Factory: Processing

CHEMISTRY OF SALT-CATALYZEDDEGRADATION OF SUCROSE

IN CONCENTRATED AQUEOUS SOLUTIONS

G. Egglestonl, J.R. Vercellotti', L.A. Edye2 & M.A. Clarke2

Southern Regional Research Center, USDA-ARS,
1100 Robert E. Lee Blvd., New Orleans, LA 70179
Sugar Processing Research Institute, Inc.,
New Orleans, LA 70124

ABSTRACT
Effects of salts on d e m o n of highly pure sucrose in concentrated aqueous solutions (-65" brix) at 100°C were
investigated. Polarimetry and ion chromatography with pulsed amperometric detection (IC-PAD) were used,to
qua&fy degrada4on. Pseudo-first order initial degradation rates, measured by IC-PAD, were generally higher than
polarhetry rates due to trace secondary products, which have a positive optical rotation. Na+, Mg2+and Ca2+-water
structure enhancers-slightly increased initial degradation; the latter two ions increased subsequent accelerated
d e m o n . Highly charged cations (e.g., A13+)increased sucrose degradation through polarited hydrated ionslacidic
pH effects. Large cations (e.g., K' reducing water structure) increased degradation. Solutes with hydrophobic and
non-ionic character, net water structure enhancers (e.g., ethyl alcohol) markedly stabilize sucrose. In comparison,
water structure breakers (e.g., urea) increased degradation although under alkaline conditions, pH effects were more
critical than water structure effects. Other possible mechanisms of salt-catalyzed degradation of sucrose are discussed.
Keywords: Sugarcane, sucrose degradation, water structure, ion chromatography, polarimetry, salt catalysis.
INTRODUCTION
Chemical losses of sugar result when sucrose in highly concentrated solution degrades under heat and other stresses
in the factory and refinery. Impurities such as salts are known to increase the thermal degradation rate of sucrose
under processing conditions although literature sources conflict on the extent of this (Clarke et a1 1977, Kelly & Brown
1978, Parker 1969 & Richards 1988), and the mechanism of action has still to be ascertained.
An advanced understanding of the mechanism of thermal degradation of sucrose in the presence of salts would be
to c l a m the role of water structure. We recently (Eggleston et a1 1995a & b) described the effects of simple salts
and solutes on water structure, which are largely determined by specific attractive forces between the solute and
neighboring water molecules (Dobbins 1973, Fennema 1976). Three distinct classes have been postulated:
Small or highly charged ions; e.g., Mg2+, Na+, which attract water through strong iondipole forces, resulting in
high local water structure around the solute ion.
Larger, monovalent ions; e.g., K+ and Rb', which have relatively weaker attractive forces to the surrounding
.
.
water, which leads to reduced water structure.
* Large ions or solutes with considerable organic, hydrophobic character; e.g., alcohols, which repulse water, but
this results in a tightening of the water structure around the solute; i.e., water structure is enhanced. The degree
of water structure around the hydrated sucrose molecule would be expected to affect the mobility and activity of
protonated water and therefore affect the initial first protonation step of sucrose degradation.
This study uses model sucrose-salt systems to determine the initial degradation rates of concentrated solutions of
sucrose (-65" brix) at 100"C, using no buffers to eliminate interfering ion effects and to assess the contribution of
natural pH changes.
MATERIALS AND METHODS
Materials. Sucrose, salts and solutes were all analytical grade.
Sucrose-salt model systems. See Eggleston et al (1995a).
Polarimetry. Optical rotation (OR or pol) measurements of diluted samples were recorded at 589 nm, in a 10-cm
cell, on an Optical Activity Limited AAlO (ISS) Polarimeter at room temperature. Results are expressed as
specific rotations [=I = = I C.L, where a = measured rotation, C = concn of sugar (gI100 ml of solution),
L =cell length (dm).
 G. Eggleston, et al

Ion chromatography (IC-PAD). Cadmhydrates (sucrose and degradation products) were separated on a Dionex
CarboPac PA-1 analytical anion exchange cohunn, at flow rate 1.0 ml/min at -25°C. See Eggleston et a1 (1995a)
for column and integrated pulsed amperometric detector conditions and quantitative analyses.
RESULTS AND DISCUSSION
Very little sucrose degradation was observed in the model system containing only BakerTManalytical sucrose
(control) over the first 4 h (-3.8%), with subsequent accelerated degradation from 4-6 h (Fig. 1). The initial lag
phase is slow but finite. The first step in acid degradation of sucrose is protonation of the glycosidic oxygen Wchards
1988) to form a Sucrose oxonium ion, which undergoes a scission reaction to produce a fructose carbocation and
glucose. The carbocation is lost by several reaction channels (Richards 1988) including nonspecific degradation to
a range of secondary products including organic acids and 5-hydroxymethylfurfural (a color precursor). The initial
trace amounts of organic acid secondary products formed (i.e., levulinic acid) induce accelerated degradation (Fig.
1) by further protonation of sucrose (Richards 1988). The ensuing organic acid formation is responsible for inducing
the pH drop during accelerated degradation reaction time (in this example pH dropped from 6.46 to 5.13 in 6 h).
Salt catalysis experiments were considered in relation to their effect on water structure around the sucrose. The
first class of salts studied was small or highly charged cations, which attract water and enhance overall water structure;
e.g., Li+, Na+, M%+, c&+ a n d ~ f .+ LiCl sigmf'icantly increased the degradation of sucrose (Fig. I), and no lag
phase was apparent. LiCl was expected to enhance water structure and therefore stabilize the sucrose solution.
Howevei the low chargelionic radius ratio of Li+ (1.5) may have limited this effect.
I Salt effects were more striking when pseudo-first order kinetics of initial degradation over the lag phase period,
' as measured by OR (pol) and IC-PAD, were calculated (see Eggleston et a1 1995a & b).
Although IC-PAD is an accurate technique for measuring sucrose degradation because it measures actual
' sucrose, it can be tedious to operate. In com$irison, measurement of sucrose by OR (pol) is more convenient and
is still used by the majority of the sugar industry. It.!svery precise, provided that no other optically active
compounds are present. Nevertheless, we found (Eggleston et al-l99k& b) the rate values measured by OR
(pol) tended to be sigmficantly lower than those calculated from IC-IPAD data (see Fig. I), which suggests that
trace compounds with a high positive rotation were present. The OR (pol) data may therefore have introduced an
absolute error in tbe rate measurements, but the pattern was generally the same for OR (pol) as IC-PAD.

0.4
--m- - - Control ( Y l )
0.2 - A LlCl OR (YI)
+ LICI IC-IPAD (V2)
0 , I I I I I 1 0
0 1 2 3 4 5 0

Reaction time (h)

Figure 1. Effect of LiCl bn sucrose degradation as monitored by OR (pol) and IC-PAD.

 Factory: Processing

10
NaC1, MgC1, and CaCl, shortened the initial lag phase with respect the control, but the extent varied. MgC1,
shortened the initial lag phase from -4 h (as in the control) to -2 h. NaCl and CaCl, shortened the lag phase even
-
further to 1 h and had slightly higher initial rates than MgCl,. Furdemore, accelerated degradation was higher
for the divalent cations. Degradation rate increases in the presence of these neutral salts are difficult to explain with
respect to enhanced water structure. The mechanisms proposed (Richards 1988) for sucrose degradation are
heterolytic, therefore, it may be possible that these salt effects occurred because of increases in dielectric constants
of the sucrose model solutions.
The addition of AlCl, had a remarkably different effect on sucrose degradation. The solution was highly acidic
(initial pH 1.3) and acid d e m o n was extremely rapid; a dark brown, viscous solution formed after 3 h. Hydrated
metal cations-if highly charged and small enough; e.g., A13+(chargelio'nic radius = 6.7)-can act as a Lewis acid
and attract the unshared electron pairs of water molecules. The strength of attraction increases with charge of the ion
-and is strongest for the smallest cations. The resulting polarized water molecules bound to the metal ion are more
acidic than those in the bulk solvent, increasing the tendency to transfer a proton to another electron donor such as
the glycosidic oxygen of sucrose. Overall, this can increase sucrose acid degradation. This phenomenon may also
explain the unexpectedly high accelerated rates of sucrose degradation in the presence of the divalent cations Mg2+
and Ca2+,with chargelionic radii of 3.1 and 2.1, resp., especially as pH reduction was more marked than for the
control (pH 6.25 to 3.54 and 7.29 to 3.5 for MgZ+and Ca2+,resp.).
The second class of salts studied was larger ions (e.g., K+ and Rb'), which act to reduce water structure. Both
-
KC1 and RbCl shortened the initial lag phase to 1 h and slightly increased the initial degradation rate. Reduced
water struclure in the model systems may therefore have increased degradation by destabilizing the sucrose although
I
W e r verification with, e.g., NMR (nuclear magnetic resonance) studies, is required.
I The third class of salts studied was large ions and solutes with hydrophobic character, which enhance water
structure (see Eggleston et al 1995a). Within experimental error, ethyl alcohol did not significantly increase initial
degradation as measured by OR (pol) and IC-IPAD. Moreover, the larger and more hydrophobic tert-butyl alcohol
had a slightly greater stabilizing effect than ethyl alcohol, because the water adjacent to the nonpolar hydrophobic alkyl
groups becomes more structured in an amount proportional to the size of the nonpolar groups (Frank & Wen 1957,
Dobbins 1973).
Water structurelhydrogenbond breakers, guanidine-HC1 and urea were also compared (Eggleston et al 1995a).
Guanidine-HC1markedly increased the acid degradation of sucrose over 6 h; in contrast, urea only increased sucrose
degradation over the first hour when the pH was favorable for acid degradation (Parker 1969). Thermal hydrolysis
of urea produces ammonia; consequently, the solution became alkaline (-pH 8.9) after the first hour, causing
sigmficant alkaline stabilization of the sucrose. Therefore, under acid degradation pH conditions (i.e., < pH 8.3;
Parker 1969), urea increased sucrose d e m o n . As urea is non-ionic, it would not be expected to affect the thermal
s t a b w of sucrose by electrostatic principles; therefore, reduced water structure must have played a role. In W e
conditions, however, pH effects were more critical than water structure effects.
CONCLUSIONS
There is no simple relationship evident to relate salt effect to thermal degradation of concentrated solutions of
sucrose. It is possible that the introduction of a salt could affect the water around the sucrose, not only by altering
the bulk structure of water, but also by displacing water from the sucrose hydration shell (preferential solvation) or
altering the sucrose conformation, which in turn affects sucrose stability. s ore over,salts may affect the stability of
sucrose in a way not related to effects on water structure. Direct salt-sucrose complexation and electrostatic effects
may be involved. Further studies to confirm salt vs pH effects, where the pH is kept constant over reaction time by
using an automatic titrator, are presently in progress.
REF'ERENCES
Clarke, M.A.; Brannan, M.A. & Carpenter, F.G. (1977). A study of sugar inversion loss by high performance
chromatography (HPLC). In Proc. Technical Session on Cane Sugar Refining Res., New Orleans, LA, 1976, pp
46-56.
Dobbins, R.J. (1973). Solute-solvent interactions in polysaccharide systems. In R.L. Whistler & J.N. BeMiller (eds),
Industrial gums, polysaccharides and their derivatives. 2nd ed. Academic Press, New York, pp. 19-25.
G. Eggleston, et a1

Eggleston, G.; Vercellotti, J.R.; Edye, L.A. & Clarke, M.A. (1995a). Behavior of water structure enhancing and
breaking solutes on the degradation of sucrose. J. Carbohyd. Chem. (in press)
Eggleston, G.; Vercellotti, J.R.; Edye, L.A. & Clarke, M.A. (1995b). Effects of salts on the initial thermal
degradation of concentrated aqueous solutions of sucrose. J. Carbohyd. Chem. (in press)
Fennema, 0. (1976). Water and ice. In 0.Fennema (ed), Principles of food science, Part 1 . 0 . F e ~ e m a(ed). M.
Dekker, New York, pp. 13-39.
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Parker, K.J. (1969). Chemical problems in the sucrose industry. Sucr. Belge 89; 119-126.
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processing of sugarbeet and sugarcane, Chapt. 14. Elsevier, Amsterdam, pp 253-264.