Thermodynamic Property

Relations
Gibbs & Helmoltz Functions
Gibbs Function and Helmoltz Function
• 1st Gibbs equation is: du = Tds – Pdv … (1)
• Also enthalpy is defined as: h = u + pv
• The enthalpy h can be differentiated to give: 
• dh = du + pdv + vdP … (2)
•  Combining (1) & (2):
• dh = Tds + vdP
•  The coefficients T and v are partial derivative of
h(s,P) such that:  h 
  T and
 h 
  v
 s  P  P  s
• Since v > 0, an isentropic increase in pressure will result in an
increase in enthalpy.
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Gibbs Function and Helmoltz Function
• We introduce Helmholtz function: a = u – Ts
•  Combine Gibbs equation with the differential of a,
•  da = (du – Tds – sdT) = (– Pdv – sdT)
•  The coefficient –P and –s are the partial derivatives
of a(v,T), therefore:  a   a 
   P and    s
 v T  T  v
• Similarly, using the Gibbs function: g = h – Ts
•  dg = (dh – Tds – sdT) = (vdP – sdT)
•  Consequently,  g 
   v and
 g 
   s
 P T  T  P

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Gibbs Function and Helmoltz Function
 Consider: da = (– Pdv – sdT) or – da = (Pdv + sdT)
 The decrease in Helmholtz function of a system sets
an upper limit to the work done in any process
between two equilibrium states at the same
temperature during which the system exchanges
heat only with a single reservoir at this temperature.
 Since the decrease in the Helmholtz potential
represents the potential to do work by the system, it
is also a thermodynamic potential.

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Gibbs Function and Helmoltz Function
 Now consider: dg = (vdP – sdT)
 For isothermal process: dg = vdP or g1 – g2 = –∫ vdP
 Thus decrease in Gibbs function equals the amount of work
done by a steady-flow system in which ke = pe = 0.
 If the system exchanges heat only with the surroundings at T0,
The max. work out put is:
 wmax = h1 – h2 + qmax = h1 – h2 + T0(s2 – s1) =
 wmax = h1 – T0 s1 – (h2 – T0 s2) = g1 – g2
 Thus decrease in Gibbs function represents the maximum
work is done when the process is isothermal as well as
isobaric.
 Gibbs function is also called Chemical Potential.
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IMPORTANT REMINDER!
For ready reference you MUST have the text
book with you during my lecture in the class!

Thermodynamics: An Engineering Approach (7th Ed.)

by
Yunus A. Cengel, Michael A. Boles
McGraw-Hill
REFERENCE BOOK:
Thermodynamics: An Engineering Approach (7th Ed.)
Yunus A. Cengel, Michael A. Boles
McGraw-Hill

Thermodynamic Property
Relations
The Maxwell Relations
Art: 12-2
Page 663 (YC)
 The Maxwell Relations
• The Maxwell Relations are equations that relate the
partial derivatives of properties P, v, T, and s of a
simple compressible system to each other.
• They are obtained from the two famous Tds
equations, Helmholtz function (a) and the Gibbs
function (g) defined as:

and

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 The Maxwell Relations
• Differentiating a and g we get:

• Using the Tds equations the above two are reduced to

the form:

• Hence we obtain the following four equations:

and

• Note that u, h, a, and g are all properties and thus have

exact differentials.
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 The Maxwell Relations
• One may note that the four relations are of the form:
where
• Taking the partial derivative of M with respect to y
and of N with respect to x yields:

• The two differentials are identical, such that:

… (12–5)
• This relation forms the basis for development of the
Maxwell relations

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 The Maxwell Relations
• From Gibbs equations we obtain the following four
Maxwell Relations:
• 1. from du = Tds – Pdv … (12–16)

• 2. from dh = Tds +vdP … (12–17)

• 3. from da = – sdT – Pdv … (12–18)

• 4. from dg = – sdT + vdP … (12–19)

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 The Maxwell Relations
• Entropy change in a system cant not be measured
directly.
• The Maxwell Relations are very useful in this regard
as these provide a means of determining the change
in entropy by simply measuring changes in properties
P, v, and T.
• For non-simple systems those involve electrical,
magnetic, and other effects other similar relations
can easily be obtained.

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REFERENCE BOOK:
Thermodynamics: An Engineering Approach (7th Ed.)
Yunus A. Cengel, Michael A. Boles
McGraw-Hill

Thermodynamic Property
Relations
The Clapeyron Equation
Art: 12-3
Page 664 (YC)
 The Clapeyron Equation
• Clapeyron equation enables us to determine the
enthalpy change associated with a phase change
(such as the enthalpy of vaporization hfg) from a
knowledge of P, v, and T data alone.
• These are obtained using the Maxwell relations.
• Consider the third Maxwell relation:
… (12–18)

• Since during a phase-change process, Psat = f (Tsat),

partial derivative can be expressed as a total
derivative .

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 The Clapeyron Equation
• Note that represents the slope of the saturation
curve on a P-T diagram at a specified saturation state.
• This slope is independent of
the specific volume
• Thus it can be treated as a
constant during the
integration between two
saturation states at the
same temperature.

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 The Clapeyron Equation
• For an isothermal liquid–vapor phase-change process,
for example, the integration yields:
or
… (12–20) … (12–21)

• Since the phase-change process is also isobaric:

• Or

• Thus we obtain the Clapeyron equation:

Eq. 12–22
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 The Clapeyron Equation
• Claperyon equation enables us to determine the
enthalpy of vaporization hfg at a given temperature
by simply measuring:
– Slope of the saturation curve on a P-T diagram and
– The specific volume change vfg at the given temperature
• The Clapeyron equation is applicable to any phase-
change process that occurs at constant temperature
and pressure.
• It can be expressed in a general form as:
Eq. 12–23
 Here the subscripts 1 and 2 indicate the two phases
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 The Clapeyron  Clausius Equation
• The Clapeyron equation can be simplified for liquid–
vapor and solid–vapor phase changes by utilizing the
following approximations:
– At low pressures vg >> vf , and thus vfg  vg.
– By treating the vapor as an ideal gas, we have
vg = RT/P.
• Substituting these approximations into Eq. 12–22, we
get:
or

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 The Clapeyron  Clausius Equation
• For small temperature intervals hfg = hfg)avg = constant
so the integration of equation yields:

Eq. 12–24

• This equation is called the Clapeyron – Clausius

equation, and it can be used to determine the
variation of saturation pressure with temperature.
• It can also be used in the solid–vapor region by
replacing hfg by hig (the enthalpy of sublimation) of the
substance.
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REFERENCE BOOK:
Thermodynamics: An Engineering Approach (7th Ed.)
Yunus A. Cengel, Michael A. Boles
McGraw-Hill

General Relations

For du, dh and ds

Art: 12-4
Page 667 (YC)
 Basis for the General Relations
• Using Maxwell’s relations, we develop general
relations for changes in:
– internal energy,
– enthalpy, and
– entropy
• In terms of:
– pressure,
– specific volume,
– temperature, and
– specific heats alone.

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 Relation for Internal Energy Changes
• We choose the internal energy to be a function of T
and v; i.e. u = u(T, v)
• Take its total differential:
• Using the definition of cv: … (12–25)

• Now choosing entropy to be a function of T and v;

i.e. s = s(T, v) and taking its total differential yields:

… (12–26)

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 Relation for Internal Energy Changes
• Substitute eqn (12-25)
into the 1st Gibbs equation i.e. du = Tds  Pdv gives:
… (12–27)

• Equating the coefficients of dT and dv in Eqs. 12–25

and 12–27 gives:

… (12–28)

• Using the third Maxwell relation, we get:

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 Relation for Internal Energy Changes
• Substituting this into Eq. 12–25, we obtain:
… (12–29)

• Hence for a process between states (1) and (2) the

change in the internal energy may be obtained from:

… (12–30)

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 Relation for Enthalpy Changes
• For enthalpy changes we choose the enthalpy to be a
function of T and P, i.e. 2nd Gibbs Equation:
• dh = Tds + vdP
• Take its total differential:
• Using definition of cp: … (12–31)

• Now choose s = s(T, P) and take its total differential:

… (12–32)

• Substituting into dh = Tds + vdP gives:

… (12–32)
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 Relation for Enthalpy Changes
• Equating the coefficients of dT and dP in Eqs. 12–31
and 12–33, we get:

… (12–33)

• Using the fourth Maxwell relation results in:

… (12–34)

• Substituting this into Eq. 12–31, we obtain:

… (12–35)
• Between states (1) and (2) the change in enthalpy is:
… (12–36)

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 Relation for Entropy Changes
• For a simple compressible system TWO relations for
entropy change are developed.
• First Relation:
• Consider 12-26, i.e. … (12–26)

• By replacing first partial derivative in of the eqn.

12–26 by eqn. 12–28 i.e. and the second
partial derivative by the third Maxwell relation i.e.
we get: … (12–38)

such that:
… (12–39)

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 Relation for Entropy Changes
• Second Relation:
• Consider eqn 12-32:
• Replacing first partial derivative by eqn. 12–34, and
the second partial derivative by the fourth Maxwell
relation, we get: … (12–40)
• or
… (12–41)

• Either relation can be used to determine the entropy

change depending on the available data

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