ChemE 101 – 11.

6 Worksheet Department of Chemical Engineering

1st Semester AY 2020-2021 University of the Philippines Diliman
VLE calculations on ideal binary systems

Name ChemE 101 Section

Instructions: Fill in any missing information in the provided solution to each problem. You may print this worksheet, or, in the absence of a
printer, write the complete solution on another sheet of paper.

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Problem 1
Instructions: To answer this problem, recall that the phase envelop of a binary system is a three-dimensional surface of
pressure, temperature, and composition. A P-T diagram is provided for this problem, where the axis of composition ,
would be a line shooting out of the page towards you. Antoine constants are also given.

An ideal solution of 10 mole of benzene and 10 mole toluene is placed in a piston

and cylinder assembly, where moving the piston varies the pressure and an external
heating/cooling changes the temperature. This system is made to undergo a process
consisting of the following steps:
 Step 1: The solution initially at 1 atm and 25°C is heated isobarically (at
constant pressure) until the temperature reaches 85°C.
 Step 2: The pressure is decreased isothermally (at constant temperature)
until the liquid composition became 50% benzene.
 Step 3: Through a special port in the piston, 400 moles benzene at 1 atm and 25°C is injected, while linearly increasing
the pressure toward 1 atm as the temperature is decreased toward 25°C, until the temperature becomes 75°C.
 Step 4: The pressure is lowered isothermally until all the pressure is 0.2 bar.
 Step 5: The temperature is cooled isobarically to 45°C.

1. Trace all the five steps on the P-T diagram of benzene and toluene.
2. Determine the state, amount and composition of the phases present at the end of each step, e.g., initially, the system
exists as a single phase consisting of 20 moles of liquid with a composition of 0.50.

Solution:
The approach we are adapting here would be a hybrid of graphical and analytical, and the reason behind it will become
apparent as we go through the calculations. Since the binary system is ideal, we can perform the calculations analytically using
Raoult’s law and Dalton’s law, and use the diagram to visualize and confirm the changes occurring in the system. We recall
that Raoult’s law and Dalton’s law relates total pressure, temperature, and compositions (liquid and vapor). For binary
systems, Gibbs’ phase rule tells us that 3 intensive variables are needed to specify state of the system outside the phase
envelope, while 2 intensive variables are enough when inside the phase envelope.

Step 1 involves moving horizontally on the P-T diagram (isobaric process) from 1 atm/25°C to 1 atm/85°C.
Using Raoult’s law and Dalton’s law, at 85°C,
1.1785 bar, 0.4607 bar
!
.# $ % #.&'#(
1 → ! ! 0.7698, 1 0.2302
" . ()% #.&'#(
-" " ! #.('.)/ . ()%
"
0.8953, 1 0.1047
.# $ %
The question now is if the system is inside the phase envelope. After step 1, if the system exists as two phases at 1
atm/85°C, it should consist of a liquid with composition 0.7698 and a vapor with composition 0.8953. Since
0.50 initially, a material balance will reveal that, for the system to have these liquid and vapor compositions, it
will result to negative quantities, which are physically impossible.
1 2 3 1 2 20
0 →5 → 1 62.9960 mol, 2 42.9960 mol
1 2 43 0.76981 0.89532 10
To understand better what is happening, we can view step 1 on a P-x,y diagram at 85°C.

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 We can see that the system is outside the phase envelope. From the P-x,y diagram, we can infer that the system is in
the phase envelope if its overall composition 4 is between and at 1 atm/85°C—this should allow us to infer
whether our system is inside or outside the phase envelope without having to consult a P-x,y diagram. We can also see
from the diagram that the system stays as a single liquid phase. Just be wary of the placement of your bubble lines and
dew lines as it will depend on which component the composition axis is based on. For example, our system is located left
of the bubble line when the composition axis is based on benzene(1); it becomes located on the right of the bubble line
when the composition axis is switched to toluene(2).

An alternate way (and arguably safer way) would be to determine the pressure on the bubble line at the composition of
our system. At 0.5, 1 0.50 / 1.1785 1 0.50 / 0.4607 0.8196 bar. We know
that for all pressures higher than on the bubble line, the system exists as a liquid. Since 0.8196 bar < 1.01325 bar, our
system is a liquid. Regardless of the approach you take, the key for solving these types of problems is to be able to
visualize where you are on the phase diagram.

So, to summarize, after step 1, our system is still 20 moles of liquid with a composition of 0.50 at 1 atm and 85°C.

Step 2 involves moving vertically (isothermal process) from 1 atm/85°C to 0.50/85°C.

Using Raoult’s law and Dalton’s law, at 85°C,
XXXXX bar, XXXXX bar
1 XXXXX / XXXXX bar 1 XXXXX / XXXXX bar 0.8196 bar.
-" " ! ;;;;;
"
XXXXX, 1 XXXXX
#.) .'
1 2 3 1 2 XXXXX
0 →5 → 1 20 mol, 2 0 mol
1 2 4 3 XXXXX1 XXXXX2 XXXXX
Therefore, the system is only composed of 20 moles of liquid with composition XXXXX and 0 moles of vapor of
XXXXX at 0.8169 bar and 85°C.

Step 3 involves moving along the line passing through the system at 0.8196 bar/85°C and the benzene fed at 1 atm/25°C on
the P-T diagram until the temperature of the system is 75°C. The moles of the system increase by 400 moles benzene.
Using Raoult’s law and Dalton’s law, at 75°C,
XXXXX bar, 0.3262 bar
1 / XXXXXbar 1 / 0.3262 bar.
We would want to find the pressure that would coincide with the one of the pressure values found on the linear path
taken by the system in step 3.
.# $ % #.) .' .# $ % #.) .'
<bar= 0.8196 ><°C= 85 0.8196 75 85 XXXXX bar
% )% % )%
! ;;;;; #.$ '
Thus, ! ! ;;;;; #.$ '
0.9738, 1 0.0262
"
-" " ! #..($)/;;;;;
"
XXXXX, 1 XXXXX
;;;;;
Let AB moles of benzene added
1 2 3 AB 1 2 XXXXX
0 →5 → 1 XXXXX mol, 2 XXXXX mol
1 2 4 3 AB 0.97381 XXXXX2 XXXXX
Therefore, the system is composed of XXXXX moles of liquid with composition 0.9738 and XXXXX moles of vapor
of XXXXX at 0.8519 bar and 75°C.

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Step 4 involves moving vertically (isothermal process) from 0.8519 bar/75°C to 0.2 bar/75°C.
From the P-T diagram, the system is well below the phase envelope and hence exists only as XXXXX. Therefore, the
system is only composed of XXXXX moles of XXXXX with XXXXX at 0.2 bar and 75°C.

Step 5 involves moving horizontally (isobaric process) from 0.2 bar/75°C to 0.2 bar/45°C.
Using Raoult’s law and Dalton’s law, at 45°C,
XXXXX bar, XXXXX bar
! ;;;;; ;;;;;
1 → ! ! ;;;;; ;;;;;
XXXXX, 1 XXXXX
"
-" " ! ;;;;;/;;;;;
"
;;;;;
XXXXX, 1 0.2442
1 2 3 1 2 XXXXX
0 →5 →1 371.00 mol, 2 791.00 mol
1 2 4 3 XXXXX1 XXXXX2 XXXXX
The presence of negative values suggest that the system is outside the phase envelope. We can argue using material
balances whether our system is only liquid or vapor. If the system is completely liquid, 1 XXXXX mol and the amount
of benzene at the bubble line should be XXXXX1 XXXXX mol. If the system is completely vapor, 2 XXXXX mol and
the amount of benzene at the dew line should be XXXXX2 317.44 mol. Since our system actually has 410 mol >
317.44 mol, our system is completely vapor.
Therefore, the system is only composed of XXXXX moles of vapor with XXXXX at 0.2 bar and 45°C.

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 E
Antoine equation, log # <bar= D F<°G=HI
Substance Temperature range valid (K) A B C
benzene 279.64 to 377.06 3.98523 1184.240 217.572
toluene 286.44 to 409.61 4.05043 1327.62000 217.62500

After finishing this worksheet, please answer the Learning Log Link assigned to your instructor so that
we could better gauge your progress and adapt as necessary. The link can be found in our ChemE 101
course main page in UVLê