Influence of Polar, Aprotic Solvents on the

Acid-Catalyzed Dehydration of Fructose

Joann M. Sutyak1, William A. Elliott1, Max A. Mellmer3, Isabel Burgos1, James A. Dumesic3, Robert M. Rioux1,2
Department of 1Chemical Engineering and 2Chemistry, The Pennsylvania State University, University Park, PA 16802
Department of Chemical and Biological Engineering3, University of Wisconsin, Madison, WI 53706

Kinetics of Fructose Dehydration

Abstract
Polar, aprotic solvents have been shown to increase the rate of acidcatalyzed reactions by 35 to 55 times, however the origins of such increase are
unknown. One possible explanation for this phenomenon is that the acid
catalyst (H+) is stabilized to a greater extent in water due to hydrogen bonding,
thus decreasing the reactivity relative to an aprotic solvent which lacks
hydrogen bonds. The following research examines the thermodynamics of
acid catalysts and the effect on kinetics towards fructose dehydration in three
polar, aprotic solvents: Acetonitrile, -valerolactone, and Dimethyl Sulfoxide.
Specifically, acid strengths in the solvents were determined through
conductivity, and the transfer enthalpy of the acidic catalyst proton (H+) from
water to the solvents was measured using solution calorimetry. These aprotic
solvents can be applied in the conversion of biomass-derived intermediates to
fuel or chemicals, a topic of interest in providing clean energy for the future.

Acetonitrile (MeCN)

-valerolactone (GVL)

Dimethyl Sulfoxide (DMSO)

Conductivity for Determining Acid Strength in Solvents

H+

HMF

Fructose

Table 1. Rate Constants for the Dehydration of Fructose

Solvent

Acid

k ([M]-1 ks-1)

Water
90% GVL
90% GVL
90% GVL
90% Dioxane
90% Dioxane
80% MeCN
80% MeCN
90% DMSO
90% DMSO

200mM HCl
5mM Sulfuric
5mM Triflic
5mM HCl
5mM Sulfuric
5mM HCl
5mM Sulfuric
5mM HCl
5mM Sulfuric
5mM HCl

0.140 0.008
20.5 1.3
22.0 3.6
61.8 4.9
10.2 1.6
94.7 5.4
5.88 0.92
10.9 1.6
20.5 1.0
23.2 3.5

Solution Calorimetry

= [0 0 , , ,

1/2
=
1 + 1/2

Figure 2. TAM III

Solution Calorimeter
used for measuring
the transfer enthalpy
of the acid proton
(H+) from water to
90% GVL.

2 2
=
1

= log( )

Table 2. pKa of acids in 90% solvents compared to pKa in water

Solvent-H2O

H2O

MeCN

GVL

DMSO

Weight %
Mole %
Acid
Trifluoroacetic acid
Hydrochloric Acid
Methanesulfonic Acid
Triflic Acid

100
100

90
80

90
62

90
67

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pKa
3.00
2.42
2.31
0.97

2.98
1.80
1.81
0.22

2.28
1.03
0.91
<0

H2SO4
MeSA
TFA

-100
-90
-80
-70
-60
-50
-40
-30
-20
-10
0

Hsol (kJ/mol)

Figure 1. Molar conductivity was measured through diluting a solution of

trifluoroacetic acid in 90% GVL. The curve is fit to the Pitts conductivity
equation and used to calculate a pKa of 2.98.

0.23
-7
-1.92
-12

rate = k Fructose [HBo

-3 H2O

0.2

0.4

0.6

0.8

Mole fraction GVL

Figure 3. Enthalpy of Solvation for Acid Protons in GVL-water solutions

References

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J. M. R. Gallo, D. M. Alonso, M. A. Mellmer, J. A. Dumesic, Green Chem., 2013, 15, 85-90.
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Manov, G. G. et al., S. F., J. Am. Chem. Soc. 65, 17651767 (1943).
Pitts, E., Proc. R. Soc. Lond. A Math. Phys. Sci. 217, 4370 (1953).
Rosenfarb, J. & Caruso, J. A., J. Solution Chem. 5, 355361 (1976).