Fluid Phase Equilibria 296 (2010) 37–41

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Fluid Phase Equilibria

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Study on the effect of increasing the chain length of the alkanol in excess molar
enthalpies of mixtures containing 2-methoxy-2-methylpropane, 1-alkanol,
decane
Marta M. Mato a,1 , M. Illobre a,1 , Pedro V. Verdes a ,
José Luis Legido b , María Inmaculada Paz Andrade a,∗
a
Departamento de Física Aplicada, Campus Universitario Sur, Universidad de Santiago, E-15782 Santiago de Compostela, Spain
b
Departamento de Física Aplicada, Facultad de Ciencias, Universidad de Vigo, E-36310 Vigo, Spain

a r t i c l e i n f o a b s t r a c t

Article history: Excess molar enthalpies for the ternary system {x1 2-methoxy-2-methylpropane + x2 ethanol +
Received 13 October 2009 (1 − x1 − x2 ) decane} and the involved binary mixture {x ethanol + (1 − x) decane} have been measured
Received in revised form 13 February 2010 at the temperature of 298.15 K and atmospheric pressure, over the whole composition range. No exper-
Accepted 15 February 2010
imental excess enthalpy values were found in the currently available literature for the ternary mixture
Available online 23 February 2010
under study. The results were fitted by means of different variable-degree polynomials. Smooth repre-
sentations of the results are presented and used to construct constant excess molar enthalpy contours on
Keywords:
Roozeboom diagrams. The excess molar enthalpies for the binary and ternary system are positive over
Excess molar enthalpies
Ternary mixtures
the whole range of composition. The binary mixture {x ethanol + (1 − x) decane} is asymmetric, with its
Binary mixtures maximum displace toward a high mole fraction of decane. The ternary contribution is also positive, and
2-Methoxy-2-methylpropane the representation is asymmetric.
Ethanol © 2010 Elsevier B.V. All rights reserved.
Decane

1. Introduction
The study on mixtures containing branched ethers has been an
active research area over the last few years due to the interest of
this type of compounds as additives in the formulation of com-
bustibles. These ethers are also increasingly used as solvents or
chemical reactants.
Mixtures of alkanols and ethers present a complex structure
resulting from the partial replacement of alcohol–alcohol interac-
tions by alcohol–ether OH–O bonds. Complexity is increased when
the mixture also contains one or more alkanes. The data presented
here are useful if a wide study on the involved interactions is envis-
aged.
In this context, this work contributes to the series of ternary
mixtures reported in earlier works [1–11] where excess molar
enthalpies of binary and ternary mixtures containing 2-methoxy-
2-methylpropane (MTBE), alkanols and alkanes, as components,
are presented. All of them are part of the scientific project
entitled “Study on physical properties of mixtures hydrocar-
∗ Corresponding author.
E-mail address: inmaculada.paz.andrade@usc.es (M.I.P. Andrade).
1 atmospheric pressure. The binary experimental data for the mix-
Present address: Departamento de Física Aplicada, Facultad de Ciencias, Univer-
sidad de Vigo, E-36310 Vigo, Spain.
bon + alcohol + ether like alternative fuels”, where the main
objective has been the characterisation of non-electrolyte liquids,
and their mixtures, through experimental determination of ther-
mophysical properties on mixing.
The series including the ternary systems MTBE +
ethanol + alkane (hexane [6], heptane [3] or octane [4]) or
MTBE + alkanol (1-propanol [2] or 1-pentanol [10]) + decane, are
now continued, considering ethanol and decane as the second and
third component, respectively.
Other papers report excess molar enthalpies of the ternary
mixtures MTBE + 1-alkanol + alkane [12–14] are available in the lit-
erature at 298.15 K. Nevertheless, we are not aware of any previous
E
measurement of Hm,123 of the ternary mixture to which this study
is directed.
This should help to study the molecular interactions of these
mixtures and to examine the effect of the enlargement of the CH2
unit in the alkanol or alkane.
So, as an extension of these earlier investigations we have
now measured, using a Calvet microcalorimeter, experimen-
tal excess molar enthalpies, over the whole composition range,
for the ternary system {x1 2-methoxy-2-methylpropane + x2
ethanol + (1 − x1 − x2 ) decane} and the involved binary mixture
{x ethanol + (1 − x) decane} at the temperature of 298.15 K and
tures {x 2-methoxy-2-methylpropane + (1 − x) ethanol} and {x

0378-3812/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2010.02.012
38 M.M. Mato et al. / Fluid Phase Equilibria 296 (2010) 37–41

2-methoxy-2-methylpropane + (1 − x) decane}, were reported in Table 1

E
Experimental binary excess molar enthalpies, Hm , at
previous works [6,10]. The results were fitted by means of poly-
298.15 K for the binary system x ethanol + (1 − x) decane.
nomials of different variable-degree.
−1
The group of literature referring to the binary systems {x 1- x E
Hm /J mol
alkanol + (1 − x) alkane} is very large. Christensen et al. [15] have 0.0881 503
determined Hm E data for binary system {x ethanol + (1 − x) decane} 0.1338 595
at 298.15 K and 170 kPa. Kwon and Wang [16] have published 0.1766 664
0.2665 726
excess molar enthalpies at 313.15 K for the same mixture. How-
0.3141 737
ever only Tong et al. [17] and Wang et al. [18] have measured excess 0.4314 738
enthalpy values for the binary mixture {x ethanol + (1 − x) decane} 0.5931 674
at 298.15 K and atmospheric pressure. The experimental results of 0.6501 641
this paper are then compared with those found in literature for the 0.7248 591
0.7837 535
similar conditions of temperature and pressure. 0.8079 516
0.8480 441
2. Materials and methods 0.8829 374
0.9377 241
0.9620 159
The chemical substances employed were commercial products
of the best quality grade. The sources and purities of the chem-
icals substances employed were: MTBE (Aldrich > 99.8%), ethanol tures {x 2-methoxy-2-methylpropane (MTBE) + (1 − x) ethanol}
(Scharlau > 99.8%), decane (Aldrich > 99%). All products were kept and {x 2-methoxy-2-methylpropane (MTBE) + (1 − x) decane} were
in argon (N-55) atmosphere, degassed by ultrasound technique and reported in previous papers [6,10].
used without further purification other than drying with Union Car- This set of data was fitted to a variable-degree polynomial sug-
bide 0.4 nm molecular sieves to remove residual traces of water. The gested by Myers–Scott [25]:
handling and disposal of the chemicals used has been done accord-
x(1 − x) 
n
ing to the recommendation of the CRC Handbook of Chemistry and
Physics [19].
E
Hm /J mol−1 = Ai (2x − 1)i−1 , (2)
1 + k(1 − x)
The experimental excess molar enthalpies were measured at i=1
298.15 K using a Calvet microcalorimeter equipped with a device E obtained for the binary mixture {x
The experimental values of Hm
allowing operation in the absence of vapour phase, and having a
ethanol + (1 − x) decane} measured in this work are compared in
calorimeter-cell volume of approximately 10 cm3 . The tempera-
Fig. 1 with those measured in the early papers [6,10] for the other
ture was controlled using a digital thermometer and was regulated
two involved binary mixtures. Furthermore, in it were compared
to better than ±0.01 K. The mixtures were prepared by mass
the experimental values of this work with those have been found
using a Mettler H51 balance (precision ±1 × 10−5 g), ensuring a
probable error in the mole fraction less than 10−4 . All molar quan-
tities are based on the IUPAC relative atomic mass table [20]. A
Philips PM2535 voltmeter and a data acquisition system were
linked to the microcalorimeter. Calibration was performed elec-
trically using a Setaram EJP30 stabilised current source. Further
details about the experimental method have been published earlier
[21,22]. The apparatus and procedures were tested by determining
excess enthalpies for the standard system hexane + cyclohexane at
298.15 K, and the results were found to differ by less than 1% from
those of Marsh [23] and Gmehling [24]. The uncertainty in excess
molar enthalpy measurements is estimated to be better than 1%.
Three experimental measurements were carried out for the
ternary compositions resulting from adding decane to a binary
mixture composed of {x1 MTBE + x2 ethanol}, where x2 = 1 − x1 .
The ternary mixture is then a pseudobinary mixture composed of
decane and a mixture of MTBE and ethanol with constant x2 . Thus,
the ternary excess molar enthalpy at the pseudobinary composition
x1 , x2 (x3 = 1 − x1 − x2 ) can be expressed as
E E E
Hm,123 = Hm, + (x1 + x2 )Hm,12 , (1)
E
where Hm, is the measured excess molar enthalpy for the pseu-
E
dobinary mixture and Hm,12 is the excess molar enthalpy of the
initial binary mixture {x1 MTBE + x2 ethanol}. Values of Hm,12
E at
different mole fractions were interpolated by using a spline-fit
method. Eq. (1) does not involve any approximation.

3. Results and discussion

Experimental values of Hm E for the binary mixture {x
ethanol + (1 − x) decane} are listed in Table 1. The experimen-
tal data, the fitting parameters and the standard deviations
of excess molar enthalpies, corresponding to the binary mix-
E −1
Fig. 1. Excess molar enthalpies Hm /(J mol ) at 298.15 K of binary mixtures: {x
ethanol + (1 − x) decane}, 䊉 experimental values from this work, 夽 from Ref. [17], 
from Ref. [18]; {x MTBE + (1 − x) decane},  experimental values from Ref. [10]; {x
MTBE + (1 − x) ethanol},  experimental values from Ref. [6], (—) Fitting curve from
this work, (- - - - -) fitting curve from Ref. [17], (· · · · · · ·) fitting curve from Ref. [18].
 M.M. Mato et al. / Fluid Phase Equilibria 296 (2010) 37–41 39

Table 2
E
Excess molar enthalpies, Hm,123 , at 298.15 K for the ternary system x1 MTBE + x2 ethanol + (1 − x1 − x2 ) decane.a .

E −1 E −1 E −1 E −1
x1 x2 Hm, /J mol Hm,123 /J mol x1 x2 Hm, /J mol Hm,123 /J mol
−1
x1 = 0.2478, Hm,12
E
= 288 J mol
0.2415 0.7329 104 385 0.1610 0.4885 687 874
0.2351 0.7137 193 467 0.1165 0.3536 761 896
0.2276 0.6907 282 546 0.0979 0.2971 751 865
0.2124 0.6446 426 673 0.0646 0.1961 674 750
0.2023 0.6141 500 735 0.0384 0.1165 557 602
0.1758 0.5337 629 834
−1
x1 = 0.4956, Hm,12
E
= 486 J mol
0.4639 0.4722 208 663 0.2725 0.2773 727 994
0.4367 0.4444 349 777 0.1988 0.2024 727 922
0.4135 0.4208 443 849 0.1655 0.1684 691 853
0.3936 0.4006 506 893 0.1093 0.1113 598 706
0.3662 0.3727 579 938 0.0692 0.0704 490 558
0.3423 0.3483 630 966
−1
x1 = 0.7418, Hm,12
E
= 512 J mol
0.6852 0.2385 214 688 0.3819 0.1330 693 957
0.6522 0.2270 314 764 0.3238 0.1127 691 914
0.6071 0.2114 426 845 0.2975 0.1036 676 882
0.5622 0.1957 507 896 0.2053 0.0715 589 731
0.5218 0.1817 569 930 0.1464 0.0510 493 594
0.4421 0.1539 675 981
a
Three experimental series of measurements were carried out for the ternary compositions resulting from adding decane to a binary mixture composed of {x1 MTBE +
x2 ethanol}, where x2 = 1 − x1 .

in the literature for the binary system {x ethanol + (1 − x) decane}
at 298.12 K and atmospheric pressure. It can be seen that the exper-
imental values of this work are in very close agreement with the
literature values by Tong et al. [17] and Wang et al. [18]. We decided
to measure experimental excess molar enthalpies for the system {x
ethanol + (1 − x) decane} in order to use experimental values mea-
sured with the same microcalorimeter for all the binary systems
involved in the ternary system.
The measured of ternary excess enthalpy values, Hm,123 E , listed
in Table 2, were correlated using the following equation:
E
Hm,123 (J mol−1 ) = Hm,bin
E
+ x1 x2 (1 − x1 − x2 )123 ,
where 123 , was fitted to the expression suggested by Morris et al.
[26] of the form:
123
= (B0 + B1 x1 + B2 x2 + B3 x12 + B4 x22 + B5 x1 x2 + B6 x13
RT
+ B7 x23 + . . .),
The fitting parameters k, Ai and Bi were computed from the
unweighed least-squares method using a non-linear optimization
algorithm due to Marquardt [27]. The number of parameters was
determined by applying to every new parameter the F-test pro-
posed by Bevington [28].
The fitting coefficients and the corresponding standard devia-
tions from experimental values are presented in Table 3.
Fig. 2 shows the pseudobinary representation of the measured
experimental values of the Hm,123 E , together with the correlated
curves, where Eq. (4) was applied to fit the ternary contribution.
E
The lines of constant ternary excess molar enthalpy, Hm,123 cal-
culated using Eq. (3) are plotted in Fig. 3a. Fig. 3b represents the
ternary contribution, x1 x2 (1 − x1 − x2 )123 , to the excess molar
enthalpy correlated with Eq. (4).
The excess molar enthalpy for the ternary system is positive
over the whole range of composition, showing a maximum value
(3) E
at x1 = 0.3530, x2 = 0.2470, x3 = 0.4000, Hm,123 = 984 J mol−1 .
E
The excess molar enthalpy Hm,123 of the ternary systems
MTBE + ethanol + alkane (hexane [6], heptane [3], octane [4]) is
also positive over the whole composition diagram, reaching its
E
maximum values at x1 = 0.3960, x2 = 0.2490, x3 = 0.3550, Hm,123
E
(hexane) = 802 J mol−1 ; x1 = 0.3270, x2 = 0.2510, x3 = 0.4220, Hm,123
(4)
(heptane) = 894 J mol−1 .; at x1 = 0.3480, x2 = 0.2410, x3 = 0.4110,
E
Hm,123 (octane) = 920 J mol−1 , respectively. Similar behavior is
shown in the experimental data published by Zhu et al. for
MTBE + ethanol + hexane [12] or octane [13].
The ternary contribution is also positive, and the representation
is asymmetric. This means that, as can be seen in Fig. 3b, the posi-

Table 3
Fitting parameters, Ai , Bi , and standard deviations.a .

A1 A2 A3 A4 A5 k s

x MTBE + (1 − x) ethanol a

1955 1034 698 510 – – 4

x MTBE + (1 − x) decaneb
2016 −167 −402 728 619 – 3

x Ethanol + (1 − x) decane
2857 1732 1408 1755 – 0.8623 5

B0 B1 B2 B3 B4 B5 B6 B7 B8 s

x1 MTBE + x2 ethanol + (1 − x1 − x2 ) decane

4.132 −8.301 −17.005 21.010 35.433 22.540 −8.231 −21.160 −29.795 8.764
a
Ref. [6].
b
Ref. [10].
40 M.M. Mato et al. / Fluid Phase Equilibria 296 (2010) 37–41

Fig. 2. Pseudobinary representation of ternary excess molar enthalpies

E −1
Hm,123 /(J mol ) for {(1 − x) (x1 MTBE + x2 ethanol) + x decane} at 298.15 K: 䊉
x1 = 0.2478, x2 = 0.7522;  x1 = 0.4956, x2 = 0.5044;  x1 = 0.7418, x2 = 0.2582;
— correlated using Eqs. (3) and (4).

tion of the maximum does not coincide with the center of the Gibbs
triangle. The maximum values of the ternary contribution to excess
molar enthalpy are reached at x1 = 0.4740, x2 = 0.1520, x3 = 0.3740
E
Hm,123 = 241 J mol−1 . The value of the maximum ternary contribu-
tion is about 25% of the value of the ternary enthalpy itself. That
means that the ternary contribution in this case is very important,
and can be attributed to crossed energetic interactions between the
associated compound (the hydroxyl group in the alkanol molecule),
the molecule of MTBE, and the non-polar alkane.
The endothermicity observed for all ternary mixtures MTBE + 1-
alkanol + alkane suggests that the positive contributions to the
excess enthalpy, namely the breaking of interactions present
in the pure liquids (hydrogen bonding, dipolar interaction, and
orientational order) are energetically more important than the neg- Fig. 3. Representation for {x1 MTBE + x2 ethanol + (1 − x1 − x2 ) decane} at 298.15 K
ative contribution, which is a specific interaction between unlike of: (a) curves of constant ternary excess molar enthalpy, Hm,123E −1
/(J mol ). (b) Curves
molecules. So, the main contribution to this behaviour may be of constant ternary contribution, x1 x2 (1 − x1 − x2 )123 , to the excess molar enthalpy
E −1
attributed to breaking of alcohol hydrogen bonding autoassoci- Hm,123 /(J mol ), calculated with Eq. (4).
ation, added to two other effects as breaking of dipole–dipole
interactions of MTBE, and the contribution due to the loss of orien- pentanol, like the trend obtained with the binary mixtures of alka-
tation order between alkane linear molecules, are more significant nol + alkane.
than the cross association between MTBE–ethanol, the crossed Alkanols are polar liquids, strongly self-associated by hydrogen
interactions dipole-induced dipole, and the weak ethanol–decane bonding that may differ depending on chain length and position
interactions due to dispersive forces. of the hydroxyl group. In this case, the alkanol chain length is an
The excess molar enthalpy Hm,123 E of the ternary sys- important parameter that must be taken into account to explain
tems MTBE + alkanol (propanol [2] or pentanol [10]) + n-decane the behaviour interaction of the MTBE + alkanol + alkane mixtures.
is also positive over the whole composition diagram, reach- E
The diminution of Hm,123 observed is in agreement with the pre-
ing its maximum values at x1 = 0.2842, x2 = 0.2477, x3 = 0.4681, dominance of the breaking of the existing hydrogen bonds of the
E
Hm,123 (propanol) = 1058 J mol−1 and at x1 = 0.3630, x2 = 0.2520, pure alkanol and it can be interpreted as reflecting the decrease of
E
x3 = 0.3850, Hm,123 (pentanol) = 978 J mol−1 , respectively. the strength of alkanol–alkanol hydrogen bonds with the alkanol
Comparing the present experimental data with the excess molar chain length.
enthalpy values obtained in a previous work [2,10] for ternary Besides, in MTBE + alkanol systems, Hm E increase, from methanol

mixtures of MTBE + alkanol + decane, we conclude that the excess to propan-1-ol and then Hm E is nearly constant for butanol [29] and

enthalpies increase from ethanol to propanol and decrease for the pentanol [10]. This may be because the decrease in alcohol–alcohol
 M.M. Mato et al. / Fluid Phase Equilibria 296 (2010) 37–41 41

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