One of the
non-obvious outcomes of structural identification using spectroscopy
(particularly NMR and MS) is reduced experience with distillation among organic synthetic chemists. This is because even an inexperienced student researcher can now routinely
identify a substance using milligrams of a pure compound; first using flash chromatography. Then high-performance preparative liquid chromatography or preparative gas chromatography can
replace old-fashioned distillation for making samples big enough for identification of the products from most steps in laboratory synthesis.
Corroborating this trend is the virtual
disappearance of boiling points as part of physical characterizations in the
chemical literature.
Finally, as the
catalogs of suppliers of chemical intermediates become thicker, more of the products of early steps in syntheses can simply be purchased. It is these lower molecular
weight entities that formerly were prepared and distilled in the lab.
Standard
distillation has an inherent problem that became a further reason for the substantial abandonment of distillation from the laboratory. Unless a small-scale distillation column receives an input of
heat supplied by vigorously boiling the liquid
mixture in the still pot, it cannot achieve liquid-vapor equilibrium. Thus, on
the lab scale, there is a hold-up of distillate that is inevitably lost and this
can be up to 30%. Compounding this inherent difficulty is the annoyance
that all glass laboratory distillation equipment is expensive and does not
easily accommodate the particular amount of crude that you may have. That is,
the amount of crude distillate must be selected to fit the size of the physical
assembly that you have and not the other way around. Fractional distillation
assemblies are not available in your lab drawer in 100 ml, 200 ml, 500 ml, 1L, 5L, and 15L sizes like round bottom flasks are!
The days when
distillation units were patched together with hardened cork or rubber stoppers
between pieces of blown glass are long past. Now all glass assemblies are a
single piece or pieces joined with ground glass joints.
Because of this, now more than ever,
distillation assemblies for vacuum distillation often use the same equipment as
for simple distillation and lab workers don’t appreciate the special requirements imposed
by the low-pressure condition. The boiling point of
the fluid mixture in the still pot of a distilling assembly depends upon the pressure at the surface of the liquid, not the pressure recorded on a pressure
gauge, which may be, and usually is, closer to the vacuum pump. For pressures from
760 mm down to 15 mm of mercury, a regular distillation flask is satisfactory.
For pressures below this level, and particularly pressures 2 mm or less, the
diameter and location of the vapor port linking the distillation portion of
the apparatus to the condensing portion become very important. This is not
usually understood.
The increment in
vapor pressure at the surface of the boiling liquid, over and above the vacuum
pressure reading taken at the receiver is proportional to the length and
inversely proportional to the fourth power of the diameter in centimeters of
that sidearm plus any other narrow portion of the path between still pot and
condenser.
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