Week 13.

Thermodynamic Property
Relations I

GENESYS Laboratory
 Objectives
1. Develop fundamental relations between commonly encountered
thermodynamic properties and express the properties that cannot be
measured directly in terms of easily measurable properties
2. Develop the Maxwell relations, which form the basis for many
thermodynamic relations
3. Develop the Clapeyron equation and determine the enthalpy of
vaporization from P,v, and T measurements alone
4. Develop general relations for Cv, Cp, du, dh, and ds that are valid for all
pure substances
5. Discuss the Joule-Thomson coefficient
6. Develop a method of evaluating the ∆h, ∆u, and ∆s of real gases through
the use of generalized enthalpy and entropy departure charts

GENESYS Laboratory
 Partial Differentials
• The variation of z(x, y) with x when y is held constant is called the partial
derivative of z with respect to x, and it is expressed as

 z   z  z ( x  x, y )  z ( x, y )

  x0   x0
lim  lim
 x  y  x  y x

• The symbol  represents differential changes, just like the

symbol d.
• They differ in that the symbol d represents the total
differential change of a function and reflects the influence Geometric representation of
partial derivative (z/x)y.
of all variables, whereas  represents the partial
differential change due to the variation of a single
variable.

• The changes indicated by d and  are identical for independent variables,

but not for dependent variables.

 x  y  dx  z  y  dz
GENESYS Laboratory
 Partial Differentials
• To obtain a relation for the total differential change in z(x,y) for simultaneous
changes in x and y, consider a small portion of the surface z(x,y) shown in Figure
• The dependent variable z changes by z , which can be expressed as
z  z ( x  x, y  y )  z ( x, y )
Adding and substracting z ( x, y  y ), we get
z ( x  x, y  y )  z ( x, y  y ) z ( x, y  y )  z ( x, y )
z  x  y
x y
using the definitions of partial derivatives,
the fundamental relation for the total differential of
a dependent variable in terms of its partial derivatives
with respect to the independent variables is
 z   z 
dz    x    y
 x  y  y  x
Geometric representation of total
derivative dz for a function z(x, y)
GENESYS Laboratory
 Partial Differentials Relations

The order of differentiation is immaterial for

properties since they are continuous point
functions and have exact differentials. Thus,

Demonstration of the reciproci

ty relation for the function z +
2xy  3y2z = 0.

Reciprocity relation

Cyclic relation
GENESYS Laboratory
Ex 3) Verification of Cyclic and Reciprocity Relations
Using the ideal-gas equation of state, verify (a) the cyclic relation, and
(b) the reciprocity relation at constant P.

GENESYS Laboratory
 The Maxwell Relations
• The equations that relate the partial derivatives of properties P, v, T, and s of a
simple compressible system to each
Helmholtz function

Gibbs function

Maxwell relations are extremely valua

ble in thermodynamics because they p
rovide a means of determining the cha
nge in entropy, which cannot be meas
ured directly, by simply measuring the
changes in properties P, v, and T.
These Maxwell relations are limited to
simple compressible systems.
Maxwell relations
GENESYS Laboratory
The Maxwell Relations

GENESYS Laboratory
Ex 4) Verification of the Maxwell Relations
Verify the validity of the last Maxwell relation for steam at 250oC and 300 kPa.

GENESYS Laboratory
 The Clapeyron Equation
The Clapeyron equation enables us
to determine the enthalpy of vapor
ization hfg at a given temperature
by simply measuring the slope of
the saturation curve on a P-T
diagram and the specific volume of
saturated liquid and saturated
vapor at the given temperature.

General form of the Clapeyron

equation when the subscripts 1
and 2 indicate the two phases.

GENESYS Laboratory
Ex 5) Evaluating the hfg of a Substance from the P-v-T Data
Using the Clapeyron equation, estimate the value of the enthalpy of vaporization of
refrigerant-134a at 20oC, and compare it with the tabulated value.

GENESYS Laboratory
 The Clapeyron Equation
• The Clapeyron equation can be simplified for liquid–vapor and solid–vapor phase
changes by utilizing some approximations.
At low pressures

Treating vapor
as an ideal gas The Clapeyron–Clausius
Substituting these equations into the equation can be used to
Clapeyron equation 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.
Integrating between two saturation states

Clapeyron–Clausius equation
GENESYS Laboratory
General Relations For du, dh, ds, Cv, And Cp
• The state postulate established that the state of a simple compressible system is
completely specified by two independent, intensive properties.
• Therefore, we should be able to calculate all the properties of a system such as
internal energy, enthalpy, and entropy at any state once two independent,
intensive properties are available.
• The calculation of these properties from measurable ones depends on the
availability of simple and accurate relations between the two groups.
• General relations could be developed for changes in internal energy, enthalpy, and
entropy in terms of pressure, specific volume, temperature, and specific heats
alone.
• The relations developed will enable us to determine the changes in these
properties.
• The property values at specified states can be determined only after the selection
of a reference state, the choice of which is quite arbitrary.

GENESYS Laboratory
Internal Energy Changes

GENESYS Laboratory
Internal Energy Changes

GENESYS Laboratory
Enthalpy Changes

GENESYS Laboratory
Enthalpy Changes

GENESYS Laboratory
 Entropy Changes

The first relation is

where
and

GENESYS Laboratory
 Entropy Changes

The second relation is

and

GENESYS Laboratory
Specific Heats cv and cp

GENESYS Laboratory
Specific Heats cv and cp

GENESYS Laboratory
Specific Heats cv and cp

Mayer
relation GENESYS Laboratory
Ex 9) The Specific Heat Difference of an Ideal Gas
Show that cp-cv=R for an ideal gas.

GENESYS Laboratory