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stillation Theory Boiling PointThe boiling point of a pure liquid is defined as the
temperature at which the vapor pressure of the liquid exactly equals the pressure
exerted on it by the atmosphere and is one of its characteristic phy sical
properties. The boiling point is used to characterize a new organic liquid, and
knowledge of the boiling point is used to compare one organic liquid with another,
as in the process of identify ing an unknown organic substance. The boiling point of
a mixture is a function of the vapor pressures of the various components in the
mixture. Impurities either raise or lower the observed boiling point of a sample,
depending on how the impurity interacts with the compound for which the boiling
point is being measured.Consider, for example, the boiling characteristics of a
mixture of pentane and hexane. Pentane and hexane are miscible (mutually soluble),
and their molecules interact with one another only by weak van der Waals forces. A
solution composed of both pentane and hexane will boil at temperatures intermediate
between the boiling points of pentane (36 oC) and hexane (69 oC). If pentane alone
was present, the vapor pressure above the liquid would be due only to pentane.
However, with pentane as only a fraction of the solution, the vapor pressure
exerted by pentane (P) will be equal to only a fraction of the vapor pressure of
pure pentane at the same temperature (Po), where X is the mole fraction of pentane,
the fraction of pentane molecules in solution. The same is true for the hexane
component.Phexane = PohexaneXhexane (1)Ppentane = PopentaneXpentane (2)Using
Dalton's law of partial pressures, we can now calculate the total vapor pressure of
the solution, which is the sum of the partial vapor pressures of the individual
components.Ptotal = Ppentane + Phexane (3)Being able to calculate the total vapor
pressure of a solution can be extremely useful to a chemist; knowing the
composition of the vapor above a solution can be just as important.Here is an
illustration of how it is done: Apply ing the ideal gas law to the mixture of gases
above a solution of pentane and hexane, we have equation 4. Y is the fraction of
pentane molecules in the vapor above the solution.Ypentane = Ppentane
PtotalWith the fact that the total mole fractions of pentane and hexane must equal
one, a single expression for the total vapor pressure of the solution (equation 5)
can be derived.Xhexane + Xpentane = 1Ptotal = Xpentane (Po pentane Po hexane) +
Po hexane (5)Finally , the combination of equations 4 and 5, plus Raoult's law,
allows the calculation of the mole fraction of pentane in the vapor state.Ypentane
=
Po pentane Xpentane
(6)
Xpentane (Popentane P o hexane) + P o hexaneSo, if y ou know the vapor pressures
of pure pentane and pure hexane at various temperatures and the composition of the
liquid y ou can calculate the fraction of pentane in the vapor above the solution.
This kind of calculation can be used to construct a temperature-composition
diagram, sometimes called a phase diagramSimple Distillation#Figure 1.2 Estimated
temperature-composition diagram for pentane-hexane solutions at 1.0 atm pressure.It
is useful to follow the dotted line in, moving from L1 to V1 to L2, etc. Point L1
indicates a boiling point of 44 oC at atmospheric pressure for a solution
containing a 1:1 molar ratio of pentane to hexane. Upon removing a sample of the
vapor, we find that it has a molar composition of 87% pentane and 13% hexane as
indicated by point V1. The mole fraction of the component with the lower boiling
point is greater in the vapor than in the liquid. If the vapor at V1 condenses, the
liquid that collects (L2) will have the same composition as the vapor (V1). Now, if
the condensed liquid (L2) is revaporized, the new vapor will be even richer in
pentane (V2). Repeating the boiling and condensing several more times allow us to
obtain pure pentane,uncontaminated by hexane.As pentane is removed in the vapor,
the composition of the liquid, originally L1, becomes richer in hexane, the
component with the higher boiling point. As the mole fraction of hexane in the

liquid increases, the boiling point of th liquid also increases until the boiling
point of pure hexane, 69 oC, is reached. In this way pure hexane can also be
separated.In a simple distillation, only one vaporization and condensation occurs,
corresponding to points L1 and V1. This process would not effectively separate a
mixture such as pentane and hexane. If a 1:1 solution of pentane and hexane
undergoes a simple distillation, the first vapor that condenses has a molar
composition of 87% pentane and 13% hexane. The molar composition of the remaining
liquid now contains more hexane and less pentane than originally ; consequently , the
boiling point of the mixture will increase. As additional vapor condenses into the
receiving flask, the boiling point of the remaining mixture continues to increase.
We can represent this graphically by a distillation curve showing vapor temperature
versus volume of distillate for the simple distillation of our pentane-hexane
mixture#Figure Distillation curve for a simple distillation of a 1:1 molar solution
of pentane and hexane.The initial distillate is collected at a temperature above
the boiling point of pure pentane and the final distillate never reaches the
boiling point of pure hexane, a result indicating a poor separation of the two
compounds. Even though simple distillation does not effectively separate a mixture
of liquids whose boiling points differ by less than 60-70 oC, organic chemists use
simple distillations in two commonly encountered situations. The last step in the
purification of a liquid compound usually involves a simple distillation to obtain
the pure product and determine its boiling point. Simple distillation is also used
to remove the solvent when recovering an organic compound with a high boiling from
a solution.
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