Introduction to Chemical Engineering Institute of Process Engineering

Solution 7: Liquid-vapor equilibrium

7.1 Binary liquid-vapor equilibrium

4.1 Part (a)

According to the general accepted standard, the more volatile component (that is in this case acetone) is
assigned the index 1. The overall composition is:
1
z1 = = 0.2 (1)
4+1
As the pressure in the box is equal to 1 bar, we may use the T − xy diagram (for P = 1 bar). At T = 40◦ C
the whole content of the box is liquid: X
VL = viL ni (2)
i
where the molar volume of the liquid phase is
Mi
viL = (3)
ρi (T )

v1L = 0.073 L mol−1 and v2L = 0.018 L mol−1 so that VL = 0.146 L.

At a temperature of T = 120 ◦ C the whole content of the box is vapor, the EOS for the gas phase applies:
nRT
VV = = 163.4 L (4)
P

At a temperature of T = 80◦ C the system is in the two phase region. Using the diagram, we can read the
composition of the vapor and the liquid phase. Using the lever arm rule we can calculate the amount of
vapor and liquid. Please note that the distances in the lever arm rule depend on the scale of your print-out!.
3.2 cm
nL = 5 mol = 3.2 mol (5)
5 cm
1.8 cm
nV = 5 mol = 1.8 mol (6)
5 cm
The composition of the liquid phase can be read from the blue curve: x1 = 0.05 ⇒ x2 = 0.95. The vapor
composition is given by the red curve: y1 = 0.5 ⇒ y2 = 0.5. So finally we calculate:

VL = nL (x1 v1L + x2 v2L ) = 0.069 L (7)

and
nRT
VV = = 52.8 L (8)
P

Exercise 4.1 Part (b)

All vessels start at the same temperature. As the contents is liquid and assuming constant specific heat
capacities cL L
p , temperature rises linearly in all three vessels (depending on the value of cp ). In the case of
pure components, when reaching the boiling temperature, the temperature stays constant until all liquid has
been evaporated. Afterwards, the temperature increases again (most likely with a different slope according
to the value of the vapor phase specific heat capacity cVp ).
In the case of the mixture, temperature increases when moving through the two phase region.
Note that the time and slopes of the lines are arbitrary as information about heat capacities is not available.
The drawing is strictly qualitative.
Introduction to Chemical Engineering Institute of Process Engineering

140

mixture
120
acetone
100
water
temperature [°C]

80

60

40

20

0
time [arbitrary units]
Introduction to Chemical Engineering Institute of Process Engineering

7.2 Dew and Bubble point calculation

(i) Pressure at the bubble point can be calculated applying the equilibrium conditions for the three
components and the stoichiometric equation (cf script 1.13.2. P-xy diagrams):

equilibrium : pyi = psi xi

X
stoichiometric : yi = 1
i
p = 6.66 atm

The pressure at the dew point can be calculated by the same conditions, but keeping in mind that
the gas phase compositions yi are known. Therefore:

equilibrium : pyi = psi xi

X
stoichiometric : xi = 1
i
p = 0.188 atm

(ii) Temperature at the bubble point:

yi X X
xi = → yi = 1 = zi Ki (T )
Ki (T )

Through the secant method (’Regula falsi’), one obtains:

yn,small
xn+1 = xn,small − (xn,big − xn,small )
yn,big − yn,small

P
T [K] K1 K2 K3 (zi Ki ) − 1
127 1.04 0.003 2.23e-7 0.608
208 20.53 1.012 0.011 -0.845
176.3 9.00 0.212 7e-04 -0.43
189.5 13.21 0.437 0.003 -0.097
192.1 14.14 0.497 0.003 -0.018
192.5 14.31 0.51 0.003 -0.003
193 14.49 0.52 0.004 0.013

The bubble temperature is in between 192.5 K and 193 K, therefore with an accuracy of 1◦ C it could
be said: TBubble = 192.5 K.
(iii) Mass balance and equilibrium:
V
zi = φyi + (1 − φ)xi with φ =
F
yi = Ki xi

zi Ki zi
→ xi = and yi =
φ(Ki − 1) + 1 φ(Ki − 1) + 1
P P
Since xi = yi = 1
X (Ki − 1)zi
f (φ) = =0
φ(Ki − 1) + 1
i

Given that f(0) = 1.22 > 0 and f(1) = -14.97 < 0 a solution exists for 0 < V < 1. → c) is verified.
Introduction to Chemical Engineering Institute of Process Engineering

(iv) The Newton method is used to locate the ”zero” of the function:

f (φn )
Newton : φn+1 = φn −
f 0 (φn )

where:
X (Ki − 1)zi X −(Ki − 1)2 zi
f (φ) = and f 0 (φ) =
φ(Ki − 1) + 1 [φ(Ki − 1) + 1]2
i i

f approaches zero after 4 Newton iterations with initial guess φ0 = 0.5.

φ0 φ1 φ2 φ3 φ4
0.5 0.265 0.215 0.217 0.217

Therefore one can obtain for x = (0.008, 0.485, 0.507) and for y = (0.203, 0.784, 0.013).
Introduction to Chemical Engineering Institute of Process Engineering

7.3 Graphical solution of a flash distillation process

Part (a)

For the solution of the isothermal flash, with a given temperature, we first use the T − xy diagram to
find the compositions x, y of the liquid phase and of the vapor phase. x and y refer to the more volatile
component, in this case ethanol. The feed composition is given as z = 0.3.
Figure 1a shows the T −xy diagram with compositions x and y marked for the three requested temperatures.
The overall compositions are marked with crosses. To find the liquid and vapor flow rates L and V , we can
apply the lever-arm rule:
L y−z
= (9)
V z−x
Once the compositions are known, we can draw the operating lines in the x − y diagram (Figure 1b). The
operating lines go through the points which represent the composition of the two phases, ie. the point
with coordinates (x, y) and the diagonal at the feed composition, ie. the point with coordinates (z, z). The
equation for the operating line is
L F
y =− x+ z (10)
V V
which means that the slope of the operating line is −L/V , which gives us another method to calculate the
liquid and vapor flow rates L and V .
In order to draw the solution in the H − xy diagram (Figure 1c), we need to convert the concentration
units to weight fractions. For the feed, we obtain a concentration

0.3 · 46.07 g/mol

zw = = 0.52 (11)
0.3 · 46.07 g/mol + 0.7 · 18.15 g/mol

To draw the points corresponding to the liquid and vapor phases, we use the tie-lines corresponding to each
temperature. The mixture points are located at the coordinates (zw , hF + Q/Fw ) for each temperature.
The end-points (circles) at the bottom represent the liquid phase, while the end-points at the top represent
the vapor phase (we could apply the lever-arm rule in this diagram to calculate the liquid and vapor flow
rates. We would obtain a different ratio compared to the two other diagrams, due to the different units).
The bottom cross marks the point with coordinates (zw , hF ), which is the enthalpy of the feed. This point
is known, since it is stated that the feed enters at the boiling point of the mixture (ie. the feed point must
lie on the boiling line). To calculate the specific heat input for each case, we take the difference between
the mixture point and the feed point. To calculate the total heat input required, we need to multiply the
specific heat input by the feed flow rate on a mass basis Fw :

Fw = 100 mol/s (0.3 · 46.07 g/mol + 0.7 · 18.15 g/mol) = 2653 g/s = 2.65 kg/s (12)

All the results are summarized in Table 1.

Introduction to Chemical Engineering Institute of Process Engineering

105 1.0

0.9

100
0.8

0.7
95
0.6
T [ o C]

83 o C

yEtOH
90 0.06 0.36 0.5
85 o C

0.4
0.13 0.48 90 o C
85
0.3
0.54
0.22
0.2
80

0.1

75 0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
xEtOH, yEtOH xEtOH

(a) T − xy (b) x − y

(c) H − xy

Figure 1: Graphical solution of isothermal flash in T − xy, x − y and H − xy diagrams.

(a) In the T − xy diagram, the circles mark the compositions at each requested temperature. The points
on the left represent the liquid phase, and the points on the right represent the vapor phase. The points
marked with crosses represent the overall composition in each case.
(b) In the x−y diagram, the operating lines connect the feed point on the diagonal to the points representing
the compositions of the two phases, ie. points with coordinates (x, y).
(c) In the H − xy diagram, the circles again mark the liquid and vapor states. They lie on the tie-lines for
the three temperatures requested. From these, we could calculate the compositions of the two phases. The
overall compositions are marked using crosses, as is the feed (on the boiling line). These points are used to
calculate the (specific) heat input required.
Introduction to Chemical Engineering Institute of Process Engineering

Table 1: Compositions, flow rates and heat inputs for the three requested temperatures

T, ‰ x y L, mol/s V , mol/s Q, kcal/s

83 0.22 0.54 75.33 24.67 402.8
85 0.13 0.48 51.43 48.57 556.5
90 0.06 0.36 20.00 80.00 795.0

Part (b)

To solve the adiabatic flash, we need to start with the H − xy diagram, since the temperature is yet
unknown. The feed compositions is the same as above, zw = 0.52, and the feed enthalpy is given as
hF = 310 kcal/kg. The heat input Q is zero, since the flash is adiabatic. With this information, we can
‰
draw the feed point with coordinates (zw , hF ). This point lies on the isotherm for T = 87 , which gives
us the temperature of the flash unit. At the end-points of this isotherm, we find the composition xw = 0.17
at the bottom, and the composition yw = 0.64 at the top end. Using the lever-arm rule, we find a ratio
Lw /Vw = 0.34, which gives us values of Vw = 0.67 and Lw = 1.98 (using Fw = 2.65, as given by Eq. 12).
In mole fractions, the values are:
xw
46.07 g/mol
x= (1−xw )
= 0.07 (13)
xw
46.07 g/mol + 18.15 g/mol
yw
46.07 g/mol
y= yw (1−yw )
= 0.41 (14)
46.07 g/mol + 18.15 g/mol
 
xw 1 − xw
L = Lw + = 35 mol/s (15)
46.07 g/mol 18.15 g/mol
V = F − L = 65 mol/s (16)
Introduction to Chemical Engineering Institute of Process Engineering

Figure 2: Graphical solution of adiabatic flash in H − xy diagram.