
==== Front
Data Brief
Data Brief
Data in Brief
2352-3409
Elsevier

S2352-3409(24)00784-4
10.1016/j.dib.2024.110820
110820
Data Article
A comprehensive database showing quantitative mixing effects related to volume and enthalpy in systems of dibromomethane with alkylalkanoates and with alkanes
Ortega Juan juan.ortega@ulpgc.es
⁎
Fernández Luis
Domínguez Leandro
Division of Thermal Engineering and Instrumentation (IDeTIC), University of Las Palmas de Gran Canaria, 35017 Las Palmas de Gran Canaria, Spain
⁎ Corresponding author. juan.ortega@ulpgc.es
10 8 2024
10 2024
10 8 2024
56 11082020 3 2024
26 7 2024
5 8 2024
© 2024 The Author(s)
2024
https://creativecommons.org/licenses/by-nc/4.0/ This is an open access article under the CC BY-NC license (http://creativecommons.org/licenses/by-nc/4.0/).
The data presented in this article are part of a very extensive project on studies of solutions of halogenated compounds with alkanes, esters, alcohols, etc. The contribution presented focuses on original data regarding binaries formed by dibromomethane with a set of 21 alkyl esters and with 6 alkanes. The data show a database on changes in volume and on the energy experienced in the mixing processes, with a contribution of more than 900 points (x1,yE=hE or vE). The provided information is original and was measured in the laboratory at a constant temperature of 298.15 K and atmospheric pressure. Brominated compounds are of interest in various industrial applications, such as pharmaceutical, chemical, agriculture, and others. As these compounds are typically found in solution the information provided has significant value. In addition, scientists use this information for theoretical purposes to develop behavioural theories.

Keywords

Mixing properties
Alkyl alkanoate
Alkane
Dibromomethane
Mixing enthalpy
Mixing volume change
==== Body
pmcSpecifications TableSubject	Chemical Engineering: Process chemistry and technology	
Specific subject area	Thermodynamics, Theoretical Studies on Structural Behavioural, Applications on chemical engineering design.	
Data format	Raw	
Type of data	Table, graph	
Data collection	Volume change data calculated from direct density measurements and the mixing energy values corresponding to direct measurements due to mixing effects are presented	
Data source location	Division of Thermal Engineering and Instrumentation (IDeTIC), University of Las Palmas de Gran Canaria, 35017 Las Palmas de Gran Canaria, Spain	
Data accessibility	Repository name: Mendeley Data
Data identification number: 10.17632/mkky9snd4c.1
Direct URL to data: https://data.mendeley.com/datasets/mkky9snd4c/1	
Related research article		

1 Value of the Data

• The volume change data and those of energetic nature generated by mixing processes provide fundamental information on the behaviour of the solutions because they are the consequence of the effects of the different molecular interactions caused by the molecular rearrangement of liquids in solution. These include intramolecular interactions between identical molecules, typical of pure products, but also intermolecular interactions between molecules of different compounds. The information provided is important for studying the behaviour of the solutions and for interpreting the molecular structure of the resulting final solution. Other researchers will be able to use the information presented in this work on macroscopic thermodynamic properties, both to contrast their own results, even if they are of a different nature, and to guide and validate theoretical studies, especially those developed from a quantum point of view.

• The development of industrial chemical processes requires precise information on various properties of the solutions to be worked with, since their implementation in modeling and design operations requires rigor. In this sense, the experimental information provided on binary solutions of dibromomethane with esters and saturated hydrocarbons can be useful in the development of certain processes, either as reactants or as products, i.e.: in esterification processes from haloalkanes, or as solvents in some processes of different nature.

• The value of the data presented, both for theoretical studies and for practical applications, is of particular interest in the field of predictive modeling. Estimation models are fundamental tools in the initial stages of scientific research, as they allow to focus the theoretical/practical efforts on the most promising systems, especially in the basic engineering stages, where a rapid description of the process is required without reaching a high level of knowledge and without real data. However, the establishment of both semi-theoretical (i.e.: COSMO-RS or PC-SAFT) and strictly empirical (i.e.: UNIFAC, neural networks) predictive models requires reliable information from a selection of systems with known characteristics. Therefore, the database provided can be used for the development and training of different predictive models. There is great interest in systems containing halogenated compounds due to the formation of specific interactions in some solutions in which they are involved.

2 Background

As mentioned, solutions of dibromoalkanes with esters and with alkanes are found in several applications related to industrial processes, such as the synthesis of certain esters [1], their use as solvents [2], or in agriculture sector [3], among others. Accurate information on the properties of these solutions, including densities as well as mixing energies, is essential to achieve the optimization of the associated chemical processes. Furthermore, that experimental information provides useful clues for understanding the physicochemical nature of the interactions present in the solution. These and other considerations have led our research group to develop, as part of its working-lines, a systematic investigation to improve the knowledge of this family of halogen-containing fluid systems. To date, several works [[4], [5], [6], [7], [8]] have been published on brominated compounds, but the available information does not include data on the behaviour of mixtures with dibromomethane, so a dense database has been developed with the participation of this molecule. The published literature only gives data on the volumetric behaviour of the binary dibromomethane+ethyl acetate [9] and on the mixing energetic effects of a binary with hexane [10].

3 Data Description

Experimental data of densities and mixing energies were measured directly, while the volume variation of the final solution was determined by the corresponding calculation from the densities of the pure compounds and the mixture. All the above numerical information was compiled in a single Word document (.docx), available in the Mendeley repository [11], where each binary system is presented in a single sheet containing the following information: the mentioned properties, the plot of each experimental point as a function of the composition of each binary, the correlation curve of the data with the equation used and the parameters of the model obtained by fit. Fig. 1a shows the variation of the equimolar pvE and hE values as a function of the alcoholic and acid ester chains. As shown, the systems containing esters present positive pvE values, indicating an expansive volumetric behaviour of the final solution, but the mixing energetic effects are exothermic in most of the binaries due to specific interactions. Fig. 1b shows the variation of the same properties with the composition and the number of carbon atoms of the alkane. In this case the pvE/hE quantities are positive, i.e., showing expansive/endothermic effects. As indicated in Section 4.2, the commercial characteristics of the products used to generate this database were of high purity.Fig. 1 (a) Variation of the equimolar properties pvE and hE with the alcoholic v and acid u chains of the binary mixtures x1Br2CH2+x2Cu-1H2u-1CO2Cv-1H2v+1(u = 1–5, v = 1–5). (b) Experimental points and fitting curves (solid-lines) of pvE and hE as a function of ester composition x1, for the binaries x1Br2CH2+x2C2nH4n+2(n = 3–8).

Fig. 1

4 Experimental Design, Materials and Methods

4.1 Experiment design

To have sufficient experimental information on the binary solutions formed by dibromomethane with esters and to analyze the influence of their alcoholic and acid chains on the results, a dense experimentation covering a set of compounds was planned. It refers to 21 binary systems expressed empirically as: x1Br2CH2+x2Cu-1H2u-1CO2Cv-1H2v+1(u = 1–5, v = 1–5). The experimental determination of the binaries formed by dibromomethane and linear chain hydrocarbons was also considered necessary. Therefore, the database created includes the information corresponding to six binary systems empirically defined as: x1Br2CH2+x2C2nH4n+2(n = 3–8). The set of points (x1,yE=hE or vE), determined at atmospheric pressure (≈99 kPa) and at a temperature of 298.15 K, represents more than 900 values that are contributed to the bibliography.

4.2 Materials

The chemicals used were purchased commercially from several companies and were selected from those of the highest quality. The origin of each of the products and the purity indicated by the manufacturer are listed in Table 1. However, before use, all products were degassed with ultrasound and stored for several days in the dark on a 0.3 nm Fluka molecular sieve to partially remove the moisture. After these operations, the purity of all the compounds was checked by gas-chromatography in a Varian 450-GC equipment, and slightly better values than those declared by the manufacturers were obtained. In addition, the quality of the products was confirmed by density measurements ρ, and refractive indices nD, at a temperature of 298.15 K. Table 2 shows the values obtained for these properties together with the corresponding values found in literature for comparison [5,[12], [13], [14], [15], [16], [17], [18], [19]]. In general, the agreement is acceptable.Table 1 Commercial characteristics of the pure products.

Table 1Compound	Supplier	Purity (w/w)	Supplier	Purity (w/w)	Supplier	
dibromomethane	Aldrich	>98.5 %	pentyl propanoate	Aldrich	>99.0 %	
methyl methanoate	Fluka	>99.0 %	methyl butanoate	Fluka	>99.0 %	
ethyl methanoate	Aldrich	>97.0 %	ethyl butanoate	Fluka	>98.0 %	
propyl methanoate	Aldrich	>97.0 %	propyl butanoate	Fluka	>99.0 %	
butyl methanoate	Aldrich	>97.0 %	butyl butanoate	Fluka	99.0 %	
pentyl methanoate	Aldrich	>96.0 %	methyl pentanoate	Fluka	99.0 %	
methyl ethanoate	Fluka	>99.5 %	ethyl pentanoate	Aldrich	99.0 %	
ethyl ethanoate	Fluka	>99.5 %	pentyl pentanoate	Fluka	>97.0 %	
propyl ethanoate	Aldrich	99.0 %	hexane	Supelco	>99.0 %	
butyl ethanoate	Fluka	>98.5 %	octane	Aldrich	99.0 %	
pentyl ethanoate	Supelco	>98.0 %	decane	Aldrich	>99.0 %	
methyl propanoate	Fluka	>99.0 %	dodecane	Aldrich	>99.0 %	
ethyl propanoate	Fluka	>99.0 %	tetradecane	Aldrich	>99.0 %	
propyl propanoate	Fluka	>99.0 %	hexadecane	Aldrich	>99.0 %	
butyl propanoate	Aldrich	99.0 %				

Table 2 Properties of pure compounds. Densities and refractive indices measured at T = 298.15 K and p ≈ 99 kPa.

Table 2Compound	CAS	ρ / kg·m−3	nD	
exp.	lit.	exp.	lit.	
dibromomethane	79-95-3	2479.14	2484.2 [12]	1.5394	1.5389 [12]	
methyl methanoate	107-31-3	966.83	966.40 [13]	1.3415	1.3415 [13]	
ethyl methanoate	109-94-4	915.82	915.30 [13]	1.3570	1.3575 [13]	
propyl methanoate	110-74-7	899.81	899.60 [13]	1.3740	1.3750 [13]	
butyl methanoate	592-84-7	888.85	886.90 [13]	1.3866	1.3874 [13]	
pentyl methanoate	638-49-3	882.27	881.90 [12]	1.3970	1.3977 [12]	
methyl ethanoate	79-20-9	926.51	926.73 [5]	1.3585	1.3589 [13]	
ethyl ethanoate	141-78-6	894.10	894.55 [13]	1.3700	1.3698 [13]	
propyl ethanoate	109-60-4	882.16	882.60 [12]	1.3815	1.3828 [13]	
butyl ethanoate	123-86-4	876.12	876.36 [13]	1.3927	1.3918 [13]	
pentyl ethanoate	628-63-7	871.86	871.90 [13]	1.4002	1.4000 [14]	
methyl propanoate	554-12-1	910.18	910.18 [5]	1.3740	1.3742 [15]	
ethyl propanoate	105-37-3	884.11	884.00 [12]	1.3820	1.3814 [13]	
propyl propanoate	106-36-5	875.77	875.61 [16]	1.3905	1.3920[15]	
butyl propanoate	590-01-2	871.11	871.40 [12]	1.3985	1.4000[12]	
pentyl propanoate	624-54-4	867.93	867.80 [14]	1.4052	1.4053[14]	
methyl butanoate	623-42-7	892.40	892.42 [5]	1.3850	1.3847[12]	
ethyl butanoate	105-54-4	873.94	873.94 [13]	1.3890	1.3900[15]	
propyl butanoate	105-66-8	867.93	867.90 [16]	1.3980	1.3976[15]	
butyl butanoate	109-21-7	864.84	864.67 [17]	1.4035	1.4029[15]	
methyl pentanoate	624-24-8	884.84	884.59 [5]	1.3940	1.3947[18]	
ethyl pentanoate	539-82-2	869.41	869.28 [19]	1.3985	1.3981[19]	
pentyl pentanoate	2173-56-0	861.16	860.64 [14]	1.4144	1.4146[14]	
Hexane	110-54-3	654.86	654.84 [13]	1.3723	1.3723[13]	
Octane	111-65-9	698.61	698.62 [13]	1.3951	1.3951[13]	
Decane	124-18-5	726.08	726.35 [13]	1.4098	1.4097[13]	
Dodecane	112-40-3	744.99	745.18 [13]	1.4196	1.4195[13]	
tetradecane	629-59-4	759.00	759.20 [13]	1.4271	1.4263[13]	
hexadecane	544-76-3	769.79	769.94 [12]	1.4325	1.4325[12]	

4.3 Equipment and procedures

The experimental determination of the mixture densities was carried out using a digital densimeter, Anton-Paar DMA 60/602, calibrated with double-distilled water and nonane [20]. Solutions of known composition covering the entire range of x1∈(0.1) were synthetically prepared by weighing on a Kern balance, model ALJ 220–4NM, (m ± 0.0001 g). The resulting uncertainty in the composition of the solution is x1±0.0002. The densities, ρ±0.02 kg·m–3, of each sample were measured twice in the densimeter to ensure the final value, at T=(298.15±0.01) K, keeping the temperature constant using a water circulation bath, Julabo F-20. The data obtained were used to calculate the excess volumes, vE, with a cumulative uncertainty of vE±2·10−9 m3·mol−1. On the other hand, the mixing enthalpies were measured directly at T=(298.15±0.01) K in a Calvet-type conduction calorimeter, model MS80D, from Setaram, with an accuracy of ±1 %·hE, previously calibrated [21], with an accuracy in the composition of ±0.0005 units.

The correlation of experimental data of each system was carried out with a polynomial model used by us [4], using the regression method proposed by Nelder-Mead modified by Lagarias et al. [22] implemented in MATLAB®, and minimizing the following objective function:(1) s(yE)=(∑i=1N(yi,calE−yi,expE)2/N)0.5

where yE represents the mixing property considered in the fit (yE=vE or hE) and N is the number of experimental data considered in the fit.

Limitations

None.

Ethics Statement

The authors have read and follow the ethical requirements for publication in Data in Brief and they confirm that the current work does not involve human subjects, animal experiments, or any data collected from social media platforms.

CRediT authorship contribution statement

Juan Ortega: Conceptualization, Methodology, Validation, Investigation, Writing – review & editing, Visualization, Supervision, Project administration, Funding acquisition. Luis Fernández: Investigation, Writing – original draft, Data curation, Resources. Leandro Domínguez: Investigation, Formal analysis, Resources.

Data Availability

Database of mixing properties of the binaries (dibromomethane+an alkyl alkanote, or +an alkane) (Original data) (Mendeley Data)

Acknowledgements

This research was funded by the 10.13039/501100004837 Spanish Ministry of Science and Innovation , grant number PID2021-127970OB-I00 .

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
==== Refs
References

1 Jadhav A.H. Lee K. Koo ab S. Seo J.Gil Esterification of carboxylic acids with alkyl halides using imidazolium based dicationic ionic liquids containing bis-trifluoromethane sulfonimide anions at room temperature RSC Adv. 5 2015 26197 26208 10.1039/c5ra00802f
2 Hon Y.S. Liu Y.W. Hsieh C.H. Dibromomethane as one-carbon source in organic synthesis: a versatile methodology to prepare the cyclic and acyclic α-methylene or α-keto acid derivatives from the corresponding terminal alkenes Tetrahedron 60 2004 4837 4860 10.1016/j.tet.2004.04.013
3 Dagani M.J. Barda H.J. Benya T.J. Sanders D.C. Bromine Compounds, in: Ullmann's Encyclopedia of Industrial Chemistry 2012 Wiley-VCH Weinheim 331 358 10.1002/14356007.a04_405
4 Ortega J. Navas A. Plácido J. Toledo F. Thermodynamic study of (alkyl esters+α,ω-alkyl dihalides) II. HmE and VmE for 25 binary mixtures {xCu−1H2u−1CO2C2H5+ (1−x)α,ω-BrCH2(CH2)v−2CH2Br}, where u=1 to 5, α=1, and v=ω=2 to 6 J. Chem. Thermodyn. 38 2006 585 598 10.1016/j.jct.2009.05.006
5 Ortega J. Navas A. Plácido J. Thermodynamic study of the mixtures (alkyl esters+α,ω-alkyl dihalides) IV. HE and VE for 25 binary mixtures {xCu-1H2u-1CO2CH3+(1-x)α,ω-BrCH2(CH2)v-2CH2Br}, where u=1 a 5, α=1 and v=ω=2 to 6 J. Chem. Thermodyn. 39 2007 128 141 10.1016/j.jct.2006.05.004
6 Navas A. Ortega J. de la Nuez I. Thermodynamic study of (alkyl esters+α,ω-alkyl dihalides) VI. and for 20 binary mixtures {xCu−1H2u−1CO2(CH2)3CH3+(1−x)α,ω-BrCH2(CH2)v−2CH2Br}, where u=1 to 5, α=1, and v=ω=2 to 6 J. Chem. Thermodyn. 41 2009 1222 1231 10.1016/j.jct.2009.05.006
7 Navas A. Ortega J. Martín T. Palomar J. Thermodynamic analysis of systems formed by alkyl esters with α,ω-alkyl dibromides: new experimental information and the use of a dense database to describe their behavior using the UNIFAC group contribution method and the COSMO-RS methodology Ind. Eng. Chem. Res. 49 2010 12726 12739 10.1021/ie101479v
8 Navas A. Ortega J. Palomar J. Díaz C. Vreekamp R. COSMO-RS analysis on mixing properties obtained for the systems 1-butyl-X-methylpyridinium tetrafluoroborate [X=2,3,4] and 1,ω-dibromoalkanes [ω=16] Phys. Chem. Chem. Phys. 13 2011 7751 7759 10.1039/C0CP02169E 21437322
9 García-Giménez P. Gil-Hernández V. Velasco I. Embid J.M. Otín S. Temperature and pressure dependence of the volumetric properties of binary liquid mixtures containing dihaloalkanes Int. J. Thermophys. 26 2005 665 678 10.1007/s10765-005-5570-x
10 Blanco S.T. Muñoz-Embid J. Otin S. Excess enthalpies of dibromoalkane + tetrachloromethane mixtures. Measurement and analysis in terms of group contributions (DISQUAC) Fluid Phase Equilib. 91 1993 281 290 10.1016/0378-3812(93)85104-T
11 Ortega J. Fernandez L. Dominguez L. Database of mixing properties of the binaries (dibromomethane+an alkyl alkanote, or +an alkane) Mendeley Data v1 2024 10.17632/mkky9snd4c.1
12 Thermodynamic Tables T.R.C. Hydrocarbons & Non-Hydrocarbons 1987 Texas A&M University System College Station, TX, USA
13 Riddick J. Bunger W.B. Sakano T.K. Organic Solvents: Physical Properties and Methods of Purification 4th ed. 1986 Wiley-Interscience New York Vol. II
14 Chaar M. Ortega J. Toledo-Marante F.J. González C. Thermodynamic properties of (a pentyl ester+a n-alkane). XIV. The HmE and VmE for (an ester+a n-alkane) J. Chem. Thermodyn. 33 2001 689 710 10.1006/jcht.2000.0798
15 Daubert T.E. Danner R.P. Data Compilation Tables of Properties of Pure Compounds 1984 AIChE/DIPPR New York
16 Marrero E. Ortega J. Palomar J. Thermodynamic study of (alkyl esters+α,ω-alkyl dihalides) VII. HEm and VEm for 20 binary mixtures {xCu−1H2u−1CO2C3H7+ (1−x)α,ω-ClCH2(CH2)v−2CH2Cl}, where u=1 to 4, α=1 and v=ω=2 to 6. An analysis of behavior using the COSMO-RS methodology J. Chem. Thermodyn. 41 2009 367 382 10.1016/j.jct.2008.10.007
17 Gonzalez E. Ortega J. Densities and isobaric vapor-liquid equilibria of butyl esters (methanoate to butanoate) with ethanol at 101.32 kPa J. Chem. Eng. Data 40 1995 1178 1183 10.1021/je00022a004
18 Ortega J. Espiau F. Tojo J. Canosa J. Rodríguez A. Isobaric vapor-liquid equilibria and excess properties for the binary systems of methyl esters+heptane J. Chem. Eng. Data 48 2003 1183 1190 10.1021/je030117d
19 Pérez N. Fernández L. Ortega J. Toledo F.J. Wisniak J. Correlation and prediction of mixing thermodynamic properties of ester-containing systems: ester + alkane and ester + ester binary systems and the ternary dodecane + ethyl pentanoate + ethyl ethanoate J. Chem. Thermodyn. 54 2012 41 48 10.1016/j.jct.2012.03.011
20 Ortega J. Matos J.S. Estimation of the isobaric expansivities from several equations of molar refraction for some pure organic compounds Mater. Chem. Phys. 15 1986 415 425 10.1016/0254-0584(86)90025-8
21 Rios R. Ortega J. Sosa A. Fernández L. Strategy for the management of thermodynamic data with application to practical cases of systems formed by esters and alkanes through experimental information, checking-modeling, and simulation Ind. Eng. Chem. Res. 57 2018 3410 3429 10.1021/acs.iecr.7b04918
22 Lagarias J.C. Reeds J.A. Wright M.H. Wright P.E. Convergence properties of the Nelder-Mead simplex method in low dimensions SIAM J. Optim. 9 1998 112 147 10.1137/S1052623496303470
