CHEMICAL ENGINNERING

THERMODYNAMICS

Unit 2
VOLUMETRIC BEHAVIOR OF
REAL SUBSTANCES
CHEMICAL ENGINEERING THERMODYNAMICS
 2. Volumetric behavior of real
substances:
2.1 Solids and Liquids

2.2 Real Gases

2.2.1 Ideal Gases
2.2.2 The corresponding states principle
2.2.3 Volumetric cubic equations of state
2.2.4 Correlations
CHEMICAL ENGINEERING THERMODYNAMICS
 2. Volumetric behavior of real
substances:
2.1 Solids and Liquids I
Idealization: VS or VL constants for any T or P variations
Valid for small to moderate ΔT or ΔP when no high precise
estimations are needed.

For big ΔT or ΔP or high precise estimations:

Isothermal compressibility:
kT = - (1/V) (∂V/∂P)T
Isobaric coefficient of thermal expansion:
αP = (1/V) (∂V/∂T)P
CHEMICAL ENGINEERING THERMODYNAMICS
 2. Volumetric behavior of real
substances:
2.1 Solids and Liquids II
Thermal Physical Properties Constants for Selected pure
Substances at 298 K, 1 bar
CHEMICAL ENGINEERING THERMODYNAMICS
 2. Volumetric behavior of real
substances:
2.2 Real Gases
2.2.1 Ideal Gases
As P → 0, PV → NRT, and U only changes with T and no with P,
CP = f(T, P) ≈ g(T)
But as P increases PV = ZNRT and U = u(T, P)
Where Z≠ 1, compressibility factor

2.2.2 The corresponding states principle

Pc and Tc are added to get better estimations
Relative properties Pr = P/Pc, Tr = T/Tc, Vr = V/Vc and Pr Vr = NRTr
generates more precise estimations but in many cases not enough
precise.
Not only Pc and Tc must be known to describe the volumetric behavior of
CHEMICAL ENGINEERING THERMODYNAMICS
 2. Volumetric behavior of real
substances:
2.2.2 The corresponding states principle
CHEMICAL ENGINEERING THERMODYNAMICS
 2. Volumetric behavior of real substances:
2.2 Real Gases
2.2.3 Cubic state equations
Equation of state f(T, P, V) = 0, where V = V/N
Van der Waals: P = RT/(V – b) – a/V2
Where a and b can be estimated from experimental data or calculated from
the critical variables of the corresponding substance. At the critical point:
(∂P/∂V)Tc = (∂2P/∂V2)Tc = 0
This two equations allow the estimation of a and b if the critical values of
the substance are known
a = 27 R2 Tc2 / (64Pc) and b = R Tc / (8 Pc)
In reduced variables vdW eq: Pr = 8 Tr / (3 Vr -1) – 3 / Vr 2
Therefore Zc = 3/8 = 0.375, which is not true for all the real gases. A third
parameter
CHEMICAL ENGINEERING THERMODYNAMICS
 2. Volumetric behavior of real substances:
2.2 Real Gases

From the different third parameter proposed (in addition to Tc and Pc, Zc
was proposed), the most used one is the acentric factor:
Z = Z(0)(Tr, Pr) + ω Z(1)(Tr, Pr)

Where ω = - log10 Pvap,r│Tr = 0.7 – 1 is the acentric factor

Pvap,r│Tr = 0.7 = Pvap(0.7 Tc)/Pc, just one experimental measurement for each
fluid allows the determination of the corresponding acentric factor

Z(0)(Tr, Pr) from the volumetric behavior of Argon (monoatomic noble gas).
And for Argon ω = 0. Other gases ω > 0
CHEMICAL ENGINEERING THERMODYNAMICS
 2. Volumetric behavior of real substances:
2.2 Real Gases
CHEMICAL ENGINEERING THERMODYNAMICS
CHEMICAL ENGINEERING THERMODYNAMICS

For example:
RKS:
a = ac f(ω, Tr) = ac [1 + k (1-Tr1/2)]2
Where ac = 0.42748 R2 Tc2.5/Pc, b = 0.08664 R Tc/Pc
k = 0.48508 + 1.55171 ω – 0.15613 ω2

PR:
a = ac α(ω, Tr) = ac [1 + k (1-Tr1/2)]2

Where ac = 0.445724+ R2 Tc2/Pc, b = 0.07780 R Tc/Pc

α(ω, Tr) = [1 + k (1-Tr1/2)]2
2
 CHEMICAL ENGINEERING THERMODYNAMICS
Virial equations of state:

P = RT/V + BRT/V2 + CRT/V3 + … = RT (ρ+Bρ2+Cρ3+…)

Or Z = PV/(RT) = 1 + B/V + C/V2 + … = 1+Bρ+Cρ2+…
Or Z = 1 + B´P + C´P2 + D´P3 + ….
B´= B/(RT), C´= (C - B2)/(RT)2, D´= (D - 3BC - 2B3)/(RT)3

This equation is used truncated with 2 or 3 terms only

For gases if ρr < 0.5, just 2 terms provide good results:

Z = PV/(RT) = 1 + BP/(RT) or P = RT/(V - B)
And B = RT[B(0)) + ω B(1)]/Pc
B(0) = 0.083 – 0.422/Tr1.6 and B(1) = 0.139 – 0.172/Tr4.2
CHEMICAL ENGINEERING THERMODYNAMICS

For non-polar or slgihtly polar compounds a generalized

correlation can be used. In order to use computers the
original correlation (Z = Z(0)(Tr, Pr) + ω Z(1)(Tr, Pr), where
Z(0)(Tr, Pr) and Z(1)(Tr, Pr) were taken from the Lee-Kessler
tables) was modified to:

Z = Z(0)(Tr, Pr) + (ω/ω(r)) Z(r)(Tr, Pr)

Where the 0 superindex corresponds to fluids with ω(0) = 1

(monoatomic noble gases) and the r (reference)
superindex corresponds to n-Octane ω(r) = 0.398. ω is the
acentric factor of the fluid whose Z is to be estimated.

Both Z(0) and Z(r) where calculated from the Benedict-

Webb-Rubin equations for Argon and n-Octane.