TWO-PHASE FLUID-SOLID FLOW

FREDERICK A. ZENZ
New York University, University Heights, N . Y .

i)

Results of a series of experiments to determine the flow

characteristics of particle-fluid mixtures are presented as
a guide to more extensive work on the pressure losses in
catalyst carrier lines and flowing fluid beds. Quantitative
data are presented for the vertical and horizontal flow of
three essentially uniform particles 0.0231,0.0366, and 0.066
inch in diameter, and a material of 0.0066-inch mean diameter exhibiting a fivefold variation in particle size. The
experiments were all carried out in a 1.75-inch inside
diameter Lucite tube with air as the fluid medium.

N R E C E N T years the advances in catalytic cracking and

fluid bed processes have created new interest in the subject
of the behavior of solid particles in a stream of carrier gas. The
general subject would appear at first to be routine to those
interested in the design of pneumatic conveying and separation
systems. However, investigation of the published literature
indicates that pneumatic conveying is an extremely empirical
art. Rather high velocities are recommended for conveying
specified grains (1, 17), and up until the past year very little
basic information (7, 11, a4, 2%) was available concerning the
effects of variation in particle size, velocity, loading, etc. The
recent, more thorough, studies (9, 14, 83, 26) in this field have
been carried out in pipes with rather small diameters at velocities
considerably greater than the particle terminal and fluidization
velocities thus entirely masking the relation of fluid-particle
flow t o the equilibria a t fluidization. The experiments described in this paper were undertaken, therefore, with the hope
of obtaining fundamental qualitative, and somewhat quantitative, data to establish certain regions of the so-called phase diagram for solid particle-gas systems.

cylinder. I n order to determine whether the flow rates would be

affected by a flow of air past the valve tending t o pull material
through a t possibly a faster rate, the calibrations were repeated
with the hopper in operating position and the air control valve
wide open. No effect of air rate was detectable.
The main object of these experiments was to obtain a qualitative understanding of the relationships between the various phases
of fluidization and the flow chatacteristics of solid-fluid suspensions and, therefore, the adequacy of the calming length prior to
the test section was not taken into serious consideration. The
length of pipe in which the solids undergo acceleration, thereby
considerably increasin the pressure drop, is a t present being
thoroughly investigate8 by Russ ( d 3 ) who reports it t o be a function of solids flow rate W , fluid velocity, and particle characteristics. The effect of the accelerating distance is important
in design calculations inasmuch as Rusa reports acceleration t o
persist in many instances as far as 15 feet from the solids feed
point. I n the concurrent vertical flow arrangement, shown in
Figure 1, A , the solids feed point was followed by a straight section 20 inches in length, then a long sweep elbow of 12 inches
radius and another straight vertical section of 20 inches, prior
t o the lower pressure tap. In the arrangement given in Figure
1, B, the horizontal distance between the solids feed point and the
upstream pressure tap was 4 feet.
It was planned to do a systematic study of the uniform spherical, angular, and mixed-size materials ranging in each category
from 0.06 inch in diameter down to possibly 0.002 inch or smaller.
However, the difficulty in obtaining small uniform spheres and the
complexity of the changing flow characteristics of mixed-size
material made i t advisable first to conduct exploratory tests with
a few more easily obtainable particles for orientation purposes
before altering the equipment to make more thorough quantitative investigations. The characteristics of the materials reported in this study are given in Table I. Note t h a t the rape
seed, sand, and glass beads may each be considered essentially
uniform size material, that they cover nearly a threefold change
in density and particle size between the three different particles,
and include one angular and two spherical shapes. Salt is the
only quantitatively reported mixed-size material and according
t o the screen analysis exhibits approximately a fivefold skewed
probability distribution in particle size.

EXPERIMENTAL PROCEDURE

Figure 1 illustrates the arrangements of the apparatus for

GRAPHICAL REPRESENTATION OF DATA
studying vertical and horizontal flow. The experiments were
carried out batchwise using a vacuum system in order t o simplify
The experimental results for these four materials in vertical
the construction of the apparatus. I n carrying out a run, the
and horizontal flow are shown in Figure 2. The nearly vertical
solids feed hopper was filled with the material to be investigated,
dotted lines, in the four upper charts for vertical flow, represent
the blower started, and the air control valve fully opened. The
the disperse phase fluidization curves. This manner of plotting
solids feed control valve was then opened a specified number of
fluidization data enables clearer visualization of the relationships
turns and pressure drops recorded a t various air rates as the air
between particle-gas flow and the process of fluidization. The
controlvalve was set to more
closed positions. This resulted
in a series of pressure drop and
air velocity measurements for
TABLE
I. CHARACTERISTICS
OF MATERIALS
USED
a given solids feed control valve
position, corresponding t o a
zu$$l
Rape seed
Sand
Glass beads
Salt
Peter Henderson Port Washington, Minnesota Mining
General Foods Corp.,
given value of W , established
Seed Co.
L. I.
and Manufacturing Diamond Crystal
by calibration of the valve.
Co., Scotohlite
The solids feed control valve
Shape
Spherical
Sharply angular
Spherical
Granular
was calibrated with a stop
Density, p9, lb./ou. it.
68
165
155
131
Diameter, inch
watch using various quantities
0,066
0.0366
0.0231
0,0066
,of each material. It was found
Screen analyses=,U. S.
Standard Mesh No.
that none of the materials in10
0.9
...
...
...
vestigated exhibited any fluid
12
98.6
...
property of increasing flow rate
14
0.1
10:3
...
...
20
0.4
83.5
0.2
...
with increase in head of
.
.
.
30
0.2
98.6
material in the feed hopper.
40
...
...
1.0
0.2
60
...
...
0.2
40.2
Each calibration run was re80
...
...
...
5.8
peated several times with the
100
...
...
...
27.0
.solids d i s c h a r g i n g t h r o u g h
120
...
...
...
11.0
170
...
...
...
13.6
the valve into a large open
200
...
...
...
1.3
. . I

1 Present address, Hydrocarbon

Research, Inc., 115 Broadway, New
York. N . Y .

Through 200
...
Screen analyses before and after the flow experiments indicated no changes i n particle size.
I

2801

0.9

INDUSTRIAL AND ENGINEERING CHEMISTRY

2802

Vol. 41, No. 12

unit length. This typical fluidizat,ion

curve shown in Figure 3, G , also intersects the pressure drop line for the
empty pipe a t the terminal velocity of
t'he particles. As noted in Figure 3 ,
G, the fluidization curve becomes nearly
vertical a t high voidages; it is this portion of the curve that is represented by
the dotted curves in the upper charts
of Figure 2. The lines labeied W = 0
(Figure 2 ) are the observed pressure
drops for the flow of air only, with no
suspended solids (corresponding to the
E = 1.0 line in Figure 3, G).

A . D.

A.1
141 C O N C J R R E N T

VERTICAL

A.I.

FLOW

CONCURRENT VERTICAL FLOW

The upper charts of Figure 2 present the observed experimental data

LEGEND
on the concurrent flow of air-solids
A I. Room A i r I n l e t
AD
Air Discharge
suspensions in the vertical tube (Figure
E
C e n t r i f u g a l Blower
c
-T S
1, A ) recorded a t constant solids feed
A I
C
Cyclone
control valve position, or solids mass
CV-I
Air C o n t r o l v a l v e
CV-2
Solldr Feed C o n t r o l Volve
velocity, W . In these experiments i t
H
solids F e e d H o p p e r
(8) H O R I Z O N T A L
FLOW
was noted t h a t a t velocities below that
M
A8r R o l a m e l e r
R
Sollds Receiver
a t which the curves show minimum
T.S.
44" T e s l S e c t i o n
pressure drops, the particle velocities
Figure 1. Arrangement of Equipment for Vertical and Horizontal Flow
decrease, there is a considerable increascx
Experiments
in holdup of particles in the tube, and
solids flow apparently continues through
pressure drop-velocity curves for fluid beds ( 1 9 , ,936) are usually
the increasingly dense mass of slowly moving particles float.ing in
depicted as shown in Figure 3, F , in which the pressure drop across
the tube, The weight of material holdup, slowly ascending in the
the entire bed is plotted versus velocity. The E $ fixed-bed line
tube,
accounts for the increascd pressure drop. As the air velocrepresents the typical curve which may be computed from the
i t y was decreased, the movement, of the particles became exwell known Chilton-Colburn ( 6 ) correlation. As the gas velocity
is increased to the point a t which the bed is lifted, the particles
bremely turbulent and the holdup of material increased unt,il
may rearrange themselves in as loose as possible, but yet fixedeither the blower could no longer provide the pressure different,ial
bed configuration. The voidage in this loosest possible conrequired to support the material and the bed collapsed causing
figuration, designated as emf, has been correlated empirically with
all flows to cease, or until slugging occurred to such an extent
particle size and shape ( 1 9 , 10)and is illustrated diagrammatically
in the comparison of Figures 3, A and B, where e 8 is a lower voidage
that manometer readings, fluctuat,ing in some instances by as
representative of a more densely packed or settled bed. At,
much as' 10 inches of water, indicated extremely unst,eady and
velocities (through the loosest possible fixed-bed configuration)
undesirable flow conditions. In the vertical flow chart,s of
great enough to give a pressure drop equal to the weight of maFigure 2, the onset of slugging is indicat,ed by the dashed lines
terial in the bed per unit area of tube cross section, the bed expands so that all the particles are no longer touching and the bed
representing the voidage, e,iu0, or rather solids concentration
is in the so-called fluid state. Further increase in velocity is
within the tube, at which flow becomes erratic and slugging is
accompanied by further increase in bed expansion, or voidage,
observed. Slugging is also prevalent in fluidization experiments
as shown in Figures 3, C and D; the pressure drop, Lip, across
(4,19, 13, 66). It has been observed that if the gas velocity
the entire bed (recorded by the pressure taps on the left sides of
the columns) in both cases remains equal to the weight of bed,
through a dense fluid bed is increased, a velocity is finally reached
as shown in Figure 3, F . The line in Figure 3, F , labeled E = 1.0
at which slugging sets in; if the velocity is still further increased
is the pressure drop curve for the fluid flowing in the empty
till the voidage becomes rather high (approximately within the
tube as may be calculated from the Fanning equation. The
range 0.9 to l.O), smooth disperse phase fluidization is established
horizontal fluidization line in Figure 3, F , intersects the E = 1.0
curve a t the velocity, ut, required to balance or support a single
again. The minimum values of E , corresponding to maximum
particle in the tube. This balancing velocity usually is taken t o
solids concentrations, for smooth disperse phase fluidization of the
be equal to the terniinal or free-fall velocity as computed from
particles investigated in this work are indicat,ed by the interdrag coefficient correlations (18). It is assumed that in calculasection of the dashed slugging loci with the dotted fluidization
tions for any particular case, due corrections will be applied to
the standard drag coefficient correlations. By due corrections
curves in the upper charts of Figure 2 . The values of estuv are
is meant taking into account the wall effect, as cited by Ladenindicated on the charts, The fact that a considerably denser
burg (16); the relative tube and particle Reynolds number, to
concentration (lower E ) of rape seed can be maintained in stable
account for the controlling flow pattern (the difference between
suspension possibly is associated wit,h the considerably lower
actual balancing velocity and terminal or free-fall velocity can be
density of these particles. Fluid bed studies have shown t h a t
appreciable); and the e8ect of vessel height (the differences in
velocities required t o support or balance single particles 2, 5 ,
the closer the density of the solid material to that of the fluidizing
10, 20, etc., feet up from the bottom of a vertical tube have been
medium, the narrower the range of velocities within which slugreported t o vary considerably).
ging is observed, The ratio of solids t o fluid density is, how-ever,
I n a tube in which a continuous fluid-particle flow is mainonly one of the many factors affecting the slugging tendencies of
tained, the pressure drop generally is discussed in terms of unit
fluid-solid systems.
length of tube. Because a fluid bed const,itutes a form of such
continous flowing system, in which, however, there is only a net
The vertical flow data of Figure 2 indicate t h a t the fluid
flow of fluid, i t seems reasonable to make a plot of fluid bed presvelocity, uCh,at which a solids mass upward flow, W t ,chokes the
lure drop on a unit-length-of-bed basis. Such a plot is illustube, may be related t o t,he superficial fluid velocity, U E , ~a~t ~ ,
trated in Figure 3, G, where the pressure drop, across the taps on
which a disperse fluidized suspension begins to slug, by the equathe right sides of the columns depicted in Figures 3, A to E,, is
tion:
plotted versus velocity. As the bed expands, the voidage increases and there is less weight of charge material within a unit
t = P P (1 - W V Q ) ( U c h - %slug)
length of the bed, thus giving lower pressure drop across such

INDUSTRIAL AND ENGINEERING CHEMISTRY

December 1949

-Rape

Seed-

3----. Glass

Beads

-MIXED-SIZE

UNIFORM- S I Z E PARTICLES

2803

c--- Sand-

I
MATERIAL I

Salt

Superficial A i r Velocity, u , ft./sec.

Figure 2.

Experimental Data on Vertical and Horizontal Flow of Dispersed Air-Solids Suspensions i n a 1.75-Inch
lnside Diameter Lucite Tube

This indicates the desirability of establishing a fluidization correlation permitting prediction of the slugging range of a given
particle-fluid system. This will become more apparent in the
discussion of the so-called phase diagram for fluid-solids-flow.
HORIZONTAL FLOW

A,

The charts in the lower half of Figure 2 present the observed

experimental data for the horizontal flow (Figure 1,B)of air-solids
suspensions. The breaks in the curves are due t o the settling
out of particles in the tube. This is a very sharply defined phenomenon exhibiting a very definite relationship between the rate
of flow of solids and the gas velocity, U S , at which particle settling
begins. At a constant solids flow rate (fixed solids feed valve
position), i t was found that when the air rate was decreased t o a
certain velocity, us, the particles began t o settle out in the tube
and continued t o settle out until the tube was nearly half full,
before a steady state was again established and the discharge
rate, W , equaled the feed rate. At velocities lower than us
more material settled out, filling the tube with a deeper layer of
particles and creating a n increase in pressure drop. The particles t h a t settled out in the tube remained stationary; there was
no rolling of the material or pushing of the entire layer through
the tube, though a few of the particles on the surface of the layer
were bounced along in the direction of gas flow. The steady flow
of solids, W , occurred in the well dispersed, solid-gas mixture
flowing in the space above the settled layer of particles in the
same manner as in flow a t velocities greater than uQ. The curves

were duplicated exactly when approached from low velocities,

less than us. When the air rate attained the value at us, the
tube became completely cleared of all settled material and steady
flow of a well dispersed particle-gas mixture continued. Repeated experiments a t the settling velocities showed t h a t there was
no consistent tendency for the material t o begin settling out either
at several or at any one particular point in the tube. It is felt,
however, t h a t this settling velocity may be somewhat dependent
on the characteristics of the inner surface of the pipe, a rougher
surface tending to induce settling a t possibly lower velocities due
to increased turbulence at the pipe wall. The effect is probably
small.
The superficial horizontal fluid velocity at which material
settles out of the flowing suspension has been termed the saltation velocity (28). Comparison of horizontal and vertical
flow data for the uniform particles shown in Figure 2 resulted in
the surprising observation t h a t choking in vertical flow occurred
at the same velocity as saltation in horizontal flow. I n other
words, at a given solids flow rate
u& equals us for uniform particles. This was not observed in the salt experiments. Inasmuch as salt has a fivefold particle size range, this may be explained as a consequence of particle-to-particle contacts because
of the differences in velocities between larger and smaller particles. I n horizontal flow it is conceivable t h a t the differences
in the particle velocities may cause larger and smaller particles t o
collide thus tending to produce a certain degree of aggregation
which would tend t o cause saltation a t velocities higher than
might otherwise be expected. A plot of W versus uRfor hori-

w,

INDUSTRIAL A N D E N G I N E E R I N G C H E M I S T R Y

2804

r-

r--

Vol. 41, No. 12

were carried out with water as the fluid

medium. These water suspensions unfortunately were not investigated in both vertical
and horizontal tubes thus not permitting any
sort of comparison between us and u,,,
values.
I t is also interesting to note that the pressure drop curves for salt dropped t o the W =
0 line a t velocities greater than us; there was
no detcctable difference in pressure drop for
the flow of the mixtures and the flow of air.

i
a

.@

SCHEMATIC PHASE DIAGRAMS FOR

PARTICLE-GAS FLOW
u-

Figure 4 presents a schematic siiininary of

particle-gas flow characteristics. The notation
used in the diagram for vertical tuhes is taken
from the recently proposed fluidization nomenclature ( I O ) . The break in the fluid bed curve
between dense and disperst phases ia typical
of the experimental investigations of particlegas systems. Leva (21) and Rilhelm and
Kwaulr ( 8 6 ) report that this break was less
n
evident in experiments with water as thefluida
izing medium. Since it, was noted in the data
(3
0
of Figure 2 that the choking velocity for a
J
given solids flow could be computed from a
knowledge of t h c A voidage a t slugging and
the corresponding fluidization velocity, n correlation for predicting the width and position
(range of ealu;s) of the slugging break in the
LOG u
LOG u
fluidization curve is essential to the proper
design of vertical transport lines as well as
Figure 3. Graphical Representation of Fluidization Data
fluid-bed reactors. The curves labeled WI to
W 3 shown
,
to the right
of the dotted line representing disperse phase fluidization, are representative of the
zontal flow of salt and W versus us for horizontal flow of any of
experimental vertical flow curves of Figure 2 . The arrows
the uniform particles indicated that W does not increase as rapidly
attached to the curves indicate the direction of the solids flow
with us for the mixed-size material as with the uniform particles.
in the vertical tuhe. Countercurrent flow experiments with rape
This difference in the relationship between the horizontal salseed in a n arrangement as illustrated in Figure 1, C, establish~d
tation velocities for uniform- and mixed-size materials can also be
the shape of t h e curves shown t o the left of the disperse phase
noted by comparing the d a t a of Blatch ( 5 ) for a uniform size sand
fluidization curve in Figure 3. The experimental data are not
with those of Gregory ( I S ) and others ( 2 , 3, 12, 27) who worked
presented here, becnuse the results obtained near the slugwith clay slurries, etc The experiments of these investigators
f2

-Vertical

Tubes-

Horizontal

-Uniform-Size

Porticles-

Tubes

-Mixed-Sire

Material

c1
0
-I

LOO

Figure 4.

Sup.rlicbol

Gas

Velocity

LOG

Schematic Phase Diagrams for Particle-Gas Systems

fuperficlol

GOB

V*lnciti

December 1949

Figure 5,

INDUSTRIAL AND ENGINEERING CHEMISTRY

Pressure Drop in Horizontal Flow of Uniform

Particle-Gas Mixtures

flow locus were rather inaccurate owing to a tendency for some

of the smaller particles to reverse direction and flow concurrently
upward with the air stream. It did appear, however, that the
choking velocities in this region of countercurrent flow could
again be calculated from the disperse phase fluidization curve
by the relation:

The very limited countercurrent flow data of other investigators

(8, 15) are in agreement with the observations reported in this
study.
The typical schematic diagrams of Figure 4 for the flow of suspensions in horizontal tubes are based on the data presented in
the lower half of Figure 2. Unfortunately, none of the recent
publications on particle-gas flow in either horizontal or vertical
tubes have indicated close enough approach to the saltation or
choking velocities to permit comparison with the observations
presented in this study.
CORRELATION OF PRESSURE DROP DATA

II

Figures 5 and 6 give empirical correlations of the pressure drop

data for the uniform-size materials presented in Figure 2. Not
much time has been given to a comparison of the data of other
investigators with these correlations because of the lack of
reported saltation and choking velocities. It is felt that no
general correlations can be developed which do not take u s and
uch into account. T h e work of Cramp and Priestly (7), for
example, presents an excellent study of pressure drop in vertical
transport; however, their final equation would indicate t h a t the
pressure drop at all solids flows becomes infinite at the solids
terminal velocity ut. They failed t o note an effect of W on
ucb and assumed that Ueh equals ut for all values of W. The
equation of Vogt and White ($6)also neglects t o account for
saltation or choking velocities and in addition indicates an effect
of pipe diameter by the factor (Dt/Dp)Zwhich has been found in
practice to give extremely higher results for small size particles
than experiments have indicated. The authors themselves warn
against using the equation in cases involving fine particles in
large pipe. Though Figures 5 and 6 can hardly be considered
final correlations, it is felt that they represent a closer approach
to the form which may eventually emerge when more data are
available for correlation.
It must be remembered that the pressure-drop data reported
in Figure 2 are undoubtedly high owing to the rather short
accelerating sestion provided in these tests. In addition, the
effect of the pressure drop due to the static head of solids within
the test section was not subtracted from the over-all pressure
drops in the correlation of Figure 6 because no simple means of
trapping the particles within the test section were provided for in

2805

Figure 6. Pressure Drop in Concurrent

Upward Flow of Uniform Particle-Gas Mixtures

the construction of the apparatus, thereby not facilitating inventory measurements. Figures 5 and 6 are, therefore, very limited
in general application and are presented merely as a summary of
the pressure-drop measurements. Because of the effects of
particle acceleration and size distribution, it is nevertheless felt
that ultimately the frictional portion of the over-ail pressure drop
in two-phase flow will require correlation in terms of specific
friction, as originally suggested by Gasterstiidt (11), with proper
account taken of the choking and saltation velocities in some
manner similar to Figures 5 and 6.
CONCLUSION

These experiments have given some indication of the flow characteristics of solid particle-gas mixtures and should serve as a
guide to future investigations of the numerous facts of this
general subject. The quantitative results should be applied
with caution inasmuch as the correlations are probably not in
final form. The main purpose of this investigation was t o establish the schematic phase diagrams shown in Figure 4 and thup
illustrate the relationships between particle-gas flow and fluidiaation. An understanding of the typical so-called phase diagram
is essential to the proper hydrodynamic evaluation of standpipe,
carrier line, and fluid-bed reactor designs.
ACKNOWLEDGMENT

This investigation was conducted while the author was in the

employ of Hydrocarbon Research, Inc. The encouragement and
guidance of Arthur Squires and Manson Benedict of this organization were invaluable in the development of this study. The
author is also indebted to John Happel of New York University
for his continual encouragement and suggestions.
NOMENCLATURE

D, = particle diameter
Dt

= tube diameter

8
'ml

et

eszug

Ap =

AP=
PP

u,

Ut
UE

=a

fraction voids in bed of solids or in unit length of

flowing system, cu. ft./cu. ft.
fraction voids in densely settled fixed bed
fraction voids in loosest possible fixed bed (above which
the bed is fluid)
fraction voids in fluid bed (e, >e,$)
fraction voids in a dense or disperse phase suspension at
the onset of slugging
pressure drop across entire height of bed
pressure drop per unit length of tube or bed
densit of solid article, lb./cu. ft.
superzial f l u i t velocity, ft./sec.-e.g.,
cubic feet of
fluid flowing per second divided by the cross-sectional area of the empty pipe in square feet
superficial fluidization velocities for dense or disperse
phase fluid bed
terminal, balancing, or free-fall particle velocity
superficial fluid velocity at which saltation occurs (for a
given W , in horizontal Row)

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

28836
&h

= superficial fluid velocity a t which choking occurs

71ta1u7

= superficial fluid velocity a t which

IV

= Ib. of

a given W, in vertical flow)

(for

a disperse phase

fluidized suspension begins to slug

solids transported/(sec.)(sq. ft. of pipe cross
section)
LITERATURE CITED

(1) Alden, J. L., Heating and Ventilating, 35, 30-4 (August 1938).
(2) Ambrose, H. A , and Loomis, A. G., Phasics, 4 , 265-73 (1933).
(3) Babbitt, H. E., and Caldwell, D. H., Univ. Illinois Eng. E s p t .
Sta. Bull. Ser., No. 319 (1939).
(4) Benenati, R. F., and Cimler, E., private communication, Brook-

lyn Polytechnic Institute, 1949.

(5) Blatch, N. S.,Trans. Am. SOC.Civil Engrs., LVII, 400-8 (1906).

(6) Chilton, T. H., and Colburn, A . P., Trans. Am. Inst. Chem.
Engl-s., 26, 178 (1931).
(7) Cramp, W., and Priestly, h.,Engineer, 137, 34-6, 64-5, 89-90,

112-13 (1924).
(8) Docarmo, A. C. M.,
M.S. thesis, M.I.T., 1943.
(9) Farbar, L., IND.
ENG.C H E M . , 1184-91
~~,
(1949).
(10) Friend, Leo, et al., Chem. Eng. iVewa, 27, 686, 726 (March 7,
1949).
(11) Gasterstadt, H., Z . V e r . deut. Ing., 68, KO.24, B17-24 (1924).
(12) Gradishar, F. J., Faith, W.L., and Hedrick, J. E., Trans. A m .
Inst. Chem. Engrs., 39, 201-22 (1943).
(13) Gregory, W. B., Mech. Eng., 49, 609-16 (1927).

Vol. 41, No. 12

(14) Hariu, O.H., and Molstad, M. C., ISD. ENG.CHEY.,41, 1148GO (1949).
(15) Hettich, B. V., and Kean, A. H., M.S. thesis, M.I.T., 1943.
(16) Ladenburg, R., Ann. P h y s i k , 23, 447-58 (1907).
(17) Lambrette, il.,
Tech. maderne, 25, No. 22 (November 1933).
(18) Lapple, C. E.,
and Shepherd, C. B., IKD.ENG.CHRM.,
32, 63%
17 (1940).
(19) Leva, M., Grummer, M., Weintraub, M.,and Pollchik, MI.,
Chem. Eng. Progress, 44, 619-26 (1948).
(20) Leva, M., Grummer, M.,Weintraub, M.,and Storch, H. H.,
Ibid., 44, 707-16 (1945).
(21) Leva, M., Weintraub, M., Grurnmer, M., and Pollchik. M . ,
IXD.ENG.CHEM.,41, 1206-12 (1949).
(22) Lewis, W. K., Gilliland, E. R., and Bauer, W. C., Ibid., 1104-17
(1949).
(23) Russ, G. H., private communication, Imperial College, P h c e
Consort Road, London S.W. 7, England, 1948.
(24) Segler, G., 2. Ver. deut. Ing., 79, 558-9 (1935).
(25) Vogt, E. G., and White, R.R., IXD.EXG.CHEM.,40, 1731-8
(1948).
(26) Wilhelm, R. H., and Kwauk, M., Chem. Eng. Progress, 44, 20118 (1948).
(27) Wilheim, R. H., Wroughton, D. M.,and Loeffel, W. F., IND.
ENG.CHCM.,31, 622-9 (1939).
(28) Wood, S. A, and Bailey, A., Proc. Inst. Mech. Engrs. (London),
142, 149 (1939).
RECEIVED
February 2, 1945.

Vapor-Liquid Equilibrium Data

FOR SYSTEM CARBON TETRACHLORIDE-n-PROPYL ALCOHOL
JAMES F. CARLEY AND L. W. BERTELSEN, 111'
Cornell University, Zthaca, N . Y .
I7apor-liquid equilibrium data are given for the system
carbon tetrachloriden-propyl alcohol. The system has an
azeotrope boiling at 73.4" C., containing 81.8 mole YOcarbon tetrachloride. These data check fairly closely the
values 73.2" C. and 81.3 mole Cj" obtained by Schicktanz,
Etienne, and Steele ( 9 ) but disagree with those of Lecat
(a), who gives the boiling point as 73.1' C. with a molar
percentage of carbon tetrachloride of 75.0. Computed
values of activity coefficients agree closely with those predicted by the van Laar solutions of the Gibbs-Duhem
equation. Refractive index data for this system are also
presented.

HE proper design of distillation and other contact equipment

requires reliable vapor-liquid equilibrium data. Furthermore, the frequent necessity for estimating equilibrium relations
from incomplete data by means of the Gibbs-Duhem equation
requires that the data, though few in number, be accurate. One
apparatus for obtaining such data which is generally thought to
have very few sources of error is that designed by Jones, Schoenborn, and Colburn (6). This paper presents the results obtained
on the system carbon tetrachloride-n-propyl alcohol, using
that type of equipment.
The apparatus used was twice as large as that used by the previous investigators (6). -41~0,it was found that the Nichrome
helix inside the flash evaporator was attacked by the mixture of
propanol and carbon tetrachloride, with a partial decomposition
of the latter and the formation of hydrochloric acid. The effects
of this reaction on the experimental results were disastrous. The
Xichrome vias therefore replaced viit,h platinum, which proved
satisfactory. The total pressure of the vapors was maintained
1

Present address, Harvard Law School, Cambridge, SIass.

a t 760.0 mm. of mercury by a barostat. The boiling points were

measured to within 0.5' C. by a pair of copper-constantan thermocouples and a Leeds & Sorthrup portable precision potentiometer. The boiling point of the azeotrope was checked in a
standard Cottrell apparatus, with an error of less than 0.2" C.
Samples were analyzed by means of an Abbe refractometer and a
large scale graph of refractive index against mole fraction carbon
tetrachloride (Figure 1). The data for this graph were obtained
from mixtures of the pure liquids; the weight of each component
in the mixtures was measured with an analytical balance.
The carbon tetrachloride was the technical grade supplied by
the National Carbide and Carbon Company; from the Paragon
Testing Laboratories a pure grade of n-propyl alcohol was
obtained. Each was purified by distillation, using an adiabatic
glass column packed to a height of 4 feet with iron spirals, a t a
reflux ratio of about 30 to 1. The fraction distilling a t constant
temperature was collected for use in each case. The refractive
index of the purified propyl alcohol at 20" C. was 1.3860, in fair
agreement with published values ranging from 1.38409 (a) to
1.38642 (10). The purified carbon tetrachloride had a refractive
index of 1.3603; the published value is l.iG0 (4).

TABLE
I. REFRACTIVE
INDEX-COBIPOSITION
DATA
Mole Fraction
Carbon Tetrachloride
0.0000

Refractive Index,
n "no

0,0839

1.3958

0.3974
0.4932
0.6003
0.6929
0.7888
0.5034
i.0000

1.4411
1.4475
1.4542
1.4603

0.2108
0.2960

1.3860

1.4056
1.4126
1,4206
1 4278

1.4350