SOLUTION AND

EQUILIBRIUM
THERMODYNAMICS
Prof. Angel Darío González-Delgado
 OBJETIVOS
• Conocer y utilizar las aplicaciones de la termodinámica en
condiciones de equilibrios físicos y químicos en sistemas de
composición variable, conocer los fundamentos básicos de
la Cinética Química.
• Entender las relaciones de propiedades fundamentales
para las soluciones homogéneas de composición variable.
• Aprender a calcular las propiedades en equilibrios
termodinámicos.
• Realizar análisis termodinámicos de procesos.
• Comprender el impacto de una solución de ingeniería
utilizando la termodinámica de equilibrio y soluciones en
un contexto mundial, económico, ambiental y social
 REFERENCIAS BIBLIOGRAFICAS
• Smith, J. M., Van Ness, H. C. & Abbott, M.M. (2005) Introduction to Chemical
Engineering Thermodynamics. Ed. McGraw –Hill. 7a. Edición. New York.
• Cengel, Y & Boles, M. (2002) Termodinámica. Editorial McGraw Hill. 4ª edición.
México
• Van Wylen, G.J. & Sonntag, R.E. (1993), Fundamentals of classical
thermodynamics, SI version, 5th edition, 744 pp., (John Wiley & Sons, New York).
• Wark & Richards. Termodinámica, Sexta Edición. México. McGraw-Hill. 2006. 1164
pp. ISBN884812829X.
• Jones, J.B.& Dugan,R.E. (1997): Ingeniería Termodinámica. Prentice Hall. pp. 328.
• Sherwin,K. (1995): Introducción a la Termodinámica. Addison Wesley
Iberoamericana. pp.148.
• Prausnitz J, Lichtenthaler RN, Gomes de Azevedo E. (2000): Termodinámica
molecular de los equilibrios de fases 3a. ed. Prentice Hall.
• Dincer, I. & Rosen, M.A. Exergy—Energy, Environment and Sustainable
Development, 2nd ed. Elsevier: Oxford, UK, 2012.
Semana SABER HACER
No.
1 Relación de propiedades fundamentales. Comprender y analizar la relación
Relaciones de Maxwell. Ecuaciones Tds, entre propiedades termodinámicas
Potencial Químico como criterio para el fundamentales y el potencial químico
equilibrio de fases. Desarrollo de ejercicios de en el equilibrio de fases.
verificación de relaciones de maxwell y .
cambios de temperatura, presión y entropia.
2 Propiedades molares parciales. Mezcla de Conocer y aplicar las propiedades
gases ideales. parciales a situaciones reales.
Desarrollo de ejemplos y actividades para el
cálculo de propiedades molares parciales y a
dilución infinita. Revisión de problemas
resueltos (Hora tutoría)
3 Fugacidad y Coeficiente de fugacidad para Calcular los coeficientes de
una especie pura. Fugacidad y Coeficiente de fugacidad para especies puras y en
fugacidad para una especie en solución. solución.
Desarrollo de ejercicios de cálculo de
fugacidades de sustancias puras y mezclas
multicomponente utilizando excel. Revisión de
problemas resueltos (Hora tutoría)
Semana SABER HACER
No.
4 Correlaciones generalizadas para el Conocer la importancia de la
coeficiente de fugacidad. La solución ideal. solución ideal y las propiedades en
Propiedades en exceso. Propiedades de las exceso.
fases liquidas a partir de datos EVL.
Desarrollo de ejercicios de cálculo de
propiedades de exceso. Revisión de
problemas resueltos (Hora tutoría).
5 Modelos de composición global y local para la Conocer y aplicar los distintos
energía de Gibbs en exceso. modelos de solución para calcular
Taller: Casos de estudio utilizando Excel, la energía de Gibbs en exceso.
Matlab, Unisim u otros.
Desarrollo de ejercicios propuestos. Revisión
de problemas resueltos (Hora tutoría)
Primer examen.
6 Cambio de propiedades en el mezclado. Entender el cambio de las
Bases moleculares para el comportamiento de propiedades fundamentales en los
mezclas. procesos de mezclado.
Análisis de artículos científicos
Desarrollo de ejercicios de cálculo de efectos
de mezclado. (Hora tutoría).
Semana SABER HACER
No.
7 Naturaleza del equilibrio. Regla de las fases. Conocer, entender y saber aplicar la
Teorema de Duhem. EVL. Comportamiento regla de las fases a problemas
cualitativo. específicos de ingeniería.

8 Calculo de punto de rocío y punto de burbuja. Calcular el punto de roció y de

Calculo de evaporación instantánea. Sistema burbuja de una mezcla binaria.
soluto-solvente. Realizar cálculos de evaporación
Taller de cálculo de puntos de rocío y burbuja instantánea.
utilizando Excel, Matlab, Unisim u otros.
Desarrollo de ejercicios propuestos de cálculo
de vaporización instantánea. Revisión de
problemas resueltos (Hora tutoría).
9 Propiedades de los fluidos a partir de las  Comprender, aplicar y calcular las
ecuaciones viriales de estado. Propiedades propiedades viriales.
de los fluidos a partir de las ecuaciones  Calcular las propiedades de los
cúbicas de estado. fluidos a través de las ecuaciones
Discusión de problemas y casos (Hora tutoría). cúbicas.
 Semana SABER HACER
No.
10 Correlaciones tipo Pitzer. EVL a partir de •Entender y aplicar los conceptos de
ecuaciones cúbicas de estado. Equilibrio y equilibrio entre fases.
estabilidad.
11 Equilibrio liquido-liquido. Equilibrio vapor- Entender y aplicar los conceptos de
liquido-liquido. Equilibrio vapor sólido-liquido. equilibrio entre diferentes fases.
Equilibrio sólido-vapor.
Desarrollo de ejercicios propuestos. Revisión
de problemas resueltos (Hora tutoría)
12 Coordenadas de reacción. Aplicación de los Calcular la energía estándar de Gibbs
criterios de equilibrio a las reacciones y la constante de equilibrio para
químicas. Cambio de la energía estándar de reacciones químicas
Gibbs y la constante de equilibrio.
Segundo examen.
13 Efecto de la temperatura sobre la constante de Resolver problemas de equilibrio en
equilibrio. Evaluación de las constantes de reacciones químicas aplicados a
equilibrios. Relación de las constantes de situaciones reales
equilibrio con la composición. Conversión de Evaluar la dependencia de la
equilibrio para las reacciones individuales. constante de equilibrio con la
Desarrollo de ejercicios propuestos. Revisión temperatura y la composición
de problemas resueltos (Hora tutoría).
Semana SABER HACER
No.
14 Regla de las fases y teorema de Duhem para Conocer, entender y saber aplicar la
los sistemas reactivos. Equilibrio en regla de las fases para sistemas
reacciones múltiples. reactivos a problemas específicos de
Desarrollo de ejercicios de aplicación (Hora ingeniería.
tutoría)
15 Análisis termodinámico de procesos. Calculo Realizar análisis termodinámico de
del trabajo ideal y trabajo perdido. procesos
Desarrollo de taller de cálculo de trabajo
perdido en una etapa de proceso. Revisión de
problemas resueltos (Hora tutoría)
16 Análisis exergético de procesos de flujo en Realizar el análisis exergético
estado uniforme. Caso de estudio utilizando completo de un proceso químico,
Excel. calculando la eficiencia exergética
Proyecto de aula: diagnostico energético de un global y por etapa, las
proceso químico utilizando análisis exergético. irreversibilidades totales y la exergía
de los residuos del proceso.
Parcial Final
 OUTLINE
0. Introduction
1. Fundamental Property Relation
2. Chemical Potential & Phase Equilibria
3. Partial Properties
4. The Ideal-Gas Mixture Model
5. Fugacity & Fugacity Coefficient: Pure Species
6. Fugacity & Fugacity Coefficient: Species in Solution
7. Generalized Correlations for Fugacity Coefficient
0. Introduction
0. Introduction

Composition (α)=f(P, T, μ, xi)

 0. Introduction

1. Capacity: 80000 ton/year % w/w Compound

2. Thermodynamics package 11.3 PLO
- Chao Seader 12.7 PLP
- NRTL 6.6 OOO
- Peng-Robinson
26.2 POO
- BWRS
33.0 POP
3. Crude palm oil composition (CPO)
7.2 PPP
4. Group contribution method
3.0 Palmitic acid
 0. Introduction
Esterification

Transesterification

Washing

Methanol Glycerol separation

recovery
40-80% of plant FCI corresponds to separation equipment
 0. Introduction
The phase equilibria problem:

Source: www.cchem.berkeley.edu
 1. Fundamental Property Relation
Remember from calculus course:

if
Z  f ( x, y )
 dz   dz 
d ( z )    dx    dy
 dx  y  dy  x
d ( z )  Mdx  Ndy
 dN   dM 
  ? 
 dx  y  dy  x
 1. Fundamental Property Relation
 dN   dM 
   
 dx y  dy x
Remember from calculus course (the cyclic relation):
if
f ( x, y , z )  0
x  x( y, z )
y  y ( x, z )
z  z ( x, y )
 dx   dy   dz 
       1
 dy  z  dz  x  dx  y
Which properties of a system do you remember?
 1. Fundamental Property Relation
Let’s replace x, y and z for P, V and T (direct measurable basic
properties of a system):
f ( P, V , T )  0
P  P (V , T )
V  V ( P, T )
T  T ( P, V )
 dP   dV   dT 
       1
 dV T  dT  P  dP V
 1. Fundamental Property Relation
Example 1.1. Consider air at 300 K and 0.86 m3/kg. The state of
air changes to 302 K and 0.87 m3/kg as a result of some
disturbance. Find the change in pressure of air using:

 dz   dz 
d ( z )    dx    dy
 dx  y  dy  x

Geometric representation of the disturbance

discussed in the above example
 1. Fundamental Property Relation
Example 1.1. Consider air at 300 K and 0.86 m3/kg. The state of
air changes to 302 K and 0.87 m3/kg as a result of some
disturbance. Find the change in pressure of air using:

 dz   dz 
d ( z )    dx    dy
 dx  y  dy  x
1. Choose an EoS
2. Find dT and dV
3. Derive EoS
4. Replace terms
 1. Fundamental Property Relation
Solution: The temperature and specific volume of air changes
slightly during a process. The resulting change in pressure is to
be determined.

Assumptions: Air is an ideal gas

Analysis: Due to changes are small, the changes in T and v can

be expressed as:
𝑑𝑇 ≅ ∆𝑇 = 302 − 300 𝐾 = 2 𝐾
𝑑𝑣 ≅ ∆𝑣 = 0.87 − 0.86 𝑚3 /𝑘𝑔 = 0.01𝑚3 /𝑘𝑔
 1. Fundamental Property Relation
And ideal gas obeys the relation PV=RT. Solving for P yields:
𝑅𝑇
𝑃=
𝑉

Note that R is a constant and P=P(T, v). Therefore:

𝜕𝑃 𝜕𝑃
𝑑𝑃 = 𝑑𝑇 + 𝑑𝑣
𝜕𝑇 𝑣 𝜕𝑣 𝑇

𝑅𝑑𝑇 𝑅𝑇𝑑𝑣
𝑑𝑃 = − 2
𝑣 𝑣
 1. Fundamental Property Relation
𝑅𝑑𝑇 𝑅𝑇𝑑𝑣
𝑑𝑃 = − 2
𝑣 𝑣
𝑑𝑇 𝑇𝑑𝑣
𝑑𝑃 = 𝑅 − 2
𝑣 𝑣
0.01𝑚3
𝑘𝑃𝑎 𝑚3 2𝐾 301 𝐾
𝑘𝑔
𝑑𝑃 = 0.287 3 − 2
𝑘𝑔 𝐾 𝑚 𝑚 3
0.865 0.865
𝑘𝑔 𝑘𝑔
𝑑𝑃 = 0.664 𝑘𝑃𝑎 − 1.155 𝑘𝑃𝑎
𝑑𝑃 = −0.491 𝑘𝑃𝑎
 1. Fundamental Property Relation
Therefore, the pressure will decrease by 0.491 kPa as a result of
this disturbance.

Notice that if the temperature had remained constant (dT=0),

the pressure would decrease by 1.155 kPa as a result of the 0.01
m3/kg increase in specific volume.

𝜕𝑃
𝑑𝑣 = 𝜕𝑃 𝑇 = −1.155 𝑘𝑃𝑎
𝜕𝑣 𝑇
 1. Fundamental Property Relation
However, if the specific volume had remained constant (dv=0),
the pressure would increase by 0.664 kPa as a result of the 2 K
rise in temperature.

𝜕𝑃
𝑑𝑇 = 𝜕𝑃 𝑣 = 0.664 𝑘𝑃𝑎
𝜕𝑇 𝑣
And,
𝑑𝑃 = 𝜕𝑃 𝑣 + 𝜕𝑃 𝑇

𝑑𝑃 = 0.664 − 1.155
𝑑𝑃 = −0.491 𝑘𝑃𝑎
 1. Fundamental Property Relation
Example 1.2. Using the ideal-gas equation of state, verify a) the
cyclic relation and b) the reciprocity relation at constant P.

Analysis: The ideal-gas equation of state Pv=RT involves the

three variables P, v and T. Any two of these can be taken as the
independent variables, with the remaining one being the
dependent variable.
 1. Fundamental Property Relation
Replacing x, y and z in the following equation by P, v and T,
respectively, we can express the cyclic relation for and ideal gas
as:

𝜕𝑥 𝜕𝑦 𝜕𝑧
= −1
𝜕𝑦 𝑧 𝜕𝑧 𝜕𝑥 𝑦
𝑥
𝜕𝑃 𝜕𝑣 𝜕𝑇
= −1
𝜕𝑣 𝑇 𝜕𝑇 𝑃 𝜕𝑃 𝑣
 1. Fundamental Property Relation
𝑅𝑇 𝜕𝑃 𝑅𝑇
Where, 𝑃 = 𝑃 𝑣, 𝑇 = → =− 2
𝑣 𝜕𝑣 𝑇 𝑣
𝑅𝑇 𝜕𝑣 𝑅
𝑣 = 𝑣 𝑃, 𝑇 = → =
𝑃 𝜕𝑇 𝑃 𝑃
𝑃𝑣 𝜕𝑇 𝑣
𝑇 = 𝑇 𝑃, 𝑣 = → =
𝑅 𝜕𝑃 𝑣 𝑅
Substituting yields,
𝜕𝑃 𝜕𝑣 𝜕𝑇
= −1
𝜕𝑣 𝑇 𝜕𝑇 𝑃 𝜕𝑃 𝑣
𝑅𝑇 𝑅 𝑣 𝑅𝑇
− 2 =− = −1
𝑣 𝑃 𝑅 𝑃𝑣
 1. Fundamental Property Relation

U: Internal energy (molecular energy)

H: Enthalpy (energy in a thermodynamic system, includes
internal energy and the amount of energy required to make
room for it by displacing its environment).
𝐻 = 𝑈 + 𝑃𝑣

A: Helmholtz energy (the useful work obtainable from a closed

thermodynamic system at a constant temperature).
𝐴 = 𝑈 − 𝑇𝑆
 1. Fundamental Property Relation

G: Gibbs energy (maximum or reversible work that may be

performed by a thermodynamic system at a constant
temperature and pressure).
G  H  TS
W Re v  G2  G1

(closed system, constant T and P)

1. Fundamental Property Relation
d (u )  TdS  PdV

d ( H )  TdS  PdV  ( PdV  VdP)

d ( H )  TdS  VdP

d ( A)  TdS  PdV  (TdS  SdT )

d ( A)   PdV  SdT

d (G )  TdS  VdP  (TdS  SdT )

d (G )  VdP  SdT
 1. Fundamental Property Relation
U, H, A and G (state functions) can be used for tell us if a chemical
reaction is spontaneous or not, subject to constraints.

Chemical reaction is
Parameter
spontaneous if
U, Internal Energy dU (Constant V, S) < 0
H, Enthalpy dH (Constant P, S) < 0
A, Helmholtz energy dA (Constant V, T) < 0
G, Gibbs energy dG (Constant P, T) < 0
 1. Fundamental Property Relation
d (u )  TdS  PdV  dN   dM 
d ( H )  TdS  VdP    
 dx y  dy x
d ( A)   PdV  SdT
d (G )  VdP  SdT

 dT   dP   dT   dV 
        
 dV s  dS v  dP s  dS P
 dP   dS   dV   dS 
        
 dT V  dV T  dT  P  dP T
 1. Fundamental Property Relation

Maxwell relations are extremely valuable in

thermodynamics because they provide a means of
determining the change in entropy, which cannot be
measured directly, by simply measuring the changes in
properties P, v, and T
 1. Fundamental Property Relation
Example 1.3. Verify the validity of the following Maxwell
relation for steam at 250 °C and 300 kPa.
𝜕𝑠 ?
𝜕𝑣
=−
𝜕𝑃 𝑇 𝜕𝑇 𝑃

Analysis. The Maxwell relation states that for a simple

compressible substance, the change in entropy with pressure
at constant temperature is equal to the negative of the change
in specific volume with temperature at constant pressure.
 1. Fundamental Property Relation

Analysis. If we had explicit analytical relations for the entropy

and specific volume of steam in terms of other properties, we
could easily verify this by performing the indicated
derivations. However, all we have for steam are tables of
properties listed at certain intervals. Therefore, the only
course we can take to solve this problem is to replace the
differential quantities with corresponding finite quantities,
using property values from the tables or about the specified
state.
1. Fundamental Property Relation
𝜕𝑠 𝜕𝑣
=? −
𝜕𝑃 𝑇 𝜕𝑇 𝑃
∆𝑠 𝜕𝑣
≅? −
∆𝑃 𝑇=250°𝐶 𝜕𝑇 𝑃=300 𝑘𝑃𝑎

𝑠400 𝑘𝑃𝑎 −𝑠200 𝑘𝑃𝑎 ?

𝑣300°𝐶−𝑣200 °𝐶
≅ −
400 − 200 𝑘𝑃𝑎 𝑇=250°𝐶 300 − 200 °𝐶 𝑃=300 𝑘𝑃𝑎

𝑘𝐽 𝑚3
7.3804 − 7.7100 (0.87535 − 0.71643)
𝑘𝑔 𝐾 ? 𝑘𝑔
≅ −
400 − 200 𝑘𝑃𝑎 300 − 200 °𝐶

𝑚3 𝑚3
−0.00165 ≅ −0.00159
𝑘𝑔 𝐾 𝑘𝑔 𝐾
 1. Fundamental Property Relation
 du   du 
d (u )  TdS  PdV T    ;   P
 dS v  dV  s

d ( H )  TdS  VdP  dH   dH 
T   ;  V
 dS  P  dP  s
d ( A)   PdV  SdT
 dA   dA 
P  ;   S
 dV T  dT V
d (G )  VdP  SdT
 dG   dG 
V    ;   S
 dP T  dT  P
 1. Fundamental Property Relation
T-dS Equations: S  f (T , V )
 dz   dz 
d ( z )    dx    dy
 dx  y  dy  x
 dS   dS 
d (S )    dT    dV
 dT V  dV T
 dS   dS 
Td ( S )  T   dT  T   dV
 dT V  dV T
 1. Fundamental Property Relation
T-dS Equations: In a constant volume process: Td ( S )  CV dT
In a constant pressure process: Td ( S )  C P dT

Then:

 dP 
(1)Td ( S )  CV dT  T   dV
 dT V
 1. Fundamental Property Relation
T-dS Equations: S  S (T , P )
 dS   dS 
d (S )    dT    dP
 dT  P  dP T
 dS   dS 
Td ( S )  T   dT  T   dP
 dT  P  dP T

 dV 
(2)Td ( S )  CP dT  T   dP
 dT  P
 1. Fundamental Property Relation
Combining two T-dS Equations:
 dV   dP 
(CP  CV )dT  T   dP  T   dV  0
 dT  P  dT V
 dV   dP 
(3)(CP  CV )  T    
 dT P  dT V

Remember that: 
dP   dV   dT 
      1
 dV T  dT  P  dP V
 1. Fundamental Property Relation
 dP   dV   dP 
Some algebra:      
 dV T  dT  P  dT V

2
 dV   dP 
Replacing in (3): (CP  CV )  T     (4)
 dT  P  dV T

For all substances (dP/dV) is always

negative, which means that Cp-Cv is
always positive, or Cp>Cv
 1. Fundamental Property Relation
G  H  TS
 dG 
   S
 dT  P

As S is always a positive quantity, G decreases when

temperature increases (despite is an energy!)
WSRe v  G2  G1

If T increases, G decreases and reversible work decreases.

 1. Fundamental Property Relation

Remember that for a turbine:

WSRe v  H 2  H1

Source: www.turbinesinfo.com

So, if T2 increases and T1 remains the same, the maximum work

obtainable increases, this contradicts what is written in the
previous slide.
 1. Fundamental Property Relation

WSRe v  H 2  H1

Source: www.turbinesinfo.com

Answer: This equation only applies for Isentropic work, and

Gibbs energy takes into account entropy term.
 1. Fundamental Property Relation

Answer: This equation only applies for Isentropic work, and

Gibbs energy takes into account entropy term.
 1. Fundamental Property Relation
If we consider the temperature dependence of G/T:
 d G 1  dG   d 1
     G 
 dT T  P T  dT  P  dT T  P
1  dG   G  1  dG   G  
     2       
T  dT  P  T  T  dT  P  T  
1  G  1   H  TS  
 S     S   
T  
T T   T 
 d G H
   2
 dT T  P T
 1. Fundamental Property Relation
 d G H
   2
 dT T  P T
Gibbs-Helmholtz Equation: Shows that we can obtain a
measurement of H, by measuring the temperature-
dependence of G.

 d G  H
For any process with a defined deltaH:    2
 dT T  P T
 1. Fundamental Property Relation
If we consider the Pressure dependence of G (constant
temperature, dT=0)
d (G )  VdP  SdT
d (G )  VdP
Pf

G ( Pfinal )  G ( Pinitial )   VdP

Pi

For solids and liquids (incompressible fluids)

G ( Pfinal )  G ( Pinitial )  V ( Pf  Pi )

Gibbs energies for solids and liquids are constant with pressure
 1. Fundamental Property Relation
For ideal gases:
Pf
RT  Pf 
G( Pfinal )  G( Pinitial )  
Pi
P
dP  RT ln  
 Pi 

Gibbs energies for ideal gases are function of temperature and

pressure
1. Fundamental Property Relation
 1. Fundamental Property Relation
What does dG(P,T) mean:
1. Fundamental Property Relation

dG/dT (gases)>dG/dT (liquids)>dG/dT (solids)

 1. Fundamental Property Relation
Issues to consider:

• How do individual chemical species in a mixture, or

reactants and products in a reaction system contribute to
G?

• Can we calculate G and dG from their concentrations?

• How G is affected by fluxes of matter in/out of the system

 1. Fundamental Property Relation
Definition of Total Gibbs of any CLOSED system:
G  H  TS
d (nG )  d (nH )  Td (nS )  (nS )dT
from
H  U  PV
obtain d(nH)
d (nG )  (nV )dP  (nS )dT
 1. Fundamental Property Relation
Total Gibbs energy change of any CLOSED system:

d nG   nV dP  nS dT

*applied to a single phase fluid in a closed system wherein no chemical reactions
occurs & the composition is constant.

Therefore,  nG   nG 

 P   nV  T   nS
  T ,n   P ,n

No of moles of all chemical species are held constant.

 1. Fundamental Property Relation
For an open system:
Consider two containers at constant T and P, one contains A
and the other contains B, both connected, but initially the
valve is closed.

Source: www.chegg.com
 1. Fundamental Property Relation

Container I Container II

Since G (Gibbs energy an extensive variable:

Gtotal  GI  GII

G of all A and B in Container I G of all A and B in Container II

nGtotal  nGI  nGII
 1. Fundamental Property Relation
Now we open the valve:

nGI  nGI (nA , nB ) nGII  nGII (nA , nB )

After we open the valve, A and B will mix spontaneously,

which means that total G will decrease.
 1. Fundamental Property Relation

  (nGI )    (nGI ) 
d (nGI )    dnA    dnB Container I
 nA T , P ,nB  nB T , P ,nA
  (nGII )    (nGII ) 
d (nGII )    dnA    dnB Container II
 nA T , P ,nB  nB T , P ,nA
 1. Fundamental Property Relation

If A flows to container II and B flows to container I (and mass

is conserved)
dnA (container.II )  dnA (container.I )
dnB (container.I )  dnB (container.II )
1. Fundamental Property Relation

  (nGI )    (nGI ) 
d (nGI )    dnA    dnB
 nA T , P ,nB  nB T , P ,nA
  (nGII )    (nGII ) 
d (nGII )    dnA    dnB
 nA T , P ,nB  nB T , P ,nA

dnA (container.II )  dnA (container.I )

dnB (container.I )  dnB (container.II )
 1. Fundamental Property Relation
Combining equations, for container I:
   (nG )    ( nG )  
d (nG )    I
  
II
  dnA (container.I )
  nA T , P ,n  nA T , P ,n 
 B B 

   (nG )    ( nG )  
 I
  
II
  dnB (container.I )
  nB T , P ,n  nB T , P ,n 
 A A 

Mixing of A and B continues until dnG=0, this can happen if

dnA  dnB  0 or if the terms in blue are both zero.
 1. Fundamental Property Relation
• So, when valve is open, mixing stops when:
  (nGI )    (nGII ) 
    and
 nA T , P ,nB  nA T , P ,nB
  (nGI )    (nGII ) 
    
  nB T , P ,nA  nB T , P ,nA

• Derivatives respect to the number of moles of something are

call partial molar quantities.
• The partial molar Gibbs free energy is so important it is given
its own symbol.
  (nGI ) 
   A Chemical potential of A
 nA T , P ,nB
 1. Fundamental Property Relation
  (nGI )    (nGII ) 
    and
 nA T , P ,nB  nA T , P ,nB
  (nGI )    (nGII ) 
   
  nB T , P ,nA  nB T , P ,nA

• The spontaneous mixing of A and B will continue until the

chemical potential of a chemical specie in container I is equal
to chemical potential of that chemical specie in container II.
• The uniform chemical potential of each component of a
multicomponent system is a requirement for equilibrium.
 1. Fundamental Property Relation
We can give the chemical potential in terms of other
variables:

  (nG )    (nH )    (nA)    (nU ) 

i         
 ni T , P ,n j   ni  S , P,n j  ni V ,T , n j   ni  S ,V , n j

So, our expression of dG must include these mass

transfers, for an open system, the change of total Gibbs
energy becomes:
d (nG )  (nV )dP  (nS )dT   i dni
i
 1. Fundamental Property Relation
Chemical potential of component i:
• It correspond to the rate of change of G with ni when the
component i is added to the system at fixed P,T and number of
moles of all other species.

• The chemical potential is the partial molar Gibbs Free Energy

(or U,H, A) of component i.

• Physically this corresponds to how the volume in the system

changes upon addition of 1 mole of component ni at fixed P,T
and mole numbers of other components.
 1. Fundamental Property Relation
Issues to consider:
• How do individual chemical species in a mixture, or
reactants and products in a reaction system contribute to G?
Can we calculate G and dG from their concentrations?
d (nG )   i dni
i

• How G is affected by fluxes of matter in/out of the system.

d (nG )  (nV )dP  (nS )dT   i dni
i
 1. Fundamental Property Relation
d  nG    nV  dP   nS  dT   i dni
i

   nG      nG      nG  
Since    nV ,    nS , i   n 
 P T ,n  T  P ,n  i  P ,T ,n j
total change of Gibbs energy for OPEN system becomes:

   nG      nG      nG  
d  nG     dP    dT     dni
 P T ,n  T  P ,n i  ni  P ,T ,n j
 1. Fundamental Property Relation
For special case of one mol of solution, n=1 & ni = xi ,
d nG   nV dP  nS dT   i dni
i

becomes d  G   VdP  SdT   i dxi

i
G as a function of T, P
G  G T , P, x1 , x2 ,....xi ,.. and xi

At constant T & x: At constant P & x: At constant P & x:

 G   G 
V    G  H  G T 
S     T  P , x
 P T , x  T  P , x from H  G  TS
At T=253 K, we are 20 K below the melting
point of ice.
Water chooses to exist in the solid state.

Reason: 𝜇𝑠𝑜𝑙𝑖𝑑 < 𝜇𝑙𝑖𝑞𝑢𝑖𝑑 < 𝜇𝑔𝑎𝑠

At T=273.16 K, ice melts to form water and
these two phases coexist.

Reason: 𝜇𝑠𝑜𝑙𝑖𝑑 = 𝜇𝑙𝑖𝑞𝑢𝑖𝑑 < 𝜇𝑔𝑎𝑠

At T=330 K, water is still in
the liquid state.

Reason: 𝜇𝑙𝑖𝑞𝑢𝑖𝑑 < 𝜇𝑠𝑜𝑙𝑖𝑑 < 𝜇𝑔𝑎𝑠

At T=373.16 K, water boils
and water and steam coexist.

Reason: 𝜇𝑙𝑖𝑞𝑢𝑖𝑑 = 𝜇𝑔𝑎𝑠 < 𝜇𝑠𝑜𝑙𝑖𝑑

At T=373.16 K, water exists
as steam

Reason: 𝜇𝑔𝑎𝑠 < 𝜇𝑙𝑖𝑞𝑢𝑖𝑑 < 𝜇𝑠𝑜𝑙𝑖𝑑