Scientific Report Physical Chemistry II

STEAM DISTILLATION OF THE OIL OF ORANGE

Benitez, Jon Karlou; Flandez, Lloyd Earl

Department of Pure and Applied Chemistry, College of Arts and Sciences, Visayas State University, Visca, Baybay
City, Leyte - Philippines

Date of Experiment: March 23, 2018; Date of Report: April 4, 2018; Date Submitted: April 16, 2018

ABSTRACT

Essential oils are mixtures of organic compounds that are dominated by terpenes and terpenoids.
These oils are used in a wide variety of consumer goods (e.g. soaps, cosmetics, pharmaceuticals, food
products and insecticides), and can be extracted (without degrading its constituents) by various
conventional methods like steam distillation and solvent extraction. In this experiment, the oil of orange
was extracted using wet steam distillation process. The yielded oil of orange was colorless and expelled
a lemon-like aroma. The extraction method which were done in conventional and improved steam
distillation (CSD & ISD) process produced a manageable amount of oil in which ISD had almost twice
(1.68 g, 6.72%) the amount of oil generated compared to CSD (0.89 g, 3.56%). This result was
accounted for the additional preheating treatment process in ISD which enhances the oil’s liberation
from the cell walls of the orange rinds. Aside from the qualitative tests done (Iodine test for unsaturation
and pH test for acidity) in this experiment, which resulted positive for both tests, a more definitive test
(e.g. TLC, FTIR HPLC, etc.) should be done to quantify the constituents of the oil of orange produced.

Keywords: conventional steam distillation, improved steam distillation, orange rinds, limonene

INTRODUCTION traditional technologies pertaining to essential

oil processing are of great significance and
Essential oils are used in a wide variety of
are still being used in many parts of the
consumer goods such as detergents, soaps,
world. Such traditional and commonly used
toilet products, cosmetics, pharmaceuticals,
methods are the following: water distillation,
perfumes, confectionery food products, soft
water and steam distillation, steam distillation,
drinks, distilled alcoholic beverages (hard drinks)
cohobation, maceration and enfleurage. But this
and insecticides. The world production and
experiment will focus only on the steam
consumption of essential oils and perfumes
distillation process.
are increasing very fast. Hence, the production
technology is an essential element to improve the Essential oils are mixtures of organic
overall yield and quality of essential oil. The compounds that are dominated by the

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 Steam Distillation of the Oil of Orange 2018

terpenes and the terpenoids (oxygen containing The exact composition of these essential oils
derivatives of the terpenes). Terpenes is determined by the plant variety, the plant parts
themselves are a class of compounds built sampled, the time of year the plant is harvested,
on the five carbon skeletal fragment of and the conditions under which the plant is grown.
isoprene (Figure 1). However, most terpenes Attempting to distil these essential oils directly
are biologically synthesized from Geranyl from the plant material is generally not feasible
pyrophosphate, which contains two isoprene because in general, most of the oils' constituents
units bound together head-to-tail (Figure 2). are high boiling and will decompose under the
high heat needed to bring them to a boil. So, the
most common method used for the processing of
these essential oils is the steam distillation
process.

Figure 1. Chemical structure of Isoprene. Steam distillation is a special type of

separation process for temperature sensitive
materials like natural aromatic compounds. It
involves heating of plant components with water
or steam and collecting the liquid distillate. The
latter consists of an immiscible mixture of water
Figure 2. Chemical structure of Geranyl
and the essential oil. Also, there are two types of
pyrophosphate
steam distillation (SD), the dry and wet SD. In dry
steam SD, the distilling pot is infused with steam
So, the carbon backbones of most terpenes
(Figure 4 - A), which carries the oil’s vapor into
contain a multiple of ten Carbon atoms. For
the distilling head and then into the condenser,
example, limonene (Figure 3), the major
where the Oil and Water co-condense. In wet SD,
constituent of the oil of orange has the formula
the steam is generated in situ in the distilling pot
C10H16.
(Figure 4 - B).

Most complex organic compounds are

immiscible with water, meaning they don’t
dissolve in water but form a mixture instead (oil-
water mixture). When a mixture of two immiscible
liquids, such as water and oil, is heated, each
liquid exerts its own vapor pressure as though the
other component of the mixture is absent. Hence,
the vapor pressure exerted by the system

Figure 3. Chemical structure of Limonene increases as a function of temperature beyond

what it would be if only one of the component was

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 Steam Distillation of the Oil of Orange 2018

Multiplying each term in Equation 2 by the molar

mass (MM, g/mole) of the substance gives the
mass of water in grams that will co-distill with an
essential oil (Equation 3).

n(oil) × MM(oil)
n(H2O) × MM (H2O)

Figure 4. Two types of steam distillation mass of oil (g) Equation 3

=
A – dry SD; B – wet SD mass of water (g)
(https://infohost.nmt.edu).
Poil × MM (oil)
=
PH2O × MM (water)
present. The total vapor pressure (Ptotal) at a given
temperature is therefore equal to the sum of the
vapor pressures of the two immiscible liquids. In this experiment, conventional and

Equation 1 describes the total vapor pressure for improved steam distillation (wet) method will be

a mixture of an essential oil and water. This employed to isolate the essential oil from Orange

allows for evaporation of substances with high rinds. Improved steam distillation (ISD) method is

boiling points at much lower temperatures. just a conventional steam distillation (CSD) with
an additional step prior to the steam distillation
Ptotal = PH2O + POil Equation 1 process which is the pre-heating treatment of the
sample at a temperature of 50°C for about 30
A mixture of two immiscible liquids will boil
minutes (Pauline et al., 2015). The Oil of Orange
normally when their combined vapor pressure is
is an essential oil derived from the rind of oranges
equal to 760 mm Hg (1 atm). The boiling point of
and some other citrus fruits. It is composed of
a mixture of water and essential oil will thus be
Limonene, α and β-Pinene, Myrcene, Octanal,
less than the boiling point of either component
Decanal, δ-3-Carene, and Linalool; with
separately. This is an advantage in the distillation
Limonene comprising over 90% of the Oil derived
of natural products that have high boiling points
from common orange varieties. Further
and would decompose at high temperatures. The
processes in this experiment will involve distilling
amounts of water and essential oil that will co-
a mix of the plant material and water to obtain the
distill during steam distillation can be determined
Oil, extracting the Oil from the Water, and then
using Equation 1 and the ideal gas law. The mole
isolating the Oil from the extraction solvent.
ratio of oil and water in the distillate is equal to
their relative vapor pressures (P) at the boiling Objectives:

point (Equation 2, n = number of moles).

This experiment primarily aims to extract the
n(oil) Poil Poil oil of orange using conventional and improved
= = Equation 2
n(H2O) PH2O PH2O steam distillation (wet) method and specifically
wants to:

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 Steam Distillation of the Oil of Orange 2018

 describe the appearance and odor of the Steam Distillation of the Oil of Orange
distillate and the oil;
 determine the boiling temperature of the 1. For the distillation process, a distillation set up

mixture; was assembled properly; with a small hot plate

 identify the vapor pressure of the oil at the and a sand bath (for uniform heat distribution)

boiling temperature; as its source of heat.

 determine the mass of the oil produced;

 know the percentage yield of oil from the 2. Three medium oranges were peeled and were

orange sample; blended with a minimum amount of water to

 compare CSD and ISD in terms on their have a purée. About 25 g of the purée was
respective amount of oil produced; and weighed and was added into the distilling pot

 qualitatively identify the presence of the oil.
MATERIALS AND METHODS
(250 mL round bottom flask) using a wide-
mouth funnel and a stirring rod. An adequate
amount of distilled water was added to the
distilling pot to fill it around 50-70% of its total

Materials volume. Then, a few boiling chips were added

to the distilling pot to prevent bumping. For the
• Diethyl ether (50mL) • Wash bottle
receiver, a 250 mL flask were used or any
• Anhydrous MgSO4
• Boiling chips receiver (e.g. graduated cylinder) will do. The
(20g)
distilling pot was sealed and the condenser
• Thermometer • Beaker (qt.2 each
was activated. Then, the system was heated
• Grease – 100 & 250mL)
slowly.
• Hot plate • Distillation
• Pipet (10mL) apparatus
Note: It is important to watch the water level
• Iron stand w/ clamp • Rubber tubing
because of the high concentration of Sugar in
• Stirring rod (qt.1) • Parafilm
oranges. If the Water level gets too low, the
• Rubber stopper with • Funnel
Sugar will caramelize and burn. Also, it is
hole • Aspirator
better to add small amounts of water so that
• Round bottom Flask • pH meter or pH
the temperature doesn’t drop drastically.
(qt.1– 500mL) paper
Keep the heat at a low, steady level.
• Separatory Funnel • KI solution
(100 & 250mL) (saturated)
3. That was for the CSD; so for the ISD, prior to
• Erlenmeyer flask (qt.2 • Orange peel
step 2 sentence 2, the sample was first heated
– 125 & 250mL)
at 50°C for about 30 minutes. After the pre-
heating treatment of the sample, the
distillation process was done as the CSD
procedure.

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 Steam Distillation of the Oil of Orange
4. The distillation process was done for about 6
hours or until the condensate no longer
contains oil with the absence of its cloudy
appearance. The presence of the oil in the
condensate was identified through the cloudy
drops forming in the condenser.
Extraction of Orange Oil using Diethyl ether
5. The distillate was transferred into a 250 mL
separatory funnel. Then, to extract the oil, 20
mL of diethyl ether was added. The separatory
funnel was stoppered, shaken and vented for
5-10 times. The funnel was then set
undisturbed to have formation of layers.
Note: There must be no flame sources or hot
plates on during the use of Ether. Ether is
very, very flammable. Vapor inhalation may
cause headache, nausea, vomiting, and loss
of consciousness. Contact with eyes will be
irritating. Skin contact from clothing wet with
the chemical may cause burns
(https://cameochemicals.noaa.gov).
6. After the layers were formed, the aqueous
layer (bottom) was drained off into a 250 mL
Erlenmeyer flask. Then, the organic layer
(top) was drained into a small collection flask.
7. The extraction using ether was repeated 2-3
times to maximize the yield.
8. After the extraction, the ether was dried using
anhydrous magnesium sulfate. The
anhydrous magnesium sulfate would absorb
2018
trace amounts of water that is dissolved in
ether and would produce solid magnesium
sulfate decahydrate:
MgSO4(s) + 10 H2O  MgSO4•10H2O(s)
The system was allowed to dry for 10 - 15
minutes.
*
Magnesium sulfate, anhydrous - Green circle
- This chemical has been verified to be of low
concern based on experimental and modeled
data (www.epa.gov).
9. The organic liquid was then decanted into a
small beaker and was placed on a steam bath
in the fume hood to evaporate all of the ether,
having only the oil of the orange at the end.
10. The oil of the orange was transferred into a
massed and labelled vial. Then, the mass of
the oil was determined and its percentage oil
in the orange peel was calculated using the
formula:
𝐦𝐚𝐬𝐬 𝐨𝐟 𝐨𝐢𝐥 (𝐠)
% 𝒚𝒊𝒆𝒍𝒅 = 𝑥 100
𝐦𝐚𝐬𝐬 𝐨𝐟 𝐨𝐫𝐚𝐧𝐠𝐞 𝐬𝐚𝐦𝐩𝐥𝐞 (𝐠)
Qualitative analysis
For the qualitative analysis, iodine test and pH
test were conducted to confirm the presence of
the oil.
Iodine Test
11. A few drops of orange oil was placed in a small
test tube; then 5 mL of iodine (iodine in
saturated KI solution) was added. The test
tube was shaken and was heated in a water
bath for about 5 minutes. A changed in the
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 Steam Distillation of the Oil of Orange 2018

solution’s color to brown would indicate the of liquid with the oil at the upper portion of the
presence of the unsaturated compound (e.g. distillate which indicated that the oil was less
terpenes) in the sample. dense than the water. The obtained oil of the
orange was colorless and expelled a lemon like
pH Test
aroma which generally explained orange’s
12. If an adequate oil of the orange would be aroma.
produced, a pH meter (specific) may be used
to measure the pH value of the oil or else, a Table 1. Physical observations of the distillate
and the oil of orange.
pH paper may be used.
Description Observation
Bp = 95-97°C, the
RESULTS AND DISCUSSION Boiling point (Bp)
distillate was oily and
and Appearance of
Attempting to distill essential oils directly from formed 2 layers on
distillate
the plant material is generally not possible. It is the receiver
because most of the oil’s constituents are high Oil of orange:
Colorless with a
boiling and will decompose under these Appearance and
lemon like odor
temperature. So, instead of just using a simple odor
distillation setup, a special type of distillation
process is usually done wherein temperature
sensitive materials such as oils and resins are By having the atmospheric pressure (PT)

separated without altering their properties. In this during the conduct of the experiment (757.2

experiment, the oil of orange was extracted mmHg) and the vapor pressure of water at

through wet steam distillation process. Aside from (average of 95-97°C, 657.6 mmHg), the

the conventional steam distillation method (CSD), vapor pressure of the oil may be obtained by

improved steam distillation were also employed deriving equation 1. The calculated vapor

following the method of Pauline et al. (2015) with pressure of the oil was around 99.6 mmHg (at

some modifications. Shown in Table 1 are the 96°C). Shown in Table 2 is the Summary for the

physical observation of the distillate and the steam distillation (CSD and ISD) process of the

orange of the oil. oil of orange.

Upon the distillation process, it was observed
that the boiling point of the distillate ranged from
95-97°C. It was lower than the normal boiling
point of the water which is 100°C. This showed
that the mixture of water and oil was distilled (co-
distill) below their respective normal boiling point
(water - 100°C; Oil, Limonene - 176°C). Also, the
distillate appeared to be oily and formed 2 layers
It has been observed that the yield of orange
oil was higher in improved steam distillation than
that of the conventional steam distillation of the
orange peels. ISD’s yield (1.68 g, 6.72%) was
almost twice than the yield of CSD (0.89 g,
3.56%). The increase in ISD’s percentage oil in
orange peel is due to the reason that the orange
peels were pre-heated in this method. This

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 Steam Distillation of the Oil of Orange 2018

resulted to the softening of the cell walls of the

orange peels which are made up of cellulose,
hemicelluloses and pectin. When the preheated
peels were further subjected to conventional
steam distillation procedure, it further softened Figure 5. Possible reaction equation of iodine
and an unsaturated compound (e.g.
and opened the cell walls of the orange peels;
ethene).
thus, liberating most of the components present
in it in the form of orange oil. pH Test

Table 2. Summary for the steam distillation (CSD After the distillation, the oil sample was
and ISD) process of the oil of orange. collected and subjected to pH analysis using a pH
Type of Steam paper – pH paper, since only small amount of oil
Description Distillation was produced during the distillation process. The
CSD ISD pH value of the orange oil obtained was around 5

Boiling for both CSD and ISD, which indicated that it is

Temperature 95-97 °C 95-97 °C acidic in nature.

Distillate
Mass Oil (g) 0.89 1.68 CONCLUSION
% Yield 3.56% 6.72% Thus, the oil of orange was extracted using
Iodine Test + + both conventional and improved steam distillation
pH 5 5 (wet) process. The boiling point of the distillate
ranged from 95-97°C. Also, the distillate
appeared to be oily and formed 2 layers of liquid
Iodine Test
with the oil at the upper portion of the distillate.
Iodine test was done to assess the presence
The obtained oil of the orange was colorless and
of any unsaturated compound in the test sample
expelled a lemon like aroma. In addition, the yield
(Figure 5). Upon the addition of iodine (iodine in
of the orange oil was higher in improved steam
saturated KI solution), the colorless oil of orange
distillation than conventional steam distillation.
sample obtained from both CSD and ISD
ISD’s yield (1.68 g, 6.72%) was almost twice than
changed into brown after 5 minutes of mild
the yield of CSD (0.89 g, 3.56%). Also, the
heating. The presence of limonene and other
obtained oil showed positive results for the iodine
aromatic compounds in the sample was then
test having its color (from colorless) changed to
confirmed. The brown coloration of the solution
brown which indicated unsaturation in the sample
was due to the reaction of iodine with limonene
obtained. The pH of the oil was also recorded to
and other unsaturated compounds like α and β-
be 5, which is acidic as the sample is acidic in
Pinene, Myrcene, δ-3-Carene and linalool.
orange.

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 Steam Distillation of the Oil of Orange 2018

RECOMMENDATIONS

The following statements below are some

recommendations for the overall improvement

(outcome) of the experiment:

 Use cold water in the condenser to hasten

condensation;
 Characterize the oil obtained quantitatively
(TLC, FTIR, HPLC, etc.) to obtain a specific
component of the oil and compare it with a
literature data; and
 Try using other or same plant material
(e.g. lemongrass oil, clove oil, etc.) to extract
their oil using both wet and dry steam
distillation.

REFERENCES

PAULINE, M.N.J., B. NITHYALAKSHIMI and R.

AADHITHIYA LAKSHIMI. 2015. Extraction
of Orange Oil by Improved Steam
Distillation and its Characterization
Studies. Int. J. of Eng. Tech., Management
and Applied Sciences, 3:2, p. 1-5.

https://cameochemicals.noaa.gov/chemical/696.
Date Retrieved: February 6, 2018.

https://infohost.nmt.edu/~jaltig/SteamDistill.pdf.
Date Retrieved: February 6, 2018.

http://www.engineering.iastate.edu/brl/files/2011/
10/brl_essentialoils.pdf. Date Retrieved:
February 6, 2018.

https://www.epa.gov/saferchoice/safer-
ingredients. Date Retrieved: February 6,
2018.

https://www.flinnsci.ca/api/library/Download/ba6
ab218508047ea843bb0d9e580be16.
Date Retrieved: February 6, 2018.

https://www.worldweatheronline.com/baybay-
weather-history/leyte/ph.aspx. Date
Retrieved: March 3, 2018.