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Problem 28P Problenm Consider a closed vessel initially containing 1 mol of pure
tetrahydrofuran at 74"C and 120 kPa Imagine that pure chloroform is slowly added at constant
temperature and pressure until the vessel contains 1 mol tetrahydrofuran and 9 mol chloroform
Describe the evolution of phases and phase compositions during this process. Comment on the
practical feasibility of carrying out such a process. What sort of device would be required? How
would the total system volume change during this process? At what composition would the
system volume reach its maximum value?

Answer:

Below shown is the T x y diagram for the system containing

chloroform(1)/tetrahydrofuran(2) at 74 C and 120 kPa .


Initially, there is 1 mol of tetrahydrofuran in a closed vessel at 74 C and 120 kPa . Thus, there is


no chloroform present in the vessel, so, x1  0 . This is represented by point “a” on the T  x  y
diagram.

Now, keeping the temperature and pressure of the system constant, pure chloroform is slowly
added to the vessel until there is 1 mol of tetrahydrofuran and 9 mol of chloroform present in
the vessel. Thus, the final composition of the vessel becomes x1  0.9 .

On a T  x  y diagram for chloroform(1)/tetrahydrofuran(2) system at 74 C and 120 kPa , this



process is shown by a horizontal straight line from point “a” to point “f”.

Point “a” lies above the T  y curve, so the system is in superheated vapor state at this point
having composition,

y1  a   0.0
y2  a   1.0

Slow addition of pure chloroform gradually shifts the system from point “a” to point “b” where
is touches T  y curve which represents saturated vapor state. At this point first drop of saturated
liquid appears. Point “b” corresponds to the composition of the saturated vapor and point “c”
corresponds to the composition of the first drop (saturated liquid) which is in equilibrium with
this saturated vapor.
Therefore, the composition at this point “b” will be:

y1  b   0.11
y2  b   0.89
x1  b   0.17
x2  b   0.83

At point “c”, last bubble of the saturated vapor condenses, and system is in saturated liquid state.
Point “c” corresponds to the composition of the saturated liquid and point “b” corresponds to the
composition of the last bubble (saturated vapor) which is in equilibrium with this saturated
liquid.
The composition of the system at this point “c” will be:

x1  c   0.17
x2  c   0.83
y1  c   0.11
y2  c   0.89

In between the points “b” and “c”, both the phases saturated vapor and saturated liquid coexist in
equilibrium and overall composition of the system varies as moving from “b” and “c”.

Addition of chloroform beyond point “c” leads the system to point “d”. In this range the system
is in subcooled liquid state with overall composition of the system varying from
x1  c   0.17 to x1  d   0.72
.

At this point “d”, the system reaches the state of saturated liquid as it is on the curve T  x . At
this point, first bubble of saturated vapor appears which in equilibrium with the saturated liquid.
Point “d” corresponds to the composition of the saturated liquid and point “e” corresponds to the
composition of the first bubble (saturated vapor) which is in equilibrium with this saturated
liquid.
The composition of the system at this point “d” will be:

x1  d   0.72
x2  d   0.28
y1  d   0.82
y2  d   0.18

At point “e”, which lies on T  y curve, last drop of the saturated liquid evaporates, and system
is in saturated vapor state. Point “e” corresponds to the composition of the saturated vapor and
point “d” corresponds to the composition of the last drop (saturated liquid) which is in
equilibrium with this saturated vapor.
The composition of the system at this point “e” will be:

y1  e   0.82
y2  e   0.18
x1  e   0.72
x2  e   0.28

In between the points “d” and “e”, both the phases saturated liquid and saturated vapor coexist in
equilibrium and overall composition of the system varies as moving from “d” and “e”.

Further addition of pure chloroform to the vessel takes the system to point “f” where there is
1 mol of tetrahydrofuran and 9 mol of chloroform present. This point lies above the T  y curve
so it is in superheated vapor state. The composition at this point is y1  0.9 and y2  0.1 .

This process of the addition of chloroform to tetrahydrofuran is isothermal and isobaric.

Therefore, an Isothermal Calorimeter is used to carry out such process where the temperature
and pressure of the system is kept constant by a heating or cooling element.

As temperature and pressure of the system is kept constant throughout the process, there will be
proportional increase in the volume of the system as number of moles are increasing with the
addition of pure chloroform in the vessel.

Since, the increase in the system volume is proportional to the moles added to the system, the
maximum volume will appear at the highest number of moles present in the system, that is,
1 mol of tetrahydrofuran and 9 mol of chloroform. The composition of the system at this point
is:

y1  0.9
y2  0.1