Names: Bryle Kristiann Camarote Date Performed: December 11, 2013

Nimrod Romelo Date Submitted: January 8, 2014

Sarah Jane Valdon
Group #3

EXPERIMENT #3
Sublimation and Steam Distillation

I. INTRODUCTION

In the previous experiment, caffeine was being extracted and isolated from tea
leaves. The product that was collected still contains considerable amounts of impurities. A
compound is said to sublime if it passes from the solid state directly into a gaseous form
without first becoming a liquid. Even though it may be low, a solid does exert a vapor pressure
and vaporization directly to the gas phase does occur. Since the impurities in crude caffeine
extract do not sublime under the same condition as caffeine, sublimation will result in pure
caffeine.
Sublimation is usefully employed in reverse, as a method of purification. A solid is
typically placed in a sublimation apparatus and heated under vacuum. Under this
reduced pressure, the solid volatilizes and condenses as a purified compound on a cooled
surface (cold finger), leaving a non-volatile residue of impurities behind. Once heating ceases
and the vacuum is removed, the purified compound may be collected from the cooling surface.
Essential oils are highly volatile substances isolated by a physical process from an
odoriferous plant. They are mixtures of organic compounds that are dominated by the terpenes
and the terpenoids, oxygen containing derivatives of the terpenes. The pleasant odor that we
come across the fruits, flowers, stems, barks and roots of nearly all plants is actually due to the
presence of these essential oils.
The oils are formed in the green (chlorophyll-bearing) parts of the plant, and with plant
maturity are transported to other tissues, particularly to the flowering shoots. Essential oils are
found in the vegetable structures to which they give their characteristic odor and are intimately
connected with the vital processes that take place in plants.
Essential oils are used in a wide variety of consumer goods such as detergents, soaps,
toilet products, cosmetics, pharmaceuticals, perfumes, confectionery food products, soft
drinks, distilled alcoholic beverages (hard drinks) and insecticides.
The first step in the isolation of essential oils is crushing or grinding the plant material to
reduce the particle size and to rupture some of the cell walls of oil-bearing glands. Steam
distillation is by far the most common and important method of production, and extraction
with cold fat (enfleurage) or hot fat (maceration) is chiefly of historical importance.
Three different methods of steam distillation are practiced. In the oldest and simplest
method a vessel containing water and the chopped or crushed plant material is heated by a
direct flame, and the water vapor and volatile oil are recovered by a water-cooled condenser.
This original method is being replaced by a process in which the plant material is suspended on
a grid above the water level, and steam from a second vessel is introduced under the grid. The
volatiles are condensed and the oil is separated. In the third process, the vessel containing the
plant material on a grid is heated to prevent condensation of steam, so that dry distillation is
attained.
Citrus fruits include oranges, lemons, limes and grapefruits, in addition to tangerines
and pomelos. Not only are the citrus fruits in this diverse group delicious and refreshing, they
earn their definition of an all-star food for their richness in compounds called flavonoids, which
have anticancer properties. The plants are characterized by winglike appendages on the leaf
stalks, white or purplish flowers, and fruit (classified scientifically as a kind of berry) with a
spongy or leathery rind and a juicy pulp divided in sections. The leaves, flowers, and rind of the
fruit abound in volatile oil and emit a sharp fragrance.
Attempting to distill these essential oils directly from the plant material is generally not
feasible. In general, most of the Oils' constituents are high boiling and will decompose under
the high heat needed to bring them to a boil. Steam distillation is a much gentler method of
achieving the same end. In steam distillation, the distilling pot is infused with steam, which
carries the oil’s vapor into the distilling head and then into the condenser, where the oil and
water co-condense.
Steam distillation works because the water and the oil are immiscible. Hence, they boil
independent of each other.
So, boiling occurs when the sum of the pure vapor pressures equals the atmospheric
pressure. Thus, a mixture of two immiscible liquids boils at a temperature lower than the
normal boiling point or either component of the mixture. Because vapor pressure of water is
greater than the vapos pressure of oil, the mixture will boil at a
temperature slightly less than the normal boiling point of water. This means the oil will
vaporize under very mild conditions.
Steam distillation can allow distillation of organic materials at lower than normal
temperatures. This is especially useful when substances are prone to decomposing under
higher temperatures.
II. DATA AND DISCUSSION

In this experiment, citrus fruit peelings were used as the plant raw material for essential
oil production. Students are expected to assemble and use a simple distillation set-up in the
separation of volatile substances from non-volatile materials and utilize the density difference
for oil and water to separate the essential oil from the distillate.

Part I: Steam Distillation

About 200 grams of fresh finely cut dalandan peelings were weighed and mixed with
distilled water in the sample flask. Enough water was added such that the flask is 2/3 full. The
steam distillation flask was then assembled and cautiously checked and the sample was finally
heated. About 200 ml of distillate was collected in a 250-ml separatory funnel. Observations
were all summarized below. The numerical data obtained from the experiment are also shown
in Table 1.

In the experiment, around 200 grams of dalandan peelings were used as plant material
and the solvent used was water. The distilling flask used contained the finely cut peelings with
about 2/3 full of water and the other one contained distilled water alone. As the containers
were heated, the vapor pressure of the solution increased until it reached boiling point. Boiling
point is the temperature at which the liquid turns into vapor. During this stage, the vapor
pressure of the solution heated is equivalent to or greater than the atmospheric pressure.
Boiling point of a substance also represents the point by which the intermolecular attractions
between liquid molecules are broken with sufficient amount of heat or energy to undergo
phase change. The steam from the flask containing distilled water travelled through the U-
shaped glass tubing which connects it to the flask containing orange peelings and water.
The ease of oil vaporization from the plant material was due to the high vapor pressure
applied in the heated solution. The total vapor pressure inside the distilling flask containing the
peelings increased due to the additional vapor pressure exerted by the steam travelling from
the other flask. Thus, the solution will boil at lower temperature than the boiling point of the
components. The amount of water in the solution doesn’t affect the vapor pressure of the
solution because the liquids are said to be immiscible therefore they exert different vapor
pressures and the solution will boil at lower temperatures compared to the boiling points of the
components. Therefore, doubling the amount of the water doesn’t change anything. The
collected distillate was then transferred to a separatory funnel with the aid of a glass funnel.
 SUMMARY OF RESULTS
Wt. of Dalandan (g) 200.3835
Wt. of Vial (g) 53.0015
Wt. of evaporating dish (g) 34.0697
Wt. of evaporating dish + oil (g) 34.3056
Wt. of oil (g) 0.2359
% Recovery of oil 0.118%
Table1. Steam Distillation

Separation of the oil from the aqueous solution was done by utilizing the densities of
the liquids involved. When two liquids have different densities, they tend to separate because
they are immiscible. Oil floated above water because oil is less dense compared to water.
Salting of the solution was not done because the oil layer was quite visible, but salting could
also be done to further separate the two layers. When salt is added, water become denser and
polar, so polar molecules (water) will tend to go or bind with polar molecules while non- polar
(oil) will also follow the same principle. Then, the aqueous layer was drained slowly to lessen
the product loss. It was then transferred in a pre-weighed vial. The mass of oil obtained was
0.2359 g. This mass wasn’t pure dalandan oil because traces of water could be found. The
percentage recovery for the oil is about 0.118%. It is expected that the outcome of the mass of
oil is very small because orange essential oil contained in the rind of orange is only at around
0.3-5% depending on the variety of orange used. One factor is the maturity of the fruit used
and also the season the fruit was picked.
The total vapor pressure in the distilling flask had become higher since there was an
addition of the water’s vapor pressure. So this means that the mixture doesn’t have to apply
more energy and pressure for it to fulfill the requirement for vaporization. Thus, the mixture
with oil vaporized at a lower temperature.
For example, there is a mixture of immiscible liquids (both water-insoluble) that is
subjected to steam distillation. At 90°C, the vapor pressure of pure water is 526 mmHg. If the
vapor pressure of compound A is 127 mmHg and that of B is 246 mmHg at 90°C, the total vapor
pressure of the mixture at 90°C is 899 mmHg since you are just going to add the vapor pressure
of water, and compounds A and B. In order to find out the temperature to which it will boil, we
have the following equation:

Vp total= Vp of compound A + Vp of compoundd B+ Vp Water

= 127 mmHg + 246 mmHg + 526 mmHg
= 899 mmHg at 90 ° C
*The total vapor pressure is just the sum of the partial pressures of each component.
760 mmHg (x) = 899 mmHg (90° C)
= 76.08 °
 This mixture will boil at a temperature below 90¬O. The boiling is the point at which the
vapor pressure of the liquid is equal to that of the atm pressure. Since the BP is directly
proportional to pressure, and that the atm pressure(760mmHg) is less than the vapor pressure
of the liquid (899mmHg), the boiling point will be approximately 76.08 degrees Celsius. This
temperature had no noticeable effect on the vapor pressure and boiling temperature by
doubling the amount of water used.

On the other hand, water and oil were then vaporized, distilled, and contained in the
separatory funnel together. But since they are immiscible with one another, water and oil have
their separate layers. Oil is at the top since it is less dense than water. In order to separate the
two layers more, sodium chloride (NaCl) could be added. In our case, we didn’t. But the reason
why this compound could be added is because salt increased the separation of polar molecules
from nonpolar molecules. The polar molecules go with the polar layer and nonpolar molecules
go with the nonpolar layer.

Citrus oils are chemical compounds which contain the flavour and aroma of the fruit in a
concentrated form. These aromatic substances are seldom real oils. The term 'oil' is used
because the first essences produced by a similar process resembled oil in composition. The
finest oils are produced from flowers. Citrus oils are most plentiful in the oil glands of fruit peel.
Some oil is also extracted from fruit pulp and seeds, and another type from young leaves and
twigs.
The essential oil that we have isolated from our source is limonene (C10H16) which has an
IUPAC name of 1-methyl-4-prop-1-en-2-ylcyclohexene. Limonene is mostly found in the rinds of
different citrus fruits like lemon, grapefruit, and lime. In our experiment, we have the oranges.
Limonene occurs naturally as a hydrocarbon. It is also a cyclic monoterpene. It comprises 98%
by weight of the essential oil gained from the orange peels. Limonene has a property of being a
colorless liquid with a pleasant odor. It has a specific gravity of 0.846 at 15oC and has a boiling
point of 175oC to 176oC. Since limonene is an unsaturated terpene, one (1) molecule can
absorb 4 atoms of bromine, thereby forming a characteristic addition product wherein it melts
at 104.5oC. Limonene is utilized for flavoring and even perfuming medicines. It is somewhat
narcotic and has properties like those of an irritant. That is why it is dangerous to prepare the
oil since the people who prepare it can be subject to muscular debility, mental confusion,
neuralgia, erythema, headaches, papules, disordered digestion, and vesicles upon the skin.
 Boiling point: 222 °C(lit.)
Uses:
(a) Disinfectant – it can be added to a spray bottle of water and sprayed into the air as a
deodorizer, neutralizer, and air sterilizer
(b) Mouthwash - the disinfectant properties are great for germs in the mouth and for
neutralizing bad breath odors, as well.
(c) Energy
(d) Insect Repellant
(e) Heartburn - This is said to relieve heartburn symptoms by neutralizing the acid.
(f) Cough, Sore Throat, Fever - can help soothe a sore throat, calm a cough, and quell a fever.
(g) Lemon oil is also great nourishment for the nails and can help fight against nail fungus.

Figure1. Uses of the Essential Oil Limonene

Part II: Sublimation

This part of the experiment is actually part of the Experiment #2 on Recrystallization and
Melting Point Determination. The caffeine obtained from the said experiment was utilized here.
Sublimation served as a purifying step in order to attain purer, more impurity-free Caffeine.

The large test tube containing the crude sample of caffeine with a smaller one that has
tip were fitted together. It was made sure that the smaller test tube is about ½ inch from the
bottom of the large test tube. The smaller test tube was then removed and the larger one was
placed in the sand bath such that about I inch of the test tube is immersed. The sand bath was
heated to a temperature of 150 . When this temperature was reached, the small test tube
was placed in the large tube and was continue heated up to 180-200. Needle like crystals
deposited at the bottom and the sides of the inner tube. Results were shown in Table2 below.

Initial Temperature 30
Wt. of vial (g) 31.1584
Wt. of vial + caffeine (g) 31.1618
Wt. of pure Caffeine (g) 0.0034
Wt. of Crude Caffeine (g) 0.1269
% Purity of Caffeine 2.68 %
Table2. Sublimation
 Sublimation is a process whereby solid substances pass directly into the vapor phase
when heated, and on cooling, pass directly back to the solid phase without the intermediate
appearance of a liquid state. For sublimation to occur, it is necessary that the solid has a
relatively high vapor pressure at a temperature below its melting point. Generally, sublimation
is carried out under reduced pressure. It affords a method of obtaining a product of high purity
and is particularly valuable for the isolation of a volatile solid from colored gums and tars.
It also does not differ from distillation in any important respect, except that special care
must be taken to prevent the solid from clogging the apparatus. Rectification of such materials
is impossible. Iodine is purified by sublimation. Sublimatography is a procedure of fractional
sublimation in which a solid is separated into bands along a condensing tube with a
temperature gradient.
On the other hand, Fractional sublimation is the process of purifying a solid by
repeatedly evaporating and condensing it. However, it is noted that most solids do not turn
directly into gas when they are heated. Much like water when it's frozen, it must first turn into
a liquid before it can evaporate and become a gas. The term, sublimation, is the transition of a
solid skipping the liquid state of matter and going directly to a gas. One such gas that does this
is carbon dioxide.
From the results above, only 0.0034 g of pure caffeine was obtained out of the 0.1269 g
of the crude sample. This amount yielded only 2.68% of purity.

Solving for the chemical formula of caffeine given the percentage compositions: C –
49.69; H – 5.04; N – 29.01; and O – 16.27:

C: 49.69 g x (1 mol/12 g) = 4
H: 5.04 x (1 mol/1 g) = 5
N: 29.01 x (1 mol/14g) = 2
O: 16.27 x (1 mol/16 g) = 1

Giving us C = 2, H = 5, N = 2 and O = 1. Therefore the empirical formula of caffeine is C 4H5N2O.

*Calculating now for its empirical formula given that the molecular weight determination had
197 5:

Multiplier (n) = (Empirical Formula mass)/(202)

Multiplier (n) = 2.

Now, solving for the molecular formula we have: (C4H5N2O)n where n = 2:

The molecular formula of Caffeine is: C8H10N5O2.
III. CONCLUSIONS

Essential oils from plants have wide range of uses from pharmaceutical to cosmetics.
These oils are derived from plants with unique aromas due to volatile compounds in its parts.
Most of essential oil is sensitive to high temperatures by which it decomposes if too much heat
is applied. Extraction of such oils is done at lower temperature compared to its actual boiling
point to prevent product loss or decomposition. Thus, steam distillation is one of the
convenient ways to extract oils. Steam distillation uses the increased vapor pressure due to the
pressure exerted by the supplied steam on the container of the mixture making it boil at lower
temperatures in comparison to the boiling point of the components therefore eases the
extraction of oil from the plant material. The essential oils can be separated from the aqueous
solution using the separatory funnel because water and oil are immiscible liquids. The amounts
of essential oil extracted from plants have a wide range of differences from the method of
extraction and the plant material itself.
Steam distillation was quite convenient for laboratory purposes because the set-up is
quite simple and no hazardous solvents were used. In addition, in the extraction of the oil from
the distillate, it could be more productive if organic solvent was used to dissolve the oil and
distil it to remove the solvent but this requires more time and careful handling of solvents
because organic solvents are quite toxic. In addition, grinding of the peelings to a more refined
state would ease the oil extraction from the peelings.

IV. REFERENCES

“Analysis of the Essential Oil of the Roots and Leaves of the Medicinal Plant Kaempferia
Galenga L. (Zingiberaceae)”
http://shodhganga.inflibnet.ac.in/bitstream/10603/3904/8/08_chapter%202.pdf
“Extraction and Isolation of Caffeine from Tea Leaves”
http://chem-courses.ucsd.edu/CoursePages/Uglabs/143A_Weizman/expt_3N.pdf\
“Influence on the Quality of Essential Lemon (Citrus aurantifolia)Oil by Distillation Process”
http://www.scielo.br/pdf/bjce/v23n1/29907
“Isolation of Essential Oils by Steam Distillation”
http://users.stlcc.edu/mhauser/Essential%20Oils.pdf
“Steam Distillation of an Essential Oil”
http://infohost.nmt.edu/~jaltig/SteamDistill.pdf