Microchemical Journal 159 (2020) 105539

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Microchemical Journal
journal homepage: www.elsevier.com/locate/microc

Review Article

Deep eutectic solvents vs ionic liquids: Similarities and differences

Justyna Płotka-Wasylka a, *, Miguel de la Guardia b, Vasil Andruch c, Mária Vilková d
a
Department of Analytical Chemistry, Faculty of Chemistry, Gdańsk University of Technology, PL-80-233 Gdańsk, Poland
b
Department of Analytical Chemistry, University of Valencia, Valencia 46100, Spain
c
Department of Analytical Chemistry, Institute of Chemistry, Faculty of Science, Pavol Jozef Šafárik University in Košice, SK-04154 Košice, Slovakia
d
Laboratory of NMR, Institute of Chemistry, Faculty of Science, Pavol Jozef Šafárik University in Košice, SK-04154 Košice, Slovakia

A R T I C L E I N F O A B S T R A C T

Keywords: Deep eutectic solvents (DES) were introduced as an alternative to ionic liquids (IL) to overcome the drawbacks of
Deep eutectic solvents IL solvents. However, some authors consider them to be a subclass of ILs. In contrast, other authors emphasize
Ionic liquids that these are by their nature independent, different groups of substances. Thus, the question arises: Which
Analytical chemistry
solvent group should DESs belong to? Maybe a new class should be added to the existing ones. The aim of this
Solvents
work is to attract the attention of researchers using DES in their studies to the need for a proper use of terms.

1. Introduction the structural classification of ILs, their synthesis pathways and the
potential applications [13].
At the beginning of our century, Abbott’s group published a few DESs were introduced as an alternative to ILs to overcome the
papers that triggered research in the area we call today Deep Eutectic drawbacks of ILs. Some authors consider them to be a subclass of ILs,
Solvents (DES) [1–3]. They examined the properties of these systems and and sometimes they consider these terms interchangeable. On the other
also indicated the possibility of their use as solvents with interesting hand, other authors emphasize that despite the many similarities (See
features. There are also other terms and denominations, which may or Fig. 1), they are by their nature independent, different groups of sub­
may not denote the substances we now consider to be DESs: Low stances [14,15]. Thus, the question arises: Which solvent group should
Transition Temperature Mixtures (LTTM) [4], Low Melting Mixtures DESs belong to? The aim of this work is to attract the attention of re­
(LMM) [5] or Deep Eutectic Ionic Liquids (DEIL) [6]. When a DES is searchers using DES in their studies to the need for a proper use of terms.
composed of components of natural origin, it is defined as a natural deep Although ILs and DESs have a lot in common, especially when it comes
eutectic solvent (NADES) [7,8]. to physical properties as well as applications, from the chemical point of
On the other hand, Ionic Liquids (IL), which could be considered as view, these are two separate groups of substances. Therefore, it is still
the parents of DESs, were reported for the first time by Paul Walden in necessary to understand the specific chemical nature of DES systems in
1914 [9]. At that time, no one knew that ILs would become a very hot order to prevent a mechanistic understanding of how these systems
topic of chemistry one century later. Nowadays, some important work. In our opinion there are many more differences than similarities.
fundamental points of view are different from the original concepts, as In considering the differences between these two type of solvents, the
insights into the nature of ILs have become deeper. For instance, ILs chemical formation process as well as the source of their starting ma­
were known to be non-volatile, non-flammable and stable on air and in terials need to be mentioned [16].
water, and were considered as green solvents. Recently, it is well known
that many of them are, in fact, volatile, flammable, unstable and even 2. Starting materials and mechanism of synthesis
toxic. This situation is attributed to the large combinations of cations
and anions that meet the definition of ILs, leading to an adverse suite of DESs differ from ILs in two basic ways, namely the nature of the
behaviors. As the chemical variety of ILs has grown, they have been starting materials and the methods of their formation. ILs are a combi­
further divided into many types. Worth mentioning are: task-specific ILs nation of organic heterocyclic cations and organic or inorganic anions
(TSILs) [10], room-temperature ILs (RTILs) [11] and polyionic liquids (Fig. 2), while DESs are a combination of various hydrogen bond ac­
(PILs) [12]. Very recently Singh and Savoy summarized the literature on ceptors (HBAs) (Fig. 3) and hydrogen bond donors (HBDs) (Fig. 4). The

* Corresponding author.
E-mail address: [email protected] (J. Płotka-Wasylka).

https://doi.org/10.1016/j.microc.2020.105539
Received 3 July 2020; Received in revised form 9 September 2020; Accepted 10 September 2020
Available online 14 September 2020
0026-265X/© 2020 Elsevier B.V. All rights reserved.
J. Płotka-Wasylka et al. Microchemical Journal 159 (2020) 105539

Fig. 1. Similarities and differences of ILs and DESs.

Fig. 2. Selected cations and anions used for the synthesis of ILs.

number of potential mixtures is virtually unlimited for both ILs and DESs naturally occurring biocompatible compounds that are not hazardous if
[17]. With such a large number of suitable starting materials as well as they are released back into nature [18]. It is also important to note that
their possible combinations, they have both advantages and disadvan­ the components of DESs, unlike ILs, must not react with each other;
tages which allow the properties of these substances to be changed to therefore, it is necessary to avoid combinations of such compounds
meet the requirements of specific application (which is precisely why where this is possible.
both ILs and DESs have found wide use in various fields of science, The synthesis of ILs often involves several synthetic steps using
research and technology). The huge advantage of DESs, however, is that various reagents, organic volatile solvents; in addition, by-products and
they are made of generally nontoxic, easily accessible, cheap and sus­ waste are generated. Generally, the reaction time is long (up to 48 h)
tainable compounds. Furthermore, common components of DESs are with the temperature varying from 25 to 100 ◦ C. The synthesis of ILs

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method is the most used; the compounds are mixed and heated at
temperatures between 50 ◦ C and 100 ◦ C under constant stirring for times
spanning from minutes to hours until a homogeneous liquid forms. The
grinding method is based on mixing the compounds at room tempera­
ture and grinding them in a mortar with a pestle. A liquid formed by the
heating or grinding method is obtained with a yield of 100% and with an
atom economy of 100% [20]. Another method – freeze-drying (Fig. 2) –
is also known, but it is a bit more complicated. The separated aqueous
solutions of components are mixed together, frozen and freeze-dried to
form a clear viscous liquid [21]. From the above stated, it is clear that ILs
and DESs differ not only in the nature of the components, but also in the
methods of their formation.
The synthesis of ILs is, in general, more costly and difficult than the
preparation of DESs. The production of DESs is relatively straightfor­
ward and inexpensive and does not pose any significant post purification
or disposal problems.

3. Properties

The structure and properties of ILs as well as DESs are determined by

intermolecular interactions: Coulomb forces, hydrogen bonding and
dispersion forces. By definition, the behavior of ILs is dominated by ionic
interactions (Coulomb forces), whereas DESs, as eutectic mixtures of
two or more distinct components, exhibit a strong contribution from
hydrogen bonding [22]. Although ILs and DESs differ in the nature of
their constituents and the type of dominant intermolecular forces, they
Fig. 3. Selected HBAs for the synthesis of DESs. share many interesting properties, which can be adjusted by selecting
the nature and ratio of the constituents.

Fig. 4. Selected HBDs for the synthesis of DESs.

(Fig. 5) consists of two main steps: (i) cation formation (by protonation However, due to the large number of possible ILs and DESs resulting
of the amine by an acid or quaternization reaction of the amine with from the large number of possible combinations of starting substances, it
a haloalkane) and (ii) anion exchange (by treatment of halide salt with a is very difficult to unambiguously characterize and generalize their
Lewis acid or by anion metathesis) [19]. In contrast, DESs can be simply physical properties. We can only define some general rules and con­
prepared by heating or the grinding method (Fig. 6). The heating clusions. Both ILs and DESs have low melting points. ILs melt below

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Fig. 5. The main methods of preparing ILs.

Fig. 6. A comparison of the main synthesis processes of ILs and DESs.

100 ◦ C, while the melting temperature of DES is far below that of either toxicology, biodegradability and recyclability factors, there are several
individual component. The density and viscosity of these solvents also other assessments that influence the green-chemistry quality of ILs: the
have similar values and are strongly dependent on their composition and long reaction time at high temperatures, the use of volatile and non-
temperature. Therefore, the selection of IL and DES constituents is renewable solvents, the large quantities of chemicals, large quantity of
essential, since high viscosity and density are the main drawbacks for by-products as waste, and high stability in water (ILs become persistent
the practical use of these solvents [23–25]. Although the viscosity pollutants in wastewaters). Moreover, their different chemical proper­
problem can be solved quickly and easily in the case of DESs by using ties encourage application areas which are significantly more varied (for
water as an additional component, a large excess of water can in some example many enzymes exhibit both high activity and unexpected
cases lead to the complete decomposition of the DES [26]. In general, ILs promising stability in DESs [28]).
and DESs present high polarity. This is a great advantage of both sol­
vents, because they can solubilize a wide range of organic and bioactive 4. Applications in analytical chemistry
substances. On considering other similarities between DESs and ILs, it
could be highlighted that both systems concern a low vapor pressure and Without a doubt, DESs and ILs share many interesting properties
wide liquid range. Moreover, they are highly tunable. [20] which allow them to be applied in many fields of analytical
As we can see, the physical properties of ILs and DESs are close to chemistry (Fig. 7) [29,30]. These solvents are used in analytical chem­
each other, and what is even more important, thanks to the large number istry mainly at the sample preparation stage for solvent-based and
of possible combinations of starting materials, they are also highly sorption-based extraction of target analytes from aqueous or solid
tunable depending on the requirements for specific use. On the other samples, as stationary phase modifiers in GC, and also as mobile phase
hand, this makes it impossible to generalize about their chemical additives in LC, but in the case of DESs also for the dissolution or
properties, such as toxicity, stability, biodegradability, flammability, digestion of solid samples.
greenness, etc. From an environmental perspective, DESs are superior to Despite the fact that the application areas of DESs are very close to
ILs due to their higher biodegradability and lower toxicity. The natural those of ILs [13], the number of publications devoted to ILs is more than
origin of the constituents gives DESs a great edge over ILs, because they one order of magnitude higher than for DESs (Fig. 8) especially con­
are clearly less toxic and more environmentally friendly. Whereas IL cerning their use in analytical chemistry. This is probably because IL
components are onium salts, which show high toxicity [27]. Beside compounds were introduced into analytical science several years before

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Fig. 7. Application of ILs and DESs in the analytical chemistry.

the introduction of DESs. However, if we do not compare the absolute unknowns exist. This is why there is a continuous need for research in
number of published papers in each category but their percentage dis­ this area. On the other hand, the potential of the solvents described
tribution, the order of the categories for both solvents becomes very herein opens interesting perspectives for further research in analytical
close. The category “chemistry analytical” is in the highest positions for chemistry as well as in industrial applications.
both solvents. However, for example, the category of “green sustainable
science technology” is much higher for DES than for IL. 6. Conclusions

5. Advantages and drawbacks The aim of this work is to attract the attention of researchers using
DES in their studies to the need for a proper use of terms. Although ILs
ILs and DESs were found to be greener options when compared to and DESs have a lot in common, especially when it comes to physical
conventional solvents. In comparison to ILs, the advantages of DESs properties and applications, from a chemical point of view, these are two
concern their easy synthesis by simply mixing the components with separate groups of substances. However, from our point of view, it is
gentle heating. In addition, no future purification is required, in contrast important to focus on the mechanisms of DESs and ILs formation, as this
to ILs. Additionally, the cost of production is low due to the low prices of could explain a lot of unknowns, e.g. their differences. It also would help
synthetic raw materials. Unfortunately, their high viscosity and solid to look for new applications in many fields of chemistry and, especially
state at room temperature could be detrimental. However, the physi­ in analytical chemistry, while at the same time, correctly evaluating the
cochemical properties of DESs can be tailored by the selection of proper greenness of these new solvent systems. Considering DESs as a subtype
HBA and HBD and their molar ratio or the addition of water. of ILs will lead to the forming of confused criteria for the selection of the
Although authors often report that most of these solvents, both ILs applications in which they can be employed to enhance analytical
and DESs, are non-toxic, biocompatible and biodegradable, others state perspectives.
that more investigation is required on this matter, since the toxicity and In addition to analytical chemistry, we can expect new applications
cytotoxicity of DESs vary depending on the components. Therefore, of DESs in pharmacy, medicine, cosmetics, food science and, very
cautious handling of the terms non-toxicity and biodegradability must be importantly, new knowledge in the field of theoretical study of DESs
considered [31]. However, despite everything, DESs are believed to be concerning their composition and extraction mechanism as well.
more effective and environmentally friendly solvents than ILs.
While ILs are well understood, there are still some aspects that need
further studies. In the case of DESs, studies are still limited and many

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Fig. 8. Schematic representation of the type of chemistry categories versus percentage number of publications for ILs and DESs (performed by application of Web of
Science with permission. Keywords: Ionic Liquid, Deep Eutectic Solvent).

Declaration of Competing Interest [11] J.P. Hallett, T. Welton, Room-temperature ionic liquids: Solvents for synthesis and
catalysis. 2, Chem. Rev. 111 (5) (2011) 3508–3576.
[12] W. Qian, J. Texter, F. Yan, Frontiers in poly(ionic liquid)s: Syntheses and
The authors declare that they have no known competing financial applications, Chem. Soc. Rev. 46 (4) (2017) 1124–1159.
interests or personal relationships that could have appeared to influence [13] S.K. Singh, A.W. Savoy, Ionic liquids synthesis and applications: An overview,
the work reported in this paper. J. Mol. Liq. 297 (2020), 112038.
[14] E.L. Smith, A.P. Abbott, K.S. Ryder, Deep Eutectic Solvents (DESs) and Their
Applications, Chem. Rev. 114 (21) (2014) 11060–11082.
References [15] X.H. Yao, D.Y. Zhang, M.H. Duan, Q. Cui, W.J. Xu, M. Luo, C.Y. Li, Y.G. Zu, Y.J. Fu,
Preparation and determination of phenolic compounds from Pyrola incarnata
[1] A.P. Abbott, G. Capper, D.L. Davies, H.L. Munro, R.K. Rasheed, V. Tambyrajah, Fisch. with a green polyols based-deep eutectic solvent, Sep. Purif. Technol. 149
Preparation of novel, moisture-stable, Lewis-acidic ionic liquids containing (2015) 116–123.
quaternary ammonium salts with functional side chains, Chem. Commun. 19 [16] T. El Achkar, S. Fourmentin, H. Greige-Gerges, Deep eutectic solvents: An overview
(2001) 2010–2011. on their interactions with water and biochemical compounds, J. Mol. Liq. 288
[2] A.P. Abbott, G. Capper, D.L. Davies, R.K. Rasheed, V. Tambyrajah, Novel solvent (2019).
properties of choline chloride/urea mixtures, Chem. Commun. 1 (2003) 70–71. [17] A. Paiva, R. Craveiro, I. Aroso, M. Martins, R.L. Reis, A.R.C. Duarte, Natural deep
[3] A.P. Abbott, D. Boothby, G. Capper, D.L. Davies, R.K. Rasheed, Deep Eutectic eutectic solvents - Solvents for the 21st century, ACS Sustain. Chem. Eng. 2 (5)
Solvents formed between choline chloride and carboxylic acids: Versatile (2014) 1063–1071.
alternatives to ionic liquids, J. Am. Chem. Soc. 126 (29) (2004) 9142–9147. [18] V. Migliorati, F. Sessa, P. D’Angelo, Deep eutectic solvents: A structural point of
[4] M. Francisco, A.S.B. González, S.L. García De Dios, W. Weggemans, M.C. Kroon, view on the role of the cation, Chem. Phys. Lett. X 2 (2019), 100001.
Comparison of a low transition temperature mixture (LTTM) formed by lactic acid [19] R. Ratti, Ionic Liquids: Synthesis and Applications in Catalysis, Adv. Chem. Ser.
and choline chloride with choline lactate ionic liquid and the choline chloride salt: 729842 (2014).
Physical properties and vapour-liquid equilibria of mixtures containing water and [20] C. Florindo, F.S. Oliveira, L.P.N. Rebelo, A.M. Fernandes, I.M. Marrucho, Insights
ethanol, RSC Adv. 3 (45) (2013) 23553–23561. into the synthesis and properties of deep eutectic solvents based on cholinium
[5] G. Imperato, E. Eibler, J. Niedermaier, B. König, Low-melting sugar-urea-salt chloride and carboxylic acids, ACS Sustain. Chem. Eng. 2 (10) (2014) 2416–2425.
mixtures as solvents for Diels-Alder reactions, Chem. Commun. 9 (2005) [21] M.C. Gutiérrez, M.L. Ferrer, C.R. Mateo, F.D. Monte, Freeze-drying of aqueous
1170–1172. solutions of deep eutectic solvents: A suitable approach to deep eutectic
[6] H.R. Jhong, D.S.H. Wong, C.C. Wan, Y.Y. Wang, T.C. Wei, A novel deep eutectic suspensions of self-assembled structures, Langmuir 25 (10) (2009) 5509–5515.
solvent-based ionic liquid used as electrolyte for dye-sensitized solar cells, [22] S.P. Kelley, A. Narita, J.D. Holbrey, K.D. Green, W.M. Reichert, R.D. Rogers,
Electrochem. Commun. 11 (1) (2009) 209–211. Understanding the Effects of Ionicity in Salts, Solvates, Co-Crystals, Ionic Co-
[7] Y.H. Choi, J. van Spronsen, Y. Dai, M. Verberne, F. Hollmann, I.W.C.E. Arends, G. Crystals, and Ionic Liquids, Rather than Nomenclature, Is Critical to Understanding
J. Witkamp, R. Verpoorte, Are natural deep eutectic solvents the missing link in Their Behavior, Cryst. Growth Des. 13 (3) (2013) 965–975.
understanding cellular metabolism and physiology? Plant Physiology 156 (4) [23] B.D. Ribeiro, C. Florindo, L.C. Iff, M.A.Z. Coelho, I.M. Marrucho, Menthol-based
(2011) 1701–1705. Eutectic Mixtures: Hydrophobic Low Viscosity Solvents, ACS Sustain. Chem. Eng. 3
[8] I.M. Aroso, A. Paiva, R.L. Reis, A.R.C. Duarte, Natural deep eutectic solvents from (10) (2015) 2469–2477.
choline chloride and betaine – Physicochemical properties, J. Mol. Liq. 241 (2017) [24] M. Królikowska, M. Zawadzki, U. Domańska, D. Ramjugernath, P. Naidoo, The
654–661. influence of temperature and composition on the density, viscosity and excess
[9] P. Walden, Über die Molekulargrösse und elektrische Leitfähigkeit einiger properties of aqueous mixtures of carboxylic-based ionic liquids, J. Chem.
geschmolzener Salze, Bull Acad Imper Sci (St Petersburg) (8) (1914) 405-422. Thermodyn. 109 (2017) 71–81.
[10] K.N. Ruckart, R.A. O’Brien, S.M. Woodard, K.N. West, T.G. Glover, Porous Solids [25] M. Moghimi, A. Roosta, Physical properties of aqueous mixtures of (choline
Impregnated with Task-Specific Ionic Liquids as Composite Sorbents, J. Phys. chloride + glucose) deep eutectic solvents, J. Chem. Thermodyn. 129 (2019)
Chem. C 119 (35) (2015) 20681–20697. 159–165.

6
J. Płotka-Wasylka et al. Microchemical Journal 159 (2020) 105539

[26] M. Vilková, J. Płotka-Wasylka, V. Andruch, The role of water in deep eutectic [29] A. Shishov, A. Bulatov, M. Locatelli, S. Carradori, V. Andruch, Application of deep
solvent-base extraction, J. Mol. Liq. 304 (2020). eutectic solvents in analytical chemistry. A review, Microchem. J. 135 (2017)
[27] R. Germani, M. Orlandini, M. Tiecco, T. Del Giacco, Novel low viscous, green and 33–38.
amphiphilic N-oxides/phenylacetic acid based Deep Eutectic Solvents, J. Mol. Liq. [30] M. Opallo, A. Leśniewski, A review on electrodes modified with ionic liquids,
240 (2017) 233–239. J. Electroanal. Chem. 656 (2011) 2–16.
[28] Q.B. Cheng, L.W. Zhang, Highly efficient enzymatic preparation of daidzein in deep [31] M. Hayyan, M.A. Hashim, A. Hayyan, M.A. Al-Saadi, I.M. AlNashef, M.E.
eutectic solvents, Molecules 22 (1) (2017). S. Mirghani, O.K. Saheed, Are deep eutectic solvents benign or toxic? Chemosphere
90 (7) (2013) 2193–2195.