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1.

Definitions and principles of mass transfer
A great number of the unit operations of environmental 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 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, with
which we are primarily concerned. 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. In the mass transfer operations, mass or chemical component(s)
stream through the common boundary of phases by direct contact of two immiscible phases.
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.

1.1.

Classification of the mass transfer operations

Diffusion processes may carry out between solid-, liquid- and gas phases. The three phases
permit six possibilities of phase contact. From the six possibilities the gas-gas and solid-solid
processes are eliminated, since all gases completely soluble in each order, and the rate of
diffusion within solid phases extraordinarily slow.
1.1.1. Vapor-liquid processes
In the vapor-liquid processes all components of the system distribute between the phases at
equilibrium, the operation is known as distillation. In this case the gas phase is created from
the liquid by application of heat, or conversely, the liquid is created from the vapor by
removal of heat. For example, if a liquid solution of alcohol and water is partially vaporized
by heating, it is found that the newly created vapor phase and the residual liquid both contain
alcohol 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 alcohol
and the other richer in water, are obtained. In this way a certain degree of separation of the
original components has been accomplished.

A simple example if an acetone-water solution is shaken in a separatory funnel with carbon tetrachloride and the liquids allowed to settle. The difference is purely in the direction of solute transfer.4. sometimes as desorption. which retains it strongly. 1. Gas-solid processes Classification of the operations in this category according to the number of components which appear in the two phases is again convenient. The operation is known as gas absorption. thus leading to a separation of the gas mixture. Not all components may be present in both phases. Such an operation is known as fractional extraction. both acetone and acetic acid will be found in both liquid phases. For example. the liquid leaves the solid and diffuses into the gas. if a mixture of petrol vapor and air is brought into contact with activated carbon. we have the operation . each containing. a gas mixture may contain several components each of which is adsorbed on a solid but to different extents. from the solid to the gas phase. For example. and we get clean air. In other instances. fractional adsorption. In this case.1. the operation is known as adsorption. a solution of acetic acid and acetone can be separated by adding it to the insoluble mixture of water and carbon tetrachloride. however. if a mixture of ammonia and air is contacted with liquid water.1. On the other hand. Liquid-liquid processes Separations involving the contact of two insoluble liquid phases are known as liquidextraction operations. For example.1. will dissolve in the liquid and in this way the air-ammonia mixture can be separated. if air is brought into contact with an ammonia-water solution. an operation generally known as drying. As another possibility. Liquid-solid processes When all the constituents are present in both phases at equilibrium. a large portion of the acetone will be found in the carbon tetrachloride rich phase and will thus have been separated from the water. If the diffusion takes place in the opposite direction.1. of course. only one common component or group of components which distributes between the phases. an operation known as desorption or stripping. the diffusion is.5. but to different extents. the petrol vapor diffuses to the solid. if a mixture of propane and propylene gases is brought into contact with activated carbon.2.1. A small amount of the water will also have been dissolved by the carbon tetrachloride. the two hydrocarbons are both adsorbed. 1. but in different proportions. however.3. and a small amount of the latter will have entered the water layer. but these effects are relatively minor. but essentially no air. Gas-liquid processes In the gas-liquid process both phases may be solutions. After shaking and settling. 1. some of the ammonia leaves the liquid and enters the gas phase. if a solid which is moistened with a volatile liquid is exposed to a relatively dry gas. a large portion of the ammonia.

These mass-transfer processes are frequently used in the environmental protection too. as in processes for recovering vegetable oils wherein expression is followed by leaching. If the diffusion is in the opposite direction. Selective solution of a component from a solid mixture by a liquid solvent is known as leaching. while mass transfer methods usually permit its eventual recovery in unaltered form without great difficulty. A vapor can be removed from a mixture with a permanent gas by the mechanical operation of compression or by the mass-transfer operations of gas absorption or adsorption. the necessity for making a decision nevertheless almost always exists. and as examples we cite the leaching of gold from its ores by cyanide solutions and of sunflower oil from the seeds by hexane. 1. 1. While the choice is usually limited by the peculiar physical characteristics of the materials to be handled. from the solid to the liquid phase. A liquid solution of acetic acid may be separated by distillation. by adsorption. . of course. For example. (sometimes also as solvent extraction). Chemical methods ordinarily destroy the substance removed. especially where the former are incomplete. it may be possible to use either the mass-transfer operation of leaching with a solvent or the purely mechanical methods of flotation. There are also choices to be made within the mass-transfer operations. while if removed by diffusion methods it is associated with another substance. whereupon the colored substances are retained on the surface of the solid carbon. or by adsorption with a suitable adsorbent. Water can be removed from an ethanol-water solution either by causing it to react with unslaked lime or by special methods of distillation. by liquid extraction with a suitable solvent. or solid-liquid extraction. A gas pollutant can be removed from air by adsorption or absorption. Sometimes both mechanical and mass-transfer operations are used.of fractional crystallization. Thus. Vegetable oils can be separated from the seeds in which they occur by expression or by leaching with a solvent.2. a gaseous mixture of oxygen and nitrogen may be separated by preferential adsorption of the oxygen on activated carbon. Methods of mass transfer operations Mass transfer operations may be classified into two main groups. for example.3. Hydrogen sulfide can be separated from other gases either by absorption in a liquid solvent with or without simultaneous chemical reaction or by chemical reaction with ferric oxide. Choice of separation method The engineer faced with the problem of separating the components of a solution must ordinarily choose from several possible methods. Cases where the phases are solutions (or mixtures) containing but one common component occur more frequently. in the separation of a desired mineral from its ore. The diffusion is. One can also frequently choose between a purely mass-transfer operation and a chemical reaction or a combination of both. or by distillation. the colored material which contaminates impure cane sugar solutions can be removed by contacting the liquid solutions with activated carbon. the operation is known as adsorption. It is characteristic that at the end of the operation the substance removed by mechanical methods is pure. For example. batch and continuous processes.

2.g. or conditions of temperature or pressure. indeed.3. This may result from changes in concentrations of feed materials. stage is defined as one where the effluent phases are in equilibrium. the equilibrium. For separations requiring greater concentration changes. invariable flow of all phases into and out of the apparatus. batch operations are always of the unsteady-state type. one phase is stationary while the other flows continuously in and out of the apparatus.1. such an assemblage is called a cascade. and unchanging conditions of temperature and pressure. intimate contact throughout. The essential difference between stagewise and continuous-contact operation can be . without repeated physical separation and recontacting. a persistence of the flow system within the apparatus. However. Stagewise operation If two insoluble phases are first allowed to come into contact so that the various diffusing substances can distribute themselves between the phases.2.. In any case. flow rates. This requires continuous. constant concentrations of the feed streams.. or theoretical. Equilibrium between two phases at any position in the equipment is never established. the entire operation and the equipment required to carry it out are said to constitute one stage.3. Continuous stationary operation It is characteristic of stationary operation (or steady-state operation) that concentrations at any position in the process remain constant with passage of time.3. which carries away the vaporized moisture until the solid is dry. the result would be equivalent to the effect of an infinite number of stages. should equilibrium occur anywhere in the system.g. 1. In order to establish a standard for the measurement of performance. In semibatch operations. Batch operation It is characteristic of instationary-state (or unsteady-state) operation that concentrations at any point in the process change with time. Continuous contact operation In this case the phases flow through the equipment in continuously. all the phases are stationary from a point of view outside the apparatus. the operation can be carried on in continuous fashion (steady-state) or in batchwise fashion (unsteady state). the case of a drier where a quantity of wet solid is contacted continuously with fresh air. so that a longer time of contact will bring about no additional change of composition.2.3.1. a series of stages can be arranged so that the phases flow through the assembled stages from one to the other. 1.1. i. no flow in or out. As an example. 1. even though there may be relative motion within. Direction of flow phases inside a cascade may be crosscurrent or countercurrent. The nature of the method requires the operation to be either semi batch or steady-state.2. e. in countercurrent flow. In purely batch operations. The approach to equilibrium realized in any stage is then defined as the stage of efficiency.e. e. The well known laboratory extraction procedure of shaking a solution with an immiscible solvent is an example. and the resulting change in compositions may be equivalent to that given by a fraction of an ideal stage or by many stages. laboratory batch extraction in a separatory funnel. and if the phases are then mechanically separated. ideal..

1. or the equivalent quantity for a continuous contact device.1. Heat is necessary for the production of any temperature changes. and the energy requirements.summarized.2. 1.4. 1. equilibrium is established.4. on the other hand. Energy requirements Heat and mechanical energies are ordinarily required to carry out the diffusional operations. Time requirement In stagewise operations the time of contact is intimately connected with stage efficiency. for dispersing liquids and gases. Which method will be used depends to some extent on the stage efficiency that can be practically realized. where it leads to the determination of the cross-sectional area of the equipment. . Number of equilibrium stages In order to determine the number of equilibrium stages required in a cascade to bring about a specified degree of separation. the time of phase contact required. On the other hand. whereas for continuous contact equipment the time leads ultimately to the volume or length of the required device. It is important to recognize that. for the creation of new phases such as vaporization of a liquid. for a given degree of intimacy of contact of the phases. Material balances permit calculation of the relative quantities required of the various phases. in continuous contact operation the difference from equilibrium is deliberately maintained. Considerations of fluid dynamics establish the permissible flow rate. The rate of transfer additionally depends upon the physical properties of the phases as well as the flow system within the equipment.3. and for operating moving parts of machinery. the equilibrium characteristics of the system and material-balance calculations are required. may make the continuous contact methods more desirable for reasons of cost and certainty. after which no further diffusional flow occurs. Permissible flow rate This factor enters into consideration of semibatch and steady-state operations. In the case of the stagewise operation the diffusional flow of matter between the phases is allowed to reduce the concentration difference which causes the flow.4. the time of contact required is independent of the total quantity of the phases to be processed. and the rate of transfer of material between phases depends upon the difference from equilibrium which is maintained.4. the permissible rate of flow. 1. and the diffusional flow between the phases may continue without interruption.4. Mechanical energy is required for fluid and solid transport. If allowed to continue long enough. High stage efficiency can mean a relatively inexpensive plant and one whose performance can be reliably predicted.4. Low stage efficiency. General principles There are four major factors to be established for the diffusional operations: the number of equilibrium stages or their equivalent. The factors which help establish the time are several. 1. and material balances determine the absolute quantity of each of the streams required. The equilibrium characteristics of the system establish the ultimate concentrations possible. The rate of diffusion and the time then determine the stage efficiency realized in any particular situation.

. diffusional rates. material balances. consequently. since the equilibrium and fluid dynamics of the systems are most readily studied in such a grouping. vapor-liquid. In what follows. gas-liquid. liquid-liquid. solid-liquid and solid-fluid. requires us to deal with the equilibrium characteristics of the system. basic considerations of diffusion rates are discussed first and these are later applied to specific operations. The principal operations are divided into five categories.The ultimate design. depending upon the nature of the insoluble phases contacted.