Steam Distillation of (S)-(+)-Carvone from Caraway Seeds and (R)-(-)-Carvone from

Spearmint Leaves
Riyushi Mahadik
Introduction
Structures

(R)-(-)-Carvone
231 C
Spearmint
-61
0.96
same

(S)-(+)-Carvone
231 C
Caraway
+61
0.96
same

B.P
Smell
Optical rotation
Density
IR spectrum
Rt
The objective of this lab is to isolate carvone by steam distillation, to extract carvone from an
aqueous mixture with CH2Cl2 using a separatory funnel, to operate IR spectrometer to print out
IR peaks, to verify isolation of carvone by thin-layer chromatography comparison with authentic
samples and to confirm identity of functional groups by Baeyer test. The Rf values of the
distillate will be compared with the Rf values of an authentic sample of R-(-)-carvone and also to
examine the relationship between enantiomers of carvones using IR spectroscopy with carbonyl
and alkene groups present in the structures.
The boiling point of a substance is the temperature at which equilibrium vapor pressure of a
liquid equals to the atmospheric pressure. Boiling point is an important physical property of each
compound which determines the purity and identity of each compound. It is process when liquid
bubbles and there is a spontaneous vaporization. Compounds with higher equilibrium vapor
pressure have lower boiling points whereas compounds with lower equilibrium vapor pressure
have higher boiling points. The importance of boiling points is crucial in steam distillation to
separating the components of a mixture. The liquid boiling in a closed system increases the
number of gas molecules until the rate of the molecules entering the gas phase and liquid phase
equal out. And reach the dynamic equilibrium. This process of molecules in gas phase in a rapid
motion collides against the walls of the vessel exerting pressure. The pressure is called
equilibrium vapor pressure which is dependent on the temperature. As the temperature increases,
the vapor pressure above the boiling liquid increases. Whereas when a liquid is boiled in an open
system, the vapor above the liquid is mixed with air and the total pressure. This process is

denoted by Daltons Law of partial pressures, Ptotal = Psample + Pair. So, the total pressure above the
liquid is calculated by adding the partial pressure of each component. The partial pressure of the
sample is equal to its equilibrium vapor pressure at a given temperature.

In this lab, steam distillation will be used to separate carvone from caraway seeds and spearmint
leaves. Steam distillation can isolate liquids with high boiling points and are unstable at the
boiling temperature. This method can be applicable to substances that are immiscible with water,
are non-reactive with water, and are stable at 100 C and also for a vapor pressure greater than 5
torr at the 100 C. It is used to isolate the essential oils from caraway seeds and spearmint
leaves. For the apparatus of steam distillation, the organic compounds with water to be distilled
are placed in a round bottom flask connected with a Claisen adapter, a steelhead and a watercooled condenser as shown in Figure 1. To avoid splashing the mixture into the condenser during
the process of the distillation, a small amount of water is added from the separatory funnel
directly to the distillation flask with the organic compounds to be separated. A heating mantel is
controlled along the process while the thermometer reads the temperature of the vapor and
distillate is collected in graduated cylinder.

Figure1: Steam Distillation Apparatus

The theory behind the steam distillation is based on the partial pressure Pi of each component i of
a mixture of immiscible, volatile substances at a given temperature is equal to the vapor pressure
Pio of the pure compound at the same temperature. Thus, this equation-- Pi = Pio summarizes the
above sentences. So, this theory does not depend on the mole fraction of the compound in the
mixture and each component of the mixture vaporizes independently of the other components or
the Roaults Law. Steam distillation also follows the Daltons law of partial pressure which says
the total pressure above the liquid is calculated by adding the partial pressure of each component.
The partial pressure of the sample is equal to its equilibrium vapor pressure at a given

temperature. The total vapor pressure is always higher than the most volatiles component.
Similarly, the boiling point of the mixture is always lower hat the lowest boiling component.
Infrared (IR) Spectroscopy doesnt provide with chemical composition or quantitative data rather
it provides the peaks at certain wavenumber indicating the carbon to carbon double/triple bonds,
aromatic rings, carbonyl groups, or hydroxyl groups. IR uses the wavenumber in cm-1 which
provides direct relationship between energy and wavenumber and also proves the Hookes law.
IR measures the light transmitted by the sample than absorption. The lower % transmittance, the
greater is the absorption of light. The device used in this experiment is Attenuated Total
Reflectance (ATR) FT-IR accessory that creates graphs with peaks indicating specific functional
groups in unknown.
Increasing adsorption on polar stationary phases
RCO2H > ROH > RHN2 > RRC=O > RCO2R > ROR > C=C > R-X
Figure 2: Elutropic series for polar stationary phases.
In chromatography there are two phases that helps the mixture to separate in to components.
Mobile phase is the phase with a liquid or a gas that is passes through the stationary phase. The
mobile phase in this lab will be the solvents. The stationary phase is the fixed solid or liquid
phase. In this lab, the polar stationary phase is the silica gel. The components bind with of theses
phase in order to create the separation of pigments. The polarity also comes in the play when the
stationary phase is polar and the mobile phase in non-polar, the polar components of the mixture
bind to the stationary phase and the non-polar components would move down the mobile phase.
This hence proves the idea of like dissolves like. Based on the Figure 2 above that describes
the elutropic series, the functional groups that are more polar are the ones that have greater
affinity for the polar stationary phases. In this experiment, silica gel was used which is a polar
stationary phase and dissolves the polar components of the dyes to the stationary phase better.
Thus, the indication of the results would be that more polar substances in thin-layer
chromatography will stay at stationary phase longer period of time. In order to calculate the time
the component of the mixture spends in a particular phase, the concept of retention time can be
applied. Retention time is the time corresponds to the time spent in the stationary phase. The
more time the component spent in the stationary phase, the less time spent in the mobile phase
and thus, the retention time of that component is more. Retention factor is the calculation of a
distance travelled by the substance over the distance traveled by the solvent. This predicts that
the higher Rf values are for the non-polar substances because they would travel the most in polar
stationary phases. A mobile phase used in the experiment is the solvent system containing ethyl
acetate and hexane. The definition of Eluting power is that the ability of a mobile phase to move
a substance through a stationary phase. So, if the stationary phase is polar like Silica gel, the nonpolar mobile phases will have less eluting power to move a polar substance.
Carvone from both spearmint leaves- (S)-(+)-Carvone and caraway seeds (R)-(-)-Carvone are
monoterpenes which means they have ten carbons in terepenes and two isoprene units in
terpenes. They have an asymmetric carbon or chiral center and enantiomers. Stereoisomers are

molecules that have the same molecular formula and constitution, but different orientations of
the atoms. One of the categories of stereoisomers are Enantiomers which are mirror images
isomers, and non-superimposable. Enantiomers have same physical properties -- same boiling
point, melting point, densities, color, viscosity, infrared spectra, indices of refraction, and thin
layer and gas chromatography, but different polarimetry and odor. They have different optical
activity because of the chiral center and the directions in which they rotate polarized light are
opposite but equal magnitude. R-(-)-Carvone smells like spearmint and is the principle
component of spearmint oil and S-(+)-Carvone has an earthy smell and is the major component
of caraway seeds. The nose, being chiral, contains hundreds to thousands of olfactory receptors
can identify different molecules by sending signals to the nervous system. The optical density
and physical properties are shown in the beginning of the introduction. The R/S configuration of
the molecules does not correlate to the (+)/ (-) sings of rotation of molecule. R / S configuration
is a naming system for denoting enantiomers. It labels each chiral center R or S according to a
system by which its substituents are each assigned a priority, based on atomic number. R means
the priority of the remaining three substituents decreases in clockwise direction whereas S stands
for the priority of the remaining three substituents decreases in counterclockwise direction. An
enantiomer can also be named by the optical activity. So, if enantiomer rotates the light
clockwise then it is labeled (+) and if enantiomer rotates the light counterclockwise then it is
labeled ().
The thin-layer chromatography is used to analyze the separation of Spearmint leaves pigments
according to their polarities. This will help to analyze the extracted compounds-carvone from the
steam distillation matches the pure oil carvone. If the dots of oils are happened to travel the same
distance then all of the liquids contain carvone. This will conclude that the steam distillation was
effective in extracting out the carvone from the spearmint leaves. The retention factors of the
carvone will be based on the affinity of polar components of the mixture to the polar stationary
phase. TLC follows the capillary action that moves components upward depending on affinities
for the mobile phase.
Baeyer test uses the reagent which is potassium permanganate. The process goes through
a redox reaction in which the KMNO4 reacts with double or triple bonds (-C=C- or -CC-) in an
organic material (carvone) and displays the color from purplish-pink to brown.
The infrared spectroscopy graph of the carvone extract from caraway seeds and spearmint leaves
must be the same because enantiomers have identical IR data. Both the R and S configurations of
carvone have an alkene and a carbonyl group which will be identified through the IR graphs.
Alkenes have a frequency between 1610-1680 cm-1 and carbonyl groups is around 1675-1760
cm-1 with strong intensity. However, the alkene peak is not seen clearly in the graph for both of
the samples. The data collected also shows that the steam distillation was efficient in extracting
out the carvone oils from the leaves and seeds because the Rf values of all the spots were similar
Experimental Procedures

Steam distillation Procedures

First, the samplespearmint leaves were weighed upto 5.01 grams and then they were
transferred to a round bottom flask. The apparatus was setup for steam distillation which
included the organic compounds with water to be distilled are placed in a round bottom flask
connected with a Claisen adapter, a steelhead and a water-cooled condenser as shown in Figure
1. To avoid splashing the mixture into the condenser during the process of the distillation, a small
amount of water is added from the separatory funnel directly to the distillation flask with the
organic compounds to be separated. A heating mantel is controlled along the process while the
thermometer reads the temperature of the vapor and distillate is collected in graduated cylinder at
1 drop per second. 150 ml of hot water and leaves are added to the round bottom flask. Attach
two tubes on the condenser to water in and out. Then, using the heating mantel the apparatus was
heated upto 45 C until approximately 75ml of distillate is collected. Throughout the process, the
water was replaced in the round bottom flask from the separatory funnel. After each 10 ml of
distillate collected, the temperature was recorded.
Extraction Procedures

Figure 3: Extraction of Carvone oils in Separatory Funnel.

In a sepratory funnel, 7 ml methylene chloride was added to the extract distillate. Then, the
funnel with a stopper was inverted approximately 10 times to get the clear separation of layers.
The top layer was the aqueous layer while the bottom layer is an oil layer. This process is done
three times and the bottom layer of oil was collected three times in a 50 ml Erlenmeyer flask.
Then, approximately 1.5 grams of anhydrous sodium sulfate was added to the extract to remove
water. Then, the drying agent is removed while the top liquid was decanted into another 50 ml
Erlenmeyer flask. This solution was heated under the hood on the heating mantel until 0.5 ml of
solution was left for the last procedure.
Characterization
For the IR of the unknowns, the surface of the apparatus was cleaned with Q-tip and acetone.
Particularly, the silver disc and knob was cleaned properly. The background scan was taken and
was compared to the spectrum of the standard. After matching the standard, the liquid sample up
to five drops was added to the black disc, and the black top was covered. The commands were
followed on the computer in order to find the peaks on the graph which was printed. Again, the

disc and the knob were cleaned with Q-tip, and acetone and the black disc was placed on the
middle of apparatus.
Then, TLC plate was prepared with three dots 1 cm from bottom. Left spot was for isolated
extract oil, the middle dot for co-spot (both isolated extract oil and authentic oil of (R)-carvone,
and the right dot just for authentic oil of (R)-carvone as shown in Figure 5 in results. The 10 ml
solvent system of 1:9 ethyl acetate and hexane was poured in a beaker with the TLC plate and
covered with watch glass until the solution travelled through the top of the plate. After the test,
the plate was seen in UV light which shows the bands of the components in the mixture as shown
in Figure 4 in results. Then, the TLC plate was kept in KMnO4 solution for Baeyer Test exposing
the dots and bands from clear to light brown spots. The plate was dried with a heat gun. The
middle of the spots was marked for calculating the retention factor values.
Data Acquisition
Equations:
Dalton's Law: Ptot = Px + Py + Pz..., where:
Ptot = sum of all the partial pressure of the components in a mixture.
Retention Factor: Rf = (distance traveled by substance)/ (distance traveled by solvent)
Boiling Point (mixture) B.P= Ptot= Patm
Ptot- Total pressure above the liquid
Patm- Atmospheric pressure
Raoults Law: Pi = NiPio
Pi = Pi o
Steam Distillation
Distillate Observations:
Caraway Seeds (5 grams)

Spearmint leaves (5 grams)

Color: Brown

Color: Green

Smell: Strongly earthy

Smell: Minty

Sample: Somewhat clear

Sample: Somewhat cloudy

More than one phase: Yes

More than one phase: Yes

Our group performed steam distillation of spearmint leaves. During steam distillation,
temperature and volume at 10 mL intervals was recorded and is listed in the table below. About
80 mL of the total distillate was collected.

Table 1: Temperature at each 10 mL of Distillate Collected in Steam Distillation

Volume of Distillate (mL)
10
20
30
40
50
60
70
80

Temperature (C)
Spearmint leaves
101
101.5
101
101
101
101
101
101

Temperature (C)
Caraway seeds
100
100
100
100
100
100
100
100

Graph 1: Temperature at each 10 mL of Distillate Collected in Steam Distillation of Spearmint Leaves

101.5
101.3
Temperature (C)

101.1
100.9
0 10 20 30 40 50 60 70 80 90
Volume of Distillate (mL)

Graph 2: Temperature at each 10 mL of Distillate Collected in Steam Distillation of Caraway seeds

150
100
Temperature (C) 50
0
0 10 20 30 40 50 60 70 80 90
Volume of Distillate (mL)

The graph of temperature vs. volume for spearmint leaves is constant around 101 C and
caraway seeds is constant around 100C. There is no application of Raoults law for steam
distillation because the total vapor pressure is independent of the mole fraction of each
component of the mixture. However, Dalton's law is applicable for steam distillation which states

that the total vapor pressure of the mixture is equal to the sum of individual vapor pressures of its
components. Therefore, the total vapor pressure is always higher than most volatile component
and boiling point of mixture is always lower than the lowest boiling component (water in steam
distillation). Because of the presence of water another component of mixture boils below its
normal boiling point. According to our results, the temperature of distillation is around the
boiling point of water (100C). Even though the temperature was higher than the boiling point of
water, these differences are the results of impurities in the sample or any other errors during the
distillation process.
Infrared Spectroscopy
The IR spectrums for caraway seeds and spearmint leaves are attached to this report. There was a
little peak of Alkenes C=C which was not indicated with an intensity on both of the graphs.
Overall, the IR data for both caraway seeds and spearmint leaves are the same.
Spearmint leaves:
1671.55 cm-1 Ketones C=O strong stretch
Caraway seeds:
1668.34 cm-1 Ketones C=O strong stretch
Thin-Layer Chromatography and Baeyers Test

Figure 4: TLC plate of Spearmint Leaves in UV light

Figure 5: TLC plate of Spearmint Leaves after Baeyers Test

Figure 6: TLC plate of Caraway Seeds after Baeyers Test

Figure 5 and 6 shows the three spots corresponding to different mixture. In Figure 5, spot A
corresponds to spearmint extract, spot B is a co-spot both isolated oil and authentic oil, and spot
C is of authentic oil R-(-)-Carvone. In Figure 6, spot A corresponds to caraway seeds extract,
spot B is a co-spot both isolated oil and authentic oil, and spot C is of authentic oil R-(-)Carvone. After the spots were observed on the TLC plate, their retention factors were calculated.
Also, the solvent was prepared by using 1:9 concentrations of ethyl acetate and hexane,
respectively. The data in the table below shows that R and S carvones have almost the same Rf
values.
Table 2: Calculations of Retention Factors of Each Spot in Both Samples
Plate
Numbe
r

Sample

Pigments Observed

Distance
Traveled by
Substance
(cm)-dx

Distance
Traveled by
Solvent (cm)ds

Rf Value
(dx/ds)

Spearmint
Leaves

Extract sample

4.1

5.1

4.1 cm/5.1
cm= 0.804

Co-spot (Extract and

authentic oil)

5.1

4 cm/5.1 cm=
0.784

Authentic Oil

3.9

5.1

3.9 cm/5.1
cm= 0.765

Extract sample, Co-spot

(Extract and authentic oil),
Authentic Oil

4 cm/7 cm=
0.57

Caraway
Seeds

Conclusion

The objective of this lab was to isolate (S)-(+)-Carvone from caraway seeds and (R)-(-)-Carvone
from spearmint leaves using steam distillation and examine the properties of the enantiomers of
carvone. Since, they have similar physical and chemical properties, these characteristics of the
enantiomers of carvones were analyzed through the peaks of infrared spectroscopy data, Rf
values obtained from thin-layer chromatography, and the Baeyer test.
The extract of spearmint leaves obtained from steam distillation had minty smell, whereas
caraway seeds had a earthy odor. These differences in smell indicates that the there is a
difference in stereochemistry of these compounds. During the steam distillation, the temperature
was constant at 101 C for spearmint leaves and 100C for caraway seeds which is close to the
boiling point of water (100 C). This process is based on the Daltons Law which states that total
vapor pressure of the mixture at any temperature is higher than the vapor pressure of the most
volatile component at that temperature and the boiling point of the mixture is lower than the
lowest- boiling component. This theory proves that there was a significant separation of carvone
from the leaves and seeds because components of the mixture boiled below their normal boiling
point and close to waters boiling point.
The data collected from IR indicates the similar composition of the enantiomers but also
indicates two major functional groups- alkene and carbonyl group. In the IR of spearmint leaves,
the C=C was not observed clearly but a small peak around 1666 cm-1 Indicated its presence while
the frequency at 1671.55 cm-1 indicated ketones C=O strong stretch. In the IR of caraway seeds,
the C=C was not observed clearly but a small peak around 1666 cm-1 indicated its presence while
frequency at 1668.34 cm-1 indicated ketones C=O strong stretch. The errors might have occurred
which could cause impurities in the extract and affecting the indication of alkene groups on IR.
But the vibrational frequencies of the alkene group obtained from the IR data of the two
enantiomers are very close to each other. This shows that the steam distillation results were quite
accurate because the IR spectra for both enantiomers of carvone should be identical.
The Rf value (0.804) obtained from thin-layer chromatography of the spearmint leaves is close to
the Rf value of authentic oil (0.765). While the Rf value obtained from thin-layer chromatography
of the caraway seeds is similar to the Rf value of authentic oil which is (0.57). This proves that
the isolated oil from the leaves and seeds have similar compounds as authentic oil. Thus, data
from TLC further confirmed the accuracy of our steam distillation data.
Using the Baeyers Test data, the indication of brown spots in purple ink indicated that the oils in
all three spots travelled the same distance. This determines that the components of spots are
similar to each other and the extract of spearmint leaves and caraway seeds contain major
compound of carvone oil compared to the authentic oil.
During this lab, there were possible errors that were been corrected. First most, the setting up the
apparatus for the steam distillation was challenging. The other challenging part was to adjust the
flow of distillate collected. Sometimes, the distillate was dripping higher than 1 drop per second

or lower. Then, the setting of heating mantel was regulated according to the steady dripping of
the distillate. For the separatory funnel, it was hard to identify layers of aqueous and organic oil.
Moreover, we also had problems viewing the spots under the UV light and through Baeyer test.
As a result, thin-layer chromatography was performed twice to obtain the Rf values of the two
enantiomers of carvones. At last after TLC plate was examined in UV light, it was hard to
identify the total distance travelled by all the mixtures because there were lots of bands in
between from the impurities. But after the Baeyer test, it was much clear what each spot
indicated to calculate the Rf values.