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Furfural-Water System

EXPERIMENTAL AND THEORETICAL VAPOR-LIQUID RELATIONSHIPS


E. J. PEARCE1 AND J. A. GERSTER
University of Delaware, Newark, Del.

Vapor-liquid equilibrium relationships were experi- therefore decided to determine experimentally the isothermal
mentally determined at 100”, 150°, and 200° F. for the fur- vapor-liquid equilibrium relationships for furfural-water at three
fural-water system by the boiling point method. By this temperatures of interest in extractive distillation: 100°, 150°,
procedure the pressure at which a liquid of known com- and 200° F.
position just began to boil was carefully measured. Such
data permitted calculation of the activity coefficients and EXPERIMENTAL
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partial heats of solution for each of the two components Choice of the Method. Because of the nonideality of the
of the binary system. Attempts were made to fit the
binary mixture and the large difference in boiling points of the
extremely nonsymmetrical activity coefficient—composi- two substances, the relatively simple boiling point method was
tion plots with various theoretical equations, but only the chosen for this study. In this method, the pressure is deter-
more complex types of equations were applicable over the
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mined at w'hich a liquid mixture of known composition and at


entire composition range. The simple 3-suffix Margules
some constant temperature just begins to boil. Carlson and
equations could be adjusted to fit the experimental data Colburn (3) have shown that when this information is available,
over limited concentration ranges, while special 4- and 5- the activity coefficient for one component, ,, may then be com-
suffix Margules-type equations recently proposed by
puted from the relationship
Wohl (22) appear promising.
P =
\ + y2P2x2 (1)
useof furfural as a solvent in the refining and
inasmuch as the factors total pressure, P, liquid composition,
INCREASED
dewaxing of lubricating oils (10, 20) and in the separation of
xi and x2, and vapor pressures, Pt and P2, are all known or measur-
C4 hydrocarbons by extractive distillation (2, 8, 18) has increased
the demand for precise physical data for this material. Previous able, w'hile the activity coefficient for the other component, y2,
work in these laboratories has been reported on the solubilities may be estimated as 1.0 if that component is present in amounts
and vapor-liquid characteristics for several single C4 hydrocarbons approaching 100 mole %. For the case of interest where it is
desired to know the activity coefficient for water out of a liquid
in dry furfural as well as for mixtures of these hydrocarbons in
furfural (4, 14)· These data are valuable in design and evalua- containing mostly furfural, the method is extremely accurate,
because the water with its greater vapor pressure and large
tion of performance of extractive distillation columns employing
these substances. However, according to Happel (<5), small
activity coefficient has a partial pressure in the vapor phase
w'hich is very nearly equal to the total pressure.
amounts of water in the furfural solvent are usually employed in
this latter operation to permit the use of lower temperatures in Description of Apparatus. The equilibrium chamber itself
the solvent stripper reboilers. Vapor-liquid equilibrium deter- was a 1-liter, three-necked, borosilicate glass flask fitted W'ith a
minations for several pairs of C4 hydrocarbons in wet furfural are glass reflux condenser. Agitation of the equilibrium liquid mix-
now being carried out in these laboratories, and a knowledge of
ture w'as provided by a flat paddle, l/2 X “/i» X V32 inch thick,
inserted into the flask through a packing gland and driven by a
the simple furfural-water binary equilibrium characteristics
variable-speed motor. An electric heating coil, immersed directly
appears desirable. Such information can be used to estimate the in the liquid of the flask, consisted of 2 feet of 24-gage Chromel A
effect of water upon hydrocarbon-furfural equilibrium relation- resistance wire wound into a Vi-inch diameter coil. Although the
flask w'as immersed in a constant temperature bath, this internal
ships as well as to provide a sound basis for correlating the results coil w'as required to supply heat quickly to the equilibrium mix-
of the hydrocarbon-furfural-water systems now' under study. ture after boiling had begun. A second smaller coil consisting of
A survey of the literature for existing furfural-water equilibrium only 3/4-inch length of the same resistance wire w'as also immersed
data shows that all such determinations were made at constant near the surface of the equilibrium liquid to supply a point source
of heat to incite boiling. Also immersed in the equilibrium liquid
pressure. Mains (12) and Ridgew'ay and Furnas (17) obtained
was a Vie-inch diameter stainless steel thermocouple well which
data for this system at atmospheric pressure. The Phillips contained a calibrated copper-constantan thermocouple accurate
Petroleum Company (18) reported data at 62.4 pounds per to ± 0.1 °F.
square inch total pressure, w'hile Highhill (9) determined boiling The equilibrium flask w'as immersed in a constant temperature
oil bath which W'as controlled to within ±0.5° F. of the desired
points and vapor pressures of furfural-water mixtures at pres-
sures around 27 mm. of mercury in the high furfural concentra- temperature.
A copper tubing line connected the top of the reflux condenser
tion range. However, because of the wide difference in boiling to the vacuum system consisting of a Cenco Megavac pump,
points of the two substances—3230 F. for furfural and 212° F. for reservoir, and pressure-measuring instruments. Low pressures
water at 1 atmosphere-—such constant pressure data are not too were measured to "within 0.1 mm. of mercury by a Zimmerli gage
and cathetometer, pressures above 80 mm. of mercury by a
applicable for the calculation of activity coefficients, which are a Wallace and Tiernan precision mercurial manometer.
function of temperature. Carlson and Colburn (8) have shown Materials. The furfural w'as technical grade and w'as ob-
the advantages of using activity coefficients to interpret and tained from the Quaker Oats Company. This material was redis-
extend experimental equilibrium data, and Wohl (21) has sum- tilled by simple vacuum distillation at approximately 20 mm. ” of
marized the sound thermodynamic relationships involving the mercury where the distillation temperature ranged around 140 F.
Batches of 1000 ml. were distilled, the first 200 ml. and the last
use of isothermal activity coefficients which may be used for 200 ml. being discarded. The furfural was used within a few days
correlating and predicting vapor-liquid equilibrium data. Values of being redistilled. The w'ater employed w'as distilled water.
of heats of solution may also be computed if the change of activity Operation. After about 700 ml. of a furfural-water mixture of
desired composition had been added to the equilibrium flask, the
coefficient with temperature is accurately known (5). It was oil bath was brought to the desired temperature. As soon as the
1 Present address, Sun Oil Company, Marcus Hook, Pa. equilibrium liquid had reached this same temperature, the smaller
1418
July 1950 INDUSTRIAL AND ENGINEERING CHEMISTRY 1419

perature where the liquid first clouds is


recorded and corresponds to a definite
. water concentration. For mixtures of
high water concentration where the
method is not applicable, known quanti-
ties of dry furfural were added to the un-
knowns before analyzing.

RESULTS

Values of the total pressure at which


various furfural-water mixtures start to
boil were determined under three iso-
thermal conditions: at 100°, 150°, and
200° F. The liquid mixture composition
was varied within the two single-phase
liquid regions which were reported by
Griswold (ß) and are reproduced for con-
venience in Table I. The original data
are tabulated in Table II and are plotted
graphically in Figures 1 and 2, where the
initial boiling pressure is plotted against
liquid mixture composition. The end
values of these plots correspond to the
vapor pressures of each pure substance at
the designated temperature. Values of
vapor pressure for furfural reported by
Miner Laboratories (15) were augmented
at the lower temperatures by experimental
determinations by Mertes (IS) of these
laboratories. The resulting smoothed
data from both sources were used in this
paper and are given for convenience in
Table III.
Figure 2. Isothermal Boiling Pres- Calculation of Activity Coeffi-
sures for Furfural-Water Mixtures
in High Water Concentration Range The fundamental relationship of
cients.
X,, MOLE FRACTION WATER IN LIQUID Equation 1 assumes ideality of the vapors,
and under nonideal conditions, some
Figure 1. Isothermal Boiling Pres-
sures for Furfural-Water Mixtures procedure must be used for taking into account gas law de-
in Low Water Concentration Range viations and pressure effects on the liquid. Methods proposed
by Benedict et al. (1) and Seatchard and Raymond (19) were
of elec- shown by Mertes and Colburn (14) to be applicable for the ease
“bubble” coil in this liquid was connected to a source
tricity and the pressure was varied by application of vacuum until of relatively small deviations. Following the nomenclature
boiling just started. The equilibrium liquid in the flask was con- of (14), Equation 1 may be suitably modified as follows:
tinuously agitated to minimize local superheating and to redis-
solve quickly the liquid returning from the reflux condenser. / + / (2)
The pressure within the flask was slightly_ increased and decreased
several times above and below the boiling pressure and then where z represents the gas law deviation and liquid pressure fac-
brought back to the condition where boiling just began or tor of each component as defined by the equation
stopped. In each case the pressure and temperature of the mix-
ture were recorded. When several check values of boiling pressure zi =
Exp.!, [(Pi -

P) (Vl
-

B,)]/[2.303 RT] (3)


had been obtained, two liquid samples of 15 ml. were withdrawn
through 1-mm. glass tubing by a syringe. Values of liquid specific volume for water, v¡, were obtained
from (11), while values of liquid specific volume for furfural, v2,
The use of the smaller bubble coil was found necessary to initi- were obtained from (8). The second virial coefficients, B, and
ate bubble formation. Without the bubble coil, the mixture
B2, were computed in the manner followed by Mertes and Colburn
had a tendency to bump or to start boiling violently with an
(14), utilizing critical constants and the generalized equation of
accompanying large temperature drop. The larger heating coil Wohl (83). Values of z for each component were then computed
in the equilibrium liquid was used mainly to bring the mixture for the range of operating conditions covered in this study and
quickly to the boiling point at the start of a run, but was also are given in Table IV. Because the z values ranged only from
used intermittently to bring this liquid back to the desired 0.96 to 1.01, it is evident that they could have been neglected
temperature after a particularly long period of violent boiling had without introducing serious error.
caused a lowering of the liquid temperature.
The importance of withdrawing the liquid sample from the
flask under equilibrium boiling conditions cannot be over-
emphasized. Use of the composition of the liquid charge as the Table I. Miscibility Limits for System Furfural-Water as,
composition of the equilibrium liquid causes error, especially at Reported by Griswold (ß)
low concentrations of one of the components. Solubility of Water in Solubility of Furfural
Furfural at 2-Phase in Water at 2-Phase·
Temperature, Point, Mole Fraction Point, Mole Fraction
Analytical Procedure. The cloud point method described °
F. Water in Liquid, xi •
Furfural in Liquid, art
by Griswold et al. (7) was used to analyze the furfural-water 100 0.268 :
0.020
liquid mixtures. In this method, a mixture of Wesson oil and 150 0.364 0.026
0.036
1-hexanol is added to the unknown liquid, after which the tem- 200 0.489
perature of the composite mixture is slowly lowered. The tem-
1420 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 42, No. 7

Table II. Boiling Point and Vapor-Liquid Equilibrium Table III. Vapor Pressures of Furfural (IS) and Water
Data for System Furfural-Water ill) at Various Temperatures
Activity Temperature, Vapor Pressures, Mm. Hg
Mole Total Activity Coefficient 0
F.
Fraction Pressure of Coefficient Furfural Water
Water in Temperature Boiling for Water, Furfural, 68 1.2
Liquid, of Boiling System, 71 =
72 =
100 4.7 49.2
No" X! Liquid, 0
F. Mm. Hg Abs. 2 /- 72/P'xxx 125 10.5
150 22.2 192.3
Temperature, 100° F. 175 42.0
200 76.8 595.9
A1 0.0962 100.0 37.30 6.94 1.05 225 132
A2 0.1813 100.0 49.90 5.12 1.09 250 215
A3 0.0325 99.9 20.10 9.70 1.02
A4 0.0752 99.9 35.85 8.49 1.04
A5 0,1204 100.2 42.90 6.51 1,06
A6 0.1138 100.1 43.20 6.94 1.05 Table IV. Values of z for Furfural and Water at Various
A7 0.0243 100.0 17.48 10.81 1.01 Temperatcres and at Representative Values of Total
A8 0.0484 100.1 23.41 7.91 1.02 Pressure
A9 0.0783 99.9 29.60 6.52 1.04
A10 0.0831 100.0 35.90 7.68 1.04 Furfural Water
All 0.1053 100.0 39.10 6.70 1.05
A12 0.1472 100.0 44.50 5.55 1.07 Temperature,
0
A13 0.2037 99.9 50.10 4.58 1.11
F. Hg * Hg z
A14 0.0198 100.0 14.85 12.61 1.01 100 0 1.001 0 1.002
A15 0.0450 100.0 24.07 8.80 1.02 60 0,993 60 1.000
0.0429 100.0 23.50 8.96 1.02
A16 0.0700 100.0 30.10 7.45 1.03 150 0 1.002 0 1.004
A17 0.1064 99.9 39,90 6.79 1.. 05 210 0.983 210 0.999-F
A'18 0.1630 99.9 46.40 5.26 1.08 200 0 1.005 0
A19 0.2148 100.1 52.30 4.55 1 12 1.010
.
630 0.963 630 0.999
A20 0.2058 100.0 50.47 4.57 1.10
A21 0.2383 100.0 52.87 4.16 1.15
A22 0.9818 100.0 52.3 1.002 44.7
A23 0.9900 100.0 52.4 1.001 77.6
A24 0.9951 100.0 51.1 1.000 + 90.5
Sample Calculation for Run B-4
Temperature, 150° F.
Temp, at equilibrium ( ), 0 K. 338.6
B1 0.0246 150.0 57.80 7.53 1.03 Mole fraction water in liquid (xi) 0.0925
B2 0.0491 150.0 83.31 6.50 1.04 Mole fraction furfural in liquid (xz) 0.9075
B3 0.0658 150.0 102.3 6.39 1.04 Total pressure at boiling point (ft), mm. Hg 121.2
B4 0.0925 149.9 121.2 5.63 1.05 Vapor pressure of water (Pi), mm. Hg (Table III) 192.3
B5 0,1198 150.0 136.0 4.99 1.08 Vapor pressure of furfural (Ps), mm. Hg (Table III) 22.2
B6 0.1434 149,9 148.7 4.62 1.10 Activity coefficient for furfural (72) (Figure 3) 1.02
B7 0.1658 150.0 159.7 4.35 1.12 Liquid specific volume for water ( ) ml./gram mole (11) , 18.38
B8 0.0397 150.0 72.7 6.65 1.03 Liquid specific volume for furfural (vt), ml./gram mole (£) 87.35
B9 0.0793 150.0 115.5 6.15 1.05 Virial coefficient for water (J3i), ml./gram mole (calcu-
B10 0.2192 150.0 181.4 3.81 1.17 lated from Equation 3 of 14) -425.4
Bll 0.2856 149.9 190.4 3.10 1.25 Virial coefficient for furfural (B2), ml./gram mole (calcu-
B12 0.9898 149.9 200.3 1.001 40.4 lated from Equation 3 of 14) -1794.8
B13 0.9955 149.9 199.5 1.000 70.9 Gas constant (ft), (ml.) (mm. Hg)/(° K.) (gram mole) 62,365
BH 0.9845 149.9 207.7 1.001 50.2 zi Exp.jp {{Pi P) 0>j-
2.303 RT)
-

B15 0.9792 150.0 208.6 1.002 41.7


(192.3 121.2)(18.38 + 425.4)
-

1.0015
Temperature, 200° F. (2.303) (62,365) (338.6)
Cl 0.0267 200.0 166.5 1.03 (22.2 121.2) (87.35 -f 1794.8)
-

C2 0.0528 200.0 230.2 4'.90 1.04 zx =


Exp.10
(2.303) (62,365) (338.6)
C3 0.0812 199.9 277.3 4.19 1.05
C4 0.0920 200.0 335.9 4.77 1.06 P —
72-^2x2/32
C5 0.1028 199.9 333.2 4,25 1.06
C6 0.1549 199.9 409.4 3.66 1.10
C7 0.1958 200.0 421.4 3.00 1.15 121.2 -

(1.02) (22,2) (0.9075)/0.991


C8 0.9895 200.0 598.6 1,001 9.7 (192.3) (0.0925) / 1.002
C9 0.9958 199.9 610.8 1.000 45.7
CIO 0.9840 200.0 623.8 1,002 26.9
=
5.66
Cll 0.9823 200.0 630.0 1.002 29.5
C12 0.9723 200.1 635.2 1,004 23.2
If the activity coefficient for furfural 72 had been assumed as
equal to 1.0, the value of 71 would be 5.68, and if both z¡ and z2
had also been taken as equal to 1.0, 71 would be 5.67.
Values of activity coefficients for water in the low water con- Calculation of Heats of Solution. A knowledge of the
centration range were computed according to Equation 2, assum- heat effects upon mixing furfural and water is desirable wherever
ing the activity coefficient for furfural to be 1.0. The resulting these materials are used in chemical process work. For complex
activity coefficient values were then plotted against liquid com- systems such as the hydrocarbon-furfural-water systems em-
position and a smooth curve was drawn extending beyond the ployed in certain extractive distillation operations of commercial
miscibility limit of water in furfural to the composition corre- importance, furfural-water heat of solution data are useful in
sponding to pure water where the activity coefficient for water is estimating enthalpy values of such mixtures. Differential heats
unity. The activity coefficients for furfural were then computed of solution may be computed from activity coefficient data by the
by Equation 2 from the experimental data and the activity co- use of the equation
efficient plot just drawn for water.
The next step was to find a suitable equation to fit the relation- d log 71 Li
~
(4)
ship between the activity coefficients just computed and the d(l/T) 2.303 R
liquid composition, so that a more accurate representation of these where L¡ =
partial or differential heat of solution of component
values could be obtained in the immiscible regions where experi- 1 dissolved in a liquid of composition for which 71
mental data were lacking. As shown below, the four-suffix van applies, B.t.u./pound mole of component 1 added
Laar equations were found to fit the experimental data, and T =
partial or differentia] heat of solution of component
1 dissolved in a liquid of composition for which 71
values of 72 from these equations were then used instead of the of component 1 added
applies, B.t.u./pound mole
value of 1.0 previously assumed to make a second final calculation T =
absolute temperature, ° R.
of the water activity coefficients. This final adjustment did not R =
gas constant, 1.987 B.t.u./(pound mole)(°R).
affect the absolute values of the activity coefficients more than a
few per cent. A similar procedure was followed for the furfural The logarithms of the activity coefficient values for water from
activity coefficients. Computed results are summarized in Figure 3 were plotted against the reciprocal of the absolute
Table II and plotted as Figure 3. temperature at constant liquid compositions of 0, 0.1, and =
July 1950 INDUSTRIAL AND ENGINEERING CHEMISTRY 1421

the partial heat of solution of furfural in pure water was com-


puted.
The integral heats of solution were computed by graphical
integration of the partial heats of solution plotted as a function of
composition. Computed values of both partial and integral
heats of solution are presented in Table V. Both heat effects
represent heat absorbed during the solution process. The ab-
solute values of heat of solution are about one fifth as large as the
molar latent heats of vaporization of each component, indicating
the necessity for including heat of solution effects in design or
correlation calculations involving furfural-water mixtures.

APPLICATION OF EQUATIONS TO RESULTS

Representation of the experimental results by one or more


types of theoretical equations is indicated to check the soundness
of the data and especially to permit prediction of ternary and
more complex equilibrium relations involving these two sub-
stances. A complex analysis of such equations available for
correlation purposes has been made by Wohl (ß ), while a typical
application of the prediction of ternary equilibrium values from
three sets of binary data through the use of these equations has
been recently demonstrated (4). In this latter study, the three-
suffix Margules equations were shown to be especially valuable
because of their applicability, their comparative simplicity, and
the lack of any restrictions in their use in the ternary form. The
ternary two-suffix van Laar equations are restricted, in that all of
Figure 3. Activity Coefficients for Furfural and Water the binary constants must be related in a specified manner.
as a Function of Temperature and Composition
Simple Margules-Type Equations. The binary three-suffix
Margules equations were used in the following form to test their
0.2, inasmuch as the slope of the curve represents the left-hand ability to represent the data:
side of Equation 4. These plots are shown in Figure 4, where it is log 7, =
[Ai + 2 (A2 —

)* ]
apparent that the slopes of the curves and the resultant partial limit log 71 (xi 0) =
Ai (5A)
heat of solution values for water are affected by both temperature
and composition over the range studied. Although these changes log i| [A* + 2 (Ai A2)x21
72 = —

limit log 72 (x¡ —0) A2 (SB)


=

are slight, they appear to be both definite and consistent and were
therefore retained in the correlation. A similar plot of log 72 When constants Ai and A2 in these equations were evaluated
as the logarithms of the experimental activity coefficient values
against l/T at z2 =
0 has been included in Figure 4, from which
extrapolated in Figure 3 back to infinite dilution of each compo-
nent, the resulting correlation was not satisfactory. Lowering of
the values of Ai and A2 to 5 and 40, respectively, increased the fit

Table V. Heats of Solution for Furfural-Water


Mixtures
A. Heats Absorbed on Solution of Water in Furfural over Range 100° to
200° F.
Differential Heat of Integral Heat of
Mole Fraction Water Solution, B.t.u./Lb. Solution, B.t.u./Lb.
in Liquid, x\ Mole of H2O Dissolved Mole of H2O Dissolved
Temperature, 100° F.
0 4830 4830
0.10 2930 3900
0.20 1830 3050
Temperature, 150° F.
0 4830 4830
0.10 3870 4370
0.20 2950 3900
Temperature, 200° F.
0 4830 4830
0.10 4990 4900
0.20 4990 4980
B. Heats Absorbed on Solution of Furfural in Water over Range 100° to
200° F.
Mole Fraction Furfural B.t.u./Lb. Mole of
in Liquid, xz Furfural Dissolved
Temperature, 100® F.
0 2880

Temperature, 150° F.
1/r, 0
x 10= 0 5285
Figure 4. Logarithms of Activity Temperature, 200° F.
Coefficients for Furfural and Water
of Temperature and 0 6980
as a Function
Composition
1422 INDUSTRIAL AND ENGINEERING CHEMISTRY VoL 42, No. 7

<
tr

o
a.

Figure 6. Comparison of Experimental Activity Coeffi-


Figure 5. Comparison of Experimental Activity Coeffi- cients for Furfural and Water at 150° F. with Predicted
cients for Furfural and Water at 150° F. with Predicted Values
Values

somewhat but not sufficiently for good accuracy, as shown in the best possible fit with the experimental data. Adjustment of
Figure 5. the constants to permit a more exact fit with the van Laar equa-
A more rational basis for evaluation of constants and A2 is to tions over limited concentration ranges may be employed as
note from Equation 5A that if log yi/xl were plotted against x¡, a above for the Margules equations, because the shape of both types
straight line of slope 2(A2 —
) and intercept Ai should result. of equations becomes identical for cases where A2/A1 is unity.
Testing the experimental values of 71 in the range X\ 0 to Xi =

0.30 by this procedure, a nearly horizontal line is required to fit Thebe-Suffix Scatchard-Hamer Equations. The three-
the points. The intercept of the line corresponds closely to the suffix Scatchard-Hamer equations as presented by Wohl {SI) were
experimental value of log 71 extrapolated to x¡ 0. Thus in

also applied in an effort to correlate results. When the best pos-


order for the Margules equations to fit the data over the range
sible constants were chosen for these equations, the resulting fit
tested, constant Ai may be taken as the experimental end value,
but constant As must be chosen so that 2(A2 —

) is nearly zero. is not too good, as shown in Figure 5.


This of course means that A¡¡ must be chosen so as to be nearly Correlation with More Complex Equations. In the four-
equal to . Use of this same procedure to fit the data points for suffix type of equation, it is assumed that a more complex associa-
72 in the high water concentration range is not practical because
the solubility of furfural in water is less than 4 mole % at 200° F. tion of the component molecules of the liquid is formed. Several
Thus the concentration range is extremely small, and the slope of forms of the equation are available, depending upon the nature of
a log 72/xl versus x2 plot would be difficult to evalute. Appar- the simplifying assumptions made in the integration of the basic
ently the use of A2 = =
experimental value of log 72 at x2 0
=

equation into a usable form. A]] forms of the four-suffix equations


is satisfactory in this range. The above procedures have the dis-
available for application to the present data contain a third con-
advantage of requiring two sets of and A2 values for the two
separate composition ranges, but for the present case where a zone stant, D. in addition to constants Ai and A« used in the simpler
of immiscibility separates the two dilute regions, there are no forms. Two types of four-suffix equations were tested for ability
complications. Furthermore, only the high furfural concentration to represent the· experimental data: the four-suffix van Laar
range is at present of commercial interest. The values of A¡ and
A2 given in Table VI, when used in Equation 5A, were found to fit equations and the four-suffix Margules equations. Both were
closely the experimental data in the range of x¡ 0 to x¡
=
0.30.
= used in the form given by Wohl (SI). In applying these equa-
tions, constants and A2 were taken as the experimental values
This procedure in effect provides for a symmetrica] form of the of log 7 extrapolated to infinite dilution, while the third constant,
equations, so that an even simpler equation form might have
been used. Comparison of the excellent agreement for this case
for the high furfural concentration range may be seen in Figure 7.
Two-Suffix van Laab Equations. The simple two-suffix Table VI. Values of and As for Equation 5A
van Laar equations have been widely used to represent simple in High Furfural Concentration Range
binary systems, although limitations in use of this type of equa- Ai or Az
0
Temperature, F.
tion for ternary systems have been pointed out above. Figure 5 100 1.066
150 0.911
shows the correlation obtainable between these equations and the 200 0.780
present data when the van Laar constants were adjusted to give
July 1950 INDUSTRIAL AND ENGINEERING CHEMISTRY 1423

(Ai Ai)xl. Thus the effective Aa value would no longer be a


constant but would become a sliding value which would be


numerically equal to Ai at xi = 0 and would be equal to A2 at
= 1. When such a substitution is made, the final form of the
special four-suffix Margules equations becomes

log 7! .= [Ai + 3a:i2 (2 -

Ai)]
limit log 71 (xi —*-0) =
Ai (6A)
log 72 =
xx2 [Ai -

2 (1 + 3$i)(A2 -
Ai)]
limit log 72 (xi -*· 0) Ai =
(6B)
while the final form of the special five-suffix Margules equations
becomes

« log 71 =
x22 [Ax + 4rc!3 (Ai -
Ai)] (7A)
£
K
3 log 72 =
xp [Ai —

Xi (1 + + ixx2)(A2 -
Ai)] (7B)
oc Some idea of the usefulness of these new equations may be seen
o
in Figure 7, where the correlation obtained may be compared with
the experimental data. These equations appear to be extremely
z
111 promising, although for the present case their applicability is
O somewhat limited.
C
u.
Ill CONCLUSION
o
o
The boiling point method has offered a simple and WOrkable ex-
> perimental technique for determination of vapor-liquid equilib-
5 rium data for the case of two binary liquids of widely different vola-
< tilities. The data obtained have permitted calculation of vapor-
F liquid equilibrium values and heat of solution values over the
temperature range investigated. Activity coefficients were com-
puted and it was shown that only a relatively few of the many
equations which may be used to represent activity coefficients as a
Figure 7. Comparison of Experimental Activity Coeffi- function of composition were valid for the extremely nonideal
cients for Furfural and Water at 150° F. with Predicted mixture investigated. In order to apply the present data to com-
Values
plex mixtures involving furfural and water, it was indicated that
separate three-suffix Margules equations to apply over separate
concentration ranges, each with separate constants chosen to best
D, was adjusted by trial and error to give the best fit of the ex- fit the range covered, were most desirable. Such a procedure is
perimental data. thermodynamically sound, permits close fit of the equations to the
Results are shown in Figure 6, wdiere it may be seen that good data, and allows use of the simple Margules-type equations which
agreement is obtained over the entire concentration range with are extremely desirable for representation of ternary and more
both types of equations, although the van Laar type is somewhat complex systems.
the better. This latter correlation is remarkable when the ex-
ACKNOWLEDGMENT
treme nonsymmetry of the system is considered. It is admitted,
however, that use of such complex equations to define only a This investigation was carried out under the sponsorship of the
binary system will become cumbersome if the binary results are to Reconstruction Finance Corporation, Office of Rubber Reserve,
be applied to ternary or more complex systems containing these in connection with the government’s synthetic rubber program.
two materials. Generally, for a system such as furfural-water Special assistance was offered by Kurt Wohl in the theoretical
where the related factors of immiscibility, nonideality, and non- interpretations and by Donald Jordon in the experimental proce-
symmetry are present, application of the simpler three-suffix dures. The furfural was kindly supplied by the Quaker Oats
Margules equations using different constants for separate con- Company.
centration ranges as described above will prove a less tedious pro-
NOMENCLATURE
cedure. However, if a single set of equations employing a single
set of constants is desired for the entire concentration range, Ai = limit log 7 ( — 0)
then the four-suffix van Laar equations appear to be a satisfactory Ai = limit log 72 (x2 -* 0)
= second virial coefficient in the equation of state, ml. per
solution for the system furfural-water.
gram mole
The actual magnitude of the third constant, D, employed in L = or differential heat absorbed on solution of pure
partial
each case was much greater than would be predicted from the component in liquid solution, B.t.u. per pound mole of
theoretical relationship that D =
2.3Ai/12 for mixtures having pure component added
molecules of equal size and shape and forming no chemical com-
P = total pressure, mm. of Hg
Pi, 2 vapor pressures of pure components, mm. of Hg
=

plexes (SI). This relation would predict a value of D of 0.16 at R =


gas-law constant
150° F. compared with the value of around 1.1 actually required T = absolute temperature, ° R. or 0 K.
for the present case, indicating that furfural and water are of v =
liquid specific volume, ml. per gram mole
different molecular type and probably do associate. x = mole fraction of component in binary liquid
y = mole fraction of component in binary vapor
Special Margules-Type Equations. Wohl (22) has proposed z —
gas law deviation and liquid pressure factor of component
the use of special four-suffix and five-suffix Margules-type equa- defined by Equation 3
tions for describing the activity coefficients of a binary system 7 =
activity coefficient of component
over a wide range. He proposes to replace the end value, A2, in
the basic Margules expression involving the excess free energy of Subscripts
-1 component 1, water
=

the mixture with either the value A, + (Ai —

Ai)xi or with Ai + 2 component 2, furfural


=
1424 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 42, No. 7
LITERATURE CITED (11) Keenan, J. H., and Keyes, . G., “Thermodynamic Properties
of Steam,” New York, John Wiley & Sons, 1936.
(1) Benedict, M., Johnson, C. A., Solomon, E., and Rubin, L. C.,
Trans. Am. Inst. Chem. Engrs., 41, 371-91 (1945). (12) Mains, G. H., Chem. & Met. Eng., 26, 779 (1922).
(2) Buell, C. K., and Boatright, R. G., Ind. Eng. Chem., 39, 695-705 (13) Mertes, T. S., thesis, University of Delaware, 1948.
(1947). (14) Mertes, T. S., and Colburn, A. P., Ind. Eng. Chem., 39, 787-96
(3) Carlson, H. C., and Colburn, A. P.r Ibid., 34, 581-9 (1942). (1947).
(4) Gerster, J. A., Mertes, T. S., and Colburn, A. P., Ibid., 39, 797- (15) Miner Laboratories, Bull. 2 (1928).
804, 1520 (1947). (16) Phillips Petroleum Co., private communication,1948.
(5) Glasstone, S., “Textbook of Physical Chemistry,” New York, (17) Ridgeway, R., and Furnas, C., unpublished data, Yale Uni-
D. Van Nostrand Co., 1946. versity, 1936.
(6) Griswold, J., Klecka, M., and West, R., Chem. Eng. Progress, (IS) Scarth, V., U. S. Patent 2,404,253 (July 16, 1946).
44, 839-46 (1948), (19) Scatchard, G., and Raymond, C. L., J. Am. Chem. Soc., 60,
(7) Griswold, J., Klecka, M., and West, R., Ind. Eng. Chem., 1978-87 (1938).
Anal. Ed., 18, 696-8 (1946). (20) Skelton, W. ., Oil Gas J., 45, 137-44 (1947).
(8) Happel, J., et al., Trans. Am. Inst. Chem. Engrs., 42, 189-214 (21) Wohl, K., Trans. Am. Inst. Chem. Engrs., 42, 215-49 (1946).
(1946). (22) Wohl, K., unpublished notes. University of Delaware, 1948.
(9) Highhill, C. A., Quaker Oats Co. Tech. Div., “Furfural as a
(23) Wohl, K., Z. physik. Chem., B2, 77-114 (1929).
Selective Solvent,” 1940.
(10) Kalichevsky, V. A., “Modern Methods of Refining Lubricating
Oils,” New York, Reinhold Publishing Corp., 1938. Received December 23, 1949.

OXIDATION OF LINSEED OIL


Temperature Effects
P. S. HESS AND G. A. O’HARE, Congoleum-Nairn Inc., Kearny, N. J.

The effects which differences in the reaction tempera- peroxide value increase is independent of the temperature
ture exert on the induction period and on the built oxy- in the 84° to 200° C. range. The maximum value, how-
polymerization of raw linseed oil under otherwise con- ever, is a definite function of temperature; higher values
stant conditions of air flow and agitation have been dis- correspond to lower reaction temperatures. Ultraviolet
cussed. Within the temperature range of 84° to 200° C. absorption analyses indicate that the formation of dicon-
the initial rate of viscosity increase is identical for all tem- jugated systems reaches a maximum and that at tempera-
peratures. At a definite point in the oxidation a change tures between 84° and 200° C. the diene configuration as
in the rate of viscosity increase occurs. The existence of determined by the characteristic inflection at 232 m.u is
this rate change has made it possible to show that there never appreciably greater than 5%. Higher values are
are at least three distinct temperature regions, each char- obtained at lower reaction temperatures. The results
acterized by different types of oxidative changes. They obtained in this study are in agreement with the free
are: above 130° C.; between 84° and 130° C.; and below radical propagation theory of oil oxidation and appear to
84° C. Temperature has a distinct effect on induction indicate the formation of an intermediate prior to oxida-
period length. In the intermediate temperature range, tive molecular weight build-up. it is speculated that this
the length of the induction period decreases exponentially intermediate may be of the chelate type and that oxidative
with unit increase in temperature. At 130° C. and above, molecular weight increases may partially take place by
the induction period is of very short duration. During association of intermediates to double molecules by hy-
the initial stages of the oxypolymerization reaction the drogen bonding.

in bulk were conducted with linseed and other The length of the induction period, provided a threshold quan-
OXIDATIONS
vegetable oils with emphasis on the effect that one or tity of oxygen is present, is a function of temperature, the degree
several variables might have on the course or the product of the of refinement, length of oil storage, and the effectiveness of added
reaction. From these experiments it became apparent that re- agents such as driers or catalysts. Complete or partial elimina-
production of processing results for oils from different sources, al- tion of this inhibition period can be effected by any number of
though oxidized under the same experimental conditions, is dif- different treatments. Experimental evidence indicates that this
ficult to achieve. Differences in the methods of preparation of is caused either by destruction, removal, chemical neutraliza-
these oils, such as alkali or acid refining or treatment with bleach- tion, or by a change in molecular structure of the natural in-
ing clays, emphasize the over-all differences in the kinetics of the hibiting minor oil constituents. Compounds which have been
oxidation reaction. It could be shown that physically the reac- isolated and which were found by others to belong to the general
tion of any given oil depends on the air flow, turbulence (degree class called inhibitols are the phospholipides, carotenoids,
and type of agitation), and the temperature of the process; in gossypols, sesamoies, chlorophylls, etc. According to Powers
addition, the performance of the oil is affected by the history of the (24), ah °f the nonlipide components have been suspected of being
oil itself, such as the geographical origin, the method of expelling responsible for this inhibition effect.
from the seed, and the length of storage. Experimentally, it has been determined that both chemical and
In general, autoxidation to a certain viscosity is a function of physical changes occur in the oil during the induction period.
two distinct processes: Although these changes, when compared to differences in values
during the oxypolymerization reaction, are so minor that they
1. The induction period or the time of inhibited oxidative often have been considered nonexistent, they are nevertheless
polymerization. distinct as can be seen in Figure 1 where the viscosity, as deter-
2. The oxypolymerization reaction, a function directly de-
mined by the Ostwald-Fenske viscometer, the iodine value, the
pendent on the addition of oxygen to the reactive centers of the
oil molecule. refractive index, and the heat input necessary to maintain the