Synthesis and Physical Properties of ionic Liquids

Submitted by: Malcolm Griffith

Introduction: We currently live in world that is quickly adapting to the theme of “going green”.
Scientists are constantly searching for new and improved ways to reduce carbon emissions, save
energy, preserve nature, all in the hopes of ultimately securing a better tomorrow. The chemistry
field has emerged as the front runners in providing the answers and optimal routes to go about
saving the earth, adapting the image of a modern-day “Superman” to the masses. Ionic liquids
are now being endorsed by chemists as the safer and “greener” alternatives to industrial solvents.
Due to their non-volatile characteristic, easy synthesis (relatively inexpensive), and low toxicity,
ionic liquids are deemed as the better alternative compared to non-ionic or molecular solvents
such as; acetone and methanol. Although ionic liquids are considered to be ideal solvents for
organic, inorganic and polymeric materials, they can also exhibit acidic and basic properties,
ultimately having the potential to perform as catalysts in certain reactions. Ionic liquids are
typically salts where the ions are poorly coordinated, resulting in the solvent being in the liquid
state below 100C. In addition to this, the physical properties of ionic liquids are primarily
dependent on the affinity of the anion and cation that makes up its structure, whereby, ions that
are not closely packed together and have a low affinity, results in a lower melting point and
lower viscosity. On the other hand, ionic liquids that are comprised of ions that are closely
packed together and share a high affinity between each other typically have a high melting point
and higher viscosity.

1-butyl-3-methylimidazolium (cation) bis(trifluoromethylsulfonyl)imide anion

(NTf2)

In this lab, the ionic liquid, 1-butyl-3-methylimidazoliumbis(trifluromethylsulfonyl)imide

([bmim][NTf2], was synthesized. The temperature-dependent physical properties of the ionic
liquid of both [bmim][Br] and [bmim]NTf2] were tested and analyzed. The viscosity of the
compounds was tested and graphed, whereby the thermal stability was tested using
Thermogravimetric analysis (TGA), as well as a Differential Scanning Calorimetry (DSC) to
determine the glass transition temperature. 1H NMR was used to confirmed the identity and
structural arrangement of both [bmim][BR] and [bmim][NTf2].

Results:

Viscosity vs Temperature
3000

2500

2000
Viscosity (cP)

1500
[bmim]
[NTf2]
1000

500

0
300 305 310 315 320 325 330 335

1000/T (K-1)

Graph 1. Viscosity of [bmim][Br] and [bmim][NTf2] vs temperature in kalvins

Compound Peak # Splitting Integration PPM

[bmim][NTff2] 1 Singlet 1 9.06
[bmim][Br] 2 Singlet 1 10.27

Table 1. 1H NMR peaks for [bmim][Br] and [bmim][NTf2]

Compound TGA (Td5%) DSC

[bmim][NTff2] 373.39 C -85.94 C
[bmim][Br] 264.60 C -53.31 C
Table 2. DCS and TGA results for [bmim][Br] and [bmim][NTf2]
Discussion: The “anion exchange” reaction to synthesize [bmim][NTf 2] from [bmim][Br] was
successfully completed, whereby, the temperature-dependent properties of the two ionic liquids
were compared. A clear difference in viscosity between the two liquids was identified based on
mere observation, this difference in viscosity was then confirmed by testing both [bmim][Br]
which appeared to be thicker, and [bmim][Br], which was more fluid. Graph 1, depicts the wide
discrepancy of the viscosity between the two liquids, where [bmim][Br] had an initial viscosity
of 2700 cP at 30.1 C (303.25 K), and [bmim][NTf2] had initial viscosity of 78 cP at 30.2 C
(303.35 K). The expected decrease in viscosity was observed between the two ionic liquids as
temperature increased. The final viscosity of [bmim][Br] was measured to be 121.4 cP, which
was significantly higher than that of [bmim][NTf2], measured at 10.19 cP. This big difference in
the viscosity trend observed in graph 1, also translated to the readings of the glass transition
temperature (Tg).
The glass transition temperature in this experiment typically measured the amount of heat
required to raise the temperature of the two samples as a function over oven temperature. In
other words, the Differential Scanning Calorimetry (DSC) was used to measure the amount of
heat/energy required to allow the transition of the glassy liquid (semi-organized structure) to a
more fluid or unorganized liquid (water-like). The glass transition temperature or T g for [bmim]
[NTf2] was measured at -85.94 C (Table 2), while the Tg for [bmim][Br] was -53.31 C (Table
2). The DSC readings concluded that more heat (32.63 C) would be required to observe the
change in transition of the liquid for [bmim][Br] when compare to [bmim][NTf 2]. The reason for
the trends observed in both the viscosity and glass transition temperature is based primarily and
the structure and affinity of the ions within the different compound. Due to the fact that the
bromide ion is smaller in size and exhibit basic characteristics, this results in a higher affinity to
the acidic hydrogen of the imidazolium structure. In addition to this, the ions are packed closer
together, resulting in a more “organized” structure, hence one would observe a more viscous
liquid with a relatively high melting point. On the other hand [NTf 2] is much larger in size and
shows a much lower affinity with the imidazolium ion. This ultimately results in a more
disorganized structure, exhibiting water-like qualities in reference to its viscosity, and a lower
melting point, which was confirmed by both the DSCand viscometer readings.
 In regards to the thermal stability between the products, [bmim][NTf 2] proved to be more
thermally stable than [bmim][Br]. The thermogravimetric analysis (TGA) was used to measure
the thermal stability of the two compounds, where the T d5% [bmim][Br] was at 264.60 C , while
the Td5% of [bmim][NTf2] was at 373.39 C (Table 2). The major difference in the thermal
stability observed between the two compounds can be attributed to the chemical nature of the
ions associated in the ionic liquid. Due to the fact that bromide is a more basic anion, this
translate in the ionic liquid being less thermally stable, resulting in a faster rate of decomposition
of the liquid at a given temperature, which in this case was 373.39 K.
1
H NMR spectroscopy was used to confirm the structure and indemnity of the
synthesized product, where the key peak identified was peak 1 with an integration of 1 (table 1),
which represented the acidic proton that was more downfield at 9.06 ppm (shielded) due to the
presence of [NTf2]. Peak 2 with an integration of 1 (table 1), also illustrated the acidic proton,
however the peak was observed to be more up-field at 10.27 ppm, due to the presence of the
bromide ion making the proton more deshielded. The product obtained at the end of the
experiment was 3.209 g, resulting in a percent yield of 84%.

Experimental: Preparation of [bmim][NTf2] (1). [bmim][Br] (1.99 g) was added to a 100 mL

round bottom flask equipped with a stir bar, along with DI water (15 mL).
Lithiumbis(trifluoromethylsulfonyl)imide (2.612 g) was added to the dissolved solution, along
with DI water (5 mL) to dissolve the salt. Chloroform (20 mL) was then added to the mixture
after the first 30 mins and was left to stir for 90 mins. The contents of the mixture was
transferred to a separatory funnel after 2hrs, and the organic layer was isolated and washed 2
times with DI water (10 mL). Chloroform was removed from the mixture using a ratorvap,
resulting in a red-orange solution (1). (3.209g, 84%). 13C NMR (400 Mhz, CDCl3)  9.06 (s,
1H), 10.27 (s, 1H).

Conclusion: The ionic-reaction to synthesize [bmim][NTf 2] from [bmim][Br] was carried out
successfully, whereby, the temperature-dependent properties of both [bmim][NTf 2] and [bmim]
[Br] were analyzed. The temperature-dependent properties analyzed were viscosity, thermal
stability, and glass transitional temperature (Tg).1H NMR spectroscopy was used to confirm the
structure of the product. The percent yield at the conclusion of the experiment was calculated to
be 84 %.
 [bmim][Br]
Temp (C) Temp (K) Viscosity (cP)
30.1 303.25 2700
35 308.15 2080
40 313.15 1700
45 318.15 485.4
50.04 323.19 310.7
55 328.15 194.2
59.8 332.95 121.4

[bmim][NTf2]
Temp (C) Temp (K) Viscosity (cP)
30.2 303.35 78
35 308.15 68.69
40.1 313.25 58
45.9 319.05 46.84
49.9 323.05 21
55.1 328.25 11.41
60.1 333.25 10.19
Reference
S. T. Handy, M. Okello, G. Dickenson(2003). General format. Retrieved from
http://www.organic-chemistry.org/topics/ionic-liquids.shtm )