to do
work in a thermodynamically-closed system at constant
pressure and temperature.
• The Helmholtz free energy (F): The maximum amount of
"useful“ work that can be extracted from a
thermodynamically-closed system at constant volume and
temperature.
• Starting from the first and second laws of
thermodynamics, we drive expressions for the
differential form of four thermodynamic
potentials. They are called fundamental
equations.
 The four basic thermodynamics potentials
• In energy function U,H,G and F, considering P-V work only (
mechanical work), closed system, reversible process, and
using the concept of first and second law of thermodynamics

Therefore: thermodynamics Potentials are:

dU= 𝑇𝑑𝑆 − 𝑃𝑑𝑉 U( S,V) – Internal energy
dH= 𝑇𝑑𝑆 − 𝑉𝑑𝑃 H(S,P) - Enthalpy
dG= −𝑆𝑑𝑇 + 𝑉𝑑𝑃 G(T,P) – Gibbs enthalpy
dF= −𝑆𝑑𝑇 − 𝑃𝑑𝑉 F(T,V) – Free energy
• A thermodynamic potential for a system with variable number of
particles (compositions) should depend on {μ, N } as well as a
thermal variable and a mechanical variable, which can be
 Maxwell’s Thermodynamics Relations

• The differentiability of the thermodynamic

potentials leads to various Maxwell relations.
Below there are four Maxwell relations relating T
respective to S and P respective to V. We drop in
the following the dependence on the number of
particles N .

8
• Maxwell's relations are a set of equations in
thermodynamics which are derivable from the symmetry
of second derivatives and from the definitions of the
thermodynamic potentials.
Example: dU= TdS-PdV
(U is as a function of S and V), expand it as an exact
differential.

𝜕𝑈 𝜕𝑈 𝜕𝑈
dU(S, V) = dS + dV where: = T, and
𝜕𝑆 𝑉 𝜕𝑉 𝑆 𝜕𝑆 𝑉

𝜕𝑈
= -P
𝜕𝑉 𝑆
9
• Since this is an exact differential ( the second derivative)
𝜕 𝜕𝑈 𝜕 𝜕𝑈
=
𝜕𝑉 𝜕𝑆 𝑉
𝜕𝑆 𝜕𝑉 𝑆
𝑆 𝑉
𝜕 𝜕 𝜕𝑇 𝜕𝑃
𝜕𝑉
𝑇 𝑆 =
𝜕𝑆
−𝑃 𝑉 , then 𝜕𝑉 𝑆
= −
𝜕𝑆 𝑉

Common forms of Maxwell relations:

10
Properties of Homogeneous Mixtures (Solution)
▪ A homogeneous mixture is a mixture in which the
composition is uniform throughout the mixture.
▪ In this section, general methods for evaluating
thermodynamic properties of homogeneous mixtures will
be discuss and this will include the important properties,
partial molar and chemical potential.
▪ Mixtures, frequently called solutions, will need an
additional property, composition, to completely describe
the state of the substance.
11
• Development of the general theory is straight forward,
but application which is often difficult and uses the
concept and approximation of Ideal Mixtures
(solutions) that serves as a reference to which Real
Mixtures (solutions) may be compared.
• Ideal Mixtures:
• No interactions between different components.
• Properties depend only on composition and mole
fractions.
• Non-Ideal Mixtures:
• Real mixtures have interactions between
components, requiring correction factors.

12
 Fundamental Property Relationships for
Systems of Variable Composition
• The Fundamental Property Relationships for Systems of
Variable Composition extend the thermodynamic principles
to account for systems where the composition changes due
to the addition, removal, or exchange of chemical
components. These relationships incorporate the chemical
potential (μi) of each component and are particularly useful
in systems such as chemical reactions, phase equilibrium,
and mixing processes.

13
For no change in composition ( for homogeneous mixture)

dU=TdS-PdV dH=TdS+VdP

dF=-PdV-SdT dG=VdP-SdT

• The above fundamental energy relations for

thermodynamic system is applicable to simple
fluids or mixtures in a single phase with no
change in composition.

14
• Change in P or T may alter the composition of the
phases; mass transfer of one or more components,
or chemical reaction may change the composition.
• For a system of variable composition, the
composition Ni of the components will be the
additional property. For example
U=U(S,V,N1,N2,…….,Ni)
 U   U   U 
dU =   dS +   dV +    dN i i j
 S V , N  V  S , N i  N i  S ,V , N
j

 U   U 
  =T and   = −P
 S V , N  V  S , N
15
The chemical potential μi is defined as:
 U 
i =  
 N i  S ,V , N j

Substitution gives
 U   U 
dU =   dS +   dV +  i dN i = TdS − PdV +  dN i
 S V , N  V  S , N
i
i i

Using Gibbs function

G = G(P,T,N1,N2,…..,Ni)
 G   G   G 
dG =   dP +   dT +    dN i i j
 P T , N  T  P , N i  N i  P ,T , N j
 G 
= VdP − SdT +    dN i
i  N i  P ,T , N j 16
Adding d(PV-TS) to both sides of dU will result in
dG = VdP − SdT +   i dN i
i

 G 
Gives i = 
 N 

 i  P .T , N j

Similarly dH and dF are represented by:

dH = TdS + VdP +  i dN i
i

dF = − SdT − PdV +  i dN i
i

Similarly, from the basic definitions of H and F also

the chemical potential is defined as:
 U   G   H   F 
i =   =   =   =  
 N i  S ,V , N j  N i  P ,T , N j  N i  S , P , N j  N i T ,V , N j 17
 Partial Molar Properties
A partial molar property is a thermodynamics
quantity which describes the variation of an
extensive property of a solution or mixture with
changes in the molar composition of the mixture at
constant temperature and pressure.

18
For any extensive property Y=Y(P,T,N1,N2,…,Ni)

 Y   Y   Y 
dY =   dT +   dP +    dN i i  j
 T  P , N  P T , N i  N i T , P , N
j

What we can say that the chemical potential of a

component “i” is equal to the partial molar Gibbs energy of
such component:
The partial property or partial molar property is defined
as
 Y 
yi   
 N i T , P , N j
19
 Then, as an example for the partial molar volume
will be  V 
  = vi
 N i T , P , N j
And the total volume will be
V = N1v1 + N 2 v2 , + ........ =  N i vi
i
This specific volume could be different from that of
a pure component, vi.
Thus in general

Y =  N i yi
i

20
It follows
U =  N i ui H =  N i hi

V =  N i vi S =  N i si

Mean (specific) molar property for a mixture can be

defined as
N = total mole
Y 1
ym = =
N N
 N y = x y
i
i i
i
i i
Ni= mole of ith component

xi=Ni/N = mole fraction of the ith component.

um =  xi ui hm =  xi hi sm =  xi si vm =  xi vi
i i i i
21
Various symbols used:
Solution extensive properties Y: U,H,S,G…..
Partial molar properties yi : ui , hi , si , gi ......
Pure component properties yi: ui,hi,si,gi…….
For a single component system in single phase

Y = Ni yi and Y = Ni yi gives yi = yi

22
Partial molar properties for H and G are as follows. Others
will follow the same pattern.

H=U+PV , Differentiation at constant T,P, and Nj

 H   U   V 
  =   + P 
 N i T , P , N j  N i T , P , N j  N i T , P , N j
hi = ui + Pvi and similarly g i = i = hi − Tsi

23
A change in an extensive property when two or more
pure components are mixed at constant T and P can
be determined as:
Y = Y − Y * =  N i ( yi − yi ) V = V − V * =  N i (vi − vi )
i i

H = H − H * =  N i ( hi − hi ) S = S − S * =  N i ( si − si )
i i

(* denotes pure substance)

24
• ΔH is called change in enthalpy, or heat of mixing. It can be
added or removed from a substance upon mixing.
• The change in enthalpy of a reaction is a measure of the
differences in enthalpy of the reactants and products.
• Similarly the change of entropy can be determined from

S =  N i ( si − si )
i

• As mixing is an irreversible process, the change in entropy

must always be positive.

25
 Partial Molar Property Evaluation For Binary
Phases

• Partial molar volume, (∂V/∂Ni)T,P,Nj, can be

determined experimentally by noting the change
in volume of the mixture when a pure substance
of interest is added while the other components
remain constant. This requires great precision in
getting the experimental data.
26
Starting with the definition of mean or specific molar
property ym given by ym =  xi yi (cons tan t T & P)
i
and when applied to a two component mixture
vm = xv1 + (1 − x)v2 ( x1 = x ; x2 = 1 − x) (i )
Differentiating with respect to x gives
 vm 
  = v1 − v2 (ii )
 x T , P
Solving for v1 and v2 form (i) and (ii) will give
 vm   vm 
v1 = vm +  (1 − x) and v2 = vm −  x
 x   x 
 vm   vm 
v1 = vm − x2   and v2 = vm + (1 − x2 ) 
 x2   x2  27
The ideal solution assumption simplifies mixture
analysis as follows:
Since all intermolecular forces
Enthalpy of mixing: are unchanged in creating an
Given by H =  N i (hi − hi ) ideal solution, the enthalpy of
i
mixing is zero and the
Thus for ideal solution volume change due to
mixing is zero.
H mix = 0 and hi = hi
In a similar manner differentiating the ideal solution
equation with respect to P while holding T and N
constant will give

ΔVmix=0 vi = vi
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 The Characteristics of an Ideal Solution

➢ Ideal solution is a solution in which the interaction between

molecules of the components does not differ from the

interactions between the molecules of each component.

Ideal solution has the following characteristics:

(i) Mixing volume change should be zero.

(ii) Mixing heat change should be zero.

29
In terms of specific enthalpy and specific volume,
using the relations
hmixt =  xi hi and vmixt =  xi vi
i i

for a binary ideal mixture of components A and B

(homogenous mixture of more than one component)
hmixt =  xi hi , pure = xB hB + (1 − xB )hA
i

vmixt =  xi vi , pure = xB vB + (1 − xB )v A
i

30
 Mixing of Two Fluid Streams
• Two fluid streams both containing components A and B
(but with different composition) of low velocity enter SSSF
mixing chamber as shown in figure in next slide. Molar
flow rate of the mixture is such that

N 1 + N 2 = N 3 = 1
For substance with molar composition x1 and x2
x1 N 1 + x2 N 2 = x3 N 3 = x3
The above two equations give
 x2 − x3  x3 − x1
N1 = and N2 =
x2 − x1 x2 − x1
31
A mixing process for two binary mixtures.
59

32
1st law SSSF gives:

Q =  N i ( h + ke + pe)out − N i ( h + ke + pe)in + W
i i

Considering simple adiabatic mixing process with

negligible ke and pe and the mixing container is rigid
results in:
N 1h1 + N 2 h2 = N 3 h3 = h3
Substitution of the values of N’s gives
x2 − x3 x3 − x1
h3 = (h1 ) + (h2 )
x2 − x1 x2 − x1
x3 − x1
h3 = h1 + (h2 − h1 )
x2 − x1 33
• For a non adiabatic mixing 1st law gives

 + N h + N h = N h = h
Q 1 1 2 2 3 3 3

 = heat transfer rate per unit mole of mixture.

Q

• Substitution of N’s and rearrangement will give:

x3 − x1
h3 = h1 + ( h2 − h1 ) + q
x2 − x1

34
 MULTIPHASE- MULTICOMPONENT SYSTEMS
The concepts developed for a single phase will
be extended to mixtures existing in two or more
different phases.
Equilibrium Criteria
Properties are identified with equilibrium
condition. Criteria for existence of equilibrium
will be developed by considering a Closed
system that contains an arbitrary number of
components and phases. Entropy function will
be used as a starting point.
35
• A non equilibrium system with uniform P and T
will be considered initially.
• For the present situation the surroundings will be
considered to be in thermal and mechanical
equilibrium with the system as the system
proceeds towards equilibrium.
• Any work and heat transfer between the system
and its surrounding will be reversible.
• The system and its surroundings form an isolated
system where generally 2nd law of
thermodynamics requires that:
dSisol≥0. ie. dSt+dSsurr ≥0
36
• St represents the total entropy of all the phases within
the system.
Also Qsurr − Q since system and surroundings are
dS surr = =
Tsurr T
in equilibrium (Tsurr= T, Q is with respect to sys).
Substitution will give Q  T dS t
By considering a reversible boundary work for closed
system and Appling conservation of energy principle:
dUt = δQ - δW = δQ - PdVt This will give
δQ = dUt + PdVt and further substitution of δQ will give
dUt +PdVt – TdSt ≤ 0 37
 This equation is applicable to a system that has
uniform pressure and temperature. The equality will
hold true when the process is internally reversible.

Special cases (dUt)S,V ≤ 0 U will proceed to min. val.

(dSt)U,V ≥0 same as (dS)isol ≥0

Rewriting the equation in its complete form

dU Tt , P + d ( PV t )T , P − d (TS t )T , P  0
d (U t + PV t − TS t )T , P  0 or d(H t − TS t ) T,P  0 or dG tT, P  0
38
• Gibbs function always decreases for irreversible process (T
and P held constant) of a closed system. Equilibrium is
reached when Gibbs function is minimum. In the limit dG=0.

• Many mass transfer problems and chemical reactions at

constant T and P are governed by this condition.

• In terms of Helmholtz function similar procedures will give (T

and V held constant)
d (U t − TS t )T ,V  0 or dFTt ,V  0

• Same conclusion as that of Gibbs function. Equilibrium is

reached when Helmholtz function is minimum. In the limit
39
dF=0.
PHASE EQUILIBRIUM AND MASS TRANSFER
• Mass transfer occurs in a two phase single or
multi-component system.
• For a closed system, the overall composition and
mass will be constant. Each component’s phases
are subject to mass transfer if equilibrium does not
exist.
• For a single component (pure substance) the
condition for equilibrium was gf=gg or μf=μg.
• Direction of mass transfer and mathematical
condition for equilibrium will be determined as
follows.
40
Consider two phases (α and β) each having the same
temperature and pressure and each containing C
components. (Not necessarily in phase equilibrium).
The general criterion to be applied is
dGT,P ≤ 0
The change in Gibbs function for each phase is
dG = V dP − S dT +  i dN i i = 1,2,...., C
i

Substitution in the general criterion gives

 i i  i i 0

i

dN 
+ 
i

dN 

In the absence of chemical reactions, the mole of

each of the i species must be conserved, thus
dNi + dNi = 0 or dNi = − dNi 41
Substitution in the general criterion gives
 i i i 0
(
i
 
−  
) dN 

When the system is in total equilibrium, the equality

holds true. Since the quantity dNi can not be zero,
then:
i = i for each of the C components. This can be
extended to the general case of P phases by
successively considering the phases in pairs to give
11 = 12 = 13 =     = iP [( P − 1) equations]
i1 = i2 = i3 =     = iP 
 =  =  =  = 
1
C
2
C
3
C
P
C for C components
42
• From the above it is clear that there are C(P-1)
equations relating the chemical potentials in the
overall system.
• The inequality applies to irreversible changes of
state. In this circumstance the transfer of
component i between β and α phases
  
(i − i )dNi  0

• If we have a mass transfer from phase β to phase α

then dN i is a positive quantity. This will give
 
(i − i )  0
43
• Which shows that mass transfer tends to occur from
regions of higher to regions of lower chemical
potential. Thus the chemical potential is the
driving force for mass transfer. Diffusion of
chemical species through a system is due to the
difference of chemical potential of a given species.

44
THE PHASE RULE FOR NON-REACTIVE COMPONENTS
• We know that, single component one phase- needs
two intensive properties to fix the state. For multi-
phase, multi-component system Gibbs’ phase rule
will be developed as follows:
• Any intensive variable for a given phase depends
on P, T and Ni of C components. If molar
magnitudes are expressed in terms of the intensive
variable, mole fraction (xi) then only (C-1) mole
fractions will be required for each phase. Since T
and P are common intensive properties for both
phases, then the required number of intensive
variables will be: (C-1)+2 per phase. 45
• If the numbers of phases are P, No. of intensive
variables becomes P[C+1].

• There are three set of conditions which must be

considered when evaluating the number of independent
equations (existing equations applicable to phase
equilibrium. This involves T, P and μ as follows).

1. Thermal equilibrium: Tα = Tβ =……..=TP

There will be (P-1) equations

46
2. Mechanical equilibrium: Pα = Pβ =……..=PP
There will also be (P-1) equations

3. Phase equilibrium

11 = 12 = 13 =     = 1P i1 = i2 = i3 =     = iP

C1 = C2 = C3 =     = CP (Gives C ( P − 1) equations)

47
• The total number of independent equations
relating the intensive variables becomes [2(P-
1)+C(P-1)].

• The required number of independent intensive

properties equals the total number of intensive
properties required minus the number of
independent equations relating certain intensive
variables of the system.
48
• This gives the required number of independent
intensive properties to be

F = P(C+1) - [2(P-1)+C(P-1)] = C + 2 - P

• Known as Gibbs’ phase rule and F is called

the degrees of freedom.

• Where: C is No. of component

: P is No. of phases
49
END OF CHAPTER TWO

50