CHE302 Thermodynamics I

Chapter 6
Thermodynamic Properties of Fluids (I)
유체의 열역학적 성질 (I)

Department of Chemical Engineering, Dong-A University

Prof. Jeong-Hoon Sa

© JHS. All rights reserved. Smith, Van Ness, Abbott, Swihart, Introduction to Chemical Engineering Thermodynamics, ©McGraw-Hill Education
 2
Introduction
Application of thermodynamics to practical problems requires numerical values
of thermodynamic properties.
The necessary enthalpy or other property values must come from experimental
data or by estimation.

In Chapter 6,
§ The 1st & 2nd law → The fundamental property relations

§ Equations allowing calculation of enthalpy, H and entropy, S, from PVT and heat capacities

§ Diagrams and tables used to present property values

§ Generalized correlations estimating property values

© JHS. All rights reserved. Smith, Van Ness, Abbott, Swihart, Introduction to Chemical Engineering Thermodynamics, ©McGraw-Hill Education
 3
Contents

#6-1. Fundamental Property Relations / 기본적인 성질 관계식

#6-2. Residual Properties / 잔류 성질

#6-3. Residual Properties from Virial EoS

/ 비리얼 상태방정식에 의한 잔류 성질

© JHS. All rights reserved. Smith, Van Ness, Abbott, Swihart, Introduction to Chemical Engineering Thermodynamics, ©McGraw-Hill Education
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Fundamental Property Relations
Connecting primitive thermodynamic properties for closed PVT systems
A differential change from one equilibrium state to another for any process in a closed system

Internal Energy, U:

Enthalpy, H ≡ U + PV:

Helmholtz Energy, A ≡ U –
TS:
Gibbs Energy, G ≡ U + PV – TS = H –
TS:
*Equations are not restricted in application to reversible processes as they contain only properties of the system.

→ All other thermodynamic properties may be evaluated from it by simple mathematical operations.
© JHS. All rights reserved. Smith, Van Ness, Abbott, Swihart, Introduction to Chemical Engineering Thermodynamics, ©McGraw-Hill Education
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Exact Differential
For a function F = F(x, y), the total differential of F is

where and

and (Criterion of
exactness)

For example,
if

if

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 6
Maxwell Relations
Thermodynamic properties U, H, A, and G are known to be functions of the canonical variables.
Each of these exact differential expression are as follows;

U = U(S, V) dU = TdS - PdV

H = H(S, P) dH = TdS + VdP

A = A(T, V) dA = -SdT - PdV

G = G(T, P) dG = -SdT + VdP

The restrictions exclude heterogeneous & reacting systems, except for G ~ G(T, P)
e.g., L-V equilibria: U(S, V) depends on the relative amount of phases, but G(T, P) does not.
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 7
H(T, P) & S(T, P)
Enthalpy, H and entropy, S, are often the thermodynamic properties of interest.
T and P are the most common measurable properties of a substance or system.

Const. T
where and

Const. P
where

Maxwell
and relations

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H(T, P) & S(T, P) for Special Cases

#1. Ideal gas state: and

0

&
Hig = Hig(T)

#2. Liquid state: where Volume expansivity

and

&

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Example #6-1
Determine the enthalpy and entropy changes of liquid water for a change of state from
1 bar and 25 °C to 1000 bar and 50 °C. Data for water are given in the following table.

© JHS. All rights reserved. Smith, Van Ness, Abbott, Swihart, Introduction to Chemical Engineering Thermodynamics, ©McGraw-Hill Education
 10
Example #6-1

© JHS. All rights reserved. Smith, Van Ness, Abbott, Swihart, Introduction to Chemical Engineering Thermodynamics, ©McGraw-Hill Education
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U(T, V) & S(T, V)
In some circumstances, T and V may be more convenient independent variables than T and P.
The most useful property relations are then for internal energy, U and entropy, S.

Maxwell
Const. T relations
where and

Const. V
where

Maxwell
and relations

© JHS. All rights reserved. Smith, Van Ness, Abbott, Swihart, Introduction to Chemical Engineering Thermodynamics, ©McGraw-Hill Education
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G as a Generating Function
From the fundamental property relation for G(T, P)

*All terms are dimensionless.

where and

Given G/RT as a function of T and P, V/RT and H/RT follow by simple differentiation.
The remaining properties follow from defining equations.

& &

The Gibbs energy, G or G/RT, when given as a function of its canonical variables T and P, serves
as a generating function for the other thermodynamic properties such as V, H, S, and U through
simple mathematics, and implicitly represents complete property information.

© JHS. All rights reserved. Smith, Van Ness, Abbott, Swihart, Introduction to Chemical Engineering Thermodynamics, ©McGraw-Hill Education
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Residual Properties
The difference between the actual and ideal-gas state properties.
MR: the residual properties
where M: the actual properties at a given T and P
Mig: the ideal-gas state properties at the same T and P

e.g., the residual Gibbs energy:

the residual volume:

(1) Simple calculations for properties in the ideal-gas state

*Reflect real molecular configurations but not the intermolecular interactions.

(1) (2)
(2) Calculations for residual properties (corrections to the ideal-gas-state values)
*Account for the effect of intermolecular interactions.

© JHS. All rights reserved. Smith, Van Ness, Abbott, Swihart, Introduction to Chemical Engineering Thermodynamics, ©McGraw-Hill Education
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Fundamental Residual Property Relations
Fundamental residual property relations provide a direct link between the GR and experiment.

where &

Under constant T,
Integration

The compressibility factor, Z and its differential can be obtained from PVT data allowing evaluation
of the residual properties HR and SR for use in the calculation of enthalpy and entropy values.
© JHS. All rights reserved. Smith, Van Ness, Abbott, Swihart, Introduction to Chemical Engineering Thermodynamics, ©McGraw-Hill Education
 15
H & S from Residual Properties
The ideal-gas state properties provide the base for calculation of real-gas properties.
Hig & Sig are found by integration from an ideal-gas state at reference conditions T0 & P0
to an ideal-gas state at T and P.

#1. Calculation of enthalpy, H (real-gas)

(ideal-gas state) or
Mean heat capacity
#2. Calculation of entropy, S (real-gas)

(ideal-gas state)
or
*For gases, HR and SR are usually very small.
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 16
Example #6-3
Calculate the enthalpy and entropy of saturated isobutane vapor at 360 K from the following information:
1. Table 6.1 gives compressibility-factor data (values of Z) for isobutane vapor.
2. The vapor pressure of isobutane at 360 K is 15.41 bar.
3. Set H0ig =18,115.0 J/mol and S0ig = 295.976 J/mol·K for the reference state at 300 K and 1 bar.
4. The ideal-gas-state heat capacity of isobutane vapor at temperatures of interest is:

© JHS. All rights reserved. Smith, Van Ness, Abbott, Swihart, Introduction to Chemical Engineering Thermodynamics, ©McGraw-Hill Education
 17
Example #6-3

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Residual Properties from Virial EoS
Analytical evaluation of residual properties through equations of state.

For the two-term virial EoS that is “volume explicit”

where Virial equation of state

Evaluation of HR and SR is straightforward for given values of T and P, provided one has sufficient
information to evaluate B and dB/dT.

© JHS. All rights reserved. Smith, Van Ness, Abbott, Swihart, Introduction to Chemical Engineering Thermodynamics, ©McGraw-Hill Education
 19
Summary

Fundamental Property Relations U, H, A, and G

Maxwell Relations Mathematical relations for exact differentials

Thermodynamic Functions H(T, P), S(T, P) & U(T, V), S(T, V)

G as a Generating Function G(T, P) → V, H, S, and U

Residual Property MR = M – Mig, calculating real-gas H and S

Residual Properties from Virial EoS B & dB/dT → GR, HR, and SR
(Analytical evaluation)
© JHS. All rights reserved. Smith, Van Ness, Abbott, Swihart, Introduction to Chemical Engineering Thermodynamics, ©McGraw-Hill Education
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Questions

Q1. When two phases are under equilibrium (e.g., L-V equilibria), all
thermodynamic properties depend on the relative amounts of phases.

Q2. When G(T, P) is known, V, H, S, and U are readily obtained.

Q3. If gases in the system are at ideal-gas state, residual properties are zero.

© JHS. All rights reserved. Smith, Van Ness, Abbott, Swihart, Introduction to Chemical Engineering Thermodynamics, ©McGraw-Hill Education
 CHE302 Thermodynamics I

Chapter 6
Thermodynamic Properties of Fluids (II)
유체의 열역학적 성질 (II)

Department of Chemical Engineering, Dong-A University

Prof. Jeong-Hoon Sa

© JHS. All rights reserved. Smith, Van Ness, Abbott, Swihart, Introduction to Chemical Engineering Thermodynamics, ©McGraw-Hill Education
 2
Contents

#6-4. Generalized Property Correlations / 일반화된 상관관계식

#6-5. Two-Phase Systems / 2상계

#6-6. Thermodynamic Diagrams / 열역학적 선도

#6-7. Tables of Thermodynamic Properties / 열역학적 성질들의 표

© JHS. All rights reserved. Smith, Van Ness, Abbott, Swihart, Introduction to Chemical Engineering Thermodynamics, ©McGraw-Hill Education
 3
Generalized Property Correlations for Gases
Fortunately, the generalized methods developed for the compressibility factor, Z
are also applicable to residual properties.

With generalized forms

With the correlation for Z: &

The generalized
correlations for HR & SR:
(with acentric factor, 𝜔)

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 4
Lee/Kesler Generalized Correlations
See the Tables D.5-D.12, values of (HR)0/RTc, (HR)1/RTc, (SR)0/R, and (SR)1/R

The Lee/Kesler correlation for (HR)0/RTc as a function of Tr and Pr

© JHS. All rights reserved. Smith, Van Ness, Abbott, Swihart, Introduction to Chemical Engineering Thermodynamics, ©McGraw-Hill Education
 5
Calculations of ∆H and ∆S
For a change from state 1 to state 2,

&

where &

Step #1. “1” (T1, P1) → “1ig” (T1, P1)

Step #2. “1ig” (T1, P1) → “2ig” (T2, P2)

&

Step #3. “2ig” (T2, P2) → “2” (T2, P2)

Computational path for ∆H and ∆S calculations

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Two-Phase Systems
Derivation of the Clapeyron equation
Consider a pure liquid in equilibrium with its vapor and existing in a piston/cylinder
arrangement that undergoes a differential evaporation at T and corresponding Psat.

where G𝛼 and G𝛽 are the molar or specific Gibbs energies of the individual phases.

If the two phases continue to coexist in equilibrium throughout the T & P changes

When a pure species is transferred from 𝛼 to 𝛽 at equilibrium T & P, , and thus

e.g., L-V transition

or
(vaporization)

where

© JHS. All rights reserved. Smith, Van Ness, Abbott, Swihart, Introduction to Chemical Engineering Thermodynamics, ©McGraw-Hill Education
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Example #6-6
The Clapeyron equation for vaporization at low P is often simplified through reasonable
approximations, namely, that the vapor phase is an ideal gas and that the molar volume
of the liquid is negligible compared with the molar volume of the vapor. How do these
assumptions alter the Clapeyron equation?

© JHS. All rights reserved. Smith, Van Ness, Abbott, Swihart, Introduction to Chemical Engineering Thermodynamics, ©McGraw-Hill Education
 8
T Dependence of Psat
A plot of ln Psat vs. 1/T generally yields a line that is nearly straight.

A rough approximation of Psat(T)

from the triple point to the critical point

where A and B are constants for a given species.

Antoine equation
More satisfactory for general use

where A, B and C are available in the Appendix.

© JHS. All rights reserved. Smith, Van Ness, Abbott, Swihart, Introduction to Chemical Engineering Thermodynamics, ©McGraw-Hill Education
 9
Two-Phase Liquid/Vapor Systems
When a system consists of saturated-liquid and saturated-vapor phases coexisting in equilibrium,
the total value of any extensive property is the sum of the total properties of the phases.

where V is the molar volume for a system containing a total number of moles n = nl + nv.

Dividing by n gives
where xl and xv represent the mass fractions of the total system that are liquid and
vapor.
With xl = 1 - xv
e.g., for saturated H2O(l)-H2O(g), we only need either xv or xl to calculate V.
*Vl and Vv are given in the steam tables.

Analogous equations can be written for the other extensive thermodynamic properties.
where M represents V, U, H, S, etc.

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Thermodynamic Diagrams
Graphs showing a set of properties for a particular substance, e.g., T, P, V, H, and S.

2-phase eq. line in PT diagram

→ 2-phase eq. area in PH, TS, & HS diagrams
3-phase eq. point in PT diagram
→ 3-phase eq. line in PH, TS, & HS diagrams
*C: critical point

e.g., The boiler of a steam power plant

Liquid water (L) → Superheated steam (V)

Line 1-2: Heating at constant P to Tsat (L)

Line 2-3: Vaporization at constant T & P (L-V equilibria)
Line 3-4: Superheating at constant P (V)
Simplified PH diagram
© JHS. All rights reserved. Smith, Van Ness, Abbott, Swihart, Introduction to Chemical Engineering Thermodynamics, ©McGraw-Hill Education
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Thermodynamic Diagrams
Graphs showing a set of properties for a particular substance, e.g., T, P, V, H, and S.

2-phase eq. line in PT diagram

→ 2-phase eq. area in PH, TS, & HS diagrams
3-phase eq. point in PT diagram
→ 3-phase eq. line in PH, TS, & HS diagrams
*C: critical point

e.g., The boiler of a steam power plant

Liquid water (L) → Superheated steam (V)

Line 1-2: Heating at constant P to Tsat (L)

Line 2-3: Vaporization at constant T & P (L-V equilibria)
Line 3-4: Superheating at constant P (V)
Simplified TS diagram
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Steam Tables: Saturated Steam

*The enthalpy and entropy are arbitrarily assigned values of “0” for the saturated-liquid state at the triple point.

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 13
Steam Tables: Superheated Steam

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Example #6-9
Superheated steam originally at P1 and T1 expands through a nozzle to an exhaust pressure P2. Assuming
the process is reversible and adiabatic, determine the downstream state of the steam and ∆H for P1 =
1000 kPa, T1 = 250 °C, and P2 = 200 kPa.

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 15
Example #6-9

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Summary

Generalized Property Relations Lee/Kesler correlations → HR & SR

Calculating Real-Gas ∆H and ∆S Practical value of residual properties

Clapeyron Equation Derived from the two-phase equilibrium criteria

Clausius-Clapeyron Equation A special case for an ideal gas & Vv ≫ Vl

Thermodynamic Diagrams PH & TS diagrams

Steam Tables Saturated & superheated steam

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 17
Questions

Q1. Residual properties are used to calculate ∆H and ∆S of real gases.

Q2. Clausius-Clapeyron equation allows to get ∆H for phase transitions from

the two-phase boundaries in the PT diagram.

Q3. Two-phase equilibrium conditions (e.g., S-L, L-V, & S-V) are represented
as a line in the TS diagram.

© JHS. All rights reserved. Smith, Van Ness, Abbott, Swihart, Introduction to Chemical Engineering Thermodynamics, ©McGraw-Hill Education