52:00 – 59:00 Partially Miscible Binary Liquids

The phase diagram is temperature versus composition. The pressure will be treated as a
constant. Phase diagram is similar to the ternary system in which we had a partially miscible
liquid pair. Component A can be treated as a solvent and component B as a solute. The
corresponding solubility limit of B dissolved in A and A dissolved in B. The solubility limit of B
and A is represented by a point. If the point is below the solubility of B to A and A to B, single
phase will be present. If the point is beyond the solubility of B to A and A to B, two layers can be
expected. If B increases and A decreases, B starts to act as a solvent and A as a solute.
Therefore, If the temperature increases, the solubility of A to B and B to A increases. There will
be a curve in the diagram. If it goes beyond the curve, it is a single phase. Therefore, the
variance is equal to 2. The single phase is a homogenous liquid mixture of A and B. If it is inside
the curve, two layers can be seen. Similar to ternary phase diagram, using of tie lines to
determine the composition of the two layers is needed. The tie lines are parallel to one another.
At different temperatures, there is a corresponding tie lines. The critical temperature represents
the point at which the compositions of the A-rich and B-rich layers are the same and the
interface between the layers starts to diminish. Left side of the critical temperature represents
the composition of A-rich layers while the right side of the critical temperature represents the B-
rich layers. The tie lines can be used to determine the compositions of the layers within the
curve. If there are two systems following the tie line at a corresponding temperature, the tie lines
used are the same. Also, the solubility of A to B and B to A are the same at a constant
temperature. If the temperature increases, there will be changes on the composition of A-rich
and B-rich layers. The distributions of A-rich layers versus B-rich layers are determined by lever
rule.
59:00 – 1:06:00 Problem 3.3.2
Phenol and Water forms a partially miscible binary liquid system. Given the temperature-
composition diagram, determine the following for a mixture that contains 7.00 moles phenol and
3.00 moles water. To determine the composition of phenol-rich and water-rich layers, draw tie
lines and see where it intersects. Therefore, phenol acts as the solvent. Phenol-rich layers have
90% phenol and 10% water while the water-rich layers consist of 10% phenol and 90% water.
To determine the number of moles of the original solution that is distributed into the water-rich
layer versus phenol-rich layer at 220◦C, use lever rule. Using the level rule, determine the mole
fraction of the water-rich layer and the phenol-rich layer. The answer is 2.5 moles for water-rich
layer and 7.5 moles for phenol-rich layer. To determine the number of moles that is distributed
to the water-rich layer versus phenol-rich layer, use the composition of phenol and water-rich
layers and the number of moles solution that got distributed. The water-rich layer has 0.25
moles while the phenol-rich layer has 6.75 moles. Therefore, there are 7 moles of phenol. To
find the temperature at which the water-rich layer will be 20% phenol, follow the lines until it hits
the curve. The answer will be 260◦C.
1:06:00- 1:14:35 Completely Miscible and Completely Immiscible Binary Liquids
Completely miscible means the liquid vapor equilibrium is similar to non-ideal completely
miscible binary liquid system. With that, expect that interactions between components A and B
are not similar. For completely immiscible binary liquid, consider a system with components A
and B. If mixed together, there will be two layers. The arrangement of the layers from top to
bottom are dependent to their densities. To determine the vapor pressure of the solution with
complete immiscibility, use the formula of Dalton’s Law. For the completely immiscible binary
liquids, there are no interactions between components A and B. The partial pressures of
components in a mixture are the same as in the pure components. Therefore, the overall vapor
pressure of the mixture is independent of the composition. To calculate the vapor pressure of
the mixture, take into account the pressure-temperature diagram of the component. The curves
can be approximated using Clasius-Clapeyron equation for component A and B. At a constant
temperature, we can find the vapor pressure by adding the components A and B. Consider the
boiling pressure of the pure components versus the solution given the boiling temperature of
component A and B. The boiling temperature of the mixture is lower than either of the
components. Therefore, the mixture will always boil at a lower temperature than the pure
components.
Steam Distillation allows the separation of heat-sensitive materials at much lower
temperatures by introducing steam into the distillation. To determine the composition of
distillate, use the formula of Dalton’s Law and find the mole fraction of the vapor pressures.
1:14:35 – 1:18:19 Problem 3.3.3
Limonene is a cyclic terpene that may be extracted from the rinds of lemons via steam
distillation at 77◦C, 1 atm. If you wish to extract 100g of limonene, how much steam is required,
given the vapor pressure of water at 77◦C is 314.1 torr. To find how much water is in the
distillate, find the mole fraction of water in the distillate. The answer is 9.32 grams.