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Relative acidity measurement of Bronsted acid functional ionic liquids by UV-

spectroscopy

Article · January 2009

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Relative acidity …………. P.Elavarasan et al., Bulletin of the Catalysis Society of India 8,(2009)107-113

Relative acidity measurement of Bronsted acid functional ionic liquids by

UV-spectroscopy

P. Elavarasan, K.V.Krishna Kishore, Sreedevi Upadhyayula*

Department of Chemical Engineering, Indian Institute of Technology Delhi,
Hauz Khas, New Delhi -110016, India
*e-mail: sreedevi@chemical.iitd.ac.in
The UV-visible spectra of ionic liquids in water solvent with 4-nitroaniline was obtained.
The unique characteristic of the ionic liquids in acidic solution was determined with
different concentration 0-450 mM solution. Through spectrophotometric measurement
the Hammett function (H0) was calculated and relative acidity compared with sulfuric
acid.
Keywords: ionic liquids, acidity, Hammett function, UV-spectra.

Introduction organic cations and inorganic or organic

Ionic liquids (ILs) are generally defined anions. Any change in the structure or
as salts melting at or below 100°C. They length of the carbon side chain of both
have negligible vapor pressure and are ions leads to different chemical or
generally assumed to be stable over a physical properties. Depending on the
wide temperature range. Firstly, they application, ionic liquids can be
achieved interest as electrolytes for designed to meet the demands.
batteries [1]. During the last decades of Therefore, they are also described as
the 20th century, the applications of designer solvents and catalysts.
ionic liquids expanded from electrolytes Recently, acidic ionic liquids have been
for electrochemical devices and used as catalysts for nitration,
processes [2] to solvents and catalysts esterification and alkylation reactions
for organic reactions [3-7]. Furthermore, [11- 12]. The main property of
ILs are of great interest as solvents for functional ionic liquids is acidity, this
separation and extraction processes [8], will help establish an appropriate path of
in nano-technology [9] and as the acid catalyzed reaction. The acidity
performance additives in measurement of ionic liquids may be
oligomerization [10]. The liquid salts are done by Hammett function
basically composed of relatively large determination as relative acidity using

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Relative acidity …………. P.Elavarasan et al., Bulletin of the Catalysis Society of India 8,(2009)107-113

UV-visible spectrophotometry Chemicals Pvt. Ltd, India. In a typical

technique. In this work, systematic
analysis of UV-spectroscopy in the
presence of solvent has been done. The
UV-visible spectra of ionic liquids in
water as solvent with 4-nitroaniline
indicator were reported. The Hammett
function of ionic liquids calculated and
acidity compared with sulfuric acid.
Experiment
Catalyst Preparation
Sulfonic acid functional ionic liquids
were prepared in a laboratory following
the procedure outlined in literatures [13-
15]. N-methyl imidazole, pyridine,
triethylamine and 1,4-butane sultone
were purchased Sigma Aldrich
ionic liquid preparation procedure, N-
methyl imidazole was mixed with 1,4-
butane sultone stirring at 313-353 K for
12-24 hours. After solidification, the
zwitterions mass was washed three times
with ethyl ether and then dried under
vacuum. A stoichiometric amount of
sulfuric acid was then added to the
precursor zwitterions. The mixture was
stirred at 353 K for 8h to obtain the ionic
liquid. The structures of the prepared
ionic liquid are shown in Figure 1. All
the chemicals were research grade and
were used without further purification
unless otherwise stated.

Figure 1 Structure of Ionic Liquids

IL-1 (N-(4-sulfonic acid)butyl 8.0002, 20.6977, 22.7652, 51.0469,

triethylammonium hydrogen sulfate): 23.8737, 56.6530. Thermal
1H-NMR (D2O, 400 MHz): δ(ppm) decomposition of ionic liquid 1 observed
1.1625 (t, 9H), 1.6599 (m, 4H), 2.5862 to be 598.4 K.
(t, 2H), 3.1376 (t, 2H), 3.1995 (m, 6H); IL-2 (1-(4-sulfonic acid)
13C-NMR(D2O, 100MHz) : δ(ppm) butylpyridinium hydrogen sulfate): 1H-

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Relative acidity …………. P.Elavarasan et al., Bulletin of the Catalysis Society of India 8,(2009)107-113

NMR (DMSO, 400 MHz): δ(ppm) is usually in M-1cm-1 or L mol-1cm-1.

1.5883 (t, 2H), 2.0126 (t, 2H), 2.6204 (t, Determination of extinction coefficient
2H), 4.6336 (t, 2H), 8.1578 (t, 2H), (ε) of 4-nitroaniline in water (contains
8.6059 (t, 1H), 9.0961 (d, 2H: 13C- 1% DMSO) 6.9 mg (0.05 mmol) of 4-
NMR(D2O, 100MHz) : δ(ppm) 22.1620, nitroaniline was dissolved in 0.5 mL
30.6026, 51.1654, 61.2132, 128.9924, DMSO for 100 mM concentrated
145.6609, 146.4140. Thermal solution was prepared. 25, 50 and 75 uM
decomposition of ionic liquid 2 observed of samples prepared from the later stock.
to be 597.8 K. Absorbance of these stock solutions was
IL3: (1-(4-sulfonic acid) butyl-3- measured at 381 nm and were noted as
methylimidazolium hydrogen sulfate): 0.49366, 0.96825 and1.4687
1H-NMR (D2O, 400 MHz): δ(ppm) respectively. A plot of concentration
1.5542 (t, 2H), 1.8759 (t, 2H), 2.5957 (t, versus absorbance was drawn, the slope
2H), 3.8486 (s,3H), 4.1791 (t, 2H), of the line was noted down as extinction
7.7089 (d,1H), 9.1533 (d,1H), 10.3077 coefficient (here, εl), ε x 380 = 19,500 M
(s,1H); 13C-NMR(D2O, 100MHz) : corresponding to 4-nitroaniline in water
δ(ppm) 22.2840, 29.3126, 36.5853, solvent. From figure 2, it is clear that the
49.2827, 51.2456, 123.1597, 124.4810, indicator concentration between 25 and
137.4818. Thermal decomposition of 75uM follows the Beer-Lambert law. To
ionic liquid 3 observed to be 639.9 K. determine the acidity, a stock solution of
Procedure 4-nitoraniline was prepared at
The molar extinction coefficient (ε), also concentration of indicator (44.8 uM) in
known as molar absorptivity, is a water and absorbance measured at 380
measure of how strongly a chemical nm within Beer-Lambert law region. The
species absorbs light at a given Bronsted acidity was evaluated from the
wavelength [16, 17]. It is an intrinsic determination of Hammett acidity
property of the species. The actual functions [12, 18-20]. In a given
absorbance A, of a sample is dependent solvent(s), assumed as dissociating, the
on the path length l and the Hammett function (H0) is defined as
concentration c of the species via the H 0 = pK ( I )aq + log([ I ]s [ IH + ]s )
Beer-Lambert law, A = εcl. The unit of ε

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Relative acidity …………. P.Elavarasan et al., Bulletin of the Catalysis Society of India 8,(2009)107-113

Where pK ( I ) aq is the pK a value of and [ I ]s are molar concentrations of

the indicator (0.99 for 4-nitroaniline) protonated and unprotonated forms of

referred to an aqueous solution. [ IH + ]s the indicator in the solvent.

Figure 2 Extinction coefficient calculation for 4-nitroaniline

Result and discussion values of Hammett acidity functions is

ACIDITY OF IONIC LIQUIDS
A series of solutions (0-450 mM) for
three ionic liquids (IL1, IL2, IL3) were
prepared using above stock solution by
diluting with water. Figure 3 shows the
spectrum IL1, from the figure, it is
evident that absorbance decreases with
increase of IL1 concentration and clearly
shows that the protonation of indicator
with respect to spectra. Comparison of
acidity of ionic liquids by calculated
shown in the figure 4, from which it is
evident that the relative acidity of three
ionic liquids follows the order of
IL2>IL1>IL3. Further, the relative
acidity was compared with sulfuric acid
at 50 mM concentration and the results
were shown in the figure 5. From figure
5 it is clear, that the three ionic liquids
possess similar acidity as that of sulfuric
acid.

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Relative acidity …………. P.Elavarasan et al., Bulletin of the Catalysis Society of India 8,(2009)107-113

Figure 3 Absorption spectra of 4-nitroaniline for various concentration of IL1.

Figure 4 Comparison of Hammett acidity functional of ionic liquids in water with 4-

nitroaniline as indicator ( pK a = 0.99, Amax = 380 nm by UV-spectroscopy).

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Relative acidity …………. P.Elavarasan et al., Bulletin of the Catalysis Society of India 8,(2009)107-113

Figure 5 Comparison of Hammett functions of ionic liquids with sulfuric acid (50 mM)

Conclusion 1. H. C. De Long and R. T. Carlin,

SO3-H function ionic liquids Proceedings of the Electrochemical
were prepared and the relative acidity of Society, 94 (1994) 736 - 743.
ionic liquids was measured using 2. N. Yamanaka, R. Kawano, W. Kubo,
Hammett functions in water with 4- T. Kitamura, Y. Wada, M. Watanabe
nitroaniline indicator. The values of and S. Yanagida, Chem. Comm.,
Hammett function of ionic liquids in (2005) 740 - 742.
water are almost similar in all 3. K. N. Marsh, A. Deev, A. C. T. Wu,
concentration of three ionic liquids. The E. Tran and A. Klamt,, Korean J.
acidity of the prepared ionic liquids Chem. Eng., 19 (2002), 357 - 362.
compare well with sulfuric acid 4. S. Muthusamy and B. Gnana-
Hammett function and hence prove their prakasam, Tetrah. Lett., 46 (2005),
highly acidic property. This makes the 635 - 638.
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