E. T. Contis et al.

(Editors)
Food Flavors: Formation, Analysis and Packaging Influences
© 1998 Elsevier Science B.V. All rights reserved 615

Effect of ethanol strength on the release of higher

alcohols and aldehydes in model solutions
H. Escalona-Buendia, J. R. Piggott, J. M. Conner and A. Paterson

Centre for Food Quality, University of Strathclyde, Department of Bioscience

and Biotechnology, 204 George Street, Glasgow G l IXW, Scotland, UK

Abstract
Headspace concentrations of homologous series of higher alcohols and
aldehydes dissolved in aqueous solutions at different ethanol concentrations
were analysed by gas chromatography-flame ionisation detection. For each
volatile, activity coefficients at all ethanol strengths were estimated and
statistically compared to evaluate the effect of ethanol strength. There was a
significant reduction of the activity coefficients between 10% and 20% v/v
ethanol for all the volatiles studied. The reduction of the activity coefficients
between 10% and 15% v/v was significant only for decanol, dodecanol, octanal
and dodecanal. This confirms that there is a change in the efiect of ethanol
concentration on volatile flavour compounds in aqueous solutions at 15-20% v/v
ethanol.

1. INTRODUCTION

Higher alcohols, aldehydes and esters are important volatiles for the aroma
and flavour of wines and spirits. According to studies carried out in wine model
solutions (Voilley et al. 1990, 1991; Lubbers et al. 1994a, 1994b; Langourieux
and Crouzet 1994) and previous studies of whisky flavour (Conner et al. 1994a,
1994b), the release of volatiles is affected by other components in the solution
and, therefore, the flavour quality of the beverage may also be affected.
In model wine solutions the presence of ethanol reduced the activity
coefficients of isoamyl alcohol, octanal and ethyl esters (Lubbers et al. 1994a).
These volatile compounds are more soluble in ethanol than in water and when
they are in alcoholic aqueous solutions, an increase of ethanol concentration also
increases their solubility and, therefore, reduces their release. However, Conner
et al. (1997) reported a significant reduction of the release of ethyl esters from
alcoholic solutions above 17% v/v ethanol, while at lower strengths the activity
coefficients remained almost constant. This behaviour may be explained by
changes in the structure of ethanol-water solutions which are modified by the
616

proportions of the mixture. According to D'Angelo et al. (1994), above about 20%
v/v ethanol concentration there are non-polar interactions between the
hydrocarbon chains of the alcohol molecules, forming agglomerates or
"pseudomicelles", and interaction with other non-polar molecules in the system is
possible.
In order to evaluate the effect of ethanol strength on the release of higher
alcohols and aldehydes, the activity coeflScients of homologous series of both
groups of volatiles (C6, C8, CIO and C12) were measured in aqueous solutions at
different ethanol strengths (10%, 15% and 20% v/v). As the activity coefficient is
estimated as the slope of a linear relation between the activity and the
concentration of the solute, effects on release were evaluated by a statistical
comparison between the slopes.

2. MATERIALS AND METHODS

2.1. Model solutions

Absolute ethanol was used to prepare model solutions at 10%, 15% and 20%
v/v. Water was distilled and filtered using a Millipore-Q system. For each
volatile, stock solutions at 10 mg mL'^ were prepared in absolute ethanol. The
volatiles studied were 1-hexanol, 1-octanol, 1-decanol, 1-dodecanol and the
analogous series of aldehydes, all of them at least 95% pure. For each ethanol
concentration, series of solutions from 1 mg L'^ to 12 mg L^ for every volatile (at
least 6 different concentrations) were prepared adding different aliquots from the
stock to the model solution.

2.2 Activity coefficients determinations

The activities of higher alcohols and aldehydes were obtained by
chromatographic determinations of headspace concentrations (Grant and
Higuchi 1990; Conner et al. 1997) and activity coefficients calculated as
described by Conner et al. (1994a). Glass vials (20 mL), fitted with PTFE fined
silicone septa in plastic screw caps, were filled with 10 mL aliquots of standard
ethanolic solutions of the volatile. After equilibration in a 25 °C water bath for
at least 30 min, a 2.5 mL sample of headspace was withdrawn using a 5 mL gas
tight syringe, preheated to 50 °C. Only one headspace c-;- column injection was
made per vial and samples were analysed in duplicate on a Carlo Erba™ Mega
Series gas chromatograph using a flame ionisation detector. Peak areas were
calculated using Chromperfect™ integration software. Cold, on-column injection
used a 0.55 mm x 0.5 m ultimetal retention gap with an external gas tight
septum. For hexanal, a 0.53 mm x 12 m B P l column (df = 1) was used with
helium carrier gas at 20 kPa, holding the column at 30 °C for 1 min and
increasing to 50 °C at 18 °C min"\ For all the other volatiles, a 0.53 mm x 12 m
BP20 column (df = 1) was used with helium carrier gas at 30 kPa, holding the
column at 60 °C for 1 min and increasing to 240 °C at 18 °C min"\ The
temperature of the detector was 250 °C.
 617

3. RESULTS AND DISCUSSION

Figure 1 shows the behaviour of octanol in aqueous solution at 10%, 15% and
20% v/v of ethanol; this was the typical behaviour of all the alcohols and
aldehydes studied. A linear relation between the activities and the mole fraction
of the volatile in the ethanolic solution is observed, and a gradual reduction of
the slope of the curves, which is the numerical estimation of the activity
coefficient, as the ethanol concentration increased.

O.OOE+00 5.00E-07 l.OOE-06 1.50E-06 2.00E-06

Octanol (mole fraction)

Figure 1. Activities of increasing concentrations of octanol in 10%, 15% and 20%

v/v ethanol aqueous solutions calculated from headspace concentration at 25 °C.

Table 1 shows the activity coefficients obtained for each volatile at every ethanol
concentration. Statistical comparison of the slopes was carried out by calculation
of the 95% confidence interval (Mead and Curnow 1983), considering a difference
to be significant when there was not overlapping of the intervals. For all the
volatiles, activity coefficients were significantly reduced between 10% and 20%
v/v ethanol. This behaviour was expected according to the results reported by
Conner et al. (1997) for ethyl esters, and agreed with the concentration range
reported by D'Angelo et al. (1994) required to start deagglomeration of the
alcohol molecules in ethanol-water solutions. A continuing effect would be
expected at higher ethanol concentrations which are more favourable conditions
for the formation of agglomerates. For the higher alcohols, the higher the
number of carbons the higher is the activity coefficient. Figure 2 shows the
semilogarithmic relation between the activity coefficient and the number of
carbons in the alcohol. For all the alcohols there was a gradual reduction of the
618

activity coefficients as the ethanol concentration increased. However, for hexanol

and octanol the difference between 10% and 15% was not significant (Table 1).

Table 1
Activity coefficients at 25 "C of higher alcohols and aldehydes dissolved in
ethanol/water solutions.
Ethanol strength Activity Standard 9 5 % Confidence R^
(% v/v) coefficient error interval
Hexanol 10 566 29.4 503-629 0.96
15 497 25.0 443-552 0.98
20 393 13.2 364-421 0.99
Octanol 10 3810 113.1 3570-4050 0.99
15 3424 128.2 3138-3709 0.99
20 1926 87.8 1735-2117 0.98
Decanol 10 81746 2372 76578-86914 0.99
15 58990 3737 50765-67215 0.96
20 41221 1657 37667-44775 0.98
Dodecanol 10 844331 67658 695417-993245 0.93
15 544778 47660 436964-652593 0.94
20 270845 24098 218340-323350 0.91
Hexanal 10 1076 87.7 873-1278 0.95
15 827 86.5 628-1027 0.92
20 420 36.5 336-505 0.94
Octanal 10 6360 279.3 5738-6982 0.98
15 3829 210.7 3380-4278 0.96
20 2801 135.9 2489-3104 0.98
Decanal 10 27195 1747 23389-31001 0.98
15 22281 1762 18355-26207 0.97
20 16917 623 15545-18289 0.99
Dodecanal 10 251360 15614 216570-286150 0.96
15 181478 6153 167935-195021 0.99
20 147821 12258 120509-175133 0.94

The relation between the activity coefficients and the number of carbons for
the series of aldehydes studied is observed in Figure 3. There is the same
semilogaritmic relation and similar behaviour in comparison to the higher
alcohols. Activity coefficients for Hexanal and Decanal at 10% and 15% were not
significantly different, and only Dodecanal, which is the less polar compound,
had a significant difference between 10% and 15%, but no difference between
15% and 20%.
The gradual reduction of the activity coefficients of the volatiles studied while
ethanol concentration increases may be attributed to the increase of the
 619

solubility of non-polar compounds by the presence of ethanol in the aqueous

solution. The longer hydrocarbon chains of decanol, dodecanol, decanal and
dodecanal may be more susceptible to hydrophobic interactions explaining the
reduction of their volatility from 10% ethanol, which for hexanal, hexanol and
octanol was from 15%.

8 10 12
Number of carbons in alcohol

Figure 2. Activity coefficients of alcohols in aqueous solution at 10%, 15% and

20% v/v ethanol.

-^10%
-^15%
i 5 -i-20%
0)
o
o
^ 4
•r-H

1 3[
bo ,
o

8 10 12
Number of carbons in aldehyde

Figure 3. Activity coefficients of aldehydes in aqueous solution at 10%, 15% and

20% v/v ethanol.
620

4. CONCLUSIONS

There was a reduction in the activity coefficients of all the higher alcohols and
aldehydes studied when mixed in progressively higher ethanol concentrations.
Activity coefficients of all volatiles were significantly reduced between 10% and
20% v/v ethanol; for hexanol, octanol and hexanal there was a significant
reduction between 15% and 20% v/v. Thus not only the composition of the
volatiles but also their interactions with the matrix must be taken into account
to understand the aromatic properties of such alcoholic beverages.

5. REFERENCES

Conner, J.M., Paterson, A. and Piggott, J.R. (1994a). J. Sci. Food Agric. 66, 45-
53.
Conner, J.M., Paterson, A. and Piggott, J.R. (1994b). J. Agric. Food Chem. 42,
2231-2234.
Conner, J.M., Birkmyre, L., Paterson, A. and Piggott, J.R. (1997). Headspace
concentrations of ethyl esters at different alcoholic strengths. J. Sci. Food Agric.
In press.
D'Angelo, M., Onori, G. and Santucci, A. (1994). J. Chem. Phys. 100, 3107-3113.
Langourieux, S. and Crouzet, J. (1994). Lebensmittel-Wiss. u Technol. 27, 544-
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Grant, D.R. and Higuchi, T. (1990). Solubility Behaviour of Organic Compounds.
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Lubbers, S., Voilley, A., Charpentier, C. and Feuillat, M. (1994a). Am. J. Enol.
Vitic. 45, 29-33
Lubbers, S., Voilley, A., Feuillat, M. and Charpentier, C. (1994b). Lebensmittel-
Wiss. u Technol. 27, 108-114.
Mead, R. and Curnow R. (1983). Statistical Methods in Agriculture and
Experimental Biology. Chapman and Hall, London UK.
Voilley A., Lamer C , Dubois P. and Feuillat M. (1990). J. Agric. Food Chem. 38,
248-251.
Voilley A., Beghin V., Charpentier C. and Pe3n:*on D. (1991). Lebensmittel-Wiss. u
Technol. 24, 469-472.

Acknowledgements
The authors wish to acknowledge the UK Biotechnology and Biological
Sciences Research Council and CONACyT-Mexico (Consejo Nacional de Ciencia y
Tecnologia) for the financial support provided.