UNIT OPERATIONS

The sixth consecutive Chemical Engineering Unit Operations Review is

presented on the following pages. Sixteen sections, the same ones ap-
pearing in our 1950 review, are represented in this appearance of the
annual feature.

The 1951 volunle of Industrial and Engineering Chemistry again will

carry in September and October, respectively, the fourth Unit Processes
and fifth Materials of Construction reviews. These also have become
established annual features of the publication since their first appear-
ance in 1948 and 1947.
THE EDlTORS

Molecular Stills Used in Pilot Manufacture of Distilled Monoglycerides

COURTESY DISTILLATION PRODUCTS INDUSTRIES

 ABSORPTION AND R. L. PIGFORD received his B.S. from Mississippi State College
HUMIDIFICATION (1938) and his M.S. and Ph.D. from the University of Illinois (1940
41 and 1942, respectively). Until August 1947 he was with Du Pont,
Wilmington, Del., where he engaged in research and plant design
problems in the field of diffusional operations. Since September
1947 he has been chairman of the department of chemical engi-
neering at the Cniversity of Delaware.

ADSORPTI0N B. L. HARRIS (born in Savannah, Ga., 1917) received his B.E.

(1938) and Ph.D. (1941) in chemical engineering a t The Johns
46
Hoplcins University. A t present he is assistant professor of chemi-
cal engineering a t The Johns Hoplrins University and a consultant
in the Office of the Chief, Chemical Corps, U. S. Army. He is e
member of the American Chemical Society and associate member
of the American Institute of Chemical Engineers.

CENTRIFUGATION JAMES 0. MALONEY is head of the department of chemical engi-

neering and director of the Research Foundation a t the University
55 of Kansas. He was born in St. Joseph, Mo., in 1915, and received
his B.S.(Ch.E.) from the University of Illinois in 1936 and his M.S.
and Ph.D. from The Pennsylvania State College in 1939 and 1941,
Maloney is a member of the American Chemical Society and the
American Institute of Chemical Engineers.

CRYSTALLIZATION C. S. GROVE, JR., professor of chemical engineering a t Syracuse

University, was born in Oneida, N. Y., in 1905. Grove holds the
58
following degrees: A.B., Lenoir Rhyne College, 1925; B.S. and
Ch.E., N. C. State College, 1928 and 1932; M.S., M.I.T., 1934; and
Ph.D., University of Minnesota, 1942. He is a member of the
American Chemical Society, American Institute of Chemical Engi-
neers, and American Society for Engineering Education.

JOSEPH B. GRAY (born in 1915 a t Annapolis, Rld.) teaches ehemi-

cal engineering a t Syracuse University. He received hi5 B.A. in
chemistry from St. John’s College (1936), and B.S. in gas engineer-
ing (1938) and Ph.D. in chemical engineering (1941) from The Johns
Hoplrins University. Gray is a member of the American Chemical
Society, American Institute of Chemical Engineers, Sigma Xi,
Gamma Alpha, Phi Lambda Upsilon, and Alpha Chi Sigma.

HIGH TEMPERATURE T. J. WALSH obtained his B.Ch.E. (1939) and M.Ch.E. (1941) from
DISTILLATION Rensselaer Polytechnic Institute and Ph.D. (1948) from Case Insti-
63 tute of Technology, where he is associate professor of chemical engi-
neering. Walsh is coholder ( w i t h R. E. Burk) of U. S. patent
(assigned t o Standard Oil of Ohio) ‘$Apparatus for Liquid Con-
tracting for Fractionating, etc.” He is a consulting chemical
engineer and a member of Alpha Chi Sigma.
 HIGH VACUUM I(. C. D. HICKMAN (born in London, 1896) studied a t the Royal
DISTILLATION College of Science and London University (B.S., Ph.D.). In 1950
68 Hickman, the inventor of the modern molecular still, received
a John Price Wetherill Medal for his work on molecular distillation,
particularly for his vitamin distillation work. He is a consultant
to Eastman Kodak Company and Arthur D. Little, Inc., and is a
member of the American Chemical Society.

DRYING SAMUEL J. FRIEDMAN joined the Du Pont staff in 1941. Much

of his time has been devoted to research and development work
70 in the fields of heat transfer and drying. He was born in Cleveland,
Ohio, in 1918 and educated a t Case Institute of Technology (B.S.
and M.S.). He is a licensed professional engineer and a member of
the American Chemical Society, American Institute of Chemical
Engineers, and the American Society of Mechanical Engineers.

EVAPORATION W. L. BADGER, author of “Heat Transfer and Evaporation” and

coauthor of ‘(Inorganic Chemical Technology” and “Elements of
75
Chemical Engineering,” was born in Minneapolis in 1886. He at-
tended the University of Minnesota, M.S., 1909. Badger is a con-
sulting chemical engineer and a member of the American Chemical
Society, American Institute of Chemical Engineers, and the Execu-
tive Committee on Heat Transfer of the National Research Council.

R. A. LINDSAY was born in Detroit in 1915; he attended the Uni-

versity of Michigan and obtained his B.S. in 1939 and M.S. in 1940.
Since 1941 he has worked with W. L. Badger on heat transfer and
evaporation at Dow Chemical Company and is now a t their main
office in Midland, Mich. With coauthors, Lindsay has published
several papers on heat transfer. He is a member of the American
Institute of Chemical Engineers.

SOLVENT EXTRACTION ROBERT E. TREYBAL (born 1915, New York) is professor of

79 chemical engineering a t New York University. He received his
B.S.Ch.E. (1935)and M.S. (1936)from New York University and his
Ph.D. (1942)from Columbia University. Treybal has published the
results of many researches in extraction, and a book entitled
“Liquid Extraction” is in preparation. He is a member of the
American Chemical Society and Sigma Xi.

FILTRATION SHELBY A. MILLER was born in Louisville, Ky., in 1914. He re-

ceived degrees of B.S. from the University of Louisville in 1935,
a5
and of Ph.D. from the University of Minnesota in 1944. His present
position is professor of chemical engineering, University of Kansas.
Miller is a licensed professional engineer and a member of the
American Chemical Society, American Institute of Chemical
Engineers, and the American Society for Engineering Education.

39
 FLUID DYNAMICS 3IAX LEVA (born 1913 near Ludwigshafen, Germany) is a con-
90 sulting chemical engineer. He studied a t the University of Cin-
cinnati (B.S.) and Carnegie Institute of Technology (M.S.). While
with the Bureau of Mines Leva directed research on fluid flow, heat
flow, and fluidization. He is a member of the American Chemical
Society, the American Institute of Chemical Engineers, and is a
registered professional engineer.

11UHRAY WEINTRAUB (born in New k’orli, 1918) received his l3.Y.

in chemical engineering from The Cooper Union Institute of
Technology. He spent four years with the chemical operations
rlirision of the Huntsville Arsenal and since 1945 has been engaged
in engineering research and process development with the Bureau
of htines. Weintraub is a memher of the American Chemical
Society and American Institute of Chemical Engineers.

HEAT TRANSFER GEOHGE T. SKAPERDAS (born in New York C i t y in 1914) studied

chemical engineering at McGill University (B.Eng., 1936) and at
99 RIassachusetts Institute of Technology (S.M., 1938 and Sc.D., 1940).
He is now working on process and equipment development and
design with The R.1. W. Kellogg Company, New York, N . Y. Slia-
perdas is a member of the American Chemical Society, American
Institute of Chemical Engineers, and Sigma Xi.

BON EXCHANGE ROBERT ICLNIN (born in West New York, N. J., in 1918) recei.red
his B.S. (1939) and Ph.D. (1942) from Kutgers University. M e
102 supervises research and development of ion exchange resins for the
Resinous Product Division, Rohni & Haas Company. Kunin spent
two years as research chemist for TVA, a year a t Mellon Institute
on the Petroleum Refining Fellowship, and two years during the
war on the Manhattan Project a t Columbia University.

MATERIALSHANDLING ROBERT E. WRIGHT (born in Oconto, Wis., 1917) received his

B.S.3I.E. from the Cniversity of Wisconsin in 1940. Since then he
108
has been with Monsanto Chemical Company, working on design
and construction of chemical plants. Wright is a contributing
editor of Industrial and Engineering Chemistry on the subject
of materials handling. He is a memher of the American Society
of Mechanical Engineers and is a registered professional engineer.

MIXING .J. IIENHY RL SHTON, professor of chemical engineering is

director of the department a t Illinois Institute of Technology and
111
director of research for Mixing Equipment Company, Rochester,
N. Y. He attended the University of Pennsylvania (B.S. and
Ph.D.). Rushton is the author of numerous scientific articles.
He is a member of the American Chemical Society, American
Institute of Chemical Engineers, and Society of Chemical Industry.

SIZE REDUCTION LlNCOLN T. WORK (born 1898, Hartford, Conn.) received his A.B.,
Ch.E., and Ph.D. degrees from Columbia University. Early in
114
1949 Work resigned as director of research a t Metal & Thermit
Corporation to engage in private consulting work. He is a consult-
ing engineer and his offices are with Singmaster and Bre5er.
Work was chairman of the Division of Industrial and Engineering
Chemistry of the American Chemical Society for 1950.
 ABSORPTION AND
H U MID IFlCATlON
ROBERT L. PIGFORD
UNIVERSITY O F DELAWARE, NEWARK, DEL.
Theoretical articles on absorption have appeared more frequently during the past year
than reports of equipment performance) most of the useful performance data were presented at
the American Chemical Society’s Symposium on Absorption and Extraction. Experimental
’”
and theoretical studies of molecular diffusion have been published frequently.
P
UBLISHED research in this field included a series of papers
.. given a t the Christmas Symposium on Absorption and Ex-
traction, held by the AMERICAN CHEMICAL SOCIETY’S Division
of Industrial and Engineering Chemistry in Columbus, Ohio.
Papers on thgoretical subjects have been more numerous, how-
ever, than those dealing with operating characteristics of ab-
sorbers.
Existing performance data for cooling towers and humidifica-
tion equipment were summarized in the new, third edition of
Perry’s “Chemical Engineers’ Handbook” (70) in a completely
revised section by Hillen, Carrier, and De Flon. Little attention
is devoted to the theory of this equipment; the section is dis-
tinguished by the ease of application of data by means of align-
ment charts and graphs. A similar treatment is included in the
new, twelfth edition of Kent’s (‘Mechanical Engineers’ Hand-
book” (79). Sections 8 and 10 of Perry’s book (70)are new and
present for the iirst time in a handbook a summary of the general
principles of the several diffusional unit operations as well as an
up-to-date summary of design methods and data applicable t o
absorbers.
Van Krevelen (53) reviewed the subject of gas absorption in
general, summarizing his own previously published data as well
as some of the older American data.
DIFFUSION THEORY
Hirschfelder, Bird, and Spotz (43)gave an excellent discussion
of the new formulas which they have developed for computing
transport properties of gases and gas mixtures, including diffu-
sion coefficients. The simplest form of the gas kinetic theory was
based on the assumption of no forces acting between neighboring
molecules and led to an equation relating the diffusion coefficient
t o the temperature, pressure, molecular weights, and molecular
sizes. The familiar formula of Gilliland (33) is a semiempirical
modification of these simplest theoretical results. Hirschfelder,
et al. (43) have assumed that the repulsive and attractive forces
between adjacent molecules correspond to potential energies
x varying as the inverse twelfth and sixth powers of the distances
between centers, respectively, and have developed formulas in
which the simple 3/2 power of the absolute temperature is re-
placed by a tabulated function involving the interaction energy.
This quantity and the molecular size can be estimated from em-
pirical equations. The formulas apply only t o pairs of nonpolar
gases. m e r e applicable, the value of D probably can be corn-
puted as accurately as it can be measured, a t least a t high tem-
peratures. Winter (98) has compared Hirschfelder’s equation
with experimental data f r o q the literature and has concluded
that the agreement is good, with respect t o both actual values
and the temperature dependence of the diffusion coefficient.
Starting with Maxwell’s concept of a resistance to gaseous
41
diffusion proportional to the relative
velocities of molecules, Wilke (97)
showed that the appropriate average
diffusion coefficient for the diffusion
of a single component, A , through a
stagnant mixture of two or more
components is the harmonic mean of the diffusion coefficients of
A with each of the stagnant components, weighed with respect to
the mole fraction of the A-free mixture. Methods for calculating
rates of simultaneous diffusion of two components through a
third stagnant component have been available since the integra-
tion of the kinetic equation by Gilliland (34). The resulting
equations, though theoretically accurate, are nevertheless very
tedious to use for computation. Wilke (97) has proposed an ap-
proximate method of handling this problem, which is much simpler
t o use and gives good agreement with the exact method.
Fairbanks and Wilke (87) measured the diffusion coefficients
of organic vapors through binary mixtures of inert gases. The
experimental method is a new one and was suggested by Arnold’s
( 8 ) mathematical treatment of diffusion into a semi-infinite me-
dium. The effect of the ratio of the inert components in the
vapor on the diffusivity was experimentally in agreement with
the theory developed by Wilke (97) on the basis of the classical
diffusion theory. New data were reported (42)for the diffusion
coefficients of water vapor through hydrogen-nitrogen mixtures.
Birks and Bradley (7)determined the diffusion coefficient of
di-n-butyl phthalate in air, hydrogen, and Freon-12 by measuring
the rates of evaporation of small droplets. Bradley and Shellard
(9) made similar mwurementa in air for droplets of n-C16H3,,
n-C~,Hse, and n-ClsH38. The “wet-bulb depreasion” was deter-
mined in these testa by finding the air temperature a t which the
drops solidified. Diffusivities of about 40 organic vapors in air,
carbon dioxide, O r hydrogen were compared (66)with the Gilli-
land formula, which required a small correction. Diffusion CO-
efficient8Of acetone, benzene, methanol, and carbon tetrachloride
in air were d&~mined by a new method ($3).
TrevoY and n h k a m e r (91) determined liquid-phase diffusion
coefficients for Pairs of hydrocarbons. Eyring’s and Einstein’s
equations for diffusivity did not agree with data, but good agree-
ment was obtained with the empirical equations of Arnold ( 2 ) .
Yang (99) gave a difficult mathematical treatment of the
kinetic theory of diffusion in gases and liquids.
Hartley and Crank ($9) discussed binary diffusion in liquids
when the diffuaivity varies with the concentration and there is
a change in VOhme on mixing. The net rate of transfer is the
result of t ~ a n s f e rby Pure diffusion coupled with transfer due
to ~ m flow~ sof the whole solution. Similar problems in which
the diffusion coefficient is a function of concentration are con-
sidered mathematically by Crank and Henry (18). Calculated
Cams correspond to linear, exponential, and logarithmic relations
between D and concentration, and the results are generalized
in an approximate f d i o n to apply to any kind of relationship
between these quantities. Jest (60)also discussed solutions of
the differential equation for diffusion involving a concentration-
dependent D,including cases involving transfer across a phase
boundary.
42 INDUSTRIAL AND ENGINEERING CHEMISTRY
The mathematical problem of the convective transfer of mass
khrough the boundary layer which forms on a smooth, flat plate
parallel to which a fluid flows was solved many years ago by
Pohlhausen ( 7 I ) , but his results were limited to cases of vanish-
ingly small diffusion rates, because he assumed no influence of
*he diffusive mass transfer on the flow pattern inside the bound-
a r y layer. Eckert and Lieblein (26) have now calculated the
mutual influence of diffusion and convective flow on the velocity
and partial pressure profiles in a gaseous boundary layer. The
thickness of the boundary layer was found to increase in propor-
tion to the square root of the distance from the leading edge,
just as when diffusion is absent, but the skin friction, the mass
transfer coefficient, and the actual thickness of the boundary layer
are all affected by condensation on, or evaporation from, the
surface. Sample calculations are given for the system water-air.
The results are limited in general to pairs of substances which
do not differ greatly in molecular weight.
Pasquill (69) made an experimental study of turbulent transfer
of water vapor and heat in the lower atmosphere over level grass-
land. He concluded that when the temperature gradient corre-
sponds to neutral stability of the air the eddy diffusivities for
momentum and mass are equal. The eddy thermometric diffu-
isivity was greater than the eddy diffusion coefficient in an unstable
atmosphere (warmer a t ground level), but the two were equal
when the air was thermally stable.
Davies (22) discussed the mathematical calculation of evapora-
tion rates from a flat surface, above which the eddy diffusivity
has different values in the lateral and vertical directions.
G A S SOLUBILITIES
Solubilities of methane, ethylene, ethane, oxygen, and nitro-
gen in water a t 25" * 0.1" C. were measured by h4orrison (66),
using a continuous-flow absorber rather than the batch absorp-
tion technique which has been used frequently since Ostwald
first introduced it many years ago. The continuous method gave
slightly lower solubilities than are reported in standard tables,
but are believed by the author to be reliable. Culberson et al.
(19) determined the solubility of ethane in water a t pressures to
1200 pounds per square inch and temperatures from 100" to
840" F.
Data were reported for the solubility of chlorine in n-perfluoro-
heptane (SB),and oxygen in various organic liquids (75). Equilib-
rium vapor pressures of water over various aqueous salt solutions
were discussed by Stokes (87) and by Carr ( I S ) for use in main-
taining controlled humidities a t 25" and 90' C.
Accurate thermodynamic properties of dry and saturated air,
including enthalpy, were summarized by Goff ( S 7 ) , acting for a
committee of the American Society of Heating and Ventilating
Engineers. The chemical potentials of the several constituents
were calculated a t zero pressure by statistical mechanical methods
and the equation of state for air was used to correct the zero-
pressure properties t o finite pressures. Calculations for water-
saturated air involved the interaction constants between dry air
and water vapor. At room temperature the enthalpy is now
knotvn to a precision of *0.06%. Based on these thermodynamic
data Xottage (67') constructed a humidity chart using an oblique
enthalpy scale and an absolute humidity scale as coordinates.
The chart resembles others currently in use.
RATES OF M A S S TRANSFER A T SIMPLE SURFACES
New data were presented (62) on the rates of evaporation of
liquids into gas streams having the normal degree of turbulence
and also into streams in which extra turbulence was promoted by
forcing the gas through perforated plates. Without extra tur-
bulence the values of the mass transfer j-factor mere found to
agree remarkably well with data from the literature on mass
transfer, heat transfer, and friction. A twofold change in the
scale of turbulence had no effect, but an increase in the intensity
Vol. 43, No. 1
of turbulence from the normal level of about 4 to 24% caused the
rate of mass transfer to increase by as much as 50% at low
Reynolds numbers and by smaller amounts a t larger Reynolds
numbers. In a Dutch investigation (24) a 50% increase in the
rate of evaporation of water from blotting paper into air was
found when 5% turbulence was present.
Rossler (77) considered the transfer of heat from a hot gas to a
wet surface and developed an empirical equation for the influence
of mass transfer on the heat transfer coefficient. The result
should be applicable to "film" or "sweat" cooling operations, as
well as to webbulb measurements, and should be in agreement
with the Drew-Colburn theory (96).
The influence of surface layers of paraffin oil and benzene on
the rate of absorption of oxygen by water was investigated (81).
Only the paraffi oil was found to reduce the absorption rate.
I n order to explore the effect of the Schmidt group on mass
transfer in turbulent flow, data were obtained by Linton and
Sherwood (59) on the rate of solution in water of cast tubes,
cylinders, plates, and spheres of benzoic acid, cinnamic acid, and
2-naphthol. The diffusion coefficients of these solutes are so
small that the Schmidt numbers were in the range 900 to 2400.
The well-known Leveque equation was verified in the streamline
region for flow inside tubes and the empirical Chilton-Colburn
relation was confirmed approximately in the turbulent range for
all the shapes. According to this relationship, the rate of mass
transfer is proportional to the 2/3 power of the diffusivity,
rather than to the f i s t power, vhich might be expected for these
conditions if there were an undisturbed laminar film at the tube
wall. Following a suggestion of Lin (58),the authors pointed out
that the turbulent currents from the transition zone may prop-
agate sidewise into the laminar layer, causing the effective dif-
fusivity there to be a little higher than expected. The effect
would be very noticeable under the experimental conditions,
where the laminar layer accounted for all the diffusional resist-
ance.
Rates of mass transfer in a wetted-wall apparatus operated
both as a distillation column and as an absorber, were found (47)
to be in agreement with the Chilton and Colburn modification of
Reynolds' analogy and were about 10 to 25% smaller than the
often quoted data of Gilliland and Sherwood (36). Samples of
the liquid reflux were taken at 1-foot intervals along the appara-
tus in order to permit estimation of local values of the height of a
transfer unit. These were found to depend on the liquid com-
position in a peculiar way which was not explained, but which was
someffhat similar to an effect reported previously by Storrow
(88).
Ternovskaya and BelopolskiI (90) showed experimentally,
using a wetted-wall column for absorbing sulfur dioxide in water,
that the rate of absorption decreased when a surface-active agent
was dissolved in the water. The flow of pure water down the
vertical surface occurred with waves on the surface, whereas no
waves were present when sulfonated organic compounds were
dissolved in the water.
The temperature of small water drops was measured (48)as
they evaporated into air. The drops hung from thermocouple
wires ranging in diameter from 127 to 24 microns; an extrapola-
tion was made to zero wire size to eliminate the influence of ther-
mal conduction along the wire. The psychrometric constant for
a small drop is different from that for a wet thermometer bulb.
Higbie's data (41) on unsteady-state absorption of carbon di-
oxide by water were used by Danckwerts ( 9 0 ) in a new approach
to the kinetics of absorption. According to the data, the amount
of carbon dioxide absorbed during the first few hundredths of a
second of contact was less than would be expected from the usual
diffusion theory, which assumes equilibrium at the interface.
Danckwerts (20) found that the data agree with kinetic theory if
i t is assumed that only 4 X 10-8 of the carbon dioxide molecules
striking the liquid surface from the gas are absorbed, the re-
mainder being reflected back into the gas. The reflection coeffi-
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY
cient could not be determined accurately, however, owing to the
relatively large diffusional resistance in the liquid.
PERFORMANCE OF ABSORPTION EQUIPMENT
Tray Columns. Tray efficiencies for humidification of air and
other cases of predominating gas-film resistance have been re-
ported previously, and efficiencies of trays in which both resist-
ances are significant were published by Walter and Sherwood
(93)several years ago. New, more extensive data of the same
type have now been presented by Gerster, Colburn, Bonnet,
and Carmody (3,9),based on tests with a tray 13 inches in diam-
eter having thirteen bubble caps 1.5 inches in diameter. Rates
of desorption of oxygen gave the required information on the re-
sistance of the liquid. Based on these single-film data, tray
efficiencies were estimated for an extractive distillation column
having trays of identical design and for distillation of methanol-
water mixtures in the extractive column. I n both cases satis-
factory agreement was obtained between prediction and experi-
ment. It seems probable that further advances in the analysis
* of tray efficiencies will be based on single-film data, which are
usually easier to obtain and more directly connected with the
mechanism of interphase transfer.
Dimensions of gas bubbles formed a t single orifices immersed
in various liquids and their rates of rise have been measured by
van Krevelen and Hoftijzer (64), who conclude that when the
bubbles are formed separately their diameter is independent of
gas rate and proportional to the orifice diameter. At higher
flow rates the bubbles leave the orifice so rapidly that they form
chains in the liquid. Here the bubble diameters increase with
increasing flow rate and are independent of orifice size.
Packed Columns. Additional mass transfer coefficients for
ammonia absorption in water were measured by Parsley, Mol-
stad, Cress, and Bauer (68), using ceramic drip-point grid pack-
ing. Gas-film coefficients calculated by subtracting liquid-film
resistances, measured by desorbing oxygen from water, from the
over-all resistances were more than twice as great as would be
expected from flow inside a smooth tube. The discrepancy was due
to the influence of entrance effects in the packing. For this pack-
ing the gas-film coefficient was independent of the liquid flow
rate, possibly owing to the fact that the total area of the grids is
wet, regardless of the liquid rate.
Rates of absorption of ethyl alcohol vapor from air in water
have been measured by Molstad and Parsley (64),using a column
filled with 1-inch rings, 1-inch saddles, or drip-point grids, all of
ceramic material. The resistance was principally in the gas
phase, and the observed over-all coefficients for rings and saddles
support the current theory that the resistance to absorption can
be predicted for an untried system from separate film coefficient
data for separate systems. Deviations from predicted behavior
a t low liquid rates were considered to result from differences in
the initial distribution on the packing. Data obtained with drip-
point grids in the same apparatus were not so satisfactorily in
agreement with predictions; the over-all coefficient was found to
vary considerably with the liquid rate, whereas ammonia absorp
tion data had shown no such variation.
2. Rates of evaporation of water into air in a small irrigated
packed column were measured by Weisman and Bonilla (94) and
were compared with similar rates observed by Gamson, Thodos,
and Hougen ( 3 1 )and by Taecker and Hougen (as),using porous,
completely wetted packing pieces to find the fractional effective
surface area of the irrigated packing. Only 4 t o 25% of the sur-
face was effective for mass transfer and 13 to 42% for simultane-
ous heat transfer. The dry part of the surface is capable of trans-
ferring heat but not mass.
The effect of molecular diffusivity in the gas phase on the gas-
film transfer coefficient has been in doubt for packed towers
since 1940, when it was reported (83)that the effect was much
smaller than the 'J/8 power generally accepted for wetted-wall
43
columns. After comparing data taken with ammonia, acetone,
methanol, and ethanol in the same column, Houston and Walker
(4.6)were not able to reach definite conclusions, though the effect
was approximated by the */a power of D a t water rates below 2000
pounds/(hour)(sq. feet). Other data (78) taken in the same
laboratory and published a t the same time show that the effect of
D on rates of vaporization of different liquids into air corresponds
to only the 0.15 power. Gaffney and Drew (SO) found that the
exponent on the diffusivity should be 0.58 when organic solvents
or water are used to dissolve pellets of solid organic acids in packed
towers. The exponent was firmly established in this case because
of the large range of the Schmidt group covered (159 to 13,300).
Fujita ($9) studied various literature data on packed columns
and came to the conclusion that molecular diffusion is of negli-
gible importance in the gas phase, owing to the intense turbulence
which is present. No attempt has been made to explain t h e
discordant results obtained by the different investigators.
Mass transfer within the fluid stream which flows through a
packed bed takes place by a turbulent mechanism, as brought
out by an experimental study reported by Bernard and Wilhelm
(6). Diffusion from a point source located within the packing
was studied by measuring tbe rate of spread of carbon dioxide re-
leased into air or dye released into water. At low Reynolds
numbers and for large packing particles, eddy diffusion was
found to be influenced by the tube diameter and was produced
by eddies larger than the particles of packing. At higher flow
rates, however, and for small ratios of packing size to tube
diameter the turbulence was interstitial in character, the scale
being approximately proportional to the packing size and the!
intensity to the superficial velocity.
Studies of over 500 cooling towers in the Pacific Coast and
mid-continent regions indicated that the presence of sodium
carbonate in the water was a primary factor in the delignification
and consequent mechanical weakening of the wood packing,
according to Blohm (8).
The Venturi scrubber is a relatively new device for removing
dusts from gases (14-16) by injecting water into the Venturi
throat, using the high-velocity gas for atomization. The Venturi
expansion section is attached to a cyclone, which collectsthe water
droplets. New data were obtained ( 4 9 ) for the efficiency of
sulfur dioxide absorption and humidification in experimental
equipment of this type. As many as 2 to 3 transfer units were
obtained for dust collection, corresponding to 90% removal;
a t the same water and gas rates the number of transfer units for
sulfur dioxide absorption and for humidification were, respec-
tively, 1.4 and 3.3 times greater. In each case the number of
transfer units was proportional to the number of square feet of
drop surface area produced per cubic foot of gas. The pressure
drop required was greater than that not recovered across a Ven-
turi, owing to the momentum imparted to the liquid spray. One
throat velocity head was required to accelerate approximately ti
gallons of water per thousand aubic feet of gas. .
Data were given by Remy (74) for the absorption of sulfuric
acid fogs.
Liquid-Filled Tanks. Shulman and Molstad (84) contributed
a complete set of data for gas absorption and stripping in water-
filled gas-bubble columns. The apparatus was operated counter-
currently by forcing the gas through porous metal spargers in the
bottom of the column. The bubbles rose through the descending
water stream. At superficial gas velocities below 0.1 to 0.2
foot per second, true countercurrent action apparently was ob-
tained, but a t higher velocities the liquid tended to mix vertically,
having nearly the same composition throughout the vessel.
Values of HOLranged from about 0.3 to 3 feet a t 15" C., indicat-
ing that the mass transfer efficiency of gas-bubble apparatus is
equal in order of magnitude to that of packed towers. The
pressure drop is far greater, however, owing mainly to the liquid
head.
The mechanism of oxygen absorption by yeast and bacteria
 44 INDUSTRIAL AND ENGINEERING CHEMISTRY
dispersed in aerated nutrient broths in agitated vessels was
analyzed for the first time by Hixson and Gaden (44) and by
Bartholomew, Karow, Sfat, and Wilhelm (6). The oxygen is
transferred first across the interface separating gas bubbles and
liquid, then diffuses through the liquid and into the clusters of
organisms, and finally is absorbed by the cells. The first of these
steps had been investigated previously by Cooper, Fernstrom, and
Miller ( l 7 ) , whose results were extended and generally con-
firmed. The rate of absorption by the cells was independent of
the oxygen concentration a t the cell-liquid interface, provided
the concentration exceeded about gram mole of oxygen per
ml. During a fermentation experiment lasting 75 hours in a
5-liter vessel, the specific resistance of the cell-liquid interface
increased gradually as the reaction proceeded.
Pressure Drop and Flooding. Pressure drops accompanying
single-phase fluid flow through packed beds were studied by
Brownell et al. (IO). The authors’ new data on small clay saddles
and rings as well as on smooth and rough metal saddles and on
glass beads, and previously published data on small tower pack-
ings, were correlated with a maximum deviation of *24% and
an average deviation of *6% from a single friction factor curve
similar to that for flow inside smooth pipe. The method of allow-
ing for the influence of packing porosity differs from that em-
ployed in previous publications from the same laboratory ( I f )
and also from the methods in general use previously ( l a , 67, 78).
Rather than using a mathematical formula involving porosity,
Brownell et al. chose to give charts showing correction factors
which may be applied to the pipe Reynolds number and the
friction factor. The correction factors are functions of the
porosity, but are otherwise independent of particle roughness.
Pressure drop data for laboratory packed distillation columns
2 inches in diameter and smaller, filled with wire helices and
operated a t total reflux, were analyzed by Reed and Fenske ( 7 3 )
in terms of an equation similar to that of Carman ( 1 9 ) .
I n a study of flooding phenomena in a 3.75-inch liquid-liquid
extraction column filled with 0.5-inch Raschig rings Ballard and
Piret (4)found that the superficial velocities of the dispersed
organic liquid phase through the continuous water phase a t which
an increase in the size of the organic liquid droplets rising through
the packing was first observed could be correlated with the fluid
properties and packing dimensions. Previously published
flooding velocities of packed absorbers were found to agree ex-
cellently with the correlation of liquid-liquid transition veloci-
ties, even though the fluid properties applicable in gas-liquid
columns and in liquid-liquid columns have widely different
values.
Flooding velocities for countercurrent flow of water and air
in a wetted-wall column were determined by Fradkov ( d B ) , who
investigated the effects of liquid rate, tube diameter, and gas
pressure. A new formula was proposed ( 4 6 ) for calculating the
allowable vapor velocity in tray columns.
ABSORPTION ACCOMPANIED BY CHEMICAL REACTION
niggle and Tepe ( 7 6 ) studied the rate of absorption of chlorine
from nitrogen-chlorine mixtures in aqueous ferrous sulfate in a
tower 6 inches in diameter filled to a depth of 66 inches with 0.5-
inch ceramic Raschig rings, The solution selectively removes
chlorine from a gas also containing carbon dioxide and is there-
fore consumed less rapidly than an alkaline solution, which would
absorb both chlorine and carbon dioxide. The rates were low,
owing to the slowness of the liquid-phase reaction producing ferric
iron. T h e values of H O G varied directly with G and inversely
with L0.66, as might be expected for a case of limiting liquid-
phase resistance. At comparable conditjons, rates of absorption
in ferrous sulfate and in sodium carbonate were about equal.
T h e paper of Riggle and Tepe also contains previously unpub-
lished data of Vivian (96), for the absorption of chlorine in sodium
hydroxide solutions in a packed tower. The data are especially
Vol. 43, No. 1
noteworthy because this appears t o be one of the few experi-
mental cases of truly controlling gas-film resistance.
Simultaneous diffusion and first-order irreversible chemical
reaction in a semi-infinite liquid layer were considered mathe-
matically by Danckwerts ($I), who showed that the rate of solu-
tion depends both on the diffusion coefficient and on the reaction
rate constant. For a very rapid reaction the liquid-film absorp-
tion coefficient is shown to be independent of the time of exposure
of the liquid surface to the gas and is given by k~ = d D 2 , where
DL is the liquid diffusion coefficient and k is the first-order re-
action rate constant. When the chemical reaction involves a
second solute which is dissolved in the liquid and is depleted
appreciably by the reaction, the approximation of a pseudo-first-
order reaction is not justifiable. An expression for the rate of
solution w&s given by Danckwerts (11)for the case where the
rate of the chemical reaction is infinitely rapid and is controlled
by the rate of diffusion. The result shows that in this case the
liquid-film coefficient is a linear function of the concentration of
the dissolved reactant which is present initially in the liquid.
This result is in agreement with the experimental findings of
Stephens and Morris (86), and, except for a time factor, agrees
with the result of the steady-state zone theory of absorption and
reaction published by Hatta (40).
The mechanism of absorption of carbon dioxide by aqueous
alkaline solutions was discussed (38).
Reaction and simultaneous diffusion of chlorine into woo!
fibers were studied experimentally by rllexander, Gough, and
Hudson ( 1).
CALCULATION METHODS
.4 very clever and appealing graphical method for calculating
the changes in air humidity and temperature in air conditioning
equipment was presented by htickley ( 6 3 ) . The method eni-
ploys the specific enthalpy as a driving force acrms the gas film
and is therefore dependent on the assumption that the interfacial
areas for heat and mass transfer are equal, This is true for rc-
frigerated coil dehumidifiers, but apparently is not correct for
packed columns (60,94). Mickley’s method is an extension of the
“enthalpy potential” method originally proposed by Merkel ( 6 2 ) .
The new method permits the thermal resistance of the liquid
layer, the metal surface, and the refrigerant fdm to be allowed for.
Conditions leading to the formation of fog in the gas phase are
easily detected. The saturation curve need not be assumed to be
straight, as required in certain other methods (79).
The calculation of transfer units for countercurrent packed
columns is a simple matter when both the operating and the equi-
librium lines are straight, for in this case the average driving
force is the logarithmic mean. If either of the lines is curved,
the calculations must be made graphically, unless analytical
methods are employed which assume certain mathematical equa-
tions for expressing the curvature of the lines. White (96) pub-
lished such a method, which is similar to one previously suggested
by Scheibel and Othmer (80) in that it assumes the portion of the
equilibrium curve that lies underneath the operating line to be
represented by a parabola. By the new method the mean driving
force is calculated from the terminal and the central driving forcw
by means of a nomogram.
Tan Krevelen (59)rederived the familiar equation for composi-
tion change of a gas flowing through a countercurrent paclced
scrubber.
The transient behavior of countercurrent tray-type absorbers
and extractors was investigated mathematically by Lapidus and
Amundson ( 6 6 ) . Cross-flow operation was also studied. The
results are complex, but illustrative calculations were given for a
countercurrent absorber which is fed with a fat gas whose com-
position increases abruptly, changing from one steady value to
another one. The time required following the sudden disturb-
ance for the equipment to come within 1%of ita new equilibrium
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY
state corresponded to 2.5 changes in the total column holdup by
the liquid stream.
MISCELLANEOUS
Weller and Steiner (95) measured the permeabilities of several
thin polymeric films to oxygen, nitrogen, carbon dioxide, argon,
helium, and hydrogen, and concluded that the difference in the
rates of permeation may in some cases justify the use of a multi-
stage process of this type. T h e large degree of thermodynamic
irreversibility of the process makes the work required for pumping
the gas from stage to stage so great, however, that it would appear
unlikely that a fractional permeation process would be economi-
cally attractive unless standard methods of separation are not
‘ applicable. Rates of diffusion of organic vapors through poly-
meric films were found to be greater when the polymer and the
vapor molecules are chemically similar (86).
Rates of evaporation of water into air from fluidized particles of
silica gel and activated alumina were measured by Kettering,
Manderfield, and Smith (61). The resulting transfer coefficients
were computed from calculated curves of water partial pressure
“ 609 (1950).
versus position in the bed, u p to the point where the gas became
saturated. The heat and mass transfer coefficients are much
smaller than those for single, isolated particles of the same diam-
eter.
The composition changes accompanying simultaneous evapora-
tion of both components of a binary liquid mixture were meas-
ured by Mornick (65) and compared with the previously pub-
lished theory (8%). Excellent agreement was found.
NOMENCLATURE
D = diffusion coefficient, or diffusivity, sq. feet per hour
G = mass velocity of gas, pounds/(hour) (sq. foot)
L = mass velocity of li uid, pounds/(hour) (sq. foot)
HOQ = height of an over-&% gas-phase transfer unit, feet
HOL = height of an over-all liquid-phase transfer unit, feet
k~ = liquid-film absorption coefficient, pound mole/(hour)
(sq. foot)(pound mole/cu. foot)
LITERATURE CITED
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SOC.,45, 1109 (1949).
(2) Arnold, J. H., J . Am. Chem. Soc., 52, 3937 (1930).
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(1950).
(5) Bartholomew, W. H., Karow, E. O., Sfat, M. R., and Wilhelm,
R. H., Ibid., 42, 1801 (1950).
(6) Bernard, R. A., and Wilhelm, R. H., Chem. Eng. Progress, 46,
233 (1950).
(7) Birks, J., and Bradley, R. S., Proc. Roy. SOC.(London), A198,
226 (1949).
(8) Blohm, C. L., and Frazier, H. D., Oil Gas J., 48, No. 45, 72
(1950).
(9) Bradley, R. S., and Shellard, A. D., Proc. Roy. SOC.(London),
A198, 239 (1949).
(IO) Brownell, L. E., Dombrowski, H. S., and Dickey, C. A., Chem.
Eng. Progress, 46, 415 (1950).
(11) Brownell, L. E., and Kats, D. L., Ibid., 43, 537 (1947).
(12) Carman, P. C., Trans. Inst. Chem. Engrs. (London), 15, 150
(1947).
Ir (13) Carr, D. S., and Harris, B. L., IND.ENG.CHEM.,41, 2014 (1949).
(14) Collins, T. T., Jr., Paper I n d . Paper World, 28, No. 5, 685;
No. 6, 890; No. 7, 984 (1947).
(15) Collins, T. T., Jr., Seaborne, C. R., and Anthony, A. W., Jr.,
Paper Trade J.,124, No. 23,45 (June 5, 1947).
(16) Comings, E. W., Adams, C. H., and Shippee, E. D., IND.ENG.
CHEM.,40, 74 (1948).
(17) Cooper, C. M., Fernstrom, G. A,, and Miller, S. A., Ibid., 36,
504 (1944).
(18) Crank, J., and Henry, M. E., Trans. Faraday SOC.,45, 1119
(1949).
(19) Culberson, 0. L., Horn, A. B., and McKetta, J. J., Jr., Am.
Inst. Mining Met. Engrs., Tech. Pub. 2778; J. Petroleum
Technol., 2, No. 1, l(1950).
(20) Danckwerts, P. V., Research, 2, 494 (1949).
(21) Danckwerts, P. V., Trans. Faraday Soc., 46 300 (1950).
4s
(22) Davies, D. R., Proc. Roy. SOC.(London), A202, 96 (1950).
(23) Deryagin, B. V., Prokhorov, P. S., and Malkina, A. D., Zhur.
Fiz. Khim. (U.S.S.R.), 24, 503 (1950).
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Ingenieur (Utrecht), 61, No. 40, 25 (1949).
(25) Drew, T. B., and Colburn, A. P., Trans. Am. Inst. Chem. Engrs.,
33, 197 (1937).
(26) Eckert, E., and Lieblein, V., Forschung, 16, 33 (1949).
(27) Fairbanks, D. F., and Wilke, C. R., IND.ENG.CHEM.,42, 471
(1950).
(28) Fradkov, A. B., Zhur. Tech. Fiz., 17, 619 (1947).
(29) Fujita, S.,J. SOC.Chem. I n d . Japan, 44, Suppl. Binding, 255
(1941).
(30) Gaffney, B. J., and Drew, T. B., IND.ENG.CHEM.,42, 1120
(1950).
(31) Gamson, B. W., Thodos, G., and Hougen, 0. A,, Trans. Am.
Inst. Chem. Engrs., 39, 1 (1943).
(32) Gerster, J. A., Colburn, A. P., Bonnet, W. E., and Carmody,
T. W., Chern. Eng.Progress, 45, 717 (1949).
(33) Gilliland, E. R., IND. ENG.CHEM.,26, 681 (1934).
(34) Gilliland, E. R., Sherwood, T. K., “Absorption and Extraction,”
1st ed., New York, McGraw-Hill Book Co., 1937.
(35) Gilliland, E. R., and Sherwood, T. K., IND.ENG,CHEM.,26,
516 (1934).
(36) Gjaldbaek, J. C., and Hildebrand, J. H., J . Am. Chem. SOC.,72,
(37) Goff, J. A., Heating, Piping, A i r Conditioning, 21, No. 11, 118
(1949).
(38) Govinda Rau, M. A., and Chandrasekharan, K., Trans. Indian
Inst. Chem. Engrs., 1, 120 (1947-48).
(39) Hartley, G. D., and Crank, J., Trans. Faraday SOC.,45, 801
(1949).
(40) Hatta, S., Tech. Repts. T6haku I m p . Univ., 8, 1 (1928-29).
(41) Higbie, R., Trans. Am. Inst. Chem. Engrs., 31, 365 (1935).
(42) Hippenmeyer, B., Z . angew. Physik, 1,549 (1949).
(43) Hirschfelder, J. O., Bird, R. B., and Spots, E. L., Trans. Am.
SOC.Mech. Engrs., 71,921 (1949).
(44) Hixson, A. W., and Gaden, E. L., Jr., IND.ENG. CHEM.,42,
1792 (1950).
(45) Houston, R. W., and Walker, C. A,, Ibid., 42, 1105 (1950).
(46) Hwang, Pin-Wen, Bull. Chungking Inst. Ind. Research, No. 4
(1948).
(47) Jackson, M. L., and Ceaglske, N. H., IND.ENG. CHEM.,42,
1188 (1950).
(48) Johnson, J. C., J . Applied Phys., 21, 22 (1950).
(49) Johnstone, H. F., and Roberts, M. H., IND.ENG.CHEM.,41,
2417 (1949).
(50) Josc W.: 2. Physik, 127, 163 (1950).
(51) Kettering, K. N., Manderfield, E. L., and Smith, J. M., Chem.
Eng. Progress, 46, 139 (1950).
(52) Krevelen, D. W. van, Rec. trav. chim., 69, 503 (1950).
(53) Krevelen, D. W. van, Research, 3, 106 (1950).
(54) Krevelen, D. W. van, and Hoftijzer, P. J., Chem. Eng. Progress,
46, 29 (1950).
(55) Kuvshinskil, E. V., Zhur. Tekh. Fiz. (U.S.S.R.), 18, 909 (1948).
(56) Lapidus, L., and Amundson, N. R., IND. ENG.CHEM..42, 1071
(1950).
(57) Leva, M., Chem. Eng. Progress, 43, 549 (1947).
(58) Lin, C. C., Quart. Applied Math., 3, 293 (1946).
(59) Linton, W. H., and Sherwood, T. K., Chem. Eng. Progress, 46,
258 (1950).
(60) McAdsms, W. H., Pohlena, J. B., and St. John, R. C., Ibid.,
45, 241 (1949).
(61) Maisel, D. S,, and Sherwood, T. K., Ibid., 46, 131, 172 (1950).
(62) Merkel, F., 2.ges. Kalte-Id., 34,117 (1927).
(63) Mickley, H. S., Chem. Eng. Progress, 45, 739 (1949).
(64) Molstad, M. C., and Parsley, L. F., Jr., Ibid., 46, 20 (1950).
(65) Mornick, G. B., IND. ENG.CREM..41,2202 (1949).
(66) Morrison, T. J., and Billett, F., J. Chem. SOC.,1948, 2033.
(67) Nottage, H. B., Heating, Piping, A i r Conditioning, 22, No. 7,
121 (1950).
(68) Parsley, L. F., Molstad, M. C., Cress, H., and Bauer, L. G.,
Chem. Eng. Progress, 46,17 (1950).
(69) Pasquill, F., Proc. Roy. SOC.,A202, 96 (1960).
(70) Perry, J. H., “Chemical Engineers’ Handbook,” 3rd ed., Sec-
tions 8, 10, 12, New York, McGraw-Hill Book Co., 1950.
(71) Pohlhausen, L., Z . angew. Math. u. Mech., 1, 252 (1921).
(72) Purowsky, A. E.. and Dodge, B. F., IND. ENG.CHEM.,42, 1112
(1950).
(73) Reed, T. M., and Fenske, M. R., Ibid., 42, 654 (1950).
(74) Remy, H., Z . Ver. deut. Ing. Verfahrenslech., No. 2, 28 (1941).
(75) Reznikovski, M., Tarasova, e., and Dogadkin, B., J . Gen.
Chem. (U.S.S.R.),20, 63 (1950).
(76) Riggle, J. W., and Tepe, J. B., IND.ENG. CHEM.,42, 1036
(1950).
(77) Rossler, F., Natumuissenschaften, 35, 219 (1948).
46 INDUSTRIAL A N D ENGINEERING CHEMISTRY
(78) Rose, H. E., Proc. Inst. Mech. Enprs. (London), 153, 141 (1945).
(79) Salisbury, J. K., Power Volume of “Kent’s Mechanical Engi-
neers’ Handbook,” 12th ed., pp. 9-20 to 9-30,12-82 to 12-84,
New York, John Wiley & Sons, Inc., 1950.
(80) Scheibel, E. G., and Othmer, D. F., Trans. Am. Inst. Chem.
Engrs., 38, 339 (1942); IND. ENC.CHEM.,34, 1200 (1942).
(81) Schlapfer, P., Audykowski, T., and Bukowiecki, A., Schweiz.
Arch. angew. W i s s . u. Tech., 15, 308 (1949).
(82) Sherwood, T. K., “Absorption and Extraction,” p. 7, New
York, McGraw-Hill Book Co., 1937.
(83) Sherwood, T. K., and Holloway, F. A. L., Trans. Am. Inst.
Chem. Engrs., 36, 21 (1940).
(84) Shulman, H. L., and Molstad, M. C., IND.ENQ.CHEM.,42,
1058 (1950).
(85) Simrel, V. R., and Hershberger, A,, Modern Plastics, 27, N o . 10.
97, 98, 100, 102, 150-2, 154, 156, 158 (1950).
(86) Stephens, E. J., and Morris, G. A., paper presented at the
Montreal meetinn American Institute of Chemical En& =.-
news, September 1949.
Vol, 43, No. i
EKC. HEM,, 41, 2013
Stokes, R. H., and Robinson, R. A,, IND.
(1949).
Storrow, 3. A,, J . SOC.Chem. Ind., 66, 41, 73 (1937).
Taecker, R. G., and Hougen, 0. A., Chem. Eng. Progress, 45,188
(1949).
Ternovskaya, A. N., and Belopolskii, A. P., Zhur. Fiz. Khim.
(U.S.S.R.), 24,43 (1950).
Trevoy, D. J., and Drickamer, H. G., J . Chem. Phys., 17, 1117
(1949).
Vi;ian, J. E., Sc.D. thesis in chemical engineering, Massachu-
setts Institute of Technology, 1945.
Walter. J. F,, and Sherwood, T. K., IND.ESG. C H E X , 33, 493
(1941).
Weisman, J., and Bonilla, C. F., Ibid., 42, 1099 (1950).
Weller, S., and Steiner, W. A., J . Applied Phys., 21, 279 (1950).
White, G. E., Chem. Eng. Progress, 46, 363 (1950).
Wilke, C. R., Ibid., 46, 95 (1950).
Winter, E. R. S., Trans. Faraday Soc., 46, 81 (1950).
Yang, L. M.,Proc. Rou. SOC.(London), A198, 94, 471 (1949).
RECH~IV ~D
November 6, 1950.

ADSORPTION
HOPKINS UNlVERSlM,~BALTlMORE18, MD.

The Field of adsorption has been a very active one in all aspects. The trend toward increased preferential adsorption. Molecular
interest in the use of this tool for separation which was evidenced in previous years has con- structure was more important over
tinued and expanded. Lewis and co-workers have applied the concepts of relative volatility to silica gel than over carbon, and, in
reparation of hydrocarbons in binary and ternary gaseous separation. The reiative volatility of general, the greater the boiling point
any two compounds was found to be the same for a ternary system as for the binary system of difference of two liquids the greater
those components. Estimation of x y diagrams from pure gas isotherms is allowable for many was the relative volatility difference
systems. Chromatographic techniques have been utilized for separation of liquid mixtures of over both adsorbants. The data
gasoliner and gas oils, but no approach similar to that for the gases has been attempted. Liquid v, ere correlated by the equation
phase studies are considerably more difficult of interpretation than gas phase studies and as yet
there i s no method of correlating adsorption in the liquid phase which is as applicable for non- -&=1 hr‘
specific systems as the B.E.T. equation is for gases. Some few attempts to correlate liquid
1
studies b y this equation have not met with great success. The adsorption of high polymers
has been previously studied and presents about the same picture as other liquid phase work.
This has been extended by Tiselius and others to adsorption of colloidal particulates. A very where the h7 values refer t o the
large number of studies have been made on specific systems and preparation of adsorbants, moles of each component adsorbed
from the mixture and the primed
value refers to the capacities for

T
HERE has been a great deal more activity in the field of ad-
sorption this year than in previous years, as attested by the
large number of references. The vast bulk of this work has
been, as usual, in physicochemical equilibrium studies and inter-
pretations of these by the standard isotherm equations, the
Brunauer-Emmett-Teller, Freundlich, and others. A large per-
centage of this work has been liquid phase studies of removing
dyes or decolorizing liquids, as discussed below. However, sev-
eral articles this year are concerned with studies of a more
strictly unit operations type and: in particular, the resolution of
mixtures. Some few have been concerned with the resolution of
gaseous mixtures.
The most fundamental approach to this subject has been made
by Lewis and his eo-workers (181-186),who were concerned with
hydrocarbon mixtures and the resolution of these over ac-
tivated carbon and silica gel. They first determined the pure
gas isotherm and found that for most of the gases there was good
reversibility and no hysteresis evident. Utilizing the various ad-
sorption equilibria, they studied the xy diagrams (vapor-adsorb-
a t e equilibria) of binary gaseous mixtures of compounds of the
same number of carbon atoms as well as of some ternary systems.
The factors of molecular weight, molecular structure, and liquid
boiling point were found to be involved in the phenomenon of
the pure components. An empirical method was developed for
prediction of the adsorptive relative volatility over silica gel.
For multicomponent mixtures the relative volatilities of any two
components appear to be equal to the values obtained for the bi-
nary mixture of these components. I n many cases, the N 1 us. Nz
correlation coupled with t,he assumption of constant relative vola-
tility yields satisfactory zy diagrams, allowing estimation of mix-
ture data from pure gas isotherms. Carbons of different adsorp-
tive capacities were found to yield essentially the same equilib-
rium diagram for a given mixture.
A review by Eagle and Scott on cyclic adsorption processes (88)
underlines the great usefulness of the cyclic adsorption method for
almost quantitative separation of aromatics and olefins from other
compounds of varying feed stock. The optimum number and
size of adsorption columns were stated to be determined by the
character of the feed, the desired purity of raffinates and extracts,
and economic considerations and construction. Studies were
made in a pilot plant on various charged stocks.
Two patents were issued to Brandt (36)and to Gilliland (111)
for separation by adsorption in countercurrent flow using various
adsorbants, such as charcoal, activated alumina, and silica gel.
These closely parallel previous studies on the hypersorption
method.
46 INDUSTRIAL A N D ENGINEERING CHEMISTRY
(78) Rose, H. E., Proc. Inst. Mech. Enprs. (London), 153, 141 (1945).
(79) Salisbury, J. K., Power Volume of “Kent’s Mechanical Engi-
neers’ Handbook,” 12th ed., pp. 9-20 to 9-30,12-82 to 12-84,
New York, John Wiley & Sons, Inc., 1950.
(80) Scheibel, E. G., and Othmer, D. F., Trans. Am. Inst. Chem.
Engrs., 38, 339 (1942); IND. ENC.CHEM.,34, 1200 (1942).
(81) Schlapfer, P., Audykowski, T., and Bukowiecki, A., Schweiz.
Arch. angew. W i s s . u. Tech., 15, 308 (1949).
(82) Sherwood, T. K., “Absorption and Extraction,” p. 7, New
York, McGraw-Hill Book Co., 1937.
(83) Sherwood, T. K., and Holloway, F. A. L., Trans. Am. Inst.
Chem. Engrs., 36, 21 (1940).
(84) Shulman, H. L., and Molstad, M. C., IND.ENQ.CHEM.,42,
1058 (1950).
(85) Simrel, V. R., and Hershberger, A,, Modern Plastics, 27, N o . 10.
97, 98, 100, 102, 150-2, 154, 156, 158 (1950).
(86) Stephens, E. J., and Morris, G. A., paper presented at the
Montreal meetinn American Institute of Chemical En& =.-
news, September 1949.
Vol, 43, No. i
EKC. HEM,, 41, 2013
Stokes, R. H., and Robinson, R. A,, IND.
(1949).
Storrow, 3. A,, J . SOC.Chem. Ind., 66, 41, 73 (1937).
Taecker, R. G., and Hougen, 0. A., Chem. Eng. Progress, 45,188
(1949).
Ternovskaya, A. N., and Belopolskii, A. P., Zhur. Fiz. Khim.
(U.S.S.R.), 24,43 (1950).
Trevoy, D. J., and Drickamer, H. G., J . Chem. Phys., 17, 1117
(1949).
Vi;ian, J. E., Sc.D. thesis in chemical engineering, Massachu-
setts Institute of Technology, 1945.
Walter. J. F,, and Sherwood, T. K., IND.ESG. C H E X , 33, 493
(1941).
Weisman, J., and Bonilla, C. F., Ibid., 42, 1099 (1950).
Weller, S., and Steiner, W. A., J . Applied Phys., 21, 279 (1950).
White, G. E., Chem. E n g . Progress, 46, 363 (1950).
Wilke, C. R., Ibid., 46, 95 (1950).
Winter, E. R. S., Trans. Faraday Soc., 46, 81 (1950).
Yang, L. M.,Proc. Rou. SOC.(London), A198, 94, 471 (1949).
RECH~IV ~D
November 6, 1950.

ADSORPTION
HOPKINS UNlVERSlM,~BALTlMORE18, MD.

The Field of adsorption has been a very active one in all aspects. The trend toward increased preferential adsorption. Molecular
interest in the use of this tool for separation which was evidenced in previous years has con- structure was more important over
tinued and expanded. Lewis and co-workers have applied the concepts of relative volatility to silica gel than over carbon, and, in
reparation of hydrocarbons in binary and ternary gaseous separation. The reiative volatility of general, the greater the boiling point
any two compounds was found to be the same for a ternary system as for the binary system of difference of two liquids the greater
those components. Estimation of x y diagrams from pure gas isotherms is allowable for many was the relative volatility difference
systems. Chromatographic techniques have been utilized for separation of liquid mixtures of over both adsorbants. The data
gasoliner and gas oils, but no approach similar to that for the gases has been attempted. Liquid v, ere correlated by the equation
phase studies are considerably more difficult of interpretation than gas phase studies and as yet
there i s no method of correlating adsorption in the liquid phase which is as applicable for non- -&=1 hr‘
specific systems as the B.E.T. equation is for gases. Some few attempts to correlate liquid
1
studies b y this equation have not met with great success. The adsorption of high polymers
has been previously studied and presents about the same picture as other liquid phase work.
This has been extended by Tiselius and others to adsorption of colloidal particulates. A very where the h7 values refer t o the
large number of studies have been made on specific systems and preparation of adsorbants, moles of each component adsorbed
from the mixture and the primed
value refers to the capacities for

T
HERE has been a great deal more activity in the field of ad-
sorption this year than in previous years, as attested by the
large number of references. The vast bulk of this work has
been, as usual, in physicochemical equilibrium studies and inter-
pretations of these by the standard isotherm equations, the
Brunauer-Emmett-Teller, Freundlich, and others. A large per-
centage of this work has been liquid phase studies of removing
dyes or decolorizing liquids, as discussed below. However, sev-
eral articles this year are concerned with studies of a more
strictly unit operations type and: in particular, the resolution of
mixtures. Some few have been concerned with the resolution of
gaseous mixtures.
The most fundamental approach to this subject has been made
by Lewis and his eo-workers (181-186),who were concerned with
hydrocarbon mixtures and the resolution of these over ac-
tivated carbon and silica gel. They first determined the pure
gas isotherm and found that for most of the gases there was good
reversibility and no hysteresis evident. Utilizing the various ad-
sorption equilibria, they studied the xy diagrams (vapor-adsorb-
a t e equilibria) of binary gaseous mixtures of compounds of the
same number of carbon atoms as well as of some ternary systems.
The factors of molecular weight, molecular structure, and liquid
boiling point were found to be involved in the phenomenon of
the pure components. An empirical method was developed for
prediction of the adsorptive relative volatility over silica gel.
For multicomponent mixtures the relative volatilities of any two
components appear to be equal to the values obtained for the bi-
nary mixture of these components. I n many cases, the N 1 us. Nz
correlation coupled with t,he assumption of constant relative vola-
tility yields satisfactory zy diagrams, allowing estimation of mix-
ture data from pure gas isotherms. Carbons of different adsorp-
tive capacities were found to yield essentially the same equilib-
rium diagram for a given mixture.
A review by Eagle and Scott on cyclic adsorption processes (88)
underlines the great usefulness of the cyclic adsorption method for
almost quantitative separation of aromatics and olefins from other
compounds of varying feed stock. The optimum number and
size of adsorption columns were stated to be determined by the
character of the feed, the desired purity of raffinates and extracts,
and economic considerations and construction. Studies were
made in a pilot plant on various charged stocks.
Two patents were issued to Brandt (36)and to Gilliland (111)
for separation by adsorption in countercurrent flow using various
adsorbants, such as charcoal, activated alumina, and silica gel.
These closely parallel previous studies on the hypersorption
method.
 January 1951 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
The only other article on adsorption from binary mixtures of
hydrocarbons concerns a study by two Russian authors (263)on
the separation of carbon dioxide, ethylene, or propene from air
over activated carbon. This is primarily a stripping operation
rather than a true separation of materials, both of which might be
adsorbed.
Gases other than hydrocarbons are represented by two studies.
White and Schneider (606)studied the physical adsorption of oxy-
gen-argon mixtures on silica gel a t 0". At this relatively high
temperature, neither of the gases is adsorbed appreciably and the
adsorption is essentially a linear function of the partial pressure.
With the total adsorption so low, neither component is inhibited
by the presence of the other, so that equilibrium is obtained for
both gases a t their respective relative partial pressures, no matter
which of the gases &st came in contact with the surface. The
quantitative separation of argon from small quantities of krypton
and xenon by multiple adsorption and desorption was measured
by Gerling and Baranovskaya (110). The work described by
them was more truly separation of binary mixtures, in that the
study was conducted from -80" to -120" C. The adsorption
of the gases was stated to conform to the Freundlich equation and
the adsorption conformed to Henry's law. Krypton was de-
sorbed with greater difficulty than argon; a method was worked
out, based on calculation and conbmed by experiment to sepa-
rate argon from small quantities of krypton. The mixture was ad-
sorbed a t - 100"C. and the adsorbed gases were desorbed and re-
adsorbed in stepwise adsorbers. By this procedure, the argon
was recovered and the bulk of the krypton remained adsorbed.
Any xenon present remained with the krypton.
Selective adsorption, particularly in the liquid phase, by chro-
matographic techniques was proposed by Hibshman (138)for the
separation of is0 and normal paraffins, by Hansen and co-workers
(127)for the separation of zirconium and hafnium, and by Hopf
(143) for Separation and purification of quinidine and quinine.
The utilization of this adsorptive technique for recovery of nitro-
gen oxides by silica gel (98)and for separation of cracked gasolines
(96) was discussed, as well as the separation of hydrocarbons b y
selective adsorption (116)and the analysis of distillates by frac-
tionation (18).
Several reviews on the hypersorption process have appeared, in1
particular one by the early experimenters in this field, Berg and
co-workers (23). The removal of sulfur compounds from gas.
streams by hypersorption was discussed by Kehde and Chapin
(169).
A number of tools and mathematical correlations have appeared
during the past year, which have not been applied to the practical
problems involved in designing adsorbers but which it seems will
be applied in the future. These concern the theoretical princi-
ples of adsorption of gases by activated charcoal (114) for the
hypersorption of olefins, where in a physical mathematical study
the phenomena of the adsorption and capillary condensation in
porous media are reviewed. Theoretical analysis of the frac-
tionating process of adsorption has been approached by Mair and
co-workers (201).
The mathematics of adsorption in fluidized beds has been dis-
cussed by Kasten and Amundson (166). As in the case of pre-
* vious mathematical studies, this theory applies only to equilib-
rium isotherms and to nonequilibrium cases that are linear and
reversible. I n general, the more complicated cases are not solv-
able by direct mathematical approach.
The redistribution of the adsorbate by diffusion within the bed
has been discussed by Ledoux (179) in terms of the usual dimen-
sionless variables, so that it is possible t o use these data to deter-
mine the diffusivities in other systems. The flow of gases through
porous media has been studied by Takagi (279) and correlated
with the temperature rise of active charcoal on adsorption of
various organic solvent vapors.
The heat of adsorption, as related to the relative adsorbability
of gaseous hydrocarbons, was studied over silica gel and carbon
42
black by Smith and Beebe (279). Separation of propene and bu-
tane was attempted but not obtained. Selective adsorption of
the two components was indicated.
SURFACE AREA STUDIES
Adsorption has been used for numerous studies of surface area,
in line with the developments over the past several years. Car-
bon black, silica gel, organic materials, salts, pigments, crystalline
carbon, and carbide powders, as well as many other materials,
have been studied by various authors (16,16, 43, 168,266,313).
The use of adsorption as a tool for measuring surface area has
been compared by Arne11 (7) with the well known permeability
method. Good agreement was found for the modified Kozeny
equation.
The estimation of the surface area of powders from the tem-
perature dependence of the adsorption from solution has been in-
vestigated by Hirst and Lancaster (140). Rideal and Trapnelt.
(248)utilized chemisorption of oxygen to estimate the surface
area of tungsten used in catalytic study. This was found to ghe
good agreement with the catalytic activity of the surface.
Joyner and eo-workers (160)have compared the pore volume
distributions between the nitrogen adsorption isotherm and the
mercury porosimeter. They have con6rmed their previous stud-
ies, indicating that the pore volume distributions are in complete
agreement with the Brunauer-Emmett-Teller areas. Work on
the adsorption of krypton on paint films has extended the tech-
nique of adsorption to smaller total surface areas (309).
A rather large amount of work has been done on determining
the surface coverage of various molecules. The adsorption of
nitrogen has been used in the past as a standard method of surface
area determination by the adsorption technique, and this gas is
utilized wherever possible. For very small surfaces, krypton
adsorption has been used, and numerous articles have appeared at
various times, attempting t o correlate the adsorption of different
gases on the same surface. To date, this has been not too suc-
cessful and recent studies do not change the picture appreciably.
A rather complete study was made by Livingston (188)on the
cross-sectional areas of various gas molecules for adsorption a t
temperatures ranging from -252 O C. t o room temperature. Cor-
relations between studies on various surfaces by different
molecular species do not always agree with the data given by Liv-
ingston, but indicate rather that either the Harkins and Jura k
value or the surface area coverage assigned to a given molecular
species will vary with the surface upon which it is adsorbed (129,
286).
Studies on alumina by Russell and Cochran indicate better
agreement for stearic acid adsorption than for adsorption of
either nitrogen or butane (266, 266). A review by Dunaca has
compared the Harkins and Jura approach to the Brunauer-Em-
mett-Teller approach, according to the Anderson modification
(84). He found that the Harkins constant, k , could be estimated
approximately from the Anderson constant and a given value for
the area occupied by an adsorbed molecule. A good method of
determining the surface areas of a large number of solids to about
20% accuracy was given, based on the assumption of a value for
the Anderson constant and the linearity of the P/P,vs. l / V plot
over the range of P / P , from 0.25 to 0.75.
Studies of the anomalous adsorption of helium a t liquid helium
temperatures (10) by Band indicate that the high value of the
volume of gas that will just fill the first monolayer a t its satura-
tion density yielded by the ordinary Brunauer-Emmett-Teller
plot are real and indicate that the Brunauer-Emmett-Teller the-
ory only requires generalization.
A study of the adsorption of nonpolar gases and of water vapor
on proteins by Benson and Ellis (29) indicated that reasonable
and fairly consistent values of surface areas and heats of adsorp-
tion were found, depending only on the state of subdivision of the
protein powders. Adsorption of water, however, was immeas-
48 INDUSTRIAL AND ENGINEERING CHEMISTRY
urably fast and the value of adsorption was independent of sur-
face area.
A study by Komarov, Drozdova, and Chernikova (166) on the
adsorption of nitrogen and butane on various solids indicated that
the nitrogen adsorption was in all cases larger, as might be ex-
pected, and that, in general, three fractions of the total surfaces
exist: that rapidly accessible to butane, that slowly acceaible to
butane, and that accessible to nitrogen but not to butane.
Numerous studies have been made on the utilization of liquid
phase adsorption to surface area determination and, according t o
the published accounts, with considerably greater success than
that previously observed. The use of the iodine number (or
amount of iodine adsorbed) was found in two studies (21, 186) to
yield surface area values in complete agreement to those obtained
using the low temperature adsorption of nitrogen or area calcu-
lations from electron micrograph of carbon blacks. Stearic acid
adsorption from solution was found to be simpler and to give good
agreement with nitrogen when the nitrogen molecular area was
calculated as 17.8sq. A If the nitrogen value is taken as 16.2
sq. A., a linear correlation in the results obtained gave 16.7 sq. A.
for the molecular coverage of the stearic acid molecule (25’5,266).
The equilibrium and kinetics of liquid phase adsorption have
been discussed by Eagle and Scott (87). An approach to the use
of soap molecules from aqueous solutions was made, using sur-
faces of graphite and polystyrene (60).
Reviews of the use of surface area determinations by adsorp-
tion techniques have been published by Emmett (89), Prettre
(,941),and Taylor (184).
CHROMATOGRAPHY
Chromatographic techniques are interesting from a unit opera-
tions point of view, in that most of the work on separation of liq-
uid phase components would be so indexed. There have been
numerous studies on practical problems, particularly in the petro-
leum field, for both the separation and the analysis of complex
mixtures.
The separation of cracked gasolines by this technique was
studied by Fink and co-workers (94, 96). Factors affecting the
efficiency of the adsorption and the characteristics of the adsorb-
ant and regeneration techniques were discussed recently. The
finer silica gels are found to give more efficient separations; the
disadvantages of the h e r silica gels are obviously those of
greater pressure drop and greater difficulty in separating from
the fluid stream. In general, the adsorbing capacity of silica
gel for olefins in the same range of molecular xeights de-
creases in the order: cyclic. > branched-chain > straight-
chain olefins.
The chromatographic analysis of gas oils was investigated by
other Shell Oil chemists (63)and chromatographic analysis was
extended to several other applications, including estimation of
the hydrocarbons in primary tars by hot chromatography by
Vahrman (298), separation of chlorophylls by Wendel ( S o d ) , and
analysis of hexachlorocyclohexane (104). A review of chromato-
graphic analysis was published by Descamps (78).
Improvements in the art of chromatography were mentioned in
many of the studies, but several developments merit individual
mention. A capillary-ascent test tube method was developed by
Rockland and Dunn (261). An apparatus which records, on
photographic paper, the changes in refractive power of a solution
leaving a filter us. the amount of solution was developed by
Hellstrom and Borgiel (132), who further indicated that difficul-
ties which arose in work using a commercial model were overcome
and discussed the methods for so doing. A single apparatus for
applying pressure and suction regulation to chromatographic col-
umns was developed by Booth ($8).
The term LLpartography” was proposed by Rockland and Dunn
(&52) for paper partition chromatography. A device for rapid
and accurate reading of the separation values in paper chroma-
Vol. 43, No. 1
tography was described by them, involving a proportional divi-
der, which they have suggested be called “partogrid.” The
met’hod involves a simple mechanical device for evaluating t,he
separation coefficient.
Various uses for the separation of one material from another
have been dkcussed for bot’h inorganic and ionic systems (3,33,
105, 107, 178, 281, 311) and organic systems (8, 38, 5’7, 63, i&,
189,228,866,278,319).
The adsorption of particulates and proteins has been carried out.
by this technique. Shepard and Tiselius (867) have discussed
t’he rhromatography of proteins as affected by salt concentration
and pH when adsorbed on silica gel. The problem of separat,ing
subcellular part,iculates from the cytoplasm of cells was devel-
oped by Riley, Woods, and Burk (849). The use of chronia-
tography to obtain adsorption isotherms was attempted by Nest-
ler and Cassidy (WM), using the frontal-analysis technique in bi-
nary mixtures of fatty acid of low molecular weight,. The
Freundlich isotherm Fvas found to hold for these materials over
the range studied. The effect of the structure of the adsorhte
on the adsorption was investigated by several workers. Hydro-
gen bonding was found to be a factor, giving some rather anonxi-
lous results for certain hydroxy substituted compounds in prefer-
ence to others with slightly different structure (f44,%@).
The adsorption on carbon of ketones with varying side chains
was found to follow the rule that a decrease in the rate of movc-
ment of the ketone zone occurred with increasing mass of the side
chain. On silica gel and similar adsorbants, the reverse was
found to be true (271).
Similar relationships were found for the effect of the side chain
on the strength of adsorption with some primary aliphatic alco-
hols and amines by Monaghan, Moseley, and LeRosen (214).
This latter study also indicated irregularities in the effect of side
chain on adsorption affinity. Naturally occurring phenolic sub-
stances showed similar irregularities, although in general a
straight line was obtained for the plot of the log of the function of
the separation coefficient against the number of subst,ituent
groups of any one kind (870).
Several articles appeared on the use of paper chromatography.
General articlcs were published by Gordon (116)and Clegg ( 5 2 ) ,
and general considerations were discussed by Jones (149). An
interesting innovation was the use of alumina-impregnated filter
paper by some British authors (69). Automatic paper chronia-
tography was proposed by Muller and Clegg (216)and the kinet-
ics of paper chromatogram development was investigated, in
which the square of the radius of the colored zone on a paper disk
chromatogram was found to be proportional to the development
time for a given solvent or solute. Paper chromatography of
several substances was investigated, including a complete study
on phenolic substances (93). The improvement and various
discussions of the characteristics of different chromatographic ad-
sorbants were mentioned in these studies and specifically by sev-
eral other authors (154,156,867,196).
General review articles on chromatography in several languages
were published (148, 167, 194, 208, 277, 689, 508).
A plan was described for chromatographic separations on an in-
dustrial scale, utilizing a stationary radial chromatographic sep-
arator with an exchangeable inner container, containing the ad-
sorbant. The general plant layout for this system was provided
(195).
LIQUID PHASE ADSORPTION
The adsorption from liquid phase, either by the liquid surface
itself or by solid surfaces, has been the subject of numerous inves-
tigations. Previous work of Hansen, Fu, and Bartell (116),more
completely published now, indicated that for sparingly soluble
organic materials in aqueous solution the Brunauer-Emmett-
Teller equation of multimolecular adsorption holds fairly well.
The adsorption of electrolytes and the heats involved
therein have been measured by numerous investigators. The
 January 1951 INDUSTRIAL A N D ENGINEERING CHEMISTRY 49
adsorption of nickel and cobalt
from aqueous solutions by
manganese dioxide was meas-
ured, using the chloride and
nitrate solution. The adsorp-
tion was found to be cationic
and reversible and the anion
was not adsorbed. This was
advanced as an explanation of
the greater percenbge of nickel
oxide than of cobalt oxide in
the ores (98). The percentage
of adsorbed ions of z i w and
copper on calcium carbonate
was found to decrease as the
concentration increased. The
adsorption followed t h e
formula of Langmuir-Terrin.
Each adsorbed ion neutralized
various active centers of the
i absorbant. I n mixed solutions
of copper and zinc, the c o p
per diminishes the adsorption
of zinc to a degree to make
it negligible (42). The specific
adsorption isotherm of thio-
cyanate ion was estimated by
comparison with the adsorp-
tion of potassium chloride a t
the free surface of solution
(193). The specific adsorp-
tion of hydrogen ion a t the Adsorptive Dryer of 500-Cubic Foot Capacity
- -
free surface of solutions was
calculated by the same author and found to be nearly linear. ethyl stearate on various metal surfaces. No orientation was
Other studies were made on calcium hydroxide (85), numerous found on platinum, but on reactive metals, such as cadmium and
compounds of sodium (209), and many other materials (106, zinc, the diffraction pattern showed a change well above the melt-
119,968). ing point of stearic acid. Methyl stearate behaved similarly
Tiaelius and other authors have studied the adsorption of col- (260). Various other similar studies were made on both polar
loidal materials or the adsorption on colloidal materials in numer- and nonpolar organic compounds (%4,61,117,124).
QUS instances. The adsorption of sulfanilamide on silk fibroin The adsorption by clays and soil as related to the exchange
has been measured by Coulombre and Moore (W),and the en- capacity thereof has been rather thoroughly studied (70,106,108,
tropies of adsorption were found to be negligible. Sorption 119,197,,969)and applied to an interesting practical use wherein
isotherms of substantive dyes and humic acids by various gels in- the clay is mixed with a small amount of comminuted cellulosic
dicated the presence of sharp minima and maxima; depending material, such an wood flour; this material is extruded into
upon the water content of the adsorbant (165). small cylinders, and calcined to a content of low residual volatile
Passivation of iron was achieved with protein layers, particu- matter. The product is an adsorbant for oil, grease, water, and
larly solutions of gelatin, resulting in decreased attack of the iron other materials (197). Suggestions as to the use of clays for the
by sulfuric acid. Adsorptive passivation was found to be su- adsorption of vitamin B1 have been made by Sakurai and Hori
perior to parkerization (168). (259). In particular an approach has been made by Capon and
The adsorption of glutamic acid on aluminum oxide indicated co-workers (106)to the elucidation of the activity of the soil by
t h a t aluminum chloride is useful in increasing the adsorptive adsorptive technique involving exchange activities of cherno-
power (24'4.6). The Nobel lecture of Tiselius (288), on the use of zems.
adsorption analysis as a means for study of substances of high Of the numerous studies of adsorption of dyes, the effect of ad-
molecular weight and their decomposition products, has now been sorption on the rate of diffusion in gels merits mention because of
published (287). the postulate that there are active centers in the gel which immo-
There have been a large number of studies of adsorption from
bilize the diffusion in the gel. The result is that Fick's law is not
4 solution by various substrates. It would be impossible to survey
exactly valid, but the deviation could be related to pH (39).
these exhaustively, but mention of a few fields may be of interest.
The adsorption on metal or mineral surfaces of specifically ad- The adsorption of acid dyes on cellulose has been thermodp-
sorbed materials has been the subject of increasing interest. The namically evaluated by Peters and Vickerstaff (234).
theory of water-repellant films on solids formed by adsorption In an interesting piece of work by Dickey (74) a method has
was suggested by Cook and Nixon (68) for use in flotation studies. been reported for obtaining silica gels having specific adsorption
Physical and chemical adsorption of long-chain compounds on afEnities for certain azo dyes. The silica gel is prepared in the
metals was studied by radioactive technique and no reaction was presence of a particular dye and then as much of the dye as prac-
observed in any case of adsorption of high molecular weight alco- tical is removed by prolonged extraction. Gels prepared in this
hols on zinc, cadmium, copper, platjnuni, and gold. With stearic way were very much more powerful adsorbants for the particular
acid, however, the film reacted with zinc, cadmium, and copper dye used in their preparation than control gels.
W). As usual, there has been a great deal of activity in the adsorp-
Electron diffraction observations were made on adsorbed tion a t liquid-liquid and liquid-air interfaces. There is compara-
50 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
tively little practical significance to this work, but a great deal of
theoretical interest.
When a dry powder is wetted by a liquid, a gas is evolved. This
was quantitatively studied by KrasnovskiI and Gurevich (170),
using various oxide samples for the adsorption of palmitic
acids in toluene solutions. They stated the volume desorbed can
be used for characterizing the powder.
One interesting technique in the study of adsorption from the
liquid phase mentioned above-the use of radioactive tracer meth-
ods for determining adsorption of very small quantities of high
molecular weight materials at interfaces-was further discussed
(109, 145).
P R E P A R A T I O N AND PROPERTIES OF V A R I O U S A D S O R B A N T S
Chemically inert gel bas been prepared by Biget (28)by coagu-
lating acetone solutions of cellulose acetate with aqueous solutions
of metallic perchlorates. Gels containing as little as 2y0 acetate
were obtained. These were inert to solutions of p H 0 to 9, and
were unaffected by many organic substances. Those materials
which caused dehydration, hardening, or plasticizing of the gels
rapidly destroyed them.
Barrer ( I S ) has prepared crystalline hydrogen zeolites by heat-
ing the corresponding ammonium zeolites in oxygen. The hy-
drogen zeolites of mordenite and chabazite were found to be ex-
cellent adsorbants and to take u p propane more rapidly than the
natural zeolites.
The decolorizing efficiency of fuller's earth (196) was improved
by extruding the earth mixed with a small concentration of aque-
ous sodium hydroxide and neutralizing the extruded material by
sufficient mineral acid to react with the alkaline reagent. The
earths so treated were stable after repeated regeneration.
Montmorillonite was activated by treatment with sulfuric acid.
The specific surface tended toward a maximum and then de-
creased as increasing amounts of aluminum, iron, and magnesium
oxides were removed from the siliceous material. The surface
areas were studied by both x-ray and gaseous adsorption tech-
niques. When sodium montmorillonite was dried a t successively
higher temperatures, the sample increased to a maximum area of
90 square meters per gram when approximately half the water had
been removed. The area and water content then decreased to ap-
proximately 0 as the sample was dried a t successively higher tem-
peratures, in the range of from 300' t o 900" C. Calcium montmo-
rillonite reacted similarly, except that two maxima were ob-
served (191, 192). Activation of bentonite and other clays con-
taining montmorillonite was reported by Hickey (134) to result in
catalysts for hydrocarbon conversion, or in contact adsorbants for
aqueous or organic impurities in oils and fats, or as decolorizing
agent for oils, sugar, and process waters. The use of hydrochloric
acid or sulfuric acid was found to be preferable to mineral acid for
activation. The maximum level of activation was achieved by
removal of 20 to 45% of the lattice aluminum. For use as a cata-
lyst, the treated clay was calcined a t 400' to 600" C. Bentonite
and similar materials can be activated to remove considerably
more of the water content by partial drying and then extraction
with a water-soluble liquid such as ethyl alcohol (49). When
bentonites are heated, the exchange capacity to lithium ions is
lost (141). Spherical particles of highly acid treated bentonites
were prepared by mixing a finely powdered bentonite with alumina
sol, dispersing the mixture in butanol, and agitating the disper-
sion until the sol sets to the hydrogel, forming spherical particles
of alumina hydrogel and bentonite.
The well known preparation of activated carbon by impregna-
tion of the starting material with zinc chloride and subsequent
calcination has been studied by several authors (2, 78, 81). The
yield, homogeneity and activity of the product were found to de-
pend on the uniformity of contact between the steam used for ac-
tivation and the carbon and on the temperature of the steam. The
yield of carbon activated by zinc chloride was found to be consid-
erably greater than that obtained in activation by carbon diox-
Vol. 43, No. 1
ide. For birch charcoal the adsorption of dyes indicated that
when large excesses of zinc chloride compared to organic material
were used the resultant pores in the charcoal were accessible to
colloidal particles. Activation of sugar carbon by heat treatment
from 500" to 1100' C. was found to result in maximum adsorption
at about 800" for organic acid of low molecular weight (186).
When activated carbon was oxidized by boiling in nitric acid, a
high adsorption for hydrogen sulfide was obtained, in contrast to
unoxidized charcoal which did not adsorb the gas. The 10% ni-
tric acid treatment was better in this respect than more concen-
trated solutions. Preliminary adsorption of hydrogen sulfide on
the oxidized carbon was found to raise its adsorption capacity for
benzene (291).
Electron microscope studies (S42) of active carbon indicated
that the material was not uniform, as would be expected, and that
the dimensions of the visible pores increased when the total pore
volume was increased by longer heating.
Electron microscope studies of silica gels indicated that, in gen-
eral, they belong to one of three classes: a transparent gel which
bad no pores and was similar to quartz fragments, gels con-
sisting of crystals 500 to 1000 A. in size with pores between the
particles of 160 to 600 A., and intermediate structures. These
data agreed with adsorption data (248). The elastic properties of
silica gels were examined by Munro (618), who found that
Young's modulus was not independent of load and increased with
the age of the gel, as well as the concentration. Increased tem-
perature increased the modulus of acid gels, whereas alkali gels
showed a higher modulus a t room temperature and a lower elastic
recovery.
Modifications and production of silica and other gels have been
the subject of numerous studies. A process and apparatus for
continuous manufacture were described by Weir (303). Silica-
alumina catalysts were prepared by mixing alumina trihydrate
with silica sol containing an excess of sulfuric acid. The gel was
soaked in ammonia to precipitate alumina in the body of the silica
matrix (55). A similar catalyst was prepared by depositing on ac-
tivated alumina an organic compound capable of producing hy-
drated silica when subjected t o heat (2.9'7). If the silica-alumina
sol has incorporated in it a small percentage of powder under 50
microns in size and is fusible at 1000" F., a catalyst of greater par-
ticle strength isobtained ($IS),which can be subjected to more se-
vere drying conditions.
Preparation of gels by spraying tbe sodium silicate solution into
a n agitated sulfuric acid solution a t relatively low temperatures
was developed by Archer and Dunn (6). In this method the gel
was allowed to age for some time before washing. Other methods
involving aging of the gel were developed by Ashley and Jaeger
(9) and Higuchi (135). High speed agitation of the sulfuric acid
solution used for precipitation o l the silica-alumina gel resulted in
controlled particle size (6).
Hydration of gels which decrepitate in contact with liquid wa-
ter can be accomplished by an addition of ice, allowing the mix-
ture to stand for extended periods of time (4). Other general im-
provements in silica and other gels have been put forth in produc-
tion (112, 17'7, 629), washing (66), drying (172, 394), and heat
treatment (997). Production of spherical gel materials has been
the subject of a number of publications (191,203, 904, 836-,998).
Forming of viscous inorganic sols into any desired shape-rods,
disks, or spheres-and hardening the resultant shapes by immer-
sion in liquid ammonia or exposure to gaseous ammonia were de-
veloped by Marisic and Griest (804). Molded active materials
were prepared by coating pieces of refractory inert solids with
wax and applying a layer of the wet, workable mass. On drying,
a hard shell of the adsorptive material developed with a hard in-
ner core (91).
KINETICS OF A D S O R P T I O N
The kinetics of hydrogen adsorption on nickel was utilized b y
Sadek and Taylor (868)in the study of nickel catalyBt prepara-
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY
tions. Both physical adsorption and chemisorption were ob-
served and the different preparations adsorbed different relative
amounts by the two types. The data did not support an inter-
pretation based either on solubility of hydrogen in the lattice or on
a n exothermic entry of hydrogen into the nickel lattice a t low
temperatures. The kinetics of desorption of hydrogen was stud-
ied by Cornault and by Keier and Roginskii (59, 160). If de-
sorption was stopped before complete degassing and more hydro-
gen was added, this was adsorbed more rapidly than during the
primary adsorption, indicating that desorption does not appear
to start from patches least active in adsorption on sugar charcoal,
The adsorption of hydrogen on reduced copper was found to be
very slow and equilibrium was not reached after 66 hours (174).
Methane was chemisorbed on a composite nickel-alumina-man-
ganese-kieselguhr catalyst and found to obey a simple Langmuir
rate equation with desorption neglected (294). The desorption
of the methane was not observed, but instead the evolved
gas was hydrogen. Tbe rate of the hydrogen desorption did not
result in a simple Langmuir equation, indicating surface hetero-
.. geneity. Chemisorption of oxygen was used by Rideal and Trap-
ne11 (248) to estimate the surface area of tungsten used for chemi-
sorption studies of hydrogen. The equilibrium adsorption of
hydrogen was found to change very slowly with temperature and
pressure and to fit a Freundlich isotherm. The heats of adsorp-
tion were calculated by the Clausius-Clapeyron equation. The
observed decrease of heat of adsorption with coverage could not
be accounted for on the basis of simple electrostatic dipole-dipole
repulsion. The thermodynamics of an adsorbate on an adsorb-
a n t is discussed by Hill (133, giving particular attention to the
heat of adsorption. It was found that the true equilibrium of ad-
sorbate was given by --( ”) fi = m2
AH
with fi as the two-dimen-
sional spreading pressure. Hansen (125) derived the Clapeyron
equation thermodynamically as applied to calculation of heats of
adsorption from adsorption isosteres and came to the conclusion
that the derivation should be evaluated a t a constant number of
adsorbed molecules per unit surface area of the solid rather than
the usual isosteric evaluation.
Cremer (64) explained deviations from the Langmuir a d s o r p
tion formula on the hypothesis that the surface had centers with
different heats of adsorption. Adsorption begins a t centers of
high energy and the number of adsorption centers having a given
heat has an exponential dependence upon the heat. This theory
takes into account a factor characteristic of the disorder of the
surface and the degree of adsorbability of the substances adsorbed.
The number of active catalytic centers was found to increase ex-
ponentially with the heat of adsorption.
Beebe and co-workers (16.9) measured the differential heats of
adsorption of nitrogen and oxygen on titanium dioxide and calcu-
lated the partial molal entropy of the adsorbed gas. The results
show that the partial molal entropy of the adsorbed gas is less
than the partial molal entropy of the bulk three-dimensional liq-
uid or solid phases a t coverages less than a monolayer, as defined
by the Brunauer-Emmett-Teller equation, for all the systems in-
vestigated; a t coverages greater than a monolayer, the value a p
proached the entropy of the three-dimensional liquid or solid.
ri
The entropy requirements of the Brunauer-Emmett-Teller theory
were shown to be incompatible with the experimental evidence a t
coverages lesa than a monolayer.
Other heat of adsorption studies were made on silica gel (86,
872), on carbon (17,19,21012S1,2S2, 2S5,264, 261, B O ) , and on
miscellaneous other solids (14, 62,178-176,198,211, SOi? 81s) for
various adsorbates. The adsorption of dissolved substances and
vapors on liquid surfaces was examined by Gyani (18s). Systems
were chosen so as to have ideally homogeneous adsorbing surfaces.
I n many ca6es a very good agreement was found. The transitory
motion of the adsorbed molecules was confined rigidly to one
plane. Adsorption among some adsorbed molecules was indicated
on the adsorption of some polar molecules on mercury.
51
Surface diffusion of adsorbed molecules of organic materials in
silica gel and active carbons a t low temperature waa reported by
Haul (ISO), utilizing a direct weighing method to measure the dif-
fusion. The ink bottle mechanism for hysteresis was stated a s
being confirmed by a theoretical paper by Katz (157). A deter-
mination of the pore size distribution, by applying the ink bottle
theory to previous data, yielded results compatible with expected
values by statistical consideration.
Todes and Bondareva (290), making the assumption that ex-
perimental deviations from Langmuir’s adsorption isotherm are
determined by heterogeneity of the surface and with disregarded
interaction between adsorbed molecules, established integral
equations for the distribution function of portions of the surface
with values of adsorption coefficient. Solutions of these integral
equations were sought by choosing empirical functions which
agreed best with experimental values. After a thorough-going
discussion of mathematical techniques for solving this type of
equation, they stated a preference for Roginskii’s approximation,
and use of Taylor’s series after the first term.
The Langmuir isotherm for localized unimolecular adsorption
was generalized by Hill (iS7-169), using statistical methods in or-
der to discuss adsorption on a heterogeneous surface, with and
without interactions between adsorbed molecules. The configu-
rational entropy and the nature of the phase changes on a random
heterogeneous surface were discussed. The theory predicted, a t
least for one special case, that condensation would occur in two
steps. The application of the thermodynamic methods enabled
thermodynamic functions to be calculated from the Brunauer-
Emmett-Teller statistical model.
INDIVIDUAL STUDIES OF EOUILIBRIUM DATA
The large number of references published during the past year
preclude complete discussion of individual studies of equilibrium
data. For the convenience of persons interested in such studies,
a cross-index reference list follows.
Adsorbants of Major Interest. CHARCOAL.( 2 , 17, S6, 46, 48,
76-79,81, 82, 88,1OS, 111, lis, 1S0, 161-165,181-186, 210, 220,
2S1, 2.92, 242,246, 2624 264, 271, 272,276,879, 280,286,295, SOO,
306).
CARBON (other than charcoal). (9.8.15. 16. 19. 2i. SO. 76. 80.
82, 88, 103,‘126, 151, 152, 160, 164,18h1186, $09; 810, 8i8,h 4 ;
2S5, 246,247, 261, 27S1291, 298, 896).
GELSOTHERTHAN SILICA.(4,5,15,28,S6, S9,66,85, 87, 112,
1S1,164,165, 172, 177, IOS, 204, 211,815,227, 829, 236,255,266,
268, SOS).
CLAYS. (@, 70,108,119,1S4,1.61,191,192, 190,197,199, $00,
259, 274, 286).
OXIDESOTHERTHAN GELS. (S8, 4 4 92, 99,109,140,155,164,
165,167,171,187,19O12S0, 244, 255-267,276,281, SOO, S14).
METALS. (46, 90,117, 124, 128,129,152,162, i66,169,17S-
176, 198, 216, 2SS,848, 258,260,864).
Adsorbates of Interest. NITROGEN. (15, 16, 9 2 , 43, 90, 97,
129, 150, 158, 16S, 166,188, 192, 210, 233, 246,263, 255, 26‘1, 286,
so9, Sf s, S14).
RAREGASES. (10, 97,99,110,158,188,190,210,J05, SO9,
818, 314).
WATERVAPOR. (22, 40,41, 67, 77,97,129,142,164, 188,811,
226, WSS,2S8, 2@, 254,26S, 265, S06,515).
HYDROCARBONS AND NONPOLAR ORGANIC VAPORS. (15,18,19,
%2,S8,89,51, 5.3, 59, 61, 6S, 69, 70, 78, 79, 85,87, 88, 95, IOS, 114,
122,124, 126,129, 1S0, 1S5, 144, 162, 166,170,181, 182, 18s-185,
188,201 , 21 9,225, 251,245, 25S, 255,256, 961,263,270, 272, 276,
279,280, 286, 291, 294).
POLAR ORGANIC VAPORS. (1, 25, S5, 58,51, 58, 60, 69, 80, 86,
91, 102, 1 W , 109, 117, 122, 124, 126, 129, 1S0, 144,168, 164, 165,
187, 188, 210, 225, 2S1, 236, 244,250, 254, 261, 26S, 270, 276,280,
291, 298).
52 INDUSTRIAL AND E N G I N E E R I N G CHEMISTRY
General Subdivisions of the Field. HEATSOF ADSORPTION AND
THERMODYNAMIC CONSTANTS.( I S , 17, 19,22, 69, 62, 64,86, 106,
166, 136, 163, 173-175, 198, 810, 211, 231, 232, 235, 248, 254,
281, 272, 273, 279, 280, 295, 301, 513).
SURFACE AREA. ( 7 , 10, 15, 16, 21, 22, 40, 43, 60, 84,89, 124,
126, 129, 140, 147, 150, 158,166, 175, 175, 186, 188,191, 192, 241,
247, 848, 266, 256, 261, 265, 273, 279, 284, 286, 509, 313).
CHROMATOGRAPHY. (3, 8, 39, 33, 38, 52, 53, 57, 63, 69, 72, 95,
94, 95, 104, 10.5, 107, 116, 132, 145, 144, 148, 149, 154, 155, 167,
178, 189, 194, 196, 208, $14,216, 217, 220, 228, 249, 251, 252, 257,
262, 666, 267,270, 271, 277, 278, 281, 289, 296, 298, 304, 308, 31 1 ,
312.
Reviews Dealing with Adsorption. (11, 13, 23, 34, 37, 38, 57,
72, 73, 76, 79, 86, 88, 89, 101, 106, 207, 113-116, 118, 132, 135,
148, 149, 164, 167, 180, 194, 199, 206, 214, 230, 241,266, 273, 277,
282-284, 287-289, 508, 310 )
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Hutchinson, Eric, Trans. N . Y . Acad. Sci., 11, 266-70 (1949).
Innes, W. B.,“Rapid Automatic Surface Area and Pore Volume
Determination by a New Adsorption Method,” 117th Meet-
ing AM. CHEM.SOC., Houston, Tex., 1950.
Jacobs, Ph. (Utrecht, The Netherlands), Pharm. Weekblad, 84,
717-25, 734-9 (1949).
Jones, T. S. G., Chemist & Druggist, 153,247-9 (1950).
Joyner, L. G., Barrett, E. P., and Skold, R. V., “Comparison
of Pore Volume Distributions Determined from Nitrogen
Adsorption Isotherms and by Mercury Porosimeter.”
117th Meeting AM. CHEM.SOC., Houston, Tex., 1950.
53
(151)Juza, R., Chem.-Ztg., 74, 55-7 (1950).
(152) Juza, R., and Grasenick, F., 2. Elektrochem., 54,145-52 (1950).
(153)Juza, R.,and Tentschert, H., Z. anorg. C h m . , 262, 165-74
(1 950).
(154)Kaplan, S.,and Meller, F., J . Gen. Chem. U.S.S.R., 19,No. 11,
a507-12 (1949)(English translation).
(155)Kaplan, S., and Meller, F., Zhur. Obschchei K h i m . ( J . Geu,.
Chern.), 19, 2038-44 (1949).
(156)Kasten, P. R.,and Amundson, N. R., IND.ENG.CHEM.,42,
1341-6 (1950).
(157)Kats. S. M..J . Phws. & Colloid Chem.. 53. 1166-86 (1940).
(158j Keenan, A. G., a n i Holmes, J. M., J . Phys. & Colhid-Chem.
53, 1309-20 (1949).
(159)Kehde, Howard, and Chapin, E. €I., “Removal of Sulfur Com-
pounds from Gas Streams by Hypersorption,” 117th Meet-
ing AM.CHEM.SOC., Houston, Tex , 1950.
(160) Keier, N. P., and Roginskiy, S. Z.,Dokladu A k a d . .Vauk S.S.S.R.
57, 157-9 (1947); Chem. Zentr. (Russian Zone E d . ) , 1948,
11, 471.
(161)Keier, N.P., and Roginskii, S.Z., Zhur. Fiz. Khzm., 23,897-916
(1949).
(162)Kemball, C.,Proc. R o y SOC.(London), A201,377-91 (1950).
(163) Kington, G. L., Beebe, R. A., Polley, A t . H., and Smith, W. R.,
6.Am. Chem. Soc., 72, 1775-81 (1950).
(164)Kiselev, A. V., and Smirnova, I. V., Zhur. F i z . K h i m . , 23,1018-
24 (1949).
(165) KoganovshiI, A.M., Kolloid. Zhur., 11, 237-43 (1949).
(166) Xomarov, V. A,, Drozdova, V. M., and Chernikova, E. A,,
Zhur. Fiz. Khim., 23, 1141-51 (1949).
(167)Konstantinova-Shlezinger, M. A., and Gorbacheva, N. 4.,
Zhur. Anal. K h i m . , 3,213-19 (1948).
(168) Koshurnikov, G.S.,Zhur. Priklad. K h i m . ( J . A p p l i e d Chem.),
22, 698-702 (1949).
(169)Kozakevitch, P.,J . Chem. Phus., 47,24-32 (1950).
(170) Krasnovski:, A. A., and Gurevich, T. N., Kolloid. Zhur., 11,
172-5 (1949).
(171) Krishnamoorthy, C., and Overstreet, R., Science, 111, 231-2
(1950).
(172)Kumberlin, C. N., and Pierce, J. A., U. S. Patent 2,503,913
(-4pril 11, 1950).
(173) Kwan, T., J . Research Inst. Catalysis (Hokkaido Univ.) 1,81-94
(1949).
(174)Ibid., pp. 95-9.
(175)Ihid., pp. 100-9.
(176)Ibid., pp. 110-16.
(177)Layng, E. T.,U. S. Patent 2,487,564(Nov. 8, 1949).
(178) Lederer, M., Science, 110, 115-16 (1949).
(179) Ledoux, Edward, J . Phys. & Colloid Chem., 53,960-6 (1949).
(180)Leenheer, L., Bull. soc. belge geol. paleontol. hydrol., 57,299-320
(1948).
(181)Lewis, W.K., Gilliland, E. R., Chertow, B., and Cadogan, W.
P., IND. ENG.CHEM.,42,1319-26 (1950).
(182)Ibid., pp. 1326-32.
(183)Lewis, W.K., Gilliland, E. R., Chertow, B., and Hoffman, W.
H., J. Am. Chem. SOC.,72, 1153-7 (1950).
(184)Lewis, W.K.,et al., Ibid., 72, 1157-9 (1950).
(185)Ibid. pp. 1160-3.
(186)Linner, E. R., and Williams, A. P., J . Phys. & Colloid Chem.,
54,605-18 (1950).
(187)Lipets, M. E., and Trapeznikov, A. A , , Zhur. Fiz. K h i m . , 23,
981-92 (1949).
(188) Livingston, H.K., J . Colloid Sci., 4,447-58 (1949).
(189)Loeb, C., and Lichtenberger, J., Bull. 8oc. chim. France, 1950,
362-3.
(190) Long, E. A., and Meyer, L., Phys. Rev., 76,440-1 (1949).
(191)Longuet-Escard, J., J . Chim. phys., 47, 113-17 (1950).
(192) Longuet-Escard, J., Mering, J., and Perrin-Bonnet, I., Ibid., 47,
234-7 (1950).
(193)Lorenz, P. B., J . Phys. & Colloid Chem., 54,685-90 (1950).
(194) Lynam, C. G., and Weil, H., Brit. Patent 635,271 (April 5,
1950).
(195) Lynam, C. G., and Weil, H., Mfg. Chemist, 21, 1959, 205
(1950).
(196) McCarter, W.S. W., U. S. Patent 2,477,386(July 26, 1949).
(197) Ibid., 2,480,753(Aug. 30, 1949).
(198) McClellan, A. L., and Hackerman, Norman, “Sorption of
Gases on Metals a t Room Temperature,” 117th Meeting
AM.CHEM.SOC., Houston,Tex., 1950.
(199) MacEwan, D. M. C., Nature, 162,No. 4128,935-6 (1948).
(200) McLaughlin, R. R.,and Azis, D., J . Chem. Education, 26,325-6
(1949).
(201) Mair, B. J., Westhaver, J. W., and Rossini, F. D., IND. ENG.
CHEM.,42, 1279-86 (1950).
(202) Marcelin, A., Research (London), Suppl., Surface Chemistry
1949,223-31(in French, English summary).
 INDUSTRIAL AND ENGINEERING CHEMISTRY
Marisic, M. M., and Griest, E. M., U. S. Patent 2,492,167
(Dec. 27,1949).
Ibid., 2,492,808 (Dec. 27, 1949).
Matsunaga, Yoshiaki, Bull. Nagoya Inst. Technol., 1, 260-70
(1949).
Maxted, E. B., J . Chem. SOC.,1949, 1987-91.
Meister, H., Swiss Patent 237,380 (Aug. 1, 1945).
Meng. K. H., E. S. Patent 2.487.574 (Nov. 8. 1949).
Merrill, R. C., and Getty, R., J . P h i s . & Colloid‘Chem., 54,
489097
_. .. . (1950).
--,
Millard, Ben, Cynarski, Jeanette, and Beebe, R. A,, “Calori-
metric Heats of Adsorption of Nitrogen, Argon, and
Methanol on Several Carbon Pigments of Widely Different
Physical Characteristics,” 117th Meeting Ax. CHEM.SOC.,
Houston, Tex., 1950.
Milligan, W. O., and Morgan, C. S., Jr., “Adsorption of Water
Vapor on Ferric Oxide-Chromic Oxide Gels,” 117th Meet-
ing Ani. Cmm. SOC., Houston, Tex., 1950
Milligan, W. O., and Morgan, C. S.,Jr., “High Temperature
-4dsorption Apparatus,” 117th Meeting AM. CHEM. SOC.,
Houston, Tex., 1950.
Milliken, T. H., U. S. Patent 2,487,065 (Sov. 8, 1949).
-Monaghan, P. H., Moseley, P. B., and LeRosen, A. L., “Effect
of the Side Chain on the Strength of Adsorption of Some
Primary Aliphatic Alcohols and Amines,” 117th Meeting
- 4 ~CHEM.
. Sac., Houston, Tex., 1950.
Mostovetch, Nicolas, Compt. rend., 228, 1702-4 (1949).
Mtiller, R. H., and Clegg, D. L., Anal. Chem., 21, 1123-5
(1949).
Ibid., pp. 1429-30.
hIunro, L. A., McNab, J. G., and Ott, W. L., Can. J . Research,
27B, 781-90 (1949).
Murphree, E. V., U. S. Patent 2,515,134 (July 11, 1950).
Nestler, F. H. M., and Cassidy, H. G., J . Am. Chem. Soc., 72,
680-9 (1950).
Ono, Syu,J. Chem. Phys., 18, 397 (1950).
Ono, Syu, M e m . Faculty Eng., K y u s h u Univ., 12, 1-8 (1950).
Ibid., pp. 9-19.
Owen, J. J., U. S. Patent 2,475,984 (July 12, 1949).
Pal’velev, V. T., Doklady A k a d . N a u k S.S.S.R., 65, 875-8
(1949).
Pamfilov, A. V., Devyatyhk, G. G., and Shirshova, L. V.,
Zhur. Fiz. K h i m . , 24, 292-8 (1950).
Pardee, W. A., and Elliott, G. E., U. S. Patent 2,493,896 (Jan.
10, 1950).
Partridgc, S. M., and Westall, R. G., Biochem. J., 44, 418-28
(1949).
Patrick, W. A., U. 8. Patent 2,503,168 (April 4,1950).
Perchet, R., Genie civil, 126, 208-9 (1949).
Perreu, Jean, Compt. rend., 229, 195-7 (1949); 228, 1427-9
(1949).
Tbid., 230, 642-4 (1950).
Perrot, M., and Arcaix, S., Ibid., 229, 1139-42 (1949).
Peters. R. H.. and Vickerstaff.. T... Proc. Rou. SOC.(London).
A192, 292-308 (1948).
Pierce, C., and Smith, R. N., J . Phys. & Colloid Chem., 54, 354-
64 (1950).
Pierce, J. A., U. S. Patent 2,506,316 (May 2, 1950).
Pierce. J. A.. and Kimberlin, C. N.. Jr. (to Standard Oil De-
velopment Co.), U. s. Patent 2,474,910 (July 5 , 1949).
Plank, C. J., Ibid., 2,499,680 (March 7, 1950)
Polak, Feliks, Roczniki Chem., 22, 181-90 (1948).
Pouradier, J., and iibribat, M., Research (London), Suppl.,
Surface Chemistry 1949, 135-44 (in French, English sum-
mary).
Prettre, Marcel, J . chim. phgs., 47, 99-103 (1950).
Radushkevich, L. V., and Lukyanovich, V. M., Zhur. Fiz.
Khim., 24, 21-42 (1950).
Rao, K. S., Rao, M. B., Vasudevamurthy, A. R., and Rao B. S.,
Proc. Nall. Inst. Sci. India, 16, 1-4 (1950).
Rauen, H. M., and Wolf, L., Z . physiol. Chem., 283, 233-42
(1948).
Ray, G. C., and Box, E. O., Jr., IND. ENG.CHEM.,42, 1315-18
(1950).
Reyerson, L. H., and Wertz, J. E., “Sorption of the Oxides of
Nitrogen on Carbon Surfaces,” 23rd Colloid Symposium.
Reyerson, L. H., and Wertz, J. E., “Sorption Studies on the
Bromine-Graphite System,” 23rd Colloid Symposium.
Rideal. E. K., and Trapnell, B. M. W., J . chim. phys., 47, 126-
38 (1950).
Riley, Vernon, Woods, M. W., and Burk, Dean, “Chromatog-
raphyas an Approach to the Problemof Separating Subcellular
Particulates,” 117th Meeting AM. CHEW SOC., Houston,
Tex., 1950.
Robinson, D. A., and Mills, G. F., IND.ENG.CHEM.,41,22214
(1949).
Vol. 43, No. 1
Rockland, L. B., and Dunn, M. S., Science, 109,539-40 (1949).
I b X , 111,332-3 (1950).
Roginskii, S. Z., and Yanovskii, hl. I., Zhur. Fiz. Khim., 24,
137-43 (1950).
Runov, A. D., Kiselev, A. V., Kiselev, V. F., and Alekseev, S.
N., Ibid., 23, 1005-17 (1949).
Russell, A. S.,and Cochran, c. N., IND. ENG.Cmbr., 42,1332-5
(1950).
Ibid., PP. 1336-40.
Sacconi, Luigi, Xature, 164, 70-1 (1949).
Sadek, H., and Taylor, H. S., J . Am. Chem. SOC.,72, 1168-75
(1950).
Sakurai and Hori, Bull. Inst. Phys. Chem. Research (Tokyo), 22,
760-8 (1943).
Sanders, J. V., Research (London), 2, 586-7 (1949).
Schaeffer, T.V. D., Polley, M. H., and Smith, W. R., J . Phys. &
Colloid Chem., 54, 227-39 (1950).
Schroeder, W. A,, “Hydrogen Bonding and Relative Adsorption
Affinities of Certain Derivatives of Diphenylamine and N -
Ethylaniline on Salicylic Acid,” 117th Meeting AM. CHEM.
SOC., Houston, Tex.
Seelioh, F., Monatsh., 79, 338-47 (1948).
Shafrin, E. G., and Zisman, W. A., J . Colloid Sci., 4, 571-90
(1949).
Shapiro, I., and Kolthoff, I. M., J . Am. Chem. Soc., 72, 776-82
(1950).
Shemyakin, F. A I . , and Mitselovskil, E. S.,Zhur. Anal. K h i m . ,
3, 349-53 (1948).
Shepard, C . C., and Tiselius, A., Discussions Faraday SOC.,No.
7, 275-85 (1949).
Shishniashviy, M. E., Isvest. A k a d . N a u k S.S.S.R., 1950, 169-
77.
Sierra, F., and Monllor, E., Anales As. y quim. (Madrid), 41,
234-48 (1945).
Smith, E. C. B., and Westall, R. G., Biochim. et Biophys. Acta,
4, 427-40 (1950) (in English).
Smith, E. D., and LeRosen, A. L., “Effect of Side Chain on
Chromatographie Adsorption of Some Ketones on Carbon,”
117th Meeting AM. CHEM.SOC., Houston, Tex., 1950.
Smith, W. R., and Beebe, R. A., IND.ENQ.C H E ~ 41, . , 1431-5
(1949).
Smith, W. R., and Schaeffer, W. D., Proc. 2nd Rubber Technol.
Conf. (London) 1948,403-13.
Standard Oil Development Co., Brit. Patent 590,252 (July 11,
1947).
Starodubstev, S. V., Zhur. Eksptl. Teoret. Fiz., 19, 215-24
(1949).
Stengler, G., and Krenkler, K., Erdol u. Kohle, 3, 120-4 (1950).
Strain, H. H., Frontiers in Chem. 8, (Frontiers in Colloid Chem-
istry) 29-63 (1950).
Strain, H. H., IND.ENG.CHEM.,42, 1307-10 (1950).
Takagi, Sadashige, J . Chem. SOC.J a p a n , 68, 5-6 (1947).
Tamaru, S., and Sato, K., Rev. Phys. Chem. J a p a n , Shinkichi
Horiba Commem. Vol., 1946, 1-5,
Tanaka, M., Ashizawa, T., and Shibata, M., Chem. Researches
( J a p a n ) , 5, Inorg. and Anal. Chem., 35-52 (1949).
Taylor, H. S., Adaances in Catalysis, 1, 1-26 (1948).
Taylor, H. S., Frontiers in Chem. 8, (Frontiers in Colloid Chem-
istrv). 1-28 (1950).
Taylor,”. S., i.ch&. p h w . , 47, 74-81 (1950).
Teichner, S., Ibid., 47, 118-21 (1950).
Tendeloo, H. J. C., Mans, A. E., and deHoogh, G., V I I Congr.
intern. inds. agr., Paris, 2, 182-8 (1948) (in English).
Tiselius, Arne, Naturwissenschaften, 37, 25-33 (1950).
Tiselius, Arne, Prix Nobel, 1948, 102-21.
Titov, E. M., Zavodskaya Lab., 13, 1359-64 (1947).
Todes, 0. &I.,and Bondareva, A. K., Zhur. Priklad. K h i m . ( J .
Applied Chem.), 21, 693-707 (1948).
Toropov, S. A., and Pylaev, A. V., Ibid., 22, 568-71 (1949).
Trapeznikov, A. A., Kolloid. Zhur., 12, 67-80 (1950).
Trillat, J. J., and Millet, J., J . recherches centre natl. recherche
sci. (Paris), 1950, No. 10, 32-5.
Troesch, A., J . chim. phys., 47, 145-7 (1950).
Ibid., pp. 148-56.
Trueblood, K. N., and Malmberg, E. W.,Anal. Chem., 21,
1055-8 (1949).
Utterback and Bergstrom, U. S. Patent 2,477,019 (July 26,
1949).
Vahrman, hl., Nature, 165, 404-5 (1950).
Vinogradov, G . V., and Borodulina, L. P., Zhur. Priklad. Khim.
( J . Applied Chem.), 21, 249-50 (1948).
Vogt, H., Pharm. Zentralhalle, 87, 38-44 (1948).
Vol’kenshtein, F. F., Zhur. Fio. Khirn., 23, 917-30 (1949).
Weatherburn, A. S., Rose, G. R. F., and Bayley, C. H., Can. J .
Research, 27F, 179-93 (1949).
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY 55
(303)Weir, H. M., U. S. Patent 2,485,249(Oct. 18, 1949). (311) Yang, J. T., and Haissinsky, M., Bull. SOC. chim. France, 1949,
(304) Wendel, K.,Planta, 37, 604-11 (1950). 540-7.
(305) White, L.,and Schneider, C. H., J . Am. Chem. SOC.,71,2945-6 (312) Zafir, M., Folia Pharm. ( T u r k e y ) , 1, No. 3, 29-31 (1949) (in
(1949). German).
(306)Wiig, E. O.,and Juhola, A. J., Ibid., 71,561-8 (1949). (313) Zettlemoyer, A. C., Chand, A., and Gamble, E., J. Am.
(307) Wilga, J., Mindler, A. G., and Gilwood, M. E., “Decolorieing Chem. Soc., 72, 2752-7 (1950).
Solutions by a Granular Synthetic Resin,” 117th Meeting (314) zettlemoyer, A. c.9Healey, F. H., and Fetsko, J. M., “Adsorp-
AM. CHEM.SOC., Houston, Tex., 1950. tion of Gases on Cadmium Oxide,” 117th Meeting Ana.
(308) Williams, T.I., Anal. Chim. Acta, 2,635-48 (1948)(in English). CHEM.SOC., Houston, Tex., 1950.
(309) Wolock, I., and Harris, B. L., IND. ENG.C H ~ M42, . , 1347-9 (315)zhdanovg s* Dokl&J Ahad* S*S-S*R*v681 99-102
(1950). (1949).
(310) Wustefeld, H., Arch. Metallcunde, 3, 223-4 (1949). RECEIVED
November 13, 1950.

CENTRIFUGATION ~ - - _ _ _ _
9m JAMES 0.MALONEY
UNIVERSITY OF K A N S A S , LAWRENCE, K A N .

A marked improvement in the material available on centrifugation i s noted. Several in- flow relationships in a basket centri-
vestigations obtained sufficient data to permit a comparison of theory-with practice (77, 58). fuge has been presented by Burak and
A new textbook (76) on unit operations provides an improved treatrnent,of centrifugation. Con- Storrow (17). They pointed out t h e
tinuous centrifuges for handling solids and liquids have been combined with mixers to extract limitations of the equation suggested
castor oil, linseed oil, and soya oil from the ground seeds continuously (6). The First unclassified by Maloney (479, and developed
information on the separation of uranium isotopes using centrifuges has appeared (74). others suitable for experimental veri-
fication. I n their experimental study
they suspended maize starch particles

D
URING the past year several books appeared containing
sections on centrifugation. The most voluminous treatment
occurs in Perry’s third edition of the “Chemical Engineers’
Handbook” (SO). -Only minor changes have been made in this
material since the first edition of 1934. The section might have
been improved by providing a bibliography on the subjeot, by
including descriptions and performance data on the units for
continuously handling slurries, and by bringing the cost in-
formation up to date. All of the information necessary is readily
available (27, 47-61, 68, 81). The discussion by Brown et al.
(16) represents a marked improvement over those in earlier texts.
These authors give, for the first time, an illustrated description
of modern equipment, a discussion of the theoretical aspects of
the subject, a bibliography, and some problems. But this dis-
cussion, like those in all the other standard texts, might be im-
proved by the inclusion of illustrative examples and a comparison
of calculated results with actual performance data. Such ex-
amples and comparisons are furnished in relation to other opera-
tions b u t not for centrifugation. Golding (35) has published
an adequate treatment of centrifuges for laboratory use. His
discussion includes a number of illustrative examples exhibiting
the method for calculating; the time required for certain particles
to be separated by centrifugal action; the relative centrifugal
force in test tube units; and the pressures developed in the
centrifuging tubes. The account could serve.as an introduction
to the field. Nichols and Bailey ( 6 4 ) have written extensively on
N the ultracentrifuge as a laboratory device.
Review articles on the subject have continued t o appear.
They include a description of lubricating oil centrifuges together
with operating instructions ( I O ) ; a review of applications of the
ultracentrifuge in research and practice (45); and a review (in
German) of American centrifugal practice and its developments
(63).
F U N D A M E N T A L STUDIES
Noteworthy progress is being made in the development of
fundamental information in this field. Investigators are begin-
ning t o study the variables affecting the performance of cen-
trifugal machines. One of the few theoretical treatments of the
of about 12 microns in diameter in water and centrifuged them in
a perforated basket fitted with a fabric medium. A comparison of
data on cakes of various thicknesses showed t h a t the starch was
uniformly packed. The rate of passage of water through various
thicknesses of previously deposited cake was not proportional
to the square of the speed of rotation, as predicted by the theo-
retical equations. The authors attempted, without success, to
correlate the data by putting the deviations into the permeability
term. Then they made filtration studies on deposited filter cakes
and also on cakes first formed in the centrifuge and then carefully
inserted into the filter cell. Their results were somewhat confus-
ing and bear out the results of Wilcox (81),who was forced t o
conclude that his filter-cell experiments did not give results com-
parable with those obtained in a centrifuge. I n such a study,
some simplification might have been obtained by the employment
of carefully sized and incompressible materials, such as silica.
German workers (14) reported descriptions and performance
data on several centrifuges that were used for separating gaseous
isotopes. Studies were conducted on xenon, krypton, selenium,
and uranium isotopes. The rotors were of the tubular variety
subdivided into from 1 to 10 chambers. The rotor diameters
were as great as 12 cm. and the lengths were as great as 67 cm.
Speeds u p to 60,000 revolutions per minute were employed. In
the separation of UFc isotopes, the separation factors ranged
from 1.01 to 1.06.
An extensive study of the variables affecting the clarification
of sulfate liquors in a Bird continuous centrifuge has been re-
ported (68). The main value of this investigation to readers
outside the paper industry lies in the proof that the performance
of this machine is qualitatively predictable from theoretical
considerations. Conclusions of general interest include: The
percentage of solids in the liquor in the centrifuge increased
rapidly above a certain feed rate; a decrease in the operating
temperature of the feed liquor from 195’ to 165” F. roughly
doubled the percentage of solids in the effluent; a marked in-
crease in the percentage of solids in the effluent occurred if the
feed liquor contained more than 10% of solids. Richardson and
Lyons (60)have obtained operating information on the dewater-
ing of coal in a Bird continuous unit (Figure 1). Because of the
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY 55
(303)Weir, H. M., U. S. Patent 2,485,249(Oct. 18, 1949). (311) Yang, J. T., and Haissinsky, M., Bull. SOC. chim. France, 1949,
(304) Wendel, K.,Planta, 37, 604-11 (1950). 540-7.
(305) White, L.,and Schneider, C. H., J . Am. Chem. SOC.,71,2945-6 (312) Zafir, M., Folia Pharm. (Turkey), 1, No. 3, 29-31 (1949) (in
(1949). German).
(306)Wiig, E. O.,and Juhola, A. J., Ibid., 71,561-8 (1949). (313) Zettlemoyer, A. C., Chand, A., and Gamble, E., J. Am.
(307) Wilga, J., Mindler, A. G., and Gilwood, M. E., “Decolorieing Chem. Soc., 72, 2752-7 (1950).
Solutions by a Granular Synthetic Resin,” 117th Meeting (314) zettlemoyer, A. c.9Healey, F. H., and Fetsko, J. M., “Adsorp-
AM. CHEM.SOC., Houston, Tex., 1950. tion of Gases on Cadmium Oxide,” 117th Meeting Ana.
(308) Williams, T.I., Anal. Chim. Acta, 2,635-48 (1948)(in English). CHEM.SOC., Houston, Tex., 1950.
(309) Wolock, I., and Harris, B. L., IND. ENG.C H ~ M 42,. , 1347-9 (315)zhdanovg s* Dokl&J Ahad* S*S-S*R*v681 99-102
(1950). (1949).
(310) Wustefeld, H., Arch. Metallcunde, 3, 223-4 (1949). RECEIVED
November 13, 1950.

CENTRIFUGATION ~ - - _ _ _ _
9m JAMES 0.MALONEY
UNIVERSITY OF K A N S A S , LAWRENCE, K A N .

A marked improvement in the material available on centrifugation i s noted. Several in- flow relationships in a basket centri-
vestigations obtained sufficient data to permit a comparison of theory-with practice (77, 58). fuge has been presented by Burak and
A new textbook (76) on unit operations providesan improved treatrnent,of centrifugation. Con- Storrow (17). They pointed out t h e
tinuous centrifuges for handling solids and liquids have been combined with mixers to extract limitations of the equation suggested
castor oil, linseed oil, and soya oil from the ground seeds continuously (6). The First unclassified by Maloney (479, and developed
information on the separation of uranium isotopes using centrifuges has appeared (74). others suitable for experimental veri-
fication. I n their experimental study
they suspended maize starch particles

D
URING the past year several books appeared containing
sections on centrifugation. The most voluminous treatment
occurs in Perry’s third edition of the “Chemical Engineers’
Handbook” (SO). -Only minor changes have been made in this
material since the first edition of 1934. The section might have
been improved by providing a bibliography on the subjeot, by
including descriptions and performance data on the units for
continuously handling slurries, and by bringing the cost in-
formation up to date. All of the information necessary is readily
available (27, 47-61, 68, 81). The discussion by Brown et al.
(16) represents a marked improvement over those in earlier texts.
These authors give, for the first time, an illustrated description
of modern equipment, a discussion of the theoretical aspects of
the subject, a bibliography, and some problems. But this dis-
cussion, like those in all the other standard texts, might be im-
proved by the inclusion of illustrative examples and a comparison
of calculated results with actual performance data. Such ex-
amples and comparisons are furnished in relation to other opera-
tions b u t not for centrifugation. Golding (35) has published
an adequate treatment of centrifuges for laboratory use. His
discussion includes a number of illustrative examples exhibiting
the method for calculating; the time required for certain particles
to be separated by centrifugal action; the relative centrifugal
force in test tube units; and the pressures developed in the
centrifuging tubes. The account could serve.as an introduction
to the field. Nichols and Bailey (64)have written extensively on
N the ultracentrifuge as a laboratory device.
Review articles on the subject have continued t o appear.
They include a description of lubricating oil centrifuges together
with operating instructions ( I O ) ; a review of applications of the
ultracentrifuge in research and practice (45); and a review (in
German) of American centrifugal practice and its developments
(63).
F U N D A M E N T A L STUDIES
Noteworthy progress is being made in the development of
fundamental information in this field. Investigators are begin-
ning t o study the variables affecting the performance of cen-
trifugal machines. One of the few theoretical treatments of the
of about 12 microns in diameter in water and centrifuged them in
a perforated basket fitted with a fabric medium. A comparison of
data on cakes of various thicknesses showed t h a t the starch was
uniformly packed. The rate of passage of water through various
thicknesses of previously deposited cake was not proportional
to the square of the speed of rotation, as predicted by the theo-
retical equations. The authors attempted, without success, to
correlate the data by putting the deviations into the permeability
term. Then they made filtration studies on deposited filter cakes
and also on cakes first formed in the centrifuge and then carefully
inserted into the filter cell. Their results were somewhat confus-
ing and bear out the results of Wilcox (81),who was forced t o
conclude that his filter-cell experiments did not give results com-
parable with those obtained in a centrifuge. I n such a study,
some simplification might have been obtained by the employment
of carefully sized and incompressible materials, such as silica.
German workers (14) reported descriptions and performance
data on several centrifuges that were used for separating gaseous
isotopes. Studies were conducted on xenon, krypton, selenium,
and uranium isotopes. The rotors were of the tubular variety
subdivided into from 1 to 10 chambers. The rotor diameters
were as great as 12 cm. and the lengths were as great as 67 cm.
Speeds u p to 60,000 revolutions per minute were employed. In
the separation of UFc isotopes, the separation factors ranged
from 1.01 to 1.06.
An extensive study of the variables affecting the clarification
of sulfate liquors in a Bird continuous centrifuge has been re-
ported (68). The main value of this investigation to readers
outside the paper industry lies in the proof that the performance
of this machine is qualitatively predictable from theoretical
considerations. Conclusions of general interest include: The
percentage of solids in the liquor in the centrifuge increased
rapidly above a certain feed rate; a decrease in the operating
temperature of the feed liquor from 195’ to 165” F. roughly
doubled the percentage of solids in the effluent; a marked in-
crease in the percentage of solids in the effluent occurred if the
feed liquor contained more than 10% of solids. Richardson and
Lyons (60)have obtained operating information on the dewater-
ing of coal in a Bird continuous unit (Figure 1). Because of the
56 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 43, No. P

est to anyone confronted with a

similar problem.

N E W EQUIPMENT

The new equipment which has

come to the reviewer's attention
during the last year is listed in
Table I, together with the source
and the field of application.

APPLICATIONS

Figure I. Bird Centrifugals for Dewatering Fine Coal after Washing
These epnbilugals handle feeds
K e x applications of centrifugal
equipment are listed in Table 11.
Some of them, however, deserve
special mention. A three-stage sol-
vent extraction process suitable for
recovering castor oil, linseed oil, or
soya oil has been developed, which
uses continuous Bird centrifuges to
separate the solids from the solvent
after they have been combined in
the mixers (6). The margarine,
lard, and other edible oil industries
are turning to centrifugal methods
as a solution to their separation
problems (20, 6 7 , 79). T h e
pharmaceutical houses are using
c e n t r i f u g e s m o r e and more in
production operations (66).
UP to 500 gallons per minute and coal up to 60 tons per hour
N E W TECHNIQUES AND AUXlLlARlES

specific nature of the operation and of certain operational diffi-
cultiw, only limited conclusions could be drawn.
Quartz sands containing 8 to 10% moisture were successfully
dewatered in a sugar refinery centrifuge (82). As would be ex-
pected, the residual moisture decreased with the decreasing thick-
ness of the sand layer. It ranged from 2.2 to 2.8%.
Adler and Blanchard (1j made an analysis of the errors in-
herent in the Lamm scale method for the measurement of con-
centration gradients in the ultracentrifuge. They found that
under the condition usually applied, the Lamm formula gives a
systematic error of about 1%. The theory of the separation of
suspended particles in a supercentrifuge has been elaborated (71).
T h e effect of gradients of centrifugal force on the potential of
siniple galvanic cells has been studied ( 4 6 ) ; in the experiment,
the method of making the electrical connections between the
rotating apparatus and the measuring equipment will be of inter-
A technique for using centrifugal force for the filtration of
materials out of blood and plasma has been described (40). In
certain cases it is necessary t o maintain materials being centri-
fuged just above 32" F. A simple procedure for doing this hae
been described (7%). I n determining the sedimentation con-
stants of materials by means of the ultracentrifuge, one must
know the temperature of the solution. A device has been de-
scribed which permits the determination of' the solution's tem-
perature to within 0.1"C. (26). The application of centrifugal
techniques to the separation of small quantities of material has
been reported by Feldman el al. (29). A new and versatile micro-
centrifugation apparatus has been described ($6).
Auxiliaries of interest to centrifuge users include: a plastic
cover ior a 40-inch centrifuge which permits the operator to
observe the filling operation and prevents spillage and spashing
( 7 ) ; an acrylic rotor for the Fisher-Stern ultracentrifuge (11);

Table 1. N e w Equipment Developments in Centrifugals

Name Application Manufacturer or Designer Reference
S-15 continuous centrifuge For relatively free-draining materials Baker Perkins, Inc. (46)
HS-24 universal centrifuge For filtering finely divided solids Baker Perkins, Iuc. (46)
Wort clarifier Brewing industry De Lava1 Separator Co. (62)
Beer clarifier Brewing industry De Lava1 Separator Co. (62)
Dorr Clone .4 separator employing a high velocity stream directed in Dorr C o .
a circular path to separate solids from liquids
Special basket For throwing down mercury in thermometers Fletcher Works, Inc.
Portable refrigerated Centrifuge For biological, pharmaceutical,. and other applications International Equipment Go. (8%
where temperature control IS important
R-8 laboratory unit Small unit for research and development work Memo Centrifugal Co.
Batch centrifugal clarifier Study of desliming operations prior to selection of Bird Sackett
continuous machine
PY-14 cylindrical Super-D-Cantor Continuous Separation of liquids from solids with good Sharples Corp.
liquid clarity
DV-2 controlled solids discharge Clarification of flnids containing solids (pineapple juice) Sharples Corp.
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY S?
(21) Demmerle, R. L., et al.,IND.
Table 11.Applications of Centrifugal Equipment ENG. CREM., 42, 2-12
(1950).
Manufacturing Procass Type of Unit Materials Separated Denhard, H. W., U. S.
Diammonium phosphate Perf orate basket Diammonium phosphate crystals Patent 2,490,421(Dee. 6,
Potassium salts Bird continuous KCI and KISO~crystals 1949).
Reagent grade chemicals Perforate basket BaCh Mgsor, Fe “4)2, Sod,
KIbc, NHnCsHrS,brH, CuCNS Dixon, A. G., private com-
Worts m u n i c a t i o n (October
Ground beans 1950).
Intermediates
Various colloida Druel, M., and Huit-Fidor.
Dextrose G., French Patent 933,500
Edible oils De Lava1 n:i
F-Actomyoinn Ultracentrifuge F-Actomyoin (April 22. 1948).
Lard Sharples tubular Lard Dubbs, C. A., Anal. Chem.,
Margarine Tubular unit Oil 21, 1273-6 (1949).
Melamine Perforate basket Melamine crystals Ecker, P. G., etal., Rev. Sci.
Pawr Hydroclone Forei n material from paper s t ock
Paper Tangential injector Dirt Jrom paper stock Instruments, 20, 799-801
Phloroglucinol Perforate basket Trinttrobenzene (1949).
Phloroglucinol Eckhardt, H., Chem. Eng.,
Phenol Bird Continuous Sodium sulfate crystals 54,NO. 5 , 121-3 (1947).
Phenol recovery Perforate basket Sodium phenolate Evans, H. C., and Winsor,
Proteina Uftracentrtfu a1 Protein muscle P. A., Proc. Inst. Sewage
Sugar Perforate bastet Sugar
Wool scouring ......... Grease P u r t & u t h (Enol.) 1949,
a Not a commercial operation. 365-70.
Feldman, I., et al., Anal.
C h m . , 22, 837-8 (1950).
” Flowers, A. F.,and Hull, S.
H.. in “Chemical Enei-
a spring for adjusting the belt tension on the Merco centrifuge neers’ Handbook,” 3rd ed., pp. 992-1013,New York, McGraG-
(9) (Figure 2); a new method of manufacturing the drip pan for Hill Book Co., 1950.
Foa, Mario, Ital. Patent 443,602 (Dee. 29, 1948).
the Sharples centrifuges (IS); and removable screen plates and Gerard, F., Bull. assoc. anciens 6tud. brass. univ. Louvain, 45,
wear plates for the McNally-Carpenter centrifugal dryer (8). 149-58 (1949).
Golding, H.B.,in “Technique of Organic Chemistry,” Vol. 111,
RECENT PATENTS pp. 143-70, New York, Interscience Publishers, 1950.
Hessey, R. W. G., and Manning, R. N., Proc. Qzaemland SOC.
The recent patents issued are tabulated below: Sugar Cane Technol., 16,87-107 (1949).
Centrifugal apparatus for aerosol production (31 ) Hoover, M. M., Chem. Eng., 57,No.4,132-4 (1950).
Centrifugal concentration of latex ( 3 7 ) Industria mecannica moline ed affini, Ital. Patent 443,510
(Dec. 27, 1948).
Centrifugal foam breaker (66) Jones, E. P., U. S. Patent 2,475,141(July 5,1949).
Centrifugal ore concentrates (19) Kastens, M.L.,and Kaplan, J. F., IND. ENO.CHEM.,42,402-13
Centrifugal separator of entrained oil from steam (18) (1950).
Centrifugal separator for sour cream products (4.4) Kenyon, R. L., and Boehmer, N., Ibid., 42, 1446-55 (1950).
Latner, A. L.,and Slack, E. B., Nature, 165,530-1 (1950).
Centrifuge for clarification of wines and juices (36) Lindgren. H.O.,U. S. Patent 2,478,971(Aug. 16,1949).
Centrifuge for extruding fibers, particularly glass fibers (56) Lipecomb, G., U. S. Patent 2,506,882(May 9,1950).
Centrifuge for the purification of liquids (78) Loewe, H., PkurmaZie, 4, 416-24 (1949).
Centrifuge for washing paper pulp (4%) Lundal, I. J., U. 8.Patent 2,485,209(Oct. 18, 1949).
MacInnes, D.A,, and Ray, B. R., J . Am. C h m . Soc., 71,2987-92
Combined centrifugal and vacuum dryer of pharmaceutical (1949).
preparations (15 )
Continuous operation centrifuge ( 7 3 )
Extracting oil, etc., from soybeans ($4)
Foam breaker in the form of a basket centrifuge (28)
Multistage separation of starch tailings ( 7 4 )
Purifying sugar juice ( 4 1 )
Separation of aconitic acid from moIasses (3)
Vertical continuous centrifuge ( 7 7 )

LITERATURE CITED
(1) Adler, F. T.,and Blanchard, C. H., J . Phys. & Colloid Chem.,
53,803-10 (1949).
(2) Amberson, W. R., et al., J. Biol. Chem., 181,405-13 (1949).
(3) Ambler, J. A,, and Roberts, E. J., U. S. Patent 2,481,557(Sept.
13, 1949).
(4) Anon., Chem. Eng., 57,No. I, 168-71 (1950).
(5) Ibid., No. 6,p. 146.
1
(6) Anon., Chem. Inds., 64. 926-9 (1949).
(7) Ibid. 66. 266 (1950).
\ - I

i8) Ibid.: p. 580.

(9) Anon., Machine Design, 22,No.5,106 (1950).
(10)Anon., Marine Eng., 54,No.5, 66 (1949).
(11) Anon., Modern Plastics, 26,No. 4, 115 (1948).
(12) Anon., Product Eng., 21, No. 1, 100 (1950).
(13) Armstrong, T. R., private communication (October 1950).
(14) Beyerle, K.,et al., Chem. Ing. Tech., 21,331-4 (1949).
(15) Bierwirth, R. A., U. S. Patent 2,512,604(June 27, 1950).
(16) Brown, et al., “Unit Operations,” pp. 258-68, New York, John
Wiley & Sons, 1950.
(17) Burak, N., and Storrow, J. A,, J . SOC.Chem. Ind. ( L d o n ) ,
69,8-13 (1950).
(18) Campbell, J. A., U. S. Patent 2,511,967(June 20, 1950).
(19) Chisholm, G. G., Ibid., 2,502,704(April 4, 1950).
(20) Deatherage, F. E., FoodZnds., 21, 1749-52, 1894-5 (1949). Figure 2. N e w Design of Merco Centrifuge
58 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 43, No. 1
(46) Mack, K. A., private communication (October 1950). (64) Sackett, E. L. H., Eng. Mining J., 151, No. 4, 79-80 (1950).
(47) Maloney, J. O., IND.E N G .CHEM.,38, 24-5, 37 (1946). (65) Seidel, K., Brauwelt, 4, 53-6 (1949).
(48) Ibid., 39, 16, 35 (1947). (66) Sharples, L. P., U. S. Patent 2,489,678 (Nov. 29, 1949).
(49) Ibid., 40, 8-9 (1948). (67) Shearon, W. H., Jr., IND.E K G .C m x , 42, 1266-78 (1950).
(50) Ibid., 41, 19-21 (1949). (68) Smith, J. C., Chem. Inds., 65, 357-64 (1949).
(51) Ibid., 42, 25-6 (1950). (69) Snellman, 0.. and Erodos, T., Biochim. et Biophys. Acta, 3,
(52) Meystre, F. J., Jr., private communication (October 1950). 523-6 (1949).
(53) Miessner, H., Chemie Ing. Tech., 21, 409-12 (1949). (70) Sokolov, V. I., Kolloid. Zhur. 9, 447-9 (1947).
(54) Nichols, J. B., and Bailey, E. D., in “Technique of Organic (71) Sokolov, V. I . , Zawdskaya Lab., 14, 4 3 5 4 0 (1948).
Chemistry,” 2nd ed., Vol. I, pp. 621-730, New York, Inter- (72) Stocking, C. R., and Weier, T. E . , Science, 111, 520 (1950).
science Publishers, 1949. (73) Stolbovoi, F. K., Russ. Patent 69,430 (Oct. 31, 1947).
(55) Olive, T. R., Chem. Eng., 56, No. 10, 112-13 (1949). (74) Strezynski, G. J., U. S. Patent 2,488,747 (Nov. 22, 1949).
(56) Peyches, I., U. S. Patent 2,497,369 (Feb. 14, 1950). (75) Thompson, H. L., et al., IND. E K G .CHEM.,42, 2176-82 (1950).
(57) Pomeroy, H. H., private communication (October 1950). (76) Thompson, N. B., Sewage and Ind. Wastes, 22, 205-6 (1950).
(58) Reed, A. E., and Gillespie, W. F., Tech. Assoc. Pulp Paper Ind., (77) Vidman, A. I . , Russ. Patent 69,996 (Dec. 31, 1947).
32,529-34 (1949). (78) Wieland, C. W., Swiss Patent 238,684 (Kov. 16, 1945).
(59) Reynolds, V. L., Ibid., 32, 454, 457 (1949). (79) White, E . D., Food Inds., 22, 1538-41 (1950).
(60) Richardson, A. C., and Lyons, 0. R., Mining Eng., 187, 381-4 (80) White, W.A., Paper Trade J., 130, KO.4, 76, 78-83 (1950).
(1950). (81) Wilcox, A. C., University of Kansas, thesis, 1947.
(61) Rogge, R. H., IND.E N G .CHEM.,41, 2070-5 (1949). (82) Zhitomirskaya, E. Z., and Meitina, V. A., Stekol’naya i Keram.
(62) Rometsch, W. H., private communication (October 1950). Prom., 6, No. 8 , 15-16 (1949).
(63) Rostripenko, I. A., Sakharnaya Prom., 23, No. 2, 32-3 (1949). RECEIVED
October 24, 1950.

RYSTALLIZATION
C. S. GROVE, JR., AND J. B. GRAY
SYRACUSE UNIVERSITY, EAST SYRACUSE, N. Y.

Few advances in theoretical correlation of crystallization phenomena have been reported theory and practice. It is stated
during the past year. Emphasis has been placed on the effects of additions, as chemical ions, that new nuclei may originate in situ
or physical treatments on both rate of crystallization and crystal habit. M u c h work has been in one or more of the following ways:
reported on oriented growth of crystals on other crystalline or amorphous surfaces. A new 1. By spontaneous n u c l e a t i o n
field of application of crystallization has been opened up b y the use of crystalline complexes from unseeded solution
2. By attrition of existing crystals
of urea and straight-chain hydrocarbons to separate straight-chain from branched and cyclic 3. By mechanical impact
hydrocarbons. Processes for growing piezoelectric crystals have been improved. When ethylene 4. By formation of new crystals
because of the inoculating influence
glycol and ethyl alcohol are added to aqueous solutions of sodium sulfate, the deposition of of crystals already present
solids on heating surfaces due to a lower solubility in water at higher temperature is avoided. 5. BY nucleation in restricting
zones c a k e d by local variations in th;
concentration of the solution

c RYSTALLIZATION processes have continued to receive

increased study and development. There have been
many investigations reported on the factors affecting the
growth of crystals and the mechanisms involved in this growth.
New techniques and improvements in industrial processes have
been described. However, a satisfactory broad theoretical treat-
ment of crystallization has not been reported.
N U C L E A T I O N AND RATE OF G R O W T H
The difficulty in formulating a complete theory describing
the rates of formation of nuclei and growth of crystals is well
expressed by Kirk and Othmer (47), who state:
The mechanism of this process is very complex, as it involves
the phenomena of diffusion, formation of nuclei, and crystal
growth, all of which can take place a t the same time. No exact
numerical calculations of the rates of any of these can be made at
the present time so that, as a unit operation, crystallization is
still highly empirfical in its methods. Because of this lack of any
precise design calculations, the types of crystallizers have been
numerous. T o add to the designer’s difficulty, it is frequently
necessary t o produce crystals of a given shape, size, uniformity,
and state of agglomeration as well as purity.
However, the current status of crystallization theory and
practice is summarized in some detail by these authors.
Brown (IO) has pointed out that the problems concerning
crystallization which are most frequently encountered deal with
yields, purity, energy requirements, shape, size, and uniformity
of the crystalline product, and rate of production of the desired
crystals. Perry (61) has summarized in detail crystallization
Umstatter and Hansen-Dannenitz (86) discuss the kinetics of
precrystalline phases in liquids. They state that the inner
friction of liquids is caused by the dispersion of transverse shear-
ing waves propagating perpendicular to the gliding planes.
The damping of these vibrations is proportional to the viscosity.
In case of nonperiodic damping the viscosity becomes infinitely
high a t certain phases of the vibrations, and at these pointscrystal
nuclei form. This indicates that the future crystal systems are
already preformed in the liquids, which are accordingly precrys-
talline systems rather than systems of complete disorder.
Becker (4) has discussed the kinetics of the formation of nuclei
on the basis of the statistical theory of condensation. Turnbull
and Fisher (84) have derived an expression for the absolute rate
of nucleation in condensed systems on the basis of a nucleation
theory. Bransom, Dunning, and Millard (9) further amplify the
theories of crystallization.
Van Hook and Bruno (88) have reported on nucleation and
crystal growth in sucrose solutions. The beginning of crystalliaa-
tion in sirups may be represented by an equation of the form:
(0 -a)t = constant
where 0 is the supersaturation, t is the time, and a is a constant,
It was found that nucleation was not affected by stirring below a
certain supersaturation; but, above this supersaturation, the
higher the concentration and the faster the stirring, the more
rapidly nucleation took place.
Crystallization from nonaqueous solutions has been studied
by Chatterji and Bose (WO), whose work shows that nonaqueous
58 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 43, No. 1
(46) Mack, K. A., private communication (October 1950). (64) Sackett, E. L. H., Eng. Mining J., 151, No. 4, 79-80 (1950).
(47) Maloney, J. O., IND.ENG.CHEM.,38, 24-5, 37 (1946). (65) Seidel, K., Brauwelt, 4, 53-6 (1949).
(48) Ibid., 39, 16, 35 (1947). (66) Sharples, L. P., U. S. Patent 2,489,678 (Nov. 29, 1949).
(49) Ibid., 40, 8-9 (1948). (67) Shearon, W. H., Jr., IND.EKG.C m x , 42, 1266-78 (1950).
(50) Ibid., 41, 19-21 (1949). (68) Smith, J. C., Chem. Inds., 65, 357-64 (1949).
(51) Ibid., 42, 25-6 (1950). (69) Snellman, 0.. and Erodos, T., Biochim. et Biophys. Acta, 3,
(52) Meystre, F. J., Jr., private communication (October 1950). 523-6 (1949).
(53) Miessner, H., Chemie Ing. Tech., 21, 409-12 (1949). (70) Sokolov, V. I., Kolloid. Zhur. 9, 447-9 (1947).
(54) Nichols, J. B., and Bailey, E. D., in “Technique of Organic (71) Sokolov, V. I . , Zawdskaya Lab., 14, 4 3 5 4 0 (1948).
Chemistry,” 2nd ed., Vol. I, pp. 621-730, New York, Inter- (72) Stocking, C. R., and Weier, T. E., Science, 111, 520 (1950).
science Publishers, 1949. (73) Stolbovoi, F. K., Russ. Patent 69,430 (Oct. 31, 1947).
(55) Olive, T. R., Chem. Eng., 56, No. 10, 112-13 (1949). (74) Strezynski, G. J., U. S. Patent 2,488,747 (Nov. 22, 1949).
(56) Peyches, I., U. S. Patent 2,497,369 (Feb. 14, 1950). (75) Thompson, H. L., et al., IND. EKG.CHEM.,42, 2176-82 (1950).
(57) Pomeroy, H. H., private communication (October 1950). (76) Thompson, N. B., Sewage and Ind. Wastes, 22, 205-6 (1950).
(58) Reed, A. E., and Gillespie, W. F., Tech. Assoc. Pulp Paper Ind., (77) Vidman, A. I., Russ. Patent 69,996 (Dec. 31, 1947).
32,529-34 (1949). (78) Wieland, C. W., Swiss Patent 238,684 (Kov. 16, 1945).
(59) Reynolds, V. L., Ibid., 32, 454, 457 (1949). (79) White, E . D., Food Inds., 22, 1538-41 (1950).
(60) Richardson, A. C., and Lyons, 0. R., Mining Eng., 187, 381-4 (80) White, W.A., Paper Trade J., 130, KO.4, 76, 78-83 (1950).
(1950). (81) Wilcox, A. C., University of Kansas, thesis, 1947.
(61) Rogge, R. H., IND.ENG.CHEM.,41, 2070-5 (1949). (82) Zhitomirskaya, E. Z., and Meitina, V. A., Stekol’naya i Keram.
(62) Rometsch, W. H., private communication (October 1950). Prom., 6, No. 8 , 15-16 (1949).
(63) Rostripenko, I. A., Sakharnaya Prom., 23, No. 2, 32-3 (1949). RECEIVED
October 24, 1950.

RYSTALLIZATION
C. S. GROVE, JR., AND J. B. GRAY
SYRACUSE UNIVERSITY, EAST SYRACUSE, N. Y.

Few advances in theoretical correlation of crystallization phenomena have been reported theory and practice. It is stated
during the past year. Emphasis has been placed on the effects of additions, as chemical ions, that new nuclei may originate in situ
or physical treatments on both rate of crystallization and crystal habit. M u c h work has been in one or more of the following ways:
reported on oriented growth of crystals on other crystalline or amorphous surfaces. A new 1. By spontaneous n u c l e a t i o n
field of application of crystallization has been opened up b y the use of crystalline complexes from unseeded solution
2. By attrition of existing crystals
of urea and straight-chain hydrocarbons to separate straight-chain from branched and cyclic 3. By mechanical impact
hydrocarbons. Processes for growing piezoelectric crystals have been improved. When ethylene 4. By formation of new crystals
because of the inoculating influence
glycol and ethyl alcohol are added to aqueous solutions of sodium sulfate, the deposition of of crystals already present
solids on heating surfaces due to a lower solubility in water at higher temperature is avoided. 5. BY nucleation in restricting
zones c a k e d by local variations in th;
concentration of the solution

c RYSTALLIZATION processes have continued to receive

increased study and development. There have been
many investigations reported on the factors affecting the
growth of crystals and the mechanisms involved in this growth.
New techniques and improvements in industrial processes have
been described. However, a satisfactory broad theoretical treat-
ment of crystallization has not been reported.
NUCLEATION AND RATE OF G R O W T H
The difficulty in formulating a complete theory describing
the rates of formation of nuclei and growth of crystals is well
expressed by Kirk and Othmer (47), who state:
The mechanism of this process is very complex, as it involves
the phenomena of diffusion, formation of nuclei, and crystal
growth, all of which can take place a t the same time. No exact
numerical calculations of the rates of any of these can be made at
the present time so that, as a unit operation, crystallization is
still highly empirfical in its methods. Because of this lack of any
precise design calculations, the types of crystallizers have been
numerous. T o add to the designer’s difficulty, it is frequently
necessary t o produce crystals of a given shape, size, uniformity,
and state of agglomeration as well as purity.
However, the current status of crystallization theory and
practice is summarized in some detail by these authors.
Brown (IO) has pointed out that the problems concerning
crystallization which are most frequently encountered deal with
yields, purity, energy requirements, shape, size, and uniformity
of the crystalline product, and rate of production of the desired
crystals. Perry (61) has summarized in detail crystallization
Umstatter and Hansen-Dannenitz (86) discuss the kinetics of
precrystalline phases in liquids. They state that the inner
friction of liquids is caused by the dispersion of transverse shear-
ing waves propagating perpendicular to the gliding planes.
The damping of these vibrations is proportional to the viscosity.
In case of nonperiodic damping the viscosity becomes infinitely
high a t certain phases of the vibrations, and at these pointscrystal
nuclei form. This indicates that the future crystal systems are
already preformed in the liquids, which are accordingly precrys-
talline systems rather than systems of complete disorder.
Becker (4) has discussed the kinetics of the formation of nuclei
on the basis of the statistical theory of condensation. Turnbull
and Fisher (84) have derived an expression for the absolute rate
of nucleation in condensed systems on the basis of a nucleation
theory. Bransom, Dunning, and Millard (9) further amplify the
theories of crystallization.
Van Hook and Bruno (88) have reported on nucleation and
crystal growth in sucrose solutions. The beginning of crystalliaa-
tion in sirups may be represented by an equation of the form:
(0 -a)t = constant
where 0 is the supersaturation, t is the time, and a is a constant,
It was found that nucleation was not affected by stirring below a
certain supersaturation; but, above this supersaturation, the
higher the concentration and the faster the stirring, the more
rapidly nucleation took place.
Crystallization from nonaqueous solutions has been studied
by Chatterji and Bose (WO), whose work shows that nonaqueous
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY
solutions may be classified in the same way as aqueous solutions.
If the attraction between lattice-forming units is low, it is possible
that no nuclei will form, even though there is a large probability
of molecular impacts.
Kaishev (44) has reported studies on hexamethylenetetramine
crystals to test the growth and disintegration mechanism of
homopolar crystals. Ubbelohde (85) has presented a discussion
of the role of diffusion potentials in the growth of ionic crystals.
Bunn and Emmett (IS) discuss layer formation on crystal faces as
growth takes place from solution.
A review of the kinetics of crystal growth has been prepared
by Thompson (80),who describes new work bearing on the ques-
tion of the reality of the Volmer layer, utilizing data obtained
by interferometric methods. The crystallochemical theory of the
actual growth of crystals in electrolysis is discussed by Gorbunova
x and Dankov ($7) in a critical review containing 31 references.
Ono (57) has considered some precipitation phenomena un-
accountable for by an induction period, saturation, or other simple
factors. This is explained by a study of the chemical equilibrium
between crystals of various sizes. An equation is derived which
w
expresses the change of concentration as a time function. The
velocities of the formation of the nucleus and of the growth of
crystals are secondary and tertiary variables. Burton, Cabrera,
and Frank (16) have examined nucleation theory and crystal
growth with particular reference to the shape of the critical nu-
cleus. Discrepancy between observed and theoretical values is
reconciled by recognizing that the crystals that grow are not
perfect, but contain dislocations. Crystals in low supersatura-
tions do not grow without the presence of dislocations.
On the basis of Gibb’s postulate t h a t the equilibrium shape of
a crystal is that of minimum total surface free energy for a given
volume, Wells (98) has derived the conditions governing the rela-
tive developments of cube and octahedron faces on a cubic crystal.
For an equilibrated crystal, grown from a pure solution, the
rate of growth normal t o a face is directly proportional to its
surface free energy per unit area.
Burton and Cabrera (16) have discussed crystal growth and its
relation to surface structure. The rates of growth of crystals
are said by Bunn and Emmett (14) to be related to concentration
gradients.
Sorgato (70) has summarized work on crystallization of anhy-
drous dextrose. A method of calculation of final crystallization
temperature to give maximum production per unit time, in proc-
esses based on temperature gradients with no evaporation of
solvent, has been given by Martinez (61);cases of ferrous sulfate
and ferric chloride are cited as examples of the method. Tipson
(82) has discussed the theory, scope, and methods of recrystalliza-
tion as applied to the separation and purification of organic
compounds.
In a description of the structure of molecular compounds,
Powell (62) has prepared crystals of quinol at high pressures
aontaining argon, krypton, and xenon. The rate of precipita-
tion of barium sulfate, when barium acetate is added t o a dilute
solution of potassium sulfate, has been found by Duke, Bever,
and Diehl (29) to be dependent on various factors, such as number
,of particles of barium sulfate per liter and the radii of the particles.
1
An equation for this rate was derived, on the assumption that ion
pairs are precursors of the crystals, that the number of particles
is set by the original concentrations of barium ions and sulfate
ions, and that the particles grow a t the same rate. The results
obtained seem to justify these assumptions.
EFFECTS OF ADDITIVES O N CRYSTAL G R O W T H
Investigations have continued on the effects of chemical ions
and physical treatments on crystal habits and rates of crystalliza-
tion, Kolb and Comer (49) have reported results on the effects
+of ions of gold, copper, magnesium, cobalt, cadmium, and
manganese on the crystal habit of ammonium oxalate.
59
The preparation of potassium chloride crystals with added
alkaline earth ions has been studied by Kelting and Witt (46).
The concentration of bivalent ions in the crystal was found to
be much less than in the melt, decreasing in the order: strontium,
barium, and calcium for equal rates of growth and equal concen-
trations in the melt. Coarse, granular potassium chloride crys-
tals can be prepared, according to Johnson and Suhr (4S),by
cooling a saturated solution containing oxides or salts of iron,
aluminum, thorium, zinc, bismuth, or lead.
Jaffe (41) has patented a process for controlling the resistivity
of ammonium dihydrogen phosphate and other piezoelectric
crystals by trace impurities. Barium and sulfate ions were found
to be deleterious, while silicate ions, in moderation, were bene-
ficial. Controlled growth inhibition in large scale crystallization
has been reported by Jaffe and Kjellgren (42).
COURTESY RUSH DWELOPMEH~_OO.
Successive Stages of Seed Growth into Final Capped Seed
Suzuki (76, 76) carried out experiments on the crystallization
of sucrose from solutions containing added manganous sulfate,
which, reportedly, speeded the evaporation, gave colorless
crystals, and prevented crystal film formation on the surface of
the evaporating solution. The additive also increased the yield
and produced less colored and less viscous sirups. Similar
experiments were carried out by Van Hook, Baril, and Maroney
(87). No effects on the crystallization behavior were found,
although inversion of the sucrose was inhibited.
Stabilization of the supersaturation of ca Icium carbonate solu-
tions has been effected by Raistrick (68) by use of anion additives.
Habit modification in crystals as a result of the introduction of
impurities during growth has been discussed by Buckley (11).
Zerfoss (102) has listed the effects of foreign ions on a crystal
growing solution as increased ease of growth, decreased sponta-
neous nucleation, and improved perfection on the basis of mor-
phology, optics, and x-rays. The total effect of an additive ion ia
dependent on its charge, size, and concentration. Butrhart and
Whetstone (17) have described the effect of dyes on the crystal
habit of oxy- salts.
Coarse-grained sodium chloride may be produced by evaporat-
ing a brine free of calcium and magnesium but containing 1p,p.m.
of a quaternary ammonium compound, such as hexadecyltri-
methyl ammonium bromide, according to a patent (23). Tilmans
(81) has reported that an addition of increasing amounts of the
ammonium salts of phosphoric, carbonic, sulfuric, hydrofluoric,
nitric, or thiocyanic acids, the outward habit of crystals of am-
monium chloride, growing from its saturated sblution, was changed
from dendrites to rosettes, then t o plates, and finally to cubes.
Iron-free aluminum sulfate may be prepared by the use of
ethyl alcohol as a precipitant, according to Gee, Cunningham,
and Heindl ($4,because the aluminum sulfate is insoluble in
ethyl alcohol, while the ferric sulfate is soluble.
Sprink and Sprink (72) have patented a process for shortening
the time of reactions, such as crystallization, involving a physico-
chemical change, by applying an electrostatic field of about 1000
volts per meter to the system. Crystals of Rochelle and other
related salts are reported, by the Mitsubishi Electrical Instruments
Co. (62), to grow more rapidly from the nucleus when sonic or
60 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
Shop Assembly of Vacuum Crystallizer
supersonic waves are passed through the contaii ing bath. The
action of a magnetic field on crystdlization of d-tartaric acid has
been studied by Blandin 6).
Based on a study of the <:rowing of octahedral sodium chloride
crystals under controlled surface tensions, Mario (50) has sug-
gested a relation between the surface tension of a mother liquor
and the habit of the crystals obtained from it.
Kay (45)has prepared single crystals of barium titanate, which
consist of multiply twinned tetragonal components with an
orientation very sensitive t o an externally applied pressure or an
electric field. The growth and solution of crystals under linear
pressure have been described by Correns (2%). Fordham (SI)
has studied the relative rates of growth of strained and unstrained
ammonium nitrate crystals.
ORIENTED OVERGROWTHS
Work on oriented overgrowth of one crystal on another has
been receiving more attention in recent researches. Willems
(95) has published a review, with bibliography, dealing with the
chemical and physical conditions governing oriented growth of
two compounds in crystal form. Misfitting monolayers and
oriented overgrowth have been discussed by Frank and Van der
Merwe (38).
About seventy pairs of organic compounds were tested by
Brandstatter (8). All organic compounds which form molecular
compounds with another compound give oriented crystallization.
Willems (96) has reported the oriented growth of hexaethylben-
zene on anthracene and of phenanthrene on hexaethylbeneene.
These are the first reported cases of hydrocarbon on hydrocarbon
growth. Deicha (%4),working on the oriented overgrowth of
alkali halides on mica, has proposed a structural interpretation of
the phenomenon.
lieuhaus (56) has stated that the nature of the binding forces
in oriented overgrowth of organic substances on inorganic carrier
lattices involves a polar center rather than a hydrogen bridge.
Willems (97) has shown that the oriented growth of organic com-
pounds depends more on the chemical bond between carrier and
VOl. 43, No. 1
COURTESY GTRUTHERS WELLS C O W .
added crystal than on the shape of the added crystal. Erlen-
meyer and Muller (30)have reported that paminobenzoic, p-
aminosalicylic, salicylic, and benzoic acids align in diagonals on
the 100 plane of sodium chloride crystals when sublimed in vacuo,
while sulfanilamide aligns in parallel.
Willems and Giltges (98) have studied the oriented overgrow-th,
by careful sublimation in vacuo, of hexa-substituted benzene
derivatives on zinc sulfide and sodium chloride. Neuhaus (66)
has used cane sugar as the lattice carrier and has listed the dimen-
sions of the overgrowths of anthraquinone, alizarin, and other
organic compounds. The structure and growth of lithium fluoride
and sodium chloride films on amorphous substrates have been
investigated by Schule (68).
PHASE EQUILIBRIA
Relatively few new data were published on the phase dia-
grams of aqueous systems with crystalline solid phasee, Zhdanov
has presented equilibrium data for the systems:
KCI-KI-H,O (106)
NaCI--n’aI-H20 (104)
and KC1---KBr--KI--H~O (108)
The system sodium oxide-silica-water has received mme
attention by Baker and Jue (3)and Wills (99). Morgan and
Walker (64)have studied the phase relations of the system, sodium
acetate-sodium hydroxide-water, for use in recrystallizing sodium
acetate from sodium hydroxide solutions.
INDUSTRIAL APPLICATIONS
The crystallization process has continued to grow in importance
and in the scope of its application in the manufacture of chemi-
cals, piezoelectric crystals, optical crystals, synthetic gems, and
other substances. Further applications of crystallization have
been made t o the separation of various substances. Many of
the papers and patents concerned with these applications describe
improvements in methods of crystallization or new techniques.
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY
The techniques of growing large single crystals have continued
to receive attention. Such crystals are used for their piezoelectric
or their optical properties, and in some cases as synthetic jewels.
A general description of methods of growth and of uses of these
crystals is presented in Fortune (32).
The growing of quartz crystals weighing up to 1 pound is
described by Walker and Beuhler (12, 91). In this process a
Red crystal is suspended in an aqueous solution of sodium carbon-
ate and silica contained in an iron bomb. I n the lower part of the
bomb are placed pieces of broken quartz, which dissolve and
deposit on the growing crystal as the result of a 10' to 20' C.
temperature gradient between the bottom and top resulting from
heating the bomb in a furnace a t 380' t o 400' C. Similar proc-
esses for growing quartz have been reported by other workers
(78, 79).
The methods used in growing calcium fluoride (fluorite) and
lithium fluoride for optical applications are described by Stock-
barger (73, 74). Equipment used for growing large anthracene
crystals is described by Hluchan (38).
The growth of piezoelectric crystals is discussed in papers by
Robinson (66) and Holden (39, 40). Tournier (83)describes the
use of ultrasonics a8 an aid in the growth of large crystals.
Chapelle (19) describes a method of growing ammonium phos-
phate, in which water is evaporated from a part of the surface of
the solution, condensed, and returned to the solution through a
sintered-glass crucible filled with feed crystals.
A new application of crystallization has been made to the
separation of n-alkanes from branches and cyclic hydrocarbons.
Zimmerschied, Dinerstein, Weitkamp, and Marschner (106)
have reported that urea forms crystalline complexes with
n-alkanes but not with branched and cyclic hydrocarbons. This
process, which has been oalled extractive crystallization, is dis-
cussed further by Weil (92).
According to Alexander ( I ) , crystallization can be used to con-
centrate the aqueous hydrogen fluoride solutions (35 to 45%
hydrogen fluoride) that are recovered from alkylation of low
boiling olefins. The solution is cooled to between -55' and
-69" C. which results in the formation of a crystalline complex
of hydrogen fluoride and water. The complex is distilled to ob-
tain anhydrous hydrogen fluoride.
Numerous improvements in processes for making crystalline
materials are described in patents and in several papers. A proc-
ess for making diammonium phosphate by feeding anhydrous
ammonia into a saturated solution of ammonium dihydrogen
phosphate is the subject of a British patent (63). A technique
for growing large ammonium sulfate crystals is claimed in a
patent by Schulte (67). Cohen, Henry, Skolnik, and Smith
(21) describe a means of growing crystals of nitroguanidine in
the form of long hollow needles. Processes described for other
substances include ammonium alum (60),calcium nitrate (255),
copper iron sulfate (It?), magnesium hydroxide (367, potassium
chlorate (la)), dextrose ( ? I ) , fructose (69), and strontium
peroxide (69).
Vener and Thompson (89) have used the addition of an organic
precipitant to effect crystallization of anhydrous sodium sulfate
in laboratory sized equipment. I n this process a saturated
1 aqueous solution of sodium sulfate was added continuously to an
electrically heated vessel containing the organic precipitant a t the
boiling point of the mixture. Crystals of sodium sulfate are
formed as the mixture of solvents boils off. When high concen-
trations of ethylene glycol were used, i t was found that the
deposition of sodium sulfate on the heating surfaces was avoided.
In water solutions of sodium sulfate such deposits result from the
decreased solubility of anhydrous sodium sulfate as the tempera-
ture increases. It was found also that the form of the crystals was
changed from light fluffy material like glass wool when no agita-
tion was used to hard uniform crystals when rapid agitation was
used. A similar effect of agitation was observed when ethyl
alcohol was used as salting-out agent.
61
COURTESY WESTERN ELECTRIC GO.
Synthetic Piezoelectric Crystals Mounted on Growing Rack
About to Be Harvested in Electronics Shop
According to Svanoe (77), however, anhydrous sodium sulfate
can be crystallized successfully from aqueous solutions without
deposits on the heating surfaces. He describes a commercial
multiple-effect vacuum crystallizer which is producing anhydrous
sodium sulfate in each effect as a by-product.
Crystallization is used not only as a means of obtaining a solid
crystalline material from a solution, but also to separate one solid
substance from another when the two substances have different
solubilities. There are a number of new applications of such a
process of fractional crystallization.
The separation of fatty substances by fractional crystallization
from acetone is described in a patent by Gee (36). Fractions are
obtained by cooling the acetone solution of the oil until a solid
phase is formed. When this solid is filtered off, the solution is
cooled further t o form another solid fraction. This process is
repeated to obtain additional fractions as desired. Soybean,
corn, palm, coconut, rapeseed, walnut, and sardine oils have been
treated in this way.
Assarsson ( 2 ) describes a process for separating potassium and
sodium chlorides by the addition of a calcium chloride solution.
The result of a fractional separation of salts from a calcium chlo-
ride brine is described by Dodonov, Eferova, and Kolosova (28).
In a study of the composition of linseed oil ( 6 ) ,fractional crystal-
lization of brominated oil is used as a supplement to spectro-
graphic and chromatographic analysis.
Other improvements in techniques of making crystalline mate-
rials are concerned primarily with the equipment or apparatus
used. A crystallization tank for making purified dehydrochloric
acid crystals is described by Klobusitsky (48). Bouttier ( 7 )
describes an apparatus for growing crystals of nitric acid and its
hydrates. A Dutch patent (26) describes a means of agitating
a solution in which nuclei and small crystals, formed when the
solution is cooled by an externally cooled wall, are dissolved by
directing the flow into a slightly warmer region of the solution.
A rotating kiln type of crystallizer in which baffles dump super-
saturated solution through cold air is described in an Italian
patent (27). The use of infrared lamps for regulating tempera-
ture in a crystallizing vessel is claimed in a Swisa patent (68).
Ridsdale (64)describes an apparatus in which crystals are grown
in an ascending current of solution which passes upward through
62 INDUSTRIAL AND ENGINEERING CHEMISTRY
sections of progressively increasing area. These sections effect a
size separation of the crystals formed. An apparatus for frac-
tional crystallization in a vacuum using glass laboratory equip-
ment is described by Scheraga and Manes (66). Werkspoor
(94) describes a method of cleaning the cooling surfaces of contin-
uous crystallizers using heated scrapers. An apparatus for pre-
paring and preserving a crystalline sugar paste with a uniform
size of nucleus is discussed by Vostokov and Zhilenko (90).
Yarmolinskil (101) describes a device for spraying water on low
grade massecuites discharged from vacuum pans, The purpose
of this spraying is to dissolve “false” grains.
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(74) I b i d , p . 299.
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(97) Ibid., 36, 373 (1949).
(98) Wllems, J., and Giltges, A., Ibid., 33, 345 (1946).
(99) Wills, J. H., J . Phys. and Colloid Chem., 54, 304 (1950).
(100) Winkler, W., Osterr. Apoth-Ztg., 2, 334 (1948).
(101) Yarmolinskii, M. B., Sakharnapa Prom., 23, No. 5, 31 (1949).
(102) Zerfoss, S., Ceram. A g e , 54, 293 (1949).
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554 (1948).
(105) Zhdanov, A. K., and Kovalinko, N., Ibid., 18, 559 (1948).
(106) Zimmerschied, W. J., Dinerstein, R. A. Weitkamp. A. W.,
and Marsohner, R. F., IND. EKG.CREM.,42, 1300 (1950).
RECEIVED
October 17,1950.
 HIGH TEMPERATURE
DISTILLATION
OF TECHNOLOGY, CLEVELAND 6, OHIO

The most important development of 1 9 5 0 in the field of high temperature distillation was This equation also represents the dits
the publication of the first group of books incorporating t h i theoretical concepts of nonideal of Rosanoff and Easley (89),which
distillations and bubble tray hydraulics. M o r e books are expected in 1951. Industrial does not cover the entire range of
x installations continued to expand using conventional distillation equipment. The trend in this compostiion.
field is to reduce costs b y improved mechanical features and assembly techniques. Equilibria The acetic acid-formic acid system
data continued to occupy. the interests of many academic groups. and the water-Freon-12 system have
vapors that deviate greatly from
ideality. The deviations must be

D
d
ISTILLATION theory and practice made fairly large steps considered in theoretical evaluation of these systems.
forward during the last decade. Until the advances are Suitable as test mixtures for vacuum columns are the systems
made part of the basic knowledge of a large group of prac- n-decane-trans-decalin, tetradecane-1-hexadecene, and toluene-
ticing engineers, further advances will come more slowly. Thus, octane. The former may be analyzed by refractive index
the incorporation of the newer developments into textbooks and and is suitable for columns having as many as 34 theoretical
handbooks is a desirable and necessary part of the growth of the plates a t 50 mm. of mercury. Also interesting is the increase in
science. this system’s relative volatility from 1.19 a t 50 mm. of mercury
Several books featuring the newer aspects of distillation were to 1.30 a t 1 atmosphere pressure.
promised during 1950. Four of these had been published at the Vapor-liquid equilibria in the presence of a nonvolatile soluble
time this review was prepared. These books make available to compound is reported for the systems ethanol-water-potassium
the student many techniques of distillation that were formerly nitrate, and acetic acid-water-calcium chloride. The results
available only in scattered journals. may be anticipated on the basis of vapor pressure lowering by a
The section on distillation in the third edition of “Chemical En- dissolved salt. With proper salt concentrations it is possible to
gineers Handbook” (76) is greatly expanded over the section in reverse the normal volatility characteristics of a pair of liquids
the earlier editions. Included in the expanded material is a dis- (39).
cussion of azeotropic and extractive distillations and a good table Azeotropes are of interest because knowledge of the composition
of azeotropes. Efficiency data for both plate and packed col- and boiling point of an azeotrope permits estimation of the equilib-
umns are useful and well presented. Calculations based on ma- ria data for a system when these data are not available. Lecat
terial balances are discussed. However, the discussion omits ref-
erence to calculations based on enthalpy balances and does not
point out the advantages that can be obtained by use of this type Table I. Equilibria Data
of balance when studying nonideal systems. Literature
The text “Unit Operations,” which has resulted from the system Cited
combined efforts of Brown and co-workers a t Michigan (8) de- 1. Acetia acid-formic acid
2. Benzene-carbon tetrachloride
velops the enthalpy calculations very well and stresses the rela- 3. Toluene-ethylene dichloride
4. Methane-propane
tionships existing among the unit operations in which mixtures 5. Propane-benzene
are separated into fractions. Bubble-tray hydraulics are also 6. Propene-1-butene
7. Tetradecane-1-hexadecane
well described in this text. 8. Toluene-octane
9. n-Decane-trona-decalin
“Laboratory Fractional Distillation,” by Carney (11) will be 10. Methanol-benzene
helpful for anyone who has the problem of operating or evaluating 11. -carbon tetrachloride
laboratory distillations. Many false ideas exist as to what may 12. -n-heptane
- be expected of laboratory distillations. This book will help dispel
13.
14.
-n-hexane
-toluene
15. Ethanol-benzene
those ideas and is filling a definite gap in the distillation literature. 16. -cyclohexane
The second edition of Kirschbaum (66) is announced from Ber- 17. -methylcyclohexane
18. %-pentane
lin. An English translation of the f i s t edition was made avail- 19. 4etraethylsilane

. able, and it is hoped that this practice will be repeated.

20.
21.
22.
-toluene
-2,2,4-trimethylpentane
-water
BASIC DATA 23. Propanol-benzene
24. Water-Freon-12
25. -furfural
The basic data for distillation calculations are the vapor-liquid 26. -acetaldehyde
equilibria for the system to be distilled. Data were reported dur- 27. -ethylene oxide
28. -ethylene glycol
ing the year for the systems listed in Table I. The conditions un- 29. -2-methyl-3-butyn-2-01
30. -2-hydroxy-3-methyl-2-butanone
der which these data were determined vary greatly, and all data
31. Pro anol-carbon tetrachloride
are not equally useful. Most data are in the form of phase compo- 32. Cyoyohexylc yclohexane-cyclohex ylbensene
sition diagrams although the data for the water-ethylene oxide 33. n-Pentaforane-n-pentane
34. 1-Butanol-water
system are in the form of an enthalpy-composition diagram. 35. Acetone-methanol-water
36. Methane-butane-decane
The relative volatility, a,a t 760 mm. of mercuky for the ben- 37. Methyl ethyl ketone-heptane-toluene
zene-carbon tetrachloride system may be related to the mole 38. Ethanol-water-potassium nitrate
39. Acetic acid-water-calcium chloride
fraction CClr, z,by a linear equation, CY = 1.203 - 0.002032.
63
64 INDUSTRIAL AND ENGINEERING CHEMISTRY
(64, 66) reporh over 400 additional azeotropic systems many of
which contain an alcohol. Denyer et al. (26) report azeotropes
formed between thiols and paraffins or naphthenes. Azeotropes
between acetonitrile and paraffins, olefins, naphthenes, and ben-
zene or toluene are reported by Bishop et al. (6).
Equilibrium constant charts for light hydrocarbons are pre-
sented by Smith and Smith (99). These may be used for calcu-
lating equilibria data for petroleum systems.
Estiniation of equilibria data from total pressure data by a
graphical integration of the Duhem-Margules equation for non-
ideal systems is proposed by Orlicek (73). Use of other equilibria
data is suggested by Wood (120) as a means of estimating the va-
por-liquid data. If the system is reasonably ideal and the boiling
points of the compounds do not vary more than a few degrees,
relative volatility may be used as a means of calculating the va-
por-liquid data. Two equations for determining the relative
volatility are proposed by Haldenwanger (48). One is for non-
polar and the other for polar mixtures. An alignment chart for
the same service is offered by Frishe (38).
Nonideal systems cannot be successfully correlated by thc rela-
tive volatility approach, and other techniques must be used.
Othiner and Ten Eyck (74) propose that azeotropic system data
be correlated by plotting as straight lines on logarithmic paper the
partial pressures, composition of either phase, or the activity coef-
ficient against the total pressure. A plot. using a temperature
scale derived from thc vapor pressure of a reference substance
may also be used. More theoretical is a theory of vapor pressures
of liquids using only the van der Waals' forces which is presented
by Wall and Stent (110). This theory permits the prediction of
the composition a t which azeotropes form. An alternate theory,
proposed by Kuhn and Rfassini (62), indicates that an azeotrope
will be formed when the difference in the boiling points of the pure
components is less than the heat of mixing divided by 5.4.
All thermodynamic data on vaporizable substances are poten-
tially useful in distillation studies. Many articles with this type
information appear each year. Only a few that seem to have im-
mediate interest to distillation students are mentioned here.
Among these are a summary of the status of thermodynamics in
the petroleum industry by Sage (94)and the continuation of the
series on applications of thermodynamics t o hydrocarbon process-
ing by Edmister (29). A method for determining the thermody-
namic consistency of vapor-liquid data is offered by Steinhauser
and White (102) and another by Gilmont et al. (42). The latter
article also includes a method of determining activity coefficients
from relative volatility.
Latent heats of vaporization of binary mixtures were st,udied
by Plewes (77). These data may be calculated from the reduced
temperature and the reduced pressure using an equation proposed
by Klein (66). An accuracy of 10% is claimed for the correla-
tion. Chu et al. (14) present a study of the effect of structure on
the latent heat of paraffis.
Bubble-plate efficiency is usually correlated with the viscosity
of the liquid on the plate. The viscosity may be correlated with
the critical constants with an accuracy of about 10%. A nomo-
graph for this correlation is presented by Grunberg and Nissan
(47).
INDUSTRIAL DISTILLATIONS
Industrially the year was notable for the amount of construc-
tion involving distillation towers. Outstanding among the new
equipment is the 49,000-barrel-per-day vacuum pipe still installed
a t the Bayway refinery of the Esso Standard Oil Company. De-
scribed by Naugle (70), this still is 93 feet high and has a diameter
of 27 feet. The flash zone of the still operates a t a temperature
of 775" F. and a pressure of 65 mm. of mercury. Williams and
Xaugle (118) claim that through a combination of vacuum dis-
tillation and other refining processes the refiner may expect an
increased yield of higher octane number gasoline and greater
VoI. 43. No. 1
flexibility of operation. Simpler construction and field erection of
equipment is helping to keep the cost of new equipment within
reasonable limits. For some time prefabricated trays have been
available for large towers. I n addition, it is now possible to pur-
chase "cartridge" type trays for installation in smaller diameter
towers. These trays with diameters from 12 to 42 inches are in-
serted into a smooth shell from the end and are complete with
spacers, downcomers, and handles for assembly and removal.
By eliminating the difficulties associated with assembling a bub-
ble-cap tower through small nianholes or handhole or the need
for nunierous flanges on small towers, the cartridge trays shift
the economic point of balance betw-een bubble-cap and packed
towers to favor use of bubble caps in smaller tovers more fre-
quently than was true earlier. White (114) describes another
type bubble cap which permit's assenibly of trays in a t'ower by
one man instead of the two usually required,
A packing reported suitable for use in towers up to 4 feet in
diameter is described by Scofield (96). Featuring low pressure
drop and a height equivalent to a theoretical plate of 1 to 2 feet,
the packing consists of multilayers of crimped metal lath.
Design of bubble-cap trays is the subject of a series of articles
just starting by Davies ($4). The &st article of the series is con-
cerned with the loading of the trays and the mechanical details
of the design.
Drainage through weep holes is correlated by Huitt et al. (49).
Holes below 0.25 inch in diameter do not drain the plates com-
pletely. Drainage through larger holes may be calculated from
the orifice equation. However, a t low Reynolds nunibere, the
orifice coefficient is a variable, and an empirical equation is used
to correlate the data. Screen-skirted bubble caps are recom-
mended for towers operating a t low vapor rates by Zenz ( 2 2 4 ) .
The operation of these caps is influenced greatly by the proper-
ties of the liquid. This reduces the utilit'y of the screen-skirted
caps.
Pictures and flow diagram of the '4rmour plant €or distilling
crude fatty acids and nitriles are featured by Potts and McBride
(78). Other notes on indust'rial distillation procesJes me: Form-
aldehyde and Z,&butanedione are found in the overhead from the
aldehyde tower of a continuous ethanol still (121). Tar distilla-
tion practice in England is reported by Curtis (23). The aging
period of rum may be shortened and the quality of the product
controlled by fractionation of the crude rum to eliminate the
light ends and fusel oil. The process described by Arroyo (5)
appears to be an azeotropic distillation with water as thc aaeo-
trope former,
Testing of commercial fractionators is frequently complicated
because the units cannot be taken off stream for the test period.
Gelus et al. (40)describe the techniques of the testing plant, e q u i p
ment producing a dimethylcyclopentane from a petroleum
naphtha for use in the production of toluene. Analysis of the
streams was by precise fractional distillation. As expected in an
extractive distillation process, the over-all tray efficiency is about
35%.
The efficiency of plate columns was also studied by Williams
e l al. (117). The conclusion reached after studying eight binary
systems is that correlation with the product of relative volatility
and viscosit'y is satisfactory a t reflux ratios up to 1.5, However
a t high reflux ratios another variable appears to be present.
The efficiency of columns as measured by a test system appears to
be independent of the number of components present of molccular
weight and type similar to the test mixture (65).
On fract'ionators making close separations, tower top tempera-
ture is not an accurate measure of the purity of the overhead
product. Under these conditions it is customary to measure the
temperature a t some other point in the tower and use this as a
control guide. Uitti (107) has determined the effect on the frac-
tionator operation of the location of the control point as the feed
composition varies. In some cases it' is better to use some other
property of the product for analysis and control. Th0ma.s et al.
 January 1951 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY 65

(104) describe a simplified automatic and continuously recording

flow refractometer which may be used for this purpose.

DISTILLATION THEORY
No outstanding developments were made in the theory of dis-
tillation during this year. At the present time the theory appears
to be well defined and is advancing through slight changes and
modifications in details. Eduljee (38) shows that entrainment in
bubble-cap trays may be correlated in terms of the vapor density
and slot velocity. He also points out that entrainment up to 10%
has a negligible effect on tray efficiency. Rose et aE. (91) present
evidence that increase in holdup is not necessarily detrimental to
the sharpness of separation in a batch distillation. Rather a criti-
cal reflux ratio exists below which increase in holdup actually im-
proves the separation. Lloyd (66) compares batch and continy-
x ous stills for a given separation. His conclusion is that a continu-
ous still will give more efficient use of a particular still column than
batch still use of the same column.
A theorem of Schreinemakers is refuted by Redlich and Kister
(85). TheQeorem states that if two impurities exist in an almost
#.
pure component, one of the impurities may be removed by distilla-
tion with greater ease than the other. A mathematical proof ia
offered showing that i t is possible that both impurities may be
equally difficult to remove.
Of interest from a theoretical viewpoint are the diffusion coef-
ficients of the components being distilled in both the vapor and
liquid phases. Trevoy and Drickamer (106) studied the diffu-
sion of paraffins into liquid benzene. The results agree with theo-
retical predictions. Wilke (116) and Fairbanks and Wilke (34)
report the results of a study to determine the average diffusion co-
efficient of a component into a multicomponent gas mixture.
Gerster et al. (41) successfully related plate efficiencies to the
separate vapor and liquid resistances. Convenient methods for
COURTESY FRITZ w.aLirscH AND SONE
combining film resistances to predict the plate efficiency are pro-
posed. Cartridge-Type Bubble-Cap Tray, 19.5-Inch Diameter
One- and two-directional mass transfer in a wetted-wall col-
umn are compared by Jackson and Ceaglske (61). Both are en- sary to make a given separation with the r e h x ratio when the
tirely similar. The j~ correlation is adequate for both types of minimum number of theoretical plates and the minimum reflux
mass transfer. Some indication is found that the composition ratio necessary for the same separation are known. Donne11 and
has an effect on the mass transfer. The area of contact in bubble Cooper (87) claim a better correlation between plates and vapor
contactors was studied by van Krevelen and Hoftijaer (61). Two rates. Their results are clear, but some difficulty was experienced
cases are reported: (a) single bubbles a t low gas rates have diam- in attempting to check the development of their curve, 1.
eters independent of the flow rate and proportional to the cube Calculation of the minimum reflux ratio for multicomponent
root of the orifice diameter; (b) chain flow bubbles a t high gas mixtures is seldom exact. Shiras et al. (97) point out that the
rates have diameters independent of the orifice diameter and a conditions existing in the column a t the minimum reflux ratio
function of the flow rate. Weisman and Bonilla (118) propose depend on whether only two components are distributed between
equations for evaluating mass transfer area in packed columns. the products or more than two components are distributed.
Yu and Coull (193) distinguish between adiabatic and nonadia- Rigorous solutions are possible for the first condition only. With
batic distillations. The process of nonadiabatic distillation is de- the second condition plate-to-plate calculations must be used for
veloped as a thermodynamic operation. the solution of the general problem where the relative volatility
and the molal reflux vary. May (67) presents a precise solution
DISTILLATION CALCULATIONS
of the problem where the relative volatility and the reflux ratio
Calculations for multicomponent mixtures are mainly based on are constant.
the equations of Underwood (109). These equations assume a Calculation of the number of required plates for multicompo-
constant relative volatility and a constant molal reflux rate. A nent mixtures by a graphical method is described by Coulson and
4 numerical example of previously derived equations is also given by Fyffe (98). The method amounts to setting up a pseudoequilib-
Underwood (108). The same equations are rearranged t o permit rium curve for the key components. This curve is developed by
the use of determinants by Alder and Hanson (1). Murdoch (69) making a plate-to-plate calculation a t total reflux.
defines “doublet separations” as those with only two distributed Batch column operation with appreciable holdup is calculated
Components. Equations for doublet separations are relatively by Rose et al. (90). The resulting calculated curves are compared
simple. with experimental curves. Similarity between the families of
Graphical solutions*to the number of transfer units is indicated curves justify the work of the plate-to-plate calculations. Chu
by White (116). The approach used here amounts to replacing (13) applies Smoker’s equation to similar batch column calcula-
the equilibrium curve with the arc of a parabola whose extension tions.
does not necessarily pass through the origin of the coordinate dia- A method of making flash equilibrium calculations is proposed
gram. The chart presented is based on the assumption of a by Montross (68). Flash equilibrium curves may be calculated
straight operating line. Yu and Coull (199)give a graphical cor- from the true boiling point curve by a method proposed by Oka-
relation for the variation of the number of theoretical plates neces- moto and van Winkle (72). This method differs from previous
66 INDUSTRIAL AND ENGINEERING CHEMISTRY
Prehbricated Bubble-Cap Tray, IO-Foot Diameter
methods for achieving the same result in that the compressibility
of the gas is considered. The reverse calculation, predicting the
true boiling point curve from the flash vaporization curve, is con-
sidered by Edmister and Bowman (SO), who also propose a
method of estimating the flash vaporization curve (31). Rumpf
(93) points out that distillations of crude oils may be plotted as
straight lines if the reciprocal of the absolute temperature is
plotted against a probability distribution function.
Mechanical computations are helpful Then used within the lim-
its of their development. B nomograph for solving the van Laar
equations is offered by Chu and Tung (16). Aslide rule for evaluat-
ing the vapor-liquid equilibria data from relative volatility is illus-
trated by Chu et al. (15). Weil (112) tells of a news release from
Northwestern University describing the use of their electronic
computer to solve multicomponent distillation problems when
the relative volatility and the reflux ratio vary.
PACKED C O L U M N S
The packing recommended by Scofield (96) for use in industrial
size columns was mentioned above. Koch and van Raay (57) de-
scribe a modification of Stedman packing in which the lower por-
tion of the packing has a raised edge whose diameter is slightly
greater than the diameter of the column into which the packing is
to be placed. The efficiency of the packing is less than that
claimed for Stedman packing but column assembly is easier.
Watson (111)indicates that double gauze packings are 35% more
efficient than single gauze packings of the same shape. The test
mixture used in this study was 3% ethanol in water.
The effect of vacuum operation on the efficiency of packed col-
umns was studied by Berg and Popovac (5) and by Struck and
Kinney (103). Both articles report little variation in efficiency
with pressures between 10 mm. of mercury and 1 atmosphere.
The effect of channeling on efficiency was studied by Jalota and
Nandi (52). Further effects of hydrodynamics in packed col-
umns are reported by Reed and Fenske (84). The effects of phase
densities on the flood point are discussed.
L A B O R A T O R Y E Q U I P M E N T AND D I S T I L L A T I O N S
Analytical procedures involving distillation are reviewed by
Rose (92)in the second “Annual Review of Analytical Chemis-
try.”
An improved apparatus for measuring boiling points at at-
mospheric pressure is described by Eblin (68)and s tensimeter
still for measuring vapor pressures in the range from 0.02 to 10
mm. of mercury by Ratchford and Rehberg (80).
Vol. 43, No. 1
Stills for determining vapor-liquid equilibria are
described in several articles. Rieder and Thomp-
son (86) present data on the equilibria relations of
the ethanol-water system as measured in a
Gillespie still. The data show slightly less separa-
tion at low alcohol concentrations than values
previously published. A slight modification of the
still is suggested. Smith and Bonner (100) de-
scribe a still for partially miscible liquids. Pearce
and Gerster (76) describe a technique for evaluat-
ing vapor-liquid equilibria from boiling points
measured a t k e d temperatures. Feller and
McDonald (56) describe a technique and apparatus
for determining dew points and bubble points for
binary systems that areliquid a t room temperature.
Laboratory still columns ranging in diameter
from 2.5 to 12 inches are described by Carpenter
and Helwig (12). Another two-column fully
automatic unit is described bv French (57). . ,
This column, which contains 100 theoretical plates,
is claimed to have separated a cut containing 89%
thiophene from crude coke oven benzene. The
still is used to reduce the time needed for a distillation b y elim-
inating the period of total reflux operation a t night.
A semimicrocolumn capable of fractionating 20 ml. of liquid
with an efficiency of twelve theoretical plates is described by
Dixon (26). Operation of a Podbielniak Hyd-Robot column
at rates as high as 100 ml. per minute with little contamination
of one fraction by another is found possible by Starr et al. (101).
A high rate of approach to equilibrium is reported by Irlin and
Bruns (60) for a rotating tube glass column, 5 or 6 minutes being
sufficient to establish equilibrium.
Electrical equipment suitable for Engler distillations is de-
scribed by Cooper and Medcalf (21). An internal-type immersion
heater is the essential element of this still.
An Alnico magnet, used to operate the distributor for a sample
collector suitable for vacuum columns, is described by Rock and
Janz (88). Control of still-head pressures during an isothermal
distillation is achieved by use of the mercury manometer thermo-
stat developed by Booth and Jarry ( 7 ) .
Microdistillation equipment includes an isothermal distilla-
tion-diffusion unit (54)and a simplified reflux still for the deter-
mination of iodine (105).
WATER DISTILLATION
Improved equipment for the automatic distillation of water
is reported by Reynolds and Swanson (85) and Nickels (71).
Scale corrosion of sea water distillation equipment may be re-
duced by circulating the brine through a layer of a stabilizing
contact material placed in a separate compartment. Langelier
et al. (63) report that the operating cycle of this type equipment
may be extended to 1000 hours by this change. Kolarow (58)
reports that an electrostatic precipitator with a potential of 50
kilovolts will reduce the carry-over of dust with the vapor in a
water distillation, thus improving the purity of the distilled
water.
A Z E O T R O P I C AND EXTRACTIVE D I S T I L L A T I O N
The calculations associated with azeotropic and extractive
distillations are reviewed by Colburn (18). The low efficiencies
associated with extractive distillations are attributed to the
resistance of the liquid film. The efficiency of columns separating
C4 hydrocarbons by extractive distillation with furfural is re-
ported by Grohse et al. (46).
Purification of the extractive distillation solvent is necessary
in the continuous extractive distillation of xylenes from hydro-
carbons with nitrobenzene. Woerner (119) proposes distillation
January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY
of 10 to 20% of the circulating solvent to remove gum formed
and accumulated during the distillation.
Azeotropic batch distillation may be used to increase the re-
covery of the bottoms product if the effect found by Berg et al.
(4) is general. The percentage recovery of bottoms product
found with five different systems seems to be independent of the
charge composition and is greater than the recovery by non-
azeotropic distillation.
RADIANT ENERGY
* and Colburn, A. P., Chem. Eng. Progress, 45,725 (1949).
The use of selective absorption of radiant energy to separate
components having the same vapor pressure is proposed by
Schlesman (95). Separation of methyl ethyl ketone from iso-
propyl alcohol is described as an example.
LITERATURE CITED
(1) Alder, B. J., and Hanson, D. N., Chem. Eng. Progress, 46, 48
(1950).
(2) Alpert, N. L., and Elving, P. J., IND.ENG. CHEM.,41, 2864
(1949).
(3) Arroyo, R.; Sugar, 44, No. 7,34 (1949).
(4) Berg, L., Carpenter, H. C., and Daly, J. B., Chem. Eng. Prog-
ress, 46, 283 (1950).
(5) Berg, L., and Popovac, D. O., Zhid., 45,683 (1949).
(6) Bishop, R. B.. and Denton, W. I., IND. ENQ.CHEM.,42, 883
(1950).
(7) Booth, H. S., and Jarry, R. L., Anal. Chem., 21, 1416 (1949).
(8) Brown, G. G., and Associates, “Unit Operations,” New York,
N. Y., John Wiley & Sons, 1950.
(9) Bushmakin, I. N., and Voeikova, E. D., Zhur. Obshchei Khim.,
19. 1615 (1949).
(IO) Carley, J. F., and Bertelsen, L. W., IND. ENQ. CHEM.,41,
2806 (1949).
(11) Carney, ‘ T. P., “Laboratory Fractional Distillation,” New
York, N. Y., The Maomillan Co., 1950.
(12) Carpenter, J. K., and Helwig, R. W., IND. ENG.CHEM..42,
571 (1950).
(13) Chu, J. C., Chem. Eng. Progress, 46,215 (1950).
(14) Chu, J. C., Dmytryszyn, M., Moder, J. J., and Overbeck, R. C.,
IND. ENQ.CHEM.,41, 131 (1949).
(15) Chu, J. C., Robinson, W. D., and Doll, D. P., Chem. Eng., 57,
No. 1, 108 (1950).
(16) Chu, J. C., and Tung, C. C., Chem. Eng. Progress, 46,44 (1950).
(17) Chu. J. C., and Yang. W. J., IND. ENG.CHEM..42.373 (1950).
(18) Colburn, A. P., Can.-Chem. Process I d s . , 34,298 (April’l950j.
(19) Coles, K. F., and Popper, F., IND. ENQ.CHEM.,42, 1434 (1950).
(20) Conner, A. Z., Elving, P. J., Benischeck, J., Tobias, P. E., and
Steingiser, S., Ibid., 42, 106 (1950).
(21) Cooper, H. B. H., and Medcalf, E. C., Anal. Chem., 22, 587
(1950).
(22) Coulson, J. M., and Fyffe, W. J. H., Znd. Chemist, 25, 543
(1949).
(23) Curtis, A. L., Trans. Znst. Chem. Engrs. (London), 25, 122
(1947).
(24) Davies, J. A,, Petroleum Refiner,29, No. 8,93 (1950).
(25) Denyer, R. L., Fidler, F. A., and Lowry, R. A,, IND.ENG.
CBEM.,41, 2727 (1949).
(26) Dixon, 0. G., J . SOC.Chem. Ind. (London),68,299 (1949).
(27) Donnell, J. W., and Cooper, C. M., Chem. Eng., 57, No. 6, 121
(1950).
(28) Eblin, L. P., J. Chem. Education, 27,67 (1950).
(29) Edmister, W. C., Petroleum Refiner, 28, No. 9, 95; No. 10,
143; No. 11, 149; No. 12,140 (1949).
(30) Edmister, W. C., and Bowman, J. R., presented a t Houston
Meeting, Am. Inst. Chem. Engrs. (February 1950).
(31) Edmister, W. C., and Bowman, J. R., presented at Minneapo-
lis Meeting, Am. Inst. Chem. Engrs. (September 1950).
(32) Eduljee, H. E., Trans. Znst. Chem. Engrs. (London),24, 128
(1946).
(33) Elsey, H. M., and Flowers, L. C., Refrig. Eng., 57, 153 (1949).
(34) Fairbanks, D. F., and Wilke, C. R., IND. ENG.CHEM.,42, 471
(1950).
(35) Feller, M., and MoDonald, H. J., Anal. Chem., 22,338 (1950).
(36) Fenske, M. R., Myers, H. S., and Quiggle, D., IND.ENQ.
CHEM.,42, 649 (1950).
(37) French, K. H. V.,Gas World, 130 (3381) Coking Sec., 65 (1949).
(38) Frishe, W. C., Petroleum Refiner,29, No. 1, 137 (1950).
(39) Garwin, L., and Hutchison, K. E., IND. ENQ. CHEM.,42, 727
(1950).
(40) Gelus, E., Marple. S., Jr., and Manning, E., Jr., Chem Eng.
Progress, 45, 002 (1949).
61
(41) Gerster, J. A., Colburn, A. P., Bonnet, W. E., and Carmody,
T. W.,Zhid., 45,716 (1949).
(42) Gilmont, R., Weinman, E. A., Kramer, F., Miller, E., Hash-
mall, F., and Othmer, D. F., IND.ENQ. CHEM.,42, 120
(1950).
(43) Glanville, J. W., Sage, B. H., and Lacey, W. N., Zbid., 42, 508
(1950).
(44) Goff, G. H., Farrington, P. S., and Sage, B. H., Ihid., 42, 735
(1950).
(45) Griswold, J., and Wong, S. Y., presented a t Minneapolis Meet-
ing, Am. Inst. Chem. Engrs. (September 1950).
(46) Grohse, E. W., McCartney, R. F., Hauer, H. J., Gerster, J. A.,
(47) Grunberg, L., and Nissan, A. H., IND.ENG.CHEM.,42, 885
(1950).
(48) Haldenwanger, H., Chemie-Ing.-Tech., 22, 8 (1950).
(49) Huitt, J. L., Zeigenhain, W. C., Fowler, F. C., and Huntington,
R. L., Petroleum Refiner,28, No. 11, 143 (1949).
(50) Irlin, A. L., and Bruns, B. P., Zhur. Anal. Khim., 5,44 (1950).
(51) Jackson, M. L., and Ceaglske, N. H., IND.ENG. CHEM.,42,
1188 (1950).
(52) Jalota, P. L., and Nandi, 5. K., Trans. Zndian Znst. Chem. En-
grs., 1, 53 (1947).
(53) Kincannon, C. B., and Manning, E., Jr., IND. ENG.CHEM.,42,
1386 (1950).
(54) Kirk, P. L., Anal. Chem., 22, 611 (1950).
(55) Kirschbaum, E., “Destillier und Rektifziertechnik,” Zweite
Auflage, Berlin, Springer-Verlag, 1950.
(56) Klein, V. A,, Chem. Eng.Progress, 45, 675 (1949).
(57) Koch, H., and van Raay, H., Chemie-Zng.-Tech., 22, 172 (1950).
(58) Kolarow, N., Ostew. Chem.-Ztg., 50, 180 (1949).
(59) Kretechner, C. B.,and Wiebe, R., J. Am. Chem. SOC.,71, 1793
(1949).
(60) Zbid., p. 3176.
(61) Krevelen, D. W. van, and Hoftijzer, P. J., Chem. Eng. Progress,
46, 29 (1950).
(62) Kuhn, W., and Massini, P., Helv. Chim. Acta, 33,737 (1950).
(63) Langelier, W. F., Caldwell, D. H., and Lawrence, W. B., IND.
ENG.CBEM.,42, 126 (1950).
(64) Lecat, M., Ann. SOC. sci. Bruxelles, 63, 111 (1949).
(65) Lecat, M., Bull. classes&, Acad. i o y . Belg., 35,484 (1949).
(66) Lloyd, L. E., Petroleum Refiner,29, No. 2, 135 (1950).
(67) May, J. A., IND. ENG.CHEM.,41,2775 (1949).
(68) Montross, C. F., Chem. Eng. Progress, 46, 105 (1950).
(69) Murdoch, P. G., Zbid., 46, 36 (1950).
(70) Naugle, J. M., Petroleum Processing, 4, 1346 (1949).
(71)Nickels, J. E., J. Chem. Education, 26, 533 (1949).
(72) Okamoto, K. K., and van Winkle, M., Petroleum Refiner, 29,
No. 1, 91 (1950).
(73) Orlicek, A. F., Osterr. Chem.-Ztg., 50, 86 (1949).
(74) Othmer, D. F., and Ten Eyck, E. H., Jr., END. ENO.CHEW.,41,
2897 (1949).
(75) Pearce, E. J., and Gerster, J. A., Zbid., 42, 1418 (1950).
(76) Perry, J. H., editor-in-chief, “Chemical Engineers Hand-
book,” 3rd ed., New York, McGraw-Hill Book Coo,1950.
(77) Plewes, A. C., Chem. in Canada,2, No. 5, 19 (1950).
(78) Potts, R. H., and McBride, G. W., Chem. Eng., 57, No. 2, 124
(imw.
(79) Raimuiien, R. R., and van WinkIe, M., IND. ENG.CHEM.,42,
2121 (1950).
(80) Ratchford, W. P., and Rehberg, C. E., Anal. Chem., 21, 1417
(1949).
(81) Reamer,“. H., Fiskin, J. M., and Sage, B. H., IND.ENQ.
CHEM.,41, 2871 (1949).
(82) Reamer, H. H., Sage, B. H., and Lacey, W. N., Zbid., 42, 534
,-
(1 --m-,.
w
(83) Redlich, O., and Kister, A. T., J . Chem. Phys., 18, 1108 (1950).
(84) Reed, T. M., and Fenske, M. R., IND. ENG. CIIEM., 42, 654
(1950).
(85) Reynolds, J. G., and Swansoh, B. IT7.,Anat. Chem., 21, 1396
.--
11949).
~ - ,
(86) Rieder, R. M., and Thompson, A. R., IND.ENG.CHEM.,41,
2905 (1949).
(87) Ihid., 42,379 (1950).
(88) Rock, E. J., and Janz, G. J., Anal. Chem.,22,626 (1950).
(89) Rosanoff, M. A., and Easley, C. W., J . Am. Chem. SOC.,31, 953
(1909).
(90) Rose, A., Johnson, R. C., and Williams, T. J., IND.ENG.
CHEM.,42, 2145 (1950).
(91) Rose, A., Williams, T. J., and Prevost, C., Ibzii., 42, 1876
(1950).
(92) Rose, Arthur, Anal. Chem., 22,59 (1950).
(93) Rumpf, K. K., Era62 u. Kohle, 3,21 (1950).
(94) Sage, B. H., IND. ENQ.CBEM.,42,631 (1950).
(95) Schlesman, C. H., U. 5. Patent 2,455,812 (Dec. 7,1948).
(96) Scofield, R. c., Chem. Eng. PTOgTe8S,46,405 (1950).
68 INDUSTRIAL AND ENGINEERING CHEMISTRY
(97) Shiraa, R. N., Hanson, D. K , , and Gibson, C. H., IND.EZTG.
CHEM.,42, 871 (1950).
(98) Simons, J. H., and Dunlap, R. D., J . Chem. Phgs., 18, 335
(1950).
(99) Smith, K. A., and Smith, R . B., Petroleum Processing, 4, 1355
(1949).
(100) Smith, T. E., and Bonnex, R. F., IND.ENG.& E x , 41, 2567
f 1949).
(101) Starr, E’., Jr., Anderson, J. P., and Davidson, V. &I., Anal
Chem., 21, 1197 (1949).
(102) Steinhauser, H. H., and White, R. E , IND.ENG.CHEM.,41,
2912 (1949).
(103) Struck, R. T., and Kinney, C . R . , Ibid.,42,77 (1950).
(104) Thomas, G . R., O’Konski, C. T., and Hurd, C . D., 9 7 m l . Ciiem.,
22, 1221 (1950),
(105) Thomas, J. W., Shinn, L. A , , Wiaenian, H. G., and Moore, I,. ‘4..
Ibid., 22, 726 (1950).
(108) Trevoy, D. J., and Drickamer, H. G., J . Chem. Phys.. 17, t 117
(1949).
(107) Uitti, K. D., Petroleum Processing. 5 , 41 (1950).
(10s) Underwood, A. J. V., Chem. Eng. Progress, 45, fi09 (1949).
Vol. 43, No. 1
(109) Underwood, -4. J V., IND.ENG.CHEM.,41, 2844 (1949).
(110) Wall, F. T., and Stent, G. S., J . Chem. Phus., 17, 1112 (1949).
(111) Watson, H. E., Ind. Chemzst, 25, 503 (1949).
(112) Weil, B. H., PetroZellnzProcessing,5 , 13 (1950).
(113) Weisman, J., and Bonilla, C . F.. IND.ENG.CHem. 42, 1099
(1950).
(114) White, B. C., U.S. Patent 2,488,249 (Nov. 15,1949).
(115) White, G. E., Chern. Eng. Progiess, 46, 363 (1950).
(116) Wilke, C. R., Ibid., 46, 95 (1950).
(117) Williams, G. C., Stigger, 1;. K., and Sichoia, J. H., Ibid., 46, 7
(1950).
(118) Williams, R. K . , and Kaugle. J. &I., Gil Gas .I., 48,S o . 46, 241
(1950).
(119) Woerner, R. C., U. S.Patent 2,494.274 (Jan. 10, 1950).
(120) Wood, S.E., IND.E m . CHEX, 42, 660 (1950).
(121) Yamada, S.,Oganai, S., and Chuno, T.. J . SOC.Brewin47 Japan,
43, 37 (1948).
(122) Yu, K. T., and C o d , J., Clteni. Eng. Progress, 46, 89 (1950).
(123) Yu, K. T., and Coull, J., J . Inst. Petroleum, 35,770 (1949).
(124) Zenz, F. A,, PetToZezim Refiner,29, No. 6, 103 (1960).
RECEII.
X D Ortober 17, 1950.

HIGH VACUUM ISTILLATlON

- __ _ _ ~ - __- -. - -__-_
KENNETH C. D. HICKMAN
56 THACKERAY ROAD, ROCHESTER 10, N. Y.

T h e two outstanding events of the year in high vacuum distillation were the introduction of
molecularly distilled monoglycerides of fatty acids and the continued industrial expansion of
fruit juice dehydration b y removal of water vapor at low temperatures. A pilot plant single
stage and a research multistage falling Rlm still were also described.
ONOGLYCERIDES, custom-tailored by molecular dis-
tillation to fit special requirements, have emerged from
Embree’s laboratory a t Distillation Products Industries
into large supply during 1950. Glycerol, reacted with un-
saturated fatty acids ( 2 2 ) has found favor in the baking indus-
try, where the purified monoesters are said to possess “light-
ening” qualities unexpectedly enhanced by the absence of di-
esters (41). Produced as a heart cut from the crude reaction
miuture, the monoesters are one of the few main products (in
contrast with stripping cuts and vitamins) obtained in quantity
by molecular distillation.
Vacuum dehydration has continued its phenomenal expansion.
In 1950, upwards of 120,000,000 gallons of fruit juices are said
by Morse to have been concentrated, four to one, for freeze
canning, This evaporation (If, 29, SI, @), which is done a t
8 t o 12 mm. of mercury. involved the total removal of some 180
billion cubic feet of vapor. Steam ejection, single and multiple
effect, heat pump cycles employing ammonia compressors (30)
and combinations thereof have performed the transfer of water
from juice to condensate. I n addition to orange, lemon, pine-
apple, grape, and apple juices (5-7, f b , 49) an important new-
comer is a soluble coffee (6, 6, 11, 19,43, 45), which is being pro-
duced at a water-vapor pressure of about 1 mm. and a residual
air atmosphere of less than 30 microns. Here indeed is an ex-
tension of megavacuums into the true high vacuum field.
Items of news in industrial short-path distillation are few,
but they show two significant trends: on the one hand to de-
glamorize and on the other to explore new fundamental phe-
nomena. Spence (47) describes a falling-film still of pilot plant
capacity, to be operated a t relatively high saturation pressures
and without benefit of condensation pump. Dioctyl phthalate
can be distilled with a feed rate of 370 pounds per hour to yield
a water-white distillate, 85 to 60 A.Ph.A. color; a still with a
rapacity of 1. ton an hour is projected. A falling-film evaporator
by Benner and DiNardo (2) with tubular, remote condense1
(this still and the previous one
use grooved evaporating sutfaces,
strikitlglg reminiscent of the re-
viewer’s own early labors) is oper-
ated with residual pressures in thP
micron range. Both papers pre-
sent a wealth of authentic operating data.
Assigned to the Socony Vacuum Oil Company, a patent issued
to Schlesman and Fawcett (42)describes a short-path still in which
the evaporating surlace is heated by radiation selectively ah-
sorbed by the “wanted” molecule. Schlesman offers an inter-
esting modification (4f)wherein energy of radio frequency is used
to prevent condensation of a constituent of a mixture. Examples
of compounds which can be separated in this manner range from
phenyl nitrite to tryptane. Although not strictly in the prov-
ince of this review, the effect of sound waves on attainment
of equilibrium in packed columns (9) may be compared with
the above. A variant of the hot-cold still should also receive
notice ( 1 3 ) .
Laboratory high vacuum distillation has advanced more in
techniques and application than in design A complete falling-
film installation (36) for drug research is generically a descendant
of the Quackenbush and Stembock design with stirred evaporator.
Stills for small samples, milligrams (8) t o a few grams ( 3 7 ) have
made their long-awaited appearance. The well known (pre-
1939) glass falling-film installation offered by Schott and Genos-
sen has been redesigned (39) to permit recirculation of residue.
comparable to the operation of a cyclic-batch still.
Madorskg and associates have continued their noteworthy
researches in high vacuum chemistry, pyrolysis, and distillation.
Of particular interest is a 10-column falling-film still (25)with the
columns arranged side by side on the bench and interconnected
by magnetic pumps which combine and recirculate residues and
distillates in appropriate directions. That such an assembly can
be operated a t all, in mutual balance, is a tribute to operative
skill, but the cost has been high:
To keep the system in balance it is necessary to have the same
pumping rate for all columns and to evaporate exactly half the
liquids. The evaporating rate is more difficult to control: in
order to blanket any deviation from conditions of balance the
evaporating rates were adjusted to a little over 5OVo of the amount
of liquid pumped into the crown of each column. I n experi-
68 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 43, No. 1
(97) Shiraa, R. N., Hanson, D. K , , and Gibson, C. H., IND.EZTG. (109) Underwood, -4. J V., IND.ENG.CHEM.,41, 2844 (1949).
CHEM.,42, 871 (1950). (110) Wall, F. T., and Stent, G. S., J . Chem. Phus., 17, 1112 (1949).
(98) Simons, J. H., and Dunlap, R. D., J . Chem. Phgs., 18, 335 (111) Watson, H. E., Ind. Chemzst, 25, 503 (1949).
(1950). (112) Weil, B. H., PetroZellnzProcessing,5 , 13 (1950).
(99) Smith, K. A., and Smith, R . B., Petroleum Processing, 4, 1355 (113) Weisman, J., and Bonilla, C . F.. IND.ENG.CHem. 42, 1099
(1949). (1950).
(100) Smith, T. E., and Bonnex, R. F., IND.ENG.& E x , 41, 2567 (114) White, B. C., U.S. Patent 2,488,249 (Nov. 15,1949).
f 1949). (115) White, G. E., Chern. Eng. Progiess, 46, 363 (1950).
(101) Starr, E’., Jr., Anderson, J. P., and Davidson, V. &I., Anal (116) Wilke, C. R., Ibid., 46, 95 (1950).
Chem., 21, 1197 (1949). (117) Williams, G. C., Stigger, 1;. K., and Sichoia, J. H., Ibid., 46, 7
(102) Steinhauser, H. H., and White, R. E , IND.ENG.CHEM.,41, (1950).
2912 (1949). (118) Williams, R. K . , and Kaugle. J. &I., Gil Gas .I., 48,S o . 46, 241
(103) Struck, R. T., and Kinney, C . R . , Ibid.,42,77 (1950). (1950).
(104) Thomas, G . R., O’Konski, C. T., and Hurd, C . D., 9 7 m l . Ciiem., (119) Woerner, R. C., U. S.Patent 2,494.274 (Jan. 10, 1950).
22, 1221 (1950), (120) Wood, S.E., IND.E m . CHEX, 42, 660 (1950).
(105) Thomas, J. W., Shinn, L. A , , Wiaenian, H. G., and Moore, I,. ‘4.. (121) Yamada, S.,Oganai, S., and Chuno, T.. J . SOC.Brewin47 Japan,
Ibid., 22, 726 (1950). 43, 37 (1948).
(108) Trevoy, D. J., and Drickamer, H. G., J . Chem. Phys.. 17, t 117 (122) Yu, K. T., and C o d , J., Clteni. Eng. Progress, 46, 89 (1950).
(1949). (123) Yu, K. T., and Coull, J., J . Inst. Petroleum, 35,770 (1949).
(107) Uitti, K . D . , Petroleum Processing. 5 , 41 (1950). (124) Zenz, F. A,, PetToZezim Refiner,29, No. 6, 103 (1960).
(10s) Underwood, A. J. V., Chem. Eng. Progress, 45, fi09 (1949). RECEII.
X D Ortober 17, 1950.

HIGH VACUUM ISTILLATlON

- __ _ _ ~ - __- -. - -__-_
KENNETH C. D. HICKMAN
56 THACKERAY ROAD, ROCHESTER 10, N. Y.

T h e two outstanding events of the year in high vacuum distillation were the introduction of
molecularly distilled monoglycerides of fatty acids and the continued industrial expansion of
fruit juice dehydration b y removal of water vapor at low temperatures. A pilot plant single
stage and a research multistage falling Rlm still were also described.
ONOGLYCERIDES, custom-tailored by molecular dis-
tillation to fit special requirements, have emerged from
Embree’s laboratory a t Distillation Products Industries
into large supply during 1950. Glycerol, reacted with un-
saturated fatty acids ( 2 2 ) has found favor in the baking indus-
try, where the purified monoesters are said to possess “light-
ening” qualities unexpectedly enhanced by the absence of di-
esters (41). Produced as a heart cut from the crude reaction
miuture, the monoesters are one of the few main products (in
contrast with stripping cuts and vitamins) obtained in quantity
by molecular distillation.
Vacuum dehydration has continued its phenomenal expansion.
In 1950, upwards of 120,000,000 gallons of fruit juices are said
by Morse to have been concentrated, four to one, for freeze
canning, This evaporation (If, 29, SI, @), which is done a t
8 t o 12 mm. of mercury. involved the total removal of some 180
billion cubic feet of vapor. Steam ejection, single and multiple
effect, heat pump cycles employing ammonia compressors (30)
and combinations thereof have performed the transfer of water
from juice to condensate. I n addition to orange, lemon, pine-
apple, grape, and apple juices (5-7, f b , 49) an important new-
comer is a soluble coffee (6, 6, 11, 19,43, 45), which is being pro-
duced at a water-vapor pressure of about 1 mm. and a residual
air atmosphere of less than 30 microns. Here indeed is an ex-
tension of megavacuums into the true high vacuum field.
Items of news in industrial short-path distillation are few,
but they show two significant trends: on the one hand to de-
glamorize and on the other to explore new fundamental phe-
nomena. Spence (47) describes a falling-film still of pilot plant
capacity, to be operated a t relatively high saturation pressures
and without benefit of condensation pump. Dioctyl phthalate
can be distilled with a feed rate of 370 pounds per hour to yield
a water-white distillate, 85 to 60 A.Ph.A. color; a still with a
rapacity of 1. ton an hour is projected. A falling-film evaporator
by Benner and DiNardo (2) with tubular, remote condense1
(this still and the previous one
use grooved evaporating sutfaces,
strikitlglg reminiscent of the re-
viewer’s own early labors) is oper-
ated with residual pressures in thP
micron range. Both papers pre-
sent a wealth of authentic operating data.
Assigned to the Socony Vacuum Oil Company, a patent issued
to Schlesman and Fawcett (42)describes a short-path still in which
the evaporating surlace is heated by radiation selectively ah-
sorbed by the “wanted” molecule. Schlesman offers an inter-
esting modification (4f)wherein energy of radio frequency is used
to prevent condensation of a constituent of a mixture. Examples
of compounds which can be separated in this manner range from
phenyl nitrite to tryptane. Although not strictly in the prov-
ince of this review, the effect of sound waves on attainment
of equilibrium in packed columns (9) may be compared with
the above. A variant of the hot-cold still should also receive
notice ( 1 3 ) .
Laboratory high vacuum distillation has advanced more in
techniques and application than in design A complete falling-
film installation (36) for drug research is generically a descendant
of the Quackenbush and Stembock design with stirred evaporator.
Stills for small samples, milligrams (8) t o a few grams ( 3 7 ) have
made their long-awaited appearance. The well known (pre-
1939) glass falling-film installation offered by Schott and Genos-
sen has been redesigned (39) to permit recirculation of residue.
comparable to the operation of a cyclic-batch still.
Madorskg and associates have continued their noteworthy
researches in high vacuum chemistry, pyrolysis, and distillation.
Of particular interest is a 10-column falling-film still (25)with the
columns arranged side by side on the bench and interconnected
by magnetic pumps which combine and recirculate residues and
distillates in appropriate directions. That such an assembly can
be operated a t all, in mutual balance, is a tribute to operative
skill, but the cost has been high:
To keep the system in balance it is necessary to have the same
pumping rate for all columns and to evaporate exactly half the
liquids. The evaporating rate is more difficult to control: in
order to blanket any deviation from conditions of balance the
evaporating rates were adjusted to a little over 5OVo of the amount
of liquid pumped into the crown of each column. I n experi-
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY
mental tests with a binary mixture, the ten-column molecular
still gave at e uilibrium a se aration of the two constituents
equivalent to %out thirteen tteoretical plates. The operation
was continuous lasting several weeks at a time and requiring very
little attention.
Madorsky (86) and Wsterman et al. (60) have severally de-
scribed spring balance evaporative stills for microanalysis.
Madorsky’s experiments (84) with the fission of hydrocarbon
chains by heat show that macromolecules break a t random until
a fragment can escape by evaporation.
Turning now t o studies with the molecular still, a complete
account of distillation of tocopherol-bearing oils is offered by
Green and Watt (16). Using the cyclic-batch still of Hickman,
the elimination techniques of Embree and Hickman, and much
of the data of Baxter, Rawlings, and associates, they succeed in
.. pointing to the disturbing fact that the elimination maximum
of the mixed tocopherols occurs at quite different temperatures
according to the oil of origin. Your reviewer accepts this as a fact
with which future research must cope. It is curious, however,
that the authors, who are so well informed in the field, should
A,
advance the statement that such work involves chemical concen-
tration of tocopherols either before or after molecular distillation
and that there has been little or no reference t o the practical
aspects of large scale tocopherol concentration. To correct the
record, it should be pointed out that hundreds of tons of raw
vegetable oils have been stripped in commercial routine and the
strippings redistilled in molecular vacuums to 20 to 50% tocopher-
ols without chemical intervention, Together with the concentra-
tion of deodorizer sludge, these operations constitute a sizable
industry. A patent issued this year (go), assigned to Distillation
Products Industries, describes the conversion of 7- t o a-to-
copherol, a process which should not be without influence on the
natural resources of “potent” vitamin E.
The sum total of knowledge of vapor pressures of phlegmatic
liquids, including phthalate esters, plasticizers and glycerides,
has been increased by two excellent papers by Perry et al. (34,
36). The pendulum tensimeter, redesigned for use with an air
box instead of the previously used oversized and dangerous oil
bath, has provided the data. The accuracy of individual points
has suffered slightly but unimportantly, considering that many
of the substances measured could not be of pedigree purity. As
an orienting gesture, the work will prove invaluable.
Concerning the theory of molecular distillation and compu-
tations necessary as a base for advance in devices for self-managed
multiple stills (molecular fractionation), the reviewer cannot but
be impressed with the analogy between the distribution curves
for multiple series solvent extractions and the molecular elimi-
nation curves. Papers by Nichols (SS),Tipson (48),and Golum-
bic ( 1 4 ) will repay study, together with one by Bradley and
Shellard ( 4 ) which bears more directly on unit distillations.
Some prominence was given to vacuum coating of metals and
glasses in the last review, but this year a statement that prog-
rem (10, 18) is toward bigger and better rather than novelty
will suffice. Instrumentation includes two minor modifications
of the McLeod gage (1,16) and an improved Knudsen (88, &).
Considerable activity is noted in setups for measuring the gases
4 Schwartz, C. M., and Lavender, R., Rev. Sci. Instruments, 19,
evolved from vacuum fusion (17,83), and vacuum fusion itself
finds expanded application. The device of the year in vacuum
aids which, if not new is certainly not well enough known, is a
valve for placing two mechanical vacuum pumps 6rst in parallel
and then in series as high vacuum is attained (3). Reviews are
less in evidence (H); exceptions are two lengthy illustrated ac-
counts (@, 4 4 ) of molecular distillation (38,40)in foreign jour-
69
nals. Descriptions of advanced vacuum engineering (38) con-
tinue to be released by government agencies.
LITERATURE CITED
(1) Azelband. M. A.. Reu. Sci. Inst.. 21, 511-13 (1950).
Benner, F. C., and DiNardo, A., IND.ENQ. CHEM.,42, 1930-4
.----,
(1950).
Blasco, E., and Miranda, L., Anales real SOC. espair. fis y quim,
46A,69-75 (1950).
Bradley, R. S., and Shellard, A. D., Trans. Faraday SOC.,45,
501-7 (1949).
Business Week, 62 (Feb. 4,1950).
Ibid.., 37 ..
- (Ami1 29. 1950).
~
Chem. Eng. News, 27,3880 (1948).
Chin, H. S.,J . Chem. Eng. China, 15,28-33 (1948).
Coffin, C. C.,and Funt, B. L., J . Phys. & Colloid Chem., 53,
891-4 (1949).
Diminick, Glen L. (to Radio Corp. of America), U. S. Patent
2,482,329(Sept. 20, 1949).
Fortune, 40, 121 (September 1949).
Food I d . , 68-70 (July 1949).
Goldsbarry, A. W. (to Pure Oil Co. of Ohio), U. S. Patent
2,477,595(Mar. 10, 1948).
Golumbic, Calvin, Anal. Chem., 22, 579-85(1950).
Green, J., and Watt, P. R., J . Sci. Food and Agri., 1, 157-62
(1950).
Groszkowski, Janusz, Nature, 164,886-7 (1949).
Gulbrauser, E. A., and Andrew, K. F., IND.ENG.CHEM.,41,
2762 (1949).
Guldner, W. G., and Beach, A. L., Anal. Chem., 22, 366-7
(1850).
Hellier, E.G.,Food I d a . , 21, 1191-3 (1949).
Hickman. K. C. D., and Weissler, L. (to Distillation Products,
Inc.), U. S. Patent 2,486,540(Nov. 1, 1949).
Khurt, N. H., and Welch, E. A,, J . Am. Oil Chemists SOC.,27,
344-6 (1950).
Khurt, N. H.,Welch, E. A., and Kovarik, F. J., Ibid., 27,310-
13 (1950).
McGeary, R. K.,Stanley, J. X., and Yensen, T. D., Trans.
Am. Soo. Metals, Preprint No. 10 (1949).
Madorsky, 6. L., J . Research Natl. Bur. Standards, 40, 417-
25 (1948).
Ibid., 44, 135-9 (1950).
Madorsky, S. L., Rev. Sci. Instruments, 21,393-4 (1950).
Masch, L. W., Chem. Eng. Tech., 22, 141-6 (1950).
Meers, J. T.,and Parduo, L. A., Phys. Rev., 74,119 (1948).
Morse, R.S.,Chemistry & Industry, 1948,13-19.
Ibid., p, 14.
Morse, R. S.,IND.ENG.CHEM.,39,1064 (September 1947).
Natl. Nuclear Energy Ser., Div. I, 1, “Vacuum Equipment
and Techniques” (1949).
Nichols, Peter L., Anal. Chem., 22,915-18 (1950).
Perry, E. H., and Weber, W. H., J . Am. Chem. SOC.,71, 3726-
30 (1949).
Perry, E. H., Weber, W. H., and Danbert, B. F., Ibid., 71,
3720-6 (1949).
Prignar, M., Wilt, W. A., and Nachod, F. C., Anal. Chem., 22,
1065-6 (1950).
Roper, J. N., Jr., Ibid., 21, 1575 (1949).
Sakurai, Toshio, J . J a p a n Chem., extra edition No. 1, 83-98
(May 1949); No. 2,98 (July 1949).
Santiago, E. B., and Gonyales-Montes, L. M., I o n , 9,273-82
. ~ - ~
(1949).
I
Ibid., pp. 338-51.
Schlesman, Charleton H. (to Socony Vacuum Oil Co.), U. 5.
Patent 2,455,812(Dec. 7, 1948).
Ibid., 2,486,684(Nov. 1, 1949).
Schroeder, A. L., and Schwarz, H. W., Chem. Eng. Progress,
45, No. 6,370-6 (June 1949).
814 (1948).
Schwarz, H. W., IND. ENQ.CEEM.,40,2028 (1948).
Schwarz, H. W., and Penn, F. E., Ibid., 40, 938-44 (1948).
Spenoe, LeRoy U.,Ibid., 42,1926-9 (1950).
Tipson, R. Stewart, Anal. Chem., 22,628-36 (1950).
W a l l St. Journal (Nov. 29, 1949).
Waterman, H.I., Rec. trao. chim., 68,939-44 (1949).
REC~;IVED
October 28, 1950.
 SAMUEL J. FRIEDMAN, ENGINEERING DEPARTMENT,
E, I. DU PONT DE NEMOURS & CO., INC., WILMINGTON, DEL.

Literature in the field of drying was not lacking in quantity during the past year, but the tech- drying was limited in the textile in-
nical information content was somewhat lower than in previous years. Infrared drying was still dustry and was not adaptable to wool
popular as a subject. The combination of infrared with sublimation drying has stimulated further processing. Infrared applications in
work in the field of low temperature drying. Spray drying also appears to be becoming en- the rubber industry were outlined by
trenched in the process industries. Interest in dielectric drying is waning except for specialized Budig (IS). Applications of infrared
applications. The fundamentals and art of drying textiles are receiving increasing attention. drying of foods (69),paper (Ire),
Unfortunately, however, the basic knowledge required to estimate the drying rates and their plywood and lumber (l81), and
influencing factors in a large number of the commonly used dryers i s still lacking. The literature ceramics (48) were reported,
during the past year offered little for the engineer along this line. Hanvey (76) described the a p
plication of infrared energy furnished
by infrared bulbs to the drying of

T
HREE books having general discussions ot the theory and ap-
paratus used for drying m‘ere published during the past year.
Razous (141) revised his “ThBorie e t Pratique du a c h a g e
Industriel” for the fifth edition. Many dryers not ordinarily
used in the United States were described. Weissberger (178)
included an elementary chapter on drying in his “Technique
of Organic Chemistry.” An up-to-date review of United States
drying equipment and practice was prepared by Marshall and
Friedman (117). Drying theory for all types of dryers was re-
viewed, and descriptions, design information, and cost data for
most of the common dryers were presented.
Maleady (114) reviewed forced convection ovens commonly
used in process engineering and listed some of the design details
which should be considered. Recently developed ovens and
kilns were described by Uihlein (170). A cursory review of some
of the modern types of dryers was published (26). The National
Fire Protection Association has specified new standards for Class
A ovens and furnaces (198).
Infrared Drying. Although infrared drying was the subject of
much discussion during the past year, Garber and Tiller (61)
presented the only outstanding contribution to the technology of
this method of drying. They presented equations and graphs
for calculating the time-temperature relationships of the top,
middle, and bottom of low thermal conductivity slabs, such as
wood, irradiated with infrared energy. These equations were
extensions of the usual unsteady-state heating equations, sui&
ably modified to take into account radiation to the surface as
well as convection from the surface. Horgan (84) and Landfer-
mann (98) briefly reviewed the principles of infrared heating
and drying, Uses for gas-fired radiant panels were outlined by
Hess (79).
Drying of finishes is still the largest use for radiant heating.
The factors influencing the choice between convection and radiant
heating are still being delineated with particular emphasis on
gas-radiant heating which can utilize convection heat in the
products of combustion (49). General reviews of theory,
particularly applicable to lacquer and paint drying, were pre-
sented by Brugel (12) and Tetrel (166). Mew (190) reviewed
some German developments, Herbig (78) compared induction,
high-frequency, and infrared drying of paints and enamels.
Lohausen (107) found the drying time of lacquers was propor-
tional to the thickness of the lacquer, the specific heat of the
lacquer carrier, and its reflectivity. Several specialized applica-
tions to paint drying were described (96,199,146).
Rapid drying of hides by infrared was reported by Ddribdr6 (41)
and Franwschi (68). Kuepper (97) described infrared drying of
molding cores, The use of infrared in the textile industry,
particularly for boosting existing capacity, was described by
Korner (94). Schneider (150)concluded that the use of infrared
70
high-cost ore concentrates in a screw conveyer. Uses of infrared
ovens for laboratory and analytical work were reported (11,77).
Monnier and Besso (124) found that many reagents and precipi-
tates unstable to ordinary oven drying could be dried satis-
factorily with infrared energy.
Spray Drying. If literature is any criterion, spray drying is
finding increasing use in the process industries. Extensive treat-
ment of this method of drying can be found in the work of Seltzer
and Settelmeyer (16S), who summarized the spray-drying art as
applied to the food industry, gave detailed descriptions of
most of the common spray dryers, and reported valuable operat-
ing information and know-how. This represents the best modern
treatise on spray drying available.
Quantitative information on spray drying was presented by
Folger et al. (66),who analyzed data obtained in a tower and a
Bowen spray dryer. They reported heat-transfer coefficients
ranging from 4 to 10 B.t.u./(hour) (cu. feet of dryer volume)
(” F.) for this equipment when drying sulfite waste liquor. The
validity of their use of a log-mean temperature difference is
questionable, however. Smith (169) outlined a general classi-
fication for spray dryers as well as commenting on dryer and
atomizer design and dryer operation. A new laboratory spray
dryer was announced (97). Settelmeyer (164) reported on an air
sweeper which materially aided the operation of spray dryers
on some food products.
May (119) described a centrifugal disk atomizer driven by an
air turbine which could be operated to produce droplets of very
uniform size. The flow patterns of liquids leaving high-speed
rotating cups were investigated by Hinze and Milborn (88).
They found three distinct flow rbgimes, and listed some drop-
size analyses of the sprays.
Butler (19) reviewed current practice in apray drying calcium-
base sulfite liquor, while Gol’denberg (67) reported on the drying
of sulfate solutions in essentially a spray diyer operating a t 2
atmospheres’ pressure, Spray drying of washing powders was
advocated (8,161) and Porter (189) reported the use of ultrasonic
energy as an aid to spray drying soap. Information was also
available on the spray drying of urea and melamine resine (136),
wheat gluten (108), milk (89), and clay slip ($1).
Sublimation Drying. The most extensive work on sublimation
drying (removal of moisture from a frozen material by sublima-
tion) published during the past year was by Floerdorf (64). Thia
book contains an excellent review of the applications, techniques,
and equipment used for sublimation drying. However, the
small amount of quantitative engineering information i t con-
tains is not always accurate. General reviews of sublimation
drying were also made available (18, 96).
M e (47’) presented an excellent analysis of the physical
phenomena of drying by sublimation and reported carefully per-
 January 1951 INDUSTRIAL A N D E N G I N E E R I N G C H E M I S T R Y 71

formed experimental data to substantiate his analysis. Evapora-

tion rates were measured for ice in which were embedded copper
filings to decrease its thermal resistance. The rate of evaporation
could be expressed as a function of the mean air pressure of the
system, the difference in vapor presmre between the evaporating
surface and the condenser, and the diffusivity and density of
water vapor. This method was used to analyze data on the
sublimation drying of green peas (48). Higher than ordinary
rates of drying were used without impairment of final quality,
A new method of heating materials during sublimation drying
(24, 28) consists of applying radiant energy to the bottom of a
frozen mass through a tray bottom transparent to infrared
rays. By utilizing this method, drying rates two to five times
greater than those ordinarily encountered were obtained without
melting of the frozen material. The process of “dehydro-
- freezing,” a combination of drying followed by freezing, was
also described (108). Typical applicstions of sublimation drying
to storage battery plates and gelatin (123) and drugs (28) were
reported.
High-Frequency Drying. Work reported on this method of
d drying, which depends upon generation of heat within the ma-
terial to be dried from dielectric losses when the material is placed
in a high-frequency electrical field, continues to indicate that its
most promising use is for drying bulky materials. Busat,h (17)
has briefly reviewed some of the possible applications of high-
frequency drying.
Foundry cores are particularly susceptible to economical high-
frequency drying. Kuepper (97) compared its use for cores
with other more conventional drvine ” - methods. TvDical
” _ Dro-
duction installations of high-frequency core drying were de- Freeze-Drying Unit
scribed by Dawson (S9),Griffith (71), and Hillman (81). Appli-
cations to the drying of textiles (in bulk or oake form) (116),
moisture to be removed arid the diameter oi the coal particles.
ceramic materials such as brick and tile (9), and paint films (78)
Bainbridge (6) explained the Fleissner process for drying coal,
were also reported.
Drying in Kilns. Drying is often accomplished in kilns, al- which consists in treating it with high-pressure steam followed
though they are usually thought of aa calcining or roasting equip- by rapid release of the steam pressure. Factors were listed which
ment. The general principles of heat transfer in this equipment should be considered in the design and operation of a large plant.
may be expected to be the same for drying as for the other opera-
DRYING O F SPECIFIC MATERIALS
tions. The transmission of heat in rotary kilns was discussed a t
length by Anselm ( 1 ) . Jaspers reported on the heat distribution Drying of Textiles. Few new fundamental studies on the dry-
in the combustion zones of kilns (87) and the transmission of ing of textiles were reported during the past year. Perhaps the
heat from the hot gases to the solid materials (88). One method best experimental work in this field was the investigation of the
of calculating over-all heat quantities in lime kiln installatione reliability of several electrical moisture meters reported by Whit-
was outlined by Gibbs (66). Methods of calculating heat losses well et al. (17~2,180). Most electrical meters were found re-
from rotary kilns were presented by Guye (73) and Matouschek liable, provided they were calibrated a t the use temperature for
(118). The operation of an indirect-fired rotary kiln was the material being tested.
described by Gibaldo (64). Several descriptive articles on typi- Several descriptions of moisture meters baaed on measuring
cal rotary kiln installations are available (22, 104, 182, 138,188, the dielectric constant of textiles were available (14, 62, 176).
172). Coles (80)discussed how a meter of this type could be used for
Miscellaneous Drying Methods. The results of several years of automatic control. Mahlo (110, 111) and Dirks (48) gave
vapor drying of railway ties, as described by Burpee (16), general descriptions of moisture meters for the textile industry.
+ indicated that thio method of drying wood was less expensive Haller (74) cautioned that moisture content of textiles must be
than other methods and resulted in a marked reduction in ma- carefully controlled for best printing and recommended that
terial losses. Expansion of existing vapor drying systems was electrical moisture meters be used to control the moisture con-
reported (60). The use of fluidized-bed techniques for drying tent of textiles leaving the dryer prior to the printing operation.
as developed by the Dorr Co. was reported (26). Counselman The general principles of automatic control in the textile industry
* (32) claimed that for granular materials this method of drying were outlined by Walter (176). Textile sheet guiding in drying
might give better control and lower costs than more conven- machines was described by Ullrich (171).
tional dryers. Lauer et al. (99, 100) made an extensive study of the drying of
Tamblyn (166) described “flash drying” of bark in detail. A viscose fibers. They found that cross-linking bonds were formed
new automatic level control for a double-drum dryer was de- during the drying process. This phenomenon could be either
scribed by Fox (67). reversible or irreversible, depending upon the drying conditions.
A new method of drying fruit, in which it is subjected to a Increasing drying temperatures gave decreasing swelling values
vacuum of a few millimeters of mercury and sprayed with hot and poor dye receptivity. Schaeffer (148) studied the behavior
vegetable oil, was reported (66). The resultant fruit is puffed of cellulosic fibers in drying. He found that temperatures ex-
and has a moisture content of ‘2% or less and an oil content rang- ceeding 80” C. caused physical and chemical changes to the
ing up to 20%. The drying of coal by immersion in hot oil was fibers. Wet neutral fibers could be dried a t 100’ C. and cotton
reported by Burr et al. (16). Equations were presented for calcu- a t 120’ C. without fiber damage. Small traces of alkali reduced
lating the drying time required as a function of fraction of the permissible maximum drying temperature to 65” C.
 72 INDUSTRIAL AND ENGINEERING CHEMISTRY
Thomas (168) presented a good picture of trends in textile
drying and a comparison of the relative efficiency of several
different drying methods. Schneider (149) also summarized the
textile drying art and gave detailed descriptions of a number of
different textile dryers with a brief discussion on the theory of
their operation. Manschke (115) outlined a sound method
whereby the operation of installed textile dryers can be evalu-
ated. Principles involved in the drying of textiles by hot air
were discussed by Net2 (189) for batch and continuous dryers of
various types. Elementary fundamentals of drying as applied
to textiles were outlined by Fleming (65). Even more ele-
mentary was the discussion by Laurie (101).
The development and use of nozzles to promote heat transfer
in tenter, festoon, and fixed-roll dryers for textiles were reviewed
by Friedemann (60). School (151) described dryers applicable to
the handling of print goods. Spooner (168) discussed the
operating principles of dryers used in the wool industry. Franz
( 5 9 ) described the types of dryers applicable to the woolen in-
dustry and some of their operating principles. Some applications
of infrared drying (94, 150) and high-frequency drying (116) in
the textile industry were discussed.
Klingenberg ( 9 3 ) discussed the use of hot air, steam-heated
cylinders, infrared, and high-frequency energy for slashing.
Jones (90) believed that cylinder slashing had some advantages
over hot air slashing, particularly if air was passed rapidly over
the cylinder (Shirley accelerated drying device). Methods of
improving cylinder dryer operation were outlined by Hicks ( 8 0 ) .
Some difficulties encountered in print drying were reported
( 1 6 7 ) . Bergdolt (7) discussed the drying and forming of women’s
hose.
Drying of Ceramic Materials. In addition to the descriptive
articles on infrared ( 4 Z ) and high-frequency drying (9), a few
other articles on the drying of ceramic materials appeared.
Wride (189) recommended rapid drying with low-humidity air
until the free moisture content of the ware is just above the
shrinkage limit, then slow drying through the critical range of
moisture content, and finally rapid finish drying. Laurin (102)
presented an extensive review of the theory and practice of dry-
ing ceramics. The principles involved in drying ceramics were
outlined by Robinson (143). Drying equipment for clay was
described by Coulhon (SI). Watts (177) and Garve (63)de-
scribed several types of ceramic dryers. Bailly ( 4 ) reported on
some new developments in firing and drying. General principles
and methods of saving fuel in firing ceramic ware were reported o n
by Letort (105).
Drying of Paper. Milnes (181) outlined the heat-transfer
mechanisms in cylinder dryers and discussed in detail several
different condensate and air-removal systems. The need for more
fundamental data on paper drying was pointed out by Mont-
gomery ( 1 M ) in a discussion of the causes of poor paper drying.
Smith (160) ascribed the cockling and curling of paper to strains
set up in the paper during drying. A new dryer for glazed
paper was reported (51). Murphy and Davis (127) described a
double-arch dryer employing impinging air jets for drying paper
coated with photographic emulsion a t speeds up to 1000 feet per
minute. Use of infrared for boosting existing paper machini.
capacity was recommended by Van Kampen ( 1 7 4 ) .
Drying of Leather. Roddy et al. (144)concluded that there was
little significant difference in the properties of leather dried by
pasting and leather dried by toggling or hanging. I n a study of
the curing of goatskins, Lloyd et al. (106) found that rapid drying
tended to produce a leather more greasy and susceptible to
greater rehydration than slow drying. Cox and Roddy (3s)
studied paste-drying of leather and found that the tendency of
leather to atick during drying was more a function of the condi-
tion of the leather grain eurface than the type or concentration
of the pasting agent. Increased fat in the leather decreased ad-
hesion. Kremen (96) described the use of an electrical meter
Vol. 43, No. 1
for determining the moisture content of leathers. Infrared dry-
ing of leather was reported (41, 68).
Drying of Finishes. Other than the articles on infrared drying
of paints and lacquers (12, 49, 78. 96, 107, 120, 188, 146, 1/36),
little was reported on the drying of finishes. The Shell Evapo-
rometer was described by Curtis et aE. (35). Evaporation rates
measured with this instrument indicated that atmospheric
humidity, nature of film support, and chemical constitution of
the solvents and solute8 had a much greater effect on the evapora-
tion rate from thin films than from bulk liquids. A similar in-
vestigation employing another, more sensitive device waa de-
scribed by Rudd and Tysall (145). GrenebDelide ( 7 0 ) de-
scribed a much less elaborate and probably less accurate ap-
paratus. A method of evaluating drying based on the set, dust-
free, tack-free, solid, and hard states was proposed by Arzens and
Nijveld (8). Greenawald and Gort ( 6 9 ) reported on the effect
of temperature, humidity, air flow circulation, light, film thick-
ness, soaking of dryers, resins, and pigments, and solvents on the
drying time to a tack-free state for a number of different coating
materials.
Drying of Foodstuffs. Consumer opposition to dried foods,
with some exceptions, is reflected in the much fewer investiga-
tions reported last year as contrasted to three or four years ago,
Barry ( 6 ) reviewed the literature on the processes and equipment
usually employed for food drying. Sybel (164) also presented a
summary of the art. Infrared drying for food was reviewed by
Finzi ( 5 2 )
The best fundamental work on food drying was presented by
Earle and Ceaglske ( 4 6 ) , who studied the factors causing check-
ing of macaroni. They found that moisture stresses during
drying mexe much larger than thermal stresses; checking of dried
macaroni might even be expected from relatively large changes
in the relative humidity of the air surrounding the dried product.
Hummel ( 8 5 ) reported on the principles of drying and the types
of dryers used for drying spaghetti dough.
The development and application of a number of different
dryers for hay and grains were reviewed by Darling (37). Hlynka
et a2. (83) compared ten different electrical meters for detprmining
the moisture content of wheat. Resistance meters seemed to be
slightly more reliable than dielectric meters Bose and Majumder
( 1 0 ) reported on the optimum conditions for the drum-drying of
date-tree juice. Flow diagrams for the handling of whey in
batch tray dryer, combined twin- and double-drum dryers,
combined spray, pneumatic conveying, and rotary dryers mere
presented by Stringer ( 1 6 5 ) .
Drying of Miscellaneous Materials. Deahl et al. ( 4 0 ) studied
more than 1000 samples of official drugs, chemicals, and reagents
to establish the proper drying conditions. Vacuum drying a t
either normal or elevated temperatures could be used satisfac-
torily for almost all materials. Oven drying a t 105” C. was
satisfactory for most. Rumpelt (147) described the use of
vacuum tray, multiple-band, and conveying-screen dryers for
dyes and pigments. The advantages of using reoirculation in
dryers for foundry molds were stressed by Rigaut and Ulmer
(142). Bachle (5) made an exhaustive study of the influences
of temperature, film thicknese, humidity, air velocity, and com-
position on the drying of latex films. Ueno and Imade (169) de-
termined the rate of drying of soaps when in the form of chips,
cubes, pyramids, spheres, and cylinders. Per unit of surface the
rate of drying decreased, as might be expected, in the order of:
spheres, cylinders, cubes, pyramids. Zilske (184) discussed the
effect of the cooling and drying processes on the final quality of
toilet soaps. Healey (76) outlined some of the more common ink
drying problems. A device called the “dryograph,” used for de-
termining the drying time of printing inks, was described by
Carman (go).
 January 1951 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
M O I S T U R E EFFECTS AND M O V E M E N T
Moisture Equilibria. The rate and extent of drying during the
final stages of moisture removal frequently depend on the
equilibrium moisture relationships of the material being dried.
Dole and Faller (44) investigated the equilibrium moisture of
eleven different synthetic linear polymers. The adsorption of
water vapor by casein was studied by Green (68),who found that
the method of drying had some effect on the equilibrium moisture
at low relative humidities. Jacobi (86) found that untreated
wool which was easily wettable and extracted wool which was
hydrophobic had about the same equilibrium moisture relation-
ships despite their difference in wettability. Guthrie (7@ re-
ported that small changes of relative humidity result in changes
in moisture regain which stay within the normal sorption-
desorption hysteresis loop for cotton. The moisture regain iso-
~
therms of collagen, commercial hide powder, and several vege-
table- and chrome-tanned leathers were determined a t three dif-
ferent temperatures by Kanagy (91). Free energies, heata of
adsorption, entropy, and surface areas were calculated data.
Ranby and Grinberg (140) determined the 20" C. sorption iso-
* into a laminar boundary layer of gas surrounding it was preeented
therms for water vapor on hydrocellulose and on cellulose micelles
of different origins. Methods of drying jute to evaluate its regain
moisture were investigated by Macmillan and Mukherjee (109)
Moisture Movement. Before moisture can be removed from a
material, it must first get to the surface of that material. The
process whereby this movement occurs is, therefore, important,
Pfalzner (137) found that, when a total pressure differential was
set up across a wood membrane, water vapor would pass through
the membrane ten times as rapidly as when the same pressure in
the form of partial vapor pressure of water was set up across the
membrane with equal total pressures on the two sides. An ex-
tensive study of the rnechaniam of water vapor permeability of
Jeather was reported by Kanagy and Vickers (92). Above 20%
relative humidity, the permeability increased markedly, indicat-
ing that pure gaseous diffusion was not the complete mechanism
of transfer. No11 (131)determined the water-vapor permeability
of a number of different materials, including papers, rubber, foils,
and fabrics. The permeability of polymeric films to water vapor
(173), organic vapors (1579, and gases (168) was reported. The
gas permeabilities were so low compared to the vapor perme-
abilities that it was concluded that vapor transmission must be
accompanied by a condensation phenomenon (168). Schultz
et ul. (162)measured the permeability of pectinate films to water
vapor and found the usual variation with relative humidity.
Newns (130) summarized the experimental methods which have
been used to measure water vapor permeability and outlined the
inherent sources of error in each. Zwolinski, Eyring, and Reeae
(186)presented a novel, detailed mathematical analysis of the
process of diffusion through membranes. They considered dif-
fusion to be a aeries of molecular jumps from one equilibrium
position to another governed by a rate constant.
Signer and Roth (156) measured the rate of evaporation of
water from wicks made of different textile fibers. The rate did
not seem to be affected by the moisture absorption of the indi-
vidual fibers.
Morrison et ul. (126) carried out experiments to determine
L
the minimum vertical thermal gradient required to set up con-
vection in liquids entrapped in porous media.
Drying and Evaporation Rates. A number of experimental in-
vestigations of evaporation rates were reported during the past
year. Maisel and Sherwood (112)investigated the evaporation
rate of water into air from plane surfaces, cylinders, spheres, and
disks; water into carbon dioxide and helium from cylinders;
and benzene and carbon tetrachloride into air from spheres.
Their results confirmed data of earlier investigators. I n another
study (113) they investigated the effect of artificially induced
turbulence on the rate of evaporation and found that evapora-
tion rates could be substantially increased by this technique,
73
O'Brien and Stutzman (135) measured the evaporation rate of
water, acetone, n-propyl alcohol, benzene, and toluene into
air from a pan suspended in a square duct. They found that a
j-factor-Reynolds number plot would correlate the data. The
evaporation rate of water from pans of different sizes into air was
reported by Yamamoto (183). He subtracted the evaporation
caused by natural convection from the total evaporation rate to
obtain a corrected forced-convection evaporation coefficient.
His data agree with other meteorological data which are in sub-
stantial agreement with the data of Maisel and Sherwood (112).
Shikher et al. (166) studied the evaporation rata into air of
solvents containing paraffi. Although a small fraction of
paraffi (0.12%) did not lower the vapor pressure, it was effective
in reducing the evaporation rate by a factor of 10 to 50. The
concentration of para& required to reduce the evaporation rate
corresponded exactly to the solubility of p a r a 5 in the eolvent.
Davies (38)derived equations for evaporation from rectangular
pans or lakes into air, taking into account lateral diffusion of the
water vapor in the air as well as vertical diffusion. A mathe-
matical analysis of the transfer of matter from a plane surface
by Eckert and Lieblein (46). They indicated"that, if the partial
pressure difference for mass transfer is large, the rate cannot be
calculated by analogy from heat transfer. Claims have often
been made that increased humidity in the drying gas will increase
the drying rate from materials that tend to form a skin when
drying. This has been attributed to increased permeability of
the skin at higher humidities. Crank (34) has proved mathe-
matically that this is impossible because the increase in permea-
bility cannot possibly be great enough to compensate for the re-
duced rate caused by the loss in humidity driving force.
Psychrometry. Nottage (134) has prepared a new psychro-
metric chart. Goff (68) presented the h a 1 report of the working
subcommittee of the International Joint Committee on Psychro-
metric Data, whioh consisted primarily of definition of terms and
agreements on constants, It appears to define the adiabatie
saturation temperature incorrectly as the wet-bulb temperature.
Johnson (89)measured the surface temperature of evaporating
small drops of water. Confirnation was obtained of Fuchs's
theory that the temperature is determined by the difference be-
tween the ambient air density and the saturated vapor density
of an evaporating drop.
CONCLUSIONS
There is still a severe need for accurate operating data on plant
drying equipment. Published information is usually too in-
complete to permit compariuon with theoretical performance OP
with performance of other equipment. There is also a need for
fundamental studies on more common dryers, such as drum,
vacuum-rotary, pneumatic conveying, and spray dryers. The
literature of the past year was ineffective in relieving these needs.
LITERATURE CITED
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Bachle, O., Kautachuk u. Cummi, 2, 337-43 (1949).
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114 INDUSTRIAL AND ENGINEERING CHEMISTRY
(16) Burr, A. C., Oppelt, W. H., and Kamps, T. W., Proc. N.Dakota
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(17) Busath, H., Kunstseide u. Zellwolle, 27, No. 9,319-23 (1949).
(18) Business Week, 1950, No. 1078, 37, 39,42, 44.
(19) Butler. R. T., Pulp Paper Mag. Can., 50, No. 11, 108-21
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(20) Carman, Everett, iim. Ink Maker, 27, No. 4, 30, 31, 59 (1949).
(21) Carothers, T. E., Ceram. Ind., 54, KO.6,101-2, 120 (1950).
(22) Cement & Lime Mfr., 22, S o . 6,105-9 (1949).
(23) Chambers, M. A., and Nelson, J. W., J . Amer. Pharm. Assoc.,
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(24) Chem. A g e , 62,780 (1950).
(26) Ibid., pp. 398-400.
(26) Chem. Eng., 57, No. 6, 110 (1950).
(271 Chem.
\-.I - Inds.. 65. S o . 5. 778-80 (1949).
, I
(28) Ibid., 66, No. 4, 572 (i950).
(29) Chem. Trade J.,127, S o . 3299, 459 (1950).
(30) Coles. R. V.,Electronics, 22, No. 11,82-6 (1949)
(31j Coulhon, A., Ind. ceram., 1948, No. 374, 207-10; NO. 375,
203-4: NO. 377, 241-4 (1947); SO.383, 3 2 4 ; NO. 384,
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(32) Counselman, T. B., Eng. Mining J., 151, No. 3, 84-5 (1950).
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(34) Crank, J., Proc. Phys. Soc.. 63B, Pt. 7, No. 367, 484-91 (1950).
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(36) Daniels, G. W., Proc. Ins!. Refrig. (London), 44, 147-70
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. . Darling, C. S., Ind. Heating Engr., 11, No. 50, 212-14 (1949):
(371
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64-73 (1950).
(39) Dawson, J., Irdn Age, 165, No. 18,90-3 (1950).
(40) Deahl, N. L., Powers, J. L., and Green, M. W., Bull. Natl.
F m u l a r y C m m . , 16, 153-204 (1948).
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(42) DBribBrB, M., I d . ceram., 1948, No. 393,259-61.
(43) Dirks, R., Textil-Praxis, 5,51-4 (1950).
(44)Dole, Malcolm, and Faller, I. L., J . Am. Chem. Soc., 72, 414-19
(1950).
(46) Earle, P. L., and Ceaglske, N. H., Cereal Chem., 26, 267-86
(1949).
(46) Eckert, E., and Lieblein, V.. Forschung, 16, 33-42 (1949).
(47) Ede, A. J., J . Soc. Chem. I n d . (London),68, 330-2 (1949).
(48) Ibid., pp. 336-40.
Ekctrophting, 2, S o . 7, 449-65 (1949).
Elec. World, 133,21 (May 15, 1960).
Engineer, 189, No, 4917,487 (1950).
Finzi, E., Alimenti, 5,14-16 (1949).
Fleming, M. T., Textile J . Australia, 23, 1014, 1032 (1949).
Floadorf, E. W., “Freeze-Drying,’’ New York, Reinhold Pub-
lishing Corp., 1949.
Folger, H. H., Herbolzheimer, F., Stinchfield, R. M., and Jen-
neea, L. O., Tappi, 32, 389-93 (1949).
Food Inds., 22, 1203 (1950).
Fox, H. H., Chem. Eng., 57, No. 9, 122 (1950).
Franceschi, Rodolfo, and Cuoio, Pelli, Mat. concianti, 25, 3 8 4 0
(1949).
Franz, F., Textil-Praxis, 5, 54-8 (1950).
Friedemann, R., Ibid., 5, 54-8 (1950).
Garber, H. J., and Tiller, F. M., IND. ENG.CHEM.,42, 456-63
(1960).
Garland, T., Indian Textile J., 59,876-8 (1949).
Garve, T. W., Ceram. A g e , 55, No. 1, 27-8,85-7, 154-5 (1950).
Gibaldo, F., Rock Products, 52, No. 9, 63-4 (1949).
Gibbs, Ralph, Paper I n d . &Paper World, 31, 1070-3 (1949).
Goff, J. A., Trans. Am. SOC.Mech. Engrs., 71, 903-13 (1949).
Gol’denberg, L. G., Stekol’naya i Keram. Prom., 4, N o . 4, 3-6
(1947).
Green, R. W., Proc. Roy. SOC.New Zealand, 77, 313-17 (1949).
Greenawald, F. S., and Gort, W. J., Oficial Digest Federation
Paint & Varnish Production Clubs, 1950, No. 307, 560-73
(1950).
Grenet-Delisle, C., Peintures, pigments, vernis, 26, No. 7, 270-3
(1950).
Griffith, B., Western Metals, 7, S o . 8, 26-9 (1949).
Guthrie, J. C., J . TextileInst., 41, No. 3, T124-5 (1950).
Guye, F., Ruder Rundschau, 1949, 172-6.
Haller, R., Ciba Rev., 7, 2835-6 (1949).
Hanvey, J. T., Jr., Eng. Mining J., 150, No. 9,82-3 (1949).
Healey, A. C., Am. I n k Maker, 27, No. 12,26-8,51 (1949).
Henke, L. K., J . Chem. Educution, 26,512-13 (1949).
Herbig, Wolfgang, Farbe u. Lack, 55, 367-9 (1949).
He=, F. O., Am. Cas J., 172, No. 2,16-18,42-3 (1950).
Vol. 43, No. 1
(80) Hicks, T. G., Textile World, 100, No. 2, 149, 151 (1950).
(81) Hillman, V. E., Iron A g e , 163, No. 5, 116-21 (1949).
(82) Hinze, J. O., and hlilborn, H., J . Applied Mechanics, 17, 145-
53 (1950).
(83) Hlynka, I., Martens, V.,and Anderson, J. A , , Can. J . Research,
27F, 382-97 (1949).
(84) Horgan, M. O’C., Fuel Econ. Rev., 28, 63-8 (1949).
(85) Hummel, C., Schweiz. Bauztg., 67, No. 35, 472-6 (1949).
(86) Jacobi, O., Kolloid-Z., 114, 88-103 (1949).
(87) Jaspers, M. J. M., Rev. mathiaux construction trav. pub., Ed. C ,
NO.410,373-8 (1949).
(88) Ibid., No. 411, 421-5.
(89) Johnson, J. C., J . Applied Phys., 21, 22-3 (1950).
(90) Jones, E. H., Textile Inst. J., 40, 907 (1949).
(91) Kanagy, J. R., J . A m . Leather Chemists’ Assoc., 45, 12-41
(1950).
(92) Kanagy, J. R., and Vickers, R. A.. Ibid., 45, 211-42 (1950).
(93) Klingenberg, G., TextiGPrazis, 5,37-40 (1950).
(94) Korner, H., Ibid., 5, 67-9 (1950).
(95) Kremen, S. S., J . Am. Leather Chemists’ Assoc., 44, 774-83
(1949).
(96) Krupp, P. H., I n d . Finishing, 26, No. 4, 20, 23-4, 26, 28
(1950).
(97) Kuepper, J., Neue Cfiesserei, 2, No. 3, 78-85 (1949).
(98) Landfermann, C. A., Chem. Ing. Tech., 22, No. 1, 5-7 (1950).
(99) Lauer, K., etal., Kolloid-Z., 116, 31-3 (1950).
(100) Lauer, K., Bezner, O., and Dobberstein, O., Ibid., 116, 28-31
(laj0).
(101) Laurie, K. S., J . Soc. Dyers Colourists, 66, 225-9 (1950).
(102) Laurin, Fernand, I d . ceran., 1948, S o . 382, 6-8; N o . 383,
24-6; NO. 384, 51-3; NO. 385, 78-80; SO.386, 99-101
No. 388, 146-150: Nos. 389/390, 183-4.
(103) Legault, R. E., and Talburt, W. F., Refrig. Eng., 57, 1175-7
(1949).
(104) Lenhart, W.B., Rock Products, 52, No. 2, 88-90 (1949).
(105) Letort, Yves, Ind. ceram., 1948, No. 385, 68-74.
(106) Lloyd, D. J., Humphreys, F. E., and Pankhurst, K. G. A . , J .
SOC.Leather Trades’ Chemists, 33, 216-33 (1949).
(107) Lohausen, K. A., Metalloberjlache, 2, 257-61 (1948).
(108) Lusena, C. V., and Adams, G. A.. Cereal Chem., 27, 186-8
(1950).
(109) Maomillan, W. G., and Mukherjee, R. R., Fibres, 11, 173-81
(1950).
(110) Mahlo, H., TeztiGPrazis, 5,73-6 (1950).
(111) Mahlo, H., and Thym, K., Ibid., 5. 176-80 (1950).
(112) Maisel, D. S.,and Sherwood, T. K., Chem. Eng. Progress, 46,
131-8 (1950).
(113) Ihid., pp. 172-5.
(114) Maleady, N. R., Ind. Heating, 17, No. 1, 105-6, 108, 110, 112,
114-5 (1950).
(115) Manschke, W., TextiGPraxis, 5, 44-6 (1950).
(116) Mansmann, E., Ibid., 5,69-72 (1950).
(117) Marshall, W.R., and Friedman, S. J., “Chemicai Engineers’
Handbook,” J. H. Perry, ed., 3rd ed., section 13, S e w York,
McGraw-Hill Book Co., 1950.
(118) Matouschek, F., Reu. mdteriaux construction trav. pub., Ed. C,
NO.401,43-6 (1949).
(119) May. K. R., J . Applied Phys., 20, 932-8 (1949).
(120) Mers, A., We-rkstofle u. Korrosion, 1, 263-5 (1950).
(121) hlilnes, Albert, Paper Trade J., 129, No. 3, 37-41 (1949).
(122) Miskella, W. J., Ind. Finishing, 26, No. 3, 10-2, 17-18, 20, 22
(1950).
(123) ModernInd., 19, No. 6, 99 (1950).
(124) Monnier, D., and Besso, Z . , Helv. Chim. Acta, 32, 1870-1
(1949).
(125) Montgomery, A. E., Tappi, 33, S o . 5,64A, 66A, 68A (1950).
(126) Morrison, H. L., Rogers, F. T., and Horton, C. W., J . Applied
Phus., 20, 1027-9 (1949).
(127) Murphy, E. K., and Davis, H. G., Paper I n d . and Paper World.
31, 596-9, 607 (1949).
(128) Natl. Fire Protection Assoc., Advance Reports, 54th Annual
Meeting, May 15 to 18, 1950, “Report of Committee o n
Ovens and Furnaces,” pp. 197-263.
(129) Nets, H., TestiGPraxis, 5, 11-15 (1950).
(130) Newns, A. C., Shirely Inst. Memoirs, 24, 27-66 (June 1950).
(131) Noll, A., Wochbl. Papierfahr., 77, 287-99 (1949).
(132) Nordberg, B., Rock Products, 52, No. 6, 96-9, 128 (1949).
(133) Ibid., 52, N0.8,127-31,172 (1949).
(134) Nottage, H. B., Heating, Piping A i r Conditioning, 22, No. 7,
121-8 (1950).
(135) O’Brien, L. J., and Stutaman, L. F., IND.ENG.CHEM.,42,
1181-7 (1950).
(136) O’Connor, J. A., Chem. Eng., 56, No. 12,88-91 (1949).
(137) Pfalzner, P. M., Can. J . Research, 28A, 389-410 (1950).
(138) P i t & Quarru, 42, No. 1,92-5 (1949).
(139) Porter, R. W., Chem. Eng., 55, No. 3, 115 (1948).
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY
Ranby, B. G., and Grinberg, B., Compt. rend., 230, 1402-4
(1950).
Razous, P., “ThBorie et Pratique du SBchage Industriel,” 5th
ed., Paris, H.Dunod, 1949.
Rigaut, P., and Ulmer, G., Fonderie, 38,1491-3 (1949).
Robinson, R. R., J . Can. Ceram. SOC.,18,35-9 (1949).
Roddy, W. T., Jacobs, J., and Jansing, J., J . Am. Leather Chem-
ists’ ASSOC.,
44,308-20 (1949).
Rudd, H. W., and Tysall, L. A., J . Oil Colour Chemists’ Assoc.,
32, 546-63 (1949).
Rudolph, W., Ind. Finishing, 26, No. 4, 30-2, 34, 37-8, 40
(1950).
Rumpelt, H., Farbe u. Lack, 55,271-4 (1949).
Schaeffer, A., Textil-Praxis, 5,3-6 (1950).
Schneider. J., Kunstseide und Zellwolle, 28,264-78 (1950).
Schneider, J., Melliand Textilber., 31,No. 4,2846 (1950).
School,K.,TextiLPraxis, 5,32 (1950).
Schultz, T.H.,Miers, J. C., Owens, H. S.,and Maclay, W. D.,
J . Phys. & Colloid Chem., 53,1320-30(1949).
Seltzer. E.. and Settelmever. J. T.. “Advances in Food Re-
search,” Vol. 11, “Spray Drying of Foods.” pp. 399-520,
New York, Academic Press, 1949.
Settelmeyer, J. T., Food Inds., 22,272,376, 378 (1950).
Shikher, A. G..Shikher. M. G., and Petrova, N. Ya., Zhur.
Priklad. Khirn., 22,947-51 (1949).
Signer, R., and Roth, M.,Makromol. Chem., 3,281-5 (1949).
Simril, V. L.,and Hershberger, A.,Modern Plastics, 27,No. 10,
97,98,100,102,150-2,154,156,158 (1950).
Ibid., 27,NO.11, 95-6,98,100,102 (1950).
Smith, D. A.,Chem. Eng. Progress, 45,703-7(1949).
Smith, S. F., Paper-Makers (London), 119, 185-8, 190-2
(1950).
Soap Sanit. Chemicals, 26, No. 9,61-2 (1950).
Spooner, W. W., Ind. Heating Engr., 12,No. 52,50-2 (1950).
Stringer, W. E.,Food Inds., 21,892-5 (1949).
75
Sybel, H. v., Z. Ver. deut. Ing., Verfahrenstech., No. 3, 59-62
(1941).
Tamblyn, W. G., P u l p Paper Mag. Can., 50, No. 12, 101-7
(1949).
Tetrel, R., Rev. prod. chim., 53, No. 3-4, 26-7, 9,31, 33: No.
5-6,48-51(1950).
Textile Age, 14,No.1, 104-6, 108-12 (1950).
Thomas, F. W., J . SOC.Dyers Colourists, 65,478-83 (1949).
Ueno, Seiichi, and Imade, Hiroshi, J . Nippon Oil Technol. SOC.,
2,No.1, 1-4 (1948).
Uihlein, Z. H., Chem.-Ztg., 74,No. 28,388-93(1950).
Ullrich, E.,Tezti,?-Praxis, 5,130-3 (1950).
Utley, H. F.,Pit & Quarry, 41,No. 5,1046 (1948).
Vandoni, R., and Boivin, M., Mem. sewices chim. Qtal. (Paris),
33,239-46(1947).
Van Kampen, G. R., Paper Trade J., 128,No. 14,26-7 (1949).
Varley, J., Am. DyestuffReptr., 39,367-8 (May 29,1950).
Walter, L.,Tertile-Mfr., 75,No. 894,282-4 (1949).
Watts, A.J. C., Trans. Brit. Ceram. Soc., 49,No. 2,43-55,55-7
(1950).
Weissberger, A., “Technique of Organic Chemistry,” Vol. 111,
New York, Interscience Publishers, 1950.
Whitewell, J. C., Bowen, C. F., and Toner, R. K., Textile Re-
search J., 26,400-9 (1950).
Whitwell, J. C., and Toner, R. K., Ibid., 19, No. 11, 755-8
(1949).
Woodcock, R.W., Elec. World, 132,100 (Nov. 5,1949).
Wride, W. J.,Iowa State Coll. J . Sci., 24,122-4 (1949).
Yamamoto, Gi-ichi, Trans. Am. Oeophys. Union, 31, No. 3,
349-56 (1950).
Zilske, Heinz, Seifen-~Ze-Fette-Wachse, 76, 89-93, 111-13
(1950).
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Colloid Chem., 53,1426-53 (1949).
RECEIVED
October 30, 1950.

EVAPOR AT1ON
w. L. BADGER, ANN ARBOR,MICH.
R. A. LINDSAY, THE DOW CHEMICAL CO., MIDLAND, MICH.
AS has been true in the past several years, there is but little advance in the past year in the In the long-tube vertical evapo-
theory of evaporation or the design and operation of evaporators. There is evidence of in- rator i t is probably necessary to con-
creased interest in the range of film boiling, whereas in the past the major emphasis has been sider three zones within the tube
in the nucleate boiling range. This interest i s probably due to evaporation problems arising instead of two as previously thought
in jet engines and atomic energy work, where it is necessary to cool from a very high tem- of: a nonboiling section, a boiling
perature level. The most prolific source of published information on evaporators continues to section with subsequent recondensa-
be the paper industry, and if one i s to judge by the amount of work reported, the problem of tion, and a true boiling section in-
scale in sulfite waste evaporators is the most important stumbling block in the field of evaporation. stead of the simpler assumption of
The use of evaporation as a tool to secure ion-free water and to recover values from dilute nonboiling and boiling sections. This
solutions continues to decline in favor of ion exchange. Such work as presented b y Prescott (37) section of boiling and subsequent con-
and others is evidence of this. Furthermore, the possibility exists that ion exchange may sup- densation was shown to have a heat
plant in some instances both formation of the solution and its concentration. In theory it is transfer coefficient exceeding those
possible with the proper exchange resins to take a dilute salt solution and convert it into a predicted by any standard formula
concentrated caustic solution. The food and pharmaceutical industries continue to apply for liquid heating. In many in-
evaporation technique learned in the heavy chemicals field. The illustration shows a unit for vestigations of heat transfer coeffi-
concentrating a heat-sensitive product in these fields. cients in evaporators, the so-called
“nonboiling” section has revealedsuch
c coefficients. In some recent work

P
ROBABLY the most important recent contribution to the
understanding of evaporation problems is that of McAdams
et al. (966). This paper presents a very thorough investiga-
tion of the physical phenomenon of heating liquids, where the heat
transfer area temperature exceeds the boiling point of the liquid
under the pressure existing at the surface. The investigation was
performed with the use of high heat flux by means of a hot wire to
liquid inside a vertical glass tube. It was noted and observed
with high speed photography that vapor formed a t the surface
subsequently was recondensed in the body of the Iiquid. It is
obvious that in every natural circulation evaporator this situation
must occur in some section of the heating area.
on Dowtherm boilers, coefficientsin the liquid preheating section
were found to be much higher than those expected. In view of
McAdam’s work it i s certain that surface boiling was encountered.
It had been thought previously that the known information on
physical property was inaccurate, and the cause of the lack of
correlation between the experiment and the calculated data.
The authors in this paper report a heat flux in the neighborhood of
2,000,000 B.t.u. per square foot. As the liquid was subcooled
below the boiling point the heat flux was higher. Increasing the
velocity with other conditions remaining constant did not change
the temperature difference a t which the boiling occurred, but did
increase the maximum heat flux obtained.
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY
Ranby, B. G., and Grinberg, B., Compt. rend., 230, 1402-4
(1950).
Razous, P., “ThBorie et Pratique du SBchage Industriel,” 5th
ed., Paris, H.Dunod, 1949.
Rigaut, P., and Ulmer, G., Fonderie, 38,1491-3 (1949).
Robinson, R. R., J . Can. Ceram. SOC.,18,35-9 (1949).
Roddy, W. T., Jacobs, J., and Jansing, J., J . Am. Leather Chem-
ists’ ASSOC.,
44,308-20 (1949).
Rudd, H. W., and Tysall, L. A., J . Oil Colour Chemists’ Assoc.,
32, 546-63 (1949).
Rudolph, W., Ind. Finishing, 26, No. 4, 30-2, 34, 37-8, 40
(1950).
Rumpelt, H., Farbe u. Lack, 55,271-4 (1949).
Schaeffer, A., Textil-Praxis, 5,3-6 (1950).
Schneider. J., Kunstseide und Zellwolle, 28,264-78 (1950).
Schneider, J., Melliand Textilber., 31,No. 4,2846 (1950).
School, K.,TextiLPraxis, 5,32 (1950).
Schultz, T.H.,Miers, J. C., Owens, H. S.,and Maclay, W. D.,
J . Phys. & Colloid Chem., 53,1320-30(1949).
Seltzer. E.. and Settelmever. J. T.. “Advances in Food Re-
search,” Vol. 11, “Spray Drying of Foods.” pp. 399-520,
New York, Academic Press, 1949.
Settelmeyer, J. T., Food Inds., 22,272,376, 378 (1950).
Shikher, A. G..Shikher. M. G., and Petrova, N. Ya., Zhur.
Priklad. Khirn., 22,947-51 (1949).
Signer, R., and Roth, M.,Makromol. Chem., 3,281-5 (1949).
Simril, V. L.,and Hershberger, A.,Modern Plastics, 27,No. 10,
97,98,100,102,150-2,154,156,158 (1950).
Ibid., 27,NO.11, 95-6,98,100,102 (1950).
Smith, D. A.,Chem. Eng. Progress, 45,703-7(1949).
Smith, S. F., Paper-Makers (London), 119, 185-8, 190-2
(1950).
Soap Sanit. Chemicals, 26, No. 9,61-2 (1950).
Spooner, W. W., Ind. Heating Engr., 12,No. 52,50-2 (1950).
Stringer, W. E.,Food Inds., 21,892-5 (1949).
75
Sybel, H. v., Z. Ver. deut. Ing., Verfahrenstech., No. 3, 59-62
(1941).
Tamblyn, W. G., P u l p Paper Mag. Can., 50, No. 12, 101-7
(1949).
Tetrel, R., Rev. prod. chim., 53, No. 3-4, 26-7, 9,31, 33: No.
5-6,48-51(1950).
Textile Age, 14,No.1, 104-6, 108-12 (1950).
Thomas, F. W., J . SOC.Dyers Colourists, 65,478-83 (1949).
Ueno, Seiichi, and Imade, Hiroshi, J . Nippon Oil Technol. SOC.,
2,No.1, 1-4 (1948).
Uihlein, Z. H., Chem.-Ztg., 74,No. 28,388-93(1950).
Ullrich, E.,Tezti,?-Praxis, 5,130-3 (1950).
Utley, H. F.,Pit & Quarry, 41,No. 5,1046 (1948).
Vandoni, R., and Boivin, M., Mem. sewices chim. Qtal. (Paris),
33,239-46(1947).
Van Kampen, G. R., Paper Trade J., 128,No. 14,26-7 (1949).
Varley, J., Am. DyestuffReptr., 39,367-8 (May 29,1950).
Walter, L.,Tertile-Mfr., 75,No. 894,282-4 (1949).
Watts, A.J. C., Trans. Brit. Ceram. Soc., 49,No. 2,43-55,55-7
(1950).
Weissberger, A., “Technique of Organic Chemistry,” Vol. 111,
New York, Interscience Publishers, 1950.
Whitewell, J. C., Bowen, C. F., and Toner, R. K., Textile Re-
search J., 26,400-9 (1950).
Whitwell, J. C., and Toner, R. K., Ibid., 19, No. 11, 755-8
(1949).
Woodcock, R.W., Elec. World, 132,100 (Nov. 5,1949).
Wride, W. J.,Iowa State Coll. J . Sci., 24,122-4 (1949).
Yamamoto, Gi-ichi, Trans. Am. Oeophys. Union, 31, No. 3,
349-56 (1950).
Zilske, Heinz, Seifen-~Ze-Fette-Wachse, 76, 89-93, 111-13
(1950).
Zwolinski, B.J., Eyring, Henry, and Reese, C. E., J . Phys. &
Colloid Chem., 53,1426-53 (1949).
RECEIVED
October 30, 1950.

EVAPOR AT1ON
w. L. BADGER, ANN ARBOR,MICH.
R. A. LINDSAY, THE DOW CHEMICAL CO., MIDLAND, MICH.
AS has been true in the past several years, there is but little advance in the past year in the In the long-tube vertical evapo-
theory of evaporation or the design and operation of evaporators. There is evidence of in- rator i t is probably necessary to con-
creased interest in the range of film boiling, whereas in the past the major emphasis has been sider three zones within the tube
in the nucleate boiling range. This interest i s probably due to evaporation problems arising instead of two as previously thought
in jet engines and atomic energy work, where it is necessary to cool from a very high tem- of: a nonboiling section, a boiling
perature level. The most prolific source of published information on evaporators continues to section with subsequent recondensa-
be the paper industry, and if one i s to judge by the amount of work reported, the problem of tion, and a true boiling section in-
scale in sulfite waste evaporators is the most important stumbling block in the field of evaporation. stead of the simpler assumption of
The use of evaporation as a tool to secure ion-free water and to recover values from dilute nonboiling and boiling sections. This
solutions continues to decline in favor of ion exchange. Such work as presented b y Prescott (37) section of boiling and subsequent con-
and others is evidence of this. Furthermore, the possibility exists that ion exchange may sup- densation was shown to have a heat
plant in some instances both formation of the solution and its concentration. In theory it is transfer coefficient exceeding those
possible with the proper exchange resins to take a dilute salt solution and convert it into a predicted by any standard formula
concentrated caustic solution. The food and pharmaceutical industries continue to apply for liquid heating. In many in-
evaporation technique learned in the heavy chemicals field. The illustration shows a unit for vestigations of heat transfer coeffi-
concentrating a heat-sensitive product in these fields. cients in evaporators, the so-called
“nonboiling”section has revealedsuch
c coefficients. In some recent work

P
ROBABLY the most important recent contribution to the
understanding of evaporation problems is that of McAdams
et al. (966). This paper presents a very thorough investiga-
tion of the physical phenomenon of heating liquids, where the heat
transfer area temperature exceeds the boiling point of the liquid
under the pressure existing a t the surface. The investigation was
performed with the use of high heat flux by means of a hot wire to
liquid inside a vertical glass tube. It was noted and observed
with high speed photography that vapor formed a t the surface
subsequently was recondensed in the body of the Iiquid. It is
obvious that in every natural circulation evaporator this situation
must occur in some section of the heating area.
on Dowtherm boilers, coefficientsin the liquid preheating section
were found to be much higher than those expected. In view of
McAdam’s work it i s certain that surface boiling was encountered.
It had been thought previously that the known information on
physical property was inaccurate, and the cause of the lack of
correlation between the experiment and the calculated data.
The authors in this paper report a heat flux in the neighborhood of
2,000,000 B.t.u. per square foot. As the liquid was subcooled
below the boiling point the heat flux was higher. Increasing the
velocity with other conditions remaining constant did not change
the temperature difference a t which the boiling occurred, but did
increase the maximum heat flux obtained.
76 INDUSTRIAL AND ENGINEERING CHEMISTRY
Xeuville (36)reportfi on a mathematical formula for multiple-
effect evaporators based on the observed fact that with equal areas
and no vapor removal from any of the effects the pressure dif-
ference between effects is always the same. The evaporation in
each effect is shown to be proportional to the pressure difference.
This formula is limited in scope, as heat effects introduced by feed
conditions can make a considerable difference in the evaporation
ratio between effects. Vedrilla (44) presents a simple formula
and illustrates its application for chemical processes by calculating
the heat losses and capacities of an evaporator and other chemical
equipment.
The coefficient encountered in film boiling from a horizontal
tube is given by Bromley (?), who undertook the work to solve
problems arising in the design of jet engines where the tempera-
ture difference exceeds the critical for nucleate boiling. The film
is described as continuous with ripples of varying thickness along
the length of the tube. Variation in film thickness also occurs
with time a t k e d point on the area. This results in a coefficient
that is higher than would be predicted if the film were of uniform
thickness. The result can be compared to a finned tube, in that
the phase boundary between the vapor and the liquid is extended,
The metal surface is important, but much less so than in nucleate
boiling. It is shown that liquid-vapor surface tension is an
important factor in the size of the critical heat flux, as is the total
pressure on the system. Bromley presents a formula for stable
film boiling along with experimental data.
Fatica and Kata (16) report on dropwise condensation and a
formula for predicting it. This matter is of considerable interest
in the design of forced-circulation and long-tube vertical evapora-
tors where it is often possible to obtain boiling coefficients
exceeding the steam-film coefficient. A discussion of the effect
of surface roughness indicates that the commercially available
surfaces are generally so rough as to forbid the possibility of any-
thing but film condensation, because of the many peaks presented
and their relation to the contact angle b e h e e n the surface and
liquid condensate.
Maisel and Sherwood ($7, 68) present data on the evaporation
of various liquids into turbulent gas streams. They cover evapo-
ration from planes, cylinders, spheres, and disks. TTlater evapo-
ration was investigated irom ail surfaces into air Water into
carbon diovide and helium, benzene into air, and carbon tetra-
chloride into air were investigated from cylinders. The effect of
velocity, shape, liquid properties, and pas properties is presented
and the correlation of mass and heat transfer is shown.
Boiling coefficients from iinned tubes are reported by Zieman
and Katz (48). The tubes investigated had an area ratio of 2.4
to 1 and the heat flux per lineal unit is shown to be 1 4 to 2 0
times as great as with a smooth tube Data are shown for hexane
and isobutane. The nork revealed that the problem of con-
densate removal from the inside of the tube was of extreme im-
portance. When the %foot tube was tilted to a total of 2 inches
the over-all coefficient increased by 8%. Partial condensation
of the steam was used to investigate the sweeping effect of steam
velocity on condensate removal. Inlet steam velocities up to 40
feet per second gave over-all coefficients of 500, a t 240 feet per
second the coefficient was 750, and at 300 and above it was 900.
.4 short tube of 0.65 foot, compared to 3 feet, gave a coefficient of
1000 a t a nominal inlet steam velocity
Witzig, Penney, and Cyphers ( 4 6 )present data on the evapora-
tion of Freon-12 from inside of a copper tube, 0.305 inch in inside
diameter. The effect of flow rate, oil contamination] and tem-
perature difference was investigated. The results show that
temperature difference has a big effect, while evaporation tem-
perature, flow rate, and oil contamination are of decreasing im-
portance. The problem of evaporating organic liquids is consid-
ered by Klein (22), who presents a formula for estimating the
latent heat, relating it to the critical state. Data are presented
for many liquids and the formula is shown to give results which
compare well with experimental data. Berman ( 4 ) shows the
Vol. 43, No. 1
effect of noncondensable gases OD steam film coefficients. This
problem is particularly important in multiple-effect evaporators,
where the steam source is often under a vacuum and complete air
exclusion is impossible. It is shown that the decrease in coeffi-
cient is considerably greater than the percentage of nonrondens-
able present.
McAdams (66) lectures on the present-day level of our knowl-
edge of heat transfer, including evaporation. He shows that
as a liquid is heated for evaporation it is first heated by natural
convection and the coefficient is proportional t o the temperature
difference to the five-fourths pon-er. Secondly heat is transferred
by nucleate boiling where vapor bubbles are formed on the
heating surface and are displaced with liquid In this range the
heat flow varies as the temperature difference to the nth pon-er,
where n ranges from 3 to 4. Next, i t is transferred where part of
the surface is continuously covered by vapor. Fourth is transfer
to vapor, where the surface is completely covered by vapor and
heat is transferred by conduction and radiation through the vapor
film to the liquid. Lastly, it is transferred where the area is a t a
high enough temperature so that radiation controls the rate of
heat transfer. It is pointed out that one of the conventional
problems yet to be completely investigated is the pressure drop
and heat transfer rate in natural-circulation evaporators. One of
the stumbling blocks in this investigation is the fact that it is
impossible to separate completely the various methods of transfer
that occur in this type of evaporator. Even in a simple unit like
a natural evaporator heat transfer occurs by natural convection,
boiling with subsequent condensation, and eventually by nucleate
boiling.
Instruments and controls for paper-industry evaporators are
discussed by Murphy (81) I t is shown that by the proper
operation of the evaporators a considerable increase in the recov-
ery of chemical values can be realized. Malikov (29) shows a
control method for a sugar plant where all of the process is syn-
chronized with the evaporator operation. A complete discussion
of instruments and their use, including control of salt concentra-
tion in evaporators, is presented by Broadhurst et al. (6).
Among the several papers covering the handling of sulfite
waste liquors is one by Samuelson (39) who presents data on the
precipitation of calcium sulfate and the type of hydrate formed.
The minimum solubility occurs a t a p H of 3.5, as shown by graphs
and tables. The amount of calrium sulfate precipitated increases
with higher temperatures, and seeding with fine crystals increases
the rate of precipitation. The amount of total solids present has
little effect on the amount or rate of precipitation. Laboratory
work was checked on a plant unit showing less scale with neutral
liquor than was experienced with acid liquor. Examination of
the crystals by x-ray revealed that anhydrite material is pre-
cipitated a t 130" C. and above, and the hemihydrate from 100" to
130' C. Nyman (33) discusses the treatment of sulfite waste
liquor by adjusting the pH to 6 to 6.5 with sodium carbonate.
This is reported to form a suspension of calcium sulfite which is
coprecipitated with calcium sulfate and results in a scale that can
be easily removed with acid. Butler (9) reviews 51 references on
the evaporation and burning of calcium-base sulfite liquors.
Grewin and Lindberg (18)disclose a method of scale removal by
alternating the steam and liquor flow every 30 hours. The steam
is mixed with sulfur dioxide from the liquor and the condensate
removes the scale.
The evaporation of su!fite liquor has always been a serious
problem because of the presence of large amounts of calcium
sulfate. Several companies in Sweden are now evaporating
sulfite liquors with one or the other of two relatively new processes.
The RosenbIad (24,38) system uses a plate-type heating element
in which the even-numbered passages are used for liquor and the
odd-numbered passages for the heating steam. After a certain
number of hours, by an ingenious arrangement of valves, the flow
is switched so that the liquor goes through the odd-numbered
passages, and the steam goes through the even-numbered passages.
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY

The condensate dissolves off the calcium sulfate scale. This

system has been installed in four mills.
The Ramen system, which has not been described in the litera-
ture, is based on the fact that the solubility of calcium sulfate in
sulfite liquors is very much higher at room temperatures than in
pure water. The system uses an evaporator with a considerable
number of effects. The liquor is concentrated first in the lowest
temperature effects, where the solubility is greater and the liquor
does not reach saturation at these temperatures. The liquor is
then heated by the direct injection of first effect vapors to such a
temperature that a considerable amount of calcium sulfate i s
thrown down. This liquor is then evaporated in intermediate
effects, still below the saturation of calcium sulfate. It is then
heated again by the direct injection of high pressure steam, to
such a temperature that most of the calcium sulfate remaining is
- thrown down, and then evaporated in the first effects of the mul-
tiple. By such a cycle, the evaporator bodies proper are always
operating below the saturation point of calcium sulfate; the
reheating where calcium sulfate is precipitated i s done in appara-
* tus in which scale does not form because the heat does not pass
through a heating surface; and the calcium sulfate is thus thrown
out as insoluble anhydrite, whose rate of solution is so slow that it
does not redissolve appreciably during the time the liquor is in the
evaporator. This system is installed, with variations, in four
mills in Sweden. Some mills use falling-film, long-tube evapora-
tors with forced circulation, but a t present these installations are
considered obsolete, because they require very frequent cleaning
to remove calcium sulfate scale.
A system similar to the Rosenblad is presented by Franklin
and Goddard (17), using steam pressures from 200 t o 250 pounds
per square inch gage. The vapor from the evaporators can be
used to generate low-pressure steam for other plant uses. They COURTe8Y SWENSON EVAPORATOR 00.

suggest the use of three heaters alternately, with one being cleaned
with acid condensate from the low-pressure steam generator a t all
times. The unit described discharges a 60% solids products
and the economics of the operation are presented. A similar
high-temperature evaporator for sulfite waste liquors is presented
by Aspegren ( 1 ) . Brauns (6) discusses a proposed sextuple-
effect evaporator for high-temperature operation Superheated
steam a t 240' C. is added t o the third effect to remove sulfate
A diagram is shown along with heat and material balances for
a unit to concentrate a feed containing 10.9 to 50% solids. An
electrically heated evaporator for sulfite waste liquor is re-
ported by Beath and Hill (3). In the ha1 pilot plant design the
liquor flows through a perforated grounded electrode, past a
high-voltage electrode, through a second grounded electrode, and
past a valve into a vapor release space. Power input waR regu-
lated by the steam bubble formation in the electrode chamber and
the liquor concentration controlled by feed and withdrawal rates.
I n the pilot plant voltage was varied from 700 to 1000 with the
power a t 65 kw. Operat,ion of the unit a t 150 pounds per square
- inch gage caused 10% decomposition of the solids in the feed.
This increased the heating value of the product, but made the
solution viscous and difficult to handle.
Collins ( 1 1 ) discusses the scale and slime problem in water
evaporators. The discussion following the paper describes a
brine evaporator holding 50,000 gallons.
The brine contains calcium sulfate, which resulted in a scale
0.5 to 0.75 inch thick which was so hard that the turbine cut
through the tubes rather than the scale. Chemcal treatment
with 50% caustic was used. Neither lime nor sodium sulfate is
soluble in 50% caustic. During treatment the unit was kept at
230' F. for 5 days with the liquor circulated continuously. At
the end of 3 days the caustic concentration had dropped from
49.6 to 47.6% and the suspended lime and sodium sulfate gave
a magma density of 15%. This slurry was removed and the unit
recharged with fresh caustic solution. Intermediate inspection
revealed no improvement in the appearance of the deposit. After
2 more days the caustic concentration had dropped t o 45.4%, it
T
was evaporated to 48.270, and fresh 50 caustic was added.
After another 1.75 days the concentration ad dropped to 46.9%.
Compound Triple-Effect Long-Tube Vertical Evaporator
for Heat-Sensitive Food Products
The liquor sludge had overloaded the pump and it was necessary
to shut down. The evaporator was about 90% clean and the
liquor contained 14% solids.
John (20)discusses mechanical tube cleaners and illustrates the
better known types. The compression-type sea water evaporator
and scale removal with sodium bisulfate and hydrochloric acid
are discussed by Campobasso and Latham (IO). The unit is ca-
pable of handling 200 to 300 gallons per square foot before cleaning
is required, and the use of chemical treatment will avoid the need
for mechanical cleaning. It is reported that vacuum operation
at 150" F. offers the possibility of avoiding scale entirely. Pich-
ardo and Romero (36) report on the history of the addition of
tetraphosphoglucosate for the control of scale in sugar evapora-
tors A 6% solution in water is added a t the rate of 205 ml. per
hour to evaporator feed and a like amount into the body of the
fourth effect. This treatment decreased the steam consumption
and reduced the down time from 2.29 to 0.9770. Hopper (19)
also discusses the use of tetraphosphoglucosate in a commercial
unit. He reports that at the end of 6 weeks' operation the unit's
efficiency had dropped to 90 to 95%, whereas without treatment
for a similar period t8heefficiency was only 75 to 80%. After the
run with treated liquor there was very little scale except in the
bottom of the third and fourth effects. Montgomery (30) uses
Nalco number 918 a t the rate of 0.0031 to 0.025 pound per ton
of juice to decrease scale formation. Such scale as is formed is
easily removed. The treatment gives best results when used in
the third effect as well as in the feed liquor.
Petaold (36) presents graphs for the steam consumption of
thermocompression evaporators. Vapor jet compressor data are
used along with an enthalpy-entropy diagram to derive the infor-
mation. Performance data for commercial equipment are
shown to verify the theory presented. A review of the principles
and use of the heat pump is presented by Peter (34),who covers
recompression cycles for heat interchange and evaporation.
78 INDUSTRIAL AND ENGINEERING CHEMISTRY
In practice it is possible to obtain more than 4000 kg.-cal. equiva-
lents for heating and more than 20,000 for evaporation per kilo-
watt-hour input. As a rule of thumb it is suggested that the heat
pump becomes economical when the cost of 1 kw.-hr. of electric
energy is not more than 0.5 lrg. of coal in the case of its use in heat
exchange and not more than 1 kg. of good coal in the case of an
evaporation process. Landorff (83) discusses the use of vapor
thermocompression in sugar refineries. A Swiss patent (16)
discloses a method of operating the boiling pans completely and
the evaporators partly by thermocompression. A plant is
described and the heat balance is shown.
The use of thermocompression in the evaporation of sulfite
waste liquor is presented by Elgee et al. ( 1 4 ) , who report that 4
hours' cleaning with acid condensate after 20 hours' operation
keeps the unit in good condition and that no less scale is encoun-
tered if the feed is preheated, The use of foam inhibitors made the
scale easier to remove. Thewritersreport their pilot plant required
22 kw.-hr. per 1000 pounds of evaporation. I n commercial oper-
ation they estimate 106 kw.-hr. will be required per ton of 50%
solids recovered from a 10%feed. Smith (40)reports on a similar
unit requiring 160 kw.-hr. per 1000 gallons of evaporation. He
states that a commercial unit should not require more than 111
kw.-hr. per 1000 gallons of evaporation or 107 kw.-hr. per ton of
50% solids recovered from a 10% feed, The steam required for
1000 gallons of evaporation would amount to 1520 pounds per ton
of 50% solids.
The corrosion of lead linings in rayon spin-bath evaporators is
discussed by Kleinert and Pospischill (89). This problem is
ascribed to electrochemical effects caused by lack of homogeneity
in the lining and by local concentration differences in the bath
liquor being evaporated, as well as depolarization of hydrogen in
the lead by contact with air (seam leaks). Corrosion is enhanced
by recrystallization of the lead, forming cracks, and by sulfur
attack at g a i n boundaries. Beamer and Fuqua (2) describe a
method of lining sulfuric acid concentrators by coating with
carbon. This is accomplished by filling the unit with dilute acid
containing organic material and heating for several hours. The
evaporation of hydrocyanic acid is disclosed by Cook and Rosen-
bloom (18). The unit operates under a vacuum with a hydrogen
cyanide vapor removed by a liquid-operated eductor. The re-
moval of sulfate from a mineral containing magnesium is dis-
closed by Burke, Smith, and Manning (8). The salt Is dissolved
and evaporated until 2MgS0,.K2S04 is crystallized. When fur-
ther evaporated until MgSOI.Ht0 can be removed, the product is
suitable for use as cell feed. Szekely (41) reveals an apparatus
for the evaporation of special pharmaceutical liquids. Zellner
( 4 7 ) describes a piece of laboratory equipment for both evapora-
tion and distillation. A multipurpose unit suitable €orthe evapo-
ration of foaming liquids is disclosed by Techochemie A.-G. (42).
Vedrilla (46) presents data on the dimensioning of evaporators,
and Ebert (IS) covers vacuum technique in laboratory evapora-
tions. Trub (a) reviews the types of evaporators and methods
of evaporation used in Russian sugar factories.
LITERATURE CITED
(1) Aspegren, J. A., Swed. Patent 124,414 (March 22, 1949).
(2) Beamer, C. M., and Fuqua, M. C., U. S. Patent 2,478,680 (Aug.
9, 1949).
(3) Beath, L. R., and Hill, H. S., P u l p & Paper Mag. Can., 50, No.
8, 89-94 (1949).
(4) Berman, L. D., Chem. Zentr., 1947, 11, 779-80.
(5) Brauns, O., Svensk Papperstidn., 50, No. 11B, 61-2 (1947).
(6) Broadhurst, J. W., Broderick, T. C., Foster, A. W., and Wheel-
don, G. E., J . Inst. Elec. Engrs. (London),u, 94, 79-90
(1947).
(7) Bromley, L. A,, C h m . Eng. Progress, 46, 221-7 (1950).
(8) Burke, W. E., Smith, W. A., and Manning, P. D. V., U. 5.
Patent 2,479,001 (Aug. 16, 1949).
(9) Butler, 1%'. T., P u l p & PapeT Mag. Can., 50, No. 11, 108-21
(1949).
(10) Campobasso, J. J., and Latham, A., Jr., Trans. Am. SOC.Mech.
EngTs., 71, 837-8 (1949).
Vol. 43, No. 1
Collins, L. F., Ibid., 71, 871-4 (1949).
Cook, L. H., and Rosenbloom, W. J., U. S. Patent 2,489,703
(Nov. 29, 1949).
Ebert, H., Chem. Tech., 1, 19-23 (1949).
Elgee, H., Craig, D., and Russell, J. K., Pulp h Paper Mag.
Can., 51, No. 3, 178-89 (1950).
Esoher Wyss Maschinenfabriken A,-G., Swiss Patent 262,257
(Sept. 16, 1949).
Fatica, N., and Kata, D. Lo,Chem. Eng. Progress, 45, 661-74
(1949).
Franklin, J. N., and Goddard, H. O., P u l p h Paper Mag. Can.,
51, NO.3, 139-46 (1950).
Grewin, F. mi., and Lindberg, S. G., U. S. Patent 2,490,750
(Dec. 6, 1949).
Hopper, L. A., Repts. Hawaiian Sugar Technol., 8th Ann. RIeet-
ing, 1949, 85-6.
John, A., Trans. Am. SOC. Mech. Engrs., 71, 825-9 (1949).
Klein, V. A., Chem. Eng. Progress, 45, 675-6 (1949).
Kleinert, Th., and Pospischill, F., Mitt. Chem. Forsch.-Inst.
I n d . Osterr., 2, 45-8 (1948).
Landorff, B., Sucr. belge, 68, 312-14 (1949).
Lockman, C. J., U. S. Patent 2,488,598 (Nov. 22, 1949).
McAdams, W. H., Chenr. Eng. Progress, 46, 121-30 (1950).
McAdams, W. H., Kennel, W. E., Minden, C. S., Carl, R.,
Picornell, P. &I., and Dew, J. E., IND. Exa. CEIEM.,41, 1945-
53 (1949).
Maisel, D. S., and Sherwood, T. K., Chem. E n y . Progress, 46,
131-8 (1950).
Ibid., pp. 172-5.
Malikov, A. D., L7.S.S.R. Patent 69,613 (h-ov. 30, 1947).
Montgomery, J. W.,Repts. Hawaiian Sugar Technol., 8th Ann,
Meeting, 1949, 83-4.
Murphy, E. A., Paper Trade J., 129, No. 5, 23-26 (1949).
Neuville, P., V I I Congr. Intern. Ind. AUT.Paris, 1, Pt. 2, 15-16
(1948).
Nyman, C. H., U. S. Patent 2,484,046 (Oct. 11, 1949).
Peter, R., Chimia (Switz.), 3, 114-18 (1949).
Petzold, M., Chem. Ing. Tech., 22, 147-50 (1950).
Pichardo, G. -V., and Romero, J. J. L., M e m . asoc. le'cnicos
azucur. Cuba, 22, 187-92 (1948).
Prescott, W. G., Brit. Patent 630,979 (1949).
Rosenblad, C., P u l p h Paper Mag. Can., 51, No. 5 , 85-94
(1950).
Samuelson, O., Saenslc Papperstidn, 52, 283-9 (1949).
Smith, H. L., Jr., P u l p & Paper Mag. Can., 50, No. 9, 84-6
(1949).
Szekely, G., U. S. Patent 2,472,992 (June 14, 1949).
Teohochemie A.-G., Swiss Patent 249,100 (March 16, 1948)
Trub, I. A., Sakhar Prom., 22, No. 11, 36-9 (1948).
Vedrilla, St., Mitt. Chem. Forsch.-Inst.-Ind. Osterr., 3, 6 G 7 0
(1949).
Ibid.. DD. 117-20.
Wita'ig,*W.F.. Penney, G. TT., and Cyphers, J. 8 . ,Rejrig. Eng.,
56, 153-7 (1948).
Zellner, H., Osterr. Chem.-Ztg., 50, 97-100 (1949).
Zieman, 11'. E., and Katz. D. L.. Petroleum Refiner. 26, h-0. 8.
78-82 (1947).
RECBIVED
Sovernber 16, 1950.
 SOLVENT EXTRACTION
ROBERT E. T R E Y B A L
N E W Y O R K UNIVERSITY, NEW YORK 53, N. Y.

Reports of active work in liquid-liquid extraction have increased in numbers considerably The distribution of methanol be-
during the past year. M a n y new ternary phase equilibria have been determined, and there tween water and nitrobenzene (181);
was much interest in the distribution characteristics of metallic compounds between selective of nicotine between water and kero-
solvents. A n increased number of studies have been made in the field of fractional extraction sene from 5 ” to 98’ C. (81); of oxalic
with double solvent systems, from the mathematical as well as from the process point of view, and succinic acids between water
Relatively few new equipment types have been proposed, but extensive laboratory investiga- and amyl alcohol ( 4 ) ; of acetic acid
tions of the operating characteristics of conventional equipment, such as packed and spray and acetone between xyIene and
towers, were reported. In the field of extraction processes, several new plants for vegetable water, and acetic acid between
and mineral oil extractions have been described, but relatively few new solvents for these methyl isobutyl ketone and water
materials were proposed. There was special interest in the selective separation of aromatics (160); and of diethylamine between
from hydrocarbon mixtures, penicillin from fermentation broths, and the continuous hydrolysis water and toluene from 20” to
4
of fats, In the nerd of solid-liquid extraction, now approaches to the calculations of counter- 58’ C. (110, 175) have been re-
current decantation, and extensive studies of the mechanism of leaching have appeared. The ported.
processes of extraction of oils from seeds, tannin from barks, and alumina from bauxite received Considerable work was done on
special attention, and several new designs for beet sugar diffusion batteries were proposed. the distribution of metallic com-
pounds between organic solventa
and water. Comprehensive studies

A
DVANCES in liquid-liquid extraction during the past year
have been considerable, stimulated to a large extent by the
Absorption and Extraction Symposium of the Division of
Industrial and Engineering Chemistry of the AMERICAN CHEMI-
CAL SOCIETYin December 1949. Although no startling new
techniques or applications have been reported, contributions
to the understanding of the basic mechanisms of the unit operation
have been most significant.
Several very thorough reviews have appeared. Elgin’s recent
comprehensive treatment of all aspects of the subject (48) has
been supplemented by his annual review in the present series
(43). Craig has reviewed laboratory techniques (87, 88) and
analytical applications (86).
EQUILIBRIA, T H E R M O D Y N A M I C S , DlFFUSlON
Table I gives new systems for which substantially complete
liquid equilibrium data have been accumulated. Smith (157)
has compiled a complete listing for ternary and quaternary sys-
tems for which a t least two tie lines are known, and Smith (156)
has discussed the significance of “solutropy,” the comparatively
rare phenomenon of reversal of selectivity in ternary liquid sys-
tems. Two liquid phases were observed in the system ethanol-
water-potassium nitrate (140).
A large number of distribution data have been reported, only
a portion of which can be mentioned here. Golumbic and co-
workers have continued their study of the distribution of phenols
between cyclohexane and water (125). Golumbic has further
studied the distribution of polycyclic aromatic compounds be-
. tween aqueous ethanol and cyclohexane (59), and has demon-
strated the usefulness of this solvent combination for separating
these compounds according to chemical type. The extraction of
a variety of aliphatic and aromatic sulfur compounds from hep-
tane with anhydrous hydrogen fluoride has been studied by
Lien et al. ( 9 4 ) , who found this solvent to be variously effective
depending on the nature of the distributed solute. Collander
(94)studied the contributions of various structural groups and
hydrogen bonding t o the distribution coefficients for some 200
organic compounds between ether and water. Marvel and
Richards (103) have shown that the relative effectiveness of a
number of organic solvents is the same for extracting various
mono- and polybasic acids from water and have confirmed dis-
tribution measurements with experimental fractional extractions.
79
of the partition between aqueous hydrochloric acid and
isopropyl ether have been made for ferric chloride (63,118) and
gallium chloride (113); in both cases, three liquid phases are
formed a t certain concentrations. Distribution studies of the
nitrates of metals likely to contaminate uranium indicated that
uranyl nitrate can readily be purified by water extraction of its
ether solutions ( 5 ) . Distribution of rare earth nitrates between
water and hexanol show the increased extractability into the
alcohol which occurs with increased atomic number of the metal
(163). Study of the distribution of metal complexes indicates
the separability of zirconium and hafnium by extraction (95, 7 7 ) ;
the partition of the cupferates 6f iron (144), copper, molyb-
denum, and uranium (50) between chloroform and water were
studied in detail.
The miscibility of binary liquid mixtures of chlorex with w
octane, 2,2,4-trimethylpentane ( 1 70>, the Ct to Cs aliphatic
alcohols, and with halohydrocarbons (169) has been studied, and
two-phase diagrams for ethylene-chlorohydrin-cyclohexane are
reported (79). The effect of various additives on the miscibility
of benzene and water was investigated (139). Hildebrand has
made ZI thermodynamic study of the solubilities of water and
hydrocarbons in general (76), whereas Brodin (16) related mis-
cibility to compressibilities. Domadia and Kane (36) show that
the lower the aniline point of certain petroleum derivatives, the
higher is their miscibility with castor oil. Booth and Everson
(19)have studied the extraordinary solubility of a variety of
compounds in hydrotropic solutions, which is of potential inter-
est in extraction, and Francis (49) has compiled an extensive
table and bibliography of critical solution temperatures.
Herington ( 7 2 ) has developed methods for testing the consist-
ency of data for two-phase ternary systems, and has established
guides for the choice of separating agents useful in both extractive
distillation and solvent extraction. An outline for the calcula-
tion of ternary equilibria, with allowance for the temperature
dependence of activity coefficients, was provided by Wood (182)
which should be most useful in predicting extraction equilibria.
Practical methods for estimating distribution coefficients were
demonstrated by Scheibel (148).
A large number of diffusivity measurements have been made
which cannot be outlined here. The fundamental studies of
Crank and eo-workers (89, 66) on the effect of concentration on
liquid diffusivities is of general interest, however.
80 INDUSTRIAL AND ENGINEERING CHEMISTRY
BUBBLES, DROPS, E M U L S I O N S
The rate of fall of small mercury drops in viscous liquids was
found to depend on the distance between coneecutive drops and
the presence of surface active agents which reduce tangential
motion in the drop surface (6). Hayworth and Treybal ( 6 8 )
studied the size and uniformity of liquid drops forming in an
immiscible liquid from simple nozzles as influenced by the
physical properties of the liquids, nozzle diameter, and flow rate of
dispersed liquid. They developed an empirical relation with
which t o predict drop sizes. The rate of extraction from isolated
drops rising or falling in a liquid medium, as affected by circula-
tion currents developed in the drops, was investigated mathe-
matically by Kronig and Brink (89). Licht and Conway (93)
postulated t h a t extraction from drops in spray extraction towers
occurs during drop formation, during rise or fall of the drops,
and during their coalescence into the liquid layer at the end of the
tower. By means of an ingenious device they were able to isolate
these effects for single drops; they found t h a t over-all transfer
coefficients increased with decreased drop size during drop forma-
tion and were substantially independent of drop size during the
falling period.
The use of substances which promote formation of water-in-
oil emulsions, such as some metallic soaps, was proposed as a
means of preventing emulsions in the solvent refining of mineral
~ i l s(19.8). D r y powdered soda ash resolves emulsions formed
during the water washing of aromatic nitrocompounds (1?1),
and chlorophyll similarly assists in the chloroform extraction of
alkaline solutions of alkaloid drugs (40). Separation of liquid
dispersions can be carried out in a bundle of horizontal or inclined
tubes, with one of the liquids escaping through openings in the
walls of the tubes (119); the use of silicone-treated mineral wool
as a coalescing medium was suggested ( 7 3 ) .
DESIGN M E T H O D S
Diacussionsof the accepted methodsof calculatingthe number of
stages required for simple extraction flow sheets were given by
Jodra (81) and Naudet (115); special applications to the fat
industry were emphasized by the latter. Rometsch (142) simi-
larly considered continuous countercurrent fractional extraction
or the separation of mixtures by the use of two immiscible
solvents, and experimentally demonstrated determination of the
effective distribution coefficients of several systems. Asselin
and Comings (4) studied this type of extraction also and in addi-
tion derived a graphical means of determining the number of
stages required when reflux is returned at either end of the ex-
traction plant. In such systems, reflux is not necessarily as
effective as with analogous processes in distillation. These
authors demonstrated the correctness of their methods by sepa-
rating oxalic and succinic acids using water and amyl alcohol as
solvents and neodymium and thorium nitrates with the same sol-
vents in the presence of ammonium thiocyanate in a laboratory
apparatus containing five stages of the mixer-settler type.
Several studies have been made of unsteady-state extraction.
Lapidus and Amundson (91) presented a mathematical considera-
tion of transient and unsteady-state operation of both counter-
current extraction and multiple extraction with fresh solvent.
Equations were derived permitting the computation of the varia-
tion of compositions with time which can be used, for example,
t o calculate the time required to return to equilibrium when varia-
tions in the feed occur. An extensive mathematical study of
what occurs when a fixed quantity of solute mixture is injected
suddenly into countercurrently flowing solvents was made by
Johnson and Talbot (82). They concluded t h a t the most
favorable separation of two solutes present in equal proportions,
when introduced centrally into the extraction cascade, will occur
when the ratio of the solvent feed rates is the inverse of the geo-
metric mean of the distribution coefficients, as in steady-state
operation. This was verified by the experimental separation of
Vol. 43, No. 1
oxalic and succinic acids with water and butanol in 2- and 19-
stage laboratory apparatus. Piret and co-workers considered
continuous flow stirred-tank reactor systems, both for steady-
state (41) and transient (104) operation. Both of these studies
are applicable to extraction systems of the discrete-stage type.
Sayre (146) has proposed a new graphical representation of
quaternary systems in two dimensions by which separation prob-
lems can be conveniently solved.
EQUIPMENT
Comparatively few new equipment types have been described.
Van Dijck (33,120) has proposed a discrete-stage type comprising
alternate mixers and settlers installed in a nearly horizontal tube,
with the mixer sections provided with agitators mounted on a
common spindle. A new mixer for treating light oils with sulfuric
acid is described by Goldman (68),and Scheibel's agitated, packed
column has been patented (149). A variety of wetted-wall
column, in which the light liquid enters the bottom of a rapidly
rotating cylinder and rises to the top in a thin film on the vessel
wall, is discussed by Hertzberg (74). I n this apparatus, the heavy
liquid is sprayed into the vessel, penetrates the film of light liquid,
and also leaves a t the top.
The relative lack of new equipment types is compensated for
by the excellent description of existing commercial units by
Morello and Poffenberger (111). I n this comprehensive review,
all types of commercial extractors are classified, and a compila-
tion is made of the performance characteristics of all actual in-
stallations for which the authors could obtain significant informa-
tion. Many of these data are made available here for the first
time.
Several new laboratory devices have been devised (51,63, 05,
118, 138, i71,177).
M A S S TRANSFER AND C A P A C I T Y D A T A
Extraction Rates. Considerable attention was given t o the
rates of extraction in continuously operated laboratory towers.
Laddha and Smith ( g o ) , using a 2-inch diameter column as a
spray tower, as well as with l/h- or */,-inch ring packing, investi-
gated the individual film mass transfer resistances in the systems
isobutyraldehyde-water and pentanol-water. The height of a
transfer unit (H.T.U.) for the dispersed phase was found to be
substantially constant with changing rates of flow of either con-
tinhous or dispersed liquids. End effects in the spray tower
extraction of ferric chloride from aqueous hydrochloric acid by
isopropyl ether were determined by Geankoplis and Hixson
(53). An internal sampling device was employed with a 1.45-
inch diameter tower to investigate concentration gradients, and
contrary to previous experience the entire end effect was pro-
duced a t the continuous phase inlet. Morello and Beckmann
(110) extracted diethylamine from water with toluene in a 1.375-
inch column packed with 4-mm. glass beads at three tempera-
tures, the toluene dispersed. H.T.U. for the water film was sub-
stantially zero and t h a t for the toluene film decreased with in-
crease in temperature; empirical relationships involving tempera-
ture and Schmidt number were developed. Temperature waa
similarly found to be an important variable in the rate of extrac-
tion of nicotine from water by kerosene in measurements of
H.T.U. in a 1.875-inch tower packed with 1/4- or saddles
and a/s- or 1/2-inch rings by Clrtffey et al. ($1). The extraction
of benzoic acid from benzene by water in the presence of surface-
active agents which lower the interfacial tension was studied by
Chu, Taylor, and Levy ($0). Over-all values of H.T.U. were
consistently lowered by highly active agents, but minima were
observed in the variation with concentration of weak agents. A
few experimental runs in a 4-inch column packed with 1/2-inch
rings were reported by Clegg and Bearse ($2) in the extraction of
thiodiacetic acid from a water solution containing sodium salts by
methyl ethyl ketone.
 January 1951 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY 81

Stage efficiencies in a 1-inch diameter agitated packed column

for the separation of ethanol from water by the double-solvent Table 1. Liquid Equilibrium Data for Systems of Three or More
systems glycol-o-xylene and glycol-methyllt-amy1 ketone range Components
from 10 to 100% as the packed height varies from 1 to 8 inches, Temperature, Literature
System c. Cited
as reported by Scheibel (14.8). Mixing sections were l/&nch Ammonia-sodium-sodium iodide Various (SO, f66)
long, and agitator speed 2250 r.p.m. Scheibel proposed the Ammonia-potassium-potassium iodide -31, -33 (80)
Aniline-water, with
economical recovery of anhydrous ethanol from its dilute aqueous Benzene
solutions by these processes using glycol-ketone solvents for the n-Heptane
Methylcyclohexane
recovery of the pure product or glycol-xylene for the recovery of Cod liver oil-ethanol-free fatty acids
Cod liver oil-ethanol-nonsaponifiables
a denatured alcohol. Scheibel and Karr (160),using a similar Cod liver oil-methanol-free fatty acids
column but of 12-inch diameter, extracted the solutes, acetone, Cod liver oil-methanol-nonsaponifiables
Diethylamine-water-toluene
and acetic acid with the solvent pairs, water-methyl isobutyl Dioxane-water-magnesium chloride
Ethanol-water, with
ketone and water-o-xylene. Stage efficiencies, which were re- Ethyl acetate
ported over a wide range of flow rates and agitator speeds, may Potassium hydroxide
Sodium hydroxide
reach 100% and the throughput a t flooding was found to be Hake-liver oil-ethanol-free fatty acids
Hake-liver oil-methanol-free fatty acids
several times as great as that in a 1-inch column. Hake-liver oil-methanol-nonsaponifiables
Perforated-plate columns were studied by Pyle et al. (I$'?), Methanol-water, with
who extracted acetic acid from water with ether in an 8.63-inch EgZ&me-p-cresol
Hexadeoane-2-naphthol
diameter column. Perforation size seemed to influence the Hexadecane-p-tert-butylphenol
extraction rates relatively li,ttle, but a high percentage of hole Hexadeoane-methylnaphthalene
Methylnaphthalene
* area was advantageous. For high flow capacities, downspouts Methylnaphthalene-p-lert-butylphenol
Methylnaphthalene-p-cresol
should be flush with the plate from which they lead the continuous Methylnaphthalene-p-cresol-2,2,4-
phase. The thickness of the coalesced layers of dispersed liquid trimethylpentane 35
Methylnaphthalene-2-naphthol 35
underneath the plates was related to the pressure drops in the Methylnaphthalene-phenol 25, 35
Methylnaphthalene-phenol-2,2,4-
system, and orifice coefficients for the perforations were reported. trimethylpentane
Flow Capacities. Breckenfeld and Wilke (14) investigated Phenol
X lene
flooding in a 2.6inch tower packed with 1/4-inch carbon rings Metgylnaphthalene-p-cresol-water
Palm oil-methanol-free fatty acids
and '/rinch saddles, using a variety of liquid pairs as a means of n-Propanol-n-propyl acetate-water
varying the pertinent liquid physical properties. For the first Thiodiacetic acid-2-butanone-salt solution
(HnO, NaCl, NazSOd
time interfacial tension was introduced into the resulting empirical
correlations for flooding. Ballard and Piret ('9, on the other
hand, used columns of 2.03- and 3.75-inch diameters, with l/4- and
l/Tinch ring packing. A variety of liquids was used with water, propane for the fractionation of vegetable and fish oils into frac-
and the latter preferentially wet the '/*inch rings. For water tions separately comprising color bodies, drying oils, edible oils,
dispersed, flooding as observed by others occurred, but for water and vitamin concentrates. Mattikow reviewed the use of liquid
as the continuous phase a new phenomenon-transition below propane as a degumming solvent for fatty oils (106), and Moore
flooding rates to a flow regime involving considerable coalescence has given a very complete description of a large commercial
-was encountered, and major attention was paid to this. A installation for the decolorization of tallow with this solvent
correlation which agrees with gas-liquid flooding rates was (109). General process descriptions of furfural and propane
offered. refining of vegetable oils were given by Steinbock (160).
A most promising approach to flooding problems in spray The continuous hydrolysis of fats (fatrsplitting) by counter-
columns was presented by Elgin and Foust ( 4 4 , who proposed current contact with water at high temperatures is in part an
that the same basic relationship exists as for solid particles falling extraction operation, Mills and McClain (107) provided basic
through a countercurrently flowing liquid. The velocity of data for the splitting of tallow and coconut oil from measurements
individual drops a t flooding is related to the dispersed phase hold- in a batch autoclave. Ittner (78) and Brown (17) provided de-
up, and these authors show that the holdup data obtained with tailed descriptions of equipment for the continuous process, and
'
fluidized beds of solids are applicable to the estimation of spray Seaman (164) reviewed recent developments. Kenyon et al.
tower flooding rates, if no more specific data are a t hand, (86) reviewed the industrial fat processes generally, including the
continuous splitting process; a complete industrial installation is
LIQUID EXTRACTION PROCESSES described by Potts and McBride (133).
Petroleum. In the field of conventional solvent refining,
Oils and Fats. Methanol was proposed as an extraction Terres (164) reviewed theoretical considerations and presented
\.
solvent for removal of palm fatty acids from the neutral oil (109), data on the extraction of Iraq and mixed-base oils with liquid
whereas ethanol was found to be more selective in the similar sulfur dioxide and the mixed solvents, benzene-sulfur dioxide
purification of fish-liver oils (141). Both solvents were further and phenol-chlorex. Kalichevsky (83) described the standard
investigated for the removal of nonsaponifiables from cod- and processes generally. Reeves and Hardin (139) reported studies
* hake-liver oils (80). Investigation of the systems involving in the three-stage extraction of several mid-continent and coastal
cottonseed oil, oleic acid, hexane, water, and isopropyl alcohol led distillate lubricating stocks and showed that a temperature gra-
to the development of a process for separating cottonseed mis- dient of 30" to 40" F. between extract and raffiate has an insig-
cella into purified oil and a mixture of fatty acids and other non- nificant effect on product yield and quality. Washing the ex-
glyceride substances (66). Laboratory fractional extraction of tract from a propane refining process with extract from which the
soybean oil with hexane-furfural and hexane-nitroparaffin sol- solvent has been removed, with maintenance of a temperature
vents rtssisted in leading Dutton et al. to the conclusion that this gradient, is said to produce improved carbon residue (121).
oil does not follow the common conception of even glyceride dis- Liquid butane was found to behave somewhat similarly t o propane
tribution (39). Technical monoglycerides can be purified from in asphalt extraction (169). Solvent removal of paraffin wax
38.9 to 80% monoglyceride by the double solvents, hexane with from oils with a large number of solvents was studied by Kr6ger
aqueous methanol or ethanol (46). Esters of the higher fatty and Luther (88). Weber (174)surveyed lubricant relining ca-
acids and monohydric alcohols can be prepared by direct counter- pacities by company, revealing a trend toward larger plants, and
current contact (48). Palmer (128) proposed the use of liquid several descriptions of new industrial installations have been
82 INDUSTRIAL AND ENGINEERING CHEMISTRY
made-propane deasphalting and phenol extraction (166,167),
furfural extraction (92), and Duo-Sol treating ( 1 ) .
The separation of aromatics from petroleum products has
received increased attention. Obergfell ( l a d ) reviewed the recent
improvements in the Edeleanu process for treating light distillates
and recommended its application to catalytic cracking recycle
stocks to increase capacity. The Baytown Ordnance Works
processes for the manufacture and the separation of aromatics
by liquid sulfur dioxide were described by Marshall (100).
Extraction of wax-free lubricants with sulfur dioxide-benzene for
production of soft resins from the extracted aromatics was sug-
gested (114). Medcalf et al. (106) suggested dicyanoethylamine
for extracting naphthalene and its homologs from petroleum
products. The separation of toluene from hydroformed naphtha
with water (6) and aqueous solutions of ammonia and ethylene
glycol (3) were studied in detail by Arnold and Coghlan The
glycol gave the best process. Hepp (71) suggested extracting
olefins from aromatics with liquid aluminum chloride-hydrocar-
bon complex.
Details of the Mercapsol process for sweetening gasolines with
aqueous caustic containing naphthenic acid and cresol were
described (136), and the desirability of eliminating oxygen and
gum-forming substances from mercaptan extraction processes was
pointed out (163). Cleanup of caustic solutions following
mercaptan removal can be carried out by extraction with aromatic
nitrogen bases (9). Sweetening with aqueous caustic methanol
sweetens gasoline more effectively than hypochlorite solutions
(57),and hydrogen sulfide can be removed with 80% aqueous di-
ethanolamine (56).
Hydrocarbons from alkylation processes containing less than
1% hydrogen fluoride and hydrogen sulfide can be freed selec-
tively of the fluoride by extraction with aqueous sodium fluoride
(85). After extraction of petroleum sulfonates with aqueous
isopropyl alcohol, the solvent can be freed of inorganic salts and
concentrated by extraction with 20 to 40% aqueous sodium aul-
fate (23). Details of the extraction of butadiene from hydro-
carbon mixtures with ammoniacal copper acetate solution and the
recovery of the diolefin xere given bv Wilson (178); aqueous
solutions of cuprous salts containing amines such as methylamine
and pyridine effectively separate olefin mixtures such as 1-pentene
from isoprene and Zpentene (45).
Manufactured Gas Processes. A preferred method for re-
covery of pyridine involves its extraction from crude light oil
v i t h aqueous sulfuric acid, whereby 95 t o 98yo recovery is ob-
tained (117). Phenols extracted from t a r oil with methanol are
superior to caustic-extracted products and the costs are less,
according t o Dierichs (32). Prutton and eo-workers (135) pre-
sented extensive data for new solvents for the removal of tar
acids. Priestley reviewed new developments in the dephenoliza-
tion of ammoniacal liquor by butyl acetate and benzene extrac-
tion (134).
Pharmaceuticals. Liquid extraction continues to be a n im-
portant operation in this field. The propane extraction of vita-
mins A and D from fish oils was described in detail by Diclcinson
et al. (31). Material of high vitamin E activity may be pro-
duced from tocopherols extracted from soybean oil with meth-
anol, ethanol, or furfural (75). Much work on penicillin ex-
traction was reported (8, 35, 37, 99, 129, 131, 143, 159, 161, 179,
180); other drug products such as antimycin A (38), circulin
(116), aspergillic acid (60),antihistamines (54), and digitalis (87)
have received attention.
Miscellaneous Processes. Typical of the diverse separations
t h a t have received attention are the following: vanillin from
alkaline liquor solutions with tert-butanol (146); acetic acid from
water by various solvents (126); glycerol from fermentation
concentrates by isopropyl alcohol (108) ; hydrocarbons from
organic nitrites by methanol solutions of calcium chloride (97);
caffeine from coffee extracts with water, ether, and chloroform
(69);ketones from their mixtures with aqueous alcohol by whit?
Vol. 43, No. 1
mineral oil (66); halogenated aromatic hydrocarbons from those
containing no halogen with furfural, ethanol. and water (147);
ethyl ether from impurities with aqueous sodium bisulfite (34);
concentrated or even anhydrous hydrogen fluoride from water
by oyclo-olefins such as cyclohexene ( 1 9 ) ; various organic com-
pounds produced in the Fischer-Tropsch process (18); water from
tetrahydrofuran by glycerol (15); organic acids from each other
by fractional extraction (172); m- and p-cresols from each other
by aqueous caustic soda and benzene (173); wax from cachaza
by heptane in a liquid-liquid process (162); metallic lead from tin
by molten stannous chloride (10); americium from some rare
earth metals in aqueous hydroxamic acid with chloroform (165);
zirconium from hafnium in aqueous hydrogen chloride with ben-
zene-trifluoroacetylacetone (161); neptunium from impurities
with ether (47); and various rare earth nitrates from each other
with several solvents (11). A review of liquid-liquid extraction
processes for waste sulfite liquor was made by McLaughlin
(98)*
Extraction in Analysis. Analytical applications were reviewed
by Craig (26). Quantitative analysis of organic acids by ex-
tration wag studied comprehensively by Tsai and Fu (168).
Other applications include the determination of uranium (96,
153) and other metals (55),water in hydrocarbons (64),mercap-
tans in refinery caustic solutions (84),acetic acid in the presence
of hydrochloric acid (127), and penicillin (13, 70).
LEACHING
Fundamental Studies. Theoretical equations for countercur-
rent leaching have been derived (225). -4simplified approach t o
countercurrent decantation calculations resulted from the use
of a volumetric rather than a weight basis in a study by Mastin
(61g); Grosberg has developed methods of dealing with constant
and varying underflow and nonequilibrium conditions (198).
The mechanism of leaching as applied to vegetable seeds in-
volves diffusion, dialysis, and solution of the solute, according to
Karnofsky (608). A continuation of this extensive study devel-
oped the hypothesis t h a t the rate of solution of oil is dependent
mainly on the soaking time rather than concentration of the
leaching solution ( I @ ) ,and also considered the effect of particle
size on the rate of leaching (189). -4general kinetic treatment
showing the relationship between the rate of leaching and the
individual rates of the diffusion, chemical reaction, or other
processes has been attempted (222). Gaffney and Drew (196)
measured the rate of solution of pellets of organic acids in a fixed
bed when leached by various solvents and established the
influence of flow rates and diffusion coefficients. The use of
transparent models of diffusion battery cells provided means for
studying flow patterns in such equipment (221).
Vegetable Oil Processes. Several new types of apparatus
particularly suitable for oil-seed leaching have been proposed
(184,199,204,919, 228, ass), and details of the Rotocel extractor
as installed in 76- and 250-ton-per-day installations have been
described (206, 210). A general review of such processes was
prepared by Cofield (190). Recycling results in solvent econo-
mies in the isopropyl alcohol extraction of cottonseed (200);
pre-extraction of cottonseed with alcohol (232) or soap in meth-
anol (220)removes undesirable color bodies and fatty acids which
then do not contaminate the oil. A detailed laboratory study of
the extraction of soybean oil by trichloroethylene as well as de-
scriptions of a commercial plant were given by Sweeney and co-
workers (229, 230). The extraction of sesame oil (183) and of a
vitamin B concentrate from rice bran (213) were studied, and a
general review listing properties of common commercial oil-seed
solvents was prepared by McInnes ( 6 l f ) .
Miscellaneous Processes. Various improvements in the de-
sign of diffusion battery equipment (191, 192, 195, 197, 608) and
methods of operation (193, 616) have been proposed. One
apparatus utilizes continuous countercurrent flow of beet chips
and extracting solution (194). The use of methanol as a solvent
January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY
in the leaching of sugar cane was proposed by Othmer and Luley
( m y ) .
Several laboratory studies of the leaching of tannin from various
barks (186, 187, 207, 826), o f alkaloids from cinchona barks
(186, a i d ) , and o f vitamin C from walnut hulls (206)were re-
ported. Data for the tower process for leaching alumina from
bauxite (23.4) as well as the results of laboratory studies (22.4)
and Chinese technology in this field (636) were made available.
Extraction of alumina from calcium aluminates was studied by
Thompson et al. (831) and a new process was proposed (827).
Leaching of montan wax from American lignites (216), bitumen
from asphalt rock (209),aluminum from crude aluminum-silicon
alloys (828), uranium and vanadium from ores (218), and man-
ganese from low grade ores (201) have been given detailed atten-
tion. The chlorides of aluminum and iron can be separated by
leaching with titanium tetrachloride (206).
LITERATURE CITED
Albright, J. C., Petroleum Engr., 22C,No. 2,11 (1950).
Arnold, G. B., and Coghlan, C. A., IND.ENG. CHEM.,42,
177 (1950).
Ibid., p. 1217.
Asselin, G. F.,and Comings, E. W., Ibid., 42,1198 (1950).
Backelet, M., Cheylan, E., and Bris, L., J . chim. phys., 47,
62 (1950).
Bagotskaya, I.A., J . Phys. Chem. (U.S.S.R.), 24, l(1950).
Ballard, J. H., and Piret, E. L., IND.ENQ. CHEM.,42,1088
(1950).
Bartels, C. R., and Dolliver, M. A., J . Am. Chem. SOC.,72,11
(1950).
Berger, C. W. (to Inventors’ Guild), U. S. Patent 2,474,028
(June 21,1949).
Billiton Maatschappij, N. V., Brit. Patent 631,784(Nov. 9,
1949).
Bock, R., and Bock, E., h’aturwksenschaften, 36,344 (1949).
Booth, H. S., and Everson, H. E., IND.ENQ. CHEM.,41,2627
(1949);42,1536 (1950).
Boxer, G . E., and Everett, P. M., Anal. Chem., 21,670 (1949).
Breckenfeld, R. R., and Wilke, C. R., Chem. Eng. Progress,
46, 187 (1950).
Brenner, J., Coats, R., Hodgson, M., and Imperial Chemical
Industries, Ltd., Brit. Patent 630,149(Oct. 6,1949).
Brodin, J., Ann. phys., [I214, 422 (1949).
Brown, A. C. (to Emery Industries, Inc.), U. s. Patent 2,486,-
630 (Nov. 1, 1949).
Burton, W. P. (to M. W. Kellogg Co.), Ibid., 2,505,752(May 2,
1950).
Carnell, P. H. (to Phillips Petroleum Co.), Ibid., 2,498,789
(Feb. 28,1950).
Chu, J. C., Taylor, C. C., and Levy, D. J., IND.ENG.CHEM.,
42,1157 (1950).
Claffey, J. B., Badgett, C. O., Skalamera, J. J., and Phillips,
G. W. M., Ibid., 42,166 (1950).
Clegg, J. W., and Bearse, A. E., Ibid., 42,1222 (1950).
Cohen, C. A. (to Standard Oil Development Co.), U. S. Patent
2,497,152 (Feb. 14,1950).
Collander, R., Acta Chem. Scand., 3,717(1949).
Connick, R. E., and McVey, W. H., J . Am. Chem. SOC.,71,
3182 (1949).
Craig, L. C., Anal. Chem., 22,61 (1950).
Craig, L. c., Fortschr. Chem. Forsch., 1, 292 (1949).
Craig, L. C., in “Techniques of Organic Chemistry,” Vol. 111,
New York, Interscience Publishers, 1950.
Crank, J., and Henry, M. E., TTans. Faraday SOC.,45,1119
(1949).
Cubiciotti, D. D., J . Phys. & Coll. Chem., 53,1302 (1949).
Dickinson, J. T.,Morfit, O.,and Van Orden, J. J. (to M. W.
Kellogg Co.), U. S. Patent 2,499,991(March 7,1950).
Dierichs, A., Chem. Tech., 2, 79 (1950).
Dijck, W. J. D. van (to Shell Development Co.), U. S. Patent
2,488,884 (Nov. 22,1949).
Directie van de Staatsmijnen in Limberg, Dutch Patent 63,768
(July 15,1949).
Distillers Co., Ltd., and Corrie, J. G., Brit. Patent 626,405
(July 14,1949).
Domadia, M. H., and Kane, J. G., J . Sci. Ind. Research (India),
8B,No. 11, 208 (1949).
Dunn, C. L., Souders, M., and Groot, C., U. S. Patent 2,481,-
092 (Sept. 6,1949).
Dunshee, B. R.,Leben, C., Keitt, G. W., and Strong, F. M.,
J . Am. Chem. Sac., 71,2436 (1949).
83
Dutton, H. J., Lancaster, C. R., and Brekke, 0. L., J . Am.
Oil Chemists’ SOC.,27,25 (1950).
Edmundson, I. C., and Wilkins, B. J., Analyst, 75,169 (1950).
Eldridge, J. W., and Piret, E. L., Chem. Eng. Progress, 46,
290 (1950).
Elgin, J . C., in “Chemical Engineers’ Handbook,” 3rd ed.,
D. 713.New York. McGraw-Hill Book Co., 1950.
El&, J. C., IND. EN@.CREM.,42,47(1950).
Elgin, J. C., and Foust, H. C., Ibid., 42,1127 (1950).
Faace, E. V. (to Standard Oil Development Co.), U. S. Patent
2,497,159 (Feb. 14,1950).
Feuge, R. O., and Gros, A. T., J . Am. Oil Chemists’ SOC.,27,
117 (1950).
Fields, P., Natl. Nuclear Energy Service, Div. IV, 14B,pt. 11,
1128 (1949).
Fish, W. R. (to Swift and Go.), IJ. S. Patent 2,486,938(Nov. 1,
1949).
Francis, A. W.,“Physical Chemistry of Hydrocarbons,”
Vol. I, p, 215,New York, Academic Press, Inc., 1950.
Furman, N. H , Mason, W. B., and Pekola, J. S., Anal. Chem.,
21,1325 (1949).
Furst, A., and Lacy, C.. Chemist-Analyst, 38,88 (1949).
Gathman, A., and Egberts, R. W. (to Standard Oil Develop-
ment Co.), U. 5. Patent 2,487,124fNov. 8, 1949).
Geankoplis, C. J., and Hixson, A. N., IND. ENQ. CHEM.,42,
1141 (1950).
Geiev. A. G.. Swiss Patent 260.996(Aua. 1.1949).
(55) Gegiry, C. H. R., and Sherrington,-L. G., Analyst, 75, 17
(1960).
Giidler-Corp., Brit. Patent, 631,704(Nov. 8, 1949).
Glaser, R., and Kuropieska, J., Nafta, 5,372(1949).
Qoldman, B., U.8. Patent 2,491,656 (Den. 20,1949).
Golumbic, C., Anal. Chem., 22,679(1950).
Goth, A., U. S. Patent 2,500,921(March 21,1950).
Griswold, J., Chew, J., and Klecka, M. E., IND.ENQ. CHEM.,
42,1246 (1950).
Griswold, J., Chu, P. L., and Winsauer, W. O., IND.ENQ.
CHEM.,41,2352(1949).
Grubhofer, N., Chem.-Ing.-Tech., 22,209 (1950).
Hanna, W. S.,and Johnson, A. B., Anal. Chem., 22,555 (1950).
Harris, W.D., Hayward, J. W., and Lamb, R. A., J . Am.
Oil Chemists’ SOC., 26,719 (1949).
Hartley, G. D., and Crank, J., Trans. Faraday SOC.,45,801
(1949).
Hartley, J., J . SOC.Chem. Ind., 69, 60 (1950).
Hayworth, C. B.,and Treybal, R. E., IND.ENQ. CHEM.,
42,1174 (1950).
Hendrix, W. H., Dutch Patent. 65,777(May 15,1950).
Henstock, H. I., Nature, 164,139 (1949).
Hepp, H. J. (toPhillips Petroleum Co.!, U. S. Patent 2,483,492
(Oct. 4,1949).
Herington, E. F,G., Research (London),3,suppl., 41 (1950).
Hersberaer. A. B. (to Atlantic Refining Co.), Can. Patent
458,556(Aug. 2,1949).
Hertzberg, A. M., J . I m p . Coll. C h m . Eng. SOC.,4, 46 (1948).
Hickman, K. C. D., and Weisler, L. (to Distillation Products,
Inc.), U. S. Patent 2,486,540 (Nov. 1,1949).
Hildebrand, J. H., J . Chem. Phys., 17,1346 (1949).
Huffman, E. H., and Beaufait, L. J., J . Am. Chem. SOC., 71,
3179 (1949).
Ittner, 11. H. (to Colgate-Palmolive-Peet Co.), U. S. Patent
2,480,471(Aug. 30,1949).
Jasper, J. J., and Pohrt, H. B., J . Chem. Education, 26,485
(1949).
Jodra, L. G., Analesfis. y. quim. (Madrid),45B,1453 (1949).
Jodra, L. G., Rev.cienc. aplicada (Madrid),3,321 (1949).
Johnson, J. D. A., and Talbot, A., J . Chem. Soc., 1950,1068.
Kalichevsky, V. A.. Petroleum Processing, 4,415 (1949).
Karchmer, J. H., and Dunahoe, J. W., Anal. Chem., 20, 915
(1948).
Kelley, C. S. (to Phillips Petroleum Co.,), U. S. Patent 2,487,-
142 (Nov. 8,1949).
Kenyon, R. L., Stindey, D. U., and Young, H. P., IND. ENG.
CHEM.,42,202 (1950).
King, R. E., and Griswold, O., J . Am. Phurm. Assoc., 39,
109 (1950).
Kroger, C., and Luther, Iz.,Brennstof-Chem., 30,226 (1949).
Kronig, R., and Brink, J. C., Applied Sci. Research, A2,
.
142 (195-0-),.
(90)Laddha, G. S.,and Smith, J. M., Chem. EM. Progress, 46,
195 (1950).
(91)Lapidus, L., and Amundson, N., IND.ENO. CREM.,42,1071
(1950).
(92)Lee, J. A., Chem. Eng., 57,No. 3, 94,170 (1950).
(93)Licht, W., and Conway, J. B., INP. ENQ. CHEM.,42, 1151
(1950).
 I N D U S T R I A L A N D ENG I N E E R I N G C H E M I S T R Y
Lien, A. P., McCauley, D. A., and Evering, B. L., Ibid., 41,
2695 (1949).
Lochte, H. L., and Meinschein, G. W., Petroleum Engr.,
22C, No. 3, 41 (1950).
Lyunggran, G., et al., Saensk Kem. Tid., 61, 170-213 (1949).
MoKinnis, A. C. (to Union Oil Co. of Calif.), U. S. Patent
2,503,119 (April 4, 1950).
McLaughlin, R. R., P u l p & Paper Mag. Can.,50, No. 7, 91
(1949).
McMillan, G. W. (to Commercial Solvents Corp.), U. S.
Patent 2,477,192 (July 26 1949).
Marshall, C. H., Chem. Eng. Progress, 46, 313 (1950).
Martin, A. E. (to Shell Development Co.), U. S. Patent
2,499,927 (March 7, 1950).
Martinez-Moreno, J. M., and Paniaqua, C., Bull. SOC. chim.
France, 1949, 388.
Marvel, C. S., and Richards, J. C., Anal. Chem., 21, 1480
(1949).
Mason, D. R., and Piret, E. L., IND.ENG. C ~ e n r . ,42, 817
(1950).
XIattikow, M., J . A m . Oil Chemists’ Soc.. 27, 11 11950).
Medcalf, E. C., Cooper, H. B. H., and Sisco, W. E. (to Ameri-
can Cyanamid Co.), U. 8.Patrnt 2,489,042 (Nov. 22,1949).
Mills, V., and McClain, H. K., IND.FNG.CHEM.,41, 1952
(1949).
Mnookin, N. M. (to Colgate-Palmolive-Peet Co.), U. S.
Patent 2,478,417 (Aug. 9, 1949).
Moore, E. B., J . Am. Oil Chemists’ Soc., 27, 75 (1950).
Morello, V. S., and Beckmann, R. B., IND.EHG. CHEM.,42,
1078 (1950).
Morello, V. S., and Poffenberger, E., Ibid., 42, 1021 (1950).
Myers, R. ,J., and Metzler, D. E., J . A m . Chem. SOC.,72,
3767, 3772, 3776 (1950).
Nachtrieb, N. H., and Fryxell, R. E., Ibid., 71, 4035 (1949).
Narracott, E. S. (to Anglo-Iranian Oi! Co.), U. S . Patent
2,485,911 (Oct. 25, 1949).
Naudet, M., Bull. Mens. I T E R G , 3, 405 (1949).
Nelson, H. A., DeBoer, C., and DeVries, W H., TND. ESG.
CHEM., 42, 1259 (1950).
Nettenbusch, L., Brennstof-Chem., 30, 185 (1949).
Nolan, L. S., Anal. Chem., 21, 1116 (1949).
N. V. de Bataafsche Petroleum Alaatschappij, Dut,ch Patent
64,165 (Sept. 15, 1949).
Ibid., 64,170 (Gct. 15. 1949).
Ibid., 64,174 (Oct. 15, 1949).
Ibid.,64,867 (Dec. 15, 1950).
Ibid., 64,995 (Jan. 16, 1950).
Obergfell, P., Petroleum Processing, 4, 660 (1919).
Orchin, M., and Golumbic, C., J . A m Chem. Soc., 71, 4151
(1949).
Othmer. D. F.. Brit. Patent 623.991 (hlav 26. 1949).
Pagel, H. A.,’Toren, P. E., and McLafferty, F. TF’., Anal.
Chem., 21, 1150 (1949).
Palmer, G. H. (to M. W, Kellogg Co.), U. S. Patent 2,505,338
(April 25, 1950).
Petty, R. D., and Rirkabaugh, C. A. (to American Cyanamid
Co.), U. S. Patent 2,488,875 (Nov. 22, 1949).
Peyronel, G., Gazz. chim. ital., 79, 792 (1949).
Pierotti, G., Souders, M., and French, F. A. (to She11 Develop-
ment Co.), U. s. Patent 2,488,558 (Nov. 22, 1949).
Pospelova, K. A,, Kolloid Zhur., 11, 157 (1949).
Potts, R. H., and McBride, G. W., Chem. Eng., 57, KO. 2,
124, 172 (1950).
Priestley, J. J., Gas J.,260, 532 (1949).
Prutton, C. F., Walsh, T. J., and Desai, A. M., IND.ENG.
CHEM.,42,1210 (1950).
Pure Oil Co., Brit. Patent 629,914 (Sept. 30, 1949).
Pyle, C., Colburn, A. P., and Duffey, H. R., IND.ENCI. CHEx
42, 1042 (1950).
Raymond, S., Anal. Chem., 21, 1292 (1949).
Reeves, E. J., and Hardin, E. P., PetroZeum Refiner, 29, KO. 1,
89 (1950).
Rieder, R. M., and Thompson, A. R., IND. ENG.CHEM.,42,
379 (1950).
Rius, H., and Jodra, L. G., Andeafis. Q. quim., 45B,245 (1949).
Rometsch, R., Helv. Chim. Acta, 33,184 (1950).
Rowley, D., Steiner, H., and Zimkin, E. (to Petrocarbon,
Ltd.), U. S. Patent 2,452,938 (Sept. 27, 1949); Brit. Patent
625,097 (June 22, 1949).
(144) Sandell, E. B., and Cummings, P. F., Anal. Chem., 21, 1356
(1949).
(145) Sankey, C. A., and Marshall, H. B. (to Ontario Paper Co.,
Ltd.). U. 5. Patent 2.489.200 (Nov. 22. 1949).
(146) Sayre, E. V., J . Am. C h a . SOC.,71.3284 (1949).
(147) Sohaeffer, €3. B. (to Mathieson Chemical Corp.), U. S. Patent
2,484,469 (Oct. 11, 1949).
Vol. 43, No. 1
(148) Scheibel. E. G.. INDENG.CHEM..42. 1497 11950).
(149) Soheibel. E. G. (to Hoffmann-La Roche,’Inc.): U. S. Patent
2,493,265 (Jan. 3, 1950).
(150) Scheibel, E. G., and Karr, A. F., IND.ENG. CHEY., . 42,. 1048
(1950).
(151) Schultz, B. G., and Larsen, E. M.,J . Am. Chem. Soc., 72,
3610 (1950).
(152) Sohweyer, H. E., and Brown, 0. X I . , PetroZeum Processing, 5,
151 (1950).
(153) Scott, T. R., Analyst, 74, 486 (1949).
(154) Seaman, J., Soap, Perfumeru & Cosmetics, 22, 254 (1949).
(155) Sienko, hf. J., J . Am. Chem. SOC.,71, 2707 (1949).
(156) Smith, A. S., IND. ENG.CHEM.,42, 1206 (1950).
(157) Smith, J. C., Ibid., 41, 2932 (1949); 42, 1438 (1950).
(155) Smith, T. E., and Bonner, R. F., Ibid., 42, 896 (1950).
(159) Souders, Mott (to Shell Development Co.), U. S. Patent 2,-
488,559 (Nov. 22, 1949).
(160) Steinbock, S. R., Can. Chem. Process I d s . , 34, 28 (1950).
(161) Steiner, H. M. E., Zimkin, E., and Petrocarbon, Ltd., Brit.
Patent 632,576 (Nov. 28. 1949).
(162) Swenson, 0. J. (to Cuban-American Sugar Co.), U. S . Patents
2,499,008 (Feb. 28. 1950) and (to S. C. Johnson and Son,
Inc.), 2,508,002 (May 16, 1950).
(163) Templeton, C. C., J . Am. Chem. Soc., 71, 2187 (1949).
(164) Terres, E., Chem.-Ing.-Tech., 21, 209 (1949).
(165) Thompson, S. G., Morgan, L. 0.. James, R. A., and Perlman,
I., Natl. Nuclear Energy Service, Div. IV. 14B. pt. 11,
1339 (1949).
(166) Thornton, D. P., Petroleum Processing, 4, 1207 (1949)
(167) Ibid.. 5, 245 (1950).
(168) Tsai. K. R., and Fu, Y.. Anal. Chem.. 21.818 (19491.
(169) Tschamler, H., Richter, E., and M‘ettig, F., Monatsh, 80,749
856 (1949).
(170) Tscharnler, H., Vettig, F., and Rlohtcr, E., Ihid.. 80, 572
(1949).
(171) Tschesche, R , and Xonige H. B., Chem.-Ing.-Tech., 22, 214
(1950).
(172) Twigg, G. H., 12’atzare. 163, 1006 (1949).
(173) Walker, C. A., IND.ENG.CHEM.,42, 1226 (1950).
(174) Weber, G , OtZ Gas J., 48, N o . 6, 82 (1949).
(175) Wehn, F.E., and Franke, N. W., IND.ENG.CHEM.,41, 2853
(1949).
(176) M’eicksel, J. A., and Lynch, C. C., J . Am. Chem. SOC.,72, 2632
(1950).
(177) Weygand, F., Chem.-Ina.-Tech., 22, 213 (1950).
(178) Wilson, S. W. (to Standard Oil Development Co.), U. S.
Patent 2,483,863 (Oct. 4, 1949).
(179) Wintersteiner, O., hfacPhillamy, H. B., and Menzel, A. E.
(to E. R. Squibb and Sons),Ibid., 2,480,991 (Sppt. 6, 1949).
(180) Wirtel, A. F., and Blair, C. M. (to Petrolite Corp., Ltd.),
U.S. Patent 2,505,374 (April 25, 1950).
(181) Wittenberger, W., Angew. Chem., 61, 412 (1949).
(152) Wood, S E., IND.ENG.CHEW,42, 660 (1950).
LEACHING
(183) Andraos, V., Swift, C. E., and Dollear, F. G., J . A m , Oil
Chemists’ Soc., 27, 31 (1950).
(184) Beeson, B. B. (to French Oil >Ell Machinery Co.), U. S. Patent
2,512,710 (June 27, 1950).
(185) Bhumvara, N. B., and Khorana, M. L., Indian J . Pharm.,
11, 145 (1949).
(186) Bishop, C. T., Harwood, V. D., and Purves, C. R., P u g
Paper Mna. Can., 51. No. 1. 90 (1950).
(157) Bohm, E., and Technochemie A.-G., Swiss Patent 251,111
(July 16, 1948).
(188) Coats, H. B., and Karnofsky, G.,J . Am. Oil Chemists’ Soc.,
27, 51 (1950).
(189) Coats, H. B., and W‘ingard, M. R., Ibid., 27,93 (1950).
(190) Cofield, E. P., Georgia Inst. Technol., State Eng. Exptl Sta..
Circ. 28, (1950).
(191) Danil’trev, V. A., U.S.S.R.Patent 69,141 (Aug. 31, 1947).
(192) Drefenbach, A., Ital. Patent 438,056 (July 23, 1948).
(193) Dronov, S. F., Sakharnuya Prom., 23, No. 6, 18 (1949).
(194) Dubouig, J., E.S.Patent 2,496,523 (Feb. 7, 1950).
(195) Frynta, V. (to Skoda Works, Kational Corp.), Zbid., 2,502,939
(April 5, 1950).
(196) Gaffney, R. J., and Drew, T. B., IKD.ENG. CHEM.,42, 1120
1950).
(197) Golovin, P. V., U.S.S.R. Patent 69,145 (Aug. 31, 1947).
(198) Grosberg, J. A,, IND.ENG.CHEM.,42, 154 (1950).
(199) Haroourt. G. N. (to Blaw-Knox Co.), U. S. Patent 2,610,221
(June 6, 1950).
(200) Harris, W.D., and Hayward, J. W., J . Am. Oil Chemists’ Soc.,
27, 273 (1950).
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY 85
(201) Hoak, R. D.,and Coull, J., Chem. Eng. Progrees, 46,158 (1950). (221) Pluhacek, R., and Slavicek, E., Lis& Cukronur. 65, 125 (1949).
(202) Xarnofsky, G.,Chem. Eng., 57,No. 8,108 (1950). (2221 Rotinyan, A. L.,and Drozdov, B V., Zhur. Obshchei Khim.,
(203) Xarnofsky, G.,J . Am. Oil Chemists’Soc., 26,664(1949). 19. 1843_
-., _ (1949).
~ .
\ - - - - I -

(204) Encaide, C.R., U. 8. Patent 2,491,116(Dea. 13,1949).
(206)Klose, A. A.,et al., IND.ENO.C H ~ M42,. , 387 (1960).
(206) Krchma, I. J., and Schaumann, H. H. (to Du Pont Co.),
U. 8.Patent 2,502,327(March 28, 1960).
(207) Kurth, E. F.,Hubbard, J. R., and Gekelea, M., Leather and
Shoes, 118,No. 20,22 (1949).
(208) Lemoine, J. L., French Patent 940,159 (Dec. 6,1948).
(209) Logan, V. R., U. 8. Patent 2,453,633(Nov. 9,1948).
(210) McCubbin, K., and Ritz, G . J., Chem, I d s . , 66,354(1950).
(211) McInnes, C.A., Am.Paint J., 34,No. 30,86(1960).
(212) Mastin, M. G.,C h a . Eng., 57,No. 1, 100 (1950).
(213) Mernke, W. W.,Holland, B. R., and Harris, W. D., J. Am.
Oil Chemists’ Soc., 26,532 (1949).
(214) Mukherjee, S.,and Gupta, M. L. S., J . PTW.Inst. Chemists
(India), 21,45 (1949).
(215) Naudet, L., In&. agr. et aliment, 66,107(1949).
(218) Ode, W. H.,and Selwig, W. A., IND.ENQ. CHSM., 42, 131
(1950).
(217) Othmer, D.F.,and Luley, A. H., Food, 18,81 (1949); Sugar,
44, No. 7,26 (1949).
(218)Paovna. Arnold. U.9.Patent 2.485.841 (Oct. 25. 1949).
(219) Pascal, M. W. (to Sherwin-Williams Co..), U. S.’Patent 2,505,-
139 (April 25, 1950).
(220)Perez, A. (to Phillips Petroleum Co.), Ibid., 2,485,916(Oct. 25,
1949).
(223) St. Clair, H. W., and Blue, D. D., U. S. Bur. Mines, Rept.
Inwest. 4535 (1949).
(224) Skow, M. L., and Conley, J. E., Ibid., 4649 (1950).
(225) Slavicek. E.,Listu Cukrmar. 65,89 (1949).
(226) Snow, E. A., and Bailey, L. F., J. Am. Leather Chemists’
Assoc., 44,737 (1949).
(227)Societe des cimenta franpais, Brit. Patent 632,079 (Nov. 16,
(1949).
(228) Sweeney, 0.R.,and Arnold, L. K. (to Iowa State College
Research Foundation), U. S. Patents 2,497,700 (Feb. 14,
1950) and 2,501,880(March 28,1950).
(229) Sweeney, 0.R.,and Arnold, L. K., J. Am. OiE Chemists’ Soc.,
26 697 (1949).
(230)Sweeney, 0.R.,‘Arnold, L. K., and Hollowell, E. G.,Iowa
State Coll. Exptl. Sta., Bull. 165 (1949).
(231)Thompson, M. R.,McLeod, H. M., and Skow, M. L., U. S.
Bur. Mines, Rept. Invest. 4528 (1949).
(232)Trottman, C., U. S. Patent 2,489.599(Nov. 29,1949).
(233) Watson, Thomas S. (to Huebach Mfg. Co.), Ibid., 2,501,460
(March 21, 1950).
(234)Wittig, R.,Chem.-lag.-Tech., 22,81 (1950).
(235) Yuan, H., Xuo, F., and Huang, Y . , Science and Technol.
(China), 2,21 (1949).
R E C E I VOctober
~D 11, 1950.

FILTRATION
mg SHELBY A. MILLER
UNIVERSITY OF KANSAS, LAWRENCE, KAN.

N e w contributions to filtration theory include an analysis of continuous vacuum filtration and a given remains one of the most useful
study of the resistance identified with the initial stages of cake formation. Equipment advances in existence. The material on filter
have been mostly in the nature of improvements: Among them are a compact high-capacity mediums has been brought u p to
porous-metal element, a cake sluicing mechanism for precoat filters, and a tilting Alter press. date and several new filters have
Dyne1 and Hastelloy filter fabrics now are commercially available, and a new fiber, Terylene, been added to those described.
looks promising as a filter medium material. Rotary vacuum filters have been evaluated for a The chapter on filtration (2%) in
variety of applications: petroleum dewaxing, sewage sludge dewatering, paper pulp recovery, the new textbook on unit operations
and oil-waste emulsion breaking. A paper on whisky clarification excellently typifies the prepared by University of Michigan
correct approach to filter selection. Interesting data are reported also on viscose filterability and chemical engineers is well written.
on the refining of metals b y filtration of solid constituents from molten metal suspensions. A More than half the chapter is de-
number of outstanding reviews of filtration theory, equipment, and methods bring the occasional voted to mathematical correlating re-
user of filters generally up to date for the first time in several years. lationships, which include not only
the conventional Poiseuille-Darcy

c
ONVENTIONAL filtration-the separation of undissolved
solids from liquids by methods other than centrifugation,
sedimentation, and adsorption-was the subject of more
publications in the Year ending October 1950 than in m Y of
several immediately preceding years. This review attempts to
,* cover those of particular value to the chemical process industries
and includes uncritical citation of many (although by no means
all) of the patents which have been issued. AS in
previous tmnual reviews Of this series, the scope gas
clarification, centrifugal and sedimentary separation, adsorptive
* ings.
percolation, and biofiltration.
GENERAL REVIEWS
Those intereskd in unit have welcomed several new
books devoted to this field. Three are general and include
filtration in their coverage.
The long-awaited third edition of Perry’s “Handbook” carries
a section on filtration (76) which is the same in arrangement and,
to considerable extent, in content as that of previous editions.
The unfortunate interval between copy deadline and publication
date prevented the inclusion of the most recent advances in
theory; but the summary of theoretical and empirical equations
c o n s t a n t- p r e s su r e and constant-
rate equations (written explicitly in terms of cake porosity)
but the recent Brownell-Kats attack from the standpoint of a
modified Fanning group including particle and cake character-
istics. The reader is prepared for the latter approach by two
preceding chapters (91) devoted to the Brownell-Katz method.
Fifteen problems at the end of the chapter illustrate filterdesign
calou]ations. The description of equipment is brief and includes
only the best known types of filters; i t is supplemented, how-
ever, with a number of clear, chosen photographs and draw-
A superior summary of filtration in the laboratory is presented
(43) in a new reference book of organic chemical technique. The
extensive theoretical review and the thorough analysis of the
problems posed by various instances of filtration make this
chapter valuable to the engineer and plant supervisor as well as
to the chemist and laboratory technician.
I n the periodical literature, Heertjes (66) has prepared a n ex-
cellent review of the methods of correlating and analyzing filtra-
tion data and of the nature of specific cake resistance. Authori-
tative and complete, clear and concise, i t is unequaled in the
filtration literature. Friedel (66) has given a qualitative dis-
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY 85
(201) Hoak, R. D.,and Coull, J., Chem. Eng. Progrees, 46,158 (1950). (221) Pluhacek, R., and Slavicek, E., Lis& Cukronur. 65, 125 (1949).
(202) Xarnofsky, G.,Chem. Eng., 57,No. 8,108 (1950). (2221 Rotinyan, A. L.,and Drozdov, B V., Zhur. Obshchei Khim.,
(203) Xarnofsky, G.,J . Am. Oil Chemists’Soc., 26,664(1949). 19. 1843_
-., _ (1949).
~ .
\ - - - - I -

(204) Encaide, C.R., U. 8. Patent 2,491,116(Dea. 13,1949).
(206)Klose, A. A.,et al., IND.ENO.C H ~ M42,. , 387 (1960).
(206) Krchma, I. J., and Schaumann, H. H. (to Du Pont Co.),
U. 8.Patent 2,502,327(March 28, 1960).
(207) Kurth, E. F.,Hubbard, J. R., and Gekelea, M., Leather and
Shoes, 118,No. 20,22 (1949).
(208) Lemoine, J. L., French Patent 940,159 (Dec. 6,1948).
(209) Logan, V. R., U. 8. Patent 2,453,633(Nov. 9,1948).
(210) McCubbin, K., and Ritz, G . J., Chem, I d s . , 66,354(1950).
(211) McInnes, C.A., Am.Paint J., 34,No. 30,86(1960).
(212) Mastin, M. G.,C h a . Eng., 57,No. 1, 100 (1950).
(213) Mernke, W. W.,Holland, B. R., and Harris, W. D., J. Am.
Oil Chemists’ Soc., 26,532 (1949).
(214) Mukherjee, S.,and Gupta, M. L. S., J . PTW.Inst. Chemists
(India), 21,45 (1949).
(215) Naudet, L., In&. agr. et aliment, 66,107(1949).
(218) Ode, W. H.,and Selwig, W. A., IND. ENQ. CHSM., 42, 131
(1950).
(217) Othmer, D.F.,and Luley, A. H., Food, 18,81 (1949); Sugar,
44, No. 7,26 (1949).
(218)Paovna. Arnold. U.9.Patent 2.485.841 (Oct. 25. 1949).
(219) Pascal, M. W. (to Sherwin-Williams Co..), U. S.’Patent 2,505,-
139 (April 25, 1950).
(220)Perez, A. (to Phillips Petroleum Co.), Ibid., 2,485,916(Oct. 25,
1949).
(223) St. Clair, H. W., and Blue, D. D., U. S. Bur. Mines, Rept.
Inwest. 4535 (1949).
(224) Skow, M. L., and Conley, J. E., Ibid., 4649 (1950).
(225) Slavicek. E.,Listu Cukrmar. 65,89 (1949).
(226) Snow, E. A., and Bailey, L. F., J. Am. Leather Chemists’
Assoc., 44,737 (1949).
(227)Societe des cimenta franpais, Brit. Patent 632,079 (Nov. 16,
(1949).
(228) Sweeney, 0.R.,and Arnold, L. K. (to Iowa State College
Research Foundation), U. S. Patents 2,497,700 (Feb. 14,
1950) and 2,501,880(March 28,1950).
(229) Sweeney, 0.R.,and Arnold, L. K., J. Am. OiE Chemists’ Soc.,
26 697 (1949).
(230)Sweeney, 0.R.,‘Arnold, L. K., and Hollowell, E. G.,Iowa
State Coll. Exptl. Sta., Bull. 165 (1949).
(231)Thompson, M. R.,McLeod, H. M., and Skow, M. L., U. S.
Bur. Mines, Rept. Invest. 4528 (1949).
(232)Trottman, C., U. S. Patent 2,489.599(Nov. 29,1949).
(233) Watson, Thomas S. (to Huebach Mfg. Co.), Ibid., 2,501,460
(March 21, 1950).
(234)Wittig, R.,Chem.-lag.-Tech., 22,81 (1950).
(235) Yuan, H., Xuo, F., and Huang, Y . , Science and Technol.
(China), 2,21 (1949).
R E C E I VOctober
~D 11, 1950.

FILTRATION
mg SHELBY A. MILLER
UNIVERSITY OF KANSAS, LAWRENCE, KAN.

N e w contributions to filtration theory include an analysis of continuous vacuum filtration and a given remains one of the most useful
study of the resistance identified with the initial stages of cake formation. Equipment advances in existence. The material on filter
have been mostly in the nature of improvements: Among them are a compact high-capacity mediums has been brought u p to
porous-metal element, a cake sluicing mechanism for precoat filters, and a tilting Alter press. date and several new filters have
Dyne1 and Hastelloy filter fabrics now are commercially available, and a new fiber, Terylene, been added to those described.
looks promising as a filter medium material. Rotary vacuum filters have been evaluated for a The chapter on filtration (2%) in
variety of applications: petroleum dewaxing, sewage sludge dewatering, paper pulp recovery, the new textbook on unit operations
and oil-waste emulsion breaking. A paper on whisky clarification excellently typifies the prepared by University of Michigan
correct approach to filter selection. Interesting data are reported also on viscose filterability and chemical engineers is well written.
on the refining of metals b y filtration of solid constituents from molten metal suspensions. A More than half the chapter is de-
number of outstanding reviews of filtration theory, equipment, and methods bring the occasional voted to mathematical correlating re-
user of filters generally up to date for the first time in several years. lationships, which include not only
the conventional Poiseuille-Darcy

c
ONVENTIONAL filtration-the separation of undissolved
solids from liquids by methods other than centrifugation,
sedimentation, and adsorption-was the subject of more
publications in the Year ending October 1950 than in m Y of
several immediately preceding years. This review attempts to
,* cover those of particular value to the chemical process industries
and includes uncritical citation of many (although by no means
all) of the patents which have been issued. AS in
previous tmnual reviews Of this series, the scope gas
clarification, centrifugal and sedimentary separation, adsorptive
* ings.
percolation, and biofiltration.
GENERAL REVIEWS
Those intereskd in unit have welcomed several new
books devoted to this field. Three are general and include
filtration in their coverage.
The long-awaited third edition of Perry’s “Handbook” carries
a section on filtration (76) which is the same in arrangement and,
to considerable extent, in content as that of previous editions.
The unfortunate interval between copy deadline and publication
date prevented the inclusion of the most recent advances in
theory; but the summary of theoretical and empirical equations
c o n s t a n t- p r e s su r e and constant-
rate equations (written explicitly in terms of cake porosity)
but the recent Brownell-Kats attack from the standpoint of a
modified Fanning group including particle and cake character-
istics. The reader is prepared for the latter approach by two
preceding chapters (91) devoted to the Brownell-Katz method.
Fifteen problems at the end of the chapter illustrate filterdesign
calou]ations. The description of equipment is brief and includes
only the best known types of filters; i t is supplemented, how-
ever, with a number of clear, chosen photographs and draw-
A superior summary of filtration in the laboratory is presented
(43) in a new reference book of organic chemical technique. The
extensive theoretical review and the thorough analysis of the
problems posed by various instances of filtration make this
chapter valuable to the engineer and plant supervisor as well as
to the chemist and laboratory technician.
I n the periodical literature, Heertjes (66) has prepared an ex-
cellent review of the methods of correlating and analyzing filtra-
tion data and of the nature of specific cake resistance. Authori-
tative and complete, clear and concise, i t is unequaled in the
filtration literature. Friedel (66) has given a qualitative dis-
a6 INDUSTRIAL AND ENGINEERING CHEMISTRY
cussion of hypotheses concerning the role of surface phenomena
and adsorptive forces in medium plugging and filter-aid action.
In addition to a very brief summary of recent advances (33),
two papers have dealt with industrial filters and their selection
and performance. Miller’s descriptive review (102) includes a
discussion of clarifying as well as cake filters and lists most of
COURTESY FILTRATION ENOINEERS, INC.
Pilot Plant Rotary Vacuum Filter
the United Statesmanufacturers of filtration equipment. h.Iiess-
ner (100) has summarized important performance and price data
for the past several years; most of his information is derived
from the American literature.
THEORY, E X P E R I M E N T A L DATA, AND DESIGN
Further attempts have been made to characterize the action of
rotary vacuum filters. Mondria (103) succeeded in analyzing a
continuous filtration process a t constant pressure to arrive a t
relationships which will permit easier prediction of the effects of
drum speed and cloth blinding on filtration rate. His equations
obviate the necessity of the abRolute evaluation of eake resistance
and filter-medium resistance. The data they require for cloth
blinding will be difficult to obtain, but the drum-speed data are
easily available and may be simulated by use of a teat leaf.
Reeves (117) considered the operation of washing a rotary-filter
cake and derived expressions for the maximum amount of wash
which can be applied under various conditions of solvent dilution
and filtrate recirculation. Implicit in his analysis are the as-
sumptions of negligible filter medium resistance and simple dis-
placement of filtrate by wash liquor. He concluded that re-
circulation of part of the filtrate may improve washing effective-
ness (with a viscous prefilt), but will do so at the expense of filter
capacity. Brownell’s earlier work is applied in an additional
paper (24) to the problem of prediction of air rate and tempera-
ture required for a top-feed vacuum filter-dryer. The porosity,
permeability, and “residual saturation” of the a t e r cake must be
known for the calculation to be made. Camp and Phillips (28)
conducted a careful experimental investigation of the perform-
ance of a pilot plant precoat vacuum drum filter in the treatment
of water-in41 emulsions and sludges, which shows the effect of a
number of variables on vacuum filter operation.
Heertjes and Haas (67) reported an investigation of the re-
sistance of a filter fabric and of the initial layer of solids de-
posited upon it. The resistance of the initial solid layer, they
found, is importantly affected by the concentration of the slurry
from which i t is deposited, and may have the characteristics of
complete-blocking filter-medium filtration, of cake filtration, or
of any condition between these extremes. Ishikawa (76) inde-
Vol. 43, No. 1
pendently studied the same problem, but apparently interpreted
his results in a different manner. Because this reviewer only
recently became aware of Ishikawa’s work and has not yet ob-
tained a copy of his paper, he cannot report on it until a later time.
Burak and Storrom (27) pursued the analogy proposed by
Maloney (96) between centrifugation and filtration. They
found the resistance of a centrifugally deposited cake to be con-
siderably different from that of a cake of the same material de-
posited in ordinary filtration. Maloney (97) has given a more
extensive review of their work.
The so-called “filtration effect,” believed by some to be re-
sponsible for part of the resistance identified mith filter mediums,
is the subject of two Russian papers (87, 109).
EQUIPMENT
Claude (42) has described the vertical-leaf precoat pressure
filter and discussed briefly its use in American plants for filtering
water, oil and varnish, and general chemicals. The advantages
and some of the limitations of this type of filter have been sum-
marized by one of its manufacturers (%’), a firm which has re-
cently offered a new type of oscillating and reciprocating mani-
fold for rapid flushing of the cake from the leaves (40). A filter
press that can be tilted to combine the advantages of vertical
and horizontal frame positions is now manufactured by an
American company (34), and a continuous pressure filter has
been invented in Russia (15). Tessmer (134) has proposed an
improved drainage surface for a pulp-cell filter press. Krack-
Iauer (89) patented a “stirring screen” to protect the filter
medium in a horizontal pressure filter during mechanical removal
of cake. Two patents deal with the modification of granular-
bed filter shells: One (101) describes an improved false bottom
for drainage, and the other (148) suggests compartmentiaing the
tank to permit a lower water flow rate for satisfactory back-
washing.
One of the manufacturers of rotary vacuum drum filters has
issued a new catalog (53) which describes the construction and
operation of this type of machine; the same firm offers for rental
a flexible semiworks model of its filter (S8). A patent (58) has
been issued covering a vacuum disk filter design which involves
tangentially bounded sectors, a shape which results in more
effective use of the filter area. -4novel vacuum filter comprising a
band of discrete filter cells is the subject of a Dutch patent (145).
Among new items of clarifying equipment are a compact pack-
age unit comprising a filter cartridge of small holdup volume and
a pump (41), and an edge filter, the slots of which are formed by
meshing teeth a t the peripheries of two coaxial disks (1). Other
contributions to the field of clarifying equipment are principally
in the form of patented improvements to filter element design.
The most interesting of these are Micro hIetallic’s Surfamax and
Gravitain elements (35, 99), assemblies of coaxial disks, the
conical surfaces of which are of porous stainless steel. Strass-
heim (131) also has developed a porous-metal element, formed
from corrugated porous sheet, Other inventions include a felt-
covered polishing element (%), a zigzag paper or cloth element
and a screen support for i t (20),and a cartridge element with a
settling trap in its core for the collection of heavy suspended
particles (11). Two patents (30,79) describe movable elements
which are shifted automatically into a flushing position when
cleaning is required.
This reviewer’s attention has been directed to several foreign
patents whose content is unknown but whose titles indicate that
they describe filtration equipment. The subjects treated are:
a concentric filter bag ( 4 4 , a filter for liquids (llS), an apparatm
for filtering distillates (96), an industrial vacuum filter (110),
a drum-type filter with a continuously renewed filtering surface
(@), an improved scraper for removing fibrous cake from a drum
filter (l14), a filter having multiple elements and automatic
application of wash liquor (81), and a device for washing filtering
areas of filter presses (150).
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY
METHODS AND APPLICATIONS
The detailed investigation by Samuelson and his co-workers
of the filtering properties of viscose spinning solution has con-
tinued (198-130). These authors now conclude (199) that the
clogging of secondary filters is caused by gel particles extruded
through the &st filter rather than by agglomeration of dispersed
material after filtration. According to Kleinert and Moessmer
(86),the gel which clogs filters is highly polymerized cellulose.
The filterability of difficultly filterable viscose is improved by
the addition of certain wetting agents (198), and is apparently
independent of the presence of small amounts of calcium silicate
precipitated from impurities in pulp and in mercerizing liquor
(130). Wehrung (144) has commented on the importance of ade-
quate filters t o minimize spinning interruption; filtration is not
enough, however, because afterprecipitation of solute in the warm
spinnerette can occur. Various arrangements of filters in series
and in parallel have been devised to allow servicing without
interruption of the spinning solution stream (14, G). Vosters
(142), objecting to the usual procedure for determining viscose
filterability, proposed an alternative constant-rate method.
* The use of rotary vacuum filters by the petroleum industry in
solvent dewaxing processes is spreading. Kalichevsky (80) and
Reeves ( 117) have discussed optimum operating conditions for
such filters. Slack wax sweating can be eliminated advanta-
geously in favor of the use of a new ingenious continuous pressure
filter, according to Weber (143). The filtration of lubricating
oil in situ is vital for the protection of machines, as emphasized
by Vokes (140). A recent investigation (6) showed the reduc-
tion in machine wear resulting from the installation of partial-
flow or full-flow filters in the lubrication system. If heavy-duty
oil is being used, however, the filter must be selected carefully
to minimize the adsorptive removal of detergent from the oil;
cellulose, cotton, and clay filters are particular offenders in this
respect (3). Kipp (84), on the other hand, has proved the value
of continuous by-pass filtration of transformer oil through an
adsorbant to prolong oil life and inhibit sludge formation.
The role of filtration in good electroplating practice has been
discussed by Faint (61)and by Carr (99). Filtration may be
effected by external filters (99)or by cloth or paper diaphragms
within the plating cell (94,136).
Filters used t o thicken or dewater paper stock have been
described by several authors. Two new vacuum thickeners
(4, 120) and one new continuous gravity filter (19) have been re-
ported for this use. Kassing (82) has pointed out that paper-
making itself is essentially an application of filtration and should
be guided by the principles of this operation.
Filtration has long played an important part in wet metal-
lurgy. Woolf and Bethune (149) have given a detailed descrip-
tion of the Burt filter, a rotating batch pressure filter, and of its
use in zinc leaching. Ross (124) wrote of the performance of
rotary vacuum filters in handling difficultly filterable cyanide
pulp, and proposed a definition of washing efficiency. Bryant
(26) reported a cobalt refining process involving the filtration of
precipitated metal salts. Somewhat newer is the use of filters
to refine molten metals by the removal of a crystallized phase.
A great deal of the pioneering experimentation on this operation
t
was done in Germany before and during World War I1 and has
been documented by Reinacher (118,119). St. Clair (197) has
summarized the PBL report (119) and some additional similar
work done in Canada.
Miscellaneous industrial applications of filtration described in
the recent literature include the straining of paint and varnish
(88), the reduction of the bacterial count in milk by precoat
filtration (74), the sterilization of beer by filtration through pulp
sheet in a presterilized filter (lor), and the clarification of
whisky (64). The latter reference is the report of a careful,
thorough plant study, the object of which was to determine the
most effective and economical type of filter for each of the three
87
clarification stages involved The process industries well might
take its approach as a model in intelligent evaluation of equip-
ment. Bastone and Babcock (9) have investigated the factors
affecting the washing of sugar liquor from a bone-char filter.
Hoover (68) has devised an ingenious method of solid-liquid
separation that is in essence a filtration for which the filter
medium is a mass of solid particles suspended in a liquid.
WATER, SEWAGE, AND INDUSTRIAL WASTES
The processing of water and wastes, if not the chief concern of
the chemical process engineer, is for him an insistent problem.
For this reason and because the filtration difficulties encountered
often are similar to those met in orthodox chemical processing,
representative portions of the literature on the physical filtration
of water and sewage are included in this review.
Rapid sand filters continue to be the most popular type for
water clarification. Further data from Chicago’s well publicized
plant (10)and detailed data from Groton (61) have been re-
ported. New installations are being made regularly for in-
dustrial (6)as well as for municipal water plants, and in some
instances anthracite is preferred over sand as the medium (69).
The use of rapid sand filters to prepare water for the rayon and
beverage industries has been mentioned (66). Installations to
provide industrial water in Germany (12) and in Russia (86)
have been described. Ullrich (137) has discussed generally the
design and maintenance of rapid sand filters.
Tankard (132) has summarized difficulties encountered in
(but not necessarily peculiar to) pressure filter operation for
water clarification. Lane and Smith (91) found an anthracite
pressure filter satisfactory for removing colloidal clay from water
if activated silica pretreatment was used; their work emphasizes
the importance of prefilt condition to the succem of filtration.
Robinson (193) has outlined the procedure for cleaning fouled
filter beds with chemical solvents, notably hydrochloric acid.
Boucher (17) invented an unusual gravity water filter in the form
of a rotating cylinder whose surface is the filter medium-finely
woven wire (aperture dimension no greater than 10 microns).
More and more sewage disposal plants are turning to vacuum
drum filters for sludge dewatering (126). Certain mechanical
features and corrosion problems identified with their use were dis-
cussed by Flood (64). Operating data, including filter capacity
and cake moisture .content, have been reported from many dif-
ferent plants (77,83, 161). Mick (98) found that spray-washing
the filter medium is instrumental in prolonging its life and that
there is an optimum interval between washings, even when the
filter is so modified that the cloth can be washed without inter-
rupting the filtration. Richter (191)stated that the cord filter
(a drum on which overlapping cords, which are the filter medium,
are continuously wound and unwound) is superior to a con-
ventional drum filter for sludge dewatering. Treated sewage
effluent may be clarified by passage through a slow sand filter
(141).
The paper industry’s problem of recovering fiber loss, eliminat-
ing stream nuisance, and minimizing water make-up can be re-
duced by clarification of white-water through sedimentation,
flotation, or filtration. These three techniques have been com-
pared and discussed (49, 69). A new vacuum filter, the Wac0
filter, is effective for white-water clarification (16). It consists
of a cylindrical drum over which an endless screen belt, carrying a
precoat of fiber, travels (104). Alternatively, the white-water
can be clarified by coagulation and sedimentation , followed by
the polishing of the supernatant in a precoat plate-and-frame
press (47). The settled sludge can be dewatered successfully by
an ordinary vacuum drum filter (60).
The processing of wastes from an oil refinery involves the
separation of oil-water emulsions which are stabilized by the
presence of fine solids. Recent studies indicate that both water-
in-oil (28) and oil-in-water (69,146) emulsions can be broken
88 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
and the suspended dirt removed by the uae of rotary vacuum
precoat filters. Experimental data have been reported for a
pilot plant filter in each type of application.
FILTER M E D I U M S
Three useful summaries of the physical and chemical properties
of synthetic fibers now available have appeared within the year
( I S , 69, 70). They suggest two additional candidates as ma-
terial for filter fabrics: the polyester of ethylene glycol and
terephthalic acid (called Terylene by I.C.I., Delvon by Du
Pont), a chemically inert, extremely strong fiber; and poly-
ethylene (made by Du Pont and by I.C.I.), also chemically inert.
The latter is less likely to succeed because it is available only in
monofils, from which satisfactory fabric is difficult to produce
(70). Filter cloths made from Dyne1 (Vinyon-N staple, Carbide
& Carbon Chemicals Corp.) are now available and are said to
be superior because they not only are chemically resistant but
possess a softness and body which enable them to seal a press
against leakage (36). Nylon is now used not only in filter fabrics
but as a re-enforcing fiber in papermaking felts (63, 116). Acid-
resistant filter fabrics also are made from nitrated cotton (106)
and from Hastelloy B and C (Sa).
New bulk mediums that have been proposed are cellulosic
sponge (8) and a bulk of parallel sheets of resin-bonded cellu-
losic tissue, about 240 per inch of thickness, through which the
filtrate may pass parallel to the sheets (158). Additions to the
family of rigid porous mediums are Oilite stainless steel element8
(Sg), available in a variety of shapes and porosities, and a pressed
agglomerate of spheres of synthetic resin, directions for the
preparation of which have been provided by Gebert (57).
Riddick (198) has presented a summary of specifications for
filter sand.
FILTER A I D S
Diatomaceous silica is still the most popular filter aid. An in-
dustrial bulletin explains its use in water filtration (78), and a
British patent describes its application in gold and silver cyanide
metallurgy (78). Pernoux (111) examined diatoms with the
electron microscope and found the pore diameter to be 0.5 micron.
After treatment with hot 5% aqueous sodium carbonate, shown
by Teichner (1%) to attack the silica appreciably. the pores were
somewhat enlarged.
Claude (41) emphasized the use of fibrous material, such as
cellulose, as filter aids. Finely ground bagasse has been used to
improve the filtration of mud from sugar cane juice (55, 147).
Fibrous cellulose filter aids have been described by two 6rms that
market them (13, 7 3 ) .
Two special filter aids have been described: diatomaceous earth
or bentonite coated with a vinyl resin (60), and insoluble in-
organic salt crystals to assist the filtration of viscous liquids
(116).
L A B O R A T O R Y A P P A R A T U S AND M E T H O D S
Improved apparatus and methods for vacuum filtration in the
laboratory have been proposed. These include adapters to per-
mit the use of ordinary funnels and flasks for vacuum filtration
(go), to prevent spattering at the funnel discharge (91), to ob-
viate the necessity of a rubber or cork stopper in the filter flask
by the substitution of a grease-sealed glass plate (93), and to
allow the ready interchange of receivers between 0.5 ounce and
5 quarts in capacity (1.35). An improved Biichner funnel with a
removable bottom plate (2) and a filter flask modified to elimi-
nate the side arm in favor of a grommeted hole (18) have been
proposed. Rothman (115) has constructed an all-glass ap-
paratus for filtering and dispensing solutions in a closed system.
Dubbs (46) has developed an apparatus in which an astounding
number of operations-among them, filtration-can be accom-
pliahed without the sample’s being removed.
A method of constructing a sintered-glass filtering element has
Vol. 43, No. 1
been disclosed by Versa1 and Kruppe ( I S Q ) ,and tt method of clean-
ing such an element by use of a fused organic salt has been
recommended by Budde and Potempa (96). Nikonorov (105)
advised the replacement of paper by a sintered-glass element in
phosphorus determinations (105). Hueckel and Pietsch (71)
have given directions for the production of a collodion membrane
for ultrafiltration.
Laboratory procedures published which importantly involve
filtration include the analysis of water for iron by hydroxide
precipitation and filtration on a membrane filter ( 7 ) and the
rapid determination of silica in water by precipitating i t a t such
a p H as to make it readily filterable (111). Ospenson (108) re-
ported that certain surface-active agents ndl prevent the “crawl-
ing” of nickel dimethylglyoxime precipitates and therefore will
accelerate the filtration and washing of this material.
CONCLUSION
The appearance of a number of up-to-date reviews and sum-
maries of useful theory, commercially available equipment, and
established methods puts the user of filters in his best position
for perhaps a decade. While these general references constitute
probably the most outstanding feature of the filtration literature
of the past year, the period has been exceptional also in that it
has produced several signififioant contributions to the further de-
velopment of filtration theory and data interpretation. Equally
gratifying has been the publication of a few quantitative, de-
tailed reports from the process industry on the performance and
selection of filters. These important new papers have all come
from universities or from users of filtration equipment; it i s
hoped that in the future more contributions from the designers
and manufacturers of filters will take their place beside those
from other sources.
LITERATURE CITED
Algemeene Kunstzijde Unie N.V., Dutch Patent 64,709 (Oct.
15, 1949).
Anon., LabOTatOTy, 20, No. 1 , 2 2 (1950).
Anon., Petroleum (London), 11, 206 (1948).
Anon., Svensk Pappemtidn., 53, 14-15 (1950).
Anon., World’s Paper Trade Rev., 132, No. 15, Tech. Suppl.,
86-8 (1949).
Automobile Engr., 38, 15-20 (1948): 39, 12 (1949).
Baier, C. R., Wasser, Vom, 17, 93-102 (1949).
Banigan, T. F., and White, W. D., Can. Patent 458,964 (Aug.
16, 1949).
Bastone, H. J., and Babcock, A. B., Proc. Tech. Session Bone
Char, 1949,149-64.
Baylis. J. R.. J . Am. Water W o r k s Assoc., 42, 687-700 (1950).
Becker, 0. A., U.S. Patent 2,481,489 (Sept. 13, 1949).
Belan, F. I., Stal, 8, 822-6 (1948).
Bendigo, C. W., and Scott, R. C., Tertile World. 99, No. 9, 111-
30 (1949).
Birsch, E. T., and Silcox, W. D., U. S. Patent 2,454,124 (Nov.
16, 1948).
Bobrik, I. P., and Parfenov, E. G., Russ. Patent 69,593 (Oct.
31, 1947).
Bolin, G., Svensk Papperstidn., 52, 214-16 (1949).
Boucher, P. L., U. S. Patent 2,462,604 (Feb. 22, 1949).
Bretherick, L., Chemistry & Industry, 1949, 268.
Breyfogle, R. H., Can. Patent 463,622 (March 14, 1950); U. S.
Patent 2,476,131 (July 12, 1949).
Brixius, J. K., U. S. Patent 2,479.722 (.4ug. 23, 1949).
Brown, G. G., et al., “Unit Operations,” Chap. 16-17, New
York, John Wiley & Sons, 1950.
Ibid., Chap. 18.
Brown Co., New York, “Solka-Floc ns Filter Bid,” undtited.
Brownell, L. E., and Crosier, H. E., Chena. Eng., 56, No, 10,
124-7, 170 (1949).
Bryant, P. S., Inst. M i n i n g Met., Symposium o n fiefining N o n -
Ferrous MetaZa, 1949, 259-79.
Budde, W. M., and Potempa, S. J., Anal. Chent., 22, 1072
(1 950).
Burak, N., and St,orrow,J. A,, J . SOC.Chem. I n d . (London), 69,
8-13 (1950).
Camp, E. Q., and Phillips, C., OiZ Gas J.. 48, No. 46, 214-15,
341, 343-5 (1950).
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY
(29) Cam, K.L., Finish, 7,NO.5,29-30 (1950).
(30) Carrier, W. W., U. S. Patent 2,480,320(Aug. 30,1949).
(31) Chaffey, R. H., Ibid., 2,510,378(June 6,1950).
(32) Chem. Eng., 56,No. 10,136(1949).
(33) Ibid., No. 11, p. 109.
(34)Ibid., 57,No. 1, 138 (1950); Chem. Inds., 66,96(1950).
(35) Chem. Eng., 57,No. 6,152 (1950); Chem. Inds., 66,900 (1950).
(36) Chem. Eng., 57, No. 7, 160, 162 (1950); Chem. Inds., 67, 102
(1950).
(37) Chem. Eng. Progress, 46,No. 2,27A (1950).
(38) Chem. Inds., 65,619(1949); Sewage W w k s Eng., 20,520(1949).
(39) Chem. Inds., 65,776(1949).
(40)Ibid., p. 937; FoodInds., 22,106 (1950).
(41) Chem. Inds., 65,937-8 (1949).
(42)Claude, R., Chimie & industrie, 64,48-51 (1950).
(43)Cummins, A. B., in A. Weissberger’s “Technique of Organic
Chemistry,” Vol. 3, Chap. 6, New York, Interscience Pub-
lishers, 1950.
(44) Danil’tsev, V. A., Russ. Patent 69,259(Sept. 30,1947).
(45) Davidson, H.O.,U. S. Patent 2,469,293(May 3,1949).
(46) Dubbs, C. A,, Anal. Chem., 21,1273-6 (1949).
(47)Ehemann, G. C.,Burnett, L. K., and Waddell, J. C., P u l p &
Paper Mag. Can., 51,No. 7,107-11 (1950).
(48) EllilB, K. L., Swed. Patent 126,303(Oct. 4,1949).
. (49) Emes, Papierfabr. Wochbl. Papierfabr., 78,176-8 (1950).
(50) Erspamer, A. S.,and Rice, W. D., IND.
(1949).
ENC.CHEM.,41,1806-9
(51) Faint, H.W., Finish, 7,No. 6,25-6,64 (1950).
(52) Faulconer, F. M., McCann, D. L., and Bedell, H. L., Pefroleum
Engr., 21C,No. 12,26-32 (1949).
(53) Filtration Engineers. Inc., Newark, N. J., “FE Rotary
Vacuum Filters,” Bull. 103 (1949).
(54) Flood, F. L., Sewagelnd. Wastes, 22,307-14 (1950).
(55) Freeman, L., U.S. Patent 2,500,065(March 7,1950).
(56) Friedel, F. A., Chem. Ing. Tech., 21,382-3 (1949).
(57)Gebert, A.,Swiss Patent 263,031 (Nov. 1,1949).
(58)Genter, A.L., U. S. Patent 2,464,223(March 15,1949).
(59) Georgia, F. R., J . Am. Water W o r k s ASSOC.,41,1047-52 (1949);
Water & Sewage Works, 97,223-8 (1950).
(60) Goetz, A., U. S. Patent 2,508,602(May 23,1950).
(61) Greenleaf, A. C., J. New Eng. Water Works Assoc., 64,97-106
(1950).
(62) Gustafsson, K.F., Svensk Papperstidn., 52,210-13 (1949).
(63) Hall, E. H., U. S. Patent 2,506,667(May 9,1950).
(64) Harmer, D.M.,Kolachov, P. J., Smith, L. A., and Willkie, H.
F., Chem. Eng. Progress, 46,203-8(1950).
(65) Haywood, R. W., Jr., and Wells, B. H., J. Am. Water Works
Assoc., 41,856-64 (1949).
(66)Heertjes, P. M., Research (London),3,254-9 (1950).
(67) Heertjes, P. M., and Haas, H. v. d., Reo. trav. chim., 68,361-83
(1949).
(68) Hoover, C. O.,U. S. Patent 2,472,976(June 14,1949).
(69) Horst, W. P.t., Chem. Inds., 66,521-6 (1950).
(70) HONlett, F., J. TextileInst., 41,P124-31 (1950).
(71) Hueckel, W., and Pietsch, H., Suomen Kemistilehti, 22B, 1-7
(1949).
(72) Huntington, Heberlein and Co., Brit. Patent 633,203 (Dec. 12,
1949).
(73) Industrial Chemical Sales Division, West Virginia Pulp and Pa-
per Co., New York, “Polycel Purified Wood Cellulose,”
1948.
(74) Ingelsent, H., and Storrow, J. A., Food, 19,25-6 (1950).
(75) Irvin, D.F., and Bellas, H. W.. in J. H. Perry’s “Chemical En-
gineera’ Handbook,” 3rd ed., pp. 964-92, New York, Ma-
Graw-Hill Book Co., 1950.
(76) Ishikawa, H., Waseda Applied Chem. Soc. Bull., 19, 51-69
(1 942).
(77) Jepson, C., and Greene, G., City of Manchester (England),
Rivers Dep., Rept. 55 (1948).
(78) Johns-Manville Celite Division, New York, “Celite Diatoma-
0 oeous Earth Powder for Economical Filtration of Water,”
undated.
(79) Jokel. W.. U.8. Patent 2.475.968 (Julv 12.1949).
(80) Kalichevsky, V. A., Petroleum Processing, 4 , 1468 (1949).
(81) Kantelius, K. E.H., Swed. Patent 126,731(Nov. 22,1949).
(82) Kassing, B. L., Paper Ind. and Paper World, 32,430-3 (1950);
Paper M i l l News, 73,No. 25,9-10, 18 (1950);Paper Trade
J.,130, NO.24,874 (1950).
(83) Keefer, C. E.,Sewage Works J.,21,554-76 (1949).
(84) Kipp, E. M., Lubrication Eng., 4,122-4 (1948).
(85) Kleinert, T., and Moessmer, V., Oesterr. Chem.-Ztg, 51, 29-32
(1950).
(86) Klyachko, V.A., Stal., 8,818-22 (1948).
(87) Korzhinskii, D. S.,Bull. m a d . sci. U.R.S.S., S b . gdool., 1947,No.
2,35-48.
(88) Kraoklauer, A. C., Finish, 7,No. 4,2&6,73 (1950).
89
(89) Kracklauer, A. C., U. s. Patent 2,460,423(Feb. 1,1949).
(90) KrejEI, R., Chem. Listy, 33,382 (1939).
(91) Lane, M., and Smith, L. G., J . New Enol. Water Works Assoc.,
63,209-20 (1949).
(92) Liang, Shu-Chuan, J.Chinese Chem. SOC.,16,14-15 (1949).
(93) Longuet, P.,Rec. materiaus construction trav. publ., Ed. C ,
NO.400,13-16 (1949).
(94) McCahan, R. H., MacKinnon, C. E., and Swalheim, D. A.,
Proc. Am. Electroplaters’ SOC.,35,203-13 (1948).
(95) Majosi, K.,Hung. Patent 139,662 (July 15, 1949).
(96) Maloney, J. O.,IND.ENQ.CHEW,38, 24-5, 37 (1946).
(97)Ibid.. 43. 55 (1951).
(98j Mick, K. L.,. Sewage Works Eng., 20, 73-4 (1949); Sewage
Works J., 21,334-9 (1949).
(99) Micro Metallic Corp., Brooklyn, N. Y., “Surfamax SMX Fil-
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(100) Miessner, H., Chem. Ing. Tech., 21,409-12 (1949).
(101) Miller, G.,U. S. Patent 2,499,325(Feb. 28,1950).
(102)Miller, S.A., Chem. Inds., 66,38-48 (1950).
(103) Mondria, H., Applied Sci. Research, A2, 165-83 (1950).
(104) Nesbitt, W. P.,P u l p & Paper M a g , Can., 51, No. 4, 82-5
(1950).
(105) Nikonorov, K. V., Zhur. Anal. Khim., 5,124 (1950).
(106) Oeda, H., and Mizuta, A., Japan. Patent 175,430(Dec. 27,1947).
(107)Osgood, G.,Brewers’ GuiZdJ., 36,No. 424,41-60 (1950).
(108) Ospenaon, J. N., Acta Chem. Scand., 3,630-8 (1949).
(109)Ovchinnikov, L. N., and Maksenkov, V. G., Bull. m a d . sci.
U.R.S.S., St. g60l., 1949,NO.3,82-94.
(110) Pajetta, R., and Turati, V., Ital. Patent 436,961 (June 18,
1948).
(111)Pernoux, E., Compt. rend., 228,1646-7 (1949).
(112) Proskuryakova, G. F.,Zavodskaya Lab., 16,364-5 (1950).
(113) Puech, E.,French Patent 940,201(Dec. 7,1948).
(114)Pustynskii, A. K.,Russ. Patent 69,570(Oct. 31,1947).
(115)Reed, H. G.,and Beasley, J. K., U. S. Patent 2,494,143(Jan,
10, 1950).
(116)Rees, E.A., and Dahlberg. H., Paper Trade J., 130, 21 (1950).
(117)Reeves, E. J., Petroleum Processing, 4, 885-6 (1949); Petro-
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(118) Reinacher, G.,Metal Ind. (London), 75, 183-7, 211-13 (1949).
(119) Reinacher, G.,Office of Technical Services, U. S. Dept. Com-
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(120)Richter, J. C. F. C., Can. Patent 452,267(Nov. 2, 1948); U. 5.
Patent 2,510,254(June 6,1950).
(121)Richter, P. O.,SewageInd. Wastes, 22,994-6 (1950).
(122) Riddick, T. M., Water & Sewage Works, 97, No. 5, R76-7
(1950).
(123) Robinson, B. P.,Southern P u l p Paper J., 13, No. 7, 42, 44
(1950).
(124) Ross,R. H., Deco Trefoil, 14,No. 2,7-22 (1950).
(125) Rothman, S.,Anal. Chem., 22,367 (1950).
(126) Rudolfs, W., et al., SewageInd. Wastes, 22,613-14 (1950).
(127)St. Clair, H. W., U. S. Bur. Mines, Rept. Invest. 4614 (1949).
(128)Samuelson, O.,Svensk K e m . Tid., 61,227-34 (1949).
(129)Samuelson, O.,Svensk Papperstidn., 52,465-73(1949).
(130) Samuelson, O.,and Jansen, H., Ibid., 52,448-50 (1949).
(131) Strassheim, F. W., U. S. Patent 2,463,825(March 8,1949).
(132) Tankard, E.E.,J . New Enol. Water W o r k s Assoc., 64,299-300
(1950).
(133) Teichner, S.,Compt. rend., 228,1644-6 (1949).
(134) Tessmer, R. G.,U. 8. Patent 2,508,976(May 23,1950).
(135) Thom, A. S.,Pharm. J., 164,225 (1950).
(136) Thurber. A. E..U. S. Patent 2.487.399 (Nov. 8.1949).
(137) Ullrich, A. H.,’Water & Sewage Works; 96,381-4 (1949); 97,
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(138)Valente, J. E.,and Wink, K. R., Can. Patent 459,852(Sept. 20,
1a m i
(139) Verzal, A. I., and Kruppe, G. A., Zavodskaya Lab., 15, 126
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(140) Vokes, C. G., Trans. SOC. Engrs. (London), 1948, 91-117;
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(141) Vosloo, P. B. B., Inst. Sewage Purif., J . and Proc., 1947,Part
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(142)Vosters, H.L., Svensk Papperstidn., 53,29-34,59-64 (1950). .
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(146) Weston, R. F., IND. ENG.CHEM.,42,607-12 (1950).
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(148) Woods, C. W., U. S. Patent 2,459,353(Jan. 18,1949).
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October 30, 1850.
RECEIVED
 I
e!! MAX LEVA, P I 9 EAST G A R D E N R O A D , PITTSBURGH 27,
MURRAY WEINTRAUB, BUREAU OF MINES, BRUCETON,
PA.

PA.

This article reviews the literature on most phases of fluid dynamics which has appeared between profile for turbulent flow in smooth
October 1949 and September 1950, with numerous references to material published earlier pipes by assuming that shearing stress
in foreign journals. Major emphasis has been placed on subjects usually covered in engineering is a specified function of density, ra-
curricula. Of particular interest has been the increased appearance OF European sources which diaI velocity gradient, and a “mean
were mainly concerned with reviewing developments made i n the United States during recent free path of eddies.” Ross and
years. Readers interested i n Flow through apparatus will Find the review papers by WolFe, Robertson (267) verified experimen-
Jaeschke, and Hahnemann OF interest. Engineers and designers of piping should find the book tally that the velocity profile in the
by Friend and Samoiloff of great help. Other papers on resistance through piping and fittings turbulent boundary layer can be de-
were contributed by Foxhall, Pigott, Leys, and Martin. To students OF dimensional analysis termined from a knowledge of the
the paper by M u r p h y should b e of value. Excellent papers on heat Flow and friction through shear stress.
tube bundles and various types of baff’ed and unbaffled heat exchangers were due to Bergelin An analysis of oil flow through
e t a / , Donohue, Kuehne, and Schultz. Students interested in flow OF gas bubbles through trunk lines was made by Anclei son (4).
liquid columns will find the papers by Shepherd, V a n Krevelen, Pattle, Spells and Bakowski, An approach was suggested for esti-
and Verschoor of general orienting value. Lubin presented new data on flow through a packed mating flow capacity, making allow-
column 24 inches i n diameter and Rose and Rizk extended their earlier pressure drop studies. ance for the pressure effect on the
A most informative paper on the measurement of the extent of wetted area i n a Raschig ring b e d oil viscosity. A practical papcr on
was contributed by Weisman and Bonilla. The hypersorption process was well described by pressure loss through sinuous pipe was
Berg e t a/., and Wilhelm and co-workers contributed significantly toward a better understanding contributed by Foxhall (104). The
OF turbulent diffusion i n packed beds. Breckenfield and W i l k e and Ballard and Piret were calculation method utilizes the con-
concerned with liquid-liquid Flow i n packed columns and an interesting correlation for liquid cept of equivalent pipe length as
vapor flow through distillation columns was proposed by Reed and Fenske. In the field of applied to 180” bends. Pressure drop
fluidization the most comprehensive paper i s probably that of Reis. Elgin and Foust demon- in round pipe was the subject of a
strated the basic similarity between droplet flow through spray towers and fluidization phe- book by Friend and Samoiloff (106).
nomena. Dotson e t a/. suggested a method For measuring the relative proportion of solids and Since the book contains a large num-
gas i n any particular place in a fluidized bed. Kettenring e t a/. and Jolley discussed internal ber of excellent charta for the rapid
heat transfer i n the Fluidized bed. Design engineers will find the papers b y Sandaker e t a/. solution of pressure drop and pipe
dealing with design OF high pressure piping and by Karassik, discussing characteristics of pumps, sizing problems, it should be of
generally of value. great value to design and oper-
ating engineers. Luss (192) wrote
on pumping costs and head losses

T
HE literature on most phases of fluid dynamics which has
appeared since the 1949 review, together with numerous
references to material published earlier in foreign journals is
presented here. Themajor emphasis is on subjects usually covered
in engineering curricula. Of particular interest has been the in-
creased appearance of European sources which were mainly con-
cerned with reviewing developments made in the United States
during recent years.
FLOW T H R O U G H A P P A R A T U S
Friction. A series of three comprehensive reviews on various
aspects of pipe flow were contributed by Wolfe (336). I n the
first paper, he derived the flow equation using dimensional analy-
sis, and elaborated on various correlations of the pipe friction
factor. I n the second paper, velocity distribution in circular
conduits and surface roughness was reviewed, while the third
paper dealt mainly with Prandtl’s generalized roughness function.
A brief paper describing energy losses in pipe lines (10) also
reviewed friction loss and pipe surface roughness in water con-
duits. An examination of effect and magnitude of the dynamic
forces in turbulent flow on individual pipe wall protrusions was
made by Einstein and El-Samni (90) and significant lift forces
were observed. Jaeschke (151), similar to Wolfe, reviewed the
more recent advances in flow through pipes with emphasis on
evaluation of the friction factor and effect of surface roughness.
A similar review covering pipe flow and other topics was given
by Hahnemann (126). Maurer (201)made an entropy analysis of
incompressible fluids through smooth cylindrical tubes and
showed t h a t the critical Reynolds number (limit of laminar flow)
is 1440. Prandtl (233)derived the equation defining the velocity
90
in pipes, estimated by the formulas of Manning and Kutter.
Harding and Mort (129) proposed charts which were based
on the Hardy-Gross method for solution of flow problems.
Folquier (100) discussed flow distribution in pipe networks on the
basis of Kirchhoff’s l a w , an analysis similar to that of Fair and
Hatch. Davis (78) gave a nomograph for estimating pressure
drop in lines carrying fibrous suspensions, such as are met in
paper manufacture. Other papers covering reviews of pressure
drop calculations in various forms were contributed by Buthod
(69),Biard (40),Renauldon (241), Dutoit (87),and Seiferth and
Krueger ($73). Various nomographs for calculating quantity
of flow ( 1 4 , sizing of steam lines, and Reynolds number were
proposed by Gibbons (111)and Arnold (17). Pigott (229) wrote
on pressure loss in tubing and fittings. He emphasized that losses
in rough fittings were composed of a true bending loss component
to be superposed on the loss due to roughness. As the most
reliable method of evaluation, he recommended the equivalent
pipe-length method. Losses through various types of elbows
and influence of change of sectional and branching losses were
discussed by Leys (186). Practical considerations in interpreta-
tion of commonly used formulas for estimating resistance in pipe
bends, obstructions, and fittings were proposed by Martin (196).
Fluid Flow and Heat Flow. A condensed informative pres-
entation of dimensional analysis wm presented by Murphy
($09). It deals with definition of concepts, basic methods, elimi-
nation of trial and error calculations, and the subject of simi-
larity. Another comprehensive presentation of the principles of
dimensional analysis was given by Martinot-Lagarde (198). It
stressed application to a variety of flow problems, such as ships,
pipes, and compressible viscous fluids. Other discussions of
 January 1951 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
dimensional analysis and dimensional similitude were contributed
by Ciborowski (63)and Craya (74). Bergelin e l al. (56) continued
their investigations into heat and fluid flow through tube bundles.
They studied effects of tube spacing and diameter on pressure
drop and heat transfer. Using a variety of pattern settings, they
reported the highest heat transfer coefficients when the smallest
tubes were on the smallest pitch. Pressure drops were correlated
best by a modification of the Chilton-Genereaux method, wherein
volumetric equivalent diameters were used. Donohue (88)
discussed heat transfer and pressure drop in heat exchangers
carrying various types of baffles. In general, for equal flows
disk-and-doughnut type b d e s gave better heat transfer coeffi-
cients than segmental baffles. Pressure drops, when reported in
the form of friction factor plots, scattered much more than com-
parable heat transfer data. This was attributed to the fact that
pressure drop is proportional to the square of mass velocity as
compared to the 0.6 power for heat transfer. A brief discussion
of laminar and turbulent flow in heat exchangers was also given
by Kuehne (178). Schultz (267) showed how the Reynolds
analogy can be used in heat exchanger design. Thompson (801)
suggested a graphical method, also based on the Reynolds’
analogy, to correlate variables involved in heat transfer to a gas
moving a t high velocity through a passage. Businger (68) made
an analysis of heat exchanger economics on the basis of a compari-
$on of Nusselt numbers and pipe friction factors.
Two-Phase Flow. Two-phase flow problems arise in all
engineering fields. Owing to this wide and general distribution
and the many aspects involved, little fundamental progress has
been made toward achieving generalized engineering correlations.
Liquid-gas and liquid-liquid flow through packed coIumns, most
common in chemical engineering practice, is probably best under-
stood and this subject has been covered in greater detail under
packed beds. I n this section some of the less understood appli-
cations of this field will be covered.
Pressure drop data observed in the field, pertaining to simul-
taneous gas and oil flow through a %inch pipe line, were compared
satisfactorily by Van Wingen (312) to values estimated with the
correlations of Martinelli and co-workers. Gilmour (118) esti-
mated gas-oil ratios for oil wells flowing through surface chokes
or beans. The problem of handling pressure drop in long gas and
steam pipes involving phase changes was handled by Baer (21).
Experimental data on the simultaneous flow of air-water and
steam-water mixtures through glass and brass tubes were ob-
tained by Widell (330). The data did not agree with the measure-
ments of Martinelli, and a correlation was suggested where the
ratio of the pressure drop of the mixture to that of the gas alone
was related to friction factors. More experimental work on air-
water flow was reported by Kosterin (174): The resistance
coefficient when related to the liquid-gas ratio passed through
a maximum as the latter decreased. The range of data was char-
acterized by the Froude number range 0.1 to 1000, and velocities
P were above 10 feet per second. Keulegan (163) investigated flow
of liquids over each other which are ordinarily miscible. He
found that mixing begins a t a critical relative velocity which is a
function of viscosities, densities, and density difference. Data
on flow of Freon 12 and sulfur dioxide through capillaries were
collected by Marcy (I%), and a method for calculating capillary
iength in adiabatic expansion was given.
Subjects related to two-phase flow is the motion of send by wind
a n d in river beds. Papers on this and similar topics were written
by Kawamura (169),Labaye (180), and Kurihara (179). Data on
flow of dust-iaden air through nozzles, and estimation of particle
size therein were reported by Barth (29). Probably related to
two-phase flow is the work of Jones (166),which describes use of
the Venturi scrubber for removal of dusts and fumes from gases.
Spencer et al. (286) studied the compactness and frictional forces
in powders acted on by limited fluid forces.
Passage of gas bubbles through liquid columns is an example
of two-phase flow which has wide applications and where as yet
91
no generalized correlation was achieved. A review in thia field
was given by Shepherd (276). Van Krevelen and Hoftijzer (177)
reported new measurements and observations on bubble passage
through liquid columns. Pattle (221) presented a paper on aera-
tion of liquids. He was concerned with solution rates of gases
and how these are influenced by the distribution device, as well
as the mechanics of bubble release from porous aerating devices
and the effect of the presence of organic substances on bubble size
and bubble release from the pores. Spells and Bakowski (884)
investigated the mechanism of bubble release from single slots
submerged in water, and Verschoor (316)examined the mechanics
of the passage of swarms of bubbles through liquid columns.
Drop formation from nozzles in two-liquid phase systems was
investigated by Hayworth and Treybal (133).
Packed Beds. An extensive study of flow through a tower
of %inch diameter was made by Lubin (190). Using a wide
variety of Raschig rings and Berl saddles these packings were
investigated under dry as well as irrigated conditions with water
and sugar solutions as the liquid phase. Empirical equations for
gas pressure drop through rings and saddles were presented and
comparisons of the new data with correlations of other investiga-
tors were also made. The irrigated tower data are in accordance
with the data of Tillson, reported for similar conditions in a
20-inch diameter tower. Observing also flooding and holdup
data, Lubin suggested an improved flooding correlation for
rings and saddles, using a variable exponent on the liquid vis-
cosity and taking into account the free space reduction due to
liquid holdup. h o t h e r comprehensive flow study using air and a
wide variety of packing materials ranging jn shape from spheres
to nails was reported by Rose and Rizk (866). The correlating
equation, partly derived through dimensional analysis, was
claimed to apply to voidages up t o 90%. The correlation con-
tains an empirical shape factor which is of an additive nature and
comprises primarily the ratio of the maximum and minimum
length dimensions of the particles. Coulson ( 7 3 ) investigated
flow through granular beds further with particular emphasis on
effect of shape and voids in the streamline range. After a thor-
ough review of the classical developments, Couslon concluded
that more general formulations are required for describing ade-
quately the flow through nonspherical beds. Brownell et al. (64)
chose to revise the correlation of Brownell and Kata. The effect
of surface roughness on pressure drop in turbulent flow was dis-
missed on the basis of data with so-called “roughened” metal
saddle bodies. Sokolovskir (282) discussed equations for flow
through porous mediums and proposed a modification of D’Arcy’s
law that allows for turbulent flow. Fox (108)investigated the on-
set of turbukence in packed beds. Working with perfect spheres
as well as irregular shapes, such as marble chips, it was concluded
that shape imperfections have little effect on onset of turbulence.
For perfect spheres the critical modified Reynolds number was
equal to about 24, whereas for the chips it waa near 8. A
study of effective area in packed spherical and ring beds wa+s
made by Weisman and Bonilla (386). Measuring absorption
capacity data for the air-water system, a comparison of the
Coefficients with the data of Taecker and Hougen pertaining to
totally wetted particles disclosed that in heat transfer only ap-
proximately 50% of the total packing area was effective. The
data were roughly in agreement with the direct measurements of
Mayo and Grimley, but were essentially lower than the values
suggested by van Krevelen. Arthur et al. (20) studied air flow
through a layer of granules. The data could be correlated by the
Kozeny equation; flow distribution measurements revealed higher
values near the Verne)!wall than in the core. Flow of heteroge-
neous fluid mixtures through porous mediums was discussed
by Brinkman (68). The basis of discussion was the work
of Muskat. A description of the hypersorption process for
separation of gases and liquids was presented by Berg et al. (85)
in which unit assembly as well as individual unit details were
given. Munroe and Amundson (208) presented a mathematical
92 INDUSTRIAL A N D ENGINEERING CHEMISTRY
treatment of the problem of heat flow b e t w e n fluids and a moving
bed of solids. A study of turbulent diffusion in beds of packed
solids was reported by Bernard and Wilhelm (57‘). Extensive
data were obtained on the diffusion of a methylene blue solution
into water as well as carbon dioxide into air. Turbulent diffu-
sion was significantly influenced by gross wall-generated eddies,
Singer and Wilhelm (279) studied heat flow through packed beds,
and also attempted to ascertain the importance of turbulent dif-
fusivity of the fluid in its relation to heat transfer. The effect of
thermal gradients in fluids passing through porous mediums upon
convection currents was investigated by Morrison et al. (205). A
paper of a somewhat different character was contributed by
Schwertz (269). The specific surface of sintered glass as measured
by adsorption studies was compared to that obtained by gas pene-
tration. The adsorption method gave somewhat higher values
of surface area, indicating the presence of pits and pores in the
material which were not ordinarily available to gas flow through
the material. Other papers on flow through sand filters, soils,
and porous mediums, as encountered in oil reservoirs, were con-
tributed by Grantham el al. (180), Klyachko (169), Van Everdin-
gen (311), and Van Deemter (510).
A few papers appeared on liquid-liquid and liquid-vapor flow
through packed columns. Breckenfield and Wilke (51) experi-
mented with various sizes of rings, saddles, and spheres, and a
rather broad selection of fluids. They suggested two correlation
methods. In the Srst method the ratio of the velocities of the
continuous and discontinuous phases was related to a grouping
of system properties, whereas in the second method the sum of the
square roots of the velocities was related to a somewhat different
grouping of variables. A good generalization for all packings
resulted when packing factors similar to those used in flooding
and loading work were included. Ballard and Piret ($5)made a
similar investigation with small rings. A “transition point” was
defined as that condition beyond which flow increase of the con-
tinuous phase causes flooding or other changes in the flow pat-
tern. A proposed generalized correlation is somewhat similar to
t h a t of Breckenfield and Wilke. Main differences are that a
fluid density ratio was involved along with the velocity ratio
and the packing factors entered the grouping of variables dif-
ferently. An interesting approach to the problem of liquid-
vapor flow through packed distillation columns was given by
Reed and Fenske (857). Using dimensional analysis an equation
of the Kozeny-Carman type was derived in which the column
voidage was corrected by subtracting the liquid holdup. Working
with a wide variety of liquids and packings such as wire helices,
rings, and saddles the random scatter of the data, though appre-
ciable, indicated the fundamental soundness of the approach.
I n a study of gas-liquid contacting in bubble columns by Shulman
and Molstad (278) which mainly intended to measure the
H.T.U. for this type of equipment with the gas entering the
column through porous metal disks, limited gas flow pressure drop
data through such plates were given with the plates wet. A tower
packing test study on Raschig rings, Prym rings, star bodies,
spools, and Berl saddles was made by Schumacher (268). A
new tower packing intended as a fractionating tower packing was
described by Scofield (270). The packing has the shape of
corrugated trays of multilayer expanded metal lath. Packing
factors were very much smaller than those of conventional
ceramic packings and the resulting flow capacities were corre-
spondingly higher.
FLUIDIZATION
During the last year significant contributions were made on
fundamentals of fluidization as well as along process development
lines.
Fundamental. A comprehensive review of basic work in the
United States was given by Wilhelm (552). New data in labora-
tory equipment were presented by Ciborowski (66) and the mini-
mum flow for fluidization was believed proportional both t o
Vol. 43, No. 1
particle diameter as well as solids density. Further expansion
data of sands and glass powders in water, collected by Verschoor
(515), seemed t o indicate that, the ordinary laws that apply t o
flow through fixed packed beds are not strictly applicable t o
expanded columns, if the voidage is essentially in excess of 80%.
I n a series of three comprehensive papers, Reis (240) reviewed
many of the fundamental aspects, particularly those advanced in
the United States. H e also described a photoelectric method
of analysis for studying density changes and the general uniform-
ity of the fluidized column and he presented a statistical approach
as to mechanism. Elgin and Foust (91) investigated the flow
mechanics in spray towers and were able t o present their d a i s
in a form closely related to the fluidization correlations of Wil-
helm and Kwauk. An entirely mathematical treatment of
adsorption in fluidized beds was given by Kasten and Amundson
(168). I n their development of theory they resorted to the sim-
plification that the solids are uniform, porous, spherical particleb
A method for measuring the relative porportion of solids and gas
in a fluidized column JTas reported by Dotson et al. (86). Working
with the coal-air system, changes in the dielectric constant of the
column were found useful for this purpose. An alignment chart
by Weintraub and Leva (585)permitted estimation of the onset
of fluidization and solution of pressure drop problems for viscou,
flow through Lyed beds. An alignment chart by Gary (108)
allowed prediction of space velocities in catalytic cracking units.
Rates of heat transfer and mass transfer withjn fluidized beds
were reported by Kettenring et al. (Is$),as well as by Jolley (154).
Kettenring et al. worked with silica gel and activated alumina
particles, ranging from 48 to 14 mesh. Working in the dense
phase with no net particle motion both heat transfer as well as
mass transfer coefficients were reported to be only a fraction of
that e.xpected in h e d beds under comparable particle size and
flow conditions. Jolley, on the other hand, worked with coal
particles ranging from 1/,6 inch to subsieve sizes and reported
fluidized coefficients several times in excess of fixed bed data.
It is possible that the discrepancy is related to the mode of d e k i -
tion of the temperature driving force. While Kettenring et al.
assumed that the solids temperature in the bed was unchanged
along the vertical axis of the column and obtained the driving
force from this value, and the gas temperature by means of
graphical integration, Jolley actually measured the rate of heat
transfer calorimetrically by dipping metal blocks into fluidized as
well as fixed beds, thus eliminating the need for measuring the
driving force.
Problems pertaining to pneumatic transport are related to
dilute phase fluidization. Korn (173) gave a brief review of air-
solids flow in pipes, presenting empirical correlations of pressure
loss, friction factor, and specific solids loading factor. A paper
on the same subject, but of a theoretical nature, was given by
Wagon (523). Similarly, B paper by Bhandari (59) described
effect of drag and turbulence of flowing water on material trans-
port in horizontal channels.
Process. A review of fluidization applications to the oil and
gas industry, based mainly on practice in the United States was
given by Hancock (128). He also proposes a generalized correla-
tion of data, based essentially on the resistance encountered when
spherical particles fall through fluids. Additional applications
were reported by Ellis (92). Williamson and Garside (334)
discussed the purification of coal gas by using a fluidized iron
oxide bed. Madson (194) suggested using the fluidized technique
for purifying town gas in order to prevent hardening of the tower
charge and minimizing back pressure. Coal gasification data,
using carbon dioxide at 785 to 985’ C. and atmospheric pressure,
were reported by Novella (218)and data were reported in general
(9) on such processes as the Lurgi process, Koppers dust gasifica-
tion, and Winkler process, using noncoking coals. An interesting
gasification study, though not in the fluidized state, was reported
by Perry et al. (,9,94). Using a vortex-type combustion chamber,
carbon convelaion and operational limits were closely related to
 January 1951 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
uniformity and distribution of coal in the machine. Kia-Ting,
Wang (166)applied fluidization to coal carbonization and claimed
t h a t under his particular condition, carbonization proceeded at a
good rate at 350’ C., a temperature well below conventional
values. Process data on the fluidized hydrogenation of Wyoming
coals under only 1000 pounds per square inch, which is substan-
tially lower than pressures used in European practice, were re-
ported by Clark et al. (64). A description of a fluidized pilot plant
with operating data for the purpose of distilling oil from Alberta
bituminous sands a t about 500” C. was described by Gishler
(115)and Peterson and Gishler (886). A process for obtaining
thiophene from hydrocarbons and sulfur dioxide was described
by Conary e t al. (66),carbonization of red wood (8)and a fluid-
ized-type furnace were described (13); Counselman (73)reviewed
fluidized solids ore roasting practices.
VlSCOSlM
The importancse of the viscosity function in estimation of fluid
flow creates constant interest in the evaluation, prediction, and
proper use of viscosity values. The large number of fluids for
1) which viscosity is now known to be a function of rate of stress
has focused attention on such “non-Newtonian” fluids. Two
books by Reiner (638, 239) describe the basic analysis necessary
for understanding the flow of complex fluids. Kirkwood, Buff,
and Green (167) present a statistical mechanical theory of trans-
port processes. Rivlin (260)attempted to find, from kinematic
and dynamic considerations, the most general equations govern-
ing the motion of non-Newtonian fluids and then (84.9) applied
his equations to flow through a tube of circular cross section.
Fromm (107)calculated the laminar flow of a fluid for which the
stress was a simple function of rate of strain; Shchipanov (876)
developed formulas for rate of flow and pressure distribution in
tubes and annuli, allowing for point-to-point variation in both
viscosity and limiting shear stress of the fluid. Van Olphen
($13) analyzed the pressure drops through various components
of the drilling mud c i r c u i t i . e . , annulus of casing, drill bit, etc.
$haw (274) pointed out that until a more thorough knowledge
of viscosity variation is obtained, viscosities should be measured
at pumping velocities. The pumping of highly viscous materials
is discussed by Worcester (338).
The viscosity-temperature relationship is the subject of study
by Goettner (117, 118) who found fault with the present vis-
cosity index, and by Sanderson (869)who developed a new index
of viscosity-temperature variation. Donovan (84) presented a
nomograph for the viscosity-temperature relationship for petro-
leum oils, and Hennenhoefer (134) reported data for lubricating
oils at very low temperatures.
Keyes (164) made a critical survey of recent work on the vis-
cosity of steam. More complex fluids reported on included
pulping waste liquors (170),caustic solutions (814), and cement-
water pastes (124). The fact that the mechanics of even “simple”
fluids is not well understood is shown by the number of papers
x
(181, 168, 139,186,333) published on the estimation of the vis-
cosity of gas and liquid mixtures. Rivlin (861) made a mathe-
matical analysis of the motion of a molecule relative t o its center
. of gravity when situated in a given force field, and showed that
the flow properties of solutions of macromolecules are a function
of interatomic forces and orientation within the molecule. Pan-
chenov (218) derived a n expression for viscosity of a liquid in
terms of molecular radius, latent heat of evaporation, and other
measurable properties.
Other attempts t o solve some of the mysteries of the forces
creating viscosity in fluids included the study of high polymer
solutions. Hermans (136)studied cellulose nitrate solutions.
Ferry and co-workers (96) studied energy absorption from two
different types of sources. Mason and co-workers (800)measured
the viscous response of solutions to ultrasonic frequencies. Fox
and Flory (103)paid special attention to the discontinuities in
properties of polystyrenes when going from liquid t o glass.
93
Robinson (264) showed that a modification of Einstein’s
viscosity equation described the behavior of suspensions of 10-
t o 30-micron glass spheres in six different liquids up to concentra-
tions of 65% by volume. Ballantyne (24)and Alfrey and Rode-
wald (8) studied the thixotropic behavior of bentonite suspen-
sions.
The complexity of the viscosity phenomenon is reflected in the
numerous types of viscometers presented in current literature.
D e Bruyne (81) describes a viscometer for thick liquids; Stock
(298) describes one for very mobile liquids. Daniel (77) con-
structed a viscometer for low temperatures, Fokeev (@), one for
high pressures. Two papers (11, 506) described convenient
industrial methods of viscosity measurement. Two groups of
investigators (66, 806) used flow through capillaries for highly
viscous greases.
The rotary-type viscometer received a considerable amount of
attention. Roscoe (866)studied the flow of viscous fluids around
the plane paddle of such an instrument. Three other papers
(18,49, 887) described forms of rotating viscometers in which
different types of electrical systems provide the driving and meas-
uring force. Perhaps one of the best types of viscometer for non-
Newtonian liquids is described by Egginbotham (137). He
rotated a flat plate and measured the force necessary t o prevent
motion of a cone whose tip rests on the center of the plate. The
fluid under study is between the cone and plate. Even for non-
Newtonian fluids, a simple relation exists between the applied
force and the apparent viscosity, because in this system the rate
of shear of the fluid, and hence the shearing stress, is constant.
INSTRUMENTS AND MEASUREMENT
The methods and problems of flow measurements received
considerable attention during the past year, with the major por-
tion going, as usual, t o the orifice meter and its modifications.
Valby (309) and Taylor (899) gave elementary discussions of
the principles of orifice metering. Jacobson (149) and Martin
(197) reviewed the practical aspects of orifice meter calculations
and Arnold (18)presented a nomographic aid. Constance (68)
gave a brief discussion of the related problem of estimation of free
discharge rates of water from orifices.
Linden and Othmer (188) studied flows through orifices of
l / t ~o a/le-inch diameter. Collacott (66) measured discharge
coefficients through chamfered orifices and nozzles and showed
that the best angle of chamfer was a function of the flow rate.
Stringer (894) discussed the metering of liquid fuel flow and the
accuracy of orifice meters. Folsom (101)investigated the various
dimensional parameters of nozzle flowmeters, while Beitler and
Masson (33) measured coefficients for eccentric and segmental
orifices. Belcher and Ingram (S4) discussed capillary orifices as
wide range flowmeters. Finniecombe (97) and Perry (2%)
both discussed gas flow in the critical range.
The development and application of the variable area (rotam-
eter) type of flowmeter was discussed by Bourne and Wunderle
(48), Krause (1761, Hoffman (I@), Hicks (136), and Fritzsche
(106). Hartzell(131) made a thorough study of the fundamentals
of the basic weir formula, while Stancati (288) discussed the
various types of weirs in use with their respective discharge
equations. The theory of the hot wire anemometer was the
subject of two thorough papers by Kovasznay (176) and by
Corrsin (70), while Middlebrook and Piret (808) described some
of the techniques involved in the use of this device. Thrasher
and Binder (302)showed t h a t the proper position of the static
hole of the Pitot tube is a function of the velocity when the fluid
is a gas of Mach number greater than 0.25. Goudy and Colvin
(119) described s device similar to multiple Pitot tubes which,
without moving parts, gives both velocity and direction of gas
flow. Other papers describing modifications of the Pitot tube
were those by Stoll(893), First and Silverman (98), and Girerd and
Guienne (114).
 94 INDUSTRIAL AND ENGINEERING CHEMISTRY
Burwell et al. ( 6 7 ) described the use of wet test meters for gas
flow measurements. Three other papers (id?‘, 266, 344) dis-
cussed the measurement of small flows in the laboratory.
Practical problems in meter applications were the subject of a
number of reports. Parsons (220) described the problems en-
countered in metering oxygen. Work (339) discussed the me-
chanical characteristics of ring balance-type meters. The effect
of oscillations in metered systems is considered by Kito (168),
Yates (3&), Cuenod (76),Schaaf and Cyr (860),andTaback (296).
‘ The latter author points out the possible deleterious effect
when the lines transmitting the pressures to the instruments
have natural resonating frequencies close to that of the system
oscillations. Other aspects of flow metering, industrial appli-
cations and flow controlling, were covered by other writers (67,
110, i62,193,811).
New instruments described include a mass-rate flowmeter (ago),
a torsion balance (93),a thermal anemometer ( I S $ ) , a subsurface
oil-well flowmeter (291 ), and three types of electronic pressure
change detectors (19, 79, 80) capable of high speed of response.
MECHANICAL
Piping. A very large number of papers have appeared on
piping. Many of these were concerned with purely mechanical
features and economic analyses and, although related t o fluid
flow, the subject matter was frequently too removed from the
primary purpose of this review t o be included in great detail.
Sandaker, Markovits, and Bredtschneider (658) reported on
high pressure piping (10,300 pounds per square inch), as is used
in coal hydrogenation work. The authors have described con-
struction of such elements as joints, fittings, and valves. Expan-
sion joints and their proper use were also the subject of a paper by
Wolosewick (337). Miller (208) wrote on the effect of external
and internal loading on stresses and size of pipe. Other papers
on methods and designs of supports for piping for wide applica-
tions were contributed by Soronen (883), Blick (46),York ( 3 4 3 ) ,
and Bridge (62).
A note on the relative merits of gate and globe valves, when
used as throttle valves was sent in by Reynolds (242). On the
basis of simple circuit diagrams, Pellettere (223) discussed sizing
and selection of control valves.
A displacement method based on the injection of aqueous
ammonia a t a definite point into a line and observing the rate of
travel downstream was suggested by Wright (340)for measuring
gas flow rate. In a similar method of measurement (16) the salt
injection was suggested for water caprying lines. Specifications
appeared (6, 7) on stoneware pipes and fittings as well as specific
data pertaining to lead pipe, such as chemical composition, wall
thickness, and metal grain details.
A review of piping in chemical plants waa given by Waeser
(322),and general design conditions of a transcontinental line were
given by Ricketts (247). Methods of cleaning the surface of
pipe prior t o coating with bitumen were reported by Mudd (807);
Stephens (290) described an exTansible fluid-actuated pipe-line
cleaner. Whalley ( 3 6 8 )and Stegner (289)reviewed principles and
practices of protection of lines by cathodic means. Cost figures
and economic analyses were given by Fernandino (96) and
Dickson (82).
pumps and Compressors. Many papers have appeared
which deal with construction and operation of machines for fluid
handling. Since many of these types are probably covered under
‘%faterials Handling” in this Unit Operations Review, only a few
papers will be mentioned here which more directly involve funda-
mental considerations.
Beck et al. (31) developed a bellows-type pump for handling
gases up to 500 pounds per square inch. By using an oil system,
a counterbalancing pressure is maintained on the outside of the
bellows. A review of the development of centrifugal pumps,
especially in Germany, was given by Huebner (144). Baird and
Bechtold ( 2 2 )wrote on the generation and nature of gas-pressure
Vol. 43, No. 1
pulses, resulting from reciprocating compressor action. Voorhees
(321) described construction of a pump for feeding fluidized
catalyst masses into reactors, maintained under pressure.
Design factors required for pumps to handle efficiently highly
viscous fluids were stressed by Riester (848). Wright (341) re-
ported on basic facts related t o proper selection of pumps. A
most comprehensive survey of centrifugal pumps, their construc-
tion, performance, auxiliaries, etc. was given by Karassik (167).
Construction of constant feed laboratory pumps and a diffusion-
type machine was described by Brain et al. (60) and Harrington
(150). Various other papers on turbines and compressors were
contributed by Walti (324), Pantell (619), Martinuzzi (199),
Smith ($go), Kohl (I%‘), and Richter (246).
Cavitation. Accelerated cavitation tests were described by
Rheingans (243), using a vibratory-type accelerated cavitation
machine. Pfleiderer (228) pointed out that pumps and water
turbines operate most economically when their speed is just below
cavitation speed and he also emphasized how this limiting speed
is related to construction features of the machines. The growth
and collapse of cavitation bubbles were investigated by Plesset
(230). Vogelpohl(818) reported on foam formation in oils caused
by cavitation. Petracchi (227’)is of the opinion that the destruc-
tive nature of cavitation is not caused directly by the resulting
mechanical stresses, but rather by the corrosive action, primarily
electrical, which the mechanical stresses set up. He suggested,
therefore, a possibility of protection by cathodic coupling.
Other papers related to cavitation were contributed by Birkhoff
and Caywood (44), Gawn ( l o g ) , and Daily (76).
MATHEMATICAL AND THEORETICAL ASPECTS
Mathematicians and aerodynamicists have published a consid-
erable amount of work which is of interest t o chemical engineers.
The following section is a survey, not a thorough review, of the
many fields investigated by these two groups of scientists.
General. Schlichting (864) presented an article on the
theory of turbulence. Sears (272) discussed flow in the transonic
range-Le., in the velocity range close to that of sound. Von
Neumann and Richtmeyer (319) simplified the differential
equations of hydrodynamics so that they became amenable to
numerical integration for conditions of supersonic Aow. Prim
( 2 3 4 ) showed that a streamline pattern uniquely describes a
flow-i.e., all flows described by a given set of streamlines have
simply proportional velocity fields. Schafer and Tollmein
(266) integrated the flow equations in a simple form. Rebesin
and Johnson (236) analyzed the effect of friction a t high velocities
on the flow equations due to changes in temperature and, conse-
quently, in other properties of the field, while Eggers (89) and
Millsaps ( 2 0 4 ) studied the effect on supersonic flow of deviations
from the ideal gas laws. Supersonic flow patterns against various
boundaries were studied by Schaefer (26f),Hudimoto (1,459,
Kawamura (160),Barry and co-workers (87), and Allen ( 3 ) .
Three groups of investigators (210, 835, 253) reported on the
related problem of high speed flow into ducts, such as jet air in-
take. Howarth ( f d l ) , Cap (60), and Bannister and Mucklow
(26) investigated unsteady flow in different aspects of supersonic
and high subsonic flow.
Boundary Layer. When a fluid and solid have high relative
velocities, the properties and behavior of the layer of fluid ad-
jacent to the surface have a most important influence on the
forces acting between the fluid and solid.
The National Advisory Committee for Aeronautics (N.A.C.A.)
( 2 6 6 ) has published a translation of a series of lectures given in
1941 by Schlichting on the theory of this “boundary layer”’ in
both laminar and turbulent flow. The paper presents a com-
prehensive, if somewhat dated, study of the subject. Another
N.A.C.A. translation ( 1 4 6 ) presents an involved mathematical
study of the laminar boundary layer and a method of plotting
velocity profiles. Trilling (806) developed approximate solutions
of the differential equations for a boundary layer with arbitrary
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY
pressure and suction distribution, while Wieghardt (331 ) carried
out an experimental investigation of turbulent boundary layers.
Another interesting analysis by Goertler (116)of the flow patterns
of a laminar boundary layer along a plate of periodic wave surface
showed t h a t under some conditions the drag on such a surface
may be less than t h a t for a plane surface.
Jets. The dynamics of jet flow from orifices was studied from
several viewpoints.
Viand (317) analyzed flow from ram-jets in the practical terms
of static pressure, thrust, and fuel consumption. Pack (216)
made a theoretical study, with some experimental verification of
the “wave length” of small fluctuations in a uniform supersonic
jet as a function of mean velocity. Corrsin and Uberoi ( 7 1 )
investigated turbulence levels, temperature fluctuations, and
temperature-velocity correlations on a heated turbulent air jet.
The mixing of jets with the surrounding air was studied in terms
of local gas velocities by Chapman (61), Squire (286), Hinze
and Zijnen (I%), and Pai (217), while Bershader and Pai ( 3 8 )
studied the same phenomenon in terms of local density variation.
Flow around Objects. Mathematical and experimental
* study of the flow around objects immersed in a fluid was under-
taken by a number of investigators.
Whitham (329) developed a theory of supersonic flow past a
body of revolution sufficiently far from the axis that the linear
approximations used by others no longer hold. He presented
equations for the shocks formed and also developed a theory for
slender bodies which is presumably valid at all distances from the
axis.
Tomotika rand Aoi (303) studied flow patterns, pressure drag,
and viscous drag of a viscous fluid around a sphere and a circular
cylinder, while Shiffman (277)and Birkhoff (43) both undertook
the study of the drag produced by the cavity formed behind an
obstacle immersed in a flowing incompressible fluid.
Flow around a multiplicity of objects was analyzed by Snedden
and Fulton (281) for the case of two spheres in series within a
stream of perfect incompressible fluid, Ackerett and Rott (1)
for air flowing at sonic velocities through an unstaggered grating
of symmetrical profiles, and LoitsyankiI (189)for compressible
flow over a cascade of profiles at subsonic velocities. Tyler
(308)‘describes several different available theoretical methods for
calculation of two-dimensional flow past cascades of air foils.
Study of somewhat more complex systems was made by Taylor
(197) for air flow through a porous plate; Taylor and Batchelor
(298) studied the effect of wire gauze on turbulence reduction in a
gas stream and on damping of small disturbances superimposed on
a uniform flow.
Flow through Channels. Flow through simpler paths has
not been neglected either. Starting with Mikuradse’s clmsical
data, Legendre (184) derived a velocity distribution equation
somewhat similar to t h a t of von KhrmBn, but more complex, and
representing the original data more closely at the wall and axis.
Tomotika and Hasimoto (304)made a mathematical analysis of
c
gas flow through an axially symmetric nozzle. Falkovich (94)
also studied nozzle flow, more specifically in th,e velocity range of
transition from subsonic to supersonic.
. Pekeris (222) studied the damping and propagation of small
disturbances in laminar flow of fluid between parallel fixed walls
while Laufer (182) made detailed measurements of velocity
fluctuations, correlations, and microscales throughout a turbulent
channel and its laminar sublayer. Flow over weirs took on an
international aspect with studies of three different phases by
Vedernikov (ais),Veronese (SIC), and Lamoen (181). Gilmore,.
Plesset, and Crossley (111) showed the resemblance between hy-
draulic jump equations and shock equations and discussed the
analogy method for the study of shocks.
Unsteady flow of liquids through circular conduits resulting in
“water-hammer” is also reported on. Dvukhsherstov (88)
investigated the effect of elasticity and shape of the conduit on
pressure and speed of propagation of the shock caused by rapid
95
valve closing. Kerr, Kessler, and Gamet (161) discussed the
influence of fluid compressibility and Ludwig (191), the effect of
pipe-line friction on the same problem.
Flow through geometrically more complex channels was inves-
tigated by Taylor (196) who made some interesting analyses of
flow through a swirl chamber spray nozzle, Binnie and Davidson
( 4 2 ) who studied the whirlpool formed when liquid flows by
gravity through an orifice in the bottom of a large reservoir and
also the jet emerging from it, and Kirkham (166) who analyzed
the flow into discontinuities in an impermeable tube laid hori-
zontally in the ground below a water table. Sretenskif (687) dis-
cussed the period of the annular waves formed in a fluid rotating
in a circular cylinder of infinite depth. The hydrodynamics of oil
films in bearings is involved in papers by Barwell and Milne (50),
Roach (962), and Cope (69), while Balje ( 2 3 ) uses aerodynamics
to compute the efficiencies and characteristics of radial compres-
sors and turbines.
Laboratory Equipment. Many of the difficulties involved in
the study of flow patterns and of high velocity flow are derived
from the lack of instruments capable of making the necessary
measurements. Solutions of these difficulties are frequently com-
plex, but also occasionally ingeniously simple.
Taylor (300) described the N.A.C.A. method of visualizing air
flow patterns by injecting finely divided balsa wood, while
Hagerty (115)utilized an optical property of glycerol-water solu-
tions to study viscous fluid flow problems. Ducker (86) describes
a graphic method for local pressure determination in nonbranch-
ing gas lines. Bleakney and Taub (4.6) describe the shock tube-a
simple device for creating and studying plane shock waves. Two
articles (6,187)describe wind tunnel equipment, and a n article by
Poritsky and co-workers (181) describes various methods of
studying two-dimensional and axially symmetrical compressible
flow. Ivey (148) presents a mechanical analogy for flows in the
hypersonic range (velocities five or more times greater than t h a t
of sound), while Becker ( 3 2 ) gives a brief review of N.A.C.A.
work on hypersonic speeds, flow visualization at pressures below
which schlieren techniques fail, and unsteady flows. Two other
papers describe schlieren equipment. The first (16) gives an ele-
mentary description of the General Electric Company’s inte-
grated schlieren light source, and the other (166) describes a
sharp-focusing schlieren source which permits study in different
planes parallel to the flow.
Miscellaneous. High velocity flow in open channels waa the
subject of a symposium by Ippen et al. (147). Gas flow in pipe
lines and deviations from ideal behavior were discussed by Owen
(216). Gundersen (193) wrote on flow measurement methods in
particular and summation of two or more flows. A theoretical
discussion of the use of models for solution of problems in fluid
dynamics was given by Barth (28). In a series of two papers
Burrows (66) described the logarithmic vector charts of Eiffel
and discussed application t o flow of liquids in full pipe lines.
Hubbard (149)proposed use of the electrical analogy method in
fluid mechanics research. Leaf and Atchison (183)have outlined
how colloidal clay solutions can be used in gas flow studies. Air
investigation of drainage of bubble cap columns was reported by
Huitt et al. (14.6); a theoretical paper discussing Bernoulli’s
theorem in relation t o viscous compressible flow was contributed
by Truesdell (307); Witty (336)wrote on gas flow in vacuum
systems; and Joffe (163) discussed storage capacity in long
natural gas pipe lines.
Rhodebush (24.4) wrote on dynamics of gas flow with emphasis
on supersonic motion and shock waves. A mathematical discus-
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diffusivity, the residence time was calculated, was contributed by
Bosworth (47).
Books by Binder (41), Scott-Blair (271), Prandtl (232),
Richardson (245),Schlag (263),Kochin (171),and Jaeger (150)on
fluid mechanics, dynamics of real fluids, and hydro- and aerody-
namics appeared.
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(314)Veronese, L4.,Energia Elett., 25,638-41 (1948).
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(1950).
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(317)Viand, L., Rec. Aeronaut. Paris, 8,53-62 (March/April 1949).
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(322)U‘aeser, B., Chem. Ing. TechnoZ., 21,461-3(1949).
(323)Wagon, H., 2. Ver. deut. Ing., 92,No. 21,577-80 (July 1950).
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(1950).
(326)Weisman, J., and Bonilla, C. F., IND. ENG.CHEM.,42,1099-
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(327)Weisz, P. B., U. S.Patent 2,485,424 (Oct. 18,1949).
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(334)Williamson, R. H.,and Garside, J. E., Gas WorEd, 130,
1999-2001 (1949); 131,119-25(1950).
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY
(335)Witty, R., J . Sci. Instruments, 26, No. 9, 316 (September
1949).
(336)Wolfe, 0.. Oil Gas J., 48, 189, 191-5 (Oct. 6, 1949); 91-4
(Oct. 13,1949);94-5 (Oct. 20,1949).
(337) Wolosewick, F.E.,PelroEeum Refiner, 29,No.5, 146-50 (1950).
(338)Worcester, W. E.,Ibid., 29,No.2,115-21 (1950).
(339)Work, C.W., Ibicl., 29,No. 8,89-90 (1950).
(340)Wright, J. C.,OiE Gas J., 48,99,101,102-3(March 16,1950).
f.
ms GEORGE T. SKAPERDAS
THE M,W. KELLOGG CO., NEW YORK 7, N. Y .
The last review period was marked by the appearance of an increased number of books on
heat transfer and also b y a number of excellent general papers treating various theoretical
aspects of heat transfer and other transfer processes, and the similarities between them. Un-
classified work associated with various phases of the nuclear energy effort appeared in sub-
stantial amount and much information was also added to the literature in the fields of con-
vection, boiling, condensatlon, conduction, industrial applications, and thermometry.
T
HE significant recent advances in heat transfer have been
reviewed and analyzed by McAdams (60) ; he also indicated
the fields in which further developments are needed. A
study of the theory of turbulence and its applications to fluid
friction, heat transfer, and mass transfer has been presented by
Sherwood (78). The similarities of these three transfer processes
were illustrated by the simple interrelationships of experimental
data, except for the case of fluid friction when skin friction is but
a small portion of total drag. A psychrometric study, including
theory and test data for “wet bulbs” made of volatile solids, was
presented by Bedingfield and Drew (6). Maisel and Sherwood
(63)measured evaporation rates of liquids from planes, cylinders,
spheres, and disks into a turbulent flow of air. In both of these
investigations good agreement was obtained between heat and
mass transfer. Ruhemann (69) investigated transfer of heat
and matter in an ammonia absorber, and in the case of fiuidized
beds, Kettenring, Manderfield, and Smith (48) measured heat
transfer and diffusion coefficients between air and alumina or
silica powder, presenting heat transfer coefficientscalculated from
a temperature difference integrated against bed depth. The heat
transfer coefficients were found to increase more rapidly with
mass velocity in fluidized beds than has been observed with fixed
beds.
A book by Kern (@), specifically directed to heat transfer appli-
cations in the process industries and characterized by the inclusion
r
of numerous, fully worked-out design problems, particularly for the
petroleum industry, has been published. Dusinberre (24) has
discussed the application of numerical methods to the solution of
conduction problems for which analytical solutions for steady
and transient flow become too unwieldy for general engineering
* use. A general study of thermal insulation was provided by
Wilkes (sa), and an expanded, second edition of the book by
Jakob and Hawkins (38)on elements of heat transfer and insula-
tion has been issued. An “Introduction to the Transfer of
Heat and Mass” was published by Eckert (66)and a book on heat
and temperature measurement by Weber (81) is available. An
English book on heat transfer by Fishenden and Saundera (97)
and a German book by Kiihne (61) dealing with the fundamentals
of calculation of surface requirements in heat exchangers have
been published. Although not listed in these reviews when the
“Heat Transfer Notes” first appeared, attention is drawn to
this extensive book of lecture notes that was prepared for graduate
instruction by Boelter et al. (9). Theoretical considerations are
99
(341)Wright, R. E.,IND.ENCI. CHEM.,42,81A-82A(July 1950).
(342) Yates, c. F., Gus Age, 104,25-30 (Dec. 22,1949).
(343) York, J. E.,Heating and Ventilating, 47, No. 5, 57-60 (1950);
NO.6,92-4(1950).
(344) Young, 3. W., Millet, H. M., and Pierce, A. G., Petroleum
Eng., 22B,45,48,51 (February 1950).
RECEIVED November 1, 1950. Published by permission of Director, Bureau
of Mines, Washington, D. C .
HEAT TRANSFER
treated thoroughly, and illustrative
examples are included.
Heat transfer work, stimulated by
the atomic energy program, was pre-
sented in at least three unclassified
publications. In a paper illustrated
with many examples related t o
nuclear energy, Bonilla (10) pre-
sented a concise review of the principles of steady state and
transient conduction, followed by convection and considera-
tions of pressure drop. A series of lectures sponsored by
NEPA (Nuclear Energy for the Propulsion of Aircraft) was com-
piled by Cowen (19). The subjects covered were: elements of
heat transfer by Stoever; high-density heat fluxrto water by
McAdams; calculation of conduction by Dusinberre; measure-
ment of changing temperature by Hawkins; recovery factors bv
Emmons; pressure drop in commercial exchangers by Short;
velocity gradient at a tube wall by Miller; boiling water by
Scorah; equipment by Coons; network analyzers by Bubb;
heat transfer to granular materials by Pigford; solar radiation by
Marco; infrared radiation by Garber; gravitational diffusion
by Rouse; heat transfer a t sonic velocities by Keenan; thermo-
dynamics of flow by Shapiro; radiation by Hottel; condensation
by Colburn; fixed bed converters by Wilhelm; aircraft exchangers
by Valerino; boiling under pressure by Bonilla; finned tubes by
Katz; alloys by Freeman; tubular exchangers by Bergelin;
recirculating atmosphere furnaces by Siebert; fundamental con-
siderations by Boelter; molten metals by Martinelli; and seg-
mentally baffled shell and tube exchangers by Tinker. Though
some of these papers have been published elsewhere, other im-
portant data are available for the first time in this compilation.
A handbook on liquid metals by Lyon (69) reflects the possible
use of liquid metals as heat transfer fluids where the extremely
high heat transfer rates of liquid metals would be important.
CONVECTION
Local heat trangfer coefficients for superheating steam were
determined by McAdams, Kennel, and Addoms (61) for several
sections of an electrically heated vertical annulus (0.25 and 0.382
inch in diameter and 12.3 inches long). The wide range of condi-
tions studied included pressures froni 115 to 3500 pounds per
square inch absolute, temperatures from 430’ to 1000° F., and
temperature differences of 100’ to 620’ F. The data were corre-
lated in terms of Nusselt, Prandtl, and Reynolds numbers, and
length t o diameter ratio, using the equivalent diameter and
properties a t the film temperature. With new thermal conduc-
tivities of steam, the maximum deviation of 212 points from the
resulting correlation was 17%. More data from the comprehen-
sive program for coefficients through tube banks became available
in a paper by Bergelin et al. (7). The present results showed that,
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY
(335)Witty, R., J . Sci. Instruments, 26, No. 9, 316 (September
1949).
(336)Wolfe, 0.. Oil Gas J., 48, 189, 191-5 (Oct. 6, 1949); 91-4
(Oct. 13,1949);94-5 (Oct. 20,1949).
(337) Wolosewick, F.E.,PelroEeum Refiner,29,No.5, 146-50 (1950).
(338)Worcester, W. E.,Ibid., 29,No.2,115-21 (1950).
(339)Work, C.W., Ibicl., 29,No. 8,89-90 (1950).
(340)Wright, J. C.,OiE Gas J., 48,99,101,102-3(March 16,1950).
f.
ms GEORGE T. SKAPERDAS
THE M,W. KELLOGG CO., NEW YORK 7, N. Y .
The last review period was marked b y the appearance of an increased number of books on
heat transfer and also b y a number of excellent general papers treating various theoretical
aspects of heat transfer and other transfer processes, and the similarities between them. Un-
classified work associated with various phases of the nuclear energy effort appeared in sub-
stantial amount and much information was also added to the literature in the fields of con-
vection, boiling, condensatlon, conduction, industrial applications, and thermometry.
T
HE significant recent advances in heat transfer have been
reviewed and analyzed by McAdams (60) ; he also indicated
the fields in which further developments are needed. A
study of the theory of turbulence and its applications to fluid
friction, heat transfer, and mass transfer has been presented by
Sherwood (78). The similarities of these three transfer processes
were illustrated by the simple interrelationships of experimental
data, except for the case of fluid friction when skin friction is but
a small portion of total drag. A psychrometric study, including
theory and test data for “wet bulbs” made of volatile solids, was
presented by Bedingfield and Drew (6). Maisel and Sherwood
(63) measured evaporation rates of liquids from planes, cylinders,
spheres, and disks into a turbulent flow of air. In both of these
investigations good agreement was obtained between heat and
mass transfer. Ruhemann (69) investigated transfer of heat
and matter in an ammonia absorber, and in the case of fiuidized
beds, Kettenring, Manderfield, and Smith (48) measured heat
transfer and diffusion coefficients between air and alumina or
silica powder, presenting heat transfer coefficientscalculated from
a temperature difference integrated against bed depth. The heat
transfer coefficients were found to increase more rapidly with
mass velocity in fluidized beds than has been observed with fixed
beds.
A book by Kern (@), specifically directed to heat transfer appli-
cations in the process industries and characterized by the inclusion
r
of numerous, fully worked-out design problems, particularly for the
petroleum industry, has been published. Dusinberre (24) has
discussed the application of numerical methods to the solution of
conduction problems for which analytical solutions for steady
and transient flow become too unwieldy for general engineering
* use. A general study of thermal insulation was provided by
Wilkes (sa), and an expanded, second edition of the book by
Jakob and Hawkins (38)on elements of heat transfer and insula-
tion has been issued. An “Introduction to the Transfer of
Heat and Mass” was published by Eckert (66)and a book on heat
and temperature measurement by Weber (81) is available. An
English book on heat transfer by Fishenden and Saundera (97)
and a German book by Kiihne (61) dealing with the fundamentals
of calculation of surface requirements in heat exchangers have
been published. Although not listed in these reviews when the
“Heat Transfer Notes” first appeared, attention is drawn to
this extensive book of lecture notes that was prepared for graduate
instruction by Boelter et al. (9). Theoretical considerations are
99
(341)Wright, R. E.,IND.ENCI. CHEM.,42,81A-82A(July 1950).
(342) Yates, c. F., Gus Age, 104,25-30 (Dec. 22,1949).
(343) York, J. E.,Heating and Ventilating, 47, No. 5, 57-60 (1950);
NO.6,92-4(1950).
(344) Young, 3. W., Millet, H. M., and Pierce, A. G., Petroleum
Eng., 22B,45,48,51 (February 1950).
RECEIVED November 1, 1950. Published by permission of Director, Bureau
of Mines, Washington, D. C .
HEAT TRANSFER
treated thoroughly, and illustrative
examples are included.
Heat transfer work, stimulated by
the atomic energy program, was pre-
sented in at least three unclassified
publications. In a paper illustrated
with many examples related t o
nuclear energy, Bonilla (10) pre-
sented a concise review of the principles of steady state and
transient conduction, followed by convection and considera-
tions of pressure drop. A series of lectures sponsored by
NEPA (Nuclear Energy for the Propulsion of Aircraft) was com-
piled by Cowen (19). The subjects covered were: elements of
heat transfer by Stoever; high-density heat fluxrto water by
McAdams; calculation of conduction by Dusinberre; measure-
ment of changing temperature by Hawkins; recovery factors bv
Emmons; pressure drop in commercial exchangers by Short;
velocity gradient at a tube wall by Miller; boiling water by
Scorah; equipment by Coons; network analyzers by Bubb;
heat transfer to granular materials by Pigford; solar radiation by
Marco; infrared radiation by Garber; gravitational diffusion
by Rouse; heat transfer a t sonic velocities by Keenan; thermo-
dynamics of flow by Shapiro; radiation by Hottel; condensation
by Colburn; fixed bed converters by Wilhelm; aircraft exchangers
by Valerino; boiling under pressure by Bonilla; finned tubes by
Katz; alloys by Freeman; tubular exchangers by Bergelin;
recirculating atmosphere furnaces by Siebert; fundamental con-
siderations by Boelter; molten metals by Martinelli; and seg-
mentally baffled shell and tube exchangers by Tinker. Though
some of these papers have been published elsewhere, other im-
portant data are available for the first time in this compilation.
A handbook on liquid metals by Lyon (69) reflects the possible
use of liquid metals as heat transfer fluids where the extremely
high heat transfer rates of liquid metals would be important.
CONVECTION
Local heat trangfer coefficients for superheating steam were
determined by McAdams, Kennel, and Addoms (61) for several
sections of an electrically heated vertical annulus (0.25 and 0.382
inch in diameter and 12.3 inches long). The wide range of condi-
tions studied included pressures froni 115 to 3500 pounds per
square inch absolute, temperatures from 430’ to 1000° F., and
temperature differences of 100’ to 620’ F. The data were corre-
lated in terms of Nusselt, Prandtl, and Reynolds numbers, and
length t o diameter ratio, using the equivalent diameter and
properties a t the film temperature. With new thermal conduc-
tivities of steam, the maximum deviation of 212 points from the
resulting correlation was 17%. More data from the comprehen-
sive program for coefficients through tube banks became available
in a paper by Bergelin et al. (7). The present results showed that,
100 INDUSTRIAL AND ENGINEERING CHEMISTRY
at a given pumping power loss, heat transfer decreased with pitch
and with tube diameter, and that the highest coefficients are ob-
tained with the smaller tubes and tube pitches in staggered ar-
rangements. Though a volumetric equivalent diameter appeared
useful in correlating heat transfer and pressure drop data, no
final correlations were presented in this paper. A more empirical
analysis of shell-side coefficient, based on literature data, was pre-
sented by Donohue (9@, who found that the coefficient could be
correlated satisfactorily using the geometric mean of a cross-flow
and longitudinal-flow mass velocity between baffles and through
baffle openings, respectively, for baffled shells. A correlation of
available heat transfer data was also presented for unbaffled
ahells, and pressure drop correlations were included for both types
of shells.
Another presentation of data on heat transfer to water at
high rates with and without surface boiling was offered by Kreith
and Summerfield ( & I ) , who reported that temperature difference
between the mall and the saturation temperature, rather than the
bulk temperature of the fluid was an important correlating vari-
able. In another paper (49)the same authors presented further
data on surface boiling for aniline saturated with water and for
dry butyl alcohol. Though not conclusively demonstrated, it
appeared that surface boiling, and the resulting high coefficients,
occur when the surface temperature exceeds the bubble point of
the liquid. It was also observed that after the onset of surface
boiling, heat flux was an additional variable affecting pressure
drop.
Analytical papers were presented by Seban (71) on heat trans-
fer for a turbulent flow of fluid between parallel walls, and by
Harrison and Menke (38),who made use of the data of Xikuradse
in setting u p a theory for heat transfer to liquid metals flowing in
channels heated asymmetrically.
Heat transfer of interest in fixed-bed reactors was studied in
three papera. Singer and Wilhelm (74) set up a four-step mecha-
nism for heat transfer from a gas to the walls of a packed tube.
It was assumed that heat would flow to the tube wall by con-
duction in the fluid phase, by particle-contact transfer, by solid-
to-fluid transfer, and by fluid transport. The appropriate rela-
tionships were derived and they were checked against experi-
mental data. Good agreement was obtained. Verschoor and
Schuit (SO)obtained data for steam heating of air in a vertical
tube packed with glass spheres, steel and lead balls, pumice, and
cylindrical terrana pellets. One run was also made xith hydro-
gen. The data were correlated on the basis of an equivalent
conductivity of fluid in the empty tube, and a Reynolds number
was calculated using a “diameter” equal to the volume per unit
of partide surface. In general, these Dutch results agreed well
with available American data. Heat exchange in packed re-
actors was analyzed mathematically by Munro and Amundson
(67).
Heat transfer in agitated, jacketed cast iron vessels was
investigated by Brown et al. ( 1 4 ) ; Inglesent and Storrow (37‘)
presented data on the coefficients from a coil to unstirred water.
Heat transfer and pressure drop data were presented by itIc-
Mahon et al. (66) for a new type of heat exchanger which was
developed for low temperature service. This exchanger is com-
posed of perforated aluminum plate8 held together with neoprene
gaskets. It was found that the heat transfer coefficient varied
with Reynolds number raised to an index between 0.9 and 1.14.
Ahsmann and Kronig (I) reported that the convection heai
transfer coefficient between an axial wire and a tube was increased
by the imposition of an electric field.
Stalder et al. (76) and Wimbrow (85) measured temperature
recovery factors for a flat plate and for bodies of revolution,
respectively, a t supersonic speeds. Heat transfer measurements
a t supersonic velocities were made by Scherrer and Gowen (70)
for a 20’ cone and by Wimbrow and Scherrer (86) on a body of
revolution based on a parabola. Both investigations agreed with
theoretical predictions for cones. Klunker and Ivey (46) ana-
Vol. 43, No. 1
lyzed the possible reduction of aerodynamic heating by injection
of coolant into the boundary layer (sweat cooling), and Jakob
et aZ. (39) studied heat transfer from an air jet to a plate simulatc
ing aircraft windshield icing,
Middlebrook and Piret (64) described the elimination of elec-
trolysis in hot wire anemometry applied to water.
BOILING
Larson et al. (63) presented some data on the effect of a spiral
turbulence promoter on the evaporation of Freon-12 inside hori-
zontal tubes. The effect of additional turbulence on boiling was
also studied by Haselden and Peters (33), who boiled liquid
oxygen and nitrogen from horizontal and vertical tubes. The
boiling coefficient was observed to rise rapidly with temperature
difference, and mechanical agitation increased the coefficient
a t low temperature differences; however, this increase became
smaller as temperature difference increased, disappearing at a
temperature difference of 7 ” F.
Bromley (19)presented a theory and supporting experimental
data for film boiling from a horizontal tube in the stable fiIm
range a t temperature differences much greater than the critical
value. These conditions, which normally are avoided in process
work, do provide stability for increases in heat removal because,
even a t high fluxes, the flux increases with temperature difference.
Such stability is absent in nuclear boiling close to the critical
temperature difference, where a small temperature difference in-
crease may cause vapor binding and a sharp decrease in heat
removal.
The effect of surface tension in boiling heat transfer was studied
by Morgan et al. (65) Scaling of evaporator surfaces was studied
by Langelier et al. (59) for sea water distillation, and by Vener and
Thompson (79) for evaporation of aodium sulfate solutions.
CONDENSATION
Haselden and Prosad (34) condensed oxygen and nitrogen on
the outside of small vertical tubea and got data that agreed well
with the Nusselt equation. Preliminary results on mixtures of
oxygen and nitrogen, after an allowance for temperature drop in
the vapor film next to the condensate layer, were found to lie
between the data for the pure components. Guter (SI) con-
densed nitrogen inside small vertical tubes and found t h a t upward
flow of vapor into a single condensing tube resulted in sharply
limited coefficients when free vapor entry into the tube was
blocked by condensate held up in the tube. This could be avoided
by downward vapor flow, which was also obtained by operating
tubes in parallel with the top ends opening into one common
space.
Fatica and Katz (26) presented an analytical paper on dropwise
condensation and Silver (73) studied cooling of gases with con-
densation of contained water. Gloyer (30)presented a detailed
empirical design procedure for condensers in petroleum applica-
tions and for coolers in compressor stage cooling service.
CONDUCTION
New thermal conductivity data were presented by Keyes
(M) for steam up to 150 atmospheres, and by Keyes and Sandell
(46)for steam and nitrogen up to the same pressure. These new
data were somewhat lower than recent Russian data in the case
of steam, but agreement was better for nitrogen. Lindsay and
Bromley (66)presented a correlation for the thermal conductivity
of gas mixtures, and Beatty et al. (4) reported a rapid, rigorous,
unsteady-state method of determining thermal conductivity
data for homogeneous materials. British specifications and
recommendations ( l a ) on thermal insulating materials between
200° and 450’ F. were published, and Prim et al. (68) studied
conductivity of fixed beds of powders experimentally and found
that the conductivity dropped as the pressure of hydrogen, air,
or carbon dioxide was decreased to 0.1 mm. of mercury.
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY
The theory of heat transfer t o surfaces buried in the earth, as
in heat-pump applications, was discussed by Ingersoll e2 aZ. ($6)
and the problem of radiant heating from tubes embedded in slabs
was studied on the “analogger” by Kayan (Q), and also by
Bridgers (11).
A numerical method for steady-state conduction through a
wall, based on first satisfying boundary conditions and then
checking the internal flow pattern, was illustrated by Lutz
(68).
INDUSTRIAL APPLICATIONS
I n the low temperature field, a system for cooling and purify-
ing partially dried air to liquefaction temperatures, using periodic
thawing cycles in duplicate exchangers, was described by Craw-
ford (do), and a perforated plate exchanger for reversing ex-
changer use was discussed by Williams (84). Reference may also
5
be made to a n older paper by Hausen (86),who presented a
mathematical study and experimental data for regenerators
used in air liquefaction service.
For higher temperature service, London and Kays (66) pre-
c sented a discussion on the use of compact, plate-& extended
surfaces for gas turbine regenerators, and Dinan (81) reported
heat transfer and flow friction data for plate and louvered fin
surfaces and plate and pin-fin surfaces for gas turbines suitable
for naval shipboard installation. Heat exchange equipment for
a 5000-kw. gas turbine generator was described by Fusner (88);
Trumpler et al. (77) discussed some advantages for cooling in-
corporated into a centrifugal compressor.
In the case of the more usual process exchangers, a new edition
of the Standards of the Tubular Exchanger Manufacturers’
Association was published (78). I n a comprehensive symposium
on the problem of fouling of industrial exchange equipment,
John (40) described mechanical cleaning and Loucks and
Groom (67) described chemical cleaning of fouled exchangers.
Discussions were presented by Dougherty and Brooks (23) for
cleaning tubular heat exchangers, by Butler and McCurdy (16)
for refinery exchangers, and by Weiland et al. (82) for unfired
heat exchangers. Scale formation and control in compression
distillation of sea water was studied by Campobasso and
Latham (16),and fouling of marine heat exchangers was de-
scribed by Bethon (8). The symposium included a panel dis-
cussion led by Bergelin (6).
Laughrey et al. (64) described designs of paste preheaters and
exchangers in a demonstration coal hydrogenation plant and
Bearer et al. (8) presented results of tests of ceramic pebbles
to determine suitability for pebble heater service. Typical of a
number of recent German papers is one by Kuhne (60) in which
methods of evaluatjng heat exchangers are set up. Garber and
Tiller (29)reported further work on infrared heating and Cor-
firld (18) reviewed various heat transfer fluids.
THERMOMETRY
Morgan and Danforth (66) described and tested thermo-
couples using tungsten, tantalum, and molybdenum for service
up t o 3000”C., and Allen and Hrtmm (2)reported on a pyrometer
- for measuring total temperature in low density gas streams.
Experimental data were obtained by Carbon et al. (17) €or the re-
sponse of fine wire thermocoupIes in air, and Kolomiets and
Scheftel (47) proposed the use of a semiconductor, such as
uranium oxide, in resistance thermometry. Smith (76) pre-
sented a paper on heat conduction errors in temperature measure-
ments using wells.
LITERATURE CITED
(1) Ahsmann, G., and Kronig, R., Applied Sci. Research, A2, 235
(1950).
(2) Allen, S., and Hamm, J. R., Trans. Am. SOC.Mech. Engrs., 72,
851 (1950).
(3) Bearer, L. C., Findlay, R. A., and Goins, R. R., Petroleum
Refiner, 28, No. 12, 104 (1949).
101
(4) Beatty, I(.O., Armstrong, A. A., and Schoenborn, E. M., IND.
ENQ.CHEM.,42, 1527 (1950).
(5) Bedingfield, C. H., and Drew, T. B., Zbid.,42,1164 (1950).
(6) Bergelin, 0. P., Trans. Am. SOC.Mech. Engrs., 71, 871 (1949).
(7) Bereelin. 0. P.. Brown. G. A.. Hull. H. L.. and Sullivan. F. W..
, --,- - -
Bethon, H. E., Z b k , 71, 855 (1949).
Boelter, L. M. K., Cherry, V. H., Johnson, H. A., and Marti-
nelli. R. C.. “Heat Transfer Notes,” Berkeley and Los
Angeles, Univ. of California Press, 1946.
Bonilla, C. F., Oak Ridge National Laboratory, Tech. Inform.
Div., M-4476 (1949).
Bridgers, F. H., Trans. Am. SOC.Mech. Engrs., 72, 341 (1950).
British Standards Inst:, London, S.W. 1, Brit. Standard 1588
(1949).
Bromley, L. A., Chem. Eng. Progress, 46, 221 (1950).
Brown, R. W., Scott, R., and Toyne, C., Trans. A m . Inst.
Chem. Engrs., 25, 181 (1947).
Butler, R . C., and McCurdy, W. N., Jr., Trans. A m . SOC.Mech.
Engrs., 71, 843 (1949).
Campobasso, J . J., and Latham, A., Jr., Ibid., 71, 837,(1949).
Carbon, M. W., Kutsch, H. J., and Hawkins, G. A., Zbid.,
72, 655 (1950).
Corfield, G., Gus,26, No. 2, 19 (1950).
Cowen, D., “Heat Transfer Lectures,” NEPA Division, Fair-
child Engine and Airplane Corp., Oak Ridge, Tenn.
Crawford, D. B., C h a . Eng. Progress, 46,74 (1950).
Dinan, J. J., “Report on Investigation of Basic Heat Transfer
and Flow Friction Data for Gas Turbine Plant Regenerator
Surfaces,” U. S. Naval Eng. Expt. Sta., Annapolis, Md.,
June 24, 1948.
Donohue, D.A., IND. ENG.CREM.,41,2499 (1949).
Dougherty, P. F., and Brooks, C. H., Trans. Am. Sac. Mech.
Engrs., 71, 839 (1949).
Dusinberre, G. M . , “Numerical Analysis of Heat Flow,” New
York, McGraw-Hill Book Co., 1949.
Eckert. E.. “Introduction to the Transfer of Heat and Mass,”
New York, McGraw-Hill Book Co., 1950.
Fatica, N., and Katz, D. L., Chem. Eng Progress, 45, 661 (1949).
(27) Fishenden, M., and Saunders, 0. A., “An Introduction to
Heat Transfer,” London, Oxford University Press, 1950.
(28) Fusner, G. R., Mech. Eng., 72,316 (1950).
(29) Garber, H. J., and Tiller, F. M., IND.ENG. CHEM.,42, 456
(1950).
(30) Gloyer, W., Ibid., 42, 1361 (1950).
(31) Guter, M., Inst. Chem. Engrs, and Low Temp. Group of the
Phys. SOC.(London),Advance Copy, Nov. 8,1949.
(32) Harrison, W. B., and Menke, J. R., Trans. Am. SOC.Meck.
Engrs., 71, 797 (1949).
(33) Haselden, G. G., and Peters, J. I., Inst. Chem. Engrs. and Lou,
Temp. Group of the Phys. SOC. (London), Advance copy,
Nov. 8, 1949.
(34) Haselden, G. G., and Prosad, S., Ibid., Nov. 8 , 1949.
(35) Hausen, H., 2. Ver. deut. Ing., Verfuhrenstech.,1942, 31.
(36) Ingersoll, L. R., Adler, F. T., Plass, H. J., and Ingersoll, A. C.,
Healing, Piping, Air Conditioning, 22, N o . 5, 113 (1950).
(37) Indesent, H., and Storrow, J. A., Ind. Chemist, 26, 313 (1950).
(38) Jakob, Max, and Hawkins, G . A., “Elements of Heat Transfer
and Insulation,” 2nd ed., New York, John Wiley & Sone, 1950.
(39) Jakob, M., Rose, R. L., and Spielman, M., Trans. Am. SOC,
Mech. Engrs., 72, 859 (1950).
(40) John, A,, Ibid., 71, 825 (1949).
(41) Kasan, C. F., Heating, . Pipino,
. Air Conditioning, 22, No. 5,
123 (1950).
(42) Kern, D. Q., “Process Heat Transfer,” New York, McGraw-
Hill Rook Co.. 1950.
(43) Kettenring, K. N., Manderfield, E. L., and Smith, J. M.,
Chem. Eng. Progress, 46, 139 (1950).
(44) Keyes, F. G., J. Am. Chem. SOC.,72,433 (1950).
(45) Keyes. F. G.. and Sandell. D. J., Trans. Am. SOC.Nech. Engrs.,
72, 767 (1950).
(46) Klunker, E. B., and Ivey, H. R., Natl. Advisory Comm. Aero-
naut., Tech. Note 1987 (December 1949).
(47) Kolomiets, B. T., and Soheftel, I . T., Zhur. Tekh. Fiz., 17,:1106
(1947).
(48) Kreith, F., and Summerfield, M . , Trans. A m . SOC.Mech. Engrs.,
71, 805 (1949).
(49) Ibid., 72, 869 (1950).
(50) Kuhne, H., Chmie-Ing.-Tech., 22, 168 (1950).
(51) Ktihne, H., “Die Grundlagen, der Berechnung von Oberflllcher-
Warmeaustauschern,” Gottingen, Vandenhoech and R u p >
recht, 1949.
(52) Langelier, W. F., Caldwell, D. H., Lawrence, W. B., and Spauld.
ing, C. H., IND. ENG.CHEM.,42, 126 (1950).
(53) Larson, R. L., Quaint, G. W., and Bryan, W . L., Refrig. Eng.,
57. 1193 (1949).
102 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY Vol. 43, No. 1

(54) Laughrey, P. TI’., Gwillim, W. I., Schappert, H., and Marko-
vits, J. A., Trans. Am. SOC.Mech. Engrs.. 72, 385 (1950).
(55) Lindsay, A. I,., and Bromley, L. A,, IND. END..CHEM.,42,
1508 (1950).
(56) London, A. L., and Kays, W. M., Trans. Am. Soc. Mech. Engrs.,
72, 611 (1950).
(57) Loucks, C . hf., and Groom, C. H., Ibid., 71, 831 (1949).
(58) Lutz, O., Natl. Advisory Comm. Aeronaut., Tech. Memorandum
1280 (April 1950).
(59) Lyon, R. X . , “Liquid Metals Handbook,” Department of
Navy and Atomic Energy Commission, 1950.
(60) McAdams, TV. H., Chem. Eng. Progress, 46, 121 (1950).
(61) McAdams, W-.H., Kennel, W. E., and Addoms, J. N., Trans.
Am. SOC.Mech. Engrs., 72, 421 (1950).
(62) McMahon, H. O., Rowen, R. J., and Bleyle, G. A., Jr., Ibid.,
72, 623 (1950).
(63) Maisel, D. S., and Sherwood, T. K., Chem. Eng. Progress, 46,
131 (1950).
(64) bliddlebrook, G. B., and Piret, E. L., IND.ENG.CHEM.,42,
1511 (1950).
(65) Morgan, A. I., Bromley, L. -1..a n d TYilke, C. R., Ibid., 41, 2767
(1949).
(66) Morgan, F. H., and Danforth, W. E., J . Applicd Phgs., 21,
112 (1950).
(67) Munro. W. D.. and Amundson, N. R.. IND.ENG. CHEM.,
. I
(70) Scherrer, R., and Gowen, F. E.. Natl. Advisory Comm. Aero-
naut., Tech. N o t e 2087 (May 1950).
(71) Seban, R. A., Trans. Am. Soc. Mech. Engrs., 72, 789 (1950).
(72) Sherwood, T. K., IND.ENG.CHEM.,42, 2077 (1950).
(73) Silver, L., Trans. Am. Inst. Chem. Engrs., 25, 30 (1947).
(74) Singer, E., and Wilhelm, R. H., Chem. Eng. Progress, 46, 343
(1950).
(75) Smith, L. E., Trans. Am. Soc. iMech. Engrs., 72, 71 (1950).
(76) Stalder, J. R., Rubesin, M. W.,and Tendeland, T., Satl.
Advisory Comm. Aeronaut., Tech. N o t e 2077 (June 1950).
(77) Trumpler, W. E., Frederick, R. TV., and Trumpler, T’. R.,
Trans. Am. Soc. iMech. Engrs., 72, 797 (1950).
(78) Tubular Exchanger Manufacturers’ Assoc., “T.E.M.A. Stand-
ards,” New York, 1949.
(79) Vener, R. E., and Thompson, A. R., IND. ENG.CHEM.,42, 464
(1950).
(80) Verschoor, H., and Schuit, G. C. A, Applied Sci. Research, A2,
97 (1950).
(81) Weber, R. L., “Heat and Temperature AMeasurement,” New
York, Prentice-Hall, Inc., 1950.
(82) Weiland, J. H., hfcCay, R. C., and Barnes, J. E., Trans. A m .
Soc. Mech. Engrs., 71, 849 (1949).
(83) TVilkes, G. B., “Heat Insulation,” New York, John ’Wiley Bi
Sons, 1950.
(84) Williams, R., Jr., Chet/b. Knq., 56, No. 12, 104 (1949).
(85) W5mbrow. W7. R., Natl. Advisory Comm. Aeronaut.. Tech.

42, 1481 (1950).

(68) Prins, J. A., Schenk, J., and Schram, A. J. G. L., Physica, 16,
Note 1975 (October 1949).
(86) Wimbrow, W’. R., and Scherrer, R., Ibid., 2148 (August 1950).
379 (1950).
(69) Ruhemann, M., Trans. Am. Inst. Chem. Engrs., 25, 158 (1947). REOEIVED
October 25, 1950.

EXCHANGE .________

ROBERT KUNIN
ROHM & HAAS CO., PHILADELPHIA, PA.

During the past three years, interest in ion exchange applications outside the water condi- erties. These materials have opened
tioning field has increased markedly, largely through the introduction of durable, high capacity many new fields of application to
resins having a wide range of properties. Various investigators have attempted to explain the newly recognized unit opera-
the mechanism of ion exchange without developing as yet a universally accepted theory. tion, ion exchange. There is scarcely
Studies have included the application of ion exchange in water softening, such as its use in a field of chemistry and chemical
removing residual hardness from the effluent of a hot lime-soda process. The use of ion ex- engineering that has not found this
change in deionizing photographic wash water, in the production of formaldehyde, in the unit operation of interest.
recovery of milk products, and in the sugar, ceramics, and beverage industries has received
attention. Ion exchange permits the separation of rare earth metals, amino acids, ribonu- REVIEWS
cleotides, and fission products and may also serve as an analytical tool and as a catalyst.
Biological applications include sodium reduction therapy, the treatment of ulcers, and the
During the year, several note-
reduction of the acute toxicity of atropine.
worthy reviews on ion exchange
have appeared that are of con-
siderable interest from both an in-

A
REVIEW of the developments made in the field of ion ex-
change during the past year takes on an added significance
in that the year 1950 marks the hundredth anniversary of
the f i s t publications of Thompson and Way, two English agri-
cultural chemists generally considered the discoverers of t’he
phenomenon of ion exchange. It is of considerable interest a t
this time to trace the attention given to this unit operation over
the past years. Although the importance of a unit operation may
be measured in terms of tons of chemicals produced, dollar value
of production, or size of installations involved, another significant
measure of interest or importance of a unit operation is its wide-
spread utility. A measure of interest can be determined therefore
b y the number of publications in this field and b y the distribution
of these publications in the various industries.
The results of a study of this nature are summarized in Figure 1.
Although the data need very little explanation, two striking
points are the relatively large increase in interest during the past
3 years and the widespread interest during this period in applica-
tions outside of the water-conditioning field. These developments
are a direct result of the commercial development of high capacity
and durable ion exchange materials having a wide range of prop-
dustrial and an academic point of view. Of general interest
are the review of Myers (3?),Nachod (209), Lundberg ( l 7 9 ) ,anti
Rabek (836). Of particular importance to the water-conditioning
field are the review of Kahler and Wantz (154), Siebel ($70),
Fleisher (96), and Hertz (131). Summaries of applications in the
various industries have been prepared by Austerneil (12, 13),
Demmerle (69),Futlerknecht (102), Wesly (304), and Cerriia
(45). I n England, an editor (187) presented a review of recrnt
developments in ion exchange rpsins and techniques. A most
interesting popularized review of ion exchange has been prr-
sented in the Corrosion Reporter. (61), an industrial house organ,
including an excellent discussion of the historical background of
ion exchange. Although the above reviews and summaries over-
lap considerably, they indicate conclusively the coming of age o f
ion exchange as a widely useful unit operation.
THEORY
Contributions t o the elucidation of the theory of ion exchaiige
have been many; however, a unified theory has not been univer-
sally accepted as yet. Davis ( 6 4 4 6 ) has developed further his
102 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY Vol. 43, No. 1

(54) Laughrey, P. TI’., Gwillim, W. I., Schappert, H., and Marko-
vits, J. A., Trans. A m . SOC.Mech. Engrs.. 72, 385 (1950).
(55) Lindsay, A. I,., and Bromley, L. A,, IND. END..CHEM.,42,
1508 (1950).
(56) London, A. L., and Kays, W. M., Trans. A m . Soc. Mech. Engrs.,
72, 611 (1950).
(57) Loucks, C . hf., and Groom, C. H., Ibid., 71, 831 (1949).
(58) Lutz, O., Natl. Advisory Comm. Aeronaut., Tech. Memorandum
1280 (April 1950).
(59) Lyon, R. X . , “Liquid Metals Handbook,” Department of
Navy and Atomic Energy Commission, 1950.
(60) McAdams, TV. H., Chem. Eng. Progress, 46, 121 (1950).
(61) McAdams, W-.H., Kennel, W. E., and Addoms, J. N., Trans.
A m . SOC.Mech. Engrs., 72, 421 (1950).
(62) McMahon, H. O., Rowen, R. J., and Bleyle, G. A., Jr., Ibid.,
72, 623 (1950).
(63) Maisel, D. S., and Sherwood, T. K., Chem. Eng. Progress, 46,
131 (1950).
(64) bliddlebrook, G. B., and Piret, E. L., IND.ENG.CHEM.,42,
1511 (1950).
(65) Morgan, A. I., Bromley, L. -1..a n d TYilke, C. R., Ibid., 41, 2767
(1949).
(66) Morgan, F. H., and Danforth, W. E., J . Applicd Phgs., 21,
112 (1950).
(67) Munro. W. D.. and Amundson, N. R.. IND.ENG. CHEM.,
. I
(70) Scherrer, R., and Gowen, F. E.. Natl. Advisory Comm. Aero-
naut., Tech. N o t e 2087 (May 1950).
(71) Seban, R. A., Trans. A m . Soc. Mech. Engrs., 72, 789 (1950).
(72) Sherwood, T. K., IND.ENG.CHEM.,42, 2077 (1950).
(73) Silver, L., Trans. A m . Inst. Chem. Engrs., 25, 30 (1947).
(74) Singer, E., and Wilhelm, R. H., Chem. Eng. Progress, 46, 343
(1950).
(75) Smith, L. E., Trans. Am. Soc. iMech. Engrs., 72, 71 (1950).
(76) Stalder, J. R., Rubesin, M. W.,and Tendeland, T., Satl.
Advisory Comm. Aeronaut., Tech. N o t e 2077 (June 1950).
(77) Trumpler, W. E., Frederick, R. TV., and Trumpler, T’. R.,
Trans. A m . Soc. iMech. Engrs., 72, 797 (1950).
(78) Tubular Exchanger Manufacturers’ Assoc., “T.E.M.A. Stand-
ards,” New York, 1949.
(79) Vener, R. E., and Thompson, A. R., IND.ENG.CHEM.,42, 464
(1950).
(80) Verschoor, H., and Schuit, G. C. A, Applied Sci. Research, A2,
97 (1950).
(81) Weber, R. L., “Heat and Temperature AMeasurement,” New
York, Prentice-Hall, Inc., 1950.
(82) Weiland, J. H., hfcCay, R. C., and Barnes, J. E., Trans. A m .
Soc. Mech. Engrs., 71, 849 (1949).
(83) TVilkes, G. B., “Heat Insulation,” New York, John ’Wiley Bi
Sons, 1950.
(84) Williams, R., Jr., Chet/b. Knq., 56, No. 12, 104 (1949).

42, 1481 (1950). (85) W5mbrow. W7. R., Natl. Advisory Comm. Aeronaut.. Tech.
(68) Prins, J. A., Schenk, J., and Schram, A. J. G. L., Physica, 16, Note 1975 (October 1949).
(86) Wimbrow, W’. R., and Scherrer, R., Ibid., 2148 (August 1950).
379 (1950).
(69) Ruhemann, M., Trans. A m . Inst. Chem. Engrs., 25, 158 (1947). REOEIVED
October 25, 1950.

EXCHANGE .________

ROBERT KUNIN
ROHM & HAAS CO., PHILADELPHIA, PA.

During the past three years, interest in ion exchange applications outside the water condi- erties. These materials have opened
tioning field has increased markedly, largely through the introduction of durable, high capacity many new fields of application to
resins having a wide range of properties. Various investigators have attempted to explain the newly recognized unit opera-
the mechanism of ion exchange without developing as yet a universally accepted theory. tion, ion exchange. There is scarcely
Studies have included the application of ion exchange in water softening, such as its use in a field of chemistry and chemical
removing residual hardness from the effluent of a hot lime-soda process. The use of ion ex- engineering that has not found this
change in deionizing photographic wash water, in the production of formaldehyde, in the unit operation of interest.
recovery of milk products, and in the sugar, ceramics, and beverage industries has received
attention. Ion exchange permits the separation of rare earth metals, amino acids, ribonu- REVIEWS
cleotides, and fission products and may also serve as an analytical tool and as a catalyst.
Biological applications include sodium reduction therapy, the treatment of ulcers, and the
During the year, several note-
reduction of the acute toxicity of atropine.
worthy reviews on ion exchange
have appeared t h a t are of con-
siderable interest from both an in-

A
REVIEW of the developments made in the field of ion ex-
change during the past year takes on an added significance
in that the year 1950 marks the hundredth anniversary of
the f i s t publications of Thompson and Way, two English agri-
cultural chemists generally considered the discoverers of t’he
phenomenon of ion exchange. It is of considerable interest a t
this time t o trace the attention given t o this unit operation over
the past years. Although the importance of a unit operation may
be measured in terms of tons of chemicals produced, dollar value
of production, or size of installations involved, another significant
measure of interest or importance of a unit operation is its wide-
spread utility. A measure of interest can be determined therefore
b y the number of publications in this field and b y the distribution
of these publications in the various industries.
The results of a study of this nature are summarized in Figure 1.
Although the data need very little explanation, two striking
points are the relatively large increase in interest during the past
3 years and the widespread interest during this period in applica-
tions outside of the water-conditioning field. These developments
are a direct result of the commercial development of high capacity
and durable ion exchange materials having a wide range of prop-
dustrial and an academic point of view. Of general interest
are the review of Myers (3?),Nachod (209), Lundberg ( l 7 9 ) ,anti
Rabek (836). Of particular importance to the water-conditioning
field are the review of Kahler and Wantz (154), Siebel ($70),
Fleisher (96), and Hertz (131). Summaries of applications in the
various industries have been prepared by Austerneil (12, 13),
Demmerle (69),Futlerknecht (102), Wesly (304), and Cerriia
(45). I n England, an editor (187) presented a review of recrnt
developments in ion exchange rpsins and techniques. A most
interesting popularized review of ion exchange has been prr-
sented in the Corrosion Reporter. (61), an industrial house organ,
including an excellent discussion of the historical background of
ion exchange. Although the above reviews and summaries over-
lap considerably, they indicate conclusively the coming of age o f
ion exchange as a widely useful unit operation.
THEORY
Contributions t o the elucidation of the theory of ion exchaiige
have been many; however, a unified theory has not been univer-
sally accepted as yet. Davis ( 6 4 4 6 ) has developed further his
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY
theoretical equilibrium equation by statistical thermodynamics
and has extended his theory to irregular systems and to systems
containing polyvalent ions. Krishnamoorthy and Overstreet
(162-165) have found their data on silicates and ion exchange
resins to fit this theory very well. Ekedahl, Hogfeldt, and
Sillen (89, 135, 136) have attempted to apply the Gibbs-Duhem
equation t o their cation exchange equilibrium data, assuming the
exchanger to behave as a solid solution, and have calculated the
activities of the components of the resin phase. Other ion ex-
change equilibria data and formulations have been presented by
Bhatnagar (dS), Bishop (25), Duncan and Lister (84), Gregor
(112, lis),Hamada (123), Mayer (192),and Miller (197). Char-
acterizations of ion exchangers by means of acid-base neutraliza-
tion curves have been carried out by Topp and Pepper (293) and
Gupta (116, 117) on a number of exchanger types. A complete
characterization of a strongly basic anion exchange resin has been
presented by Bauman and Wheaton (21, 306).
Considerations on the elucidation of the theory of chromatog-
raphy have been presented by Glueckauf (110), Amundsen (5),
and Gapon (103, 104) along with supporting data. Further
data t o support the ionic sieve effect in ion exchange materials
have been presented by Barrer (19, 20), Richardson (246), and
Kunin and Myers (170). Further advances in the theory of ionic
and ion exchange membranes have been made by Chatterjee and
Marshall (467, Eriksson (91),Flood and Benson (97),Jenny, Niel-
sen, Coleman, and Williams (147),Juda and McRae (161),Kress-
man (16i), Sollner (274),Wyllie and Patnode @ I S ) , and Zhukov
(310). The data obtained by Huizenga, Grieger, and Wall (140)
and Kuhn, Hargitay, Katchalsky, and Eisenberg (167) on poly-
acrylic acid systems have been helpful in explaining tho mechanism
and behavior of carboxylic acid-type cation exchange resins. A
kinetic study of isotopic exchange reactions in heterogeneous
systems has led to an equation which fails for reactions t h a t are
diffusion-controlled in the solid phase (214). Ion exchange sys-
tems involving insoluble precipitates have been studied by Grig-
orov and Tarshis (116) and Wiklander (309). An interesting
study on the thermal decomposition of the ammonium salt of ion
exchangers has been presented by Malquori and d e h g e l i s (186).
Exchange equilibria in silicates have been studied further by
Borland and Reitemeier ( 3 4 , Davydov and Lisovina (67),
Eaton (85),Mortland and Gieseking (i?O4), and Wiklander (308).
Ion exchange and other ionic equilibria have been studied for
‘various fabrics, protein, and cellular substances by several investi-
gators (33, 38, 43, 77, 90, 154, 185, 191, 192, 245, 279).
WATER SOFTENING
The water softening installation a t Los Angeles has been
described by Aultman (11), and a comparison has been made of
the performance of the inorganic gel zeolites and the polystyrene
resinous exchanger in this plant by Streicher and Bowers (282).
An interesting application of ion exchange in water softening has
t
been the removal of residual hardness from the effluent of a hot
lime-soda process using a polystyrene-type cation exchanger.
This application has been described by Page and Wantz (220)
. and Lindsay, Wirth, and Durinski (176). A review of recent
German developments in ion exchange softening has been made by
Reichelt (239, 240). The need for water softening ion exchange
Operations in several industries has been reviewed by Miedendorp
(196), Hewlett (IS$), Hammerschmidt ( 1 2 4 , and Davis (63).
The use of sea water as a regenerant has been discussed by Lind-
say (175),and the softening of sea water by ion exchange has been
studied by Juda, Kasper, and Potter (149). An economic survey
of ion exchange softening and other ion exchange’ operations has
been evaluated critically by Monet (208). Anionic softening
and total softening have been studied by Kunin and Klaas (168).
The effect of chlorine on exchanger beds and the sterilization of
water softening exchange beds has been studied by Braithwaite,
D’Amico, and Thompson (36), and Klumb, Marks, and Wilson
103
DO
?O
30
70
3
IO -
+
30
?O
‘0
0
Figure I, Distribution of Ion Exchange Publications 1907
to 1950
(168). The corrosiveness of water in water conditioning has
been reviewed by Haase (111)and the status of fluorides in waters
has been reviewed by Faber (94).
DEIONIZATION
Although over a decade old, the deionization of water by ion
exchange remains one of the most intriguing phases of ion ex-
change operations. Recent developments in this phase of the unit
operation have proved the technique to be a significant rival t o
distillation. However, a close comparison of the two unit opera-
tions, ion exchange deionization and distillation, indicates t h a t
the two unit operations will supplement each other in many in-
stances and t h a t the nature of the application will ascertain the
more suitable method of purification to be chosen. The two
modes of operation do not yield the same results. I n certain
instances, deionization by ion exchange can yield a much higher
purity than distillation; in other cases, distillation is the preferred
method.
Two large scale deionization units for industries have been
reported (48, 256). Yoder, Webb, and Baumeister (314, 315)
have compared the technical and economic aspects of ionization
evaporation and have concluded t h a t in most cases deionization is
to be preferred. Further studies on the removal of silica during
deionization have been reported by Calise and Lane (40) and
Jukkola and Roberts (162). Studies (49, 169, $00) on the mixed
bed or monobed deionization method have shown the method to
be practical on a large engineering scale; the new technique has
been preferred to the conventional mode of deionization in
many instances. Production of water having a quality of
20,000,000 ohms on an industrial scale has been achieved by
this technique. Improvements in regeneration techniques of the
ion exchange resins have been reported by Appelquest (7),
Calise (39), Gilwood and Calmon ( l o g ) , Kortschak, Gill, and
Payne (169),Mindler and Gilwood ( d o l ) , Roberts (80, 247),
and Sard (263, 864). Of considerable interest is the tech-
104 INDUSTRIAL AND ENGINEERING CHEMISTRY
nique oi Juda, Katz, and Rosenberg (150) on the use of lime to
regenerate both weak and strong base anion exchangers. Fur-
ther work has been reported (264,291) on the deionization of sea
water and brackish water. The deionization or dealkalization
ot water for the beverage industry has been considered by Hall
(122), Salac (250), Waroway (298), and Zarow (318). Gregor
and Sherman (114) have found deionization of interest for photo-
graphic wash water. Phelps (231) has considered the deioniza-
tion of water used in ceramic slip casting, and Whittaker (307) has
proposed the use of deionization for clay slurries in ceramic
applications. Eisman, Kull, and Mayer (88) have found the
deionized water obtained immediately after regeneration to be
sterile or nearly so.
The use of deionization in the various phases of sugar refining
is still receiving considerable attention. Barghi (18), Dickinson
( 7 4 , Jacobs and Rawlings ( 1 4 4 , Michener, Fitch, and Roberts
(195), Rinehart (246), Sawyer (255), and others (184) have
reported on various phases of ion exchange operation in beet
sugar refining. Henry and Clifcorn (128), Rogge (248), Taylor
(288),and others (217, 271) have studied deionization in dextrose
purification. Further studies on the use of ion exchange in sugar
have been reported by Austerweil ( 1 4 , Gayle (107), Haagensen
(110), Williams (310). and others (1-3, 215, 219, 266, 280).
Deionization in the recovery of milk products has been studied
by Gehrke and Almy (108) and Garrett (105). A palatable bev-
erage has been prepared from forage crops with the aid of deion-
ization (111). A large scale deionization plant for producing
formaldehyde has been described by Pope (233). The use of
deionization in purifying glycerol has been described by Reents
and Kahler (169, 138) and a British patent (4).
SEPARATIONS
Ion exchange continues to play an extremely important role in
the separation of ionic constituents. The technique has become a
common tool to the biochemist and the inorganic chemist inter-
ested in the rare elements. Partridge and his co-workers (221-
226), Cleaver and Cassidy (51), and others (194, 207, 269,305)
have employed ion exchange in the separation 01 the amino
acids. Cohn and his co-workers (53-58) and Loring, Luthy,
Bortner, and Levy (178) have found ion exchange most helpful
in the separation of the ribonucleotides. Cohn and Carter (58)
have separated the adenosine polyphosphates and Cohen and
McNair-Scott (53) have separated pentose phosphate from 6-
phosphogluconate with a strong base anion exchanger. Ion
exchange has been suggested for the purification of streptomycin
by Henshall, Primavesi, and Short (129) and by St. John, Flick,
and Tepe (249).
The use of ion exchange in the separation of the new and rare
elements is becoming common (9, 50, 212). Dickel (73) has
compared the ion exchange technique for isotope separation with
the electromagnetic, chemical exchange, distillation, and electro-
chemical methods and has concluded that ion exchange is advan-
tageous from an apparatus viewpoint but is slow. Berkelium,
americium, and curium have been separated and isolated by
Seaborg and his co-workers (266, $81, 289) using ion exchange
resins. Huffman and Oswalt (139) have separated promethium
and europium on a strong base anion exchanger. The hafnium
and zirconium separation has been studied by Hansen and
Gunnar (165), Huffman and Lilly (138), and Kraus and Moors
(160). Rare earth separations have been studied further with
ion exchange by Jeng-Tsong (146) and by Spedding and co-
workers (276-278). Kraus and Moore have separated proactin-
ium on a strong base anion exchanger. Atteberry, Larson, and
Boyd (10) have studied fission product separations and have
separated the halogens successfully. The ferrocyanide-ferricy-
anide separation has been accomplished by Cobble and Adamson
(52) on an anion exchange resin. The recovery of radioactive
phosphorus has been aided by the use of an ion exchange technique
(38).
Vol. 43, No. 1
RECOVERY AND PURIFICATION
The use of ion exchange in the recovery and purification of solu-
tions and water supplies containing various metals has been
studied by Bloodgood and Strickland (28), Costa (62), Imhoff
(I@), Mindler, Gilwood, and Saunders (do%),Placak and Morton
(832), and others (227, 834). Employing ion exchange, Apple-
zweig (8)and Xukherjee (205)haverecoveredalkaloids from plant
extracts. Antibiotic purification by ion exchange has also re-
ceived considerable attention (15, 99, 174). Inulin (211) and
quinolinic acid (127) have been studied with the aid of ion ex-
change. The use of ion exchange in the alcoholic beverage indus-
t r y is becoming of considerable interest (12, 14, 106, 200, 208,
151, 256). I n other food industries, various organic substances
are being recovered by ion exchange (95, 157,213, 628, 230,268).
Yorston (316, 317) employing a strong base anion exchanger has
recovered sugars from sulfite waste liquors.
PREPARATIONS
I n recent years, ion exchange has become useful on both a
laboratory and industrial scale for preparing various compounds.
Blanco and Perkinson (26) have prepared gallium citrate. Hy-
drogen peroxide has been prepared from sodium peroxide by
Campbell and Lefson (42), using a cation exchanger. Rhode-
hamel, McCormick, and Kern (244) have prepared the free base
of dihydrostreptomycin with a strong base anion exchanger.
Klement (156), Van Wazer (295),and Baker, Loev, and McCutch-
eon (16) have used ion exchange for preparing the various complex
inorganic acids. Devlin, hIcNabb, and Hazel (72) have prepared
vanadium pentoxide sols with a cation exchanger. A simple
lecture demonstration on the use of ion exchange in preparative
chemistry has been described by Keyas (155).
ANALYTICAL APPLICATIONS
As an analytical tool, ion exchange has become firmly en-
trenched in analytical chemistry. Cohn and his co-workers
(44, 66), Consden and Gordon (59, 60), and others (31, 78,
100, 148,166,258,275) have employed ion exchange in the analysis
of amino acids, nucleic acids, vitamins, antibiotics, etc. Gustav-
son (118, 119), Foreman, Thompson, and Tolliday (98), and
Kubelka (166) have studied the nature of chrome liquors with ion
exchange techniques. The use of ion exchange in determining
total salt concentrations has been investigated by several workers
(92, 93, 133, 172, 192). Schubert and his eo-workers (259-263)
have continued their studies on the use of ion exchange for obtain-
ing activities and dissociation constants. Methods for deter-
mining ion exchange capacities of inorganic and organic ion
exchangers have been reported recently (145, 190). A procedure
for the determination of sodium and potassium using ion exchange
has been reported by Beukenkamp and Rieman (22), and a
procedure for determining arsenic in insecticides has been de-
scribed by Odencrantz and Rieman (218). A method for deter-
mining the excess of phosphates in boiler water has been devised
by Edelshtein and Petatskil (86). Ion exchange procedures for
determining molybdenum in alloys (294) and nickel and copper
(180) have been reported. An ion exchange procedure for the
analysis of atmospheric precipitation has been devised by Egner
el al. (87). Samuelson (262)has analyzed Graham’s salt with the
aid of an anion exchanger. Further studies on the use of ion
exchange techniques in analytical chemistry have been reported
by Djurfeldt and Samuelson (75). Indicator dyed ion exchange
resin columns have been employed by Idler (142), Scarritt,
Senger, and Ballje (257), and Weiss (302). ’
NEW ION EXCHANGE COMPOSITIONS
Various ion exchange compositions have appeared in the litera-
ture, in particular, the patent literature. Andersen (6), Bircher
(2Q), Boyer (35), D a y ( 6 3 , Furushiro (101), Nagasawa and
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY
Nagase (NO), and Thurston (290) described the synthesis of
several sulfonic acid exchangers. Calmon (41) has described
the preparation of an aluminum silicate used in 8ea water desalt-
ing. Dudley (81-83), Herman (130), Sussman (286), and othere
(216, 273, 283) have described the synthesis of several anion
exchange resins. The preparation of a pectate exchanger has
been described by Walsh and Adams (297). A granular phenolic
resin having decolorizing properties has been described (47).
The conversion of a n anion exchanger to a n oxygen remover has
been accomplished by Mills and Dickinson (198, 199) by impreg-
nating an anion exchanger with cuprous chloride. Banks and
Barnes (17) claim the formation of a germicidal agent by treating
an anion exchanger with silver. An antifouling paint composi-
tion has been prepared by Holmes (137) by incorporating the
copper or mercury salt of a cation exchanger.
CATALYSIS
The kinetics of the inversion of sucrose by sulfonic and car-
boxylic acid cation exchange resins have been studied by Mariani
(188, 189) and Bodamer and Kunin (29). The catalytic proper-
ties of a strong base anion exchanger for aldol condensations have
been described by Meno (193). Dolnick and Potash (76) have
found a n acid cation exchanger to be effective as a catalyst for
the conversion of acetaldehyde to paraldehyde. Leum and
Macuga, and Kreps (173) have reported that an acid cation
exchanger catalyzes the production of an aliphatic ether from iso-
olefins and alcohols. The acid properties and exchange properties
of several inorganic catalysts have been described (30, 296).
BIOLOGICAL APPLICATIONS
Continued studies on the use of anion exchangers for the treat-
ment of ulcers have been made by Weiss, Espansal, and Weiss
(305) and Wirts, Rehfass, Delserone, and Wass (311). Sullivan
. and Martin (285)have found the use of ion exchange resins to be
of use in decreasing the acute toxicity of atropine. Segal, Miller,
and Morton (267) have suggested the use of the quinine salt of a
carboxylic acid cation exchanger for the determination of gastric
acidity without intubation. Heming, Flanagan, and Sax (126)
and McChesney and co-workers (183, 184) have reported the use
of cation exchange resins for sodium reduction therapy. Block
(27) has suggested the use of a n acid salt of a weak base anion
exchange resin as an anti-irritation powder. Larsen (17‘1) has
described the preparation of the ephedrine salt of a cation ex-
changer as a prolonged action vasoconstrictor.
Lo Grippo (177),Muller (,%‘06),and Zwart Voorspuij (3.91)have
employed ion exchange resins in the purification of viruses. The
use of ion exchange resins in the treatment of blood has been
described by De Nicola and Rosti (70, 71), Hussey et al. (141),
and Reid and Jones (241, 242). The adsorption of plutonium in
bone appews to be dependent upon ion exchange (260). The
importance o f ion exchange in the growth of organisms and in
fermentation processes has been discussed by Snell and Schweiger
(272),Woodard, Snell, and Nicholls (312), and Webb (299).
APPARATUS
i Ibid., p. 54.
A movable-bed chamber technique apparatus for ion exchange
has been devised by Lynam and Weil (182). A plant scale radial
chromatographic apparatus has been described by Weil and Ly-
nam (182, 301). An ion exchange dialyzing apparatus has been
patented by Zender (319). Other improvements in ion exchange
design have been described by Rasch (237), Swenson (287), and
others (79, 229).
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 INDUSTRIAL AND ENGINEERING CHEMISTRY
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Faber, H. A., Wafer & Sewage Works, 19, 465 (1950).
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Foreman, G., Thompson, P. V., and Tolliday. J.. J . A m
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(1949).
Garrett, Proc. 13th ! :wn. Dairy Gong., 3, 49 (1949).
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Gayle, F. L.. Ibid., 2,496,244 (Jan. 31, 1950).
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Gilwood, hT. E., and Calmon, C., S i n t h Proc. Eng. .Soc. West.
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Polymer Chemistry, 118th Meeting AM. CHEY. SOC.,
Chicago, I11 , 1950.
(113) Gregor, H. P., and Citarel, L , Division of Colloid Chemistry,
118th Meeting AM.CHEM.Soc., Chicago, Ill., 1950.
(114) Gregor. H. P.. and Sherman, N. N., J . SOC. MotionPictureEngr.,
53, 183 (1949).
(115) Grigorov, 0. N., and Tarshis, A., I<olloid Zhur., 11, 390 (1949).
(116) Gupta, S. L., Science and Culture, 14, 539 (1949).
(117) Ibid., 15, 325 (1950).
(118) Gustavson, K., J . Am. Leather Chemists' Assoc., 45, 536 (1950).
(119) Gustavson. K., J . Intern. Soc. Leather Trades Chemists, 34,
259 (1950).
(120) Haagensen, E. A . , U. S. Patent 2,482,765 (Sept. 27, 1949).
(121) Haase, L. W., Arch. Metallicunde, 3, 114 11949).
(122) Hall, J. R., FoodInds., 22, 61 (1950).
(123) Hamada, H., J . Japan.Chem., 2, 83 (1949).
(124) Hammerschmidt, E. G., Prtrolrum Engineer, 22, D-77 (1950).
(125) Hansen, R. S., and Cunnai, K., J . Am. Chem. SOC.,71, 4168
(1949).
Vol. 43, No. 1
(126) Heming, A. E., Flanagan, T. L., and Sax, M. I?., Division of
Colloid Chemistry, 118th Meeting AM.CHEXSoc., Chicago,
Ill., 1950.
(127) Henderson, L. M., and H. M. Hirsoh, J . B i d . Chem., 181,667
(1949).
(128) Henry, R. E., and Clifcorn, L. E., IXD. ENG.CHEM.,41, 1427
(1949).
(129) Henshall, T., Primavesi, G., and Short, J. F., Brit. Patent
625,146 (1949).
(130) Herman, D. F.. U. S.Patent 2,510,108 (Aug. 27, 1947).
(131) Hertz, D. B., Chem. Inds., 60, 512 (1950).
(132) Hewlett, A. W., Sugar, 45, 32 (1950).
(133) Hilfiger, J. P., Chim. anal., 31,226 (1949).
(134) Hoffpauir, C., and Guthrie, J., Textile ResearchJ.,20,617 (1950)
(135) Hogfeldt, E.. Ekedahl, E., and Sillen, L., Acta Chem. Scand.,
4, 828 11950).
(136) Ibid., p. 823.
(137) Holmes, E. L., Brit. Patent 630,534 (Oct. 14, 1949).
(138) Huffman, E., and Lilly, R. C., J . Am.Chem.Soc., 71,4147 (1949).
(139) Huffman, E., and Osmalt, R., Ibid., 72, 3323 (1950).
(140) Huiezenga, J., Grieger, P., and Wall, F. T., Ibid., 72, 2636
(1950).
(141) Hussey, C. J., Quick, A. J., Stefanini, M., Consolaaio, C. F.,
and Sargent, F., J . Bid. Chem., 184, 105 (1950).
(142) Idler, D. R., J . Am. Chem. Soc., 71, 3854 (1949).
(143) Imhoff, W. G., Wire and Wire Products, 24,1040 (1949).
(144) Jacobs, R. T., and Rawlings, F., IND.ENG.CHEM.,41, 2769
(1949).
(145) J . Am. Water Works Assoc., 42,489 (1950).
(146) Jeng-Tsong, Y., Anal.Chim. Acta, 4 , 59 (1950).
(147) Jenny, H., Nielsen, T., Coleman, N., and Villiams, D., Science,
112, 164 (1950).
1148) Jindra, A,, J . Pharm. Pharmacol., 1, 87 (1949).
(149) Juda, R., Kasper, A. A., and Potter, 1%'. D., Division of Colloid
Chemistry, 118thMeetingAx. CHEM.Soc.. Chicago, Ill., 1950.
(150) Juda, \V.,Katz, W. E., and Rosenberg, N. T\'., Division of
Colloid Chemistry, 118th Meeting AM. CHEM.Soc., Chi-
cago, Ill., 1950.
(151) Juda, W., and McRae, J . Am. Chem. Soc., 72,1044 (1950).
(162). Jukkola, W.,and Roberts, E., U. S. Patent 2,504,695 (April
18, 1950).
(153) Kahler, F., Chem. Eng., 57, No. 7, 109 (1950).
(154) Kahler, F., and Wants, J., Finish, 7, 23 (1950).
(155) Keyas, G., Bull. soc. chim. France. 1949, 883.
(156) Klement, R., 2. anorg. Chem., 260, 267 11949).
(157) Xlose, A . A , Stark, J. R., pur vi^. G. G.. Peat, J., and Fevold,
H. J., INTI.ENG.CHEX.,42, 3'77 (1950).
(158) Klumb, G. H., Marks, H. C., and Wilson, C., J. A m . V a t e ~
Works Assoc.. 41, 933 (1949).
(159) Kortschak, H. P., Gill, R. F., and Payne, J. H., IND.ENG.
CHEM.,41, 1406 (1949).
(160) Kraus, K. A., and Moore, G. E., J . Am. Chem. Soc., 72, 4293
(1950).
(161) Xressman, T. R. E., Nature, 165, 568 (1950).
(162) Krishnamoorthy, C., and Overstreet, R., Sciefice, 111, 231.
(1950).
(163) Krishnamoorthy, C., and Overstreet, R., SoilSci. 68,307 (1949).
(164) Ibid., 69, 41 (1950).
(165) Ihid., p. 87.
1166) Kubelka, V., Tech. Hlklka K o i e l u i s k d , 24, 97 (1949).
(167) Kuhn, \V., Hargitay. B., Xatchalsky, A., and Eisenberg, H..
Nafure, 165, 814 (1950).
(168) Kunin, R., and Klaas, R. B., Division of Colloid Chemistry,
118th Meeting AM.CHEY.Soc., Chicago, Ill., 1950.
(169) Kunin, R., and McGarvey, F. X., Division of Water, Sewage,
and Sanitation Chemistry, 117th Meeting AM. CHEM.
SOC., Detroit, Mich., 1950.
(170) Kunin, R., and Myers, R. J., Discussions Faraday Soc., No. 7
114 (1949).
(171) Larsen, D., U. 6 . Patent 2,498,687 (1950).
(172) Lee, H., J . SOC.Leather Tra4es' Chemists, 34, 150 (1950).
. , Leum. L. N.. hlacuga. S. J.. and Kreos. S . I.. U. S. Patent
1173)
2,480,940 (Sept. 6,1949).
(174) Lewis, J. C., and Jansen, E. F., Ibid., 2,495,743 (Jan. 31, 1950).
(175) Lindsay, F. K., J . Am. R'ater Works Assoc., 42, 75 (1950).
(176) Lindsay, F. K., Wirth, L. F., and Durinski, A. M., Division of
Colloid Chemistry, 118th Meeting AM.CHEWSoc., Chicago.
Ill., 1950.
(177) Lo Grippo, G. A., Proc. SOC. E x p t l . Bid. Med., 74, 208 (1950).
(178) Loring, H. S., Luthy, N., Bortner, H., and Levy, L., J . Am.
Chem. SOC.,72, 2811 (1950).
(179) Lundberg, L., Dansk Tids. Farm., 23, 227 (1949).
(180) Lur'e, Y., and Filippova, N. A,, Zaaodskaya Lab., 15,771 (1949).
(181) Lynam, C. G., and Weil, H., Mfg. C h e w k f ,21, 195 (1950).
(182) Ibid., p. 260.
January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY
McChesney, E. W., and McAuliff, J. P., Am. J . Physiol.,
160, 264 (1950).
McChesney, E. W., Nachod, F. C., and Tainter, M. L., Divi-
sion of Colloid Chemistry, 118th Meeting AM. CHEM.
SOC., Chicago, Ill., 1950.
McGrew, F., and Schneider, J . Am. Chem. SOC., 72, 2547
(1950).
Malquori, A., and deAngelis, G., Ann. chim. applicata, 38,
469 (1948).
Manufacturing Chemist, 21, 204 (1950).
Mariani, E., Ann. chim. applicata, 39, 283 (1949).
Zbid., 40, 1 (1950).
Martinez, F., Inform. quim. anal., 4, 1 (1950).
Massart, L., and VanDer Stock, J., Nature, 165, 852 (1950).
Mrtyer, S. W., J . Am. Chem. SOC., 72,2292 (1950).
Meno, Keihei, preprint, J . Chem. SOC.Japan (1950).
Merck & Co., Brit. Patent 637,592 (1950).
Michener, J. W., Fitch, B., and Roberts, E. J., IND.ENC.
CHEM.,42, 643 (1950).
Miedendorp, H., Rayon and Syn. Textiles, 31,85 (1950).
Miller. H. S..Division of Colloid Chemistry, 118th Meeting, - sented a t 188th Meeting AM. CHEM.SOC., p. 7C, 1950.
AM.CHEM.SOC., Chicago, Ill., 1950.
Mills, G., U. S. Patent 2,515,609 (1950).
Mills, G., andDickinson, B. N., IND.ENG.C H E M . ,2842
~ ~ , (1949).
Mindler, A,, Food Terhnol., 3, 43 (1949).
Mindler, A. B., and Gilwood, M. E., Seventh Proc. Eng. SOC.
West. Penn. (1949).
Mindler, A. B., Gilwood, M. E., and Saunders, G. H., Division
of Colloid Chemistry, 118th Meeting AM. CHEM.SOC., Chi-
cago, Ill., 1950.
Monet, G. P.. Chem. Eng., 57, No. 3, 106 (1950).
Mortland, M. M., and Gieseking, J. E., Soil Sci., 68, 391
(1949).
Mukherjee, S., and Gapta, M. L. S., J . Proc. Znst. Chemists
(India), 21, 45 (1949).
Muller, R. H., Proc. SOC.Exptl. Biol. Med., 73, 239 (1950).
Muntz, J. A., J . Biol. Chem., 182, 489 (1950).
Myers, W. H., U. S. Patent 2,482,862 (Sept. 27, 1949).
Nachod, F. C., Sei. Monthly, 70, 189 (1950).
Nagasawa, F., and Nagase, T., Japan. Patent 174,296 (Dec.
16, 1946).
Nagase, T., and Quda, S., Ibid., 174,275 (Dee. 10, 1946).
Nature, 166, 209 (1950).
Nichol, G. B., U. S. Patent 2,494,257 (Jan. 10, 1950).
Norris, T., J . Phys. and Colloid Chem., 54, 777 (1950).
N. V. Centrale Surker Maat., Brit. Patent 630,900 (1950).
N. V. W. A. Scholten's Aardappelmeelfabrieken, Dutch Patent
64,871 (1949).
Oct. Maat. Act., Zbid., 64,732 (Nov. 15, 1949).
Odencrantz, J., and Rieman, W., Anal. Chem., 22, 1066 (1950).
Oplatka, G., Meztigazdasctg 6s Ipar, 2, No. 6, 1 (1948).
Page, C. N., and Wantz, J. F., Power, 94, 104 (1950).
Partridge, S. M., Biochem. J., 44, 521 (1949).
Ibid., 45, 459 (1949).
Partridge, 5. M., Chemistry and Industry, 20, 383 (1950).
Partridge, S. M., and Brimley, R. C., Biochem. J., 44, 513
(1949).
Partridge, S. M., Brimley, R. C., and Pepper, K., Ibid., 46,
334 (1950).
Partridge, S. M., and Westall, R. G., Ibid., 44, 418 (1949).
Permutit Co., Brit. Patent 626,882 (July 22, 1949).
Ibid., 627,702 (Aug. 15, 1949).
Ibid., 638,956 (1950).
Ibid., 641,786 (Aug. 23, 1950).
Phelps, G., Am. Ceram. SOC.Bull., 29, 55 (1950).
Placak, 0. R., and Morton, R. S., J . Am. Water Works Assoc.,
42, 135 (1950).
Pope, L. B., Chem. Eng., 57, No. 1, 102 (1950).
Prescott, W. G., Brit. Patent 630,979 (1950).
Process Inds. Quart., 12, 10 (1950).
Rabek, T., Przemysl Chem., 27,678 (1948).
Rasch, C., U. S. Patent 2,514,415 (July 11, 1950).
Reents, A. C., and Kahler, F. H., Division of Colloid Chemistry,
118th Meeting AM.CHEM.SOC.,Chicago, Ill., 1950.
Reichelt, H., Chem. Ing. Tech., 22, 290 (1950).
Reichelt, H., Chem. Tech., 1, 28 (1949).
Reid, A. F., and Jones, F., Am. J . Clin. Path., 19,lO (1949).
Reid, A. F., and Jones, F., Division of Colloid Chemistry,
118th Meeting AM.CHEM.SOC.,Chicago, Ill., 1950.
Remington, W. R., and Gladding, E. K., J . Am. Chem. SOC.,
72, 2553 (1950).
Rhodehamel, H. W., Jr., McCormick, S. L., and Kern, S. F.,
Science, 111, 233 (1950).
Richardson, R. W., Nature, 164,916 (1949).
Rinehart, T. M., U. S. Patent 2,477,206 (July 26, 1949).
Roberts, E. J , Ibid., 2,484,647 (Oct. 11, 1949).
107
Rogge, R., IND. ENQ.CHEM.,41,2070 (1949).
St. John, C. V., Flick, D. E., and Tepe, J. B., Abstracts,
118th Meeting AM.CHEM.SOC.,p, 18B.
Salac, V., Congr. Intern. Ind. Ferment., pp. 514-25 (1947).
Samuelson, H., Swed. Patent 125,443 (1949).
Samuelson, O., Svensk Kem. Tid., 61, 76 (1949).
Sard, B. A., Brit. Patent 624,884 (Oct. 29,1946).
Ibid., 637,279 (Feb. 15, 1949).
Sawver. F. G.. IND. ENC.CHEM..41. 12 (1949). '
Scaiduia, G., k v . nit. enal., 3,177 (1950)'.
Scarritt, D. R., Senger, D. R., and Ballje, E. J., Division of
Colloid Chemistry, 118th Meeting AM.CHEM.SOP..Chicago,
Ill., 1950.
Schramm, G., and Primosigh, J., 2. phys. Chem., 282, 271
(1947).
Schubert, J., Division of Colloid Chemistry, 118th Meeting
AM. CHEM.SOC., Chicago, Ill., 1950.
Schubert, J., Finkel, M. P., White, M. R., and Hirch, G. M.,
J . Biol. Chem., 182, 635 (1950).
Schubert, J., and Lindenbaum, A., Abstracts of papers pre-
Schubert. J.. and Richter J.. J . Colloid. Sci.. 5. 376 (1950).
Schubert, J.', Russell, E., and Myers, L., J . biol. Chek., 185,
387 (1950).
Science News Letter, 38 (Jan. 21, 1950).
Ibid.. 51 (Jan. 28, 1950).
Sea&ave&mith,'H., and Cruess, W. V., Wines and Vines,
31. 29 (1950).
Segal: H.'L., -Miller, L., and Morton, J., Proc. SOC.EsptE.
Biol. Med., 74, 218 (1950).
Shawcross, R., U. S. Patent 2,522,140 (Sept. 12, 1950).
Sheehan, J. C., and Bolhofer, W. A., J . Am. Chem. Soc.,
72, 2466 (1950).
Siebel, F. P., Brewers Digest, 25, 45 (1950).
Smith, C. E., and Olson, E. K., U. S. Patent 2,490,716 (Dec.
6, 1949).
Snell, R. L., and Schweiger,L.B.,Zbid., 2,492,867 (Dec.27,1949).
Sooi6te l'aux. des Chemins de Fer, Brit. Patent 632,936 (Dec. 5,
1949).
Sollner, K., J . Electrochem. Soe., 97, 139C (1950).
Soodak, M., Pircio, A., and Cerecedo, L. R., J . Biol. Chem.,
181, 713 (1949).
Spedding, F., Fulmer, E., Butler, T., and Powell, S., J . A m .
Chem. SOC.,72, 2349 (1950).
Spedding, F., Fulmer, E., Powell, J., and Butler, R., Zbid.,
72, 2354 (1950).
Spedding, F., Fulmer, E., Powell, J., Butler, T., and Yaffe,
I. S., Division of Paper Colloid Chemistry, 118th Meet-
ing AM.CHEM.SOC., Chicago, Ill., 1950.
Steinhardt, J., and Zaiser, E. M., J . Biol. Chem., 183, 789
(1950).
Stevens, A. H., Brit. Patent 633,552 (Dee. 19,1949).
Street, K., and Seaborg, G., J . A m . Chem. Soc., 72, 2790
(1950).
Streicher, L., and Bowers, A. E., J . Am. Water Works Assoc.,
42, 81 (1950). '
Stroh, G., U. 5.Patent 2,515,142 (July 11, 1950).
Sugar, 45, No. 3,/25 (1950).
Sullivan, M. J., and Martin, G . ,Am. J . Pharm., 122, 48 (1950).
Sussman, S., U. S. Patent 2,518,956 (1950).
Swenson, W. R., Ibid., 2,517,051 (1950).
Taylor, R. L., Chem. Inds., 64, 932 (1949).
Thompson, S. G., Cunningham, B. B., and Seaborg, G . T.,
J . Am. Chem. SOC.,72,2798 (1950).
Thurston, J. T., Can. Patent 461,228 (1950).
Tiger, H. L., U. S. Patent 2,494,784 (Jan. 17, 1950).
Tolliday, J., Thompson, G., and Forman, G., J . SOC.Leather
Trade8 Chemists, 34, 221 (1950).
Topp, N. E., and Pepper, K. W., J . Chem. SOC.,1949,3299.
Usatenko, Y., and Datsenko, O., Zavodskaya Lab., 15, 779
(1 949).
(295) Van Wazer, J. R., and Besmertnuk, E., J . Phys. and Colloid
Chem., 54, 89 (1950).
(296) Walling, C., J . A m . Chem. SOC.,72, 1164 (1950).
(297) Walsh, C. L., and Adams, B. A,, Brit. Patent 641,918 (Sept.
23, 1950).
(298) Waroway, R. R., Brewers Digest, 24, 111 (1949).
(299) Webb, M., J . SOC.Chem. Znd., 68,319 (1949).
(300) Weber, G., Oil and Gas J., 49, 67 (1950).
(301) Weil, G., Can. Chem. Process Ind., 33, 956 (1949).
(302) Weiss, D. E., Nature, 166, 66 (1950).
(303) Weiss, S., Espansal, R., and Weiss, J., Rev. Gastroenkrol.,
16, 501 (1949).
108 I N D U S T R I A L A N D E N G I N E E-RI N G C H E M I S T R Y Vol. 43, No. 1
(304) Wesly, W., iMeZliand Textilber., 31, 62 (1950). - - 7

(305) Westall, R. G., J . Sci. Food and Agr., 1, 191 (1950).

(306) Wheaton, R., and Bauman, W , Division of Colloid Chem- 14 (1950).
istry 117th Meeting AM. CXEM.Soc., Houston, Tex. W. L., and Baumeister. T.. Trans. A m .
(307) Whittaker, H., U. 8. Patent 2,500,727 (1950). SOC.Mech. Engr., 72, 491 (1950).
(308) Wiklander, L., Kgl. Lanfbruks-Hogskol. Ann., 16, 670 (1949). (316) Yorston, F. H., P u l p h Paper Mag. Canada, 50, 108 (1949).
(309) Wiklander, L., Soil Sci., 69, 261 (1950). (317) Ibid., p. 111.
(310) TVilliams, K. T., Potter, E. F., Revenue, A., and Scurzi, W., (318) Zarow, A., U. S.Patent 2,520,189 (Bug. 29, 1950).
J . Assoc. Ofic.Agr. Chemasts, 32, 698 (1949). (319) Zender, J., Ibid., 2,502,614 (April 4, 1950).
(311) Wirts, C., Rehfass, hl., Delsetone, B., and Wass, B., J. Clin. (320) Zhukov, I., and Brods Koyaya, N. T., Kolloid Zhur., 11,
Inyesf.,29. 37 (1950). 332 (1949).
(312) Woodard, J. C., Snell, K. L., and Kicholls, R. S., U. S. Patent (321) Zwart Voorspuij,A. J . , E'xpwirnentia, 5, 474 (1949).
2,492,173 (Dec. 27, 1949). RECEIVDD
October 14. 19.50

_________
ATERIALS ANDLING
___ ~- - __ ~______ ____~ ~

ROBERT E. WRIGHT'
MONSANTO CHEMICAL CO.,ST. LOUIS 4, MO.

I n 1950 a number OF new devices were introduced which gave the chemical industry new t o o k electric pump unit eliminates stuffing
for the more efficient handling of materials. In addition to new devices, most manufacturers boxes, seals, couplings, and shaft
introduced new models with increased work capacity, improved efficiency, or other design im- wear, and the pump can be installed
provements. The trend toward the use of machinery to replace labor was so marked that in any position ( 2 ) . A trash pump
writers onee again began to think about the effect of technological advances up3n employment. for liquids that would clog an or-
dinary impeller pump is also new.
The impeller of this pump is bladeless
HE annual review in past years has noted the increased at- (see Figure 1). I t is said that hard-boiled eggs can pass through
tention being given to this field. During 1950 the develop- the pump whole and even apples and oranges can be handled with-
ments in the materials handling field continued at a n out bruising (8). Another pump has a new idea for automatic
accelerated rate. priming: a variable-capacity vane-type positive displacement
A number of new devices of particular interest were intro- pump mounted on the same shaft as the centrifugal impeller.
duced during the year When the piping system is filled with liquid, the priming pump
shifts to a neutral position and stops pumping (IO). Another type
of self-priming centrifugal pump, introduced during 1950, is said to
have high efficiency during the pumping stage. There is no re-
circulation after priming is completed and no bulky priming
reservoir is required. The pump is simple, yet it is said to have
the priming ability of positive displacement pumps (11).
A new pump is a v d a h l e for transmitting semisolids through a

COURTESY FAIRBANKS. MORSE d CO

Figure 1. Bladeless Impeller for Trash Pump

LIQUID AND GAS HANDLING

PUMPS.Several new types of pumps became available during

the year. One is a new centrifugal pump that is driven by a
rotor-impeller hermetically sealed in the pump housing. This
COURTESY FAIRBANKS. MORSE & CO.

1 Present address, Chemstrand Corp., 1617 Pennsylvania Blvd., Phila-

delphia 3, Pa. Figure 2. Two-Stage Packaged Compressor
108 I N D U S T R I A L A N D E N G I N E E-RI N G C H E M I S T R Y Vol. 43, No. 1
(304) Wesly, W., iMeZliand Textilber., 31, 62 (1950). - - 7

(305) Westall, R. G., J . Sci. Food and Agr., 1, 191 (1950).

(306) Wheaton, R., and Bauman, W , Division of Colloid Chem- 14 (1950).
istry 117th Meeting AM. CXEM.Soc., Houston, Tex. W. L., and Baumeister. T.. Trans. A m .
(307) Whittaker, H., U. 8. Patent 2,500,727 (1950). SOC.Mech. Engr., 72, 491 (1950).
(308) Wiklander, L., Kgl. Lanfbruks-Hogskol. Ann., 16, 670 (1949). (316) Yorston, F. H., P u l p h Paper Mag. Canada, 50, 108 (1949).
(309) Wiklander, L., Soil Sci., 69, 261 (1950). (317) Ibid., p. 111.
(310) TVilliams, K. T., Potter, E. F., Revenue, A., and Scurzi, W., (318) Zarow, A., U. S.Patent 2,520,189 (Bug. 29, 1950).
J . Assoc. Ofic.Agr. Chemasts, 32, 698 (1949). (319) Zender, J., Ibid., 2,502,614 (April 4, 1950).
(311) Wirts, C., Rehfass, hl., Delsetone, B., and Wass, B., J. Clin. (320) Zhukov, I., and Brods Koyaya, N. T., Kolloid Zhur., 11,
Inyesf.,29. 37 (1950). 332 (1949).
(312) Woodard, J. C., Snell, K. L., and Kicholls, R. S., U. S. Patent (321) Zwart Voorspuij, A. J . , E'xpwirnentia, 5, 474 (1949).
2,492,173 (Dec. 27, 1949). RECEIVDD
October 14. 19.50

_________
ATERIALS ANDLING
___ ~- - __ ~______ ____~ ~

ROBERT E. WRIGHT'
MONSANTO CHEMICAL CO.,ST. LOUIS 4, MO.

I n 1950 a number OF new devices were introduced which gave the chemical industry new took electric pump unit eliminates stuffing
for the more efficient handling of materials. In addition to new devices, most manufacturers boxes, seals, couplings, and shaft
introduced new models with increased work capacity, improved efficiency, or other design im- wear, and the pump can be installed
provements. The trend toward the use of machinery to replace labor was so marked that in any position ( 2 ) . A trash pump
writers onee again began to think about the effect of technological advances up3n employment. for liquids that would clog an or-
dinary impeller pump is also new.
The impeller of this pump is bladeless
HE annual review in past years has noted the increased at- (see Figure 1). I t is said that hard-boiled eggs can pass through
tention being given to this field. During 1950 the develop- the pump whole and even apples and oranges can be handled with-
ments in the materials handling field continued at an out bruising (8). Another pump has a new idea for automatic
accelerated rate. priming: a variable-capacity vane-type positive displacement
A number of new devices of particular interest were intro- pump mounted on the same shaft as the centrifugal impeller.
duced during the year When the piping system is filled with liquid, the priming pump
shifts to a neutral position and stops pumping (IO). Another type
of self-priming centrifugal pump, introduced during 1950, is said to
have high efficiency during the pumping stage. There is no re-
circulation after priming is completed and no bulky priming
reservoir is required. The pump is simple, yet it is said to have
the priming ability of positive displacement pumps (11).
A new pump is a v d a h l e for transmitting semisolids through a

COURTESY FAIRBANKS. MORSE d CO

Figure 1. Bladeless Impeller for Trash Pump

LIQUID AND GAS HANDLING

PUMPS.Several new types of pumps became available during

the year. One is a new centrifugal pump that is driven by a
rotor-impeller hermetically sealed in the pump housing. This
COURTESY FAIRBANKS. MORSE & CO.

1 Present address, Chemstrand Corp., 1617 Pennsylvania Blvd., Phila-

delphia 3, Pa. Figure 2. Two-Stage Packaged Compressor
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY 109

pipe. It is said that any mate-

rial which has a viscosity suffi-
cient to permit flow through a
pipe can be handled by this
pump (27). A precisely cali-
brated pump has been de-
veloped for delivering 3 to 725
ml. per hour a t pressures up to
1000 pounds per sqdare inch.
The liquid end construction is
stainless steel and the packing
is normally Teflon. Such a
pump should find use in adding
small quantities of chemicals
or vitamins to a main product
stream (3). Another interest-
ing chemical feed pump will
feed 3.38 gallons per hour
against a pressure of 30,000
pounds per square inch (3).
II
COMPRESSORS. An entirely Figure 3. Mechanical Vibration Conveyer
new design for electric'driven
compressors has been developed
which is notable for its simplicity and compactness (14). The for the return of the empty pallets. Another examiner
compressor has only two main air connections, the intake and recommended approval of the petition of fifteen large midwestern
the discharge, and the intercooler is built into the frame of the truckers for an average rate of one half of fourth class on return
compressor. The air flow from the first stage through the in- shipments of pallets, platforms, and skids @ I ) . These are note-
tercooler to the second stage is accomplished by air passages worthy developments because, if special rate schedules for return
incorporated in the compressor frame. Advantages of the new shipments of pallets become general, the economics of palletized
design are elimination of exterior piping, simplified installation, shipping is greatly improved.
and reduced floor space requirements. Aside from the unique A Swedish manufacturer has developed a new method of pallet
general design, the new compressor is said to have a number of design. Nails fastening the deck boards are locked to the
important design refinements. The machine is basically a two- stringers by a simple method which is remarkably effective. It is
stage, 80-to 125-pound-per-square-inch air compressor (Figure 2). said that the force required to break the fastening is great enough
A new oil ejector vacuum pumping unit, designated by the either to split the wood or t o exceed the yield point of the nail
manufacturer as KB-300 (6),has been introduced for pumping (20).
to atmospheric pressure large volumes of gas or air from the The Engineering Societies Library has published a comprehen-
pressure range of 10 to 300 microns, The new unit is built to sive bibliography of 114 references covering all aspects of the sub-
handle water vapor and corrosive materials; it is said to have ject of pallets, including design and construction of the different
high pumping speeds in the 50- to 500-micron pressure range, and types, the handling of various materials on pallets, the savings
below pressures of 200 microns to have more speed than ten large achieved in materials handling, and details of presentrday applica-
mechanical pumps (rated a t 100 cubic feet per minute) in parallel. tions in individual plants in a large number of industries
One of the advantages claimed for this vacuum pump is the low (6).
operating cost compared with other pumping methods. TRUCKS.Most manufacturers developed new and improved
A small portable intensifier has been made available which can fork lift trucks, but there were no unique ideas announced in
produce UP to 23,000 pounds per square inch hydrostatic pressure 1950. There is evidence of keen competition in this field, because
from an air supply pressure of
90 pounds per square inch.
The unit is compactly mounted
on rubber tires and is equipped
ready to work within a few
.. minutes (4). This intensifier
can be used in pressure testing
of boilers and piping, and
destruction tests in labora-
. tories.

SOLIDS HANDLING

The great limitation of pal-

letized shipments has been the
aost of freight on return ship-
ments of the empty pallets.
Recently, an Interstate Com-
merce Commission examiner
recommended that the com- COURTESY G E N E R A L A M E R I C A N TRANSPORTATION CORP.
mission approve a proposal
for a preferential freight rate Figure 4. Trans-Flo Car for Bulk Handling
110 INDUSTRIAL AND ENGINEERING CHEMISTRY
COURTESY HOFMAN LABORATORIES,
Figure 5. Liquid Hydrogen Container
all manufacturers of fork lift trucks now have substantially the
same attachments for the special handling of materials, the me-
chanical features are highly refined, and the fork trucks are taking
on an amazing degree of similarity.
A tiny bulldozer, weighing only 800 pounds, has been developed
for small jobs and service in close quarters (16). It has a 5-hp.,
air-cooled motor, and can be equipped with a bucket lift, dozer
blade, or snow blade assembly. The normal scoop capacity is
560 pounds of wet sand (4.5 cubic feet).
CONVEYERS.Two manufacturers (16, 68) have announced
new mechanical vibration conveyers which are said to operate at
large power savings because of operation at positive resonance
(natural frequency). The design of these conveyers isolates
vibration within the machine itself, so that the supporting struc-
tures need only be designed to carry the dead weight of the equip-
ment and its material load. It is said that abrasive wear on the
decks is negligible, owing to hopping action of the material.
Vibrating conveyers will convey hot, abrasive, or corrosive
materials in granular, pulverized, or lump form, as well as boxes
and packages. The trough can be enclosed to protect the mate-
rial or prevent the escape of dust. One type uses spring bars
(Figure 3); the other type uses coil springs.
A n interesting new self-centering roller called the Lorig
aligner has been announced. A load dropped in any position on
a roller conveyer with Lorig aligners will gradually work itself
to the center line of the conveyer as it rolls along. The load
will stay centered without guide rails even around curves or with
the conveyer a t a slight tilt. If used with a belt conveyer, the
Lorig aligners will hold the belt in the center without the use of
guiding devices, resulting in elimination of edge wear and fewer
idlers (19, 22).
Gerald Von Stroh, director of the Coal Mining Industries
mining development program, indicates that the f i s t test of a
stainless steel conveyer belt was successful (17). Although steel
has been used in conveyer belts for some time, this is believed
to be the first use of stainless steel. If the present development
work on stainless steel conveyer belts is successful, such conveyers
might find important application in the chemical industry.
There is considerable interest in a proposed belt conveyer
system to transport coal and iron ore approximately 130 miles
from East Liverpool to Lorain, Ohio, with spurs to serve Youngs-
town and Cleveland. The estimated cost of this proposed con-
veyer is $210,000,000. The c*onveyerwould require 250,000 hp.
Vol. 43, No. 1
for operation a t full capacity of 52,000,000 tons per year (18, 69).
BCLKHANDLING. Two new types of weatherproof truck trail-
ers have been developed for bulk handling: one for granular and
powdered materials and the other for handling pulverized mate-
rials. The latter design incorporates the -4ir-Slide aeration prin-
ciple and hydraulic elevation of the trailer body for speedy dis-
rharge of materials ( I d ) .
A new railroad car has been designed for the sanitary and effi-
cient bulk transportation of dry, granular, or powdered commodi-
ties such as flour, plastics, and chemicals (see Figure 4). The
Trans-Flo car is essentially a covered hopper-type car, but it
differs from the standard covered hopper car in that it is com-
posed of two large compartments each having six sets of hopper-
type bottoms, The compartments can be made of either stainless
steel or high tensile low alloy steel (9). The Trans-Flo car is
unloaded pneumatically in an operation that can be performed by
one man in less than 4 hours. It should find application for
commodities where sanitation, infestation, or high packaging
costs are problems.
Another approach to the bulk handling of materials is the
recently developed Tote Bin, an aluminum container for handling
about 4000 pounds of material. This cantainer is about thr size
INC.
o f a conventional pallet and can be handled like a pallet load (31).
Still another approach to bulk handling of materials is the
Return-0-tainer. I n effect, this is a collapsible steel box which
can be lined to be vapor- or moistureproof, if desired. The con-
tainer can be emptied with a specially designed dumping device.
When emptied, it folds down to about one-quarter size and it can
then be returned and re-used ( 7 ) .
During 1950, an increasing number of chemicals were moved
by multicargo ocean-going tankers. Warren summarizes the
current status of ocean shipping of chemicals (SO).
MISCELLANEOUS MATERIALS HANDLING DEVICES
Much attention was given during 1950 to the use of polyethyl-
ene in various forms for packaging. As a result of the wide-
spread use of polyethylene containers, a number of new machines
have been developed for automatically making, filling, and sealing
polyethylene bags.
One manufacturer (1) has started a new method for shipping
paper bags. The bags are built up on disposable, flat packed,
paper boards t o give a unit load 48 X 48 inches. The bags are
compressed in a specially designed press, and steel strapping is
fastenrd while the bags are still under pressure. The pressurized
packing is said to result in storage space savings of as much as
50%. The palletized unit load greatly reduces handling cost and
time.
A new bag packer has been developed for packing ground
chemicals which have characteristics similar to flour. The unit
consists of a screw-type feeder, an automatic scale, a packer, and a
conveyer, all of which operate together automatically to permit
one man to handle four 100-pound bags per minute. In spite of
the high output, the manufacturer claims consistent weighing
accuracy for 80% of the bags, with none of the remainder varying
more than 2 to 4 ounces from the true weight (W6).
Liquid hydrogen and liquid helium have been laboratory rari-
ties because of lack of a good means for handling and storing.
A patented new liquid hydrogen container is now available for
this purpose (see Figure 5 ) . The container is made of three con-
centric copper spheres. The inner and outer spheres form a
conventional vacuum flask with the facing interior surfaces
polished to a mirrorlike fmish. Between them is placed a third
sphere highly polished on both sides which acts as a radiation
shield. This shield is attached to the inner sphere of a smaller
side flask containing liquid nitrogen. By cooling the main con-
tainer to the temperature of liquid nitrogen, the evaporation
losses of liquid hydrogen or helium are reduced to a negligible
minimum ( I S ) .
 January 1951 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
Filling machines are now available for free-flowing and non-
free-flowing products in which rapid and dustless filling is ob-
tained by applying a controlled vacuum to the containers being
filled. Large machines operating on this principle fill as many
as 300 containers per minute with high accuracy, but small
machines are also made for filling limited production items (24).
During 1950, i t seems that all types of materials handling de-
vices were improved, even the wheelbarrow. William Gemien-
hardt, a member of the staff of the New York University College
of Engineering, has designed a new wheelbarrow with an ingenious
wheel suspension which permits a loaded wheelbarrow to ride
over a 4-inch curb with relative ease (25).
Purdue University and the American Materials Handling
Society sponsored the Second Annual Materials Handling Con-
ference at Lafayette, Ind., in February 1950. This conference i s
only one of many evidences of the increased attention being given
b
to materials handling.
In spite of increased use of new and better materials handling
equipment, great improvements can still be made in the actual
handling of materials. Perlman (93) says that only 3 hours of
a the average freight car’s day are spent in over-the-road movement,
while 21 hours are spent in terminal detention. He sags that by
adding 4 minutes per day to each car’s over-the-road movement,
the nation’s car inventory could be increased by $100,000,000.
This is only one of examples that could be cited to show the
great potential field for better handling methods and equipment.
LITERATURE CITED
( I ) Arkell & Smiths, Canajoherie, N. Y . , personal communication to
author.
(2) Atlantic Pump Corp., P.O. 6751, Philadelphia 32, Pa., unnum-
bered bulletin on Hermetik pump.
(3) CIiem. Eng. 28, 3346 (1950).
(4) CooperRessemer Corp,, Mt. Vernon, Ohio, bulletin on intensifier.
J. HENRY RUSHTON‘
ILLINOIS lNSTlTUTE OF T E C H N O L O G Y , C H I C A G O , ILL.
During the past year a large number of articles have appeared on agitation and mixing. There
has been considerable activity along experimental lines, and important engineering perform-
ance data have been reported. Several articles give equipment performance data, both
from the standpoint of power characteristics and process applications. Discussions have ap-
peared which relate fundamental fluid mechanics theory to mixing. The most significant and
valuable work available to date on mixing applied to fermentation (a gas-liquid-solid mix-
ing operation) has been published.
*
T
H E previous annual review of developments in mixing
was published in the January 1950 issue of INDUSTRIAL AND
- ENGINEERING CHEMISTRY (31) and it brought references u p
to the date of October 1949. An annual survey of new equip-
ment, as announced by equipment manufacturers, was published
in Chemical Industries (8).
A description of present theory and practice in mixing appears
in “Technique of Organic Chemistry” (33). Special attention is
directed to the proper use of mixers in organic chemical research.
The new edition of “Chemical Engineers’ Handbook’’ (39) oon-
tains a section on mixing. It includes most of the material of the
previous editions to which have been added very brief summaries
of some of the recent literature.
A list of applications for various types of mixers has been pub-
lished by Lyons (18).
1 Also director of research, Mixing Equipment Co., Rbchester. N. Y.
111
(5) Distillation Products Industries, Division of Eastman Kodak
Co., Rochester 3,N. Y., literature on KB-300 vacuum pump.
(6) Engineering Societies Library, 29 West 39th St., New York 18,
N. Y., “Bibliography on Pallets Used in Modern Materials
Handling,” 1949.
(7) Fab-Weld Corp., Pickwick and Richmond Sts., Philadelphia
34,Pa., unnumbered bulletin on Return-o-tainer.
(8) Fairbanks, Morse & Co., 600 South Michigan Ave., Chicago 5,
Ill., BUZZ. 5400 K-1.
(9) General American Transportation Corp., 135 South LaSalle
St., Chicago 90,Ill., literature and unnumbered bulletins on
Trans-Flo car.
Gilbert & Barker Mfg. Co., West Springfield, Mass., Bull. P-463.
Goulds Pumps, Inc., Seneca Falls, N. Y., Bull. 636-1.
Gramm Trailer Corp., Delphos, Ohio, bulletins on bottom
hopper dump trailor and Air-Slide trailer.
Hofman Laboratories, 216 Wright St., Newark 5, N. J., unnum-
bered bulletins on liquid helium container.
Inpersoll-Rand Co., 11Broadway, New York 4, N. Y., Bull. 3150.
Jeffrey Mfg. Co., 909 North Fourth St., Columbus 16, Ohio,
unnumbered bulletin on mechanioal vibration conveyer.
Mead Specialties Co., Inc., 4114 North Knox Ave., Chicago
41,Ill., literature on baby btdldoeer.
Mech. Eng., 71, No. 10,848 (1949).
Iba‘d., 72, No. 7, 583 (1950).
Ibid., 72,No. 10, 821 (1950).
Modern MuterTiuls Handling, 5, No. 9, 36 (1950).
Ibid., No. 10, 16 (1950).
Ibid., pp. 38, 39.
Perlman, A. E., Mech. E n g . , 72, No. 8, 641 (1950).
Pneumatic Scale Corp., Ltd., Quincy 71, Mass., unnumbered
bulletin on Vacuflow fillers.
Power Generution, 54, No. 6 (1950).
Richardson Scale Co., Clifton, N. J., Bull. 3449.
Roto-Flo Pump Corp., 2608 West Ruby Ave., Milwaukee 9,
Wis., bulletins.
Stephens Adamson Mfn. Co., Aurora, Ill., Bull. 849.
Von Thaden, H., Mech; Eng., 72,No. 7, 549-51 (1950).
Warren, R. F., Chem. Engr., 57, No. 1, 118-19 (1950).
Wright, R. E., IND.ENG.CHEM., 42,79A (June 1950).
RECEIVED October 16, 1950.
MIXING
Morello and Poffcnberger (24) pub-
lished an authoritative survey of com-
mercial extraction equipment which
includes performance characteristics
of several in which mixers are used.
A review of various methods re-
ported in the literature for assessing
the performance of mixers has been
prepared by Black (4).
POWER CHARACTERISTICS OF MIXERS
Extensive data have been published by Rushton, Costich, and
Everett (34) to establish basic mixing impeller characteristics.
The fluid mechanical basis for power correlations is developed and
shown to be an accurate basis for the correlation and interpreta-
tion of performance of the common types of mixing impellers,
Data are correlated for impellers from 3 to 48 inches in diameter
for tanks 8.5 to 96 inches in diameter, and for fluids with viscosi-
ties of from 1to 40,000 centipoises. From these data it is possible
to predict power consumption for the majority of mixers in ex-
perimental and industrial use. The significance of power charac-
eristics to proper use of impellers and tank fittings is pointed out.
A technique is outlined whereby the operating characteristics of
any impeller in any tank arrangement and fluid can be found by
only a few experimental runs made a t significant conditions.
 January 1951 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
Filling machines are now available for free-flowing and non-
free-flowing products in which rapid and dustless filling is ob-
tained by applying a controlled vacuum to the containers being
filled. Large machines operating on this principle fill as many
as 300 containers per minute with high accuracy, but small
machines are also made for filling limited production items (24).
During 1950, i t seems that all types of materials handling de-
vices were improved, even the wheelbarrow. William Gemien-
hardt, a member of the staff of the New York University College
of Engineering, has designed a new wheelbarrow with an ingenious
wheel suspension which permits a loaded wheelbarrow to ride
over a 4-inch curb with relative ease (25).
Purdue University and the American Materials Handling
Society sponsored the Second Annual Materials Handling Con-
ference at Lafayette, Ind., in February 1950. This conference i s
only one of many evidences of the increased attention being given
b
to materials handling.
In spite of increased use of new and better materials handling
equipment, great improvements can still be made in the actual
handling of materials. Perlman (93) says that only 3 hours of
a the average freight car’s day are spent in over-the-road movement,
while 21 hours are spent in terminal detention. He sags that by
adding 4 minutes per day t o each car’s over-the-road movement,
the nation’s car inventory could be increased by $100,000,000.
This is only one of examples t h a t could be cited to show the
great potential field for better handling methods and equipment.
LITERATURE CITED
( I ) Arkell & Smiths, Canajoherie, N. Y . , personal communicationto
author.
(2) Atlantic Pump Corp., P.O. 6751, Philadelphia 32, Pa., unnum-
bered bulletin on Hermetik pump.
(3) CIiem. Eng. 28, 3346 (1950).
(4) CooperRessemer Corp,, Mt. Vernon, Ohio, bulletin on intensifier.
J. HENRY RUSHTON‘
ILLINOIS lNSTlTUTE OF T E C H N O L O G Y , C H I C A G O , ILL.
During the past year a large number of articles have appeared on agitation and mixing. There
has been considerable activity along experimental lines, and important engineering perform-
ance data have been reported. Several articles give equipment performance data, both
from the standpoint of power characteristics and process applications. Discussions have ap-
peared which relate fundamental fluid mechanics theory to mixing. The most significant and
valuable work available to date on mixing applied to fermentation (a gas-liquid-solid mix-
ing operation) has been published.
*
T
H E previous annual review of developments in mixing
was published in the January 1950 issue of INDUSTRIAL AND
- ENGINEERING CHEMISTRY (31) and it brought references u p
to the date of October 1949. An annual survey of new equip-
ment, as announced by equipment manufacturers, was published
in Chemical Industries (8).
A description of present theory and practice in mixing appears
in “Technique of Organic Chemistry” (33). Special attention is
directed to the proper use of mixers in organic chemical research.
The new edition of “Chemical Engineers’ Handbook’’ (39) oon-
tains a section on mixing. It includes most of the material of the
previous editions t o which have been added very brief summaries
of some of the recent literature.
A list of applications for various types of mixers has been pub-
lished by Lyons (18).
1 Also director of research, Mixing Equipment Co., Rbchester. N. Y.
111
(5) Distillation Products Industries, Division of Eastman Kodak
Co., Rochester 3,N. Y., literature on KB-300 vacuum pump.
(6) Engineering Societies Library, 29 West 39th St., New York 18,
N. Y., “Bibliography on Pallets Used in Modern Materials
Handling,” 1949.
(7) Fab-Weld Corp., Pickwick and Richmond Sts., Philadelphia
34,Pa., unnumbered bulletin on Return-o-tainer.
(8) Fairbanks, Morse & Co., 600 South Michigan Ave., Chicago 5,
Ill., BUZZ. 5400 K-1.
(9) General American Transportation Corp., 135 South LaSalle
St., Chicago 90,Ill., literature and unnumbered bulletins on
Trans-Flo car.
Gilbert & Barker Mfg. Co., West Springfield, Mass., Bull. P-463.
Goulds Pumps, Inc., Seneca Falls, N. Y., Bull. 636-1.
Gramm Trailer Corp., Delphos, Ohio, bulletins on bottom
hopper dump trailor and Air-Slide trailer.
Hofman Laboratories, 216 Wright St., Newark 5, N. J., unnum-
bered bulletins on liquid helium container.
Inpersoll-Rand Co., 11Broadway, New York 4, N. Y., Bull. 3150.
Jeffrey Mfg. Co., 909 North Fourth St., Columbus 16, Ohio,
unnumbered bulletin on mechanioal vibration conveyer.
Mead Specialties Co., Inc., 4114 North Knox Ave., Chicago
41,Ill., literature on baby btdldoeer.
Mech. Eng., 71, No. 10,848 (1949).
Iba‘d., 72, No. 7, 583 (1950).
Ibid., 72,No. 10, 821 (1950).
Modern MuterTiuls Handling, 5, No. 9, 36 (1950).
Ibid., No. 10, 16 (1950).
Ibid., pp. 38, 39.
Perlman, A. E., Mech. E n g . , 72, No. 8, 641 (1950).
Pneumatic Scale Corp., Ltd., Quincy 71, Mass., unnumbered
bulletin on Vacuflow fillers.
Power Generution, 54, No. 6 (1950).
Richardson Scale Co., Clifton, N. J., Bull. 3449.
Roto-Flo Pump Corp., 2608 West Ruby Ave., Milwaukee 9,
Wis., bulletins.
Stephens Adamson Mfn. Co., Aurora, Ill., Bull. 849.
Von Thaden, H., Mech; Eng., 72,No. 7, 549-51 (1950).
Warren, R. F., Chem. Engr., 57, No. 1, 118-19 (1950).
Wright, R. E., IND.ENG.CHEM., 42,79A (June 1950).
RECEIVED October 16, 1950.
MIXING
Morello and Poffcnberger (24) pub-
lished a n authoritative survey of com-
mercial extraction equipment which
includes performance characteristics
of several in which mixers are used.
A review of various methods re-
ported in the literature for assessing
the performance of mixers has been
prepared by Black (4).
POWER CHARACTERISTICS OF MIXERS
Extensive data have been published by Rushton, Costich, and
Everett (34) to establish basic mixing impeller characteristics.
The fluid mechanical basis for power correlations is developed and
shown to be an accurate basis for the correlation and interpreta-
tion of performance of the common types of mixing impellers,
D a t a are correlated for impellers from 3 to 48 inches in diameter
for tanks 8.5 to 96 inches in diameter, and for fluids with viscosi-
ties of from 1to 40,000 centipoises. From these data it is possible
to predict power consumption for the majority of mixers in ex-
perimental and industrial use. The significance of power charac-
eristics to proper use of impellers and tank fittings is pointed out.
A technique is outlined whereby the operating characteristics of
any impeller in any tank arrangement and fluid can be found by
only a few experimental runs made a t significant conditions.
112 INDUSTRIAL AND ENGINEERING CHEMISTRY
O’Connell and Mack (27) published power characteristics data
o n simple paddle mixers (2, 4,and 6 flat blades) in “fully baffled
tanks.” The data can also be correlated conveniently by the
method of Rushton, Costich, and Everett; these data make very
useful additions to the constants and exponent values which are
summarized in Tables IX and X of the Rushton et al. article (34).
For those who prefer to use an alignment chart rather than a
slide rule for calculating the Reynolds number for mixing, a
small chart has been published by Schneider (36).
N E W MIXERS
A description has been given for a pendulum- or shaker-type
agitator which is useful as a high pressure autoclave (23) Poiver
requirements are given. The article also gives a very brief re-
view of power requirements to rotate Peveral types of impellers.
A tabulation of some power requirements and their relation to
effectiveness in several process applications is given by 1Iagnus-
son (19).
A rotating drum-type mixer for handling high viscosity liquids
is described briefly by Fesenko (13).
Merz (22) describes two impellers and states that they may be
used t o enhance solution processes. The radial blade turbine has
holes drilled in the disk and blades; the propeller has stabilizer
fins cast on the blades (like the stabilizer fins used in this coun-
try).
Jackson (16) has designed a new blade shape for a propeller
which is intended to chop and cut solids and aggregates in addi-
tion to creating the fluid motion required for mixing.
THEORETICAL ASPECTS OF M I X I N G
An article by Fossett and Prosser (14) on the application of free
jets to the mixing of fluids in bulk reports significant and impor-
tant data on model tests and on large tank blending operations.
Performance was determined for free jets of liquid used to mix
liquid in large cylindrical tanks. The time required to achieve
blending of gasoline in large storage tanks was measured in scale
models and full size tanks, wherein the mixing was accomplished
by one or more jets of liquid. The principles developed should
be applicable to side-entering propeller mixers which are in wide
u4e for such blending operations. The data give blending times
for various light and heavy oils. Sufficient data are given to cal-
culate power requirements for many conditions of operation.
Several examples to illustrate the application of the data are
worked out, and the theory developed enables prediction of per-
formance in the largest tanks used (144 feet in diameter, 33 feet
high).
A short article by Bershader and Pai (3) describes a technique
for measurement of flox and density distribution in the turbulent
jet of a fluid in supersonic flow. This article is of theoretical in-
terest because the principles of jet flow are applicable to mixing
and are aiding in a better understanding of the relation of fluid
motion and mixing.
A discussion of some applications of fluid mechanics theory to
mixing was presented by Rushton (32) a t the 1949 Conference on
Industrial Hydraulics. Data are presented which show the con-
ditions necessary t o produce the same flow patterns and similar
dynamic conditions in mixing tanks of two or more different
sizes. The basic fluid dynamic theory is presented whereby
scale-up to large size mixing equipment from pilot plant studies
can be made.
Serner (37) presented a discussion of an “effective radius of
agitation” in viscous liquid mixing. Some arbitrary assumptions
are made, after which data are calculated and presented in a
chart purported to show the power input necessary to achieve a
given flow turbulence at various effective radii for different vis-
cosity fluids. There are no experimental data or fluid mechanics
principles cited to justify the assumed flow patterns which are
postulated. The author states that factors of safety must be
applied in practical application of his ideas.
Val. 43, No. 1
Three recent articles (7, 9, 20) on the mixing of solid particles
are of interest in leading to a better understanding of liquid as
well as of solids mixing.
Maitra and Coulson (9, 90) discuss experiments with solids de-
signed to test theory which has previously been used in liquid
mixing processes. They were particularly interested in detrr-
mining the degree of dispersion and the rate a t which the disper-
sion can be achieved in a mixing op-ration. Bv using solids they
were able to start and stop a mixing operation a t will and thereby
to make progressive sampling and analysis in a more accurate
way than is convenient in fluid mixing. Their results check the
fist-order rate equation. The results should be directly applica-
ble to drum- or tumbler-type mixers. The authors also discuss
some of the similarities and differences betaeen liquid mixing and
the mixing of solid particles.
Buslik ( 7 ) has investigated the deviation in size in random
samples of granular solids of known size distribution. X relation
was developed between the standard deviation and size distribu-
tion and was s h o r n to be applicable t o a study of the rate of mix-
ing of solids of nonuniform size. Mixing is discussed from a sta-
tistical distribution viewpoint. The results are directly useful in
specifying sampling techniques. The statistical theory and data
are probably applicable to liquid mixing ratrs when liquid or
solid aggregates are present in a continuous liquid phase.
C O N T I N U O U S F L O W SYSTEMS
There has been need of a better understanding of mixing in ves-
sels where fluid flow is continuous. 1Iason and Piret (21) have
developed mathematical equations to account for the concentra-
tion changes which occur in continuously stirred tank reactor sys-
tems during transient periods of operation. Eldridge and Piret
(12) developed equations for the effect of the mixer on reactions
which occur in a series of continuous flow reaction vessels. Ex-
perimental data are given to show the validity of the theoretical
equations. These articles provide a sound theoretical basis to
account for the effect of changes in operating conditions and for
the effect of starting and stopping the operation in a series of re-
actors. They showed in the experimental work that a first-order
chemical reaction in a series of from one t o five reactors could be
predicted as to degree of completion on the basis of the theoretical
equations. Also, the rate constants were shown to be related t o
power input. Power input was accounted for both by t h a t due to
the rotating paddle impellers and by that due to the continuouslv
flowing feed. The experimental work was done in baffled reactor
vessels and under conditions which are reproducible in large scale
equipment. Therefore, the results are useful for fundamental
scale-up data.
Johnson and Talbot (17) described an experiment using a series
of nineteen mixers and settlers in series to study the distribution
of oxalic and succinic acid between water and butyl alcohol. The
work was done in small laboratory glassware. An equation for
the operation was developed and corresponds to one of those
given by Eldridge and Piret ( 1 2 ) .
APPLICATIONS OF MIXING T O SPECIFIC PROCESSES
Fermentation. Bartholomew and co-workers (1, 2 ) have
presented a comprehensive study of application of turbine-type
mixers to fermentation (penicillin and streptomycin). They de-
scribe a laboratory-pilot plant fermentor with a mixer, baffles,
and air-inlet. Engineering data for scale-up to larger size can be
obtained from such equipment. The important control variables
have been studied. The authors ( I , $ ) state that other laboratory
fermentors that have been described are unsatisfactory because
they are radically different from conventional large scale fer-
mentors] and thus the data obtained are not suitable for transla-
tion t o large scale. This is a n observation of utmost importance,
and the authors are the f i s t t o have published results of experi-
mental work in fermentation (gas-liquid mixing) using mixing
 January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY 113

pilot plant” or standard con-

verter had a capacity of 30
liters. The position of im-
peller, angle of blades, and
position of baffle do not cor-
respond to prevalent large scale
commercial practice, or t o con-
ditions normally considered
best for mixing or best for
scale-up data. Results for fer-
mentation were satisfactory
and the effect of air flow and
impeller speed were evaluated.
It is doubtful whether the
results can be translated to
large scale operation.
The production of circulin
was studied (26) in small scale
and in 100-gallon fermentors.
The fermentors are described,
turbine agitators were used,
but no relations are reported
for variations in impeller speed
or for variations in air flow.
Riboflavin produced by fer-
mentation was described (29)
for pilot plant operations on
two sizes. Aeration and agita-
tion (two speeds) were studied
along with other bio-variables.
One fermentor was equipped
Microbiological Pilot Plant Fermentors with a side entering propeller
agitator. Air wm introduced
through porous stones and a
techniques found to be most effective in large size fermentors. pipe-cross sparger. The other fermentors were equipped with
The science of mixing will gain markedly when small scale experi- top entering propeller agitators. The agitation used is not nor-
mentation is carried out under mixing conditions which are mally considered to be good for gas-liquid contacting, No
known to be optimum in larger scale equipment (33); Bartholo- power data are reported and no holdup data are given, so that
mew et al. give ample justification t o this point of view. a comparison cannot be made with fermentors of conventional
A theory is presented (g) for oxygen absorption by suspended types like those used by Bartholomew et al.
mycelia in aerated nutrient broth, which is complete and in ac- Petty, in a short article on fermentation (88),states that the
cord with modern chemical engineering principles. Experiments horsepower input by a mixer for fermentation varies from 0.3 t o
were performed to isolate various steps in the process, and the re- 2.0 hp. per 100 gallons. Unfortunately no mention is made of
sults clarify the concept of the mechanism of deep tank fermenta- size of equipment or other engineering variables.
tion. Data are given for rates of the several controlling steps in
the process. The effect of agitation was measured in terms of EXTRACTION AND OTHER PROCESSES
power, impeller size, and speed. The data are applicable for
scale-up purposes, and show the optimum conditions for the im- There are many types of continuous liquid-liquid extraction
portant fermentation variables. equipment, and mixing impellers are an integral part of some of
In addition to the articles just mentioned, there were six others them (24). One type which has been developed recently by
dealing with fermentation in which mixers of various types were Scheibel has been used for the extraction of acetic acid from
used. None of them give data suitable for engineering purposes methyl isobutyl ketone-water pair, and the reverse (36). The
*
as is the case for the work of Bartholomew et al. However, they performance data for a 12-inch diameter column are given. The
are of interest for various reasons and are mentioned here briefly. vertical column consists of alternate packed and open sections;
Hixson and Gaden (16) experimented with oxygen transfer in flat paddle-type impellers are rotated in the middle of each of the
submerged fermentation, They measured rates of transfer in a three unpacked sections. The object of the arrangement is to
fermentor of small diameter and without baffles. It is doubtful disperse one liquid in a secondary immiscible liquid by means of
that the data can be projected to large scale because dynamic simi- the mixing impeller, and then to coalesce the drops as they pass
larity cannot be achieved in a larger tank without baffles or their through the packed section. Thus the unit simulates the ordi-
equivalent. The data are in substantial agreement with the the- nary mixer-settler technique for liquid-liquid extraction. Contact
ory developed by the authors and by Bartholomew et al. stage efficiencies have been measured for various throughput rates
Brown and Peterson reported on penicillin fermentation in a and for various impeller speeds. It was found that there is an op-
Waldhof fermentor (6) and in a turbine-type fermentor of uncon- timum impeller speed for highest stage efficiency. High flows of
ventional design (6). The Waldhof fermentor is the type used liquids could be handled and some runs were achieved a t ef-
in some German fermentation work, No power or other data ficiencies of over 90%. Runs were also reported for other liquid
suitable for large scale design are given. Comparison was made pairs. These are the f i s t data reported in terms of engineering
with this unconventional fermentor (6) and it was concluded that variables for this type of mixer-settler-contactor .
the yields were slightly higher than in the standard fermentor, Hydrogenation and hydrogenolysis operations were discussed
“but the difference may not be significant.” The so-called “semi- by O’Boyle (26), and he gives a description and drawings for sev-
 114 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 43, No. 1

era1 large scale hydrogenators using mixing impellers to distribute Fesenko, N. G., Zavodskaya Lab., 15, 1396 (1949).
gas, mix the liquid, and transfer heat. Fossett, H., and Prosser, L. E., J . Inst. Mech. Eng., 160, No. 2 ,
224, 240, 245 (1949).
Dwyer and co-workers ( 1 0 , 1 1 ) report results of their studies on Hixson, A. W., and Gaden, E. L., Jr., IND.ENQ.CHEW.,42,
the desorption of unreacted isoprene from synthetic rubber latex. 1792 (1950).
They show the effect of mixing variables on the desorption r a k . Jackson, W.H., Chem. Eng., 57, 132 (1950).
A propeller was used, deeply submerged in a small cylindrical Johnson, J. D. A., and Talbot, A., 1 ~ a b t T e 164,
. 1054 (1949)
Lyons, E. J., Chem. Inds., 65, 517 (1949).
vessel. The data are indicative of the effect of mixing in large Masmusson. Karl. Iua. 20. 90 (1949).
scale reactors. Maytra, N. X., And Coulson,‘ J. M., J. I m p . Coll. Chem. Eng.
L A B O R A T O R Y STIRRERS SOC.,4, 135 (1948).
Mason, D. R., and Piret, E. L., IND. ENG.CHEM.,42, 817 (1950).
A number of types of small glass and metal impellers useful for Merz, O., Chemie-Ing.-Tech., 21, 99 (1949).
laboratory experimentation are shown in “Technique of Organic Mohle. Walter. Zbid.. 21. 335 (1949).
Chemistry” (35). Morello, Y. S., and Poffenberger, iY., IND. ENG.CHEM.,42, 1021
(1 950),
Potter and Kummerow (SO) described a mixer suitable for use Nelson, R. A., DeBoer, C., and DeVries, W. €Ibid.,
I., 42, 1259
with compressed air as the driving mechanism. Air is led from a (1950).
hub out through arms and discharged as in a pin wheel to give ro- O’Boyle, C. J., Ibid., 42, 1705 (1950).
tary motion to a shaft attached to the hub. O’Connell, F. P., and Mack, D. E., Chem. Eng. Progress, 46, 358
(1950),
A small stirrer drive for use in a glass-enclosed system has been Petty, R. D., Chem. Inds., 66, 184 (1950).
detailed by Tolbert, Dauben, and Rpid (38). The armature of a Pfeifer, V. F., Tanner, F. W., Jr., Vojnovich, C., and Traufler,
small induction motor is mounted in a glass cylinder attached to a D. H., IND. ENG.CHEM.,42,1776 (1950).
ground joint flask fitting. Potter, G. D., and Kummerow, F. A., Science, 110, 592 (1949).
Rushton, J. H., IND. ENG.CHEM.,42, 74 (1950).
LITERATURE CITED Rushton, J. H., Proc. Natl. Conf. I n d . Hgdraulics, 111, 119
Bartholomew, W. H., Karow, E. O., and Sfat, M. R., IND.ENG. (1949).
CHEM.,42, 1827 (1950).
Rushton, J. H., in “Technique of Organic Chemistry,” Weis-
Bartholomew, W. H., Karonr, E. O., Sfat, M. R., and Wilhelm. berger, ed., 1-01. 111, chap. 3, New York, Interscience Pub-
R. H., Ibid., 42, 1810 (1950). lishers, 1950.
Bershader, D., and Psi, S.I., J . AppEied Phys., 21, 616 (1950). Rushton, J. H., Costich, E. W., and Everett, H. J., Chem. Eng.
Black, C. R., J . I m p . CoZZ. Chem. Eng. Soc., 4, 111 (1948). Prowess. 46. 395. 467 11950).
Brown, W. E., and Peterson, W. H., IND.ENG.CHEX.,42, 1769 (35) Scheibel, E. G., and Karr, A. E., IND.ENG. CHEM.,42, 1048
(1 w,n\. (1950).
(36) Schneidcr, Robert W., Chem. Eng., 56, S o . 5, 157 (1949).
\ _ _ _ _ , _

Ibid., p. 1823.
(37) Serner, H. E., Ibid., 57, 128 (1950).
Buslik, David. A.S.T.M. Bull. 165. 66 (1950). (38) Tolbert, B. M., Dauben, William G., and Reid, James C., Anal.
Chem. Inds., 67, 275 (1950).
Chem., 21, 1014 (1949).
Coulson, J. M., and Maitra, N. X., Ind. Chemist, 26, 55 (1950). (39) Valetine, K. S., and TvIacLein, G., in section 17, “Chemical
Dwyer, 0. E., and Baumann, J. B.,IND. ENG.CHEM.,42, 1230 Engineers’ Handbook,” Perry, ed., New York, McGraw-Hill
(1950). Book Co., 1950.
Dwyer, 0. E., and Burke, L. T., Ibid., 42, 1240 (1950).
Eldridge, J. W., and Piret. E. L., Chenz. Eng. Progress, 46, 290
(1950). RECEIVED
October 24, 1950.

____
LINCOLN T. WORK
420 L E X I N G T O N A V E . , N E W Y O R K 17, N. Y .

Last year’s report on crushing and grinding indicated intensified work in this field and the from a preprint; but the papers and
past year has shown maturing results. Practically all the areas discussed in recent years are discussion have just been published
marked b y progress in technical publications. Books and symposia contribute markedly. and reviewed (66). Fischer (38) de-
Dalla Valle is developing a micromeritics laboratory at the Georgia Institute of Technology, votes a 69-page chapter to particle
and Allis-Chalmers Corp. has a basic industries research laboratory with a complete pilot scale size, covering size, its distribution, a
plant for crushing, grinding, and concentration tests, University of Minnesota workers and detailed discussion of methods of
others are getting to the hard core of the fundamentals of grinding. There is renewed activity measurement, tinting strength, over-
in jet grinding. Among developments in grinding media is the announcement of a cylindrical size particles, and data on many
ball grinding medium of superior hardness and weight. materials. The AMERICANCIIEMI-
CAL SOCIETY’S Christmas 1950 Sym-
posium under the Division of Indus-
HE report last year ( 6 7 ) indicated that work in this field had trial and Engintering Chemistry is on the subject of aerosols,

T been intensified, and this past year has shown maturing

results. Practically all t h e areas which have been dis-
cussed in recent years are marked by some progress in technical
publications, and some of the more striking of these are sum-
marized here.
Books or symposia contribute markedly. The 1950 edition of
Perry’s “Handbook of Chemical Engineering” (51) contains a
section on size reduction (KO. 16) which is a complete revision
by C. E. Berry. While plentiful in data, it gives new emphasis
to principles. A symposium was held in Britain in 1947 on
methods and applications of particle size This was revieMed
and one session is devoted t o particle size measurement (63).
Laboratory announcements have been made. Dalla Valle is
developing a micromeritics laboratory a t the Georgia Institute
of Technology ( 1 9 ) . Allis-Chalmers Corp., Milwaukee ( d ) ,
has a basic industries research laboratory to give engineering
information to guide in designing more efficient plants. It has a
complete pilot scale plant for crushing, grinding, and concentra-
tion tests.
There is renewed activity in jet grinding. The R. T. Vander-
bilt plant for grinding large quantities of talc to fine sires is now
operatingat Gouverneur, S Y. ( 1 % ) .
 114 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 43, No. 1

era1 large scale hydrogenators using mixing impellers to distribute Fesenko, N. G., Zavodskaya Lab., 15, 1396 (1949).
gas, mix the liquid, and transfer heat. Fossett, H., and Prosser, L. E., J . Inst. Mech. Eng., 160, No. 2 ,
224, 240, 245 (1949).
Dwyer and co-workers ( 1 0 , 1 1 ) report results of their studies on Hixson, A. W., and Gaden, E. L., Jr., IND.ENQ.CHEW.,42,
the desorption of unreacted isoprene from synthetic rubber latex. 1792 (1950).
They show the effect of mixing variables on the desorption r a k . Jackson, W.H., Chem. Eng., 57, 132 (1950).
A propeller was used, deeply submerged in a small cylindrical Johnson, J. D. A., and Talbot, A., 1 ~ a b t T e 164,
. 1054 (1949)
Lyons, E. J., Chem. Inds., 65, 517 (1949).
vessel. The data are indicative of the effect of mixing in large Masmusson. Karl. Iua. 20. 90 (1949).
scale reactors. Maytra, N. X., And Coulson,‘ J. M., J. I m p . Coll. Chem. Eng.
L A B O R A T O R Y STIRRERS SOC.,4, 135 (1948).
Mason, D. R., and Piret, E. L., IND. ENG.CHEM.,42, 817 (1950).
A number of types of small glass and metal impellers useful for Merz, O., Chemie-Ing.-Tech., 21, 99 (1949).
laboratory experimentation are shown in “Technique of Organic Mohle. Walter. Zbid.. 21. 335 (1949).
Chemistry” (35). Morello, Y. S., and Poffenberger, iY., IND. ENG.CHEM.,42, 1021
(1 950),
Potter and Kummerow (SO) described a mixer suitable for use Nelson, R. A., DeBoer, C., and DeVries, W. €Ibid.,
I., 42, 1259
with compressed air as the driving mechanism. Air is led from a (1950).
hub out through arms and discharged as in a pin wheel to give ro- O’Boyle, C. J., Ibid., 42, 1705 (1950).
tary motion to a shaft attached to the hub. O’Connell, F. P., and Mack, D. E., Chem. Eng. Progress, 46, 358
(1950),
A small stirrer drive for use in a glass-enclosed system has been Petty, R. D., Chem. Inds., 66, 184 (1950).
detailed by Tolbert, Dauben, and Rpid (38). The armature of a Pfeifer, V. F., Tanner, F. W., Jr., Vojnovich, C., and Traufler,
small induction motor is mounted in a glass cylinder attached to a D. H., IND. ENG.CHEM.,42,1776 (1950).
ground joint flask fitting. Potter, G. D., and Kummerow, F. A., Science, 110, 592 (1949).
Rushton, J. H., IND. ENG.CHEM.,42, 74 (1950).
LITERATURE CITED Rushton, J. H., Proc. Natl. Conf. I n d . Hgdraulics, 111, 119
Bartholomew, W. H., Karow, E. O., and Sfat, M. R., IND.ENG. (1949).
CHEM.,42, 1827 (1950).
Rushton, J. H., in “Technique of Organic Chemistry,” Weis-
Bartholomew, W. H., Karonr, E. O., Sfat, M. R., and Wilhelm. berger, ed., 1-01. 111, chap. 3, New York, Interscience Pub-
R. H., Ibid., 42, 1810 (1950). lishers, 1950.
Bershader, D., and Psi, S.I., J . AppEied Phys., 21, 616 (1950). Rushton, J. H., Costich, E. W., and Everett, H. J., Chem. Eng.
Black, C. R., J . I m p . CoZZ. Chem. Eng. Soc., 4, 111 (1948). Prowess. 46. 395. 467 11950).
Brown, W. E., and Peterson, W. H., IND.ENG.CHEX.,42, 1769 (35) Scheibel, E. G., and Karr, A. E., IND.ENG. CHEM.,42, 1048
(1 w,n\. (1950).
(36) Schneidcr, Robert W., Chem. Eng., 56, S o . 5, 157 (1949).
\ _ _ _ _ , _

Ibid., p. 1823.
(37) Serner, H. E., Ibid., 57, 128 (1950).
Buslik, David. A.S.T.M. Bull. 165. 66 (1950). (38) Tolbert, B. M., Dauben, William G., and Reid, James C., Anal.
Chem. Inds., 67, 275 (1950).
Chem., 21, 1014 (1949).
Coulson, J. M., and Maitra, N. X., Ind. Chemist, 26, 55 (1950). (39) Valetine, K. S., and TvIacLein, G., in section 17, “Chemical
Dwyer, 0. E., and Baumann, J. B.,IND. ENG.CHEM.,42, 1230 Engineers’ Handbook,” Perry, ed., New York, McGraw-Hill
(1950). Book Co., 1950.
Dwyer, 0. E., and Burke, L. T., Ibid., 42, 1240 (1950).
Eldridge, J. W., and Piret. E. L., Chenz. Eng. Progress, 46, 290
(1950). RECEIVED
October 24, 1950.

____
LINCOLN T. WORK
420 L E X I N G T O N A V E . , N E W Y O R K 17, N. Y .

Last year’s report on crushing and grinding indicated intensified work in this field and the from a preprint; but the papers and
past year has shown maturing results. Practically all the areas discussed in recent years are discussion have just been published
marked b y progress in technical publications. Books and symposia contribute markedly. and reviewed (66). Fischer (38) de-
Dalla V a l l e is developing a micromeritics laboratory at the Georgia Institute of Technology, votes a 69-page chapter to particle
and Allis-Chalmers Corp. has a basic industries research laboratory with a complete pilot scale size, covering size, its distribution, a
plant for crushing, grinding, and concentration tests, University of Minnesota workers and detailed discussion of methods of
others are getting to the hard core of the fundamentals of grinding. There is renewed activity measurement, tinting strength, over-
in jet grinding. A m o n g developments in grinding media is the announcement of a cylindrical size particles, and data on many
ball grinding medium of superior hardness and weight. materials. The AMERICANCIIEMI-
CAL SOCIETY’S Christmas 1950 Sym-
posium under the Division of Indus-
HE report last year ( 6 7 ) indicated that work in this field had trial and Engintering Chemistry is on the subject of aerosols,

T been intensified, and this past year has shown maturing

results. Practically all the areas which have been dis-
cussed in recent years are marked by some progress in technical
publications, and some of the more striking of these are sum-
marized here.
Books or symposia contribute markedly. The 1950 edition of
Perry’s “Handbook of Chemical Engineering” (51) contains a
section on size reduction (KO. 16) which is a complete revision
by C. E. Berry. While plentiful in data, it gives new emphasis
to principles. A symposium was held in Britain in 1947 on
methods and applications of particle size This was revieMed
and one session is devoted to particle size measurement (63).
Laboratory announcements have been made. Dalla Valle is
developing a micromeritics laboratory a t the Georgia Institute
of Technology ( 1 9 ) . Allis-Chalmers Corp., Milwaukee ( d ) ,
has a basic industries research laboratory to give engineering
information to guide in designing more efficient plants. It has a
complete pilot scale plant for crushing, grinding, and concentra-
tion tests.
There is renewed activity in jet grinding. The R. T. Vander-
bilt plant for grinding large quantities of talc to fine sires is now
operatingat Gouverneur, S Y. ( 1 % ) .
 *
January 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY
Among developments in grinding media is the announcement
of the U. S, Stoneware Co. of a new cylindrical ball grinding
medium of superior hardness and weight (17).
PARTICLE SIZE
Brocard (11) has published a comprehensive treatment in
French, and other examples of foreign work are of interest (49,
67). Specific developments, as with the light or the electron
microscope, are reported. Polystyrene “billiard balls” were
announced as a measuring instrument (18). The property of
polystyrene to form uniform stable emulsions of definite particle
size is utilized for calibration or comparison. Jellinek (38), in
giving mathematical treatment to the size frequency distribution
of emulsions, used the microscopic count method. Sharpe (60)
has endeavored to simplify the operation of the electron micro-
scope by devising a graticule for use in particle size analysis.
Working with radioactive aerosols, Leary and FitzGibbon (44)
employ a radioautograph for determination of particle size.
Haultain (36) has simplified his classifying device, known as the
Infrasizer, and now announces a new one where the number of
cones have been reduced from seven t o two. The report indi-
cates that glass spheres have been split quickly and accurately
a t 25 microns.
Rose (66, 66) discusses the limitations of the light extinction
method for particle size. He has designed a rough instrument
for the measurement of light extinction and light scattering.
This, combined with sedimentation, is used for determination of
size distribution. He 6nds consistently satisfactory results using
dark-colored ilmenite and light-colored zircon sand, and he is now
working toward an instrument for accurate measurement of size.
The scattering index is about 6 for sizes below 5 microns, as re-
quired by Rayleigh’s law, and it drops rapidly to a level of 2
a t larger sizes, as required by the laws of geometric optics.
Bardwell and Sivertz (7) use the Debye-Einstein equation for
determining size of small dielectric particles of latex. A Beck-
man spectrophotometer was used for turbidity measurements,
and a Zeiss dipping refractometer was used for refractive index
measurements. Eberspaecher (28) reports a direct graphic de-
termination of particle size from the half width of x-ray inter-
ference patterns.
Sane et al. (69) consider the correction factor of the Kelly tube,
which is caused by movement of fluid from the capillary, worthy
of attention, and, by means of an overflow and tilting arrangement
in which they give careful attention to measuring the angle of
inclination, they claim good results without the necessity for
this correction.
Adsorption methods have been the subject of considerable
work. Loebenstein and Deitz (46) offer a simplified technique
for determination of surface area by adsorption of nitrogen.
Bartell and Dodd ( 9 ) report on surface areas of crystalline carbon
- and carbide powders as measured by the adsorption of nitrogen.
Lauterbach et al. (45) present specific surface determinations of
uranium dusts by low-temperature adsorption of ethane. Smith
and Hurley (61) calculate particle size of carbon blacks from
adsorption of fatty acids,
- MILLS AND MILLING
The theory of reducing action has been advanced by,several
researches. Axelson and Piret (6) have subjected single par-
ticles of crystalline quartz to fracture under slow compression.
Energy concentration a t fracture ranges widely between 0.3 and
44.6 kg.-cm. per gram, with the most probable value as 1 kg.-cm.
per gram. These authors apply a simple statistical attack to
experimental data to get size distribution qualities, energy, and
efficiency for ’primary crushing conditions. Efficiencies range
from 1.7 to 26.5%, with the best value about 10. With this type
of penetrating analysis, the contrasting concepts of Kick us.
Rittinger should find their true places.
11s
Adams, Johnson, and Piret (1) have, in the series on energy-
new surface relationships, shown the impact crushing character-
istics of sodium chloride, relating permeability and surface area
measurements. The low crushing efficiency confirms earlier
work. They find for impact that energy versus new surface is
not a straight line. They offer x-ray evidence of plastic deforma-
tion. The third part of that series by Johnson, Axelson, and
Piret (39) shows application of gas adsorption measurements in
the crushing of quartz. The drop weight method here too gives
a curved relation for energy input to new surface, but with slow
compression it is a straight line. Correlation of permeability
and adsorption is good, the adsorption values being consistently
double those from the permeability test.
Von Szantho (64) has shown value for surface agents in fine
wet grinding. With the right concentration of agent, the sur-
face per unit of energy is more than doubled. Agents are selec-‘
tive on complex ores. Podszus (62), in attacking fundamentals
in the mill, considers control of flow directions and a rapid suc-
cession of impacts essential to optimum operation.
The usual announcements of new equipment (20, 41) have
been made. Many of these are small modifications, often of
great importance to the plant operator. Others are significant
in starting new trends. Noteworthy in that regard are de-
velopments in sonics. A review (13) of sonic precipitation of
smoke fumes and dust particles gives technical data on size and
amplitude ratio. St. Clair (68) discussed agglomeration of
smoke, fog, or dust particles by sonic waves. Danser and Neu-
mann (24) discussed systems, while Danser (23) discussed their
use in removing &e particles from processing exhaust gases.
This may become an important factor relating t9 aerosols from
grinding processes. Smith and Stafford (62) have reported the
A. D. Little development of the paper-asbestos filter for the Army,
which combines low pressure drop with effective filtration.
Dorrco (16) has shown marked progress with the Dorrclone sepa-
rator, €or fractionation and collection. It (14) has also an-
nounced a hydro-oscillator for classification, which, by keeping
oversize mobile, gives better classification.
There is activity in air-jet mills. The processing of talc, now
in operation (33), gives finest grade of 0.8-micron average di-
ameter. The Wheeler mill (19)is described with reference to
high capacities and fine sizes with some drying in its operation.
Andrews and Speirs ( 4 ) received a patent on a jet pulverizer and
dryer.
Ball mill grinding media, always a problem, have received more
than the usual attention. The U. S. Stoneware Co. (21) an-
nounces a new shape and type of ball, which is 75 to 80% heavier
than porcelain and much harder. The development of a cylindri-
cal shape which does not readily deteriorate to spherical gives an
action tending toward that of a rod mill. Marked improvement
in wear resistance, and less contamination coupled with improve-
ment in mill performance, are indicated. Nordquist and Moeller
(48) and Knight and Dyrenforth (42) have studied ball wear.
The latter, using different balls and ores, confirm an earlier finding
of Devany and Coghill that mill wear is proportional to mill
power rather than tonnage throughout. Payne and Steinebache
(60)report on casting grinding balls continuously.
Performance of mills has had scrutiny. Anselm ( 6 ) reports on
grinding cement in a three-chamber mill, showing the relation of
charge ball size and weight to performance. White (66) reports
on the conical trunnion overflow and cylindrical grate mills in
copper operations. Myers and Lewis (47) give a progress report
on grinding a t the Tennessee Copper Co.
Other developments are: Andersen ( 3 ) on crushing plant, de-
sign; Djingheuzian (26) with a review; Herz (37) in perspective
of milling operations; .the John T. Dyer Quarry Co. (65) on
operation of a portable mill; Pulva Corp. (16) with its swing
hammer twin-screw feed for pigments, pharmaceuticals, dyestuffs,
and the like; Craiglow (22) on the electric heating of screens to
avoid clogging; the largest deep frame jaw crusher (64); double
116 INDUSTRIAL AND E N G I N E E R I N G C H E M I S T R Y
impeller breakers with dual impact action (30); and ten ways to
cut grinding costs (39).
APPLICATIONS
A few specific industrial applications remain to be cited. Fine
(31)shows how graded glass sand is prepared by grinding and
classification. Studies in grinding cement in a cylindrical mill
are reported from Japan (40). Agreement with the Rosin-
Rammler equation is claimed. Decrease in grinding efficiency
a t elevated temperatures is attributed to changes in the gypsum
and other elements. It is noted that gypsum is ground to the
fiyer sizes, about one half of the total quantity being below 5
microns.
Tiranglen (68) shows the effect of overvoltage, cathode film,
and hydroxide formation a t the cathode as it relates to electro-
deposited metal powders, deposited either a t size or in brittle form
with subsequent grinding.
The paint industry has contributed more than its usual number
of papers in this field. Barkman (8) reviews equipment and
methods for making paints, including rolls, ball mills, and chol-
loid mills. Doubleday and Barlman (27) employ the Hegman
grind gage as a means of evaluating mill o eration. Bern-
stein (10) discloses a roller type of applicator g r a fineness of
grind gage, and with it, studies the progress of the grind and eval-
uates dis ersion on the three-roll mill. Moore (46) indicates that
jet-mille8 pigments are available at practical prices. Pigments
are chiefly of the iron oxide type, except for silica. The sixteen
materials generally show top sizes in the 5- to 10-micron range, in
comparison with normal pigments running to two or three times
that limit. Dispersible agglomerates show greater reduction
than do straight grinds, as is t,o be expected. Drying in the mill
gives superior qualities in plastics, rubber, cement colors, wall
paper, and paints, the other advantages being greater color value
and ease of dispersion. Davidson (65) endeavors to correlate
the electron microscope with color and working properties.
He compares the electron microscope for this with the visible, to
the expected disadvantage of the latter. Tinting strength, oil
absorption, mass tone, shape, and dispersion are compared.
Harris and Wolock (34, 35) have studied the permeability and
porosity of paint films. The critical pigment volume concentra-
t.ion and surface as well as general shape characteristics were in-
terrelated. The critical volume pigment concentration is clearly
critical.
Altogether there is healthy activity in the field, and progress of
a substantial nature is being made.
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(16) X d . , p. 2196.
(17) Ibid., p. 3250.
(18) Ibid., pp. 3504-5.
(19) Chem. Inds., 65, 542 (1949); Mining Eng., 187, T 369-73
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END OF SIXTH ANNUAL UNIT OPERATIONS REVIEW
Reprints of this and earlier Unit Operations reviews may be purchased for 50 cents each from the
Reprint Department, American Chemical Society, 11 5 5 Sixteeenth St., N.W., Washington 6, D. C.
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RECEIVED
Sovember 16, 1950.
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