Single Phase Systems

Dr. Rakesh Kumar Maurya

Associate Professor
Department of Mechanical Engineering
Indian Institute of Technology Ropar
IIT Ropar
Rupnagar, India (140001)
Objective of the chapter
To sort analytical, tabular, and graphic relationships of thermodynamic
properties for future reference in specialized applications.
To introduce the concept of chemical equilibrium and widen the applicability of
the exergy concepts.
To understand the framework of the Fundamental Equation – including the
geometric and mathematical relationships among derived properties (U, S, H,
A, and G)
To describe methods of derivative manipulation that are useful for computing
changes in derived property values using measurable, experimentally
accessible properties.
To introduce the use of Legendre Transformations as a way of alternating the
Fundamental Equation without losing information content

ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar

Simple System
System that is not subjected to the influence of gravitational, electrical, and
magnetic fields and inertial forces.
The system is sufficiently large so that surface (capillarity) effects can be
neglected.
Furthermore, the system is macroscopically homogeneous and isotropic; in
other words, it does not contain internal constraints (e.g., adiabatic,
impermeable, or rigid and immobile partitions; if the system is solid, it is in a
state of uniform hydrostatic compression).
Single-Phase System classify as Simple Systems
Class of systems that are general enough to serve adequately as models in
many engineering circumstances and sufficiently uncomplicated to lend
themselves to concise analytical treatment.

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Samples of Substances in Internal Equilibrium

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EQUILIBRIUM CONDITION

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EQUILIBRIUM CONDITION
relationship between the chemical composition of the simple system and other
properties such as its energy U, volume V, pressure P, and temperature T.
Thermodynamic properties of each mass reservoir are known (e.g.,h0,i and s0,i).
Ruling out the occurrence of any chemical reaction inside the system, mass
conservation principle for each species and, integrating the resulting equations over
the time interval dt,

ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar

Contd..

In conclusion, the energy of a simple system can be affected

independently by changes in its entropy, volume, and chemical
composition.

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 Contd..
We continue to identify the properties of the external system with the subscript 0. This time, however, we
assume that the original system (U,S,V,Ni) ischaracterized by one temperatureT, one pressureP, and one
chemical potential 𝜇i for each of the species that leak out of it through the semipermeable membranes.

Finally, we examine under what conditions the reservoir

parameters match the corresponding parameters of the original
system. Consider the isolated aggregate system indicated

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Contd..

dSΣ is zero if the aggregate system is internally in a state of

unconstrained equilibrium; in this case,

In conclusion, at equilibrium, the temperature, pressure, and n

chemical potentials of an open simple system are exactly the
same as their corresponding environmental values.

a simple system is internally in equilibrium if its T, P, and 𝜇i

values are the same throughout the system.

ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar

THE FUNDAMENTAL RELATION

An important assumption is that the

n+2 reservoirs, T, P, and 𝜇1,…,𝜇n , are large
enough so that their respective intensities (T,
P,𝜇1 ,…,𝜇n ) remain constant throughout the
infinitesimal change of state.

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Energy Representation
fundamental relation in energy representation, or the energetic fundamental equation

The n+2 equations of state of the simple system

The fundamental relation and the n+2 equations of state
(taken together) are equivalent

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Entropy Representation

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Extensive Properties versus Intensive Properties
In the fundamental relation, all the variables that appear in it are extensive properties. If, for example, a
simple system (A) is made up of 𝜆 identical “unit” subsystems in mutual equilibrium, the property X of the
unit subsystem is “extensive”

ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar

Fundamental Equation
In either energy or entropy representation, the fundamental equation serves as
origin for all the relations that exist between properties at equilibrium.
Since only some of these properties and relations can be measured with
relative ease (e.g., pressure, temperature, specific heat at constant pressure,
and coefficient of thermal expansion), the fundamental equation makes the
connection between direct measurements and properties that cannot be
measured directly and must be derived (e.g., internal energy, entropy, enthalpy,
and exergy).
The pivotal role played by the fundamental equation is why the treatment of
simple systems in equilibrium can begin with the postulate that a relation of
type exists.

ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar

THE ENTROPY MAXIMUM POSTULATES
These postulates are, in fact, the most natural guess that
we might make, providing the simplest conceivable
formal solution to the basic problem.

This is the principle of entropy increase or, alternatively,

entropy maximum principle.

What then is the simplest criterion that reasonably can be

imagined for the determination of the final equilibrium state?
From our experience with many physical theories we might
expect that the most economical form for the equilibrium
criterion would be in terms of an extremum.

There exists a function (called the entropy S) of the extensive parameters of any composite
system, defined for all equilibrium states and having the following property: The values assumed
by the extensive parameters in the absence of an internal constraint are those that maximize the
entropy over the manifold of constrained equilibrium states.

ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar

THE ENTROPY MAXIMUM POSTULATES
In the absence of a constraint the system is free to select any one of a number of states, each
of which might also be realized in the presence of a suitable constraint. The entropy of each of
these constrained equilibrium states is definite, and the entropy is largest in some particular
state of the set. In the absence of the constraint this state of maximum entropy is selected by
the system.
The relation that gives the entropy as a function of the extensive parameters is known as a
fundamental relation. It therefore follows that if the fundamental relation of a particular system
is known all conceivable thermodynamic information about the system is ascertainable from it.

ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar

Postulate
The entropy of a composite system is additive over the constituent subsystems. The
entropy is continuous and differentiable and is a monotonically increasing function of the
energy.
The additivity property applied to spatially separate subsystems requires the following property:
The entropy of a simple system is a homogeneous first-order function of the extensive
parameters.
The monotonic property postulated implies that the partial derivative (dS/dU)V,N is a positive
quantity.
The continuity, differentiability, and monotonic property imply that the entropy function can be
inverted with respect to the energy and that the energy is a single-valued\ continuous, and
differentiate function of S, V N....Nr.

ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar

The Euler Equation

Since T, P, and the 𝜇i ’s are intensive properties

or

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 The Gibbs–Duhem Relation

For a single-phase simple system, the change of any intensive

variable can be expressed as a function of any n +1 other
independent intensive variables.
What distinguishes this relation from the fundamental relation
(4.10) is that all the infinitesimal changes represent changes in
intensive properties. Furthermore, only n+1 of the total ofn+2
intensities can be changed independently of one another.

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The Gibbs–Duhem Relation – For Pure substance n=1

The Euler equation for n=1 reduces to

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LEGENDRE TRANSFORMS

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LEGENDRE TRANSFORMS

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Legendre transformations of the internal energy function

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Maxwells Relation

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Mnemonic Diagrams -Thermodynamic square presented
by Max Born in 1929
Good Physicists Have Studied Under Very Fine Teachers
ME579-Advanced Thermodynamics
The key to constructing Maxwell
relations is to follow around the
square’s sides through three corners,
then follow around its sides again in a
reverse direction ending on the same
side of the square. In this example the
“shared second side” is the S–V side.
Arrows within the thermodynamic
square aid in obtaining the correct signs
in the differential relations and the
Maxwell relation.
Rakesh K Maurya @ IIT Ropar
Other Mnemonic Diagram

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ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar
ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar
Scheme to obtain Maxwell Relations

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Relations Measured during Special Processes
(a) Reversible Heating at Constant Volume

(b) Reversible Heating at Constant Pressure

volumetric coefficient of thermal expansion, or the

volume expansivity

(c) Reversible and Adiabatic Volume Change

isentropic expansion exponent k

(d) Reversible and Isothermal Volume Change

isothermal compressibility

(e) Constant-Enthalpy Expansion

Joule–Thomson coefficient
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Bridgman’s Table
objective was to express all the first partial derivatives of the most frequently
used properties P, T, v, s, u, h, f, and g in terms of the measured P=P(v, T)
surface and three-dimensional slopes (first partial derivatives) that are the
easiest to measure in the laboratory, cP,𝛽,and k.

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ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar
ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar
Jacobian Method

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ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar
PARTIAL MOLAL PROPERTIES

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ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar
ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar
ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar
ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar