Liquid - Vapor Equilibrium

(Segmented Transcript)

0:00 – 5:00

In this Video Sarah May Sibug-Torres introduces the Liquid Vapor Equilibrium of binary liquid systems,
which has many applications and separation techniques like distillation. Before it begins, she considers
the variables that we'll be investigating and calculated the variance of our binary liquids system. The topic
begins in Two – Component System with general equation for variance as recall in the past chemistry
lectures.

F=2+C−P

T P

C=2
Therefore…
F=2+2–P
1

F=3–P

F is equal to 2. This 2 corresponds to temperature (T) and pressure (P) plus the number of components
minus P, which is the number of phases. Dealing with a two-component system, C is equal to 2. Now F is
equal to 2 plus 2 minus P. For the most part, however, we will be keeping either temperature or pressure
constant. So ultimately this value over here is going to be equal to one.

So overall, F is going to be equal to 1 plus 2 or 3 minus P then 3 minus P. This is when we hold either
Temperature or Pressure constant and this will be our overall variance scale. Overall, we could either plot
temperature or pressure against our composition. The types of systems that will be investigating will
include the following.

1. Completely miscible
- 1A: Ideal Solution
- 1B: Non-Ideal Solution
2. Partially Miscible
 3. Completely Immiscible

First, we will be considering a completely miscible binary liquid system so that we could consider first an
ideal solution, the simplest case and then we could extend our treatment to non-ideal solutions. After that
we'll just look at the ways that are not ideal solution can deviate from our ideal solution. And then next,
we'll look at the case and we have a partially miscible liquid system and then we'll finally look at the case
in which our system is completely immiscible. Next is to look on the first case scale, completely miscible
system. So overall, we can consider mixing two components, A and B if you consider the pure component
A.

We know that's going to be in equilibrium with its vapor. It has a corresponding vapor pressure of pure
component. A case of that is signified by P A ° and we could also consider component B, case A,

component B is also going to have its own characteristic vapor pressure, which we can call PB ° . We
know that they are completely miscible in the liquid state so if you mix them together, we form a
homogenous mixture of A and B this is going to be based on how much A and how much should be we're
going to be mixing together. However, what is going to be the composition of our vapor? In other words,
what is going to be the vapor pressure of the solution? Is it going to be just the addition of these two pure
vapor pressures?

Vapor pressure of Pure

Component A

MIX
(A + B) (l) (A + B) (g)

Vapor pressure of Pure

Component B

Recalling the Dalton's law of partial pressures, we can say that the total gas pressure of a mixtures is just
going to be the sum of the two partial pressures of the components. In this case, it's going to be the partial
pressure of A plus the partial pressure of B, this going to be equal to the pure vapor pressures. But we
have to consider the fact that A and B actually interact. There might be some changes in the
corresponding vapor pressures of our components in solution versus when it is pure state. If we have a
liquid then we have some of those molecules escaping into the gas phase so the amount that escapes into
the vapor phase at a certain temperature. This is going to be characteristic for the liquid. And it tells us
something about the intermixture, forces of attraction of that substance scale. In the overall at a given
temperature the liquid will just have a certain amount of kinetic energy and that kinetic energy can be
used to overcome some of the intermolecular forces of attraction. In general, if we have a greater
intermixture force of attraction, that means that our liquid needs more energy in order to escape into the
vapor phase. This implies that at higher Intermolecular force of attraction, we have a lower vapor pressure
gain.

Escaping tendency will depend on:

1. IFAs between like (A-A and B-B) and unlike molecules (A-B).
2. How much of each component there is the mixture.

5:00 – 10:00

Having different types of molecules interacting with one another in the liquid, the same principle holds,
however you still need to have a certain amount of kinetic energy in order to escape into the vapor phase.
So, the overall escaping tendency will depend on the different intermolecular attraction present in the
mixture. This will include the intermolecular forces of attraction between the like particles, so A and B
interactions and also for the unlike interactions. That means interactions between A and B also depend on
how much of each component there is in the mixture this will tell us how many like interactions we'll
have and how many unlike interactions we might have as well. We could characterize each of our
solutions based on the different types of intermolecular forces of attraction that we have between the like
and the unlike particles so, the first case that we'll be considering is the ideal solution.

 CASE 1A: Ideal Solution

- IFA: A-A, B-B A-B
Examples:

In this particular case, the interactions between A and B interactions are approximately equal to AB
interactions or unlike interactions. Examples of solutions that can be approximated as ideal solutions
include ethanol and methanol and benzene. Remember that they have very similar types of intermolecular
forces of attraction. This implies that if you have a mixture of these two things together the intermolecular
local force of attraction of unlike are going to be very similar to the like inter-reactions. If ever a benzene
molecule encounters a molecule is going to be treating it very similarly to if it encountered another
benzene molecule you have an ideal solution, this implies that all of these interactions we have
interactions here of AB here for the mixture.

GAS

LIQUID
In solution, molecule A interacts with another molecule A the same way as with molecule B therefore the
cases below will be equally favorable (pure components vs mixture). If we have pure B that means that all
of these interactions are equally favorable. So, the interactions of the mixture are not favored over
interactions of a pure system for one. If we consider the vapor pressure then our solution is going to be
dependent primarily then on the relative amounts of each of the components.

For example, if you have a mixture that is richer in component the vapor pressure of the mixture will be
more characteristic of the original vapor pressure of A. If you have more A in the liquid, it's also expected
that we'll have more A in the vapor phase, same thing goes if we have more B. If you have more B in our
liquid phase the vapor pressure in the entire solution will be more characteristic in the vapor pressure of
pure component B.

GAS

LIQUID Mixture has more of component A:

There is more A, therefore Psoln will have a
greater contribution from the original vapor
pressure of A.

We could express this mathematically using Raoult’s Law. Using this we can get the partial vapor
pressure of each component.

Raoult’s Law: The Partial Vapor pressure of

each component in an ideal mixture is given by
the following
Pi= X i P ° i

Mole fraction in Vapor pressure of pure

mixture component

In an ideal mixture there is more fraction of component I in the mixture times the pure vapor pressure of
component I. So that will overall give us the vapor pressure of component in the mixture. Combining
Daltons and Raoult’s law can also give us an expression for the overall vapor pressure of our solution.
Recalling from Dalton's law that we could get the vapor pressure of a solution by just adding the
corresponding vapor pressure of component a mixture plus vapor pressure of Component B in the
mixture.

Raoult's law gives us these expressions here. So overall, we know that the vapor pressure of component a
mixture is going to be equal to the more fraction of a times because it's pure vapor pressure. We also
know a similar expression for being to be equal to the more fraction of B times is pure vapor pressure.
Overall, we could get an expression for the vapor pressure of the solution as the more fraction of a case or
more fraction tells us the composition of the mixture.

Psoln =P A + P B

X A P A X B PB

Psoln =X A P ° A + X B P° B
(A + B) (l) (A + B) (g)
X A + X B=1
We could just multiply this by the corresponding pure vapor pressures of our components. This is our
expression for determining the vapor pressure off of a solution. For an ideal solution. It's going to be
dependent on composition and the corresponding pure vapor pressures of our components remember that
since we're dealing with a two-component system, this means that the more fractions of A and B is going
to be equal to one. We just need to know the composition of one of the components and we could easily
calculate for the composition of the other one. Another important thing to keep in mind here is that we
could also calculate the corresponding composition of the vapor phase. When we're calculating for the
vapor pressure of the solution the mole fraction A and mole fraction B, corresponds to the composition of
the liquid phase of the vapor phase, on the other hand this is going to have its own composition. So
overall, A and B give us the mole fractions of our components in the liquid phase Y A and Y B be on the
other hand give us the mole fractions of A and B in the vapor phase.

Y A : mole fraction of A in vapor

Y B : mole fraction of B in vapor

X A : mole fraction of A in liquid

X B : mole fraction of B in liquid

(A + B) (l) (A + B) (g)
10:00 – 15:00

We could also you make use of the principles that we know from Dalton's law in order to investigate what
the more fractions of A and B are going to be in the vapor phase. Recalling again that if we have a
mixture of gases and we're assuming that we have ideal gas behavior, we know that the P solution is just
going to be equal to P A plus PB . We could also solve this in another way and we could also write this in
terms of mole fractions scale which is the mole fraction in the gases phase we'll be using in this case. This
is going to be equal to Y A . So this is just to differentiate it from the mole fractions in the liquid phase. Y A

times P solution plus Y B times P solution. So overall, we know that P A the vapor pressure of A in the

solution is going to be equal to Y A times P solution. The derivation of is stated below.

Psoln =P A + P B

Psoln =Y A Psoln +Y B P soln

Psoln =Y A Psoln +Y B P soln

P A =Y A Psoln

PA XA P°A
Y A= =
P soln X A P° A + X B P ° B

 CASE 1A: Ideal Solution

- Vapor pressure – Composition Diagram (where B is the more volatile component)

P(atm) T =constant
P °B

P °A

A B
We can actually plot a vapor pressure composition diagram for our particular example, we'll be using B as
a more volatile component. Since we know that B is a more volatile component. This implies that it's
vapor pressure. The pure vapor pressure is going to be higher compared to that of A. The vapor pressure
of B is going to be around this value over here and we expect that the vapor pressure of pure component
A is going to be lower. To complete our phase diagram, we will be connecting these two points with sort
of a bubble, labelling all this at high pressures, we expect that our mixture is going to be in the liquid
phase. Then we have a single phase a homogenous liquid mixture.

On the bottom is a low-pressure scale we expect that we have a vapor phase. The homogenous vapor
phase P is equal to one, F is equal to two. So in between here, however, this is where we have liquid and
vapor in equilibrium with one another overall, our number of phases is equal to two. Assuming that we
have a perfectly ideal solution the vapor pressure of our solution as well as the vapor compositions can be
calculated using Raoult's law and Dalton's law. We could also investigate what happens if we have a
system of a fixed overall composition.

P(atm) T =constant
Liquid
P °B

Liquid line

Vapor + Liquid

P °A
Vapor

A B

mole % A ; mole % B
15:00 – 20:00

If we are at particular pressure, we can say that the pressure is super high, that we actually don't have any
vapor present. We only have a liquid phase scale so we could easily say that the composition of the liquid
phase is equal to our overall composition. So overall, we expect that if we decrease the pressure, we could
start to see some vapor appearing gains. If we decrease the pressure all the way to the point, we decrease
the pressure all the way to the liquid line, this is actually also known as the bubble point. remember that
we just hit this area base or in this area where we could see vapor plus liquid present. Once we just hit this
line here, this tells us that we see the first trace of vapor. the reason why it's called a bubble point is
because this first trace of vapor just appears as a tiny bubble.

The composition of this tiny bubble can be determined using a timeline. If we draw a timeline all the way
to the vapor line this tells us that the composition of this bubble here is going to be around 50 percent B,
50 percent A so we could see here actually that the component that goes into the vapor phase more easily
is the component that is volatile therefore B is the more volatile component. The vapor is always going to
be richer in the more volatile component. If we continue to decrease the pressures, we'll see now that
we're going to be in between so you can see here that we have a lot more vapor present. We could also
determine the corresponding compositions of these phases by drawing a timeline. As we continue to go
down the gains the composition of the more volatile component becomes less. Next, we could investigate
what happens once we hit the vapor line. Once we hit the vapor line this is actually also known as the so-
called dew point similar to the bubble point, the dewpoint represents when we have the last trace of liquid
this tiny thing over here represents a dewdrop.

P(atm) T =constant
Liquid P °B

Liquid line Vapor + Liquid

P °A
Vapor
A B

mole % A ; mole % B
 15 % B 50 % B
85%entire
Note that since we boiled off our A 50% A
mixture. The composition of the vapor is expected to be the
composition of our overall system. 50 percent B, 85 percent A so the composition of the dew, however,
can be determined using a timeline again it could draw a timeline from this point towards the liquid line.
And overall, if we draw a vertical line over here, we can see that we have about five percent B ninety five
percent A. If we further decrease the pressure to below the vapor line you have a vapor that is 50 percent
B eighty five percent A, just decreasing the pressure overall we could use vapor pressure composition
diagrams to investigate what happens if we have changes in pressure on the equilibrium and composition
of our completely miscible binary liquid system.

15:00 – 25:00

At Constant temperature we have an ethanol methanol ideal solution game we're also given that the liquid
solution contains 60 percent more ethanol before we begin try to sketch out really quickly a phase
diagram so we could also get a picture of what exactly were solving for.

P(mmhg) T =60 ℃
Liquid
625

Vapor + Liquid
a

d
352.7 Vapor

Ethanol Methanol
 40 % b
c
Let's say that this is one hundred percent methanol our temperature is at a constant 60 degrees Celsius.
And we have our pressure on our y axis it's also plots out the corresponding pure vapor pressures of our
components if you have pure ethanol, the pure vapor pressure of ethanol, that's going to be three fifty-two
point seven mmhg. let's just note that the pressure here is in terms of mmhg and then we also have the
higher vapor pressure of methanol it's a more volatile component so this is at six. 25mmhg. We could just
complete our phase diagram by drawing our curves we have our liquid line and we have our vapor line
over here just label the phase as we have liquid.

We have vapor plus liquid and we have vapor on the bottom here our liquid solution contains 60 percent
more ethanol. Since we have our diagram and our sketch here in terms of methanol this implies that we
have 40 percent methanol. 40 percent methanol in our liquid phase to figure out the corresponding vapor
that is in equilibrium with our liquid, we could draw out a timeline towards the vapor line.

So how about for C and D. C, it asks for the composition of the last drop of liquid before vaporization
becomes complete. The composition of the liquid at the dewpoint implies that just before vaporization
becomes complete, this means that the composition of the vapor is going to be equal to the composition of
the original liquid solution this means that the vapor. Its composition is going to be equivalent to 40
percent methanol and 60 percent ethanol.

Calculations:

a.
Psoln =PE T OH + P M ET OH

Psoln =X ETOH P ° ETOH + X METOH P ° METOH

Psoln =( 0.60) ¿

Psoln =461.6 mmhg

b.
P ETOH (0.60)(352.7 mmhg)
Y ETOH = =
P soln 461.6 mmhg

¿ 0.458 ≈ 45.8 % methanol

Y ' ETOH =X ETOH =0.60

P ' ETOH X ' ETOH P ° ETOH

Y ' ETOH = =
P ' soln X ' ETOH P° ETOH +(1− X ' ETOH )
25:00 – 30:00
We have a composition along the vapor line so this is the vapor line over all, this is going to be the
composition of the vapor at the dew point. It's going to be 40 percent methanol, 60 percent ethanol, the
same composition of the original liquid mixture so if you want to figure out the composition of the last
drop of liquid before vaporization becomes complete. Graphically this is determined by plotting a
timeline towards a liquid line. If we draw a line downwards this represents the composition of the last
drop of liquid before vaporization becomes complete, we want to figure out the pressure which the
mixture will completely vaporize at 60 degrees. This corresponds to a pressure here it's at this pressure at
which we have complete vaporization.

Times its corresponding vapor pressure. Pure vapor pressure so three fifty two point seven mmhg plus
one minus zero point sixty the fraction of methanol times is corresponding to pure vapor pressure. Six.
Twenty five mmhg. For sixty one point six mmhg this is the vapor pressure of our mixture game. We
could just specify the composition of one case or specify the composition of one component in one phase
automatically specifies the other one we know that we could define the composition of ethanol in the
vapor phase as its corresponding vapor pressure and the solution over the overall vapor pressure of the
solution.