Article pubs.acs.org/jced
Volumetric Study of 3‑Butoxypropan-1-amine + Water Mixtures between 283.15 and 303.15 K Luís C. S. Nobre,† Â ngela F. S. Santos,† Maria-Luísa C. J. Moita,‡ and Isabel M. S. Lampreia*,† †
Departamento de Química e Bioquímica, Centro de Química Estrutural and ‡Departamento de Química e Bioquímica, Centro de Química e Bioquímica, Faculdade de Ciências, Ed. C8, Universidade de Lisboa, Campo Grande, 1749-016, Lisboa Portugal ABSTRACT: Experimental density values were obtained in 30 mixtures of the binary system water + 3-butoxypropan-1-amine at five temperatures T = (283.15 to 303.15) K and over the entire composition range. The temperature and composition effects on the different molar, apparent molar, excess molar, and partial molar properties derived from density were analyzed to comprehend the effect of hydrophobic/hydrophilic balance in the aggregation patterns and hydration schemes over the whole composition range. A comparison of the different thermodynamic properties, derived for this system, with those for the aqueous system of 3-ethoxypropan-1amine with two fewer methylene groups is made.
1. INTRODUCTION Alkoxyamines are a family of compounds characterized by amphiphilic molecules having ether and amine functional groups. They have proven to be important in industry, namely, in the controlled production of polymers.1 More recently, they have been considered a new family of prodrugs against cancer. Their labile characteristics can be used in medical treatment because they can undergo spontaneous cleavage to yield free radicals, which are therapeutic agents.2,3 A recent application of the target molecule for this study, 3butoxypropan-1-amine (BPA), is its integration into the formulation of a jet printing ink, patented in 2010.4 This ink is an aqueous mixture of several components, where the 3butoxypropan-1-amine is used to improve the print quality through leakage control of the various colored ink cartridges. In our group, we have been concerned with the thermodynamic study of water + amphiphile systems5−8 aiming to get insight into molecular interactions focused on the effect of the hydrophobic/hydrophilic balance produced by changing either the chain length or the nature of hydrophilic functional groups. As far as we know, only two thermodynamic studies are available in the literature embracing water + alkoxyamine systems, both carried out in our laboratory.9,10 This time, the object of our study embraces aqueous mixtures of BPA with two more methylene groups than 3-ethoxypropan-1-amine (EPA) (previous studies), increasing the hydrophobic characteristics of the amphiphilic molecule. Density values were measured for 30 mixtures of water (1) + BPA (2), covering the whole composition range and five temperatures in T = (283.15 to 303.15) K in 5° intervals. Derived properties such as excess molar volumes and isobaric expansions, apparent and partial molar volumes, including infinite dilution data, permitted us to identify different © XXXX American Chemical Society
aggregation patterns and/or hydration schemes and the effect of the chain length on these features. A comparison is carried out with the system water + EPA.
2. EXPERIMENTAL SECTION 2.1. Materials. 3-Butoxypropan-1-amine (BPA, CAS Registry No. 16499-88-0) was obtained from Sigma-Aldrich with purity quoted as >0.99 in mass fraction and used as supplied. The water content was determined by the Karl Fischer method and was found to be 0.1.
n
V2E(T ) = a0 +
∑ aiT i
(8)
i=1
Linear representations were obtained for all of the compositions, leading to the profile for EEP,2 as a function of composition for all of the temperatures studied as depicted in Figure 5, where the equivalent curve for EPA at 298.15 K is drawn for comparison.
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AUTHOR INFORMATION
Corresponding Author
EEP,2,
Figure 5. Excess partial molar isobaric expansions, for water (1) + BPA or EPA (2) at 298.15 K: (●) BPA and (○) EPA.
*E-mail:
[email protected]. E
DOI: 10.1021/acs.jced.7b00006 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Article
ORCID
(16) Santos, A. F. S.; Lampreia, I. M. S. How Reliable are Extrapolations to Infinite Dilution of Partial Molar Properties Using Redlich-Kister Fittings? Thermochim. Acta 2011, 512, 268−272. (17) Cabani, S.; Conti, G.; Lepori, L. Volumetric Properties of Aqueous Solutions of Organic Compounds. III. Aliphatic Secondary Alcohols, Cyclic Alcohols, Primary, Secondary and Tertiary Amines. J. Phys. Chem. 1974, 78, 1030−1034. (18) Kaulgud, M. V.; Bhagde, V. S.; Shrivastava, A. Effect of temperature on the limiting excess volumes of amines in aqueous solution. J. Chem. Soc., Faraday Trans. 1 1982, 78, 313−321. (19) Lampreia, I. M. S.; Ferreira, L. A. V. Thermodynamic Study of the Ternary System NaCl-H2O-Et3N at 25 °C. Part 1.-Volumes. J. Chem. Soc., Faraday Trans. 1993, 89, 3761−3766. (20) Nishikawa, S.; Haraguchi, H.; Fukuyama, Y. Effect of Ether Oxygen on Proton Transfer and Aggregation Reactions of Amines in Water by Ultrasonic Absorption Method. Bull. Chem. Soc. Jpn. 1991, 64, 1274−1282. (21) Gianni, P.; Lepori, L. Group Contribution to the Partial Molar Volume of Ionic Organic Solutes in Aqueous Solution. J. Solution Chem. 1996, 25, 1−42. (22) Millero, F. J. The Molal Volumes of Electrolytes. Chem. Rev. 1971, 71, 147−176. (23) Mendonça, A. F. S. S.; Dias, F. A.; Lampreia, I. M. S. Ultrasound speeds and Molar Isentropic Compressions of Aqueous Binary Mixtures of Diethylamine from 278.15 to 308.15 K. J. Solution Chem. 2007, 36, 13−26.
Isabel M. S. Lampreia: 0000-0001-6862-3368 Funding
Financial support from Fundaçaõ para a Ciência e a Tecnologia, Portugal, under projects UID/MULTI/00612/2013 and UID/ QUI/00100/2013 is greatly appreciated. Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS A.F.S.S. thanks the University of Lisbon for granting a sabbatical leave of absence during the academic year 2014/ 2015. We thank Professor J. C. R. Reis for his suggestions and revision of the article.
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REFERENCES
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DOI: 10.1021/acs.jced.7b00006 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
