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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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RESULTS
P) (Vl
-
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)
-
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)
-
)* ]
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 = —
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
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.
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
—
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
=
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