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
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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
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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
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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.
