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CRET Class 01 - 10 - 2013

The document discusses phase equilibria and the phase rule for nonreacting systems. It introduces the phase rule, which states that for a system with c chemical components in p phases at temperature T and pressure P, the number of degrees of freedom is f=c-p+2. This means the number of intensive properties (like T, P) that can be independently varied is f. The document provides examples of applying the phase rule to determine the number of measurable properties needed to define the state of a multicomponent system. It also discusses constraints due to chemical potential equality between phases.

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Erj Daniyaroff
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297 views15 pages

CRET Class 01 - 10 - 2013

The document discusses phase equilibria and the phase rule for nonreacting systems. It introduces the phase rule, which states that for a system with c chemical components in p phases at temperature T and pressure P, the number of degrees of freedom is f=c-p+2. This means the number of intensive properties (like T, P) that can be independently varied is f. The document provides examples of applying the phase rule to determine the number of measurable properties needed to define the state of a multicomponent system. It also discusses constraints due to chemical potential equality between phases.

Uploaded by

Erj Daniyaroff
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Relations Among Partial Molar Quantities

H=U+PV
We can also find relations for the partial molar Gibbs Energy analogous to the Maxwell
relations:
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For example, consider the total solution enthalpy:
Since the pressure is constant:
Likewise:
Reduction of multicomponent phase equilibrium problem
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?
?
?
Multicomponent Phase Equilibria
Criterion for Chemical Equilibria:
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The Chemical Potential -The Criteria for Chemical Equilibrium
(See slide 24)
Multicomponent Phase Equilibria
Criterion for Chemical Equilibria:
Criterion for Thermal Equilibrium and Mechanical Equilibrium:
Chemical Potential
(Synonymous of Partial Molar Gibbs Energy)
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The Chemical Potential -The Criteria for Chemical Equilibrium
(See slide 24)
Closed System
For this to be true,
Similar equation applies to m species in the
system, thus, there are m different equations
like this
This is analogous to the pure species relation presented earlier:
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The Chemical Potential -The Criteria for Chemical Equilibrium
The Chemical Potential is an abstract concept that cannot be measured.
Driving Force
Chemical Potential
Temperature
Pressure
Identical
Relations
Mass Transport
Energy Transport
Momentum Transport
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The Chemical Potential -The Criteria for Chemical Equilibrium
The Chemical Potential is an abstract concept that cannot be measured.
Driving Force
Chemical Potential
Temperature
Pressure
Identical
Relations
Mass Transport
Energy Transport
Momentum Transport
T high

Energy
Transfer
T low


T final equal for both
systems

i
high

Mass
Transfer
of species i,
Diffusion

i
low

Mixture

mixture
=
i

=
i

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The Chemical Potential -The Criteria for Chemical Equilibrium
Temperature and Pressure Dependence of
i
Valid for two
phases
Vapor-Liquid
Equilibrium
Liquid-Ideal
Gas Mixture
Equilibrium
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Exercise
Tired of studying Thermo, you come up with the idea of becoming
rich by manufacturing diamond from graphite.
To do this process at 25
o
C requires increasing the pressure until
graphite and diamond are in equilibrium.
The following data are available at 25
o
C:
g(25
o
C, 1 atm) = g
diamond
g
graphite
= 2866 [J/mol]
density
diamond
= 3.51 [g/cm
3
]
density
graphite
= 2.26 [g/cm
3
]
Estimate the pressure at which these two forms of carbon are in
equilibrium at 25
o
C.
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Exercise
You wish to know the melting temperature of aluminum at 100 bar.
You find that at atmospheric pressure, Al melts at 933.45 K and the
enthalpy of fusion is:
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h
fusion
= 10711 [J/mol]
Heat Capacity data are given by:
Cp
l
=31.748 [J/(mol K)], Cp
s
=20.068 +0.0138T [J/(mol K)]
Take the density of solid aluminum to be 2700 [kg/m
3
] and liquid to
be 2300 [kg/m
3
].
At what temperature does Aluminum melt at 100 bar?
Consider a system at temperature T and pressure P with c species present in p phases. How
many measurable properties need to be determined (e.g., T, P, and x
i
) to constrain the state
of the entire system?
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Application: The Phase Rule for Nonreacting Systems
Consider a system at temperature T and pressure P with c species present in p phases. How
many measurable properties need to be determined (e.g., T, P, and x
i
) to constrain the state
of the entire system?
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Application: The Phase Rule for Nonreacting Systems
.
.
.
Consider a system at temperature T and pressure P with c species present in p phases. How
many measurable properties need to be determined (e.g., T, P, and x
i
) to constrain the state
of the entire system?
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Measurable properties (degrees of freedom) to
be determined:
This yields one constraint for each phase; the
total degrees of freedom is:
Application: The Phase Rule for Nonreacting Systems
.
.
.
Consider a system at temperature T and pressure P with c species present in p phases. How
many measurable properties need to be determined (e.g., T, P, and x
i
) to constrain the state
of the entire system?
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We are assuming equilibrium among all components; therefore, each component has (p-1)
restrictions due to the equality of chemical potentials.
For c components, the number of additional constraints is c(p-1)
Thus, = p (c - 1) + 2 c (p - 1) = c p + 2 Gibbs Phase Rule
Measurable properties (degrees of freedom) to
be determined:
This yields one constraint for each phase; the
total degrees of freedom is:
Application: The Phase Rule for Nonreacting Systems
.
.
.
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Homework #1 due on January 17, 2013
*Follow Dropbox Instructions *
Problems from Engineering and Chemical
Thermodynamics, Milo Koretsky

Chapter 6
Problems
6.9
6.12
6.14
6.20
6.22
6.39
I will make available through Moodle:
1. Chapter #6 of Engineering and Chemical Thermodynamics, Milo
Koretsky
2. Appendices A-C

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