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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