THERMODYNAMICS II

Thermodynamic Relations

From:

Koretsky, Milo. (2012). Engineering and Chemical Thermodynamics. Wiley.

Notes. Dr. Diego Fernando Mendoza.

Prausnitz J., Poling B., O’Connell J. (2001) The properties of Gases and Liquids, Fifth
Edition. MgGraw- Hill.

Moran, M. J., Shapiro, H. N., Boettner, D. D., & Bailey, M. B. (2010). Fundamentals of
engineering thermodynamics. John Wiley & Sons

ADRIANA PATRICIA VILLEGAS Q.

Ph. D. Chemical Engineering

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Koretsky (2012) Hypothetical Paths

The first step in manufacturing isobutene from isomerization of n-butane is to compress the
feed stream of n-butane. It is fed into the compressor at 9.47 bar and 80ºC and optimally exits
at 18.9 bar and 120ºC, so that it can be fed into the isomerization reactor. The work supplied
to the compressor is 2100J/mol. Calculate the heat that needs to be supplied into the unit per
mole of n-butane That passes through.

Ws

Compressor

EoS: Redlich–Kwong 2
 Hypothetical Paths

Redlich–Kwong

Solving

3
Koretsky (2012)
Koretsky (2012) Hypothetical Paths
The first step in manufacturing isobutene from isomerization of n-butane is to compress the
feed stream of n-butane. It is fed into the compressor at 9.47 bar and 80ºC and optimally exits
at 18.9 bar and 120ºC, so that it can be fed into the isomerization reactor. The work supplied
to the compressor is 2100J/mol. Calculate the heat that needs to be supplied into the unit per
mole of n-butane That passes through.
Ws

Compressor

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 Hypothetical Paths
1. Solution with T and v as independent properties (black)

From Fundamental properties

Maxwell relations

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Koretsky (2012)
 Hypothetical Paths
1. Solution with T and v as independent properties (black)

Redlich–Kwong

Koretsky (2012) 6
 Hypothetical Paths Koretsky (2012)
1. Solution with T and v as independent properties (black)

Redlich–Kwong

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 Hypothetical Paths
1. Solution with T and v as independent properties (black)

Simplifying

Integrating

Koretsky (2012)

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 Hypothetical Paths
1. Solution with T and v as independent properties (black)

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Koretsky (2012)
 Hypothetical Paths
2. Solution with T and P as independent properties (black)

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Koretsky (2012)
 Hypothetical Paths Koretsky (2012)
1. Solution with T and P as independent properties (black)

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 Hypothetical Paths
NOTE 1

Koretsky (2012) 12
 Hypothetical Paths
NOTE 1

Koretsky (2012) 13
 Hypothetical Paths
NOTE 1

vo

14
Koretsky (2012)
 Hypothetical Paths Koretsky (2012)
NOTE 2
Other possibility to calculate the enthalpy change is using the internal energy change.

Redlich–Kwong

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 Hypothetical Paths
NOTE 3. Remember that you can use the general form of CEoS for solving
problems associated to hypothetical paths.

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 Hypothetical Paths
NOTE 3. Remember that you can use the general form of CEoS for solving
problems associated to hypothetical paths.

In this order of ideas, the derivatives of interest are:

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 Hypothetical Paths
NOTE 3. 1. Solution with T and v as independent properties (Red)

It is recommendable to use PR to calculate the

volume:

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 Hypothetical Paths
NOTE 3. 1. Solution with T and v as independent properties (Red)

Suggested Path for Enthalpy:

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 Hypothetical Paths
NOTE 3. 1. Solution with T and v as independent properties (Red)

Suggested Path for Entropy:

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 Hypothetical Paths
NOTE 3. 2. Solution with T and P as independent properties (Red)

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 Hypothetical Paths
NOTE 3. 2. Solution with T and P as independent properties (Red)

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 Hypothetical Paths
NOTE 3. 2. Solution with T and P as independent properties (Red)

Suggested Path for Enthalpy:

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 Hypothetical Paths
NOTE 3. 2. Solution with T and P as independent properties (Red)

Suggested Path for Entropy:

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 Hypothetical Paths
NOTE 4.

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 Hypothetical Paths
NOTE 4.

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 Hypothetical Paths
NOTE 4.

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 Hypothetical Paths

Phase change: Δu, Δ h, Δ s

α and β and can represent any

phase: solid, liquid, or vapor. We
may be interested in any of the
following: vapor–liquid, liquid–
liquid, liquid–solid, gas–solid,

Koretsky. (2012). 28
 Hypothetical Paths Koretsky (2012)

Phase change: Δu, Δ h, Δ s

Koretsky. (2012).

The criterion for chemical equilibrium is when the Gibbs energy is at the
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minimum
 Hypothetical Paths

Phase change: Δu, Δ h, Δ s

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Koretsky. (2012).
 Hypothetical Paths

Phase change: (Wagner Correlation)

Reduced Vapor Pressure Reduced Temperature

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Prausnitz, 2001
 Hypothetical Paths Prausnitz, 2001

Phase change: (Ambrose-walton)

This set of equations was fit to the vapor pressure behavior of the n-alkanes. The quantity, ƒ(2), is
important only for fluids with large acentric factors and at low reduced temperatures 32
 Hypothetical Paths
Phase change:
Riedel Method

is the enthalpy of vaporization at the normal boiling point, and R

Is 8.314J/molK and Pc is expressed in [bar].

Chen Method

Prausnitz, 2001

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 Hypothetical Paths Prausnitz, 2001
(Wagner Correlation)

A common choice for n is 0.375 or 0.38

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 Hypothetical Paths Dahm, 2001
Examples:
Five moles of gas are confined in a piston-cylinder device. At the beginning of the process, the gas has T = 300 K and
V = 100 L. If the gas is compressed isothermally to a final volume of 15 L, how much work is required, and how much
heat is added or removed? Assume the heat capacity is constant at Cv=30 J/mol K and that the gas is modeled by the
van der Waals equation of state.

Energy Balance

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 Hypothetical Paths Dahm, 2001
Examples:
Energy Balance

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 Hypothetical Paths Smith vannes, 2001
Examples:

For an industrial process, is required 1-buteno at 293.15ºK. Assume a reference state of saturated liquid a 0ºC, in this
point, h=0 and s=0. Using this information, indicate a isobaric thermodynamic path to reach the final state and
determine the enthalpy change in each process.

Tc= 420.0 K Pc= 40.43 bar ω=0.191

Tb=266.9 K (normal boiling point)

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 Psat 38
(293.15)
Psat
(273.15)

293.15K 3

273.15K Present the

1 process
2
In P-v and T-v
coordinates

Black

vf vg v∞

Solution Slide 7-9

Redlich–Kwong

or

Solution Slides 18 and

19. PR (Please check
the limits of integration)
 Psat
(293.15)
Psat
(273.15)

293.15K 3
Red
check
273.15K Slide 14
1 2
Check ideal gas

vf vg va v∞

Solution
Slide
18 and 19

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 Psat 40
(293.15)
Psat
(273.15)

293.15K 3

273.15K
1 2

Explain the process in

vf vg v∞ Production plants