Fluid Phase Equilibria 189 (2001) 129–133

Excess molar volume of binary mixtures of

dehydrolinalool + alkanols at 308.15 K
Congmin Wang, Haoran Li, Longhua Zhu, Shijun Han∗
Department of Chemistry, Zhejiang University, Hangzhou 310027, PR China
Received 16 February 2001; accepted 22 June 2001

Abstract
Excess molar volume (VE ) of binary liquid mixtures of dehydrolinalool (DHL) with methanol, ethanol, n-propanol
and n-butanol have been determined at 308.15 K from density measurements. The values of VE are negative in all
the systems over the entire composition range. These results are correlated by the Redlich–Kister equation. The
magnitude of negative values of VE marginally decrease with the increase of the chain length of the alkanol.
© 2001 Elsevier Science B.V. All rights reserved.
Keywords: Excess molar volume; Dehydrolinalool; Alkanols

1. Introduction

Dehydrolinalool (DHL), 3,7-dimethyloct-6-en-1-yn-3-ol (CAS RN 29171-20-8), one of the interme-

diates of vitamin synthesis, is a leuco transparent liquid with a strong odor [1]. A survey of the literature
shows that there are very few reports on density measurements of DHL + alkanols. To further under-
stand the nature of DHL and the molecular interactions between the components of the mixture, the
experimental determination of excess molar volumes is indispensable.
In this paper, densities of binary liquid mixtures of DHL with methanol, ethanol, n-propanol and
n-butanol are determined at 308.15 K using a vibrating tube densimeter. Excess molar volume values
are negative in all the systems over the entire composition range and correlated by the Redlich–Kister
equation [2]. The effects of chain length of alkanols on excess molar volume have been shown.

2. Experimental section

DHL (highest commercial grade, Zhejiang NHU Co., Ltd.) was maintained under special conditions
before its use. It was distilled by using a 150 cm high column under reduced pressure. Methanol and
∗
Corresponding author. Tel.: +86-571-8795-2424; fax: +86-571-8795-1895.
E-mail addresses: han-shijun@263.net, lihr@cm163.net (S. Han).

0378-3812/01/$ – see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 8 - 3 8 1 2 ( 0 1 ) 0 0 5 7 3 - 8
130 C. Wang et al. / Fluid Phase Equilibria 189 (2001) 129–133

Table 1
The physical properties of the materials at 298.15 K
Material Density (g cm−3 ) Refractive index

Experimental Literature Experimental Literature

a
DHL 0.87415 0.8740 [1] 1.4650 (293.15 K) 1.4645a [1]
Methanol 0.78640 0.78637 [7] 1.3264 1.32652 [7]
Ethanol 0.78495 0.78493 [7] 1.3593 1.35941 [7]
n-Propanol 0.79962 0.79960 [7] 1.3833 1.38370 [7]
0.79958 [8] 1.38324 [9]
n-Butanol 0.80581 0.80575 [7] 1.3971 1.39741 [7]
0.80576 [8] 1.39702 [10]
a
At 293.15 K.

ethanol (analytical reagent grade, Shanghai Chemical Co.) were purified by the methods described by
Rao and Naidu [3]. The compounds n-propanol and n-butanol (analytical reagent grade, Shanghai Chem-
ical Co.) were refluxed over freshly activated CaO for at least 2 h and then fractionally distilled. Pure
materials were dried with molecular sieves 0.3 and 0.4 nm. The purity of these materials was checked
by gas chromatography, DHL 99.80 mass%; methanol 99.96 mass%; ethanol 99.95 mass%; 1-propanol
99.90 mass% and 1-butanol 99.94 mass%. The physical properties of materials are listed in Table 1 along
with literature values.
Densities of the pure materials and mixtures were measured with an Anton Paar DMA 602 densimeter,
with an estimated total uncertainty of 0.00001 g cm−3 [4,5]. Refractive indices were measured with an
Abbe type refractometer (WZS-I model, made in Shanghai) with a precision of ±0.0001. The densimeter
and refractometer were thermostated by a circulating-water bath with a precision of 0.01 K. All mixtures
were prepared by mass, errors in mole fractions are less than 0.0001.

3. Results and discussion

The density ρ and excess molar volume VE (cm3 mol−1 ) for binary systems of DHL with methanol,
ethanol, n-propanol and n-butanol are presented in Table 2. The VE were calculated using the following
equation:



1 1 1 1
V = M1 x1
E
− + M2 x2 − (1)
ρmix ρ1 ρmix ρ2
where ρ mix is the density of the mixture and M1 , M2 , x1 , x2 , ρ 1 and ρ 2 the molecular weight, mole
fraction, and density of pure components 1 and 2, respectively. The results of VE were fitted using the
Redlich–Kister equation
m−1

V12
E
= x1 x2 Bi (x1 − x2 )i . (2)
i=0
 C. Wang et al. / Fluid Phase Equilibria 189 (2001) 129–133 131

Table 2
Densities (ρ) and excess molar volumes (VE ) for xDHL + (1 − x)alkanol at 308.15 K
x ρ (g cm−3 ) VmE (cm3 mol−1 ) x ρ (g cm−3 ) VmE (cm3 mol−1 )

xDHL + (1 − x)methanol
0.0301 0.78972 −0.1258 0.5496 0.86006 −0.9357
0.0588 0.79970 −0.2272 0.6168 0.86234 −0.8904
0.1006 0.81169 −0.3700 0.7416 0.86525 −0.7166
0.1500 0.82261 −0.5035 0.8090 0.86630 −0.5803
0.1934 0.83050 −0.6253 0.8834 0.86715 −0.3978
0.2487 0.83820 −0.7272 0.9088 0.86729 −0.3131
0.3286 0.84667 −0.8468 0.9390 0.86749 −0.2196
0.4004 0.85226 −0.9115 0.9701 0.86765 −0.1149
0.5052 0.85812 −0.9387
xDHL + (1 − x)ethanol
0.0301 0.78570 −0.1256 0.5719 0.85413 −0.7136
0.0493 0.79094 −0.1945 0.6277 0.85672 −0.6549
0.0896 0.80076 −0.3249 0.7357 0.86086 −0.5102
0.1064 0.80441 −0.3737 0.7809 0.86230 −0.4336
0.1473 0.81240 −0.4793 0.8616 0.86461 −0.2937
0.2465 0.82760 −0.6665 0.9233 0.86616 −0.1798
0.3525 0.83916 −0.7665 0.9392 0.86648 −0.1379
0.4226 0.84498 −0.7839 0.9641 0.86711 −0.0836
0.5000 0.85017 −0.7624
xDHL + (1 − x)n-propanol
0.0297 0.79727 −0.0756 0.4923 0.84754 −0.5048
0.0594 0.80261 −0.1506 0.5544 0.8511 −0.4810
0.0917 0.80794 −0.2253 0.6484 0.85582 −0.4354
0.1201 0.81224 −0.2826 0.7314 0.85894 −0.3566
0.1589 0.81753 −0.3439 0.8560 0.86324 −0.2060
0.2529 0.82842 −0.4553 0.8675 0.8636 −0.1912
0.3436 0.83693 −0.5021 0.9198 0.86519 −0.1282
0.4635 0.84572 −0.5081 0.9706 0.86665 −0.0673
xDHL + (1 − x)n-butanol
0.04039 0.80366 −0.0789 0.54452 0.84840 −0.4234
0.06653 0.80719 −0.1330 0.59861 0.85118 −0.4094
0.09226 0.81032 −0.1621 0.64503 0.85342 −0.3734
0.12779 0.81461 −0.2233 0.74716 0.85794 −0.2945
0.15095 0.81728 −0.2624 0.83762 0.86144 −0.2039
0.2494 0.82710 −0.3600 0.86563 0.86243 −0.1718
0.33384 0.83422 −0.4063 0.92013 0.86421 −0.0926
0.38372 0.83803 −0.4300 0.94986 0.86523 −0.0688
0.50428 0.84591 −0.4289 0.97345 0.86591 −0.0267
132 C. Wang et al. / Fluid Phase Equilibria 189 (2001) 129–133

Table 3
Coefficients Bi and S.D. (σ ) for the binary systems
System B0 B1 B2 B3 σ

DHL + methanol −3.7618 0.1477 −0.2436 0.0043

DHL + ethanol −3.0333 1.0165 −0.1950 −0.1187 0.0042
DHL + n-propanol −2.0235 0.6038 −0.3030 0.0048
DHL + n-butanol −1.7480 0.3658 −0.0080 0.0055

Fig. 1. Excess molar volumes VE , at 308.15 K for x1 DHL + (1 − x1 )alkanols: methanol (䊏); ethanol (䊉); n-propanol (䉱);
n-butanol (䉲).

The coefficients of Eq. (2) were obtained by a modified Powell optimization method [6] with Eq. (3) as
the objective function F (in cm3 mol−1 )
 n 
 (Vexp E 2 1/2
E
− Vcal )i
F = (3)
i=1
n−m

where m is the number of coefficients Bi , n the number of experimental data. The coefficients Bi in Eq. (2)
and corresponding S.D. (σ ) are given in Table 3.
Fig. 1 shows the variation of VE of binary liquid mixtures of DHL + alkanols with the mole fraction
of the DHL. As can be seen from Fig. 1, VE is large and negative for the DHL + alkanols systems over
the entire range of composition at 308.15 K. For DHL + methanol, Fig. 1 presents the largest negative
value. Fig. 1 also shows the symmetry for DHL + methanol mixture, and for DHL + n-butanol. The
largest magnitude of negative values of VE are found at about x = 0.42 and 0.46 for DHL + ethanol and
DHL + n-propanol, respectively. On the other hand, Fig. 1 shows that the magnitude of negative values
of VE marginally decrease with the increase of the chain length of the alkanol.

List of symbols
B coefficients of Redlich–Kister equation
F objective function
 C. Wang et al. / Fluid Phase Equilibria 189 (2001) 129–133 133

m number of coefficients
M molar weight
n number of experimental points
V molar volume
x molecular fraction

Subscripts
cal calculated quantity
exp experimental quantity
mix mixture

Superscript
E excess

Greek letters
ρ density
σ mean S.D.

Acknowledgements

This work was financed by the National Natural Science Foundation of China (No. 29976035).

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