CHAPTER 2 Classical Thermodynamics

Mehdi Assareh
Iran University of Science and Technology

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 Introduction
Thermodynamics is originated during the middle of the nineteenth century
 From its Greek root (therme, heat; dynamis, force)
 applied to only a limited class of phenomena (such as heat engines)
 the early workers in thermodynamics were concerned only with systems of one component
 J. Willard Gibbs showed that thermodynamic methods are useful in the study of
multicomponent systems

classical problem of phase equilibrium considered here:

 Heat transfer between any two phases within the heterogeneous system. (driving force is
temperature difference)
 Displacement of a phase boundary. (driving force is temp pressure difference)
 Mass transfer of any component in the system across a phase boundary (chemical potential
difference).

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 Homogeneous Closed Systems
 A homogeneous system is one with uniform properties throughout;
 a property such as density has the same value from point to point, in a macroscopic sense.
 A phase is a homogeneous system.
 a state function whose value in a prescribed state is independent of the previous history of the
system
 A closed system is one that does not exchange matter with its surroundings, although it may
exchange energy.

the surroundings are considered to be two distinct bodies:

 a constant-volume heat bath, also at constant, uniform temperature TB in thermal contact only
with the system;
 and another external body, at constant, uniform pressure PE in "volumetric" contact only with
the system through a movable, thermally insulated piston

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 Homogeneous Closed Systems
equilibrium state
 no tendency to depart spontaneously for changes like heat, work and mass transfer across a phase
boundary.
 In an equilibrium state, the properties are independent of time and of previous history of the system; fu
 they are stable, that is, not subject to "catastrophic“ changes on slight variations of external conditions.
 We distinguish an equilibrium state from a steady state, insisting that in an equilibrium state there are no
net fluxes of the kind under consideration (heat transfer, etc.) across a plane surface placed anywhere in
the system
A change in the equilibrium state of a system is called a process.
 A reversible process is one where the system is maintained in a state of virtual equilibrium throughout the
process;
 a reversible process is sometimes referred to as one connecting a series of equilibrium states.
 Any natural or actual process occurs irreversibly
If the interaction of the system with its surroundings occurs reversibly:

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 Homogeneous Closed Systems
If the interaction between system and surroundings occurs irreversibly:

If we choose to integrate in a reversible path:

 Because U is a state function, this result is independent of the path of

integration
 it is independent of whether the system is maintained in a state of internal
equilibrium
or not during the actual process;
 it requires only that the initial and final states be equilibrium states.

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 Homogeneous Closed Systems
 If the variation dU is constrained to occur at constant S and V,

 at constant S and V, U tends toward a minimum in an actual or irreversible process in

a closed system and remains constant in a reversible process.
 Because an actual process is one tending toward an equilibrium state, an approach to
quilibrium at constant entropy and volume is accompanied by a decrease in internal
energy
 The enthalpy is defined as:
 In the same way for reversible process:
 And for irreversible process:

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 Homogeneous Closed Systems
 With definition of Helmholtz free energy:

 For reversible processes:

 For irreversible processes:

 With definition of Gibs free energy:

 For reversible processes:

 For irreversible processes:

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 Homogeneous Closed Systems

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 Homogeneous Closed Systems

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 Homogeneous Closed Systems

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 Homogeneous Closed Systems

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 Homogeneous Open Systems
 An open system can exchange matter as well as energy with its surroundings

 The total differential is then:

 Thermal potential is temperature, mechanical potential is pressure

 Chemical potential intensive quantity and depends on temperature, pressure, and composition of the
system.

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 Homogeneous Open Systems
 Other fundamental relations for open systems:

 This means that chemical potential can be defined in other ways (chemical
potential is only partial molar Gibbs free energy):

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 Homogeneous Open Systems
 the criterion for equilibrium in a closed system is that U is a minimum, and that any variation in U at
constant total entropy and total volume vanishes

 An expression for the total differential dU can be written by summing over all the phases:

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 Homogeneous Open Systems
 S, V, and total moles are constant with this
assumption we can eliminate

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 Homogeneous Open Systems

Are truly independent

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Equilibrium in a Heterogeneous Closed System
 A heterogeneous, closed system is made up of two or more phases with
each phase considered as an open system within the overall closed
system.

 the heterogeneous system is in a state of internal equilibrium with

respect to the three processes of heat transfer, boundary displacement,
and mass transfer

 thermal and mechanical equilibrium in the system, temperature and

pressure must be uniform throughout the entire heterogeneous mass.

 If μi is the intensive potential governing mass transfer, we expect that μi

must also have a uniform value throughout the whole heterogeneous
system at equilibrium with respect to this process.

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The Gibbs-Duhem Equation
 Pressure, temperature and chemical potentials are not
independent
 Assume fundamental relation of and open homogeneous
system:

 Integrate from zero mass (S,V,n1,n2, …=0) to current mass:

 Take a total differential:

 This means:

This is a fundamental relation, mostly used in consistency check

of activity coefficients as it is shown later in this course

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Phase rule
 If the heterogeneous system is not in a state of internal equilibrium,
but each phase is, the number of independent variables is

 if we stipulate that the entire system is in a state of internal

equilibrium

 This means that the degree of freedom is:

 F specifies the minimum number of independent intensive state

variable to determine all other intensive state variables

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Chemical Potentials
 phase-equilibrium thermodynamics is to describe quantitatively the distribution at
equilibrium of every component among all the phases present.
 Gibbs obtained the thermodynamic solution to the phase-equilibrium problem
many years ago when he introduced the abstract concept chemical potential.
 goal is to relate the abstract chemical potential to physically measurable quantity
like pressure, temperature and composition
 We can not compute directly the absolute value of chemical potential but we can
calculate its change as a result of change in the independent variables
 For a pure substance i,

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Fugacity and Activity
 chemical potential does not have an immediate equivalent in the physical world
 To express it in terms of some auxiliary function that might be more easily
identified with physical reality (fugacity)
 Lewis first considered the chemical potential for a pure, ideal gas and then
generalized to all system
 Substituting the ideal-gas equation:

 integrating at constant temperature:

 it simply relates a mathematical abstraction (chemical potential) to a common,

21 intensive property of the real world
Fugacity and Activity
 Lewis defined a function f, called fugacity,' by writing for an isothermal change for any
component in any system, solid, liquid, or gas, pure or mixed, ideal or not:

 For a pure, ideal gas, the fugacity is equal to the pressure, and for a component i
 in a mixture of ideal gases, it is equal to its partial pressure yiP.
 Because all systems, pure or mixed, approach ideal-gas behavior at very low pressures,
the definition of fugacity is completed by the limit
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Fugacity and Activity
 Lewis called the ratio f/f° the activity, designated by symbol a.
 The activity of a substance gives an indication of how "active" a substance is relative
to its standard state because it provides a measure of the difference between the
substance's chemical potential at the state of interest and that at its standard state.
 the temperature of the standard state must be the same as that of the state of
interest.
 The compositions and pressures of the two states, however, need not be (and indeed
usually are not) the same.
 Fugacity is a "corrected pressure“ which is more sensible than chemical potential

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Fugacity and Activity
 The fugacity provides a convenient transformation of the fundamental equation of
phase equilibrium

 Substitute the above relations in the equilibrium relation:

 suppose that the standard states for the two phases are at the same temperature but
not at the same pressure and composition. Meaning that:

 Therefore:
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A Simple Application: Raoult's Law
 the equilibrium distribution of a component in a binary system between a liquid
phase and a vapor phase.
 Behavior can be closely approximated by the assumption of several types of ideal
behavior
 For component 1, the equilibrium equation says

25  These assumptions are valid only ideal gas and ideal solution
A Simple Application: Raoult's Law

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