Thernmodynanmic properties of real

gases

Learning Objectives
IhIschapter will cnable readers to

timate the thermodynamic properties of an ideal gas in terms of P v, T and C:

lefine enthalpy. entropy and other departure functions;
lculate the departure lunctions Irom a knowledgc of the equation of state of a fluid:
alculate the departure functions from generalized RK, SRK and PR cquations of state;
alculate the departure functions using Edmistcr charts;
eiend the Lce-Kesler mcthod for the prcdiction of departure functions;
calculate the departure functions using Lee-Kesler data;
calculate the departure functions from generalized virial coefficient correlation;
calculate the required thomodynamie properties of a real gas rom the ideal gas heat capacity
and P - T data only; and
construct thermodynamic property tables and diagrams;

The relationships betweenthe nonmeasurable and measurable properties discussed in Chapter 7

are valid for any substance and the required properties can be estimated in terms of the measur-
able quantitiecs R u, 7, Cp Cor B and R. In this chapter, the estimation of enthalpy and entropy
of a real gas is discussed. Before we discuss the estimation of the properties of a real gas, let
us study the properties of an ideal gas.

8.1 Thermodynamic properties of an ideal gas

The change in the internal energy, enthalpy and entropy of a system can be estimated from the
relations

du=CdT+(P-P)d» (7.58)

dh CpdT+v(1 BT)dP (7.64)

-

dT
(OP
ds=C 8T dv
(7.67)

or ds=C-T P
dP
[See Example 7.3]
For an ideal gas:

and

( -1 =0 and
-(),)-
 Chemical engineening thenodynamics
270

u(T) only. Hence du = C,dT.

aP 0
8P . (1 - T)-0 and
(),-(),),.
or h h (T) only. Hence dh =C, dT

ds=C, 4T + R-C dT -R
Thus for an idcal gas

-car (8.1)

8--c}aT (8.2)

-- Rin (8.3)

P
or - - Rn (8.4)
where the superscript zero indicates the ideal gas properties. It can be observed from Eqns.8.1-8.4
that the properties of an ideal gas can be estimated from a knowledge of the heat capacities,
and P, v, T data.

8.2 Departure functions

Suppose it is required to estimate the changes in enthalpy or entropy of a real gas when it
changes from the initial state Pi, u, Ti to the final state Pa, v, T2. Since the change in the
property (h or s) is independent of the path, one can choose a convenient path connecting the
given initial and final states to estimate the change in the property. To illustrate the convenient
paths, let us consider the evaluation of enthalpy change. We can consider

h h(T,P)

Then dh aT) dT+ Oh

8P) dP (7.60)
Equation 7.60 can be integrated from (P, T) to (P, ) by two different paths as given below.

ha-hi #T+ ) dP (8.5)

P JP

ha-h P+) dT
(8.6)
 Thermodynamic properties of real gases 271

aath followed in Eqn.8.5 is isobaric heating (cooling) from Ti to T2 at P followed by

hhermal compression (expansion) from Pi to Pa at T2. This path is shown as ABC in
1 on the pressure versus temperature diagram. The path followed in Eqn.8.6 is isothermal
oression (expansion) from Pi to Pa at T, followed by isobaric heating (cooling) from Tto
as shown by ADC in Fig.8.1.
Tat P

o o o o o 0 o oo o oo o R

Fig&1 P-T diagram illustrating two different paths of integration.

Though the two paths ABC and ADC are convenient for integration, we face the practical
difñculty regarding the availability of heat capacities Cp = (Oh/8T) P and Cp = (Oh/3T) P
Usualy, the isobaric heat capacities are measured when the gas is in the ideal gas state (P-).
To make use of the available ideal gas state heat capacity data, it is necessary to choose the
path AEFC shown by dotted lines in Fig.8.1. That is, (ha = h) is evaluated from the relation

.P-O(8h cT (8h Oh
ha-h
aP T P+ 8T P-0o dT+ BP)T d

08h
8P) Tdr+cgar+
-
dP

or ha -

- ) (8.7)

For an ideal gas the change in enthalpy is given by Eqn.8.2. Substituting Eqn.8.2 in Eqn.8.7, we
get

(ha-h)- t -

h) =

4--T)4 (8.8)

From Eqn.8.8 one can write

(h-H)TP= PlT
(8.9)
 272 Chemical engineering thermodynamics

of a real f
The term (h h°)TP represents the difference between the enthalpies
-

ad
fluid in the ideal gas statc at the same temperature and pressure, and is called th
called the the
departure or residual enthalpy.
Similarly one can define the entropy departure or residual entropy as the difference hes..
enthalpy
entropics of a real gas and the gas in the idcal gas state at the
same temperature and nthe
In general, if M is any cxtensive thermodynamic property, then
the departure functi Sure
or the residual property M is defined as M

Departure function for M

= M - MO
or

residual property M (8.10)

where M property of the real gas at T and P, and M°= property of the gas in the ideal.
state at the same T and P. al-gas
Let us now consider the entropy departure function. The entropy change of a substance
be evaluated by integrating the relation

dP
T)p (8.11)
along path AEFC of Fig.8.1 to get

S2-S1- -
8T) P dP) .P-0 8T P.Ta
dP
(8.12)
For an ideal gas the change in entropy is given by Eqn.8.4. Substituting Eqn.8.4 in Eqn.8.12, we
get

(s2-s)-(s1 -s)
From Eqn.8.13 one can write
--)-.--G)-4 (8.13)

(s-s)r.P- ) , |4P- -4 (8.14)

where =molar entropy of a real gas at T and P, and s" molar entropy of a gas in the ideal
s =

gas state at T and P. Equation 8.14 defines the

entropy departure or residual entropy. From the
enthalpy and entropy departure functions, one can obtain the other
using the relations departure functions also, by

(u u) =
(h -

h®) -

P(v -

v®) (8.15)
(a -

a°) =
(u -

u°) - T

(s -

s) (8.16)
( g - ° ) = (h - 1°) -T(s - s°)
(8.17)
 Thermodynamic properties of real gases 213

The thermodynamic properties of a real gas can be estimated from a

Aenarture functions. For example, the knowledge of the
be
change in the enthalpy (h2 -hi) and entropy (s2-81) of
a real gas can expressed as

(h-h)-(ha hy) + (h9-h) (-h9) (ha - h) -(h -)+ (h9 -h9)

-

or (h-h) =(ha - h)-(h-) + SH' cpaT

(8.18)
(e-1)-(*2-*1) +(%-)-(-) =
(*2- &2) -(81-8) +( - )
or (1) =(2 -)-(1-s) + c dT RRInIn 2P (8.19)

8.3 Departure functions from equations of state

The P--T behavior of a fluid is conveniently
expressed in the form of an
equation
of state.
The cquations of state in common use are discussed in Section 3.3. It can be observed that the
cquations of state in common use are
pressure explicit, i.e., volume and temperature appear
as independent variables. The
evaluation of the cnthalpy and
entropy departures requires a
knowledge of the partial derivative (av/8T)P, which cannot be directly obtained from pressure
explicit equations of state. In such cases it is useful to develop alternative
departure functions as shown below. for the expressions
We know that d(Pu) = Pdv + vdP

or idP d(P) - Pdv

(8.20)
and the cyclic relation among the three variables P, and T is
v
given by

)G) =-1 or
3I)
(OP
aT), \aP),
or
(8.21)
Substituting Eqns.8.20 and 8.21 in Eqns.8.9 and 8.14, we get

(h-rP) dP

=d(P)+JP-O
(since v = 0 as P= 0)

Pu-(Pu)P-0+ )-*
P-RT+ du
274 Chemical engineering thermodynamics

(h-h°)rP= RT(Z-1)+ P du
(8.22)
(-TP
-).- dv*p
du
- ) _ R
+ / nPu
PU
OP
to + R
d In(Pi) -

R
T). Jv=0o

= R do
du
or
(s-TP R In Z+ (8.23)
Example 8.1 Evaluate the enthalpy and entropy departures for a van der Waals gas.

Solution The van der Waals equation of state is given by

P= RT or
(OP\ R
aT)
Then

(h h°) RT(Z-1)+ ).-Ha

RT(Z-1) + R + do= RT(1 =P-RT
(s-) +

V- b
R lnZ+ du = R InZ+ R In R
In ,
where = volume as P- 0, or ideal gas volume. Therefore,

v- b
-= R Rn
In Z+ RIn v - RIn
n7/po

RT)
-=R Po-)
or 8- = R lnn -
+R In po = R ln(U-6) InP(o-b)
= Rln
" P RT
 Thermodynamic properties of real gases 275

Arample 8.2 Assuming that n-octane obeys the van der Waals equation of state, calculate the
enthalpy and entroPy departure for n-octane vapor at 427.85 K and 0.215 MPa.

Solution We have v =
15.675 10-3 m'/mol (see Example 3.8). The van der Waals constants of
x

n-octane are given by a= 3.789 Pa (m'/mol)2; b 2.37 x 104 m/mol [see

=
Appendix Table A.2].
h-h=Pu-RT- U

(0.215 10 3.789
= x x 15.675x 10)- (8.314 x
427.86)15.675 x 10-3
= -

428.74 J/mol

s-s= R In -6)
RT

10
In (0.215
x x (15.675 x 10-3 -2.37x
8.314 10)=-0.5757
,

8.314 x 427.85 -0.5757 J/mol K

=
K