Volumetric Properties of Pure Fluids

Single-Phase Region
Total differential of V = V(T,P)

dV

dT

dP
T

I. Isothermal Compressibility and Volume Expansivity

Isothermal compressibility, , is the fractional change in volume of a system
as the pressure changes at constant temperature. Isothermal compressibility is
derived from the slopes of P-V diagram.

The statistical fluctuation formula in the calculation of this property is:

Where V is the volume, T is temperature and P is pressure.

The minus sign makes the compressibility positive in the (usual) case that an
increase in pressure induces a reduction in volume.
Thermal expansion coefficient is the fractional change in the volume of a
system with temperature at constant pressure. Thermal expansion coefficient is
derived from the slopes of V-T diagram. When volume expands sharply, this
temperature is called melting

temperature.

The subscript p indicates that the pressure is held constant during the
expansion, and the subscript V stresses that it is the volumetric (not linear)
expansion that enters this general definition. In the case of a gas, the fact that the
pressure is held constant is important, because the volume of a gas will vary
appreciably with pressure as well as temperature. For a gas of low density this can
be seen from the ideal gas law.
The statistical fluctuation formula in the calculation of this property is:

Where V is the volume, E is energy, T is temperature and P is pressure.

II. VIRIAL

EQUATION OF STATE

vapors,
lying
the CD curve

Isotherms for gases and

above and to the right of
shown in Figure 1.

Expression of
power series of

PV for an isotherm by a
P:

PV = a + bP + cP2 + . . .
If b = aB, c = aC, etc. then
PV = a (1 + BP + CP2 + DP3

Figure 1.

+ . . .)
Where a, B, C and etc. are constants for a given temperature and chemical
species.

A. TWO FORMS OF THE VIRIAL EQUATION

Z = 1 + BP + CP2 + DP3 + . . .
(IV.1)
Z=1+

B
V

C
2
V

D
3
V

(IV.2)
The given two forms of equations are known as virial expansions and the
letters B, C, D, etc., considered as parameters, are called virial coefficients.B
and B parameters are considered to be second virial coefficients, C and C

parameters are considered to be third virial coefficients and so on. The terms V

C
D
2 , and
V
V 3 arise on account of molecular interactions.

III. IDEAL GAS

The virial coefficients from equation IV.2 would become zero due to the
absence of molecular interactions. Therefore, virial expansion results to:
Z = 1 or PV = RT
The equation of state:
PV = RT

(IV.3)

An internal energy that is a function of temperature only:

U = U (T)

(IV.4)

The heat capacity, Cv, is a function of temperature only for ideal gas:

Cv = ( T

)V

dU (T )
dT

= Cv (T)

(IV.5)

Enthalpy is also a function of temperature only:

H = U + PV
= U (T) + RT
= H (T)

(IV.6)

Like Cv, heat capacity

temperature so:

CP = ( T

at

constant

pressure,

Cp,

is

function

)P

dH (T )
dT

= CP (T)

(IV.7)

dU = CvdT

U = CvdT

dH = CpdT

H= CpdT

Work of mechanically reversible closed-system process:

dW = -PdV
dQ dW = CvdT
dQ = CvdT + PdV
dQ = CvdT + RT

dQ = CpdT -RT

dV
V
dP
P

Isothermal Process:

U=

H
V2

Q = RTln V 1

=0

= RTln

P2
P1

dW = -RT

dV
V

dW = -RdT +RT

dP
P

of

V2
W = - RTln V 1

P2
P1

= RTln

V2

P2

Q = -W = RTln V 1

= - RTln P1

(constant T)

Isobaric Process:

U = CvdT
Q = CpdT

Q=

and

H= CpdT

and

W = -R (T2 T1)

CpdT

(constant P)

Isochoric Process:

U = CvdT
Q=

CvdT

Q=

U = CvdT

and

H= CpdT

and

W = - PdV = 0
(constant V)

Adiabatic Process; constant heat capacities:

TV

dT
T

=-

T2
T1

V2
= ( V 1 )R/Cv

T2
T1

P2
= ( P1 )R/Cp

( 1)/

TP

R dV
Cv V

= constant
= constant

and

where :

Cp
Cv

P2
P1

V1
= ( V 2 )Cp/Cv

PV

= constant

IV.ADIABATIC PROCESS EQUATIONS

Various examples of an adiabatic process are:
When gas is compressed, heat is generated, it is also an adiabatic
process. For example in a piston.
There is cooling and expansion of air, it raises that. Similarly as it
descends, it contracts and grows warmer.
The pendulum oscillating in a vertical plane is an example of it.
A quantum harmonic oscillator is also an example of adiabatic system.
When we put the ice into the ice box, no heat goes out and no heat comes
in.
A. For reversible process (Isentropic Process):

P1 V 1=P 2 V 2
Where:

Cp
Cv

Other equations:

[ ]

T 1 P1
=
T 2 P2

[ ]

V 1 P2
=
V 2 P1

[ ]

2 P2
=
1 P1

B. For irreversible process (Isoenthalpic Process):

The work done is different than in a reversible process because the "P" that appears
in the PdV expression for the work is actually the external pressure exerted on the
gas and not the pressure of the gas itself.
In this, the entropy does not remain constant or entropy varies. In such a process,

[ ]
Cv + R

T2=

Cp

P2
P1

T1

C. Brief discussion:
In adiabatic process, the heat neither enters into nor goes out the system;
thus Q=0. From the First Law of Thermodynamics (U= Q + W), the internal energy
(U) will be equal to the work done by (adiabatic expansion) or done on (adiabatic
compression) the system. If the gas expands adiabatically, the temperature
decreases. On the other hand, the temperature increases when the gas gets
compressed adiabatically.
(-Wrev) > (-Wirrev) Less work is recovered through an irreversible process.
V. IRREVERSIBLE PROCESS
Irreversible process is a process that proceeds spontaneously in one
direction. Once having taken place, the process cannot reverse itself and always
results in an increase of molecular disorder.All equations developed in this section
have been derived for mechanically reversible, closed-system processes for ideal
gases. However, those equations which give property changes dU ,dH , U and H
are valid for ideal gases regardless of the process. They apply equally to reversible
and irreversible processes in both closed and open systems, because changes in
properties depend only on the initial and final statesof the system. On the other
hand, an equation for Q or W , unless it is equal to a property change, is subject to
the restrictions of derivation.
The work of an irreversible process is calculated by a two-step procedure:

W is determined for a mechanically reversible process that accomplishes the

same change of state as the actual irreversible process.
The result from first step is multiplied or divided by an efficiency to give the
actual work. If the process produces work, the absolute value for the
reversible process is too large and must be multiplied by an efficiency. If the
process requires work, the value for the reversible process is too small and
must be divided by an efficiency.

For this topic, a sample problem is used to better expound the irreversible
process applications and calculations:
Sample Problem:

An ideal gas undergoes the following sequence of mechanically reversible processes

in a closed system:
(a) From an initial state of 700C and bar, it is compressed adiabatically to
1500C.
(b) It is then cooled from 150 to 700C at constant pressure.
(c) Finally, it is expanded isothermally to its original state.
If the processes are carried out irreversibly butso as to accomplish exactly the same
changes of state (P, T, U, H) then different values of Q and W result. Calculate Q and
W if each step is carried out with an efficiency of 80%.
Solution:
(a) The first step is to determine Q and W using mechanically reversible process
equations:
So, W=U=CVT=998 J
The second step is by multiplying/dividing the value W by an efficiency, in
this case the process requires work. Hence, W=998/0.80=1248 J.
It is aforementioned on this handout that adiabatic process equations are
only valid for ideal gases undergoing mechanically reversible adiabatic
expansion or compression. Therefore,
Q=U-W=998-1248=-250 J
(b) Following the same procedure, the work for mechanically reversible cooling
process is
W=U-Q= CVT-CPT=-998-(-1663) =665 J
For the irreversible processsince the process requires work
W=665/0.80=831 J, and
Q= U-W=-998-831=-1829 J

P3

P2

(c) For mechanically reversible process, Q=-W=RTln P1 =RTln P1 =1495 J.

As stated earlier, for a process that produces work (work is done by the
system), the absolute value of W must be multiplied by the efficiency. Hence,
W=-1495*0.80=-1196 J
Q= U-W=0+1196=1196 J
VII. APPLICATIONS OF VIRIAL EQUATION
BenedictWebbRubin equation (Extended Virial Equation)
The BenedictWebbRubin equation (BWR), named after Manson Benedict, G.
B. Webb, and L. C. Rubin, is an equation of state used in fluid dynamics. Working at
the research laboratory of M. W. Kellogg Limited, the three researchers rearranged
the Beattie-Bridgeman Equation of State and increased the number of
experimentally determined constants to eight.

BWR Equation:

Tabular or graphical data are available for many pure components; where, A,
B, C, a, b, c, and are all constants for a given fluid.

Figure 2: Compressibility Graph for Methane

VII. APPLICATIONS OF VAND DER WAALS EQUATION

The equation relates three state variables: the pressure of the fluid p, the
total volume of the fluid's container V, the number of particles N, and the absolute
temperature of the system T.
The intensive, microscopic form of the equation is:

P=

RT
a
2 ( general )
V b V

Where
particles,

- is a measure of the average attraction between

- is the volume excluded by a mole of particles,

- is the number of moles,
- is the universal gas constant, and NA is Avogadro's
constant.
The correction for volume is negative, but the correction for pressure is
positive to reflect the effect of each factor on V and P, respectively. Because
nonzero molecular volumes produce a measured volume that is larger than that
predicted by the ideal gas law, we must subtract the molecular volumes to obtain
the actual volume available. Conversely, attractive intermolecular forces produce a
pressure that is less than that expected based on the ideal gas law, so the an2/V2
term must be added to the measured pressure to correct for these effects.
Other forms:

P=

( V )
RT

(cubic)
V b ( V b ) ( V 2 +V + )

=b ,=a ( T ) ,= ( + ) b , = b2

P=

a (T )
RT

(cubic , appropriate parameters )

V b ( V b ) (V + b )

P
V

2 P
=0,
V2
T ;cr

( )

3 Vc=b+

( )

=0

T ;cr

RTc
a
ab
,3 ( Vc )2= , ( Vc )3=
Pc
Pc
Pc

Applications:
Fugacity

Fugacities are determined experimentally or estimated from

various models such as a Van der Waals gas that are closer to reality
than an ideal gas.
Gas Liquefaction
Liquefaction of gases is the condensation of gases into a liquid
form, which is neither anticipated nor explained by the kinetic
molecular theory of gases. Both the theory and the ideal gas law
predict that gases compressed to very high pressures and cooled to
very low temperatures should still behave like gases, albeit cold, dense
ones. Liquefaction can be viewed as an extreme deviation from ideal
gas behaviour. It occurs when the molecules of a gas are cooled to the
point where they no longer possess sufficient kinetic energy to
overcome intermolecular attractive forces. The precise combination of
temperature and pressure needed to liquefy a gas depends strongly on
its molar mass and structure, with heavier and more complex
molecules usually liquefying at higher temperatures.
VIII. OTHER EQUATIONS OF STATE
Other Equations of State
1.
2.
3.
4.

Benedict/Webb/Rubin Equation
Redlich/Kwong Equation
Soave/Redlich/Kwong Equation
Peng/Robinson Equation
1. Benedict/Webb/Rubin Equation

It is known as extended virial equation.

This equation has been used extensively for light hydrocarbons and
other nonpolar gases.

C0
RT
T 2 bRT a
P

V
V2
V3
a
c

6 3 2 1 2 exp

2
V
V T
V
V
B0 RT A0

2-4. Redlich-Kwong/Soave-Redlich-Kwong/Peng-Robinson

These are empirical cubic equations of state.

These equations have proven to ba robust in describing a wide variety

of systems.
These equations differ upon the assignment of parameters.

Equations used:
Equation

V
2.

aT
RT
V b
b
P
P V b V b

Z
Z Z

Z 1 q

Description
Equations used for solving V and Z in
terms of compressibility factor. Iteration
methods are used to solve these
equations. The initial value should start
for V at ideal solution (V = RT/P) and for Z
at Z = 1 until V or Z is very small.

3.

4.

RTC
PC

Tr R 2TC 2
PC

a T

A prerequisite parameter where is a

pure number, independent of substance
and determined for particular equation of
state from the values assigned to and
A prerequisite parameter where is a
pure number, independent of substance
and determined for particular equation of
state from the values assigned to and
.

Tr

5.

Tr

T
TC

Pr
;

6.

bP
RT

q
;

7.

Pr
Tr

P
PC

aT
bRT
Tr
Tr

is an empirical expression specific

to a particular equation of state based on
table of parameter assignments.
Reduced temperature and pressure
respectively. It is used.
Prerequisite parameters.

Prerequisite parameters for iterative

solution of the equations 2 and 9.

;
8.

RT bP VP
V b V b V b

Liquid or liquid like root solutions. The

initial values for V should be V = b and
for Z it should be Z = . Once the Z is

9.

known. The volume root is V = ZRT/P

1 Z

Z Z Z

Table of Parameter Assignments for Equations of State

Equation of
State
Redlich/Kwong

Tr

ZC

Tr 1/2

0.08664

0.42748

1/3

Soave/Redlich/K
wong

Refer to
table 3a
Refer to
Table 3a

0.08664

0.42748

1/3

1 2

1 2

0.07780

0.45724

0.30740

Peng/Robinson

Tr
Table of

for SRK and PR

Equation of State
Soave/Redlich/Kwong
Peng/Robinson

Tr , 1 0.480 1.574 0.176 2 1 Tr1/2

Tr , 1 0.37464 1.54226 0.26992 2 1 Tr1/ 2

SUBMITTED BY:
BSChE