Accepted Manuscript

Elucidating the triethylammonium acetate system: Is it molecular

or is it ionic?

Paula Berton, Steven P. Kelley, Hui Wang, Robin D. Rogers

PII: S0167-7322(18)32535-2
DOI: doi:10.1016/j.molliq.2018.08.006
Reference: MOLLIQ 9451
To appear in: Journal of Molecular Liquids
Received date: 16 May 2018
Revised date: 4 July 2018
Accepted date: 1 August 2018

Please cite this article as: Paula Berton, Steven P. Kelley, Hui Wang, Robin D. Rogers ,
Elucidating the triethylammonium acetate system: Is it molecular or is it ionic?. Molliq
(2018), doi:10.1016/j.molliq.2018.08.006

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 ACCEPTED MANUSCRIPT

Elucidating the Triethylammonium Acetate System: Is it Molecular or Is it

Ionic?
Paula Bertona,†, Steven P. Kelleya,‡, Hui Wangb,c, Robin D. Rogersa.c,d
a
Department of Chemistry, McGill University, 801 Sherbrooke St. West, Montreal, QC H3A
0B8, Canada
b
Department of Chemistry, The University of Alabama, Tuscaloosa, AL 35487, United States
c
Institute of Process Engineering, Chinese Academy of Sciences, No. 1 Beierjie Zhongguancun

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Haidian District, Beijing 100190, China

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d
525 Solutions, Inc., PO Box 2206, Tuscaloosa, AL 35403, United States
† Current address: Chemical and Petroleum Engineering Department, University of Calgary,

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Calgary, AB T2N 1N4, Canada.
‡ Current address: Department of Chemistry, University of Missouri, Columbia, MO 65211,
USA

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ABSTRACT
The speciation of protic ionic liquids (ILs) has attracted high attention in the recent years, due to
its effect in the properties of the resulting liquids. In this work we analyze the behavior of
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mixtures between triethylamine (N222) and acetic acid (HOAc), a system that generates
controversy about its speciation. Using different synthetic strategies, liquids were obtained with
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molar compositions that were always between 1:2 and 1:4 mol/mol N222:HOAc. However, the
experimentally observed normal boiling points indicate that the actual IL has a molar
composition of 1:4 N222:[HOAc]/[OAc]-. Furthermore, when the synthesized liquid is mixed with
the aprotic IL 1-ethyl-3-methylimidazolium acetate, more triethylamine is expelled, indicating
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that the excess N222 forms an [HN222]+-N222 complex rather than becoming ionized by the
remaining HOAc present in the system. Our experimental data emphasizes the consideration of
these systems not as mere “mixtures of ions and non-ionized molecules,” but as complex systems
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of oligomeric ions, with distinctive and characteristic properties.

Keywords: Acetic acid; Oligomeric Ions; Protic Ionic Liquid; Speciation; Triethylamine.
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* Corresponding author. E-mail: robin.rogers@525solutions.com

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INTRODUCTION
The complex speciation of protic ionic liquids (ILs) is the subject of constant discussion and high
interest [1]. Frequently synthesized from the reaction of an acid and a base, the resulting liquids
are often not fully ionized, and thus their characterization as ILs (loosely defined as organic salts
with melting points below 100 °C [2]) is still under consideration. Besides the nomenclature
debate, of specific interest is understanding the different effects that neutral acids and bases can
have on the resulting protic IL when they engage in strong, charge de-localizing interactions with
ions vs. when they behave as easily separated components of mixtures [3,4]. The presence of
hydrogen bonding in protic ILs can cause ions and neutral molecules or acid-base pairs to act as

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single species (oligomeric ions [5] and liquid co-crystals [6], respectively), affecting properties

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such as volatility, viscosity, proton conductivity, and liquid fragility [7]. The tunability of these
properties and speciation was recently demonstrated with the sole addition of excess of amine (n-

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butylamine) or acid (acetic acid, HOAc) composing the primary IL (n-butylammonium acetate,
[C4NH3][OAc]) [8].
The behavior of protic ILs cannot be generalized. It depends on both the identity of the
species and their ratio. Many protic ILs have been characterized by the Walden plot, which

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determines the ionicity of the liquid by correlating its conductivity with viscosity. This method
has given straightforward evidence that many protic ILs can be considered as mixtures of ions
and neutral molecules [9-11]. However, the Walden plot method is based on a relative scale and
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depends on assumptions about the identity of charge-carrying species. Protic ILs can also have
significant vapor pressure due to their neutral acid or base components, even for combinations of
extremely strong acids and bases, and the separation of neutral acids and bases from ions by
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distillation could be considered a physical process and therefore the separation of components of
a mixture [1,9]. However, even aprotic ILs are sometimes capable of evaporating due to retro-
reactions, the formation of neutral molecules, or even as closely bound ion pairs [12]. Thus, the
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evaporation of acids and bases from a protic IL is also not unequivocal evidence that those
species are not chemically bound to the IL. Still, understanding how to measure ionic, neutral,
and oligomerized species and defining their effects on the physical and chemical properties of
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these liquids remain an open challenge.

On the other hand, there is a huge body of evidence that the interactions between neutral
molecules and ions can lead to noncovalently bonded complexes that are effectively new
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chemical species. For example, one example is the class of “solvate ILs”, where metal salts are
liquefied by stoichiometric amounts of liquid ligands such as diglyme [13,14]. Such systems are
considered ILs because metal ions bonded to Lewis basic ligands are considered individual
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molecules (coordination complexes) by convention. Deep eutectic solvents, on the other hand,
can possess conductivity and reactivity comparable to ILs even though they are often made by
combining a salt and a neutral molecule which are not capable of forming a formal bond [15].
Our group has observed unique spectroscopic signatures for acid-base complexes that show
intermediate ion exchange [6] and the formation of compounds that have the spectroscopic
signals of charged ions but transport properties resembling neutral molecules [16]. We believe
that findings such as these argue for a more nuanced treatment of protic ILs that acknowledges
multiple, noncovalently bonded molecules may be acting as single species.
It was reported that an equimolar combination of triethylamine (N222) and HOAc (pKa 10.75
and 4.756, respectively [17]) formed a two-phase system composed of a protic IL phase and an
upper phase composed almost purely of N222 [18]. The composition of the IL was reported and
the authors postulated some reasons for the phase behavior, but no conclusive determination of

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its speciation was proposed. This system attracted our interest because of its physical uniqueness
as a combination of a liquid acid and a liquid base which gives a liquid product that is partially
immiscible with its starting materials. Such a system is intrinsically unusual for N222, which
frequently produces “true” protic ILs [19], and for protic ILs in general, in which their conjugate
acids and bases are miscible across all proportions [8,5]. Here we attempt to determine the nature
of the ionic and neutral species in this system through spectroscopic and physical property
measurements of the IL itself and of the IL dissolved in selected compounds.

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EXPERIMENTAL

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Chemicals
The IL [C2mim][OAc] was purchased from IoLiTec Inc. (Tuscaloosa, AL, USA). Before use, the

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IL was dried under high vacuum at 60 °C overnight to reduce water content to a minimum.
Methanol, triethylamine (N222), glacial acetic acid (HOAc), triethylamine hydrochloride, and
silver acetate were obtained from Sigma-Aldrich (Milwaukee, WI, USA) and used as received.

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Deuterated dimethyl sulfoxide (DMSO-d6) was purchased from Cambridge Isotope
Laboratories, Inc. (Andover, MA, USA). Deionized (DI) water was obtained from a commercial
deionizer (Culligan, Northbrook, IL, USA) with specific resistivity of 17.30 MΩ cm at 25 °C.
Synthesis of Triethylammonium Acetate
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Synthesis in solventless conditions. Following the procedures previously reported for other ILs
[20], the protic IL was synthesized by mixing equimolar amounts of N222 and HOAc under
solventless conditions. The addition of the acid was added dropwise into a round bottom flask
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containing the amine and placed in an ice bath under stirring using a stir bar. The stirring
continued for 24 h at room temperature. The unreacted starting materials were removed first
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using rotovap and then using high vacuum (12 h, 10-4 to 10-7 torr). Even after longer periods of
high vacuum (after 72 h), the resulting triethylamine:acetic acid ratio was 1:3 (analyzed by 1H
NMR). 1H NMR of the resulting IL (DMSO-d6): δ (ppm) 1.10 (t, 9H), 1.85 (s, 9H), 2.88 (m,
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6H), 12.71 (s, 1H).

Synthesis in solventless conditions, with temperature. The synthesis described above was
performed, but by mixing equal molar amount of N222 and HOAc, with stirring and refluxing at
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80 °C for 2 h. Still, the final product obtained after high vacuum drying for more than 24 h, the
triethylamine:acetic acid ratio was 1:3.
Synthesis by mixing equimolar amounts of triethylamine and acetic acid using methanol as
solvent. Following the procedure previously reported [11], [HN222][OAc] was synthesized by
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mixing equimolar amounts of N222 and HOAc using methanol as the solvent. After the reaction
was done (the dripping HOAc into the methanolic solution of N222 was performed in an ice bath,
then stirred at room temperature for 24 h), methanol solvent was removed using a rotovap and
the IL was then dried under high vacuum. Although after 8 h under high vacuum the
triethylamine:acetic acid ratio was 1:3, a longer vacuum (56 h) resulted in a molar ratio of 1:2
(analyzed by 1H NMR). The described synthesis was repeated, but adding an excess of N222 (in a
4:1 molar ratio). Still, the product obtained resulted in a triethylamine:acetic acid ratio of 1:3.
Synthesis by metathesis. The [HN222][OAc] was prepared by metathesis reaction between
triethylammonium chloride and silver acetate. Briefly, 0.8 g silver acetate was dissolved in 70
mL water (based on the solubility of silver acetate in water: 1.02 g/100 mL water). Equimolar
amounts of triethylammonium chloride were dissolved in 2 mL water. The triethylammonium

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chloride solution was added to the silver acetate solution dropwise, and the mixture was stirred
overnight. The precipitated AgCl was separated from the solution by filtration, and water was
removed using a rotovap, followed by high vacuum (16 h), resulting in a colorless solution with
triethylamine:acetic acid ratio of 1:2 (analyzed by 1H NMR).
Mixtures of N222/HOAc system with the IL [C2mim][OAc] were prepared at room
temperature by the addition of [HN222][OAc]·2[HOAc] to [C2mim][OAc] at different molar
ratios (x), in which x is the [HN222]+:[C2mim]+ molar ratio. Each sample was prepared as about
10 g samples through mass addition of [HN222][OAc]·2[HOAc]. Each system was stirred
thoroughly for 2 h, left on a bench for 1 h, and centrifuged (10 min, 3000 rpm). The different
phases obtained were analyzed using 1H NMR.

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Spectroscopy

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1
H NMR spectra were taken utilizing a 500 MHz Bruker Avance NMR spectrometer (Karlsruhe,
Germany). The synthesized protic ILs and the different phases after mixing N222 with HOAc at

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different ratios or the N222:HOAc/[OAc]- system with the IL [C2mim][OAc] were dissolved in
DMSO-d6 and spectra were collected at 25 °C. The N222:HOAc molar ratios were calculated
through direct integration of appropriate signals.
Infrared spectroscopic measurements of the DSILs were taken on neat samples by utilizing a

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Bruker Alpha Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR)
spectrometer (Billerica, MA, USA), allowing for direct observation of the liquids. Spectra were
obtained in the range of 400–4000 cm-1.
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Differential Scanning Calorimetry
Differential scanning calorimetry (DSC) was measured on a TA Discovery 2500 DSC system
(TA Instruments, New Castle, DE). The sample was cycled from 25 to -90 °C at a rate of
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5 °C/min with isotherms at the end of each heating or cooling step to allow the instrument to
equilibrate. Due to limitations of the instrument hardware, -90 °C was the lowest temperature
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that could be accessed.

RESULTS AND DISCUSSION

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In the initial report [18], ILs composed of N222 and HOAc were made by combining the neat
acid and base in equimolar amounts. It is important to recognize that in such a system, both
ionization and liquid-liquid miscibility might be strongly affected by the composition of the
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solution. This is particularly well documented in crystal structures of systems that can
disproportionate; for instance 1:1 salts of succinic acid, a dicarboxylic acid with close values for
pKa1 and pKa2, can crystallize as fully ionized salts or 1:1 co-crystals of the neutral acid and the
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doubly deprotonated dianion in an unpredictable manner [21]. We therefore investigated three

synthetic strategies to determine if the composition of the isolated IL was affected by the
presence of either starting material and if the composition could be changed by using auxiliary
solvents, to allow the salt to separate from its starting materials. These strategies were the
combination of the neat acid and base, as previously reported, the reaction of methanolic
solutions of the acid and base followed by removal of solvent under vacuum, and finally a
metathesis reaction in aqueous solution, which avoids adding the neutral acid or base to the
reaction entirely. The final compositions of the isolated liquids were determined by 1H NMR and
are given in Table 1. It should be noted that impurities in the starting materials themselves, such
as oxidation products of N222, were below the threshold of detection by NMR and thus
considered to have only a minor effect on the IL final composition, compared to the starting
materials or solvents, which were deliberately added in large amounts.

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Table 1. Comparison of the composition of the liquid obtained using different strategies.

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Molar ratio of
Synthetic strategy Color of the obtained liquid N222:HOAc/[OAc]-

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after drying
Dark brown
Acid-base with no solvent at

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1:2.6
room temperature AN
Dark yellow
Acid-base with no solvent at
1:3
80 °C
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Dark brown
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Acid-base with methanol as

1:2
solvent at room temperature
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Metathesis (using Colorless

triethylamine hydrochloride
1:2
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and silver acetate aqueous

solutions)
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In general, our observations upon combining the neat base and acid were consistent with the
previous report [18]. When N222 and HOAc were combined at a 1:1 ratio under solventless
conditions, a biphasic system was formed. The bottom phase was a liquid with a composition of
1:2.6 N222:HOAc/[OAc]-. The bottom layer could dissolve additional HOAc but remained
immiscible with any additional N222. Further, this composition was not affected by increasing the
ratio of N222 to HOAc from 1:1 to up to 4:1 during the preparation of the IL. If N222 is titrated
into HOAc, the phase separation was observed at a composition close to 1:2. When heat was
applied, the final ratio of N222 to HOAc remained as 1:3. The lower phase could not be
crystallized by flash cooling with liquid nitrogen and showed no transitions in DSC when cycled
from 25 to -90 °C. We also attempted to isolate a 1:1 salt from the liquid evaporating it under
reduced pressure to remove the neutral HOAc. The composition remained constant, indicating
that the system reached an azeotropic composition at 1:3 N222:HOAc/[OAc]-.

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Two other strategies, combinations of 1:1 mol/mol solutions of N222 and HOAc in methanol
and combinations of aqueous solutions of triethylamine hydrochloride and silver acetate also at a
1:1 ratio, were also attempted to isolate the IL. The reaction mixtures were filtered of any
precipitate and evaporated under reduced pressure. The isolated phases were again liquids rich in
HOAc. The compositions were different from the liquids isolated under solventless conditions,
although they were inevitably found within the range of 1:2 and 1:4 N222:HOAc molar ratio. A
comparison of the IR spectra of the liquid isolated from metathesis with the liquid isolated under
solventless conditions shows that nearly all of the major peaks match, although the liquid
isolated by metathesis has extra absorption in the –OH stretching region (Figure 1). This is
consistent with the presence of water (or methanol) that was not removed and suggests that the

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differences in composition are affected by contamination from solvent in the solvent-assisted

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reactions. In addition, the presence of both molecular and ionic HOAc species is evidenced by
the presence of the C=O stretching mode band at 1710 cm-1 and the C-O asymmetric stretching

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band at 1560 cm-1, respectively.
100

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80
Transmittance (%)

3400
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O-H
60 Streching
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1710
40 HOAc C=O
Streching 1560
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[OAc]-
C-O asym
20
[HN222][OAc]-acid/base solventless add
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[HN222][OAc]-metathesis
0
4000 3400 2800 2200 1600 1000 400
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-1
Wavenumber (cm )
Figure 1. Comparison of FT-IR spectra of [HN222][OAc] synthesized by different methods.
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Altogether, our attempts at synthesis indicate that a 1:1 salt of N222 and HOAc is intrinsically
unstable under ambient conditions, inevitably disproportionating into a liquid that contains
excess HOAc. The existence of acid-base mixtures with non-stoichiometric composition was
reported more than 25 years ago, when primary, secondary, and tertiary alkylamines were
described to form clusters with carboxylic acids [22]. Acetic acid, a carboxylic acid commonly
used in the protic ILs, was reported to form a dimeric species, held together by two hydrogen
bonds, species that is the main component in the liquid state of the pure acid [22]. The complete
inability to isolate a combination of N222 to HOAc at a ratio of less than 1:2 mol/mol supports the
presence of nonstoichiometric, oligomeric acetate-based anions [8,22,23].
The speciation of a protic IL can often be investigated by changes in the temperatures of
phase transitions compared to the starting materials. While melting points are particularly useful,

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the low melting point of N222 (-115 ºC [17]) made it impossible for us to conclusively explore
melting and freezing transitions for these systems. However, the unexpected azeotropic behavior
observed for the solventless IL suggested that we could measure normal boiling points (NBPs) to
get further insight into the system. Nine systems were prepared by combining a 1000 μL aliquot
of HOAc (ca. 0.0175 mol) with increasing numbers of 200 μL aliquots of N222 (ca. 0.00143 mol
each). Each of these systems was heated until they held a constant temperature for at least 30 s.
In all cases the systems were observed to bubble vigorously. The recorded NBPs vs.
compositions of the mixtures molar ratio of N222:HOAc are given in Figure 2.

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160

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Biphasic regime

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140
Boiling Point (oC)

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120
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100
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0:1
0.00 1:4 0.33
0.25 1:3 1:2
0.50 1:0*
1.00
Molar Ratio N222:HOAc
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Figure 2. Effect of the molar ratio of N222:HOAc on the boiling point of the mixture. Dashed line
indicates the boundary between monophasic and biphasic regimes. *Boiling point of 1:0
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N222:HOAc ratio (i.e., pure N222), from Ref. 24.

The analysis of the boiling points of the protic ILs was proposed by Angell et al. to
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understand the degree of proton transfer, and hence charge distribution, of these liquids [10]. It
was reported that the boiling point of the acid-base mixtures increases with the acid
concentration until a certain composition, indicating the formation of anionic and hydrogen-
bonded species in the system. It is hence expected that the activities of the individual
components will be lowered very strongly when there is a large driving force to transfer the
proton from acid to base. In the system we investigate here, there is a huge increase in boiling
point when N222 is added to HOAc (Figure 2), up to 1:4 N222:HOAc molar ratio, followed by an
almost equally steep decrease as more N222 is added to these liquids.
At approximately 1:2 N222:HOAc/[OAc]- ratio, the NBP levels out at 120 °C. Beyond this
composition, the mixtures were visibly biphasic. Since the NBP measurements were made
without agitating the liquids, the vapor pressure was determined by the composition of the phase
which made an interface with the atmosphere. In two of three cases (i.e., N222:HOAc = 1:1.75,

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and 1:1.35), the entire upper phase evaporated before a stable reading could be made, and the
NBP thus corresponds to the lower phases. These have NBPs of 118 °C and 116 °C, respectively,
which are close to each other and to the NBP of the azeotrope. In one case (N222:HOAc = 1:1.5),
the NBP of the upper phase was able to be measured at 101 °C, which is intermediate between
the published NBP of pure N222 (88.2 °C [24]) and that of the azeotrope. The increased boiling
point relative to pure N222 may be due to the dissolution of very small amounts of HOAc, which
would then form ions, although this was not detected in previous experiments by 1H NMR.
The fact that the boiling point of the azeotropic mixture is neither a maximum nor a
minimum for the system indicates that the liquid is not a binary mixture. For binary mixtures, the
twin requirements that the composition of the gas and the liquid be identical and be in

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equilibrium with each other also imposes a restriction that the derivative of vapor pressure with

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respect to composition must be zero; in other words the vapor pressure of the azeotropic mixture
is either a minimum or a maximum for the phase diagram [25]. However, for ternary mixtures,

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the derivative of vapor pressure with respect to composition is described by a Hessen matrix
composed of partial derivatives of vapor pressure with respect to the mole fraction of each
component, and depending on the determinant of this matrix the azeotropic vapor pressure can
be an extreme value (a maximum or minimum) or a saddle point [26]. N222 and HOAc thus

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appear to form a saddle azeotrope. However, this is unsurprising as the aforementioned equations
have an underlying assumption that components of a mixture are nonreactive, and HOAc and
N222 are a reactive acid-base pair. What makes this system unusual is that the product is not an
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isolable 1:1 salt, and thus the ternary phase diagram cannot be systematically explored and
instead emerges spontaneously via the partial reaction of the two components.
The magnitude of the boiling point increase is much greater than that typically observed for a
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mixture of chemically unreactive liquids, and the azeotropic composition does not occur at the
boiling point maximum. The most comparable systems in the literature are azeotropes of water
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with anhydrous mineral acids, where the azeotrope boiling point is typically 20-30 °C greater
than the maximum boiling component (water) [27]. It is generally understood that in these
systems water and the acid react to completion to give ions, with the acid acting as the limiting
reagent. It is particularly interesting that the boiling point maximum occurs at a 1:4 N222:HOAc
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molar ratio; pyridine and formic acid (another system composed solely of a liquid acid and base)
also form a crystalline, ionic compound at precisely this ratio [23]. Considering the 1:4
N222:HOAc/[OAc]- system to be an IL, [HN222][H3(OAc)4], explains the NBP trends and
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azeotropic behavior. The NBPs reflect boiling point elevation of either HOAc or N222 (whichever
is in excess) by the dissolved IL, while the azeotropic compositions are simply those at which the
thermal decomposition of the [HN222][H3(OAc)4] into its starting materials and the evaporation
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of excess N222 are occurring at the same rate. This is also consistent with the behavior described
by Angell et al. which results in boiling point elevation upon addition of acid to a protic IL.
We also investigated the miscibility of the N222:HOAc/[OAc]- system with the IL 1-ethyl-3-
methylimidazolium acetate ([C2mim][OAc]). This IL is an useful chemical probe for
fundamental investigations because it is composed of very basic [OAc]- ions which undergo
strong interactions, which leads to large effects of solutes on physical and spectroscopic
properties, but despite the strength of these interactions, [C2mim][OAc] does not crystallize. We
have investigated liquid-liquid systems of [C2mim][OAc] with aprotic ILs and liquid-solid
systems composed of [C2mim][OAc] and solid, protic [OAc]- salts [28]. In these systems, the
dissolution of the salt into [C2mim][OAc] has been found to depend on the ability of the [OAc]-
ions to form interactions with specific ions from the solute. We therefore sought to understand

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how this behavior would manifest for the N222/HOAc system, where the salt is capable of
disproportioning into an immiscible neutral liquid. [C2mim][OAc] was added to the saturated
N222/HOAc system solution at different molar ratios (calculated as mole of N222 species to moles
of [C2mim][OAc]). The mixtures were stirred for 1 h and, upon standing on the bench for 2 h and
centrifuged (10 min, 3000 rpm), biphasic systems were formed in mixtures with molar ratios
higher than 1:1 N222:[C2mim][OAc] (Figure 3). Each phase was analyzed by 1H NMR.

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Figure 3. Biphasic system after addition of [C2mim][OAc] to [HN222][OAc]·2[HOAc] (1:2
N222:[C2mim][OAc] molar ratio).

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In those systems where two phases were observed, the top phase remains rich in N222, while
the bottom phase contains [C2mim][OAc], HN222/N222, and HOAc/[OAc]- (Figure 4). This
behavior contrasts with what we observed previously for aprotic ILs with partial miscibility [29]
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and for solid protic salts dissolved in [C2mim][OAc] [28]; in both of these cases the excess solute
separates without changing its identity. It indicates that [C2mim][OAc] is able to break the
interactions between HN222/N222 and HOAc/[OAc]-, and the solubility of N222 is further
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decreased.
The amount of N222 decreases to very low (nearly zero) values when [C2mim][OAc] is in a
large excess, although HOAc does increase the solubility of N222 compared to neat
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[C2mim][OAc] (the solubility of N222 in [C2mim][OAc] is 0.017 mol/mol IL). This is likely
because HOAc interacts very strongly with [OAc]-, and thus the protonation of N222 is disfavored
in [C2mim][OAc].
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14 2.5
[C2mim]+
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N222 species
12
HOAc species
2.0
Experimental Molarity
Experimental Molarity

N222 to OAc/HOAc Ratio

10 Calculated values in broken
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lines
1.5
8

6
1.0

4
0.5
2

0 0.0
3:1 2:1 1:1 1:2 1:4 1:9 3:1 2:1 1:1 1:2 1:4 1:9

N222:[C2mim][OAc] N222:[C2mim][OAc]

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Figure 4. Molarity of the different components in the lower phase in mixtures with different
N222:[C2mim][OAc] ratios (●, broken lines: calculated values).
In conclusion, N222/HOAc shows several unusual properties, some of which are governed by
its ionic nature and others of which are typical of its molecular behavior. N222 only shows limited
solubility in polar solvents, and this is generally attributed to its ability to form limited hydrogen
bonded complexes [30]; thus the immiscibility of N222 with N222/HOAc indicates ionic character
for the liquid. The elevation of boiling point also supports ionization, suggesting that oligomeric
ions analogous to the structurally characterized [H3(formate)4]- tetrameric anion are being
formed [23]. However, because the IL contains such a large proportion of non-ionized species, it

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shows a number of behaviors indicative of molecular liquids. It can be boiled under ambient

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pressure, has very low viscosity, and does not readily freeze or undergo glass transitions. Based
on these properties, we postulate that N222 and HOAc react through a partial proton transfer but
nevertheless make a largely ionic system composed of [HN222]+ and [H3(OAc)4]-. Because the

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[H3(OAc)4]- anion has limited hydrogen bond accepting capability, the system can dissolve up to
1 eq. of N222, likely by forming a 1:1 complex with [HN222]+, but is immiscible with more N222
because all hydrogen bond donors are saturated, and there is no driving force to protonate N222

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further. Scheme 1 shows an example reaction for how a 1:1 combination of N222 and HOAc
could disproportionate into the saturated 1:2 N222/HOAc system. Of course, as a liquid the
system does not have one defined structure, but ions such as those in Scheme 1 are chemically
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feasible and offer a satisfactory explanation for miscibility behavior and the ionic properties such
as reduced volatility.
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Scheme 1. Reaction of liquid N222 and HOAc to give the proposed N222-saturated oligomeric IL
in equilibrium with excess N222.
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CONCLUSIONS
Contrary to previous publications, where the formula of the IL was reported as
[HN222][OAc]·2[HOAc], the experimental data based on boiling points indicate that the actual IL
has the formula [HN222][OAc]·3[HOAc]. The azeotrope obtained, even using different synthetic
strategies, might indicate the formation of triethylamine-triethylammonium dimers, removed
under high vacuum. The presence of excess of triethylamine in the azeotropic mixture is
evidenced with the addition of the second IL ([C2mim][OAc]): Instead of the previously
observed separation of two phases containing the different ILs once the solubility limit is
reached, only triethylamine is expelled from the DSIL.
While liquid-liquid biphasic systems are ubiquitous in both fundamental and applied
chemistry, this apparently mundane behavior undergoes a new level of complexity when ionizing

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species are involved. N222/HOAc illustrates unusual behavior that can be accessed when two
liquids capable of undergoing an ionization reaction with each other are mixed. The results and
observations here reported indicate the high complexity at the molecular level of the protic ILs,
and highlights the importance of a further understanding of their interactions. This behavior is
highly reversible and raises the possibility of temperature or composition-dependent switching
behavior such as that exploited in the methylimidazolium IL-based BASIL (Biphasic Acid
Scavenging utilising Ionic Liquids) process [31]. The system also raises new questions as to how
its immiscibility arises, particularly when apparently closely related systems such as N-
methylpyrrolidine and HOAc are fully miscible [5]. All in all, and opposite to what has been
established for this type of ILs, this system should be considered not as “a mixture of ions and

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non-ionized molecules,” but as a complex system of oligomeric ions, with distinctive and

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characteristic properties.

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ACKNOWLEDGEMENTS
We would like to thank the Novartis-Massachusetts Institute of Technology (MIT) Center for
Continuous Manufacturing (CCM) and Novartis International AG for financial support. This

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research was undertaken, in part, thanks to funding from the Canada Excellence Research Chair
Program. AN
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Graphical Abstract

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Highlights

• Mixtures of triethylamine and acetic acid yield non-stoichiometric liquids.

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• These ionic liquids (ILs) are best described as complex systems of oligomeric ions.

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• Normal boiling points indicate that the IL has the formula [HN222][OAc]·3[HOAc].

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• Excess N222 forms an [HN222]+-N222 complex rather than becoming ionized.

• N222/HOAc mixtures show the high complexity at the molecular level of protic ILs.

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