KMM3531 Chemical Engineering Thermodynamics II

Chapter 6

THERMODYNAMIC PROPERTIES OF FLUIDS

Prof. Dr. Hasan SADIKOĞLU

Yıldız Technical University
Department of Chemical Engineering
Chapter outline
• Develop from the first and second laws the fundamental property
relations which underlie the mathematical 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

• Illustrate and discuss the types of diagrams and tables used to present
property values for convenient use

• Develop generalized correlations that provide estimates of property

values in the absence of complete experimental information
 Property relations for homogeneous phases
• First law for a closed system

• U, S and V are molar values

• As equation only contains properties of system (state function) so it can be
applied to any process in a closed system (not necessarily reversible) and the
change occur between equilibrium states (constant composition)
The Gibbs Energy:
In thermodynamics, the Gibbs free energy is a thermodynamic potential that can
be used to calculate the maximum of reversible work that may be performed by a
thermodynamic system at a constant temperature and pressure

The Helmholtz Energy:

In thermodynamics, the Helmholtz free energy is a thermodynamic potential
that measures the useful work obtainable from a closed thermodynamic system
at a constant temperature and volume.
The Enthalpy:
It is defined as the sum of the system's internal energy and the product of its
pressure and volume.

The Internal Energy:

In thermodynamics, internal energy is the total energy that a thermodynamics
systems contains. It is the energy that is needed to create the system.
The primary thermodynamic properties:
The enthalpy: Energy from
environment during
The Helmholtz energy: heating

The Gibbs energy: Energy from

environment and
change in volume
For one mol of homogeneous fluid of constant composition:

These equations also apply for the

entire mass of any closed system

The criterion of exactness applies for these equations

Some Mathematical Preliminaries
Thermodynamic properties are continuous point functions and have exact
differentials. A property of a single component system may be written as general
mathematical function z = z(x,y). For instance, this function may be the pressure
P = P(T,v). The total differential of z is written as

where

Taking the partial derivative of M with respect to y and of N with respect

to x yields
Since properties are continuous point functions and have exact differentials, the following is true

Example: Assume a function of two variables z=z(x,y)

Thu
s
Now we develop two more important relations for partial derivatives—the reciprocity and the cyclic
relations. Consider the function z = z(x,y) expressed as x = x(y,z). The total differential of x is

Rearranging,

Since y and z are independent of each other, the terms in each bracket must be zero. Thus,
we obtain the reciprocity relation that shows that the inverse of a partial derivative is equal
to its reciprocal.
The second relation is called the cyclic
relation.
Maxwell Equation
• Maxwell equations gives relations which underline the
mathematical structure of thermodynamics

• Serve as the mathematical bases for evaluation thermodynamics

functions from experimental measurement of P, T, V behavior of a
fluid

• The most useful relations are for U, H, S as a function of T, P (or

specific volume)
General Equations for a Homogeneous Fluid at Constant Composition

Application is to any process in a closed PVT system resulting in a differential

change from one equilibrium state to another.
Maxwell’s Equation
∆H and ∆S as functions of T & P

Relations for Thermodynamic

Properties in term of PVT and
Specific heats
• Equations relate the change in S, U, H to
changes in only PVT.
• The right sides of the equations contain
only CP, CV, P, V, T and partial derivatives
involving P, V and T
Problem:
Show that Enthalpy and Entropy equation reduce to the correct equations for ideal gases.
Note : Drive the Entropy and enthalpy equation for ideal gas.

Solution:
The Ideal-Gas State is
Useful forms for liquids or
solids:
Volume Expansivity β Isothermal Compressibility κ
Internal Energy as a Function of P

Internal energy is related to enthalpy

Differentiation yields:

We know that
Example 6.1
Determine the enthalpy and entropy changes of liquid water for a change of state from 1
bar and 25°C to 1000 bar and 50°C. Data for water are given in the following table.
Solution 6.1
For application to the change of state described, Eqs. (6.27) and (6.28) require
integration. Enthalpy and entropy are state functions, and the path of
integration is arbitrary; the path most suited to the given data is shown in Fig.
6.1. Because the data indicate that CP is a weak function of T and that both V
and β change relatively slowly with P, integration with arithmetic means is
satisfactory. The integrated forms of Eqs. (6.27) and (6.28) that result are:
 For P = 1 bar,

For t = 50°C,

Substitution of these numerical values

into the equation for ΔH gives:

Note that the effect of a pressure change of almost 1000 bar on the enthalpy and
entropy of liquid water is less than that of a temperature change of only 25°C.
Problem Illustration
Estimate the change in enthalpy and entropy when liquid ammonia at 270 K is
compressed from its saturation pressure of 381 KPa to 1200 KPa. For saturated
liquid ammonia at 270 K, Vl=1.551x10-3 m3 kg-1, and β=2.095x10-3 K-1.

Solution

At Constant Temperature
 EXAMPLE
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.

SOLUTION The cyclic and reciprocity relations

are to be verified for an ideal gas.

Analysis The ideal-gas equation of state Pv=RT

involves the three variables P, v, and T. Any two
of these can be taken as the independent b) The reciprocity rule for an ideal gas at
variables, with the remaining one being the P=constant can be expressed as
dependent variable.
(a) If we express the cyclic relation for an ideal
gas
Internal Energy and Entropy as Functions of T and V
In some circumstances, temperature and volume may be more convenient
independent variables than temperature and pressure. The most useful property
relations are then for internal energy and entropy. Required here are the
derivatives (∂U/∂T )V, (∂U/∂V)T, (∂S/∂T )V, and (∂S/∂V)T, with which we can write:
Using Maxwell
Relations
These are general equations relating the internal energy and entropy of
homogeneous fluids of constant composition to temperature and volume.

Equation applied to a change of state at

constant volume becomes:

Alternative forms
Example 6.2
Develop the property relations appropriate to the incompressible fluid, a model fluid
for which both β and κ are zero. This is an idealization employed in fluid mechanics.

Solution 6.2
For an incompressible fluid:
 For an incompressible fluid dV=0

Because β = 0, the right side of this equation is zero, provided that the indeterminate
ratio β/κ is finite. This ratio is indeed finite for real fluids, and a contrary
presumption for the model fluid would be irrational. Thus the definition of the
incompressible fluid presumes this ratio is finite, and we conclude for such a fluid
that the heat capacities at constant V and at constant P are identical:
 Gibbs energy G = G (P,T)

Eq 6.10 Thermodynamic property of great potential utility

as it can be directly measured and controlled

Eq 6.37

Eq 6.38

Eq 6.39
G/RT = g (P,T)

The Gibbs energy serves as a generating function for the other thermodynamic properties.
Gibbs energy as generating function

This a dimensionless equation

Given G/RT as a function of T and P, V/RT and H/RT follow by simple

differentiation. The remaining properties follow from defining equations. In
particular,
Residual
properties
Unfortunately, no experimental method for the measurement of numerical values
of G or G/RT is known, and the equations which relate other properties to the
Gibbs energy are of little direct practical use. However, the concept of the Gibbs
energy as a generating function for other thermodynamic properties carries over
to a closely related property for which numerical values are readily obtained.
Residual
properties
• The definition for the generic residual property:

• M and Mig are the actual and ideal-gas properties, respectively at the same T & P
• M is the molar value of any extensive thermodynamic properties, e.g., V, U, H, S, or
G.

• The residual Gibbs energy serves as a generating function for the other residual
properties:
 const T

Eqn 6.39
Eqn 6.46
Eqn 6.49
const T

Eqn 6.3 Eqn 6.48 const T

Z = PV/RT: experimental measurement . Given PVT data or an appropriate equation
of state, we can evaluate HR and SR and hence all other residual properties.
 Any extensive Property M is
given by:
where M, Mig and MR are actual, ideal-gas-state and residual properties at the
same T and P. They represent molar values for any extensive thermodynamic
property, e.g., V, U, H, S, or G.

Sinc
e
Enthalpy and Entropy from Residual Properties
These equations provide a convenient base for real gas calculations
Example
Calculate the enthalpy and entropy of saturated iso-butane vapor at 360 K from the following
information:
1. Table 6.1 gives compressibility-factor data (values of Z) for iso-butane vapor.
2. The vapor pressure of iso-butane at 360 K is 15.41 bar.
3. Set
for the reference state at 300 K and 1 bar. [These values are in accord with the bases
adopted by R. D. Goodwin and W. M. Haynes, Nat. Bur. Stand. (U.S.), Tech. Note 1051, 1982.]
4. The ideal-gas-state heat capacity of iso-butane vapor at temperatures of interest is:
Graphical integration requires plots of and (Z-1)/P vs. P.
clear;clc;R=8.314;T=360;H0IG=18115;S0IG=295.296;
CPIG=@(T) 1.7765+33.037e-3*T;
SCPIG=@(T) (1.7765+33.037e-3*T)./T;
Z=[0.99719 0.99737 0.99753;
0.98830 0.98907 0.98977;
0.96206 0.96483 0.96730;
0.9307 0.9364 0.9413;
0.8982 0.9077 0.9153;
0.8622 0.8759 0.8874;
0.8212 0.8408 0.8569;
0.7731 0.8010 0.8232];
p=[0.1 0.5 2 4 6 8 10 12];
P=[0.1 0.5 2 4 6 8 10 12 14]
PP=[0 0.1 0.5 2 4 6 8 10 12 14 15.4]
for i=1:1:8
ZDT(i)=((((Z(i,2)-Z(i,1))/10)+((Z(i,3)-Z(i,2))/10))/2)/P(i);
ZP(i)=-((Z(i,2)-1)./P(i));
DZDT(i+1)=ZDT(i);
ZOP(i+1)=ZP(i)
end
DZDT(1)=interp1(p,ZDT,0,'linear','extrap');
DZDT(10)=interp1(p,ZDT,14,'linear','extrap')
DZDT(11)=interp1(p,ZDT,15.41,'linear','extrap')
ZOP(1)=interp1(p,ZP,0,'linear','extrap');
ZOP(10)=interp1(p,ZP,14,'linear','extrap');
ZOP(11)=interp1(p,ZP,0,'linear','extrap');
HR=-R*T.^2*trapz(PP,DZDT)
SR=R*(-T*trapz(PP,DZDT)+trapz(PP,ZOP))

H=H0IG+R*integral(CPIG,300,360)+HR
S=S0IG+R*integral(SCPIG,300,360)-R*log(15.41/1)
+SR
 RESIDUAL PROPERTIES FROM THE VIRIAL EQUATIONS OF STATE

The numerical or graphical evaluation of integrals, as in Eqs. of H R and SR, is often

tedious and imprecise. An attractive alternative is analytical evaluation through
equations of state. The procedure depends on whether the equation of state is volume
explicit, i.e., expresses V (or Z) as a function of P at constant T, or pressure explicit, i.e.,
expresses P (or Z) as a function of V (or ρ) at constant T. Equations for HR/RT and SR/RT
are directly applicable only for a volume explicit equation, such as the two-term virial
equation in P

The two-term virial equation of state:

Residual properties by equation of state: an alternative method

• The calculation of residual properties for gases and vapors through use of
the virial equations and cubic equation of state.
• Z-1 = BP/RT Eq 3-38

Eq 6-49

GR/RT = BP/RT Eq 6-54

• If Z = f (P,T):
Eq 6-46 Eq 6-48
Evaluation of residual enthalpies and residual entropies by Eqs. H R and SR, is
straightforward for given values of T and P, provided one has sufficient information to
evaluate B and dB/dT.
Equations obtained for HR and SR are incompatible with pressure-explicit equations of
state and must be transformed such that P is no longer the variable of integration. In
carrying out this transformation, the molar density ρ is a more convenient variable of
integration than V, because ρ goes to zero, rather than to infinity, as P goes to zero.
Thus, the equation PV = ZRT is written in alternative form as

Divide by

where the integral is evaluated at constant T. Note also that ρ → 0 when P → 0.

Applying this for changes with respect to T at constant ρ gives:
 Determine expressions for GR, HR, and SR implied by the three-term virial equation in volume, Eq. (3.38).

We now apply this to the pressure-explicit three-term virial equation:

Application of these equations, useful for gases up to moderate pressures,

requires data for both the second and third virial coefficients.
GENERALIZED PROPERTY CORRELATIONS FOR GASES

Of the two kinds of data needed for evaluation of thermodynamic properties, heat
capacities and PVT data, the latter are most frequently missing. Compressibility
factor are also applicable to residual properties.
Equations HR and SR are given as follows:

Equations HR and SR can be put into generalized form by substitution of the

following relations:
The first integrals on the right sides of these two equations may be evaluated numerically or
graphically for various values of Tr and Pr from the data for Z0 given in Tables D.1 and D.3 of App.
D, and the integrals which follow ω in each equation may be similarly evaluated from the data for
Z1 given in Tables D.2 and D.4.
If the first terms on the right sides of the preceding equations (including the
minus signs) are represented by (HR)0/RTc and (SR)0/R and if the terms which
follow ω, together with the preceding minus signs, are represented by (HR)1/RTc
and (SR)1/R, then:

Calculated values of the quantities (HR)0/RTc, (HR)1/RTc, (SR)0/R, and (SR)1/R as

determined by Lee and Kesler are given as functions of Tr and Pr in Tables D.5
through D.12.
As with the generalized compressibility-factor correlation, the complexity of the
functions (HR)0/RTc, (HR)1/RTc, (SR)0/R, and (SR)1/R precludes their general
representation by simple equations.

However, the generalized second-virial-coefficient correlation forms the basis for

analytical correlations of the residual properties at low pressures
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 given by following Equations:
Thus, in Fig. 6.3, the actual path from state 1 to state 2 (dashed line) is replaced by
a three-step computational path:

Step 1 → 1ig: A hypothetical process that transforms a real gas into an ideal gas at T 1
and P1. The enthalpy and entropy changes for this process are:

Step 1ig → 2ig: Changes in the ideal-gas state from (T1, P1) to (T2,T2 ). For this process,
Step 2ig → 2: Another hypothetical process that transforms the ideal gas back into a real
gas at T2 and P2. Here,

Computational path for property changes

ΔH and ΔS.

Fig. 6.3
Example 6.4
Supercritical CO2 is increasingly used as an environmentally friendly solvent for
cleaning applications, ranging from dry cleaning clothing to degreasing machine parts to
photoresist stripping. A key advantage of CO2 is the ease with which it is separated from
“dirt” and detergents. When its temperature and pressure are reduced below the critical
temperature and vapor pressure respectively, it vaporizes, leaving dissolved substances
behind. For a change in state of CO2 from 70°C and 150 bar to 20°C and 15 bar, estimate
the changes in its molar enthalpy and entropy.

Solution 6.4
We follow the three-step computational path of Fig. 6.3. Step 1 transforms the real fluid
at 70°C and 150 bar into its ideal-gas state at the same conditions. Step 2 changes
conditions in the ideal-gas state from the initial to the final conditions of T and P. Step 3
transforms the fluid from its ideal-gas state to the
real-gas final state at 20°C and 15 bar.
@ T1 =(70+273.15)=343.15 K @ Tr =(20+273.15)=293.15 K
Pr = 150 bar Pr =15 bar
(Real) (Real)

@ T1 =(70+273.15)=343.15 K @ Tr =(20+273.15)=293.15 K
Pr = 150 bar Pr =15 bar
(Ideal) (Ideal)
The residual-property values required for calculating the changes of Steps 1 and 3 depend
on the reduced conditions of the initial and final states. With critical properties from
Table B.1 of App. B:

Tc = 304.2 K; Pc= 73.83 Tr1 = (70+273.15)/304.2=1.128

Pr1 = 150/73.83=2.032
Tr2 = (20+273.15)/304.2=0.964
Pr2 =15/73.83= 0.203

Thus, for Step 1, interpolation in Lee/Kesler tables D.7, D.8, D.11, and D.12 provides the
values:
For Step 2, the enthalpy and entropy changes are calculated by the usual heat-capacity
integrals, with polynomial coefficients from Table C.1. The ideal-gas-state entropy
change caused by the pressure change must also be included.
Sums over the three steps yield overall changes, ΔH = 4734 J⋅mol−1 and ΔS = 28.6
J⋅mol −1 ⋅K −1. The largest contribution here comes from the residual properties of the
initial state, because the reduced pressure is high, and the supercritical fluid is far from
its ideal-gas state. Despite the substantial reduction in temperature, the enthalpy
actually increases in the overall process.

For comparison, the properties given in the NIST fluid-properties database, accessed
through the NIST Chemistry Webbook, are:

H1= 16,776 J ⋅mol−1 S1 = 67.66 J ⋅mol−1 ⋅K −1

H2 = 21,437 J ⋅mol−1 S2 = 95.86 J ⋅mol−1 ⋅K −1

From these values, considered accurate, overall changes are ΔH = 4661 J⋅mol−1 and ΔS
= 28.2 J⋅mol −1⋅K −1. Even though the changes in residual properties make up a
substantial part of the total, the prediction from generalized correlations agrees with
the NIST data to within 2 percent.
Redlich-Kwong equation of state
Residual Properties from the Virial Equation of State

Eq 6.49 Eq 6.54
two-term virial equation

Eq 6.46

Eq 6.55

Eq 6.56
 Three-term virial equation Eq.3.40

Eq. 6.61
Eq. 6.49

Eq. 6.62
Eq. 6.46

Application up to moderate pressure and required data for second and third virial coefficients
 Using the cubic equation of state

• The generic cubic equation

of state:
Eq 3.42 in terms of
density

Eq 6.46 Eq 3.51
Eq 6.48

Textbook – Refer to page 218

EXAMPLE: Find values for the residual enthalpy HR and the residual entropy SR for
n-butane gas at 500 K and 50 bar as given by Redlich/Kwong equation.
Eq. 3.53 Eq. 3.54

Eq. 3.52
Use Table 3.1 for data

Eq. 6.65

Eq.6.67

Eq. 6.68
 Sample Problem
Calculate the Z, HR, and SR by the Redlich/Kwong equation for one of the following and
compare results with values from suitable generalized correlations :
a. Acetylene at 300K and 40 bar.
b. Argon at 175 K and 70 bar.
c. Benzene at 575 K and 30 bar.
d. n-Butane at 500 K and 50 bar.
e. Carbon dioxide at 325 K and 60 bar.
f. Carbon monoxide at 175 K and 60 bar.
g. Carbon tetrachloride at 575 K and 35 bar.
h. Cyclohexane at 650 K and 50 bar.
i. Ethylene at 300 K and 35 bar.
j. Hydrogen sulfide at 400 K and 70 bar.
k. Nitrogen at 150 K and 50 bar.
l. n-Octane at 575 K and 15 bar.
m. Propane at 375 K and 25 bar.
n. Propylene at 475K and 75 bar.
Solution

Redlich-Kwong
equation:

Acetylene
Pc=61.39 bar
Tc=308.3 K

F=@(Z) Z-1.058+(0.29812*(Z-0.058))./((Z)*(Z+0.058))
fsolve(F,.8)=0.695
%Acetlylene
clc;clear;
T=300;P=40;R=8.314;
Tc=308.3;Pc=61.39;w=0.187;
Pr=P/Pc;Tr=T/Tc;
%Using Virial Equation State
B0=0.073-0.422./((Tr).^1.6);
B1=0.139-0.172./((Tr).^4.2);
DB0=0.675./((Tr).^2.6);
DB1=0.722./((Tr).^5.2);
VR=R*Tc./Pc*(B0+w+B1);
HR=R*Tc*Pr*(B0-Tr*DB0+w*(B1-Tr*DB1))
SR=-R*Pr*(DB0+w*DB1)
%Using Redlich-Kwong EOS
OM=0.08664;SAY=0.42748;
b=OM*Pr/Tr;q=SAY/(OM*(Tr.^1.5));
ZZ=@(z) z-1-b+q*b*(z-b)./(z*(z+b));
Z=fzero(ZZ,1);
I=log((Z+b)./Z);
HR2=R*T*((Z-1)+(-0.5-1)*q*I)
SR2=R*(log(Z-b)-0.5*q*I)
 Two-phase systems

The molar or specific volume of a

saturated liquid is very different from the
molar or specific volume of saturated
vapor at the same T and P.

This is true as well for internal energy, enthalpy, and entropy. 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.
 Two-phase systems
• Whenever a phase transition at constant temperature and pressure occurs,
• The molar or specific volume, internal energy, enthalpy, and entropy
changes abruptly. The exception is the molar or specific Gibbs energy,
which for a pure species does not change during a phase transition.
• For two phases α and β of a pure species coexisting at equilibrium:

where Gα and Gβ are the molar or specific Gibbs energies of the individual phases
The latent heat of phase transition

The Clapeyron equation

Ideal gas, and Vl << Vv

The Clausius/Clapeyron equation

 The Clapeyron equation: a vital connection
between the properties of different phases.

Temperature dependence on vapour pressure of liquids

For the entire temperature range from the

triple point to the critical point

The Antoine equation, for a specific

temperature range

The Wagner equation, over a

wide temperature range.
Example
Determine the vapor pressure (in kPa) for liquid n-hexane at 0, 30, 60, and 90°C:
(a) With constants from App. B.2. (b) From the Lee/Kesler correlation for P rs at.