Section 3.

Generalized Correlations for Liquids

Generalized Correlations for Liquids
• Generalized cubic equations of state are not
accurate.

• Lee/Kesler correlation includes data for

subcooled liquids.

• Most suitable for nonpolar and slightly polar

fluids.
Estimation of Vsat
• Estimation of molar volumes of saturated
liquids:
(Rackett equation 3.68)

• Only requires critical constants which can be

found in Table B1 of App. B.

• Accuracy up to 1 or 2%.
Two-parameter corresponding-states
Correlation for estimation of liquid V
• Reduced density r as function of Tr & Pr

• C is the density at the critical point.

• The generalized correlation is shown by Fig.

3.15
Figure 3.15: Generalized density
correlation for liquids.
A Better Procedure !!!

• V2 = required volume
V1 = known volume
r1, r2 = reduced densities from Fig. 3.15
Example 3.13
• For ammonia at 310 K, estimate the density
of:

a) The saturated liquid

b) The liquid at 100 bar
Solution 3.13(a)
• Rackett equation at Tr = 310/405.7 = 0.7641

• VC = 72.47 & ZC = 0.242

 72.47 0.242
10.76410.2857
V sat
 28.33 cm3 mol 1

• Experimental value: V = 29.14 cm3 mol-1

Difference: 2.7%
Solution 3.13(b)
• Tr = 0.764 Pr = 100/112.8 = 0.887
r = 2.38 (from Fig. 3.15)

• Eq. (3.70) & VC = 72.47

VC 72.47
V   30.45 cm3 mol 1
 r 2.38
• Experimental value: V = 28.6 cm3 mol-1
Calculated value is 6.5% higher.
Solution 3.13(b) A better solution
• Starting value:
Experimental value at 310 K, Vsat = 29.14

• At Tr = 0.764 & saturation, r = 2.34

 r1 2.34 1
V2  V1  29.14  28.65 cm mol
3

r 2 2.38

• Experimental value: V = 28.6 cm3 mol-1

Solution 3.13(b) A bad solution
• Lee/Kesler correlation:

• Calculated V = 33.87 cm3 mol-1

Experimental value: V = 28.6 cm3 mol-1

• Large error due to the highly polar nature of

ammonia.