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ELSEVIER Fluid Phase Equilibria 126 (1996) 203-223

Refractive indices, densities and excess properties on mixing of the

systems acetone + methanol + water and
acetone + methanol + 1-butanol at 298.15 K
M. Iglesias, B. Orge, J. Tojo *
Departamento de lngenierla Quimica, Universidad de Vigo, Aptdo. 874, 36200 Vigo, Spain
Received 6 January 1996; accepted 18 May 1996

Abstract

Refractive indices and densities of acetone + methanol + water, acetone + methanol + l-butanol and of the
binary mixtures acetone + water, acetone + l-butanol, methanol + water, and methanol + 1-butanol have been
determined experimentally over the entire range of composition at the temperature 298.15 K and at atmospheric
pressure. Derived excess properties were determined, variable-degree polynomials being fitted to the results.
Methods for predicting ternary excess properties from the values of the corresponding three binary mixtures
involved are tested and compared. An estimation of excess volumes is also evaluated using a modified Heller
equation (Heller, 1965) which depends on the refractive indices of the mixture. Comparison of the predictions
by different methods with the experimental values of the physical properties is made.

Keywords: Excess; Volume; Density; Acetone; Alkanol; Water

1. I n t r o d u c t i o n

Thermochemical properties of liquid mixtures that may have hydroxyl molecular groups and highly
polarizable electron pairs like alkanols or amines, depend to a large extent on the interactions of
molecular hydrogen bonding. The length of the molecular chain and the ramifications of the
molecules influence the intensity of the interactions in the mixture, there being high non-ideality in
mixtures with relatively small and non-branching molecules. Highly polar substances such as water,
produce strong interactions due to its relatively low molecular volume and large polarity. In this
paper, we report experimental values of the physical properties of homogeneous mixtures, which are
related to many conventional problems in chemical engineering (design of distillation columns,
material and energy balances including liquids, fluid phase equilibria, as well as molar fraction

* Corresponding author. Fax: + 34 86 812382 e-mail: jtojo@uvigo.es.

0378-3812/96/$15.00 Copyright 1996ElsevierScienceB.V. All fightsreserved.

PII S0378-3812(96)03130-5
204 M. lglesias et a l . / Fluid Phase Equilibria 126 (1996) 203-223

determination, research into alternative extractive agents, etc.). The studied mixtures form part of a
program to determine the thermodynamic and derived excess properties of a series of ternary systems
containing common homogeneous azeotropic binary mixtures in the chemical industry and alternative
entrainers for extractive distillation processes. This paper presents new values for binary and ternary
densities and refractive indices at 298.15 K and atmospheric pressure for the systems acetone +
methanol + water (AMW), acetone+ methanol + 1-butanol (AM1B) and of the binary mixtures
acetone + water (AW), acetone + 1-butanol (A1B), methanol + water (MW), and methanol + l-
butanol (M1B), each having been determined experimentally as a function of the mole fraction.
Binary and ternary representations by polynomial expansion like the Redlich-Kister (Redlich and
Kister, 1948) and Cibulka (Cibulka, 1982) equations are included. The validity of predicting the
ternary excess values is examined, applying different empirical equations which consider the binary
contributions to the ternary values in a different graphical way. Different types of mixing rules for the
refractive index have been applied in an expansion of the Heller equation for the prediction of the
excess volumes of binary and ternary mixtures. The substitution of Dale-Gladstone and Eykman
mixing rules (Tasic et al., 1992; Bottcher, 1952) in the Heller equation for the mixtures AMW and
AM1B showed similar accuracy to the best contribution methods in ternary volume values. Prediction
of physical property values was realized by applying different methods for density prediction
(Hankinson-Brobst-Thompson (Hankinson and Thompson, 1979), Rackett (Rackett, 1970), Spencer
and Danner modified Rackett (Spencer and Danner, 1972), Bradford-Thodos (Bradford and Thodos,
1968), Riedel (Riedel, 1954), Narsimham (Narsimham, 1967), and Yen-Woods (Yen and Woods,
1966)) and semiempirical models for refractive index estimation (Lorentz-Lorenz, Dale-Gladstone,
Arago-Biot (Tasic et al., 1992), Eykman (Bottcher, 1952), Newton (Kurtz and Ward, 1936), Oster
(Oster, 1948) and Eyring-John (Eyring and John, 1969)).

2. Experimental
2.1. Materials
Water was treated by the Millipore process, while the other substances employed were supplied by
Merck. The chemicals were recently acquired and kept in inert argon atmosphere, without any further
treatment. Precautions were taken, such as cooling chemicals before sample preparation and minimiz-
ing empty space in the vessels, in order to avoid evaporation losses during manipulations or errors in
molar fractions. Gas-liquid chromatographic testing of the solvents showed purities which fulfilled
supplier specifications. Their mole fraction purities were better than 0.998 for all the chemicals used.
Further verification was realized by ascertaining the constancy of the values of the densities and
refractive indices at 298.15 K, which were reasonably in accordance with recommended and recently
published values (Table 1).
2.2. Apparatus and procedure
The densities of the mixtures and pure liquids were measured with an Anton Paar DMA-46 type
glass-oscillator digital densimeter with a precision of + 0.0001 g cm -3 and the refractive indices by
an automatic refractometer (ABBEMAT-HP Dr Kernchen) thermostated with a PolyScience controller
bath model 9510 with a temperature stability of _ 0.01 K, which shows a precision of __+0.00001. The
densimeter determines the densities of liquid mixtures by measuring electronically the period of
 M. lglesias et al./ Fluid Phase Equilibria 126 (1996) 203-223 205

Table 1
Comparison o f data with literature data for pure liquids at 298.15 K
p / ( g c m - 3) nD

Component Exptl. Lit. Exptl. Lit.

Acetone 0.7841 0.78547 a 1.35605 1.35596 a
0.78440 b 1.35596 b
Methanol 0.7863 0.78664 a 1.32676 1.32652 a
0.78664 b 1.32652 b
Water 0.9970 0.99705 b 1.33250 1.33250 b
l-Butanol 0.8055 0.8060 b 1.39716 1.3973 b

a TRC T h e r m o d y n a m i c Tables, 1994. b Riddick et al., 1986.

oscillation of a glass oscillator. The sample is introduced into a system which can oscillate and whose
frequency is influenced by the mass of the sample. The system is a U-shaped tube which is brought to
undamped oscillation by electronic means. Both straight sections of the U-shaped tube form the spring
element of the oscillator. The direction of oscillation lies in the same plane as the tube; if the
oscillator has been filled with the sample at least up to the mounting points, then the same known
volume of sample also oscillates. The density can be calculated from the oscillation period by
considering it to be a function of the device constants, sample volume and temperature. The
refractometer determines the experimental values by placing the sample to be measured on the
polished surface of a prism made of synthetic sapphire, where a cone-shaped yellow light beam of
589.3 nm sodium D wavelength illuminates the sample from its bottom side under different angles of
reflection. In order to keep a constant temperature, the measuring prism is water-jacketed using a
temperature controller, which shows a stability of +0.01 K.
Thermostatization of the samples was realized by a Polyscience controller bath model 9510; they
were prepared by mass using a Mettler AE-240 balance with a precision of + 0.0001 g, covering the
whole composition range of the binary and ternary systems. Every sample remains in the thermostat
for at least 30 min, with three measures of density and refractive index being taken.
Besides daily testing, the instruments were calibrated in accordance with use instructions before
each series of measurements (double liquid calibration). The accuracy in the calculation of excess
molar volumes and changes in the refractive indices were determined as being better than 0.001 cm 3
mol-i and 0.0001, respectively.

3. Results and discussion

The excess molar volumes and changes in the refractive indices on mixing were computed using
Eq. (1) and Eq. (2), respectively, and are shown in Tables 2 and 3 for each composition point of the
mixtures
N
') (1)
i=1
N
~)nD = r i D - E XinDi (2/
i=1
206 M. lglesias et al. / Fluid Phase Equilibria 126 (1996) 203-223

Table 2
Densities, refractive indices, excess molar volumes, and changes of refractive index on mixing for binary mixtures at
T = 298.15 K
x p no VmE cSn D x p no VmE 6n D
g cm- 3 cm 3 tool- ~ gcm- 3 cm 3 tool-

Acetone + water
0 0.9970 1.33250 0 0 0.3171 0.8938 1.36242 - 1.458 0.0224
0.0114 0.9918 1.33504 -0.083 0.0023 0.3596 0.8830 1.36274 - 1.489 0.0218
0.0294 0.9846 1.33882 -0.223 0.0056 0.4261 0.8678 1.36299 - 1.500 0.0205
0.0411 0.9801 1.34116 -0.310 0.0077 0.4845 0.8557 1.36287 - 1.465 0.0190
0.0419 0.9799 1.34131 -0.318 0.0078 0.5824 0.8378 1.36196 - 1.331 0.0157
0.0575 0.9743 1.34417 - 0.435 0.0103 0.6883 0.8212 1.36069 - 1.098 0.0120
0.0761 0.9677 1.34680 - 0.564 0.0125 0.7403 0.8138 1.35972 - 0.945 0.0098
0.0954 0.9610 1.34963 - 0.688 0.0149 0.8256 0.8029 1.35838 - 0.670 0.0064
0.1049 0.9578 1.35071 -0.747 0.0157 0.8611 0.7986 1.35787 -0.535 0.0051
0.1416 0.9455 1.35464 - 0.946 0.0188 0.8737 0.7973 1.35757 - 0.500 0.0045
0.1601 0.9395 1.35618 - 1.033 0.0199 0.9192 0.7922 1.35676 -0.319 0.0026
0.2021 0.9264 1.35879 - 1.201 0.0215 0.9396 0.7903 1.35657 - 0.261 0.0019
0.2319 0.9171 1.36033 - 1.282 0.0224 1 0.7841 1.35605 0 0
Methanol + water
0.0151 0.9922 1.33300 -0.042 0.0006 0.4516 0.8916 1.34037 - 1.0012 0.0105
0.0467 0.9830 1.33425 - 0.135 0.0020 0.5094 0.8793 1.33959 - 1.009 0.0100
0.0654 0.9781 1.33497 - 0.196 0.0028 0.5609 0.8685 1.33873 - 0.989 0.0094
0.0986 0.9701 1.33638 - 0.310 0.0044 0.6509 0.8504 1.33678 - 0.912 0.0080
0.1287 0.9632 1.33747 - 0.411 0.0057 0.7151 0.8377 1.33509 - 0.809 0.0067
0.1611 0.9561 1.33854 -0.517 0.0070 0.8012 0.8216 1.33273 -0.636 0.0048
0.1927 0.9490 1.33943 - 0.608 0.0080 0.8558 0.8115 1.33108 - 0.487 0.0035
0.2290 0.9410 1.34021 - 0.705 0.0090 0.8959 0.8043 1.32965 - 0.366 0.0023
0.2669 0.9326 1.34073 - 0.791 0.0098 0.9271 0.7990 1.32872 - 0.274 0.0015
0.3149 0.9218 1.34102 -0.876 0.0103 0.9445 0.7960 1.32821 -0.216 0.0011
0.3545 0.9129 1.34110 -0.929 0.0106 1.0000 0.7863 1.32676 0 0
Acetone + 1 - butanol
0 0.8055 1.39716 0 0 0.7197 0.7906 1.36950 0.048 0.0019
0.0774 0.8041 1.39458 0.005 0.0006 0.7636 0.7896 1.36742 0.044 0.0016
0.1461 0.8028 1.39220 0.013 0.0010 0.7808 0.7892 1.36664 0.043 0.0016
0.2531 0.8007 1.38868 0.023 0.0019 0.8234 0.7882 1.36454 0.039 0.0012
0.3626 0.7984 1.38459 0.041 0.0023 0.8709 0.7871 1.36226 0.032 0.0009
0.4139 0.7973 1.38256 0.047 0.0024 0.9075 0.7863 1.36041 0.020 0.0006
0.5547 0.7943 1.37670 0.050 0.0023 0.9592 0.7851 1.35784 0.007 0.0001
0.6711 0.7917 1.37160 0.050 0.0020 1 0.7841 1.35605 0 0
0.6978 0.7911 1.37042 0.049 0.0019
Methanol + I -butanol
0.1074 0.8044 1.39329 0.014 0.0037 0.7267 0.7942 1.35846 0.063 0.0125
0.1941 0.8034 1.38999 0.025 0.0065 0.7599 0.7934 1.35523 0.060 0.0116
0.2738 0.8024 1.38666 0.034 0.0088 0.8056 0.7923 1.35080 0.049 0.0103
0.3427 0.8014 1.38362 0.046 0.0106 0.8346 0.7915 1.34776 0.046 0.0094
0.3743 0.8009 1.38192 0.053 0.0111 0.8935 0.7899 1.34096 0.028 0.0067
0.4970 0.7989 1.37505 0.063 0.0129 0.9253 0.7890 1.33694 0.015 0.0049
0.6422 0.7961 1.36527 0.067 0.0133 0.9682 0.7875 1.33126 0.007 0.0023
0.6877 0,7951 1.36179 0.066 0.0130 1 0.7863 1.32676 0 0
 M. lglesias et a l . / Fluid Phase Equilibria 126 (1996) 203-223 207

Table 3
Densities, refractive indices, excess molar volumes, and changes of refractive index on mixing for ternary mixture at
T = 298.15 K

xI x2 p/g cm -3 nD VmE / c m 3. m o l - 1 mixnD

Acetone + methanol + water

0.0127 0.0669 0.9736 1.33773 - 0.308 0.0053
0.0139 0.1348 0.9575 1.34027 - 0.534 0.0082
0.0173 0.3702 0.9044 1.34267 - 1.007 0.0119
0.0186 0.4792 0.8804 1.34139 - 1.036 0.0112
0.0212 0.6140 0.8529 1.33872 - 0.967 0.0092
0.0476 0.0234 0.9721 1.34305 - 0.434 0.0096
0.0584 0.2257 0.9234 1.34691 - 0.987 0.0143
0.0636 0.3134 0.9032 i .34687 - 1.105 0.0147
0.069 l 0.4145 0.8808 1.34549 - t. 143 0.0137
0.0774 0.5454 0.8534 1.34293 - 1.066 0.0117
0.1000 0.2510 0.9056 1.35006 - 1.158 0.0166
0.1115 0.3565 0.8813 1.34884 - 1.215 0.0158
0.1211 0.4782 0.8557 1.34629 - I. 135 0.0137
O. 1378 0.6316 0.8258 1.34202 - (I.883 0.0099
O. 1447 O. 1907 0.9054 1.35336 - 1.243 0.0185
O. 1575 0.2874 0.8829 1.35206 - 1.291 0.0175
O. 1749 0.4085 0.8565 1.34957 - 1.225 0.0153
0.1996 0.5700 0.8246 1.34497 - 0.935 0.0110
0.1922 0.1050 0.9084 1.35699 - 1.285 0.0206
0.2099 0.2127 0.8832 1.35540 - 1.351 0.0192
0.2343 0.3338 0.8564 1.35280 - 1.297 0.0t 67
0.2634 0.4805 0.8270 1.34848 - 1.024 0.0125
0.2684 0.1223 0.8846 1.35890 - 1.414 0.0208
0.2961 0.2485 0.8572 1.35584 - 1.366 0.0178
0.341 I 0.3888 0.8270 1.35174 - 1.087 0.0134
0.4225 0.2929 0.8266 1.35451 - i. 131 0.0137
0.4502 0.0582 0.8543 1.361 44 - 1.445 0.0187
0.5159 0.1897 0.8250 1.35711 - 1.148 0.0135
0.7566 0.0605 0.8053 1.35778 - 0.747 0.0078
0.7693 0.0740 0.8024 1.35726 - 0.673 0.0071
0.4876 0.1127 0.8395 1.35976 - 1.319 0.0164
0.6334 0.1978 0.8066 1.35556 - 0.792 0.0093
0.5065 0.3320 0.8084 1.35282 - 0.817 0.0103
0.4103 0.4406 0.8086 1.34994 - 0.788 0.0103
0.3283 0.5362 0.8081 1.34689 - 0.739 0.0097
0.2505 0.6226 0.8077 1.34364 - 0.677 0.0088
0.1755 0.6920 0.8093 1.34066 - 0.651 0.0080
0.1130 0.7668 0.8077 1.33695 - 0.563 0.0062
0.0576 0.8321 0.8059 1.33369 - 0.467 0.0046
0.7381 0.1442 0.7993 1.35572 - 0.609 0.0067
0.4012 0.2239 0.8398 1.35674 - 1.284 0.016 I
0.2540 0.4062 0.8405 1.35082 - 1.187 0.0147
0.1898 0.4850 0.8400 1.34755 - l. 101 0.0134
0.1290 0.5564 0.8403 1.34416 - 1.036 0.0118
0.0813 0.6213 0.8384 1.34086 - 0.947 0.0100
0.6739 0.2548 0.7955 1.35330 - 0.509 (/.0(164
208 M. lglesias et a l . / Fluid Phase Equilibria 126 (1996) 203-223

Table 3 (continued)
xl x2 p/g cm- 3 nD VmE / c m 3. m o l - 1 ~rnix nD
0.6844 0.1385 0.8065 1.35661 - 0.793 0.0088
0.6371 0.1357 0.8132 1.35728 - 0.944 0.0106
0.5060 0.4085 0.7994 1.35039 - 0.608 0.0083
0.5221 0.2537 0.8158 1.35499 - 0.977 0.0116
0.2728 0.6542 0.8000 1.34298 - 0.533 0.0078
0.1693 0.7605 0.7999 1.33839 - 0.462 0.0063
0.5966 0.3226 0.7977 1.35218 - 0.576 0.0075
0.5702 0.2408 0.8103 1.35492 - 0.869 0.0104
0.4321 0.5122 0.7967 1.34745 - 0.526 0.0077
0.3319 0.3465 0.8349 1.35286 - 1.189 0.0145
0.3178 0.1077 0.8751 1.35990 - 1.447 0.0205
0.1211 0.1851 0.9130 1.35211 - 1.160 0.0178
0.0596 0.6278 0.8415 1.33992 - 0.935 0.0096
0.0563 0.6717 0.8342 1.33861 - 0.863 0.0086
0.0462 0.7377 0.8242 1.33635 - 0.730 0.0070
0.0931 0.1674 0.9249 1.35021 - 1.030 0.0165
0.1763 0.1028 0.9131 1.35627 - 1.230 0.0202
0.1850 0.0564 0.9197 1.35739 - 1.202 0.0209
0.2018 0.1630 0.8945 1.35645 - 1.333 0.0201
0.3671 0.1052 0.8642 1.36032 - 1.441 0.0198
0.3540 0.0616 0.8741 1.36136 - 1.467 0.0209
0.2487 0.0746 0.8982 1.35967 - 1.374 0.0217
0.2838 0.1946 0.8687 1.35715 - 1.407 0.0191
0.3669 0.2081 0.8488 1.35733 - 1.355 0.0174
0.4256 0.2267 0.8352 1.35668 - 1.253 0.0155
0.5373 0.1397 0.8278 1.35849 - 1.193 0.0141
0.6272 0.0738 0.8216 1.35936 - 1.096 0.0125
0.7650 0.1410 0.7963 1.35556 - 0.512 0.0058
0.2872 0.5855 0.8074 1.34520 - 0.697 0.0093
0.3731 0.4832 0.8085 1.34861 - 0.769 0.0101
0.3567 0.3593 0.8286 1.35272 - 1.123 0.0139
0.4436 0.4052 0.8085 1.35079 - 0.808 0.0102
0.4118 0.3217 0.8243 1.35365 - 1.083 0.0133
A c e t o n e + m e t h a n o l + 1-butanol
0.0674 0.0810 0.8035 1.39206 0.004 0.0034
0.0629 0.4224 0.7991 1.37668 0.016 0.0118
0.0533 0.5343 0.7974 1.37021 0.017 0.0129
0.0502 0.6319 0.7957 1.36341 0.002 0.0128
0.0501 0.7123 0.7939 1.35669 - 0.004 0.0117
0.0454 0.7887 0.7923 1.34966 - 0.024 0.0099
0.0414 0.8497 0.7908 1.34328 - 0.037 0.0076
0.1753 0.0973 0.8013 1.38750 - 0.002 0.0044
0.1602 0.2599 0.7997 1.38109 - 0.022 0.0088
0.1425 0.4214 0.7978 1.37317 - 0.041 0.0115
0.1289 0.5306 0.7962 1.36667 - 0.048 0.0122
0.1209 0.6279 0.7947 1.35977 - 0.076 0.0118
0.1231 0.6847 0.7935 1.35469 - 0.094 0.0108
0.1093 0.7793 0.7917 1.34636 - 0.116 0.0086
0.2570 0.2722 0.7977 1.37633 - 0.059 0.0089
 M. lglesias et al. / Fluid Phase Equilibria 126 (1996) 203-223 209

Table 3 (continued)
x~ x2 p/g cm-3 nD Vd / c m 3 . m o l i 6mixnD
0.2255 0.4149 0.7963 1.36956 - 0.086 0.01 (19
0.2036 0.5145 0.7952 1.36365 -0.109 0.0112
0.1953 0.61 40 0.7937 1.35649 -0.147 0.0106
0.1959 0.6816 0.7924 1.35041 - O. 179 0.0093
0.1638 0.7729 0.7909 1.34316 - 0.180 0.0071
0.3746 0.1100 0.7971 1.37901 - 0.013 0.0050
0.3423 0.2567 0.7961 1.37317 - 0.075 0.0081
0.2907 0.5087 0.7936 1.35956 - O. 1 7 2 0 . 0 1 0 2

0.2652 0.6111 0.7925 1.35262 - 1).216 0.0094

0.2468 0.6893 0.7913 1.34628 - (t.238 0.0078
0.4823 0.0901 0.7950 1.37556 - 0.010 0.0046
0.4441 0.2472 0.7941 1.36903 - O. 105 0.0075
0.3987 0.3856 0.7933 1.36256 - 0.176 0.0089
0.3691 0.5015 0.7922 1.35557 - 0.232 0.0089
0.3475 0.5823 0.7914 .34994 - 0.275 0.0081
0.5888 0.0769 0.7928 .37140 - 0.012 0.0039
0.5249 0.2387 0.7925 .36557 - 0.131 0.0068
0.4707 0.3885 0.7917 ,35841 - {}.217 0.0079
0.4545 0.4630 0.7909 .35370 - {).259 0.0078
0.671 I 0.0771 0.7910 .36763 - 0.028 0.0035
0.6056 0.2327 0.7908 .36183 - 0.157 0.{X)59
0.5487 0.3723 0.7903 .35515 - 0.256 0.0068
0.7401 0.0900 0.7893 .36349 - 0.054 0.0031
0.6952 0.2126 0.7890 .35837 - O. 172 0.0048
0.8258 0.0761 0.7874 .36011 - 0.053 0.0023
0.8052 0.1566 0.7871 .35612 -0.152 0.0031
0.4009 0.1913 0.7957 1.37402 - 0.063 0.0068
0.2443 0.1 465 0.7993 1.38283 - 0.006 0.0060
0.4752 0.2909 0.7929 1.36475 - 0.147 0.(X)76
0.3098 0.2742 0.7966 1.37386 - 0.077 (}.0087
0.1107 0.3547 0.7993 1.37839 - 0.009 0.0107
0.4178 0.3239 0.7937 1.36569 - O. 144 0.0085
0.5869 0.1699 0.7918 1.36655 - 0.084 0.0055
0.2861 0.0832 0.7991 1.38395 0.013 0.0044
0.1162 0.0637 0.8029 1.39093 - 0.011 0,0030
0.2138 0.0643 0.8011 1,38763 - 0.020 0.0038
0.0492 0.1676 0.8030 1,38952 - 0.003 0.0062
0.1205 0.2107 0.8012 1.38520 - 0.020 {}.0078
0.0436 0.3385 0.8009 1.38202 0.007 0.0105
0.3165 0.3892 0.7951 1.36674 -0.146 0.0100

In these equations, p is t h e d e n s i t y a n d n D is t h e r e f r a c t i v e i n d e x , T h e Pi a n d nDi e x p r e s s i o n s are

the properties of the pure components and N is t h e n u m b e r of components in t h e m i x t u r e . The
derived binary excess properties were correlated using the Redlich-Kister expression (Eq. (3))
m

8 Q - = x i x j ~_, B p ( x i - x j ) p (3)
p=0
210 M. Iglesias et al. / Fluid Phase Equilibria 126 (1996) 203-223

where xi, Xj are the binary molar fractions, p is the grade polynomial parameter and Bp are the
fitting parameters. Fig. 1a and b show the experimental points of the binary excess properties plotted
against molar fraction of the most volatile component of the binary mixture as well as the
corresponding Redlich-Kister curves. Density and refractive index values for the mixture acetone +

(a) 0.2

0.0

-0.2

-0.4-
0

-0.6
E
-0.8

-1.0

-1.2

-1.4

I
- 1"~).0 0.5 1.0
X1

(b) 0.08

0.06

0.04

0.02

0.00
0.0 0.5 1.0
x1
Fig. 1. Variation of the (a) excess molar volumes and (b) changes in refractive index on mixing for acetone(1)+water(3)
(~), acetone(I) + l-butanol(3) (O), methanol(2) + water(3) ( zx ), and methanol(2) + 1-butanol(3) ([]) with mole fraction at
298.15 K.
 M. lglesias et al./Fluid Phase Equilibria 126 (1996~ 203-223 211

methanol are available in a previous work (Orge et al., 1994). Densities and refractive indices of the
binary mixtures are given in Table 2 with the corresponding excess values. The ternary and binary
values of the densities or refractive indices have been fitted to a polynomial expansion of the form
3 m

Q = ~'~ Y'~ a i j x / (4)

i=l j=l

where Q is p / ( g cm -3) or n D. In this equation, the polynomial grade is expressed by the parameter

(a) Methanolo
.,

\ \ \\s

0 0.5 I
Water , Acetone

(b) Methanol

/~'07. / / I I [ I I \ \ \ \9~

0 0.5 I
1-Butanol , Acetone
Fig. 2. Curves of constant excess molar volumes at 298.15 K for (a) acetone(1)+methanol(2)+water(3) and (b)
acetone(1) + methanol(2) + 1-butanol(3).
212 M. Iglesias et al. / Fluid Phase Equilibria 126 (1996) 203-223

Methanol

0 0.5 1
Water 1 Acetone
Fig. 3. Curves of 8V E = Vex
Ep - VNod
a E at 298.15 K for acetone(1) + methanol(2) + water(3).

m and the mole fraction of the component i by x i. Density values for the ternary mixtures present a
rapid regular increase as the molar fraction of the heavy component (water or 1-butanol) rises through
the composition diagram. Ternary refractive indices for acetone + methanol + water follow a particu-
lar behaviour showing a binary maxima.
The ternary excess values, which were determined by Eq. (1) and Eq. (2) are presented in Table 3.
These were correlated with the Cibulka equation, which uses the Redlich-Kister parameters in the
binary contributions
~Q123 = ~Ql2 + ~ Q l 3 + ~Q23 + XlX2(1 - Xl - x 2 ) ( C l -.I- C 2 x I -].- C 3 x 2 ) (5)

Isolines of the excess volumes for the ternary systems are presented in Fig. 2a and b. Values of
excess volumes are negative for the whole mixture acetone + methanol + water With a clear contrac-
tive trend in approximately x(3) = 0.5 molar fraction, because of the strong interaction between water
(proton donor) and acetone (proton aceptor). The ternary composition trend is in line with expectation
because a set of valleys of negative excess volumes connects the three binary minima. The molecular
packing effect increases for equimolecular binary or ternary compositions. The mixture acetone +
methanol + 1-butanol shows similar behaviour but with a minimum in the acetone + methanol system
and low maxima in the other two binaries due to the weaker cross association between 1-butanol and
the other components. Steric hindrance plays an important role in the formation of the hydrogen
bonding in self-association and association between unlike molecules for this mixture.
Comparison with computed excess volumes obtained from density measurements reported by Noda
et al. (Noda et al., 1982) for the acetone-methanol-water mixture is presented in Fig. 3, where it can
be observed that large deviations coincide with moderately high values of excess volume and where
low or null number of experimental points by these authors exist. Low deviation (the null isoline
almost encloses the whole diagram) is observed near binary bounds, showing no significant
differences between both excess volume data series.
The parameters of fitting equations (Eq. (3) and Eq. (5) for excess values and Eq. (4) for physical
 M. lglesias et al. / Fluid Phase Equilibria 126 (1996 ~203-223 213

Table 4
Parameters A i j , Bp a n d C i o f E q . ( 3 ) , E q . ( 4 ) a n d E q . ( 5 ) a n d s t a n d a r d d e v i a t i o n s s

A c e t o n e + water
V E / ( c m 3 . t o o l - l) B 0 = - 5.8012 B 1= 2.0121 B 2 = - 0.9770 B 3 = 1.4263
B 4 = 0.5791 B 5 = - 1.8248 s = 0.0051
~n D B o = 0.0736 B I = -0.0608 B 2 = 0.0476 B 3 = -0.0338 s = 0.0001

Methanol + water
V Z/(cm3 tool- i ) B 0 = -4.0347 B 1= 0.2360 B 2 = -0.0747 B 3 = -0.8389
B 4 = 0.8223 s = 0.0043
~n D B o = 0.0403 B 1= -0.0199 B 2 = 0.0094 _B 3 = 0 . 0 0 6 7
B 4 = -0.0220 s = 0.0001

A c e t o n e + 1- b u t a n o l
vE/(cm 3 tool t) B o = 0.2015 B t = 0.1093 B 2 = -0.0491 s = 0.0020
~n D B 0 = 0.0100 B l ~ -0.0007 B 2 = -0.0029 s = 0.0001

Methanol + l - b u t a n o l
V E/(cm 3 tool -~) Bo = 0 . 2 5 9 5 Bi = 0.1781 B2= -0.0607 B3= -0.1438 s = 0.0021
~n D B 0 = 0.0522 B l = 0.0200 B z = 0.0042 s = 0.0001

A c e t o n e + m e t h a n o l + water
p/(g cm -3) All ~ 0.7340 AI2 = 0.0468 AI3 = 0.0260 A14 = - 0 . 0 2 2 5
A21 ~ 0 . 8 4 9 4 A22 = - 0 . 0 6 0 8 A23 = - 0 . 0 0 2 0 A24 = 0 . 0 0 0 0
A31 = 0 . 9 0 0 3 A32 = 0 . 0 8 2 9 A33 = 0 . 0 0 4 6 A34 = 0 . 0 0 7 8 s = 0.0007
no All = 1.4306 A12 ~ - - 0 . 2 0 5 9 AI3 = 0 . 2 2 6 3 At4 = -0.0963
A21 = 1 . 3 0 5 3 A2z = 0 . 0 7 5 7 A23 = - 0 . 1 0 9 4 A24 = 0 . 0 5 5 4
A31 = 1 . 3 5 7 3 A32 = - 0 . 0 0 9 3 A33 = 0 . 0 3 9 3 A34 = - 0 . 0 5 4 2 s = 0.0009
V E/(cm3 t o o l - 1) C l = 2.4414 C 2 = -0.8447 C 3 = 4.2751 s = 0.0096
~n D C l = -0.2152 C 2 = 0.2133 C 3 = 0.0393 s = 0.0003

A c e t o n e + m e t h a n o l + 1- b u t a n o l
p/(g cm -3) All = 0.7926 A12 = - 0 . 0 2 1 6 Ai3 = 0.0221 A~4 = - 0 . 0 0 9 0
A21 = 0 . 7 9 6 7 A22 = - 0 . 0 0 9 6 A23 = 0 . 0 0 8 1 A24 = - - 0 . 0 0 8 8
A31 = 0 . 8 0 3 8 A32 = 0 . 0 0 1 5 A33 = 0 . 0 0 1 0 A34 = - 0 . 0 0 0 8 s = 0.0001
nD All = 1.3460 Al2 = 0.0149 AI3 = - 0 . 0 1 0 3 Ai4 = 0.0053
A21 ~ 1 . 3 5 4 5 A22 = - 0 . 0 2 3 6 A23 = 0 . 0 1 5 6 A24 = - 0 . 0 1 9 7
A31 = 1.4185 A32 = - - 0 . 0 2 6 6 A33 = 0 . 0 0 2 8 A34 = 0 . 0 0 2 4 s = 0.0002
vE/(cm 3 mol 1) Ct =0.1628 C 2 = -0.1105 C3=0.0273 s=0.0068
~n D C t = 0.0089 C 2 = -0.0190 C 3 = -0.0255 s = 0.0001

properties) and the corresponding standard deviations are given in Table 4. The unweighted
least-squares method was used to fit the polynomials to the data. The degree of Eq. (3) was optimized
by applying the F-test (Bevington, 1969). No significantly better standard deviations were obtained
by trying different fitting models to correlate excess values as well as physical properties, because of
the high non-ideality of water and 1-butanol-rich mixtures.
Curves of constant change of refractive indices on mixing have been plotted in Fig. 4a and b.
Mixtures of high water molar fractions and relatively low methanol values present the highest value
for acetone + methanol + water, and low acetone molar fractions and equimolecular values of
214 M. Iglesias et a l . / Fluid Phase Equilibria 126 (1996) 203-223

(a) Methanol

g
" 0
0 0.5 1
Water x~ Acetone

(~) Methanol

0 0.5 1
l-Butanol x, Acetone
Fig. 4. Curves of constant changes in refractive index on mixing at 298.15 K for (a) acetone(l)+ methanol(2)+ water(3) and
(b) acetone(1) + methanol(2) + 1-butanol(3).

alcohols for acetone + methanol + 1-butanol. Positive values of changes of refractive index on mixing
can be observed in both composition spaces.

4. Physical and derived excess properties estimation

Several methods to predict density and refractive indices of mixtures were applied to test their
validity in high polar mixtures. The density of binary and ternary mixtures was estimated by the
 M. lglesias et al. / Fluid Phase Equilibria 126 (1996~ 203-223 215

Hankinson-Brobst-Thompson, Rackett, Spencer and Danner modified Rackett, Bradford-Thodos,

Riedel, Narsimham and Yen-Woods methods using the expanded mixing rules proposed by these
authors or the Kay (modified Prausnitz-Gunn combination) rule (Reid et al., 1987). The refractive
indices were compared with the predicted results for the mixing rules proposed by Lorentz-Lorenz,
Dale-Gladstone, Arago-Biot, Eykman, Newton, Oster and Eyring-John equations (see Appendix A).
The predictive methods for excess properties (Kohler, 1960; Jacob and Fitzner, 1977; Colinet,
1967; Tsao and Smith, 1953; Toop, 1965; Scatchard et al., 1952) determine ternary excess properties
by means of additive binary contributions, using different rules to determine them. The ternary excess
properties of mixtures may be estimated from binary values applying Eq. (6) (see Appendix B)
~Qijk = E ( xixJx',x'j)~Q,i( X'i'X~) (6)
i<j

Table 5
Standard deviations of the experimental results from those estimated for densities (Hankinson-Brobst-Thompson (HBT),
Rackett (R), Spencer and Danner modified Rackett (SDR), Bradford-Thodos (BT), Riedel (Ri), Narsimham (N), and
Yen-Woods (YW)), and refractive indices (Lorentz-Lorenz (LL), Dale-Gladstone (DG), Arago-Biot (AB), Eykman (E),
Newton (N), Oster (O) and Eyring-John (EJ))
Density
HBT R SDR BT Ri N YW
Acetone + water
0.0087 0.0753 0.0441 0.0261 0.0124 0.0147 0.0097
Methanol + water
0.0217 0.0667 0.0339 0.0237 0.0117 0.0102 0.0081
Acetone + 1-butanol
0.0088 0.0244 0.0141 0.0065 0.0209 0.0179 0.0051
Methanol + l-butanol
0.0285 0.0584 0.0434 0.0118 0.0366 0.0026 0.0037
Acetone + methanol + water
0.0190 0.0506 0.0156 0.0152 0.0084 0.0190 0.0045
Acetone + methanol + 1-butanol
0.0178 0.0469 0.0298 0.0073 0.0237 0.0128 0.0032

Refractive indices
LL DG AB E Nw O EJ
Acetone + water
0.00893 0.00890 0.00890 0.00891 0.00887 0.00889 0.00892
Methanol + water
0.00786 0.00786 0.00786 0.00786 0.00785 0.00785 0.00786
Acetone + l-butanol
0.00024 0.00019 0.00019 0.00020 0.00020 0.00019 0.00021
Methanol + l-butanol
0.00034 0.00064 0.00064 0.00053 0.00097 0.00080 0.00047
Acetone + methanol + water
0.00933 0.00929 0.00929 0.00930 0.00924 0.00927 0.0093 I
Acetone + methanol + 1-butanol
0.00095 0.00079 0.00079 0.00084 0.00067 0.00073 0.00087
216 M. lglesias et al. / Fluid Phase Equilibria 126 (1996) 203-223

Table 6
Standard deviations of the experimental results from the prediction results for differentempirical equations
s (VmE) s (~n D) s (VmE) s (~n D)
Acetone+ methanol+ water Acetone+ methanol+ 1-butanol
Kohler 0.031 0.0010 0.011 0.0005
Jacob-Fitzner 0.024 0.0004 0.012 0.0004
Colinet 0.028 0.0007 0.010 0.0004
Tsao-Smith a 0.220 0.0039 0.012 0.0025
Tsao-Smith b 0.236 0.0041 0.020 0.0002
Tsao-Smith c 0.028 0.0004 0.035 0.0017
Toop a 0.078 0.0026 0.007 0.0006
Toop b 0.025 0.0011 0.013 0.0002
Toop c 0.026 0.0013 0.015 0.0008
Scatchard a 0.082 0.0026 0.007 0.0006
Scatchard b 0.021 0.0006 0.013 0.0002
Scatchard c 0.026 0.0014 0.015 0.0008

a Water is the asymmetriccomponentb Methanol is the asymmetriccomponentc Acetone is the asymmetriccomponent

For each ternary mixture the molar fractions x' may be obtained from a triangular diagram by
projecting the point representing the temary mixture onto the corresponding binary axis, using
different symmetric or asymmetric criteria of binary contribution to the ternary value. In these rules,
symmetry is understood to be the contribution of the three binaries to the temary excess, all three of
which contribute equally. Assymmetry is understood to indicate the individual contribution of one of
the binaries, the latter being normally attributed to polar components. In Tables 5 and 6, the
experimental and estimated physical properties and excess values are compared showing standard
deviations (Eq. (7)). The value of the property and the number of experimental data are represented in
this equation by z and n, respectively

= (7)
n
In ternary density estimations, the Yen-Woods method gives the smaller deviations in both
mixtures, as well as in methanol + water and acetone + 1-butanol binary mixtures. The Hankinson-
Brobst-Thompson and Newton methods show lower deviation in the acetone + water and methanol
+ 1-butanol systems, respectively. All mixing rules for refractive indices present moderate deviations
if a comparison is made with other systems, such as the same light binary with alkanols or chemicals
with similar polarity (Iglesias et al., 1995, 1996). This is due to the particular behaviour of the
non-ideality of these mixture and the assumption of additivity of volumes. The lower deviations in the
acetone + methanol + water system are determined for excess volumes by the symmetric Jacob-
Fitzner and the b-type asymmetric Toop and Scatchard equations (Table 6). Deviations from
asymmetric equations with water as the asymmetric component (or methanol in Tsao-Smith) present
the highest values. For changes in refractive index on mixing, better results were determined by
means of the symmetric Colinet and Jacob-Fitzner and the asymmetric Scatchard, Toop (type b in
both cases) and Tsao-Smith (type c). In the acetone + methanol + 1-butanol mixture, low deviations
 M. lglesias et al. / Fluid Phase Equilibria 126 (1996) 203-223 217

were determined by the a-type asymmetric Toop and Scatchard equations and the b-type asymmetric
Tsao-Smith, Toop and Scatchard equations for excess volumes and changes of refractive index,
respectively.
In the last few years, the prediction of excess volumes from refractive index mixing rules and the
relation of excess volumes with the density of the pure components has been suggested for binary
mixtures by some authors (Nakata and Sakurai, 1987; Arancibia and Katz, 1993). They have proposed
(Heller, 1965) that the mixing rules for refractive indices are functions of the volume fractions of the
mixture, since it is possible to generalize them as a function of the density of the mixture and of the
pure components as follows

f(nD ) N wif(nDi)
- - - E (8)
P i= 1 Pi

In this equation, p is the density of the mixture and Pi is the density of a component i in the
mixture, w i is the weight fraction and f is a mathematical function of the refractive indices of the
mixture (n o) and the refractive index of each component (noi) By substitution in Eq. (1), applying
some algebra and reorganizing the expression, for ternary systems the excess volume of the mixture
can be expressed as

i=l i=l De ~--~ x i M i

v = - z.., (9)
f(nD) i= 1 Pi

From this equation, considering the relation between the weight fractions and molar fractions, the
equation can be transformed so that

( ~ Mixif(noi) )
VrnE = i=1 Pi _ ~xiMi (10)
f(nD) i=i Pi

Expressed in another way, the relation of the excess volumes to the function of the refractive
indices would be

N[
VmE= E (f(nDi)--f(
i=1
no,,x,
('-'~D)-ii]O i
(11)

In this paper, the experimental and estimated values of the excess molar volumes using Eq. (11) are
compared for the binary and ternary mixtures applying Lorentz-Lorenz, Dale-Gladstone, Eykman
and Oster (Eq. (12), Eq. (13), Eq. (14), and Eq. (15), respectively) refractive index mixing rules

(n~-1)
f ( n o ) = (n~ + 2) (12)

f(nD) = nD - 1 (13)
218 M. lglesias et al. / Fluid Phase Equilibria 126 (1996) 203-223

(n 2 - 1)
f(nD) = (14)
(n o + 0.4)
+ 1)]
f(no) = n2 (15)

Absolute average deviations were determined as a function of molar fraction by substitution in Eq.
(11) of the Dale-Gladstone rule for acetone +methanol + water and of the Eykman rule for
acetone + methanol + 1-butanol. In both ternary systems, it could be observed that the deviation is
almost null in the higher excess molar volumes part of the composition diagram, while the deviations
grows slightly towards zones of low excess volume. Eq. (11) shows moderate sensibility in the
determination of low values of excess molar volume but presents much better behaviour than the other
equations proposed (Nakata and Sakurai, 1987) for the ternary estimation.

5. List of symbols

A parameters of the polynomic expansion (Eq. (4))

B parameters of the Redlich-Kister equation (Eq. (3))
C parameters of the Cibulka equation (Eq. (5))
f mathematical function
m expansion polynomial grade (Eq. (3) and Eq. (4))
M molecular weight
refractive index, number of data (Eq. (7))
N number of components
Q physical property
s standard deviation
V molar volume
W weight fraction
X molar fraction
Z value of a magnitude (Eq. (7))
Z compressibility factor (Appendix A)

5.1. Greek letters

change of a variable
A change of a variable
P density
co acentric factor (Appendix A)
4, volume fraction (Appendix A)

5.2. Superscripts

b binary mixture (Appendix B)

E excess
 M. lglesias et al. / Fluid Phase Equilibria 126 (1996; 203-223 219

J expansion polynomial grade

P Redlich-Kister polynomial grade

5.3. Subscripts

!
value as a function of graphical interpretation
b boiling point (Appendix A), binary mixture (Appendix B)
C critical magnitude (Appendix A)
D light of sodium D wavelength
exp experimental
i component of the mixture
J component of the mixture
k component of the mixture
m molar
P Redlich-Kister polynomial grade
pred prediction
r reduced magnitude
S saturated (Appendix A)
t ternary mixture (Appendix B)

Acknowledgements

The authors wish to thank Cfindida Barreiro Castro for her assistance in the experimental
development of this paper also Jos~ Luis Legido Soto for his collaboration and useful advice.

Appendix A

Predictive methods of density and refractive indices

Several equations which are dependent on critical properties of the pure components (Daubert and
Danner, 1985) have been applied to test their validity with respet to the prediction.
(1) Density
Hankinson-Brobst-Thomson

l/( ps v *) = V,')[1 - ~SR,,V~ ~']

VR(~= 1 + a(1 -- Tr) ~/3 + b(1 - Tr) 2/3 + c(1 - Tr) + d ( l - Tr)4/3 0.25 < T r < 0.95

V~~)= [ e + f i r + gTr 2 + hTrg]/(T~ - 1.00001) 0.25 < Tr < 1.0

where a, b, c, d, e, f, g and h are parameters and V * is the pure component characteristic

volume.
220 M. Iglesias et al. / Fluid Phase Equilibria 126 (1996) 203-223

Rackett

1/ps = ( RTc/Pc)Zt~ +~1- Tr)2JTj

Spencer and Danner modified Rackett

1/Os = ( R r c / P c ) Z ~ ; ~ - Tr)2J']
w h e r e ZRA is d e p e n d e n t on to (tables o f ZRA in (Reid et al., 1987)).
Bradford-Thodos

Ps/Pc = 1.0 + ( 2 . 9 2 4 - 7 . 3 4 Z c ) ( 1 - T~) - ( 1 . 1 3 9 - 3 . 7 9 6 Z c ) ( 1 - Tr) 2

+(2.785- 3.544Zc)(1- T~)~~6586zO

Riedel

Ps/Pc = 1 + ( 1 . 6 9 + 0 . 9 8 4 t o ) / ( 1 - Tr) 1/3 + 0.85(1 - Tr)

Narsimham

Ps/Pc-- I + [(0.4221ogP c + 0.981)/(1 - Tb/Tc)'4](1 - Tr) 0"40

Yen-Woods

Ps/Pc = 1 + A ( 1 - Tr) 1/3 + B ( 1 - rr) 2/3 + C(1 - T~) 4/3

A = 17.4425 - 2 1 4 . 5 7 8 Z C + 9 8 9 . 6 2 5 Z 2 - 1 5 2 2 . 0 6 Z 3

B = - 3.28257 + 13.6377Z c + 107.4844Z~ - 384.211Z 3 Z C < 0.26

B = 60.2091 - 4 0 2 . 0 6 3 Z C + 5 0 1 . 0 Z ~ + 6 4 1 . 0 Z 3 Z c > 0 . 2 6 C = 0.93 - B

(2) R e f r a c t i v e index
Lorentz-Lorenz

n~ 1 N

n-~D"-+ 2 = i= l n~i + 2
Dale-Gladstone
N
n ~ - 1 = E [~,(n~i- 1)]
Arago-Biot
N
nD = E ( ~,no~)
i=1
 M. Iglesias et al. / Fluid Phase Equilibria 126 (1996) 203-223 221

Eykman

n 2 + 0.4 = i=1 ~)i nai + 0.4

Newton
N
n2 -1= ~__,[q,i(n2i- 1)1
i=1
Oster

(n~--l)-(2n~+l)=~-'~[dPi(n2Di-1)-(2n~)i+l)]n2 i=1 n2i

Appendix B

Predictive methods of excess properties from binary mixture data

Several empirical methods have been proposed to determine excess molar enthalpies, which can
also be applied to other excess properties as excess volumes or changes in refractive index on mixing.
All of them, either in the form of symmetrical or asymmetrical equations, estimate the ternary value
from the binary contributions based on graphic criteria. The methods are:
(1) The Kohler equation

aO., = ( x, + x2)2aO.b( XU,,x~) + ( x, + x3)ZaO_b( XU,,X~) + ( X2 + XB)~AQb( xb,x~)

where x~ = 1 - xjb = X i / ( X i _~ X j)
(2) The Jacob-Fitzner equation

AQt = ( XiX2)/[( X l q- X 3 / 2 ) ( X 2 "t'-X3/2)IAQb(xb,x.~)

-'l-( Xl X 3 ) / [ ( X 1 -I'-x 2 / 2 ) ( x 3 --{- x2/2)]aQb(x~,x~)

+( x3)/[( + x , / 2 ) ( x3 + x,/e]
where x b - x jb = x i - x j
(3) The Colinet equation

AQt = [( x2//(1 - xI)IAQb (xI,1 -- Xl) -.[.-[ ( X l / ( 1 -- X2)]AQb(1 -- x2,x2)

+ [ ( x 3 / ( l - x , ) ] A Q b (x,,1 - x,) + [ ( x , / ( 1 - x3)]AQb(1 - x3,x3)
+ [(x3/(1 - x2)] AG(x2,1 - x~) + [(x2/(1 - x3)] A Q d l - x3,x3)

(4) The T s a o - S m i t h equation

AQt = [ ( x 2 / ( 1 - X,)IAQb(Xb,x b) + [ ( x 3 / ( 1 -- x , ) ] A e b ( x b , x b) + (1 -- x , ) A O b ( x b , x b)
222 M. lglesias et a l . / Fluid Phase Equilibria 126 (1996) 203-223

w h e r e x~ = x~ f o r b i n a r y s y s t e m s 1,2 a n d 1,3 a n d x b = x 2 / ( x 2 + x 3) f o r the b i n a r y 2,3.

(5) T h e T o o p e q u a t i o n

_ _ xl)]AQb( b ,,x3)+
b (1 --X I

w h e r e x b i n a r y v a l u e s are c o m p u t e d as in the T s a o - S m i t h equation.

(6) T h e S c a t c h a r d e q u a t i o n

AO, = - x,)] + [(xJ(1 - x,)] A + t,Q (x ,x3)

where the first and second parts are similar to those of the Colinet and Tsao-Smith equations.

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