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CHEN 310: CHEMICAL ENGINEERING
THERMODYNAMICS
MODULE 2
Prof. S. M. Waziri & Prof. M. S. Olakunle
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THERMODYNAMIC PROPERTIES OF FLUIDS
Learning Outcomes
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At the end of this section, students are expected to be able to:
■ Develop from the first and second laws the fundamental property
relations that underlie the structure of applied thermodynamics for
systems of constant composition.
■ Derive equations that allow calculation of enthalpy and entropy values
from PVT and heat-capacity data.
■ Discuss the types of diagrams and tables used to present property
values for convenient use.
■ Use generalized correlations that provide estimates of property values in
the absence of complete experimental information.
THERMODYNAMIC PROPERTIES OF FLUIDS
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❑ The why of thermodynamic Properties of Fluids
✓ Some thermodynamic properties can be measured directly, but many
others cannot, (Give examples).
✓ It is necessary to develop relations between these two groups so that
the properties that cannot be measured directly can be evaluated.
✓ The derivations are based on the fact that properties are point
functions, and the state of a simple, compressible system is
completely specified by any two independent, intensive properties.
THERMODYNAMIC PROPERTIES OF FLUIDS
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Thermodynamic properties of fluids can be classified into three broad groups:
❑ Reference or fundamental Properties (a.k.a. primary properties)
✓ Used to define the state of the system.
✓ Have absolute values
✓ Examples include T, P, V, S and composition (for solutions).
❑ Energy Properties
✓ All are extensive thermodynamic properties
✓ Are known relative to some reference state
✓ Examples are the internal energy (U), enthalpy (H), the Helmholtz free energy (A), and the
Gibbs free energy (G)
❑ Derived Properties
✓ These are partial derivatives of energy properties or the reference properties.
✓ Examples include specific heat (C), coefficient of expansion (β), and coefficient of
compressibility (κ).
▪ Internal energy and enthalpy were introduced in MEEN 208. In CHEN 310, the Helmholtz work
function and the Gibbs free energy will be defined.
FUNDAMENTAL PROPERTY RELATIONS
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The first law for a closed system of n moles of a substance, can be written for the special case of
a reversible process
For reversible process
Thus
• All of the primitive thermodynamic properties—P, V, T, U, and S—are included in
this equation.
• It is a fundamental property relation connecting these properties for closed PVT
systems
• All other equations relating properties of such systems derive from it.
FUNDAMENTAL PROPERTY RELATIONS
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Additional thermodynamic properties (derived) are defined for convenience
The differentials of the additional properties
Application of these four fundamental property relations is to any
process in a closed PVT system resulting in a differential change from
one equilibrium state to another.
FUNDAMENTAL PROPERTY RELATIONS
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For one mole (n=1) of a homogeneous fluid of constant composition (non reacting single liquid
or gaseous phase systems)
• The choice of which equation to use in a particular application is dictated by convenience.
• The Gibbs energy G is special, because of its unique functional relation to T and P
Molar (or unit mass) property as a function of canonical variables (i.e. a natural or special pair of
independent variables)
A thermodynamic property known as a function of its canonical variables has a unique
characteristic: All other thermodynamic properties can be evaluated from it by simple
mathematical operations.
Transformation Relationships for Systems with Two
Independent Variables
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Consider a function of two independent Important transformation formulae
variables
Total differentials
Exact Differential Expression
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In general, if F = F(x, y), then the total differential of F is defined as:
or
Where
Then
Since the order of differentiation in mixed second derivatives does not affect the result,
then
Exactness criteria: Partial derivatives relationship for
an exact differential expression
Maxwell Relations
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The thermodynamic properties U, H, A, and G are known to be functions of their canonical
variables.
Fundamental
Property
Relations
Maxwell
Relations
Gibb’s Square
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G P H
T S
A U
V
Example
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Derive general equations relating internal energy and entropy to
temperature and volume for homogeneous fluids of constant composition
By definition
Maxwell
relation
Example
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Derive general equations relating enthalpy and entropy to temperature and
pressure for homogeneous fluids of constant composition
By definition
Maxwell
relation
Special Forms
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Heat-capacity Heat-capacity Volume Isothermal
at constant volume at constant pressure expansivity compressibility
Ideal gas state
Liquids
The Gibbs Energy as a Generating Function
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The fundamental property relation for G = G(T, P)
Mathematical identity
Alternative form of Gibbs energy function
Key advantages of the alternative form
• All terms are dimensionless
• The enthalpy rather than the entropy appears on the right side.
The Gibbs Energy as a Generating Function
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In restricted forms
Remaining properties are:
The Gibbs energy, G or G/RT, when known as a function of its canonical variables T and
P, serves as a generating function for the other thermodynamic properties through
simple mathematics, and implicitly represents complete property information.
Residual Properties
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The generic residual property is defined by
where M and Mig are actual and ideal-gas-state properties at the same T and P. They represent
molar values for any extensive thermodynamic property, e.g., V, U, H, S, or G.
Example: Residual Volume
Properties for the ideal-gas state reflect real molecular configurations but presume the absence of
intermolecular interactions. Residual properties account for the effect of such interactions.
Information on ideal-gas-state properties, which depend on intramolecular interactions, is
embedded in the ideal-gas-state heat capacity, which is independent of pressure. Similarly,
information on residual properties, which depend upon intermolecular interactions, is embedded in
PVT data.
Fundamental Residual Property Relations
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The fundamental residual-property relation applies to substances of constant composition
Useful restricted forms
Thus
Enthalpy and Entropy from Residual Properties
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Recall that
Integrating the above equations from an ideal-gas state at reference conditions T0 and P0 to an ideal-
gas state at T and P give
Because
𝑇 𝑖𝑔
𝑖𝑔
𝑇𝑑 𝑃𝐶 𝑇
0
𝐶𝑃 =
𝐻 𝑇 − 𝑇0 𝑇 𝑖𝑔 𝑑𝑇
𝑖𝑔
𝑇 𝑃𝐶 𝑇
𝐶𝑃 = 0
𝑆 𝑇
𝑙𝑛 𝑇
0
TWO-PHASE SYSTEMS
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• Phase transition at constant temperature and pressure is accompanied by abrupt change in
the molar or specific values of most extensive thermodynamic properties (e.g. U, V, H, S)
• The exception is the molar or specific Gibbs energy, which for a pure species does not change
during a phase transition such as melting, vaporization, or sublimation.
• For two phases α and 𝛽 of a pure species coexisting at equilibrium (dG = 0)
where Gα and G𝛽 are the molar or specific Gibbs energies of the individual phases.
• At temperature T and corresponding vapor pressure Psat
TWO-PHASE SYSTEMS
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• Recall that (Constant P)
Integration
Clapeyron equation
Example
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The Clapeyron equation for vaporization at low pressure 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?
If 𝑉 𝑣 ≫ 𝑉 𝑙 then ∆𝑉 𝑙𝑣 = 𝑉 𝑣 −𝑉 𝑙 ≈ 𝑉 𝑣 and by the ideal gas equation 𝑉 𝑣 = RT/𝑃 𝑠𝑎𝑡
Clausius/Clapeyron equation
RESIDUAL PROPERTIES FROM THE VIRIAL EQUATIONS OF STATE
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Consider the two-term volume explicit virial equation of state
Residual Properties
RESIDUAL PROPERTIES FROM THE VIRIAL EQUATIONS OF STATE
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Consider the three-term pressure explicit virial equation of state
Residual Properties
GENERALIZED PROPERTY CORRELATIONS FOR GASES
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Starting from the two-term volume explicit virial equation of state
Pitzer correlation
Abbott equations
Lee/Kesler compressibility-factor correlation, Tables D.1 to D.4 of App. D. (Smith et. al. textbook)
GENERALIZED PROPERTY CORRELATIONS FOR GASES
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Recall that
Residual enthalpy
Residual entropy
Lee/Kesler compressibility-factor correlation, Tables D.5 to D.12 of App. D. (Smith et. al. textbook)
GENERALIZED PROPERTY CORRELATIONS FOR GASES
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The generalized correlations for HR and SR, together with ideal-gas heat capacities, allow
calculation of enthalpy and entropy values of gases at any temperature and pressure.
For a change from state 1 to state 2
Thus
Similarly
Computational path for property changes ΔH and ΔS
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GENERALIZED PROPERTY CORRELATIONS FOR GASES: EXTENSION TO
MIXTURES
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Reasonable and useful approximate results for mixtures can often be obtained with
pseudocritical parameters resulting from simple linear mixing rules according to the definitions:
The values so obtained are the mixture ω and pseudocritical temperature and pressure, Tpc and
Ppc, which replace Tc and Pc to define pseudoreduced parameters:
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Temperature Dependence of the Vapor Pressure of Liquids
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Thermodynamics imposes no model of material behavior, either in general or for particular
species. Therefore, equations presented here are empirical in nature.
Antoine equation
Wagner equation
Lee-Kesler where Trn is the reduced
equation normal boiling point
𝑠𝑎𝑡 is
temperature and 𝑃𝑟𝑛
the reduced vapor
pressure corresponding
to 1 standard atmosphere
(1.01325 bar)
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Two-Phase Liquid/Vapor Systems
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When a system consists of saturated-liquid and saturated-vapor phases coexisting in
equilibrium, the total value of any extensive property of the two-phase system is the sum of
the total properties of the phases.
Consider a property M (e.g. V, U, H, S, etc)
𝑛𝑀 = 𝑛𝑙 𝑀𝑙 + 𝑛𝑣 𝑀𝑣
𝑛𝑙 𝑙 𝑛𝑣 𝑣
𝑀 = 𝑀 + 𝑀 = 𝑥𝑙 𝑀𝑙 + 𝑥𝑣 𝑀𝑣
𝑛 𝑛
But 𝑥𝑙 = 1 − 𝑥𝑣
𝑀 = 1 − 𝑥𝑣 𝑀𝑙 + 𝑥𝑣 𝑀𝑣
𝑀 = 𝑀𝑙 + 𝑥𝑣 ∆𝑀𝑙𝑣 ∆𝑀𝑙𝑣 = 𝑀𝑣 − 𝑀 𝑙
THERMODYNAMIC DIAGRAMS
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❑ Thermodynamic charts and tables are used to present values of these thermodynamic
properties at varying conditions of temperature and pressure.
❑ The charts represent the T,P,V,U,H and S properties of a substance on a single plot.
❑ The most common charts are:
✓ T-S chart
✓ P-H chart
✓ H-S (Mollier diagram)
✓ H-T chart etc.
❑ The Steam table is the thermodynamic property tables for saturated water and
steam.
THERMODYNAMIC DIAGRAMS
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THERMODYNAMIC DIAGRAMS
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PH Diagram for R134a
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TS Diagram for Water
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HS Diagram for Water
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