FLAVOUR AND FRAGRANCE JOURNAL, VOL.

2,103-107 (1987)

Infinite Dilution Activity Coefficients and Relative Volatilities of

some Aroma Compounds
A. Sadafian and J. Crouzet
Centre de Genie el Technologie Alimentaires, UniversitP des Sciences el Techniques du Languedoc, 340M)-Montpellier CPdex

Infinite dilution activity coefficients of aroma compounds: acetaldehyde, octanal, octan-Zone, limonene, linalol,
terpenyl acetate and p-ionone were determined using the dynamic exponential method.
The values obtained for two of these compounds (acetaldehyde and octanal) agree with those previously
calculated from equilibrium data.
The high values obtained for terpenic compounds are indicative of the hydrophobic interactions between the
hydrocarbon skeleton and water. Relative volatilities of these compounds show that limonene is the more volatile,
because of its low vapour pressure, b-ionone presents a relative volatility of the same order of magnitude as that of
terpenyl acetate. Presence of a hydroxyl group on the terpene skeleton leads to a considerable decrease of activity
coefficient and relative volatility.
KEY WORDS Infinite dilution activity coefficients Relative volatilities Acetaldehyde Octanal Octan-2-
one Limonene Linalol Terpenyl acetate 0-Ionone

INTRODUCTION From this equation it appears that the volatility

of a compound is a function of its vapour pressure
During the last twenty years the development of but also of y? which is related to its ability to
analytical tools has led to an important increase of escape from the solution. In these conditions the
knowledge in the field of identification and compounds which are least soluble and possess a
quantification of volatile compounds present in high vapour pressure will be present in greater
food products and essential oils.' Among the concentration in the head space than those more
different methods used for aroma components soluble and possessing a low vapour pressure.
study, headspace analysis, related to the vapour Aroma recovery by steam stripping, aroma
pressure of volatile compounds present in the gas retention during food processing, and more
phase in static or dynamic equilibrium with the generally, transfer phenomena in food systems
product, has been largely used.' This method have also been studied.'-6
provides information on volatiles present in the The aroma retention during evaporation at
air phase at equilibrium with the food; these equilibrium or an steady state is dependent on t h e
volatiles are sniffed when the food approaches the value of aiw.'
nose or reaches the olfactory receptors by the So it is imperative that the activity coefficients
retronasal route when the food is in the mouth. of volatile compounds in very dilute aqueous
The vapour pressure Pi of a compound i present solution are known in order to interpret results
in the food (analogous to an infinitely dilute water concerning head space analysis and aroma reten-
solution) is given by Henry's law: tion. Unfortunately, although activity coefficients
p 1. = ym
1
x .
1P: have been determined for numerous compounds
of interest in the chemical and more particularly
where y,? is the infinite dilution activity coeffi- in the petrochemical industry, the data concern-
cient, xi is the molar fraction of i in the solution, ing aroma compounds are scarce.6 The com-
and p : is the vapour pressure of the pure pounds which have been studied are generally
compound i. representative of homologous chemical series:
The relative volatility of a compound i, hydrocarbons, aldehydes, ketones, alcohols or
compared to water. a , is defined by
: esters and, in most cases, irrelevant to typical
m Yi" P3 aroma compounds.
OLjw = -
Different methods are used for infinite dilution
activity coefficient determination, in some of
with p;, vapour pressure of the pure water them this value is calculated from vapour - liquid
0882-5734/87/03010~5$05.00 Received 6 November 1986
@ 1987 by John Wiley & Sons, Ltd. Accepted 29 Ju1.v I987
I04 A. SADAFIAN AND J. CROUZET
equil'ibrium data using different thermodynamic
models.'-"' According to Voiley and Loncin,' I
the activity coefficient of compounds sparingly
soluble in water is approximately equal to the
reverse of its water solubility expressed as a mole
fraction, and may be determined in this way. A
dynamic method based on the variation of vapour
phase composition with time when volatile
compounds are stripped from a highly diluted
solution by a constant flow of inert gas has
recently been developed and used to determine
activity coefficients at infinite dilution of linear
and branched alkanes. "-I4
In the present work, this method was used in
order to determine the value of infinite dilution
activity coefficients (yp") in water of some
compounds with characteristic aroma
properties:" octan-2-one, Iimonene, linaiol, ter-
penyl acetate, p-ionone. These compounds are
also used in aroma retention studies during
cooking-extrusion experiments. I" Two com-
pounds previously studied by other methods."
acetaldehyde and octanol. were also included in
this study.
EXPERIMENTAL
Acetaldehyde, octanal, octan-2-one, linalol and
limonene were obtained from FLUKA, p-ionone
from EGA and terpenyl acetate was a gift from
Givaudan.
r---i
1y
D
Fig. I . Experimental equipment used for the determination of infinite dilution activity coefficient. Re, flow rcgulator: E , and E,.
heat exchangers; C. diffusion cell; P. solid C 0 2 trap; D. flowmeter; GC, gas chromatograph; TB. thermostated hath: 0 .oven
The experimental device used was similar to
the equi ment described by Leroi et al." and
Duhem' Pand is given in Figure 1. The stripping
gas, nitrogen. and the all glass equilibrium cell,
were maintained at 25 k 0.1"C. The stripping gas
was dispersed into small diameter bubbles
through a glass frit disk (No. 4). The gas flow
rate, between 30 and 100 ml per minute according
to the nature of the volatile compound under
study, was measured with a flowmeter and
corrected for water saturation and temnerature.
According to
P:, - P k (Tf) x - T
Dcorrcctcd = Drncssurcd
P Tf
where Pi, is the atmospheric pressure, P, (Tf) is
the water vapour pressure at the temperature of
the flowmeter (Tf), P is the pressure in the cell,
and T(K) is the temperature of the cell.
Pressure in the equilibrium cell was calculated
from atmospheric valce and head loss in the
apparatus.
The gas leaving the equilibrium cell was
periodically sampled through a gas sampling
valve, maintained at 150 k 3°C in order to avoid
the condensation of the solute and injected into a
gas chromatograph.
A VARIAN 940 gas chromatograph equipped
with FID detector and a stainless steel column
(3 m x 3.17 mm i.d.). packed with 1.S% Carbo-
wax 20M on Chromosorb W DMCS 60-80 mesh
operated at 100 or 15OoC,according to the nature
0
p$t N2
TB
,
 RELATIVE VOLATILITIES OF AROMA COMPOUNDS 105

of the volatile compound studied, was used. A , calculated from the values of the slope of the
ym
Shimadzu C-R3A data processor was used for straight line obtained by plotting log S against
area determination. time (Figure 2) and constant K where
Solvent-twice distilled water-and solute
were introduced into the equilibrium cell through K = -D- p;
a septum using a syringe, the quantities used were RT N
determined by weighing. Stirring of the solution
by a magnetic stirrer and by gas bubbling lead to
equilibrium within one to five minutes. When RESULTS AND DISCUSSION
equilibrium was reached, injections were oper-
ated at regular intervals of time. As a first step, the influence of stripping gas flow
The varation of the concentration of the solute rate on the activity coefficient of acetaldehyde
in gas phase with time follows an exponential law: and octanal previously determined by equilibrium
D ;'l determinations,h was undertaken (Table 1).
log S = log so + --y,? t In the range of flow rate studied, the values
RT N obtained for the activity coefficient at infinite
where S = GLC peak area, Sl, = GLC area dilution are constant and agree with those
extrapolated to zero time, D = carrier gas flow reported by Bomben et al.,6 respectively 4.2 and
rate (ml min-I), N = moles of solvent, R = gas 17 OOO.
constant (ml atm. g mdl-' K-' ), T = temperature According to these results, stripping gas flows
(K), pr = vapour pressure of pure solute (atm.), ranging from 30 to 100 ml min-' were explored to
y,? = infinite dilution activity coefficient, and t = determine for each compound studied in the
time (min). present work, the value of flow rate allowing an

Fig. 2. Determination of infinite dilution activity coefficient of a volatile compound (terpenyl acetate) plotting log S (GLC peak
area) versus time of gas stripping
 A. SADAFIAN AND J. CROUZET

K
E
P
bl

.
u

u
L
0
0
u

0
-

10
I I0 30 (0 50
time i n minutes
60 70

Fig. 3. Determination of infinite dilution activity coefficient of terpenyl acetate: exponential decrease of the volatile compound
area as a function of time under gas stripping (43 ml min-'). 2pl of terpenyl acetate were added to 30ml of twice-distilled water

The quantity of volatile compound placed in

Table I . Influence of stripping gas flow rate on the value of
*

activity coefficient at infinite dilution of acetaldehyde and

the equilibrium cell in order to obtain an
octanal in pure water at 25°C
exponential response (Figure 3) was obtained
Volatile compounds Flow rate Activity coefficient. through preliminary studies. 2 yI were used
(ml/min) :Y except for (3-ionone (0.25 yl). The results
~ ~~~~

obtained for the infinite dilution activity coeffi-

49 4 I6 cients of the aroma compounds studied are
Acetaldehyde 80 4.20
100 4.15
reported in Table 2. Relative volatilities of these
35 17 176 compounds compared to water, are also included
Octanal 43 16 946 in this table.
54 17 205 The activity coefficient obtained for octan-2-
one is twice that calculated by Bomben el al.'The
difference between these values is due to the
accurate determination of peak area of the solute, value of the vapour pressured: 2.5 X lo-' atm. in
the equilibrium conditions being satisfied. The the work of Bomben efal. and 1.38 X lo-' atrn. in
corrected values used were 64, 31, 75, 43 and this work." It must be emphasized that vapour
66 ml min-l for octan-2-one. limonene, linalol, pressure measurements for aroma compounds
terpenyl acetate and p-ionone respectively. have been neglected. so that available data are

Table 2. Activity coefficients and rclativc volatility to water at infinite dilution at 25°C o f some iiromil compound5

Aroma Boiling Vapour Activity Re la t ivc

compounds point ("C) pressure (atm.) coefficient. vol a t i I i t y . a TU

Acetaldehyde 20.x" I .2 4.17 ? 0.05 160

Octanal 17 I" 2.2 x to ' 17.10 x 10' k IOU 1 I90
Octan-2-one 172.')" 1.38 x lo-' 13.IX x t o 7 * xo 570
Limonene 177" 2.5 x l o - ' 77.7 X 10' 5 1X)O 6150
Linalol 19%' 5,s x *
24.95 x 1 0 ' 280 435
Tcrpcnyl
acetate 10s" 1.67 x l o - " 4 I . 16 x 10" * 5500 2 I xo
p-lonone 128.9' 7.24 t310 d 1.21 x 1 0 " f 9 0 ( ~ ) 2775

"Normal presure.
'Under 1 I mm Hg.
'Under lOmm Hg.
"The value of vapour pressure o f a-ionone was used.
 RELATIVE VOLATILITIES O F AROMA COMPOUNDS
very scarce. The activity coefficient at infinite
dilution obtained for @-ionone-1.21 x 10'-is
considerable. This fact implies that hydrophobic
interactions between the hydrocarbon skeleton
and water are greater than polar interactions at
carbonyl group. However, according to the low
value for the vapour pressure of this compound,
the relative volatility of @-iononeis of the same
order of magnitude as that of terpenyl acetate.
Under these conditions, the most volatile of the
aroma compounds studied in the present work is
limonene according to its hydrophobicity and its
relatively high vapour pressure.
The presence of a hydroxyl group in the
monoterpene skeleton leads to a considerable
decrease in the activity coefficient for linalol. The
value obtained for this compound is only one-
third of that found for limonene; moreover its low
vapour pressure gives a weak volatility for linalol.
In food systems the volatility of aroma com-
pounds is dependent on the presence of non-
volatile components such as sugars, salts, fats and
macromolecular compounds. The influence of
constituents, such as starch, dextrin, p-
cyclodextrin and proteins, on infinite dilution
activity coefficient of aroma compounds is at
present being studied.
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