VLE-EOS_EtOH/Water ---- H.C.

Van Ness; January 2005

VLE for Ethanol(1)/Water(2) at 90 deg C. Calculations with

Peng/Robinson EOS. Activity coefs. by the van Laar Equation.
This is a BUBL P calculation illustrating in detail the procedure
described on pp. 569-572 of "Introduction to Chemical
Engineering Thermodynamics," 7th ed., McGraw-Hill, 2005,
by Smith, Van Ness, & Abbott.
Temperatures in kelvins; Pressures in bars. R := 83.14
Data: T := 363.15 x1 := 0.2464 x2 := 1 − x1

⎛ 513.9 ⎞ ⎛ 61.48 ⎞ ⎛ 0.645 ⎞ ⎛ 1.57892 ⎞

Tc := ⎜ Pc := ⎜ ω := ⎜ Psat := ⎜
⎝ 647.1 ⎠ ⎝ 220.55 ⎠ ⎝ 0.345 ⎠ ⎝ 0.70124 ⎠
⎯
→
T ⎛ 0.7067 ⎞
Tr := Tr = ⎜
Tc ⎝ 0.5612 ⎠
ε := 1 − 2
Table 3.1: σ := 1 + 2 Ψ := 0.45724 Ω := 0.07780
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ →
( )
α := ⎡⎣ 1 + 0.37464 + 1.54226⋅ ω − 0.26992⋅ ω ⋅ ( 1 −
2
Tr) ⎤⎦
2
α =⎜
⎛ 1.4408 ⎞
⎝ 1.4870 ⎠
⎯⎯⎯⎯⎯ → ⎯⎯⎯ →
2 2
Ψ ⋅ α ⋅ R ⋅ Tc Ω ⋅ R⋅ Tc
a := (3.45) b := (3.46)
Pc Pc
The following are final parameter values that do not change:
⎛ 1.9561 × 107 ⎞ ⎛ 54.0673 ⎞
a=⎜ b=⎜
⎜ 8.9227 × 106 ⎝ 18.9782 ⎠
⎝ ⎠
bliq := x1⋅ b1 + x2⋅ b2 (14.42) bliq = 27.6241
van Laar eqn. parameters (Table 14.4): A12 := 1.7720 A21 := 0.9042
Liquid-phase activity coefficients:
−2 −2
⎛ A12⋅ x1 ⎞ ⎛ A21⋅ x2 ⎞
lngam1 := A12⋅ ⎜ 1 + lngam2 := A21⋅ ⎜ 1 + (12.17)
⎝ A21⋅ x2 ⎠ ⎝ A 12 ⋅ x 1 ⎠
⎯⎯→
lngam ⎛ 0.6582 ⎞ ⎛ 1.9314 ⎞
γ := e lngam = ⎜ γ =⎜
⎝ 0.1379 ⎠ ⎝ 1.1479 ⎠
FIND q-VALUES FROM VAPOR-PRESSURE DATA FOR PURE
SPECIES.
This insures that the pure-species vapor pressures are reproduced
as part of the results.

⎯⎯→
a
Preliminary values: q := (14.34) (Used for initial iteration)
b⋅ R⋅ T

⎛ 11.9832 ⎞
q=⎜
⎝ 15.5722 ⎠
Updated values used in iteration:

q1 := 12.0364 q2 := 15.4551 (These are the final converged

values from iteration.)
For calculations at P=Psat:

⎯⎯→
b⋅ Psat ⎛ 2.8275 × 10− 3 ⎞
β := (14.33) β =⎜
R⋅ T ⎜ 4.4078 × 10− 4
⎝ ⎠
Solve blocks with initial estimates: Zliq := β 1 Zvap := 1
(Species 1)

Zvap − β 1
Given Zvap = 1 + β 1 − q1⋅ β 1⋅ (14.36)
( Zvap + ε ⋅ β 1) ⋅ ( Zvap + σ ⋅ β 1)
zvap1 := Find ( Zvap)

1 + β 1 − Zliq
Given Zliq = β 1 + ( Zliq + ε ⋅ β 1) ⋅ ( Zliq + σ ⋅ β 1) ⋅ (14.35)
q1⋅ β 1
zliq1 := Find ( Zliq)

Solve blocks with initial estimates: Zliq := β 2 Zvap := 1

(Species 2)

Zvap − β 2
Given Zvap = 1 + β 2 − q2⋅ β 2⋅ (14.36)
( Zvap + ε ⋅ β 2) ⋅ ( Zvap + σ ⋅ β 2)
zvap2 := Find ( Zvap)
 1 + β 2 − Zliq
Given Zliq = β 2 + ( Zliq + ε ⋅ β 2) ⋅ ( Zliq + σ ⋅ β 2) ⋅ (14.35)
q2⋅ β 2
zliq2 := Find ( Zliq)

⎛ 3.5536 × 10− 3 ⎞ ⎛ 0.9680 ⎞

zliq = ⎜ zvap = ⎜ (At P=Psat)
⎜ 5.1894 × 10− 4 ⎝ 0.9936 ⎠
⎝ ⎠
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ →
⎛ 1 ⋅ ln ⎛ zliq + σ ⋅ β ⎞ ⎞ ⎛ 0.5203 ⎞
Iliq := ⎜ ⎜ (6.65b) Iliq = ⎜
⎝ σ − ε ⎝ zliq + ε ⋅ β ⎠ ⎠ ⎝ 0.5476 ⎠

⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ →
⎛ 1 ⋅ ln ⎛ zvap + σ ⋅ β ⎞ ⎞ ⎛ 2.9125 × 10− 3 ⎞
Ivap := ⎜ ⎜ (6.65b) Ivap = ⎜
⎝ σ − ε ⎝ zvap + ε ⋅ β ⎠ ⎠ ⎜ 4.4343 × 10− 4
⎝ ⎠
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ →
⎛
( zvap − zliq) + ln ⎜
zliq − β ⎞ ⎛ 12.0364 ⎞ FINAL
⎝ zvap − β ⎠ (14.37) q = ⎜
q := ⎝ 15.4551 ⎠ VALUES
Ivap − Iliq
_________________________________________________________
Subsequent calculations require values of Z and I for the PURE
LIQUID species at system pressure P. Because P is to be
determined, an iterative procedure is initiated by a starting value for
P. A logical initial choice is the sum of the pure-species vapor
pressures at the known temperature T, each weighted by its known
liquid-phase mole fraction.
CURRENT VALUE OF PRESSURE: P := 1.3576 (Shown is the final
converged value)
⎯→
b⋅ P ⎛ 2.4311 × 10− 3 ⎞
β := (14.40) β =⎜
R⋅ T ⎜ 8.5335 × 10− 4
⎝ ⎠
Solve block with initial estimate: Zliq := β 1
(Species 1)
1 + β 1 − Zliq
Given Zliq = β 1 + ( Zliq + ε ⋅ β 1) ⋅ ( Zliq + σ ⋅ β 1) ⋅ (14.35)
q1⋅ β 1
zliq1 := Find ( Zliq)
 Solve block with initial estimate: Zliq := β 2
(Species 2)
1 + β 2 − Zliq
Given Zliq = β 2 + ( Zliq + ε ⋅ β 2) ⋅ ( Zliq + σ ⋅ β 2) ⋅ (14.35)
q2⋅ β 2
zliq2 := Find ( Zliq)
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ →
⎛
Iliq := ⎜
1 ⎛
⋅ ln ⎜
zliq + σ ⋅ β ⎞⎞ (6.65b)
⎝ σ − ε ⎝ zliq + ε ⋅ β ⎠ ⎠
⎛ 3.0556 × 10− 3 ⎞ ⎛ 0.5203 ⎞
zliq = ⎜ Iliq = ⎜ (At pressure P)
⎜ 1.0047 × 10− 3 ⎝ 0.5476 ⎠
⎝ ⎠

CALCULATION OF PARTIAL q-VALUES:

Liquid phase first; vapor phase second

bliq⋅ P −3
β liq := (14.40) β liq = 1.2421 × 10
R⋅ T
qliq := x1⋅ q1 + x2⋅ q2 qliq = 14.6127 (initial estimate)
Must update qliq as calculation progresses:

qliq := 13.9175 (converged value)

Solve block with initial estimate: Zliq := β liq

Given
⎛ 1 + β liq − Zliq ⎞
( )(
Zliq = β liq + Zliq + ε ⋅ β liq ⋅ Zliq + σ ⋅ β liq ⋅ ⎜ ) qliq⋅ β liq
(14.38)
⎝ ⎠
zliq := Find ( Zliq)
−3
zliq = 1.4978 × 10

1 ⎛ zliq + σ ⋅ β liq ⎞
Iliq := ⋅ ln ⎜ (6.65b) Iliq = 0.5374
σ−ε ⎝ zliq + ε ⋅ β liq ⎠
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→
⎡ 1 ⎡ ⎛ zliq − β liq ⎞ ⎤⎤
⋅ ( zliq − 1) − ln ⎜
b
qbarliq := ⎢ ⋅ ⎢1 − zliq + + q⋅ Iliq − lngam⎥ ⎥ (14.57)
⎣ Iliq ⎣ bliq ⎝ zliq − β ⎠ ⎦⎦
 ⎛ 10.3080 ⎞
qbarliq = ⎜ qliq := x1⋅ qbarliq + x2⋅ qbarliq (14.58)
⎝ 15.0975 ⎠ 1 2

qliq = 13.9174 (update value)

⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→
lnφhatliq := ⎡⎢
⎤
b
( )
⋅ ( zliq − 1) − ln zliq − β liq − qbarliq⋅ Iliq⎥ (14.50)
⎣ bliq ⎦
⎯⎯⎯
→
lnφhatliq ⎛ 2.1752 ⎞
φhatliq := e φhatliq = ⎜
⎝ 0.5894 ⎠
Repeat these calculations for a LIQUID phase with the VAPOR
composition. This is done by duplicating the preceding calculation
with the xs changed to ys. THE ONLY PURPOSE IS TO GET
VALUES FOR q and qbar for the VAPOR phase. These
calculations require knowledge of the vapor composition, which is
yet to be determined. Iteration is again indicated, with starting
values for the ys. They could be found from Raoult's law or by
assuming ideal solutions in both phases. The properties of this
special phase are denoted here by subscript lv:

Current value of y: y1 := .5496 (Shown is the final converged value.)

y2 := 1 − y1

blv := y1⋅ b1 + y2⋅ b2 (14.42) blv = 38.2631

qvap := y1⋅ q1 + y2⋅ q2 (initial value) qvap = 13.5761

Must update qvap as calculation progresses:

qvap := 12.5616 (converged value)

blv⋅ P −3
β lv := (14.40) β lv = 1.7205 × 10
R⋅ T

Solve block with initial estimate: Zlv := β lv

Given
⎛ 1 + β lv − Zlv ⎞
( )(
Zlv = β lv + Zlv + ε ⋅ β lv ⋅ Zlv + σ ⋅ β lv ⋅ ⎜ ) qvap⋅ β lv
(14.38)
⎝ ⎠
 zlv := Find ( Zlv)
−3
zlv = 2.1338 × 10

1 ⎛ zlv + σ ⋅ β lv ⎞
Ilv := ⋅ ln ⎜ (6.65b) Ilv = 0.5258
σ−ε ⎝ zlv + ε ⋅ β lv ⎠
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→
⎡ 1 ⎡ ⎛ zlv − β lv ⎞ ⎤⎤
⋅ ( zlv − 1) − ln ⎜
b
qbarvap := ⎢ ⋅ ⎢1 − zliq + + q⋅ Iliq − lngam⎥ ⎥ (14.59)
⎣ Ilv ⎣ blv ⎝ zliq − β ⎠ ⎦⎦

⎛ 10.6591 ⎞ qvap := y1⋅ qbarvap + y2⋅ qbarvap (14.60)

qbarvap = ⎜ 1 2
⎝ 14.8830 ⎠
qvap = 12.5615 (update value)

For the REAL vapor phase by (14.42) & (14.40):

bvap⋅ P −3
bvap := y1⋅ b1 + y2⋅ b2 β vap := β vap = 1.7205 × 10
R⋅ T

Solve block with initial estimate: Zvap := 1

Given
Zvap − β vap
Zvap = 1 + β vap − qvap⋅ β vap⋅ (14.39)
( Zvap + ε ⋅ β vap) ⋅ ( Zvap + σ ⋅ β vap)
zvap := Find ( Zvap) zvap = 0.9798

1 ⎛ zvap + σ ⋅ β vap ⎞ −3
Ivap := ⋅ ln ⎜ (6.65b) Ivap = 1.7529 × 10
σ−ε ⎝ zvap + ε ⋅ β vap ⎠
______________________________________________________
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→
lnφhatvap := ⎡⎢ ⋅ ( zvap − 1) − ln zvap − β vap − qbarvap⋅ Ivap⎤⎥
( )
b
(14.50)
⎣ bvap ⎦
⎯⎯⎯→
lnφhatvap ⎛ 0.9752 ⎞
φhatvap := e φhatvap = ⎜
⎝ 0.9862 ⎠
 ⎯⎯⎯ →
φhatliq ⎛ 2.2305 ⎞
K := (14.53) K =⎜
φhatvap ⎝ 0.5977 ⎠
Σ := x1⋅ K1 + x2⋅ K2 Σ = 1.0000 (converged value) (14.52)

The value of Σ is the key to the correct value of P. If Σ > 1, then

P is too low; if Σ < 1, then P is too high. Adjust P (back on page 3)
so that Σ = 1.
x1⋅ K1
y1 := (normalize) y1 = 0.5496
Σ

Update y first and then P. Final converged values are:

y1 = 0.5496 P = 1.3576

Experimental value of Pemberton and Mash (footnote 11; p. 573).

Vapor-phase compositions were not measured.

P ( exp) = 1.3564

NOTE THAT THIS CALCULATION IS RIGOROUS, EXCEPT FOR

THE MIXING RULE USED FOR b. The mixing rule used for q is the
summability equation, which is exact.