FLAVOUR AND FRAGRANCE JOURNAL

Flavour Fragr. J. 2001; 16: 370–373

DOI: 10.1002/ffj.1015

The essential oil co-distillation by superheated vapour of

organic solvents from aromatic plants
Josip MastelićŁ

Department of Organic Chemistry, Faculty of Chemical Technology, N. Tesle 10/V. 21000 Split, Croatia

Received 20 October 2000

Revised 27 March 2001
Accepted 2 April 2001

ABSTRACT: A method of essential oil co-distillation by superheated vapour of solvents was developed and the
apparatus was presented. As suitable solvents, pentane and ether (inert solvent with low boiling point) were used.
The method was tested on sage, Salvia officinalis L., as an aromatic plant. The essential oil of this plant was also
isolated by hydrodistillation as a standard method. The isolated volatiles obtained by two methods were analysed
using gas chromatography (GC) and gas chromatography–mass spectrometry (GC–MS). The obtained results
were compared. This method of distillation enables safe isolation of monoterpene and sesquiterpene compounds,
as well as hydrodistillation. Copyright  2001 John Wiley & Sons, Ltd.

KEY WORDS: essential oil; isolation method; superheated vapour solvent co-distillation; aromatic plant

Introduction and Nickerson,5,6 including some modifications of this

In order to study the chemical basis of essential oil and
plant volatiles, it is first necessary to isolate the volatiles
from complexes of non-volatile plant material. Distil-
lation, extraction, adsorption and other procedures are
commonly used for the isolation and concentration of
plant volatiles. In general, different types of distillations
are the most widely used procedures for the isolation of
essential oil from aromatic plants.1 Hydrodistillation at
atmospheric pressure is the most frequently used method
of distillation. The advantage over other isolation meth-
ods, e.g. extraction, is that isolates by distillation do not
include non-volatile compounds that may interfere with
chromatographic analysis. The main disadvantage is the
formation of artifacts, thermal degradation reactions and
hydrolysis, especially for aromatic plants which con-
tain unstable compounds, e.g. linalyl acetate.2 Extraction
of plant volatiles with solvents (such as pentane, ether
and dichloromethane) is used to isolate them directly
from the plant material or to separate them from dilute
aqueous solutions obtained by hydrodistillation.3,4 The
partial loss of separated volatiles during removal of
the excess solvent and contamination with non-volatile
compounds from the sample, but also from solvents,
are the main disadvantages of this method. Simulta-
neous distillation–extraction, first reported by Likens
*Correspondence to: J. Mastelić, Department of Organic Chemistry,
Faculty of Chemical Technology, N. Tesle 10/V. 21000 Split, Croatia.
method, has many advantages,7,8 for example, only small
amounts of solvents are necessary, thus minimizing
the danger of contamination, and thermal degradation
can be diminished using reduced pressure.9 S.A. Rez-
zoug et al.10 have developed controlled instantaneous
decompression as a new method of isolation of essen-
tial oil from rosemary leaves. Schultz and Randall11
reported that liquid carbon dioxide was a good solvent
with a low boiling point and high selectivity, partic-
ulary towards alcohols, aldehydes, ketones and esters
(subcritical CO2 -extraction). On other hand, supercrit-
ical gases (high-density fluids), such as carbon diox-
ide, ethylene and some fluorocarbons, have also been
used to extract many compounds. Up to now, many
herbs and spices have been extracted by supercritical
CO2 .12 – 15 Supercritical CO2 shows a high affinity not
only towards essential oil components but also towards
many other classes of non-volatile compounds, such
as waxes, fatty acids, colouring matters and resins.16,17
Indeed, supercritical carbon dioxide offers unusual pos-
sibilities for selective extractions due to control via sol-
ubility manipulation of its pressure and temperature.18,19
Co-distillation by superheated vapour of organic solvents
was developed as an interesting alternative standard tech-
nique for essential oils isolation. The aim of this paper
was to show some advantages of this isolation method,
which can diminish reactions of artifactual generation
and obtain isolates which do not contain non-volatile
compounds.

Copyright  2001 John Wiley & Sons, Ltd.

 ESSENTIAL OIL CO-DISTILLATION BY SUPERHEATED VAPOUR OF SOLVENTS 371

Experimental F

Plant Material
water out
Sage, Salvia officinalis L., was harvested in July 1999 steam in
and dried at room temperature in a shaded place. The
leaves and apical stalks were used for investigation. plant material

Isolation of Essential Oil by Hydrodistillation D glass wool

The essential oil was isolated from 100 g of plant mate-

rial by hydrodistillation in a modified Clevenger-type
apparatus for 3 hours.20 The essential oil obtained was
dried over anhydrous sodium sulphate. C
water in

Apparatus for Essential Oil Isolation by

Superheated Vapour of Solvents water out

The apparatus consists of a pear-shaped Claisen flask steam out

(A) (50 ml, with two necks, NS 14/23), Vigreux column)
(B) heater (C) (steam heated condenser), Liebig’s con-
densers (D) and (E) (with elongated central tube) and
tape with glass tube (F) (Figure 1.) On the right-hand
neck of the Claisen flask there are a Vigreux column (B) E
and a heater (C) (Liebig’s condenser, with internal diam- B
eter of 8 mm and length 350 mm). Into this heater, glass
water in
wool and ground plant material (approximately 1 g) were
inserted. On the left-hand neck, a condenser (E) with an
elongated central tube was added. The end of the tube
reaches to 2–3 mm from the bottom. The other con-
denser, (D) which has an internal diameter of 8 mm, is
added onto condenser (E). The heater (C) is plugged
and connected with the left-hand condenser by a glass
tube (outer diameter 6 mm). The outer diameter of the A
tube is less than the internal bore diameter of the con-
denser and its length must be approximately 200 mm
inside the condenser (D). The flask (A) with 10 ml sol-
vent is heated in a water bath. During the boiling the
vapour passes through a Vigreux column and heater. At
the same time, water steam heats the heater. The plant Figure 1. Apparatus for essential oil isolation by super-
heated vapour of organic solvents from aromatic plants
material and solvent vapour are heated up to 100 ° C.
Superheated vapour carries out volatile compounds from
plant material. The vapour is cooled down in condenser and flow rate are approximately constant during the iso-
(D), the condensate drops (approximately one drop per lation process. For isolation of essential oils by this
5 s) into condenser (E). The thermal insulation (thread method, pentane and ether are selected as suitable sol-
of asbestos or cotton) of the upper part of the heater) (C) vents. They are inert solvents with low boiling points
and outside part of tube (F) was eliminated by reflux of (b.p. 34–36 ° C). Essential oil was isolated from 1 g of
ground plant material for 3 h with 10 ml of solvent.
essential oil. This apparatus ensures continuous circu-
After isolation, the solution obtained was analysed by
lation of superheated vapour through the plant material
GC and GC–MS.
and the concentration of volatile compounds in a small
volume of solvent. Superheated vapour acts as a carrier
gas and liquid solvent acts as a trapping agent. Its clear Gas Chromatography
that by increasing the temperature and flow rate of super-
heated vapour through the sample we can accelerate the Gas chromatography (GC) analysis was performed
isolation of volatile compounds. In this case, temperature on a Hewlett-Packard Model 5890 Series II gas

Copyright  2001 John Wiley & Sons, Ltd. Flavour Fragr. J. 2001; 16: 370–373
372 J. MASTELIĆ

chromatograph equipped with flame ionization detector Table 1. Yields and composition of essential oil of Salvia
and capillary column (HP-101, 50 m ð 0.32 mm, officinalis isolated by different methodsa
coating thickness 0.3 µm). Chromatographic conditions A B C
were as follows: helium as carrier gas at 1.1 ml/min; X  X  X 
injector and detector temperatures, 250 ° C and 300 ° C, Peak No. Compound (%) (%) (%)
respectively; column temperature was held at 70 ° C for 1. ˛-Pinene 6.5 0.06 7.0 0.07 6.1 0.03
4 min, programmed at 3 ° C/ min to 200 ° C and held there 2. Camphene 10.2 0.09 10.3 0.08 9.1 0.07
for 15 min; volume injected, 1 µl; split ratio, 1 : 50. 3. ˇ-Pinene 2.5 0.03 1.8 0.01 2.9 0.01
4. Myrcene 1.7 0.02 1.2 0.01 0.8 0.01
5. 1,8-Cineol 14.6 0.10 14.1 0.09 14.6 0.08
6. -Terpinene 0.3 0.01 0.2 0.01 0.2 0.01
Gas Chromatography–Mass Spectrometry 7. p-Cymene 0.3 0.01 0.1 0.01 0.3 0.01
8. ˛-Thujone 19.2 0.13 18.0 0.09 18.9 0.11
9. ˇ-Thujone 4.3 0.03 4.4 0.03 3.9 0.02
Analysis was performed by a GC–MS Hewlett- 10. Camphor 22.5 0.15 21.0 0.12 20.6 0.12
Packard/Model 5890, with a mass selective detector 11. Linalool 0.5 0.02 0.5 0.01 0.5 0.01
12. Bornyl acetate 1.0 0.03 1.1 0.02 1.1 0.01
Model 5971A, using a column HP-20M (50 m ð 13. Terpinen-4-ol 0.5 0.01 0.4 0.01 0.3 0.01
0.2 mm i.d., film thickness 0.2 µm). GC operating 14. ˇ-Caryophyllene 0.5 0.01 0.9 0.02 1.3 0.02
conditions: the column temperature was held at 70 ° C for 15. ˛-Terpineol 0.2 0.01 0.1 0.01 0.1 0.01
16. ˛-Humulene 2.8 0.04 3.9 0.02 3.8 0.02
4 min, programmed at 4 ° C/ min to 180 ° C and held there 17. Borneol 2.6 0.02 2.5 0.01 2.1 0.01
for 10 min, carrier gas, helium; flow rate, 1 ml/min; 18. Leden 0.2 0.01 0.6 0.01 0.5 0.01
injector temperature, 250 ° C; volume injected, 1 µl; split 19. Myrtenol 0.2 0.01 0.2 0.01 0.2 0.01
20. Elemol 3.6 0.03 3.7 0.02 4.5 0.02
ratio, 1 : 50. MS conditions: ionization voltage, 70 eV; 21. Veridiflorol 3.0 0.03 3.6 0.02 3.1 0.02
ion source temperature, 280 ° C; mass range, 30–300 22. Manool 0.6 0.02 0.8 0.02 0.8 0.02
mass units. Yield(% w/w) 1.42 0.02 1.39 0.01 1.40 0.01
a Methods used: A, hydrodistillation; B, isolation by superheated vapour of

pentane; C, isolation by superheated vapour of ether.

Qualitative Analyses X, mean value (average values of percentages obtained by three replications);
, standard deviation.

Individual peaks were identified by comparison of their

retention indices with those of authentic samples, as well
as by comparison of their mass spectra with those stored
in the data base (Wiley library) and library data.21
Quantitative Analyses
Determination of the percentage composition was based
on peak area normalization without using correction
factors. The yields of essential oil were determinated
by two methods: by weighing after hydrodistillation, or
after careful removal of solvents for the other isolation
method for co-distillation also with internal standard, as
described previously.2,22 A good correlation was used
among the two applied methods for determination of
yields after co-distillation. All yields were calculated as
the mean values of upper methods, with respect to the
mass of starting dried plant material.
Results and Discussion
The presented apparatus is relatively simple. Isolation
and concentration of volatile compounds are performed
by a single stage. The obtained solution of volatile com-
pounds was directly analysed by GC and GC–MS. The
yields of essential oil, depending on methods of isola-
tion and chemical composition, are shown in Table 1.
The yield of essential oil obtained by hydrodistillation
was 1.42 š 0.02%, respectively, for distillation by super-
heated vapour, 1.39 š 0.01% for pentane and 1.40 š
0.01% for ether. Twenty-two identical compounds were
identified in essential oil and pentane or ether solutions.
The main components were camphor, ˛-thujone, 1,8-
cineol and camphene (monoterpene compounds). The
main sesquiterpene compounds were humulene, elemol,
veridiflorol, ˇ-caryophyllene and manool. Generally,
sesquiterpene compounds have higher boiling point than
monoterpene compounds. The highest boiling points are
found in oxygenated sesquiterpene derivates, such as
elemol, veridiflorol and manool. All these compounds
were identified with approximately same percentages,
irrespective of the isolation method. There was only
a small difference in the content of some compounds.
Finally, the presented apparatus for isolation of essen-
tial oils with superheated vapour of low boiling solvents
ensures isolation of monoterpene and sesquiterpene com-
pounds, as well as hydrodistillation. Co-distillation can
be performed with small quantities of solvents and aro-
matic plants. The isolates do not include non-volatile
compounds, unlike isolates obtained by supercritical
fluid extraction or solvent extraction. The obtained solu-
tion of volatile compounds contains a small amount of
water (only the residual water from 1 g air-dried plant
material) unlike hydrodistillation methods. The water
is a polar solvent, which accelerates many reactions,

Copyright  2001 John Wiley & Sons, Ltd. Flavour Fragr. J. 2001; 16: 370–373
 ESSENTIAL OIL CO-DISTILLATION BY SUPERHEATED VAPOUR OF SOLVENTS
especially reactions via carbocation as intermediate.
Furthermore, the presented method of co-distillation can
diminish reactions of artifactual generation, compared to
hydrodistillation.
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