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Recent Advances and Thermophysical Properties Of ienc Sc es al J c o i u m r e n a h l Losetty et al., Chem Sci J 2016, 7:2 C Chemical Sciences Journal DOI: 10.4172/2150-3494.1000128 ISSN: 2150-3494 Research Article Article OpenOpen Access Access Recent Advances and Thermophysical Properties of Acetate-based Protic Ionic Liquids Venkatramana Losetty1, Magaret Sivapragasam1 and Cecilia Devi AP Wilfred1,2* 1Center of Research in Ionic Liquids (CORIL), Universiti Teknologi PETRONAS, Bandar Seri Iskandar, Perak 32610, Malaysia 2Faculty of Fundamental and Applied Science, Universiti Teknologi PETRONAS, 32610, Tronoh, Perak, Malaysia Abstract Protic Ionic Liquids (PILs), a substantial branch of the infamous Ionic Liquids (ILs) have gained much attention in recent years. They have been the “go-to” solvent of choice in many areas such as chromatography, catalysis, fuel cells, biological applications etc., due to their thermophysical properties and their ability to be tunable based on task specificity. This review covers two parts, namely; a brief description on the thermophysical properties of acetate PILs (density, speed of sound, viscosity and decomposition temperature) and its current applications in the industry. The collation of the physicochemical data consents structure-property trends would be discussed, and these can be used as a foundation for the development of new PILs to achieve specific properties. Economically, PILs have been suggested as “greener” alternatives to conventional solvents in various industrial applications hence, in order to assess their suitability for such purposes, a thorough evaluation of their mutagenicity, toxicity and carcinogenicity is crucial. Keywords: Protic ionic liquid; Thermophysical property; Acetate cells [15] and biocatalysts [16]. PILs also have been widely used as ionic liquids a Bronsted acid or base [17] in many acid-base-catalyzed organic reactions such as Knoevenagel condensation [18], Diels-Alder reaction Introduction [19], Aldol condensation [20], Fischer esterification [21] and Pinacol Ionic Liquids (ILs) are molten salt consisting entirely of ions that rearrangement [22] because of their nontoxic, non-volatile and can be paired up by an enormous number of cations and anions. Such recyclable nature in comparison with mineral acids. examples include anions- halides, phosphates, sulphates, borates, PILs are cheaper to prepare than their counterpart, the AILS. This is acetates and cations- bulky dissymmetrical long/short alkyl chained due to the simple method for high purity preparation of PILs however, (such as trialkylphosphonium, trialkylammonium, imidazolium, even though they have been known for over a century, only recently pyridinium) [1-3]. Since it can be made up from unlimited number has their potential been recognized [23]. In comparison to the work on of cations and anions, the desired physicochemical properties AILs, there have been very few investigations into the structure of PILs such as thermal stability, miscibility in water or organic solvent, and to date has been limited to the structure of the neat PILs, without the electrochemical potential window, and electric conductivity can be effect of additives being explored. The interest in PILs sparked due to the fine-tuned depending on the field of interest. Based on the justification simple synthesis procedure, low cost of preparation and purification, of their chemical behavior, ILs can be divided in two groups namely; and also their claimed biodegradable nature [9]. However, the use of aprotic (AILs) and protic (PILs) ILs. AILs are considered to be any sort of IL requires an in depth knowledge of their thermophysical “classic ILs” and are much more studied than their counterparts, properties to deem it suitable to be extended from the laboratory to PILs. Interestingly enough, PILs are said to be less expensive than the industrial level. The scarce current knowledge of the thermophysical traditional imidazolium based AIL’s [4]. properties of PILs is a barrier for their development for industrial AILs are mainly based on bulky organic cations such as imidazolium applications [24]. However, apart from good technical performance, − − − − or pyridinium and an assortment of anions such as PF6 , Br , Cl , BF4 , the current European Union environmental legislation and REACH – N(CN)2 [5]. PILs are typically synthesized by proton transfer from a (Regulation concerning registration, evaluation, authorization and Bronsted acid to a Bronsted base [6]. The most common cations used restriction of chemicals) demands data of the safety of chemicals in PILs include primary, secondary and tertiary ammonium ions biodegradation and eco toxicity. As PILs are newly emerging, it is vital whereas the anions are of the organic species such as the carboxylate to assess their level of hazard before they can be safely employed for groups [7]. Common PILs consist of an alkylammonium cation with use [25]. This review then, encompasses the thermophysical properties either an organic or inorganic anion, analogues to the first reported of acetate PILs, which includes density, viscosity, speed of sound and ILs; ethylammonium nitrate and ethanolammonium nitrate [8]. A key characteristic of PILs are their capacity to promote hydrogen bonds, in which includes proton acceptance, proton donation and hydrogen *Corresponding author: Cecilia Devi AP Wilfred, Center of Research in Ionic Liquids bonding [9,10]. (CORIL), Universiti Teknologi Petronas, Bandar Seri Iskandar, Perak 32610, Malaysia, Tel: +6053687635; Fax: +6053656176; E-mail: [email protected] It has been demonstrated that PILs possess lower glass-transition Received March 17, 2016; Accepted May 22, 2016; Published May 27, 2016 temperatures and melting points compared to AILs. In terms of applications, researchers always tend to analyze the ionic conductivities, Citation: Losetty V, Sivapragasam M, Wilfred CDAP (2016) Recent Advances and Thermophysical Properties of Acetate-based Protic Ionic Liquids. Chem Sci J 7: 128. densities, melting points, viscosities, and thermophysical properties doi:10.4172/2150-3494.1000128 of PILs [11]. This entails well with its wide-spanned applications in gas separations [12], separating agents in extractive distillation, Copyright: © 2016 Losetty V, et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted heat transfer fluids [13], biomass processing [4,14] working fluids use, distribution, and reproduction in any medium, provided the original author and in a variety of electrochemical devices (batteries), capacitors, solar source are credited. Chem Sci J ISSN: 2150-3494 CSJ, an open access journal Volume 7 • Issue 2 • 1000128 Citation: Losetty V, Sivapragasam M, Wilfred CDAP (2016) Recent Advances and Thermophysical Properties of Acetate-based Protic Ionic Liquids. Chem Sci J 7: 128. doi:10.4172/2150-3494.1000128 Page 2 of 7 decomposition temperatures. Although the properties and applications (ρ=1.01700 g.cm-3), the deviation in density is 7.7%. However, 1-butyl of PILs have been comprehensively reviewed by Greaves and ammonium acetate showed lowest density value (0.95644 g.cm-3) Drummond their review did not cover the speed of sound properties while 2-hydroxyethylammonium acetate exhibit highest density value of PILs as well as its current application [26]. This review then bridges (1.14904 g.cm-3) among all studied ILs. The deviation in density is that gap by discussing on various thermophysical properties of acetate 16.7% at same temperature and pressure conditions. PILs as well as current applications. Speed of sound (u) General Procedure for Synthesis of PILs The speed of sound (u) is an important thermodynamic property PILS and APILs are typically synthesized by various methods like which can be experimentally determined with precision over a broad quaternization, neutralization and metathesis methods. Generally, acetate range temperature and pressure. The experimental speed of sound PILs are prepared through the neutralization process, the proton transfer relates to other thermodynamic properties such as density, heat taking place from Bronsted acid to Bronsted base. The reaction mechanism capacity, isentropic compressibility, thermal conductivity, isothermal for acetate PILs is given as Scheme 1 and the detailed synthetic procedure compressibility and excess isentropic compressibility [46]. There are for a acetate PILs synthesis is given as follows [27]: a few theories that explain the nature of these properties and their relationship to each other. These theories reflect as a vital element A particular quantity of base was taken in a 100 mL double necked for the design and optimization of various industrial and engineering round bottomed flask fitted with a pressure equalizing dropping funnel processes. The Newton-Laplace’s equation states that the relationship in an ice bath. An equimolar quantity (stoichiometric quantity) of between density, speed of sound and isentropic compressibility of acetic acid was added drop wise through the dropping funnel at low liquids [47]; Gardas et al. proposed a modified Auerbach’s equation temperature about 5-10°C in the presence of nitrogen gas. The solution which gives well-known empirical relation between the speed of sound, was then stirred to room temperature for 24 h. The main impurity of surface tension, and density of ILs [48]; Benson et al. explained the the IL is water as well as unreacted starting materials. They are removed connection between density, speed of sound,
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