862 J. Chem. Eng.

Data 2000, 45, 862-866

Surface Tensions, Refractive Indexes and Excess Molar Volumes of

Hexane + 1-Alkanol Mixtures at 298.15 K

Eulogio Jiménez,* Herminio Casas, Luisa Segade, and Carlos Franjo

Departamento de Fı́sica, Facultade de Ciencias, Universidade da Coruña, 15071 A Coruña, Spain

Surface tensions and refractive indexes for binary mixtures of {hexane + ethanol, + 1-propanol, +
1-butanol, + 1-pentanol, + 1-hexanol, + 1-heptanol, and + 1-octanol} have been measured at 298.15 K.
Surface tension deviations and changes of refractive index have been also calculated. Excess molar volumes
of {hexane + ethanol, + 1-pentanol, and + 1-hexanol} mixtures have been determined at 298.15 K from
density data and compared with literature.

Introduction Table 1. Physical Properties of the Pure Components at

298.15 K
We have initiated with this work our studies on surface
tension, which added to other thermodynamic and physical F/g‚cm-3 nD σ/mN‚m-1
properties such as viscosity, refractive index, density, substance exptl lit. exptl lit. exptl lit.
excess molar volumes, and excess molar enthalpies form hexane 0.654 77 0.654 79a 1.372 3 1.372 26b 17.89 17.88c
part of our systematic research on nonaqueous binary ethanol 0.785 53 0.785 4d 1.359 3 1.359 41b 21.74 21.82e
mixtures.1,2 Surface tension is a property of interest 1-propanol 0.799 62 0.799 60f 1.383 0 1.383 0g 23.39 23.39h
because of its applications in industrial chemistry, but 1-butanol 0.805 76 0.805 81i 1.397 3 1.397 3j 24.02 24.41h
there is a lack of reliable measurements on mixtures of 1-pentanol 0.810 83 0.810 85k 1.408 0 1.408 0b 24.97 25.30h
1-hexanol 0.815 15 0.815 15k 1.415 9 1.415 7b 25.73 25.90h
practical interest. 1.416 1j
We present here the excess molar volumes of {hexane + 1-heptanol 0.818 75 0.818 71l 1.422 4 1.422 5j 26.47 26.5j
ethanol, + 1-pentanol, and + 1-hexanol} at 298.15 K, and 1-octanol 0.821 63 0.821 62i 1.427 4 1.427 5j 27.13 27.1j
our results have been compared with those from the
a Reference 3. b Reference 4. c Reference 5. d Reference 6. e Ref-
literature. Also, surface tensions and refractive indexes of
{hexane + ethanol, + 1-propanol, + 1-butanol, + 1-pen- erence 7. f Reference 2. g Reference 8. h Reference 9. i Reference 1.
j Reference 10. k Reference 11. l Reference 12.
tanol, + 1-hexanol, + 1-heptanol, and + 1-octanol} mix-
tures have been measured at 298.15 K.
component i, respectively; F and Fi are the densities of the
Experimental Section mixture and component i; xi is the mole fraction of
component i.
The purities and the sources of the chemicals employed
Refractive indexes (nD) were measured with an Atago
were hexane (Fluka, g99.5), ethanol (Fluka, >99.8), 1-pro-
RX-1000 automatic refractometer with a reproducibility in
panol (Sigma-Aldrich, g99.5), 1-butanol (Fluka, >99.5),
the refractive index of 1 × 10-4, and the temperature was
1-pentanol (Fluka, >99.0), 1-hexanol (Fluka, g99), 1-hep-
regulated to better than (0.1 K using a Polyscience 9101
tanol (Sigma, g99), and 1-octanol (Fluka, >99.5). The
thermostat. The changes of refractive index (∆nD) were
substances were degassed by ultrasound and dried over
calculated by
molecular sieves (Sigma type 0.4 nm) and otherwise used
as supplied. Table 1 shows their measured physical proper-
ties compared with literature data.
∆nD ) nD - x1nD,1 - x2nD,2 (2)
All the mixtures were prepared by mass using a Mettler
AT 201 balance with a accuracy of 1 × 10-8 kg. where nD and nD,i are the refractive indexes of the mixture
Densities of the pure liquids and their mixtures were and the component i, respectively, and xi is the mole
measured with an Anton Paar DMA 60/602 vibrating tube fraction of component i.
densimeter. The vibrating tube temperature was regulated Surface tension (σ) was determined using a Lauda TVT1
to within (0.01 K using a Haake F3 thermostat with an automated tensiometer, which employs the principle of the
Anton Paar DT 100-20 digital thermometer. The calibration drop volume. This technique consists of measuring the
was made with doubly distilled water and with heptane volume of a drop detaching from a capillary with a circular
(Sigma, >99). Excess molar volumes were determined from cross section. The surface tension can be determined as
the density data as follows: follows:

M M1 M2 ∆FgV
V Em ) - x1 - x2 σ)
( )
(1) (3)
F F1 F2 rcap
2πrcapf
a
where M and Mi are the molar mass of the mixture and
2σ 1/2

* Corresponding author. E-mail: [email protected].

a) ( ∆Fg ) (4)

10.1021/je000060k CCC: $19.00 © 2000 American Chemical Society

Published on Web 08/01/2000
 Journal of Chemical and Engineering Data, Vol. 45, No. 5, 2000 863

Table 2. Excess Molar Volumes V E

m at 298.15 K

V Em/ V Em/ V Em/

x cm3‚mol-1 x cm3‚mol-1 x cm3‚mol-1
x Hexane + (1 - x) Ethanol
0.0465 0.0760 0.4264 0.3864 0.7172 0.3820
0.1035 0.1431 0.4790 0.3794 0.8142 0.3326
0.1604 0.2001 0.5353 0.3972 0.8397 0.3072
0.2162 0.2634 0.5649 0.3952 0.9076 0.2328
0.2647 0.3023 0.6334 0.3977 0.9244 0.2115
0.3082 0.3303 0.6678 0.3917
x Hexane + (1 - x) 1-Pentanol
0.0489 -0.0608 0.5332 -0.1173 0.8868 0.0474
0.1111 -0.1112 0.5782 -0.0938 0.9302 0.0549
0.1507 -0.1358 0.6297 -0.0646 0.9751 0.0506
0.1915 -0.1678 0.6807 -0.0395 0.9788 0.0412
0.2602 -0.1767 0.7064 -0.0231 0.9840 0.0402
0.3474 -0.1842 0.7624 0.0127 0.9893 0.0346
0.4201 -0.1712 0.7669 -0.0027 0.9949 0.0237
0.4791 -0.1423 0.8378 0.0260
x Hexane + (1 - x) 1-Hexanol
0.0544 -0.0746 0.5141 -0.2414 0.8052 -0.0792
0.1696 -0.2159 0.5316 -0.2327 0.8592 -0.0328
0.1966 -0.2313 0.5778 -0.2144 0.9095 -0.0029
0.2542 -0.2584 0.5885 -0.2208 0.9594 0.0264
0.3128 -0.2726 0.6629 -0.1848 0.9812 0.0251
0.3579 -0.2759 0.7088 -0.1509 0.9898 0.0220
0.4556 -0.2664
Figure 1. Experimental excess molar volumes V Em of b, {x
where ∆F is the density difference between liquid and vapor hexane + (1 - x) ethanol}; 9, {x hexane + (1 - x)1-pentanol}; O,
phase, g is the gravitational acceleration; V is the drop {x hexane + (1 - x) 1-hexanol}. From Jiménez et al.:14 {x hexane
+ (1 - x) 1-propanol} and {x hexane + (1 - x) 1-butanol}. From
volume, 2rcap is the outer diameter of the capillary, and f
Jiménez et al.:15 {x hexane + (1 - x) 1-heptanol} and {x hexane +
is a correction function. Detailed instrument design and (1 - x) 1-octanol}. From Heintz et al.:18 {x hexane + (1 - x)
experimental procedure have been described elsewhere.13 1-decanol}.
The accuracy of the method is (0.01 mN‚m-1. A Lauda RC6
CP thermostatic bath controlled the temperature to better
than (0.1 K. The surface tension deviations (δσ) were
calculated by

δσ ) σ - x1σ1 - x2σ2 (5)

where σ and σi are the surface tensions of the mixture and

the component i, and xi is the mole fraction of component
i.
The density data for {x hexane + (1 - x) ethanol, +
1-pentanol, and + 1-hexanol} mixtures were measured in
this work, while the {x hexane + (1 - x) 1-propanol, +
1-butanol} systems were taken from ref 14, and {x hexane
+ (1 - x) 1-heptanol, + 1-octanol} mixtures were taken
from ref 15.

Results and Discussion

Experimental excess molar volumes (V Em) of binary mix-
tures {x hexane + (1 - x) ethanol, + 1-pentanol, and +
1-hexanol} at 298.15 K are listed in Table 2. The results
were fitted to a equation of the form
Figure 2. Excess molar volumes for {0.5 hexane + 0.5 1-alkanol}
N against number of carbon atoms of 1-alkanols: b, this work; O,
∑ A (2x - 1)
k)0
k
k
Jiménez et al.;14 ], Jiménez et al.;15 3, Heintz et al.;18 0, Marsh
and Burfitt;17 +, Iglesias et al.;19 ×, Treszczanowicz and Benson.20
E
Q ) x(1 - x) (6)
1 + B0(2x - 1) hexane + 0.5 1-alkanol} against number of carbon atoms
of 1-alkanols, n. The results show that excess molar
where QE represents here V Em x is the mole fraction of volumes of {x hexane + (1 - x) 1-alkanol} decreases as the
hexane; Ak and B0 are parameters obtained by the un- chain length of 1-alkanol increases. In the case of {x hexane
weighted least-squares method. The number of parameters + (1 - x) ethanol},V Em’s are positive and the maximum is
was determined using an F-test.16 The parameters Ai and skewed toward low mole fractions of ethanol, while the
B0 are shown in Table 5. Figure 1 shows the excess molar curves of {x hexane + (1 - x) 1-pentanol, + 1-hexanol} are
volumes presented in this work besides other {x hexane + S-shaped.
(1 - x) 1-alkanol} mixtures obtained from literature.14,15,17-20 Table 3 lists the surface tensions for {x hexane + (1 -
Figure 2 shows the equimolar excess molar volumes of {0.5 x) ethanol, + 1-propanol, + 1-butanol, + 1-pentanol, +
864 Journal of Chemical and Engineering Data, Vol. 45, No. 5, 2000

Table 3. Surface Tensions at 298.15 K Table 4. Refractive Indexes at 298.15 K

x σ/mN‚m-1 x σ/mN‚m-1 x σ/mN‚m-1 x nD x nD x nD
x Hexane + (1 - x) Ethanol x Hexane + (1 - x) Ethanol
0.0448 21.10 0.4366 18.33 0.7584 17.97 0.1604 1.3619 0.5863 1.3674 0.7584 1.3694
0.1625 19.74 0.4700 18.28 0.7963 17.95 0.2162 1.3627 0.6334 1.3679 0.7963 1.3698
0.2116 19.26 0.4974 18.16 0.8500 17.93 0.3745 1.3649 0.6452 1.3681 0.8397 1.3703
0.2559 18.98 0.5863 18.12 0.9067 17.91 0.4366 1.3657 0.6678 1.3684 0.9067 1.3711
0.3034 18.83 0.6452 18.06 0.9347 17.89 0.5353 1.3669 0.7172 1.3689
0.3745 18.56 0.6841 18.02 x Hexane + (1 - x) 1-Propanol
x Hexane + (1 - x) 1-Propanol 0.0612 1.3819 0.3547 1.3774 0.6858 1.3737
0.0612 22.44 0.4621 18.96 0.7447 18.25 0.1019 1.3812 0.3606 1.3773 0.7447 1.3732
0.2219 20.62 0.5304 18.69 0.7838 18.20 0.1485 1.3804 0.4621 1.3760 0.7838 1.3729
0.2837 20.07 0.5603 18.60 0.8416 18.11 0.2219 1.3793 0.5304 1.3752 0.8416 1.3726
0.3050 19.88 0.6287 18.46 0.8740 18.06 0.2837 1.3784 0.5603 1.3750 0.8740 1.3725
0.3606 19.46 0.6858 18.34 0.9579 17.95 0.3050 1.3781 0.6287 1.3742 0.9579 1.3723
x Hexane + (1 - x) 1-Butanol x Hexane + (1 - x) 1-Butanol
0.0717 23.09 0.5116 19.22 0.7897 18.30 0.0717 1.3952 0.4114 1.3851 0.7309 1.3772
0.2085 21.49 0.5790 18.93 0.8532 18.19 0.1312 1.3933 0.4738 1.3834 0.7897 1.3760
0.2650 20.98 0.6162 18.80 0.8966 18.08 0.1742 1.3919 0.5116 1.3824 0.8532 1.3747
0.3854 20.02 0.6957 18.57 0.9488 17.99 0.2085 1.3909 0.5790 1.3808 0.8966 1.3738
0.4738 19.46 0.7309 18.44 0.2650 1.3892 0.6957 1.3780 0.9488 1.3729
0.3854 1.3858
x Hexane + (1 - x) 1-Pentanol
0.0593 24.07 0.4599 20.07 0.6903 18.84 x Hexane + (1 - x) 1-Pentanol
0.0825 23.86 0.4848 19.86 0.7744 18.57 0.0593 1.4059 0.3406 1.3955 0.6517 1.3837
0.2114 22.25 0.5547 19.43 0.8418 18.32 0.0825 1.4051 0.3938 1.3935 0.6903 1.3823
0.2250 22.08 0.5915 19.25 0.8854 18.22 0.1366 1.4031 0.4599 1.3909 0.7744 1.3794
0.3406 20.94 0.6517 19.01 0.9408 18.08 0.2114 1.4004 0.4848 1.3900 0.8418 1.3770
0.3938 20.52 0.2250 1.3998 0.5547 1.3873 0.8854 1.3757
0.2921 1.3973 0.5915 1.3860 0.9408 1.3740
x Hexane + (1 - x) 1-Hexanol
0.0642 24.82 0.4212 20.87 0.7185 19.00 x Hexane + (1 - x) 1-Hexanol
0.0853 24.52 0.4835 20.40 0.7808 18.75 0.0642 1.4135 0.4212 1.3986 0.6722 1.3871
0.2244 22.75 0.5214 20.13 0.8068 18.61 0.0853 1.4127 0.4835 1.3958 0.7185 1.3849
0.2597 22.38 0.5836 19.73 0.8840 18.30 0.1679 1.4095 0.5214 1.3941 0.7808 1.3820
0.3215 21.79 0.6174 19.52 0.9170 18.22 0.2597 1.4057 0.5836 1.3913 0.8840 1.3774
0.3550 21.45 0.6722 19.23 0.3215 1.4030 0.6174 1.3896 0.9170 1.3759
0.3550 1.4015
x Hexane + (1 - x) 1-Heptanol
0.0724 25.62 0.3850 21.82 0.6473 19.61 x Hexane + (1 - x) 1-Heptanol
0.0959 25.21 0.4528 21.16 0.6999 19.29 0.0558 1.4201 0.3763 1.4059 0.6174 1.3936
0.2476 23.32 0.5157 20.63 0.7438 19.01 0.0886 1.4188 0.4160 1.4039 0.6703 1.3908
0.2851 22.88 0.5534 20.32 0.8020 18.69 0.1607 1.4157 0.4517 1.4022 0.7212 1.3880
0.3501 22.18 0.6145 19.87 0.8965 18.35 0.2187 1.4132 0.5271 1.3983 0.7438 1.3868
0.2608 1.4113 0.5380 1.3977 0.9263 1.3765
x Hexane + (1 - x) 1-Octanol
0.3000 1.4095 0.5590 1.3967
0.0450 26.44 0.4141 21.76 0.6704 19.58
0.1039 25.66 0.4795 21.16 0.7903 18.90 x Hexane + (1 - x) 1-Octanol
0.1802 24.58 0.5215 20.72 0.8184 18.70 0.0450 1.4257 0.3823 1.4105 0.6704 1.3944
0.2707 23.53 0.5794 20.26 0.8917 18.42 0.1039 1.4232 0.4141 1.4089 0.7903 1.3870
0.3112 22.97 0.6428 19.73 0.9451 18.21 0.1742 1.4203 0.4795 1.4055 0.8184 1.3848
0.3823 22.10 0.1802 1.4201 0.5215 1.4032 0.8917 1.3799
0.2707 1.4160 0.5794 1.3998 0.9451 1.3762
0.3112 1.4141 0.6428 1.3962

1-hexanol, + 1-heptanol, and + 1-octanol} mixtures. Figure

3 shows the surface tension deviations for the mentioned
systems. As can be noted, the surface tension increases as
the chain length of the 1-alkanol does; nevertheless the
surface tension deviation does not present the same
behavior.
The refractive indexes for {x hexane + (1 - x) ethanol,
+ 1-propanol, + 1-butanol, + 1-pentanol, + 1-hexanol, +
1-heptanol, and + 1-octanol} mixtures are presented in
Table 4. Figure 4 shows the changes of refractive index.
The refractive indexes increase with increasing chain
length of the 1-alkanol, and the changes of refractive index
have the same behavior with the exception of {hexane +
ethanol}.
The surface tensions and the refractive indexes were
fitted to a polynomial equation:

n
Q ) Q2 + ∑A x i
i+1
(7)
Figure 3. Surface tension deviations of b, {x hexane + (1 - x) i)0
ethanol}; 4, {x hexane + (1 - x) 1-propanol}; ], {x hexane + (1 -
x) 1-butanol}; 9, {x hexane + (1 - x) 1-pentanol}; O, {x hexane + where Q ) σ or nD; Q2 ) σ2 or nD,2, the surface tension or
(1 - x) 1-hexanol}; 0, {x hexane + (1 - x) 1-heptanol}; 2, {x hexane the refractive index for the 1-alkanol, respectively; Ai are
+ (1 - x) 1-octanol} at 298.15 K. the fitting parameters and x is the mole fraction of hexane.
 Journal of Chemical and Engineering Data, Vol. 45, No. 5, 2000 865

Table 5. Parameters Ak, B0, and Ai of Eqs 6 and 7 and Standard Deviations s
eq A0 A1 A2 A3 A4 B0 s
x Hexane + (1 - x) Ethanol
V Em/cm3‚mol-1 6 1.5767 -0.9117 0.3497 -0.7608 0.006
σ/mN‚m-1 7 -16.640 29.404 -24.301 7.685 0.03
δσ/mN‚m-1 6 -6.39 4.49 -1.94 0.04
nD 7 0.017 81 -0.009 46 0.004 64 0.000 04
∆nD 6 0.002 53 -0.002 30 -0.000 88 0.000 02
x Hexane + (1 - x) 1-Propanol
σ/mN‚m-1 7 -15.833 14.822 -0.507 -5.800 1.813 0.019
δσ/mN‚m-1 6 -7.28 3.54 0.02
nD 7 -0.017 42 0.003 21 0.003 46 0.000 06
∆nD 6 -0.008 29 -0.001 73 -0.001 34 0.000 06
x Hexane + (1 - x) 1-Butanol
σ/mN‚m-1 7 -13.830 8.349 2.481 -3.133 0.016
δσ/mN‚m-1 6 -6.60 1.89 0.76 0.016
nD 7 -0.028 91 -0.020 20 0.071 90 -0.081 32 0.033 53 0.000 04
∆nD 6 -0.008 23 -0.000 76 -0.006 32 0.000 04
x Hexane + (1 - x) 1-Pentanol
V Em/cm3‚mol-1 6 -0.5309 1.4130 -0.7495 -0.9796 0.005
σ/mN‚m-1 7 -14.701 7.931 3.022 -3.330 0.02
δσ/mN‚m-1 6 -6.64 1.84 0.78 0.03
nD 7 -0.034 23 -0.010 54 0.009 05 0.000 04
∆nD 6 -0.002 97 -0.004 59 -0.001 09 0.000 04
x Hexane + (1 - x) 1-Hexanol
V Em/cm3‚mol-1 6 -1.0208 1.7065 -0.5777 -0.9774 0.007
σ/mN‚m-1 7 -15.035 8.381 0.660 -1.850 0.014
δσ/mN‚m-1 6 -6.15 1.55 0.47 0.018
nD 7 -0.035 67 -0.016 33 0.008 38 0.000 04
∆nD 6 0.003 79 -0.004 39 -0.001 14 0.000 04
x Hexane + (1 - x) 1-Heptanol
σ/mN‚m-1 7 -12.869 -1.415 11.164 -5.459 0.03
δσ/mN‚m-1 6 -5.76 1.29 0.04
nD 7 -0.039 17 -0.013 92 0.002 98 0.000 04
∆nD 6 0.009 43 -0.001 62 0.000 05
x Hexane + (1 - x) 1-Octanol
σ/mN‚m-1 7 -15.026 7.711 -14.240 24.945 -12.624 0.03
δσ/mN‚m-1 6 -6.32 1.76 0.04
nD 7 -0.038 39 -0.011 93 -0.009 02 0.004 23 0.000 07
∆nD 6 0.017 79 0.000 08

the values of Q for the pure components are those given in

Table 1.
On the other hand, the results of surface tension devia-
tions and changes of refractive index were fitted to eq 6,
where QE ) δσ or ∆nD. The corresponding parameters Ak
and B0 are shown in Table 5.

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Received for review February 22, 2000. Accepted June 1, 2000. The
(15) Jiménez, E.; Franjo, C.; Segade, L.; Legido, J. L.; Paz Andrade,
authors thank Xunta de Galicia for its financial support to acquire
M. I. Excess Molar Volumes of Ternary Mixtures of {x1CH3CH2-
the automated tensiometer.
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CH3(CH2)7OH} at the Temperature of 298.15 K. J. Chem. Eng.
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