Fundamental Property Relations

SOLUTIONS AND EQUILIBRIUM
THERMODYNAMICS
Prof. Angel Darío González-Delgado

agonzalezd1@unicartagena.edu.co
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.

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
Referencias Bibliográficas
• 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.
Introduction
Introduction
• We live in a world of mixtures.

• Exists mass transfer between phases
in contact.
• Mass transfer also occurs if mixtures
are in different states of aggregation.
When stops this mass transfer?

Composition (α)=f(????)
Introduction
• Mass transfer between phases

occurs until thermodynamic
equilibrium is achieved.
• Composition (α)=f(P, T, xi, nat.)
• How these concepts are related to

Chemical and Process
Engineering?
Introduction
Esterification
Transesterification
Washing
Methanol Glycerol separation

recovery
40-80% of plant FCI corresponds to separation equipment
Introduction
Purpose of solutions and equilibrium thermodynamics
The thermodynamics of equilibrium and solutions tries to

establish relationships between different properties such as
temperature, pressure and composition, which are fulfilled when
two or more phases containing mixtures reach a state of
thermodynamic equilibrium.
Introduction
Problem statement:
Source: www.cchem.berkeley.edu
1. Fundamental Property Relation
Remember from calculus course: if
Z = f ( x, y )
 z   z 
d ( z ) =   dx +   dy
 x  y  y  x
d ( z ) = Mdx + Ndy
 N 
  =?
 x  y
 M 
  =?
 y  x
 N   M 
  =  (1.1)
 x y  y x
This relation is called sometimes the Euler´s Reciprocity Relation
Now, remember from calculus course: if
f ( x, y , z ) = 0
x = x( y, z )
y = y ( x, z )
z = z ( x, y )
 x   y   z 
      = −1 (1.2)
 y  z  z  x  x  y
This is called the cyclic relation.
Which variables which can be related this way do you remember?
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 )
 P   V   T 
      = −1
 V T  T  P  P V
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
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
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
And ideal gas obeys the relation PV=RT (V as molar or masic

volume). 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 = −
𝑉 𝑉2
𝑅𝑑𝑇 𝑅𝑇𝑑𝑉
𝑑𝑃 = −
𝑉 𝑉2
𝑑𝑇 𝑇𝑑𝑉
𝑑𝑃 = 𝑅 − 2
𝑉 𝑉
0.01𝑚3
𝑘𝑃𝑎 𝑚3 2𝐾 301 𝐾
𝑘𝑔
𝑑𝑃 = 0.287 −
𝑘𝑔 𝐾 𝑚3 𝑚3
2
0.865 0.865
𝑘𝑔 𝑘𝑔
𝑑𝑃 = 0.664 𝑘𝑃𝑎 − 1.155 𝑘𝑃𝑎
𝑑𝑃 = −0.491 𝑘𝑃𝑎
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
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
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.
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
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
Let’s consider two balloons

at different pressures
connected by a mobile wall,
initially fixed by a hook.
Source:https://www.thenakedscientists.com/get-
What happens if we release
naked/experiments/balloons-tube the hook?
Where comes the energy

for moving the wall for?
U: Internal energy (molecular energy), The internal energy U

might be thought of as the energy required to create a system
in the absence of changes in temperature or volume (T and V
constants).
Consists in a microscopic kinetic energy due to molecular

rotation, translation and vibration, electron translation, and
nuclear and electron spin etc. and a microscopic potential
energy due to chemical and nuclear energy.
Let’s consider two solids in

contact at different
temperatures.
What happens?
What can we conclude from

both examples?
Source:http://umdberg.pbworks.com/w/page/7308432 Which is the price to pay for the

8/Example%3A%20Entropy%20and%20heat%20flow% thermal equilibrium?
20%282013%29
Occurs heat transfer until thermal

equilibrium is achieved.
Energy for heat transfer comes from

internal energy.
There are two magnitudes that must be

equaled for obtaining equilibrium.
Equilibrium requires energy transfer

(heat or work) provided by internal
Source:http://umdberg.pbworks.com/w/page/7308432 energy.
8/Example%3A%20Entropy%20and%20heat%20flow%
20%282013%29 Price to pay for thermal equilibrium is
entropy.
U: Internal energy (molecular energy), The internal energy U

might be thought of as the energy required to create a system
in the absence of changes in temperature or volume (T and V
constants).
But if the system is created in an environment (surroundings) of

temperature T, then some of the energy can be obtained by
spontaneous heat transfer from the environment to the
system. The amount of this spontaneous energy transfer is TS
where S is the final entropy of the system.
So, once discounted this energy that comes from the

environment to our system that is at V constant (in other
words, closed system), we have some energy that is “free” for
producing work that comes from the internal energy, this
energy is called Helmholtz “free” energy.
In other words, Helmholtz “free” energy is the energy available

for producing work, obtainable from a closed thermodynamic
system (V=constant) at a constant temperature.
𝐴 = 𝑈 − 𝑇𝑆 (1.3)
“Free” energy means the energy is available for producing work.

What happens with

PVT?
Source: Dreamstime.com
What happens with PVT?
In Yellow (open system)

P=Patm=constant
T=Tsurr=constant
V=constant (but may vary)
In red (closed system)

P≠Patm=constant (but
may vary)
T=Tsurr=constant
V=constant
What happens if I add one

drop of liquid to all cans?
In Yellow (open system)

P=Patm= Remains
constant
V=Increases
In red (closed system)

P=Increases
V=Remains constant
What about the

temperature?
At constant V: if T
increases, P increases
At constant P: If T
increases, V increases
What must I do if I want

to keep constant the
temperature but change P
or V?
Source: educacao.globo.com
What must I do if I want
to keep constant the
temperature but change P
or V?
We must add or extract

energy to/from the
system
Q or W Source: educacao.globo.com Q or W
Where the energy that

leaves the system comes
from?
?
PV
Energy comes from the

internal energy and from
U the PV work
Q (H)
The internal energy U might be thought of as the energy required to

create a system in the absence of changes in temperature or volume.
But, an additional amount of work PV must be done if the system is
created from a very small volume in order to "create room" for the
system.
H: Enthalpy, is the energy in a thermodynamic system, includes

internal energy and the amount of energy required to make room for
it by displacing its environment.
(1.4)
𝐻 = 𝑈 + 𝑃𝑉
As discussed in defining the Helmholtz free energy, an environment at constant

temperature T will contribute an amount TS to the system, reducing the overall
investment necessary for creating the system. If we remain constant pressure,
this net energy contribution for a system created in environment temperature T
from a negligible initial volume is the Gibbs free energy.
In other words, Gibbs “free” energy is the work that may be performed by a
thermodynamic system at a constant temperature and pressure.
G  U + PV − TS  H − TS (1.5)
In most of cases G, because the constant pressure is

given by nature (atmospheric pressure) and it’s free!
If we want to produce work from a system, we transform G, H or A, so in practical terms, it

is important to evaluate the changes in these properties.
W Re v  G2 − G1 (1.6)
If we take into account the changes in G, H or A, and definitions of

constant temperature and volume or pressure, we get:
 ( H ) = U + PV (1.7)
 ( A) = U − T S (1.8)
 (G ) = H − T S (1.9)
For example, the change in Gibbs free energy, ΔG, in a reaction is a very
useful parameter. It can be thought of as the maximum amount of work
obtainable from a chemical reaction.
U, H, A and G (state functions) can be used for tell us if a chemical

reaction is spontaneous or not, subject to constraints.
2NO ⎯
→ N 2 + O2 ?
 (G ) = H − T S (1.9)
For example, the change in Gibbs free energy, ΔG, in a reaction is a very
useful parameter. It can be thought of as the maximum amount of work
obtainable from a chemical reaction.

2NO → N 2 + O2 (G ) rxn = −173.4kJ


Chemical reaction is
Parameter
spontaneous if
U, Internal Energy ΔU (Constant V, S) < 0
H, Enthalpy ΔH (Constant P, S) < 0
A, Helmholtz energy ΔA (Constant V, T) < 0
G, Gibbs energy ΔG (Constant P, T) < 0
For any process (if the only work in/out the system is PV work)
Process is
Parameter
spontaneous if
U, Internal Energy ΔU (Constant V, S) ≤ 0
H, Enthalpy ΔH (Constant P, S) ≤ 0
A, Helmholtz energy ΔA (Constant V, T) ≤ 0
G, Gibbs energy ΔG (Constant P, T) ≤ 0
What if there is work done on/by the system different than PV work?
For any process (reversible or irreversible)
Parameter Process is spontaneous if

U, Internal Energy ΔU + ΔWnpv (Constant V, S) ≤ 0
H, Enthalpy ΔH + ΔWnpv (Constant P, S) ≤ 0
A, Helmholtz energy ΔA + ΔWnpv (Constant V, T) ≤ 0
G, Gibbs energy ΔG + ΔWnpv (Constant P, T) ≤ 0
U, H, A and G are called Thermodynamic potentials, because they are

scalar quantities used to represent the thermodynamic state of a
system. Thermodynamic potentials have the following properties:
• They have to be properties of the system

• They must be measured in units of energy
• Their minimal values denotes a stable equilibrium
• Their differential quantities (at constant variables) are equal to zero
at the equilibrium
From first law: U = Q +W (1.10)

d (U) = d (Q) + d (W) (1.11)
d (W) = − Pd (V) (1.12)
From second law: d (Q rev ) = Td ( S ) (1.13)
Combining (1.11-1.13): d (U) = TdS − PdV (1.14)

d (U) = TdS − PdV (1.14)
Deriving (1.4): d ( H ) = TdS − PdV + ( PdV + VdP )

d ( H ) = TdS + VdP (1.15)
Deriving (1.3): d ( A) = TdS − PdV − (TdS + SdT )

d ( A) = − PdV − SdT (1.16)
Deriving (1.5): d (G ) = TdS + VdP − (TdS + SdT )

d (G ) = VdP − SdT (1.17)
d (U) = TdS − PdV (1.14)  N   M 

d ( H ) = TdS + VdP   = 
(1.15)  x  y  y  x (1.1)
d ( A) = − PdV − SdT (1.16)
d (G ) = VdP − SdT (1.17)
 T   P   T   V 
  = −    = 
 V S  S V  P S  S P
 P   S   V   S 
  =    = − 
 T V  V T  T P  P T
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
 T   P   T   V 
  = −  (1.18)   =  (1.19)
 V S  S V  P  S  S  P
 P   S   V   S 
  =  (1.20)   = −  (1.21)
 T V  V T  T  P  P T
Example 1.3. Verify the validity of the following Maxwell

relation (Eq. 1.21) for steam at 250 °C and 300 kPa.
 V   S 
  = − 
 T  P  P T
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.
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.
𝜕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
d (U) = TdS − PdV (1.22) T =  dU  ;  dU  = − P (1.23)

   
 dS V  dV  s
d ( H ) = TdS + VdP
(1.24) T =  dH  ;  dH  = V (1.25)
 dS  P  dP  s
d ( A) = − PdV − SdT
 dA   dA 
(1.26)− P =   ;  = − S (1.27)
d (G ) = VdP − SdT  dV T  dT V
 dG   dG 
(1.28) V =   ;  = − S (1.29)
 dP T  dT  P
T-dS Equations: S = f (T ,V )
if
Z = f ( x, y )
 z   z 
d ( z ) =   dx +   dy
 x  y  y  x
 S   S 
Replacing d(S): d (S ) =   dT +   dV
 T V  V T
 S   S 
Multiplying by T: Td ( S ) = T   dT + T   dV (1.30)
 T V  V T
 S   S 
T-dS Equations: Td ( S ) = T   dT + T   dV (1.30)
 T V  V T
 H   U + PV   U 
But remember: CV =   =  at constant v: CV =   (1.31)
 T V  T V  T V
But also: d (U) = TdS − PdV (1.14)
Then, for a process at constant volume, replacing Eq. 1.14 in 1.31:

 U   T S   S 
(1.32)   =  =T   = CV
 T V  T V  T V
 S   S 
T-dS Equations: Td ( S ) = T   dT + T   dV (1.30)
 T V  V T
 S 
T  = C (1.32)

V
 T V
And from Maxwell’s relations  P   S  (1.20)
  = 
  T V  V T
Replacing Eqs. 1.20 and 1.32 in 1.30:
 P 
Td ( S ) = CV dT + T   dV (1.33)
 T V
T-dS Equations: S = S (T , P )
 S   S 
d (S ) =   dT +   dP
 T  P  P T
 S   S 
Multiplying by T: Td ( S ) = T   dT + T   dP (1.34)
 T  P  P T
 H 
But remember: CP =   (1.35)
 T  P
And also: d ( H ) = TdS + VdP (1.15)
Then, for a process at constant pressure, replacing Eq. 1.15 in 1.35:
 H   T S   S 
  =  =T  = CP (1.36)
 T  P  T  P  T  P
 S   S 
T-dS Equations: Td ( S ) = T   dT + T   dP (1.34)
 T  P  P T
 S 
T  = CP (1.36)
 T  P
 V   S 
And from Maxwell’s relations   = −  (1.21)
 T P  P T
Replacing Eq. 1.21 in 1.36 in 1.34:
 V 
Td ( S ) = CP dT − T   dP (1.37)
 T  P
 P 
Td ( S ) = CV dT + T   dV (1.33)
 T V
 V 
Td ( S ) = CP dT − T   dP (1.37)
 T  P
Combining two T-dS Equations (1.37) and (1.33):
 V   P 
(CP − CV )dT − T   dP − T   dV = 0 (1.38)
 T  P  T V
Combining two T-dS Equations (1.37) and (1.33):
 V   P  (1.38)
(CP − CV )dT − T   dP − T   dV = 0
 T  P  T V
With some algebra (Try at home or see video), we can obtain the following expression:
 V   P 
(CP − CV ) = T     (1.39)
 T P  T V
Using the Eq. 1.2 (cyclic relation), we obtain:
 P   V   P 
−    =  (1.40)
 V T  T P  T V
Finally, replacing Eq. (1.40) in (1.39):
 V   P  (1.41)
2
(CP − CV ) = −T    
 T  P  V T
 V   P 
2
(CP − CV ) = −T     (1.41)
 T  P  V T
For all substances (dP/dV) is always negative, which means that Cp-
Cv is always positive, or Cp>Cv.
From this general thermodynamic relation, we can derive specific

relations if we know a PTV equation (EoS).
Could be Cp=Cv?
 V   P 
2
(CP − CV ) = −T     (1.41)
 T  P V T
Could be Cp=Cv?
G  H − TS (1.5)
 dG 
  = −S (1.29)
 dT  P
As S is always a positive quantity, G decreases when

temperature increases (despite is an energy!)
W Re v  G2 − G1 (1.6)
If T increases, G decreases and reversible work decreases.

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.
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.
Answer: This equation only applies for Isentropic work, and

Gibbs energy takes into account entropy term.
Dependence of temperature
• G decreases when temperature

decreases (different to H and S).
• The plot is a continuous function
of T, even if there is phase change.
• Slope becomes discontinuous at
each transition.
• Slope is steepest for the vapor line
in comparison to liquid and solid
lines.
• Plot shows why solid phase is
favored at low temperature, and
vapor phase at temperatures
above boiling point.
dG/dT (gases)>dG/dT (liquids)>dG/dT (solids)
Tm Tb Tf
H (T final ) − H (Tinitial ) =  P (T )dT + H m +  P +  +  P (T )dT

S L G
C C (T ) dT H b C
Ti Tm Tb
H m H b
Tm S Tb L Tf
C (T ) C (T ) CPG (T )
S (T final ) − S (Tinitial ) = 
Ti
T
P
dT +
Tm
+
Tm
T
P
dT +
Tb
+
Tb
T
dT
• G decreases when temperature decreases (different to H and S).


each transition.
lines.

each transition.
lines.

each transition.
lines.

each transition.
lines.
If we consider the temperature dependence of G/T:
   G  1  G    1
 T   =   +G 
   P
T T  T P  T T P
1  G   G  1  G   G  
=   −  2  =   −  
T  T  P  T  T  T  P  T  
1  G  1   H − TS  
Replacing Eqs. 1.5 and 1.29, we have: = −S −   = −S −  
T  
T T   T 
   G  H
 T   = − 2 (1.42)
  T  P T
 d G H
  =− 2 (1.42)
 dT T  P T
Gibbs-Helmholtz Equation: Shows that we can obtain a
measurement of H, by measuring the temperature-
dependence of G/T, at constant pressure.
For any process with a defined deltaH:  d G  = − H

 
 dT T  P
2
T
If we consider the Pressure dependence of G (constant temperature,

dT=0)
d (G ) = VdP − SdT (1.17)
d (G ) = VdP
Pf
G ( Pfinal ) − G ( Pinitial ) =  VdP

Pi
For solids and liquids (incompressible fluids)

G ( Pfinal ) − G ( Pinitial ) = V ( Pf − Pi ) (1.43)
Gibbs energies for solids and liquids are almost insensitive to pressure
For ideal gases:

Pf
RT  Pf 
G( Pfinal ) − G( Pinitial ) = 
Pi
P
dP = RT ln  
 Pi 
(1.44)
Gibbs energies for ideal gases are function of temperature and

pressure
For real gases:

Dependence of pressure
• All curves are ascendant.

• All curves follow the shape of
equations.
• At low pressures, we find first
the gas phase
• Plot allows to conclude why
vapor phase is favored at low
pressures
Dependence of pressure
Depending on temperature chosen, plots changes their shape.
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

Definition of Total Gibbs of any CLOSED system:

G  H − TS (1.5)
d (nG ) = d (nH ) − Td ( nS ) − ( nS ) dT
from
(1.4)
H  U + PV
obtain d(nH) from d ( H ) = TdS + VdP
(1.15)
d (nG ) = (nV )dP − (nS )dT (1.45)

Total Gibbs energy change of any CLOSED system:
d (nG ) = (nV )dP − (nS )dT (1.45)
*applied to a single phase fluid in a closed system wherein no chemical reactions

occurs & the composition is constant.
 (nG )  (nG )
Therefore,  P  = nV  T  = −nS
  T ,n   P ,n
Number of moles of all chemical species are held constant.

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
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
d (nG )total = d (nG ) I + d (nG ) II
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.
  (nGI )    (nGI ) 
d (nGI ) =   dnA(C1) +   dnB (C1) Container I
 nA T , P ,nB  nB T , P ,nA
  (nGII )    (nGII ) 
d (nGII ) =   dnA(C 2) +   dnB (C 2) Container II
 nA T , P ,nB  nB T , P ,nA
If A flows to container II and B flows to container I (and mass

is conserved)
dnA(C 2) (container.II ) = −dn A( C1) (container.I )
dnB (C1) (container.I ) = −dnB (C 2) (container.II )
  (nGI )    (nGI ) 
d (nGI ) =   dnA(C1) +   dnB (C1)
 nA T , P ,nB  nB T , P ,nA
  (nGII )    (nGII ) 
d (nGII ) =   dnA(C 2) +   dnB (C 2)
 nA T , P ,nB  nB T , P ,nA
dnA(C 2) (container.II ) = −dn A( C1) (container.I )

dnB (C1) (container.I ) = −dnB (C 2) (container.II )
d (nG )total = d (nG ) I + d (nG ) II
Combining equations, in terms of container I:
  (nGI )    (nGI ) 
d (nG )Total =  dnA(C1) +   dnB (C1)
 nA T , P ,nB  nB T , P ,nA
  (nGII )    (nGII ) 
−  dnA(C1) −   dnB (C1)
 nA T , P ,nB  nB T , P ,nA
Grouping in terms of dnA and dnB....

Combining equations, in terms of container I:
   (nG )    ( nG )  
d (nG )Total =  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 d (nG )Total = 0 , mathematically, in

equation above, this can happen if:
1. dnA = dnB = 0
2. If the terms in blue are both zero.
• 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

called 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
  (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.
  (nG )
  = i Chemical potential of i
 ni  T , P , n j i
Chemical potential of component i :

• It correspond to the rate of change of nG 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 .
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
We can give the chemical potential in terms of other variables:
  (nG )    (nH )    (nA)    ( nU ) 

i =   =  =  = 
 ni  T , P , n j i   ni  S , P , n j i  ni V ,T , n j i   ni  S ,V ,n ji
So, our expression of dnG (Eq. 1.45) must include these mass transfers, then, for an open
system, the change of total Gibbs energy becomes:
d (nG ) = (nV )dP − (nS )dT +  i dni (1.46)

i
d ( nG ) = ( nV ) dP − ( nS ) dT +  i dni (1.46)
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
i
In a similar way, taking G as generating function, it can be obtained expressions for the other
thermodynamic potentials with some differentiation and algebra:
d ( nU ) = Td ( nS ) − Pd (nV ) +  i dni
i
(1.47)
d ( nH ) = Td ( nS ) + (nV )dP +  i dni (1.48)

i
d ( nA ) = − Pd (nV ) − ( nS ) dT +  i dni (1.49)

i
i
For a single component OPEN system, Equations. 1.46-1.49 become:
d ( nG ) = ( nV ) dP − ( nS ) dT +  dn
d ( nU ) = Td ( nS ) − Pd (nV ) +  dn
d ( nH ) = Td ( nS ) + (nV )dP +  dn
d ( nA ) = − ( nS ) dT − Pd (nV ) +  dn
For special case of one mol of solution, n=1 & ni = xi , eq. 1.46:
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
For a CLOSED system consisting of TWO phases in equilibrium, each individual
phase is OPEN to other (mass transfer between phases may occur).
Presumption: At
equilibrium, T & P
are the same in all
phases.
Source: www.cchem.berkeley.edu
For a CLOSED system consisting of TWO phases in equilibrium, each individual
phase is OPEN to other (mass transfer between phases may occur).
d ( nG ) = ( nV ) dP − ( nS ) dT +  i dni
  
i
phase
d ( nG ) = ( nV ) dP − ( nS ) dT +  i dni
    
i
The change in total Gibbs energy of the two-phase system is the sum of these
equations:
d ( nG ) = ( nV ) dP − ( nS ) dT +  i dni
    
i
+
d ( nG ) = ( nV ) dP − ( nS ) dT +  i  dni 
  
d ( nG ) = ( nV ) dP − ( nS ) dT +  i dni +  i  dni 

i i
Reduced to this form:

nM = (nM ) + (nM )
 
d ( nG ) = ( nV ) dP − ( nS ) dT +  i dni +  i dni    
i i
The changes of dni  & dni 
At equilibrium, result from mass transfer
between the phases.
 dni +  i dni = 0
   
i
i i
Therefore,  i

dni +  i
 
( −dn ) = 0
i

 ( )
i i
  
i − i dni = 0
i
 ( )
  
Since i − i dni = 0
i
 

Therefore, i − i = 0 or

i = i

i = i = ... = i  
(i = 1,2..., N )
Multiple phases at the same T & P are in

equilibrium when the chemical potential of
each species is the SAME in all phases.
Conditions for phase equilibrium:
 
T =T
 
P =P
 
i = i

Fundamental Property Relations

Cargado por

Información del documento

Título original

Derechos de autor

Formatos disponibles

Compartir este documento

Compartir o incrustar documentos

Opciones para compartir

¿Le pareció útil este documento?

¿Este contenido es inapropiado?

Copyright:

Formatos disponibles

Fundamental Property Relations

Cargado por

Copyright:

Formatos disponibles

SOLUTIONS AND EQUILIBRIUM

Prof. Angel Darío González-Delgado

• Conocer y utilizar las aplicaciones de la termodinámica en condiciones de

• Entender las relaciones de propiedades fundamentales para las soluciones

• Aprender a calcular las propiedades en equilibrios termodinámicos.

• Realizar análisis termodinámicos de procesos.

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

• We live in a world of mixtures.

When stops this mass transfer?

• Mass transfer between phases

• Composition (α)=f(P, T, xi, nat.)

• How these concepts are related to

Methanol Glycerol separation

Purpose of solutions and equilibrium thermodynamics

The thermodynamics of equilibrium and solutions tries to

Geometric representation of the disturbance

Solution: The temperature and specific volume of air changes

Assumptions: Air is an ideal gas

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

And ideal gas obeys the relation PV=RT (V as molar or masic

Therefore, the pressure will decrease by 0.491 kPa as a result of

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

However, if the specific volume had remained constant (dV=0),

Example 1.2. Using the ideal-gas equation of state, verify a) the

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

Replacing x, y and z in the following equation by P, v and T,

Let’s consider two balloons

Where comes the energy

U: Internal energy (molecular energy), The internal energy U

Consists in a microscopic kinetic energy due to molecular

Let’s consider two solids in

What can we conclude from

Source:http://umdberg.pbworks.com/w/page/7308432 Which is the price to pay for the

Occurs heat transfer until thermal

Energy for heat transfer comes from

There are two magnitudes that must be

Equilibrium requires energy transfer

U: Internal energy (molecular energy), The internal energy U

But if the system is created in an environment (surroundings) of

So, once discounted this energy that comes from the

In other words, Helmholtz “free” energy is the energy available

“Free” energy means the energy is available for producing work.

What happens with

What happens with PVT?

In Yellow (open system)

In red (closed system)

What happens if I add one

In Yellow (open system)

In red (closed system)

What about the

What must I do if I want

We must add or extract

Where the energy that

Energy comes from the

The internal energy U might be thought of as the energy required to

H: Enthalpy, is the energy in a thermodynamic system, includes

As discussed in defining the Helmholtz free energy, an environment at constant

In most of cases G, because the constant pressure is

If we want to produce work from a system, we transform G, H or A, so in practical terms, it

If we take into account the changes in G, H or A, and definitions of

U, H, A and G (state functions) can be used for tell us if a chemical

U, H, A and G (state functions) can be used for tell us if a chemical

2NO → N 2 + O2 (G ) rxn = −173.4kJ