CHEMICAL ENGINEERING

THERMODYNAMICS

VOLUMETRIC PROPERTIES OF PURE

FLUID
 Outline
• Generalized Correlations for Gases
• Generalized Correlations for Liquids
 Expected outcome
• Estimate volumetric properties using
generalized correlations for gases and liquids.
 Acentric Factor, ω
• Improved results are obtained through use of 3rd
corresponding states parameter, in addition to Tc and Pc.
This parameter is characteristic of molecular structure.
• Most popularly used 3rd corresponding states parameter
is ω, introduced by Pitzer et al.
• Accentric factor, ω is defined as the difference evaluated
at Tr = 0.7
𝜔 ≡ −1.0 − log 𝑃𝑟sat @𝑇𝑟 =0.7
• so, ω can be determined for any fluid from Tc, Pc, and a
single vapor pressure measurement at Tr = 0.7
Generalized Correlations for Gases

• The most popular are correlations developed

by Pitzer et al. for Z and B.

• Pitzer Correlations for Z

𝑍 = 𝑍 0 + 𝜔𝑍1 (3.57/3.53)
where Z0 and Z1 are functions of both Tr & Pr
(App. E as table E.1 through E.4)
(App. D as table D.1 through D.4)
Generalized Correlations for Gases

• When ω = 0 it’s a simple fluid correlation, so Z

= Z0 and 𝑍 0 = 𝐹 0 𝑇𝑟 , 𝑃𝑟 . This represents the
two-parameter corresponding state
correlation for Z.

• Of all Pitzer-type correlations, Lee-Kesler is the

most favorable, providing reliable results for
non-polar & slightly polar gases
Generalized Correlations for Gases
Generalized Correlations for Gases

Pitzer Correlations for the Second Virial Coefficient

• The simplest form of the virial equation

𝐵𝑃 𝐵𝑃𝑐 𝑃𝑟
𝑍 =1+ =1+ (3.61)
𝑅𝑇 𝑅𝑇𝑐 𝑇𝑟

• From this, Pitzer et al. proposed a second

correlation, which yield values for
𝐵𝑃𝑐
= 𝐵0 + ω𝐵1 (3.63)
𝑅𝑇𝑐
Generalized Correlations for Gases

Pitzer Correlations for the Second Virial Coefficient

• Combining the equations (3.61) and (3.63);
𝑃
0 𝑟
𝑃
1 𝑟
𝑍 =1+𝐵 + ω𝐵
𝑇𝑟 𝑇𝑟

• Compare with equation (3.57)

0 0 𝑃𝑟 1 1 𝑃𝑟
𝑍 =1 +𝐵 ; 𝑍 = 𝐵
𝑇𝑟 𝑇𝑟
 Generalized Correlations for Gases

Pitzer Correlations for the Second Virial Coefficient

• Second virial coefficients are functions of
temperature only.

0 0.422
𝐵 = 0.083 − 1.6 (3.65)
𝑇𝑟

1 0.172
𝐵 = 0.139 − (3.66)
𝑇𝑟4.2
 Example 1 (page 105)
Determine the molar volume of n-butane at
510 K and 25 bar by each of the following:
a) The ideal gas equation
b) The generalized compressibility-factor
correlation (Pitzer correlation for Z)
c) Equation 3.61 with the generalized
correlation for B (Pitzer correlation for
Second Virial)
Generalized Correlations for Liquids

• Molar volume of liquid can be calculated using

generalized cubic EOS.

• However, results are often not of high accuracy.

• Lee-Kesler correlation includes data for

subcooled liquids, fig. 3.13 shows curves for
both liquids and gases
Generalized Correlations for Liquids

• Generalized equations are available for

estimation of molar volumes of saturated
liquids. The simplest equation proposed by
Racket
2ൗ
1−𝑇𝑟 7
𝑉 𝑠𝑎𝑡 = 𝑉𝑐 𝑍𝑐 (3.72)

where Vsat is the molar volume of the saturated

liquid, Vc is the critical molar volume, and Zc is
the critical compressibility factor. Critical
constants are given in Table B.1
Generalized Correlations for Liquids

• Lydersen, Greenkorn & Hougen developed a

two-parameter corresponding states
correlation for estimation of liquid volumes.
𝜌 𝑉𝑐
𝜌𝑟 ≡ = (3.74)
𝜌𝑐 𝑉

where 𝜌𝑐 is the density at the critical point.

 Generalized Correlations for Liquids
• If a single liquid volume is known, then the
required volume can be calculated from
𝜌𝑟1
𝑉2 = 𝑉1
𝜌𝑟2

• V1 is the known volume

• 𝜌𝑟1 & 𝜌𝑟2 are reduced densities, obtained from
fig 3.16
 Example 2 (pg 110)
• For ammonia at 310 K, estimate the molar
volume of :
– a) saturated liquid
– b) the liquid at 100 bar
 Class activity
1 ) Calculate the pressure that will be exerted by acetylene
at a specific volume of 0.95 m3/kmol and 650 F using the
Generalized correlations.

2) The mixture of sulfur dioxide and oxygen are heated to

450°C at 101.3 kPa in the presence of vanadium catalyst to
produce sulfur trioxide gas. If the product leaves the reactor
at 550°C and 101.3 kPa, determine the volume of sulfur
trioxide produced from this reaction using the Generalized
correlations. Justify your answer.
 Tutorial
Please refer text book (6th Please refer text book (8th
ed): ed):
• 3.32 (c) • 3.44 (c)
• 3.35 (b) and (c) • 3.50 (b) and (c)
• 3.41 (a) and (b) • 3.56 (a) and (b)
• 3.50 • 3.68
THE END

Questions?