Introduction

A substantial number of the unit operations of chemical engineering are concerned with the
problem of changing the compositions of solutions and mixtures through methods not necessarily
involving chemical reactions. Usually these operations are directed toward separating a
substance into its component parts. For mixtures, such separations may be entirely mechanical,
e.g., the filtration of a solid from a suspension in a liquid, the classification of a solid into
fractions of different particle size by screening, or the separation of particles of a ground solid
according to their density. On the other hand, if the operations involve changes in composition of
solutions, they are known as the mass-transfer operations.

The importance of these operations is profound. There is scarcely any chemical process which
does not require a preliminary purification of raw materials or final separation of products from
by-products, and for these the mass-transfer operations are usually used.

Frequently the major part of the cost of a process is that for the separations. These separation or
purification costs depend directly upon the ratio of final to initial concentration of the separated
substances, and if this ratio is large, the product costs are large.

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The mass-transfer operations are characterized by transfer of a substance through another on a
molecular scale. For example, when water evaporates from a pool into an airstream flowing over
the water surface, molecules of water vapor diffuse through those of the air at the surface into the
main portion of the airstream, whence they are carried away. It is not bulk movement as a result
of a “pressure difference, as in pumping a liquid through a pipe.

In the problems at hand, the mass transfer is a result of a concentration difference, or gradient,
the diffusing substance moving from a place of high to one of low concentration.

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 CLASSIFICATION OF THE MASS-TRANSFER OPERATIONS

Direct Contact of Two Immiscible Phases

This category is by far the most important of all and includes the bulk of the mass-transfer
operations. Here we take advantage of the fact that in a two-phase system of several components
at equilibrium, with few exceptions the compositions of the phases are different. The various
components, in other words, are differently distributed between the phases.
In some instances, the separation thus afforded leads immediately to a pure substance because
one of the phases at equilibrium contains only one constituent. For example, the equilibrium
vapor in contact with a liquid aqueous salt solution contains no salt regardless of the
concentration of the liquid. Similarly the equilibrium solid in contact with such a liquid salt
solution is either pure water or pure salt depending upon which side of the eutectic composition
the liquid happens to be. Starting with the liquid solution, one can then obtain a complete
separation by boiling off the water. Alternatively, pure salt or pure water can be produced by
partly freezing the solution; or, in principle at least, both can be obtained pure by complete
solidification followed by mechanical separation of the eutectic mixture of crystals.

In cases like these, when the two phases are first formed, they are immediately at their final
equilibrium compositions, and the establishment of equilibrium is not a time - dependent
process. Such separations, with one exception, are not normally considered to be among the
mass-transfer operations.

In the mass-transfer operations, neither equilibrium phase consists of only one component.
Consequently when the two phases are initially contacted, they will not (except fortuitously) be
of equilibrium compositions. The system then attempts to reach equilibrium by a relatively slow
diffusive movement of the constituents, which transfer in part between the phases in the process.
Separations are therefore never complete, although, as will be shown, they can be brought as
near completion as desired (but not totally) by appropriate manipulations.

» The three states of aggregation, gas, liquid, and solid, permit six possibilities of phase contact.

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Gas-gas – Since with very few exceptions all gases are completely soluble in each other, this
category is not practically realized.
Gas-liquid If all components of the system distribute between the phases at equilibrium, the
operation is known as fractional distillation (or frequently just distillalion). In this instance the
gas phase is created from the liquid by application of heat; or conversely, the liquid is created
from the gas by removal of heat.

 For example, if a liquid solution of acetic acid and water is partially vaporized by
heating, it is found that the newly created vapor phase and the residual liquid both contain
acetic acid and water but in proportions at equilibrium which are different for the two
phases and different from those in the original solution. If the vapor and liquid are
separated mechanically from each other and the vapor condensed, two solutions, one
richer in acetic acid and the other richer in water, are obtained. In this way a certain
degree of separation of the original components has been accomplished.
 Both phases may be solutions, each containing, however, only one common component
(or group of components) which distributes between the phases. For example, if a
mixture of ammonia and air is contacted with liquid water, a large portion of the
ammonia, but essentially no air, will dissolve in the liquid and in this way the air-
ammonia mixture can be separated. The operation is known as gas absorption. On the
other hand, if air is brought into contact with an ammonia-water solution, some of the
ammonia leaves the liquid and enters the gas phase, an operation known as desorption or
stripping. The difference is purely in the direction of solute transfer.
 If the liquid phase is a pure liquid containing but one component while the gas contains
two or more, the operation is humidification or dehumidification, depending upon the
direction of transfer (this is the exception mentioned earlier). For example, contact of dry
air with liquid water results in evaporation of some water into the air (humidification
of the air). Conversely, contact of very moist air with pure liquid water may result in
condensation of part of the moisture in the air (dehumidification).
Gas-solid Classification of the operations in this category according to the number of
components which appear in the two phases is again convenient.

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 If a solid solution is partially vaporized without the appearance of a liquid phase, the
newly formed vapor phase and the residual solid each contains all the original
components, but in different proportions, and the operation is fractional sublimation.
 If a solid which is moistened with a volatile liquid is exposed to a relatively dry gasJ the
liquid leaves the solid and diffuses into the gas, an operation generally known as drying,
sometimes as desorption.
 If the diffusion takes place in the opposite direction, the operation is known as
adsorption. For example, if a mixture of water vapor and air is brought into contact with
activated silica gel, the water vapor diffuses to the solid, which retains it strongly, and the
air is thus dried.
o In other instances, a gas mixture may contain several components each of which is
adsorbed on a solid but to different extents (fractional adsorption). For example, if
a mixture of propane and propylene gases are brought into contact with activated
carbon, the two hydrocarbons are both adsorbed, but to different extents, thus
leading to a separation of the gas mixture.