Separation, Purification and Characterization of Organic Liquid and Solid Unknowns by means

of Simple Distillation, Extraction and Recrystallization

Anna Zurek
CHE 231L Section 202
Department of Chemistry, DePaul University, 1110 W. Belden Avenue, Chicago, IL 60614
a.k.zurek@gmail.com
2/12/2015

Abstract:
Simple distillation is used to separate clear, homogenous mixture of two unknown liquids
(unknown #6). The mixture is highly viscous and has mildly sweet odor. Once the products are
distilled, small sample of each product is heated to determine its boiling point range. The boiling
point of the lower boiling liquid (LB) is determined to be 84.3-86.1 (C) and the boiling point of
the higher boiling compound (HB) 92.3-94.0 (C). The density of the lower boiling liquid is
found to be 0.7956 g/mL and the density for the higher boiling liquid is found to be 0.849 g/mL.
The percent recovery for LB is found to be 65.077% and for HB 29.709%. The overall percent
recovery for the distillation process is determined to be 94.786%.
A mixture of two unknown solid compounds (unknown #18), one neutral and one a carboxylic
acid is separated using the acid-base extraction technique. The unknown mixture has a whiteyellow color and produces clear yellow liquid when dissolved in dichloromethane. After the

separation and evaporation of the solvent is completed, the neutral unknown compound produces
fine, canary yellow powder. Once the unknown carboxylic acid is dried in the oven it produces
considerable amounts of white powder. The crude solids unknowns are purified by the
recrystallization technique, using ethanol as the recrystallization solvent. The mass of the
purified carboxylic acid is found to be 0.0117 g (0.271 % yield) and the mass of the purified
neutral compound is found to be 0.8154 g (19.20 % yield). The melting point for the unknowns
are determined at 123.1-123.8 C for the RCOOH and 106.0-107.2 C for the neutral organic
compound.

Introduction:
Simple distillation is a basic technique, widely used in organic chemistry laboratories.1 This
technique is also utilized in a variety of an industrial settings. Additionally, the simple distillation
method can be used as a desert survival technique to isolate water from plants or soil when no
other source of water is available.2 Two unknown liquid components were separated from a
mixture using simple distillation technique. Upon the completion of the separation, the boiling
point ranges and the densities of the products were determined. Because the two compounds
were known to have the boiling point ranges different by at least 25 C and lower than 150 C at
1 atm, the simple distillation technique was chosen.3Another requirement for this technique was
that the unknown compounds had to be soluble in each other.
1 Chemistry 231 Laboratory Manual, 2015
2 Jackson and Bavel, 1965
3 Zubrick, 2014

First, a simple distillation apparatus was assembled and the unknown mixture sample was
massed and placed in the distillation flask. The mixture was then heated gently until it started to
boil. First boiling point range was recorded when the vapor temperature stabilized and the lower
boiling product started to distill into the receiving flask. The mixture was being heated until
another increase in vapor pressure was observed. At this point the distillation was terminated by
removing the distillation flask from the heat source to prevent contamination of the already
distilled product. To preserve the purity of the products the distillation temperature range was
kept within 2 C. The unknown compounds were found to have high boiling ranges (between 80100 C).
After the distillation was completed, the percent recovery was calculated for each unknown
component (Tables 1 and 2). Volumetric flasks were used to determine the densities of known
amounts of the unknowns. Finally, the boiling point ranges were measured once again by heating
each of the unknown samples in a test tube on an aluminium block.
Because the boiling point range depends on the specific intermolecular forces present in a given
compound4 different compounds are known to boil at different temperatures. The experimentally
determined boiling points (Tables 1 and 2) can hence be used to estimate the identities of the
unknown compounds by comparing the laboratory boiling ranges to their literature values. The
deviation from the literature values can also be used to determine the purity of chemical
compounds and the precision of the distillation technique used to separate them.

4 Gorzynski-Smith, 2014
3

The liquid-liquid extraction is used to separate and purify of liquid compounds. This technique
requires the use of two immiscible solvents and a separatory funnel to divide the two compounds
(or a desired compound and the impurities) between the two solvent layers5.
Two unknown solid components were separated from a mixture using acid-base extraction. The
solid mixture was dissolved in dichloromethane and water and placed in a separatory funnel.
The 1.0 M NaOH solution was added to the funnel to react with the carboxylic acid to increase
its affinity of the aqueous layer and separate it from the neutral organic compound already
dissolved in the organic layer of dichloromethane.
When the two phases were separated, the carboxylic acid was regenerated as shown below by
adding to it 6.0 M HCl.
Upon the completion of the separation the products in the organic and aqueous phases were
vacuum filtered and dried. After the dry crude products (a carboxylic acid and a neutral organic
compound) were massed, they were purified by means of recrystallization. Ethanol was chosen
to be a recrystallization solvent because of its ability to dissolve both compounds when hot, but
only one of them when cooled. Hot ethanol was added to each the aqueous layer and the organic
layer and cooled to force the crystals of the pure compounds out of the solution. The samples
were then vacuum filtered to completely isolate the purified compounds.
The mass and the percent recovery values were determined for each pure compound.
Additionally, the melting points for the purified compounds were determined. The melting points
of the solids, similarly to the boiling point values in liquids could be used to determine the

5 Chemistry 231 Laboratory Manual, 2015

4

identity of the unknown compounds.6 Additionally, any discrepancies between the literature
values and the experimental BPs and MPs would be a good indication about the purity of the
isolated compounds and the quality of the technique used to obtain them.7

Mass spectroscopy (MS) is an analytical method used to determine molecular weight and the
molecular formula of the unknown compounds8. It is widely used because it is more time
efficient than the traditional experimental methods that include measuring the different physical
and chemical properties of an unknown (ex. measuring the boiling, and melting points and
conducting assorted chemical reactions).
The MS technique requires the use of a mass spectrometer, a specialized piece of laboratory
equipment in which the sample is vaporized and then ionized by a beam of electrons9. Next, the
ionized sample passes through a magnetic field and the mass spectrometer records the mass to
charge ratio (m/z) of each ion in the sample. The abundance of each ion is then plotted vs its m/z
ratio to form the mass spectrum. The m/z of the heaviest ion in the spectrum, also known as the
molecular ion peak (M+), is used to determine the molecular mass of the sample. The M+ peak,
the base peak (most abundant ion in the sample) and other prominent peaks are used to determine
the molecular formula for the sample. Although the mass spectrometry technique does not
provide enough information about the functional groups present within an unknown molecule10
or their arrangement in space, the index of hydrogen deficiency (IHD) can be used to further
analyze the structure of an unknown compound as it indicates the number of pi bonds and the

6,8,9 Gorzynski-Smith, 2014

7 Chemistry 231 Laboratory Manual, 2015
5

number of rings in a given molecule. Usually, in addition to the M+ peak, an M+1 peak can be
observed which signalizes the presence of small amounts of the 13C isotope. When an M+2 peak is
clearly visible on the spectrum it indicates the presence of bromine (when M+ and M+2 are in 1:1
ratio), or chlorine (when M+ and M+2 are in 3:1 ratio). An odd m/z number typically signalizes the
presence of nitrogen.

The infrared (IR) spectroscopy uses the dual properties of the electromagnetic radiation to
produce IR spectra with specific absorption bands that can be directly related to chemical bonds,
their type and functional groups present within the molecules of interest8. The dual properties of
IR include the ability to behave both as waves and as particles. Because the IR radiation is
characterized by the speed of light (c=const.), an inverse relationship between the frequency and
the wavelength can be inferred (c= v). Due to the relationship between the energy and
frequency described by the Planck-Einstein equation12 (E=hv), the energy of a light particle is
directly proportional to its frequency. The above properties reveal that the energy of a photon is
inversely proportional to the wavelength of the light absorbed in the IR spectrum. This
relationship is used in the IR spectra to relate the frequencies at which different chemical bonds
vibrate to their specific energies, which in turn allows for the positive identification of the
functional groups present in the analyzed sample.
The IR spectrum is a plot of the wavelengths absorbed by the spectrophotometer vs. the
wavenumber (inversely proportional to the frequency at which chemical bonds vibrate). Each
chemical bond is visible in the IR spectrum as an absorption bond at a specific wavenumber.

810,11,12 Gorzynski-Smith, 2014

Because the different chemical bonds vibrate at their distinctive frequencies, related to their
specific energy levels, each type of chemical bond produces an absorption peak at the different
wavenumber. For example, a high-energy triple bond between the sp-hybridized carbons can
exhibit a medium intensity peak at 2250 cm-1, while the lower energy double bond between two
sp2-hybridized carbons displays a peak at 1650 cm-1. The disparity between the two absorption
peaks is due to the difference in the relative strength of the two bonds. The stronger triple bond
exhibits an absorption bond at noticeably higher wavenumber. The wavenumbers of the peaks in
the IR spectra of the unknown molecules can be compared to the literature values to predict what
functional groups are present within the unknown molecules.

The nuclear magnetic resonance spectroscopy (NMR) is an analytical tool used in analysis of the
organic compounds139. There are two types of NMR. The 1H NMR is helpful in determining the
different types of hydrogen atoms and their ratios in a molecule, and the 13C NMR is helpful in
determining the different types of carbon atoms that occur in a molecule. The NMR technique
uses low-energy radio waves (RF) that interact with atoms within the sample molecule.
Another component of the NMR technique is the magnetic field generated by the spin of charged
particles in a molecule (ex. protons). The magnetic field orients the hydrogen and carbon nuclei
in two possible directions (aligned with the field, or against it). Applying the RF radiation equal
to the energy difference between the two nuclear states can change the nuclear spins of the
investigated atoms and produce resonance signals that are used in analysis of the unknown
molecule.

913 Gorzynski-Smith (2014)

7

The 1H NMR is typically used to determine the ratios of different hydrogen types in a given
molecule. The position in the NMR spectrum (chemical shift) gives information about the
different types of hydrogen atoms present in a molecule. Additionally, the splitting pattern of
each signal indicates how many other hydrogens are present in the immediate environment of the
investigated hydrogen group. The splitting is equal to the n+1 number, where n is equal to the
number of neighboring protons (that are usually not further than three bonds away).
The integration number gives the relative ratio of each type of protons. The shielding patterns
can rely even more information about the hydrogen framework of the molecule. For example, a
hydrogen in a saturated alkane can typically be found in the range of 0-2 ppm () but a hydrogen
bound to a carbon of the carbonyl group is found between 9.5-10 ppm. On the NMR spectrum of
an aldehyde, the sp3-hybridized hydrogen that is not in close proximity to the carbonyl group
would be found to the far right of the spectrum (upfield). On the other hand, the hydrogen that is
bound directly to the carbonyl carbon would lie to the far left (downfield). The observable
difference in chemical shift is due to the electron withdrawing effects. The electronegative atoms
shift the electron density away from the hydrogen atoms which leaves the hydrogen nuclei more
exposed to the effects of the magnetic field. Those nuclei are deshielded a higher frequency of
RF is needed to change their spin.
The 13C NMR is less useful than the 1H NMR because it doesnt provide any information about
the relative ratios of different carbon atoms or the carbon-carbon splitting patterns.

Results:
A clear, translucent mixture was obtained (unknown #6, Table 1). The mixture produced intense
odor similar to acetone but milder and sweeter. Mass of the original mixture was recorded to be
8

8.0616 g and the combined masses of isolated liquid compounds to be 7.6414 g. The respective
yields for the unknown compounds were 65.077 % for the lower boiling liquid (LB) and 29.709
% for the higher boiling liquid (HB). The boiling point range of LB was determined to be 84.385.0 C and the boiling point for HB was recorded as 92.3-94.1 C. The measured densities were
0.796 g/mL for the LB and 0.849 g/mL for the HB.

Table 1. Physical properties of a mixture of liquids and isolated pure compounds (unknown #6).

Unknown Mixture #6

Lower Boiling
Temperature
Liquid
(LB)

Higher
Boiling
Temperature
Liquid
(HB)

Colorless liquid
Mild sweet odor
High viscosity

Physical composition

8.0616

Mass of original mixture (g)

Mass of product after
separation (g)
Percent recovery (%)
Boiling Point (C)
Density (g/mL)

5.2463

2.3951

65.077
84.3-85.0
0.796

29.709
92.3-94.1
0.849

As seen in Table 2 below, the obtained mixture of two solids (unknown #6) was observed to be a
blend of white powder and finer canary yellow powder. The mass of the original mixture was
4.2474 g. After the initial extraction the mass of crude carboxylic acid (RCOOH) was recorded at
2.7444 g and the mass of crude neutral organic compound (RZ) at 1.1176 g.

After

recrystallization the mass of the purified RCOOH was found to be 0.0117 g and the mass of
purified RZ to be 0.8154 g. A significant amount of RCOOH was lost during the vacuum
filtration. The combined percent recovery for the crude products was 90.929 % with 64.614 %
9

for RCOOH and 26.313 % for the RZ. The percent recovery for the purified compounds was
19.48 % with 19.20 % for the neutral organic compound and only 0.275 % for the carboxylic
acid.
The melting point range for the pure RCOOH was observed to fall between 123.1-123.8 C and
the melting point for the pure RZ was observed at 106.0-107.2 C.

Table 2. Physical properties of a mixture of solids and isolated pure compounds (unknown #18).

Unknown Mixture no. 18

Physical composition
Mass of original mixture (g)
Mass of crude product (g)
Mass of purified product (g)
Percent recovery crude
product (%)
Percent recovery purified
product (%)
Purified product melting
point (C)

Carboxylic Acid
Neutral Organic
Solid
Solid
(RCOOH)
(RZ)
White solid
Canary yellow solid
4.2474
2.7444
1.1176
0.0117
0.8154
64.614

26.313

0.275

19.20

123.1-123.8

106.0-107.2

The physical and spectral data for the isolated and purified lower boiling liquid
(LB, unknown #6) were summarized below (Table 3). The overall percent recovery for the liquid
mixture was equal to 94.786 % after isolation. The molecular formula of the compound was
found to be CH3CN with the IHD equal to 2. The isolated product was a colorless liquid that
produced sweet smell.

10

The spectral data for LB liquid were also summarized in the table below. The Molecular ion peak
for LB was found at m/z of 41 and the base peak was also observed at m/z of 41. Other notable
peaks were observed at m/z of 40, 26 and 14.
The lower boiling liquid displayed a weak, sharp absorption peak at 3200 cm-1, a medium
intensity, medium breadth peak at 3000 cm-1, very strong, very sharp peak at 2250 cm-1 and a
strong peak of medium breath at 1490 cm-1. Any peaks considerably below 1500 cm-1 were
identified as belonging to the fingerprint region and were not included in the above analysis.
The 1H NMR spectrum for LB exhibited only one resonance peak at 2.50ppm s, 3H. The 13C
NMR spectrum of the same compound exhibited two signals at 2.0 ppm and 116.5 ppm.

11

Table 3. Physical and spectral data for the lower boiling liquid (unknown #6).
Chemical Name: Acetonitrile
Unknown Code: #6
Percent Recovery
Liquid (overall)
94.79%
Physical Appearance:
colorless liquid, mildly sweet smell
MS Data
Molecular
Formula
IHD
+
M (m/z)
Base Peak (m/z)
Lost Fragments/
Other Peaks
(m/z)
Absorption Band
1
2
3
4
Proton(s)
A
Carbon(s)
1
2

CH3CN
2

26

41
41
40

14

IR Data
Wavenumber
Intensity
(cm-1)
3200
weak
3000
medium
2250
very strong
1490
strong
1
H NMR Data
(ppm)
Splitting
2.5
s
13
C NMR Data
(ppm)
2.0
116.5

12

Shape
sharp
medium
very sharp
medium
Integration
3H

The physical and spectral data for the isolated and purified higher boiling liquid
(HB, unknown #6) were summarized below (Table 4). The overall percent recovery for the liquid
mixture was equal to 94.786 % after isolation. The molecular formula of the compound was
found to be C6H12O2 with the IHD equal to 1. The isolated product was a colorless liquid that
produced sweet smell.
The spectral data for HB liquid were also summarized in the table below. The molecular ion peak
for the HB was determined at m/z of 116, while the base peak was recorded at m/z of 43. Other
important peaks for this compound included m/z of 73, m/z of 56 and m/z of 41.
The HB displayed strong, medial absorption bands at 2950 cm-1 and 1750 cm-1, and a medium
intensity, medium breadth absorption at 1480 cm-1.
The 1H NMR of the high boiling liquid exhibited five signals (units in ppm): 0.88 (t, 3H), 1.39
(m, 2H), 1.74 (m, 2H), 2.04 (s, 3H), 4.15 (t, 2H). The 13C NMR of HB displayed six resonance
signals (units in ppm): 14.0, 18.0, 21.0, 30.5, 64.0, and 170.5.

13

Table 4. Physical and spectral data for the higher boiling liquid (unknown #6).
Chemical Name: Butyl acetate
Unknown Code: #6
Percent Recovery
Liquid (overall)
94.79%
Physical Appearance:
colorless liquid, sweet smell
MS Data
Molecular
Formula
IHD
+
M (m/z)
Base Peak (m/z)
Lost Fragments/
Other Peaks
(m/z)
Absorption Band
1
2
3
Proton(s)
A
B
C
D
E
Carbon(s)
1
2

73

C6H12O2
1
116
43
56

41

IR Data
Wavenumber
Intensity
(cm-1)
2950
strong
1750
strong
1480
medium
1
H NMR Data
(ppm)
Splitting
0.88
t
1.39
m
1.4
m
2.04
s
4.15
t
13
C NMR Data
(ppm)
14.0
18.0

14

Shape
medium
medium
medium
Integration
3H
2H
2H
3H
2H

3
4
5
6

21.0
30.5
65.0
170.5

The physical and spectral data for the isolated and purified carboxylic acid
(R-COOH, unknown #18) were summarized below (Table 5). The overall percent recovery for
the solid mixture was equal to 19.48% after isolation and purification of the products. The pure
product was a crystal white solid. The molecular formula of the compound was found to be
C6H5COOH with the IHD equal to 5.
The spectral data for R-COOH were also summarized in the table below. The molecular ion peak
for the carboxylic acid was found at m/z of 122. The base peak for RCOOH was recorded at m/z
of 105, with another pronounced peak at m/z of 77.
The R-COOH exhibited a weak, broad absorption peak at 3000 (cm-1), a very strong, sharp peak
at 1700 (cm-1), a weak and sharp peak at 1610 (cm-1), and a medium intensity, sharp peak at 1450
(cm-1).
The 1H NMR of the pure carboxylic acid displayed three resonance signals at 7.45 ppm (t, 2H),
7.59 ppm (t, 1H) and 8.03 ppm (d, 2H). The 13C NMR of the same compound exhibited four
peaks (units in ppm): 128.0, 130.0, 134.0 and 172.5.

15

Table 5. Physical and spectral data for the carboxylic acid (unknown #18).
Chemical Name: Benzoic acid
Percent Recovery
Pure solids (overall)

Molecular Formula
IHD
M+ (m/z)
Base Peak (m/z)
Lost Fragments/
Other Peaks (m/z)
Absorption Band
1
2
3
4
Proton(s)
A
B
C
Carbon(s)
1
2
3
4

Unknown Code: #18

19.48%

Physical Appearance:
white solid crystals
MS Data
C6H5COOH
5
122
105
77
IR Data
Wavenumber (cmIntensity
1
)
3000
weak
1700
very strong
1610
weak
1450
medium
1
H NMR Data
(ppm)
Splitting
7.45
t
7.59
t
8.03
d
13
C NMR Data
(ppm)
128.0
130.0
134.0
172.5

16

Shape
broad
sharp
sharp
sharp
Integration
2H
1H
2H

The physical and spectral data for the isolated and purified neutral organic compound
(R-Z, unknown #18) were summarized below (Table 6). The overall percent recovery for the
solid mixture was equal to 19.48% after isolation and purification of the products. The pure
product was a yellow crystalline powder.
The molecular formula of the compound was found to be C7H5NO3 with the IHD equal to 6.The
spectral data for R-COOH were also summarized in the table below. The molecular ion peak for
the neutral organic compound was determined at m/z of 151, with the base peak also at m/z of
151. Other notable peaks for RZ were recorded at m/z of 105, m/z of 77 and m/z of 51.
The neutral solid compound displayed two strong, sharp peaks at 1900 and 1700 cm-1 and two
medium intensity, sharp peaks at 1610 and 1550 cm-1.
The 1H NMR spectrum for R-Z exhibited only two signals at 8.20 ppm (d, 2H) and 8.25 ppm (d,
2H). Additionally, the R-Z unknown displayed four 13C NMR resonance signals (units in ppm):
124.0, 130.5, 140.5 and 151.5.

17

Table 6. Physical and spectral data for the neutral organic compound (unknown #18).
Chemical Name: 4-Nitrobenzaldehyde
Percent Recovery
Pure solids
(overall)

Unknown Code: #18

19.48%
Physical Appearance:
yellow crystalline powder
MS Data

Molecular
Formula
IHD
+
M (m/z)
Base Peak
(m/z)
Lost
Fragments/
Other Peaks
(m/z)
Absorption
Band
1
2
3
4

C7H5NO3
6
151
151
77

105
IR Data
Wavenumber (cm1
)
1900
1700
1610
1550

51

Intensity

Shape

very strong
strong
medium
medium

sharp
sharp
sharp
sharp

Proton(s)
A
B
Carbon(s)
1

H NMR Data
(ppm)
Splitting
8.20
d
8.25
d
13
C NMR Data
(ppm)
124

18

Integration
2H
2H

2
3
4

130.5
140.5
151.5

Discussion:
In order to establish the chemical identity and structure of two mixtures containing four unknown
compounds (unknowns #6 and #18)
The lower boiling compound was identified as acetonitrile. The molecular ion peak (also the base
peak) for this molecule was found at m/z of 41 which indicated the presence of nitrogen. The
analysis of the IR spectrum revealed the presence of a carbon-nitrogen triple bond at 2250 cm-1.
Additionally, the absorption bands at 3200 cm-1 was identified as hydrogen bonded to a carbon
triple bonded to another element. The absorption bands at 1450 cm-1 and 300 cm-1 were identified
as alkane bends stretches respectively. After the initial analysis the molecular formula of C2H3N
was derived with the IHD equal to 2. Other pronounced peaks on the mass spectrum were
located at m/z of 26 (equal to CH3) and at m/z of 14 (which confirmed the presence of a single
nitrogen atom). The 1H NMR spectrum was used to further identify the structure. A single
hydrogen peak with the integration equal to 3H was observed at 2.50 ppm slightly more
downfield than the chemical shift range for the saturated alkanes. The difference in chemical
shift could be explained by the significant deshielding of the hydrogen atoms in the close
proximity of nitrogen. The fact that only one peak was observed indicated that only one type of
hydrogen atoms was present in the molecule. The 13C NMR has further confirmed the proposed
19

structure by revealing that the molecule contained only two types of carbons. The two observable
carbon peaks were located at 116.5 ppm (within the range of a carbon triple bonded to a
nitrogen) and at 2ppm (consistent with the chemical shift range for the saturated alkanes).
Finally, the experimental boiling point range of 84.4-85.0 was compared to the literature value
for acetonitrile equal to 81-82 C10. The three degree difference between the boiling point
maxima could be explained by the insufficient precision during the simple distillation technique.
The distilled compound seemed to be contaminated with the higher boiling compound which
lead to the higher reading of the boiling point range. The literature value for density of
acetonitrile, 0.786 g/mL15 was constant with the experimental value of 0.796 g/mL. The small
discrepancy was most likely due to the lack of precision in recording the volume of the liquid in
the volumetric flask.

The higher boiling compound was identified as butyl acetate. The molecular ion peak for this
molecule was found at m/z of 116, while the base peak was found at m/z of 43. The analysis of
the IR spectrum revealed the presence of a carbonyl bond at 1750 cm-1. The absorption band at
1250 cm-1 was identified as carbon single bonded to oxygen. The absorption bands at
2880-2970 cm-1 were identified as alkane stretches. After the initial analysis the molecular
formula of C6H12O2was derived with the IHD equal to 1. The base peak with the m/z of 43 was
identified as H3CCO which helped to identify the compound among several possible isomers.
The 1H NMR spectrum was used to further identify the structure. A triplet hydrogen peak with
the integration equal to 2H was observed at 4.15 ppm which was consistent with the hydrogens
bound to carbon that was next to the carbonyl carbon. A singlet (3H) that was observed at 2.04
1014,15 http://www.sigmaaldrich.com/united-states.html
20

ppm was consistent with the hydrogens bonded to the carbon that was directly bonded to the
oxygen. This information was crucial in rejecting methyl pentanoate as a possible isomer. Other
hydrogen peaks at 1.74 ppm (m, 2H), 1.39 ppm (m, 2H) and 0.88 ppm (t, 3H) were found within
the range of the saturated alkanes and their splitting patterns confirmed the proposed structure.
The 13C NMR has further confirmed the proposed structure by revealing that the molecule
contained 6 types of carbons. The most deshielded carbon peaks were located at 170 ppm (within
the range of esters) and at 65 ppm (consistent a single C-O bond). Other carbon peaks at 14ppm,
18 ppm, 21 ppm and 30 ppm were consisted with the range for the saturated alkanes.
Finally, the experimental boiling point range of 92.3-94.1 C was compared to the literature
value for butyl acetate equal to 124-126 C11 The approximate 32 degree difference between the
boiling point maxima could be explained by the insufficient precision during the simple
distillation technique. The distilled compound seemed to be significantly contaminated with the
lower boiling compound which lead to the lower reading of the boiling point range. The
literature value for density of acetonitrile, 0.88 g/mL17 was constant with the experimental value
of 0.85 g/mL.

The carboxylic acid was identified as the benzoic acid. The molecular ion peak for this molecule
was found at m/z of 122, while the base peak was found at m/z of 105. The analysis of the IR
spectrum revealed the presence of a carbonyl bond at 1700 cm-1 and an OH group at 3000 cm-1.
Additionally, the aromatic stretches were detected at 3100 cm-1, 1600 cm-1and 1450 cm-1.
After the initial analysis the molecular formula of C6H5COOH was derived with the IHD equal to
5. Another pronounced peak on the mass spectrum was located at m/z of 77 which confirmed the
1116,17 http://www.sigmaaldrich.com/united-states.html
21

presence of the aromatic ring. The 1H NMR spectrum was used to further identify the structure.
A doublet of hydrogens with the integration equal to 2H was observed at 8.02 ppm a triplet (1H)
was observed at 7.59 ppm and another triplet (1H) at 7.45 ppm. All of these peaks were constant
with the chemical shift for protons in the aromatic ring and their splitting patters confirmed the
proposed structure. The proton directly bonded to the hydrogen was not present on the spectrum.
This hydrogen could be further downfield and hence off the scale. This hydrogen was also in
exchange with the solvent, so it could dissociate and not be present in the spectrum. The 13C
NMR has further confirmed the proposed structure by revealing that the molecule contained only
four different types of carbons. The observable carbon peaks were located at 128.0 ppm, 130.0
ppm 134.0 ppm and 172.5 ppm. All of these chemical shifts were associated with the presence of
the aromatic ring. Because they were a little more downfield than expected, it was concluded that
an electron withdrawing group (-COOH) was bonded directly to the ring. The fifth carbon was
not present on the 13C NMR spectrum and it was concluded that due to being the most deshielded
hydrogen it was located off the scale.
Finally, the experimental melting point range of 123.1-123.8 C was compared to the literature
value for the benzoic acid equal to 121-125C12. The approximate one degree difference between
the boiling point maxima was deemed to be small enough to be disregarded. It also indicated that
the isolated compound was extremely pure.

The lower boiling compound was identified as 4-nitrobenzaldehyde. The molecular ion peak
(also the base peak) for this molecule was found at m/z of 151 which indicated the presence of
nitrogen. The analysis of the IR spectrum revealed the presence of a nitrogen-oxygen bend and
1218 http://www.sigmaaldrich.com/united-states.html
22

stretch at 1450 cm-1 and 1590 cm-1 respectively. Additionally, the absorption bands at 1700 cm-1
was identified as a carbonyl bond. After the initial analysis the molecular formula of C7H5NO3
was derived with the IHD equal to 6. The 1H NMR spectrum was used to further identify the
structure. Two different hydrogen peaks were identified at 8.25 ppm (d, 2H) and 8.20 ppm
(d, 2H). The splitting pattern revealed that the two hydrogen groups were splitting each other.
The chemical shift values were characteristic for the aromatic ring. Because only two types of
hydrogens were present in a molecule and they were located in the aromatic ring it was
concluded that a molecule has a plane of symmetry within the carbon ring.
The 13C NMR has further confirmed the proposed structure by revealing that the molecule
contained only five types of carbons. The observable carbon peaks were located at 190 ppm
(within the range of heteroarmoatics carbon closest to the nitro group), at 150 ppm (consistent
with the carbon double bonded to oxygen), at 140 ppm, 130 ppm 124 ppm (all consistent with
carbons in the aromatic ring).
Finally, the experimental melting point range of 106.0-107.2 C was compared to the literature
value for the 4-nitrobenzaldehyde equal to 103 C13. The approximate four degree difference
between the boiling point maxima was deemed to be small enough to be disregarded. It also
indicated that the isolated compound was very pure.

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23

Experimental:
Lab 2 Separation of Two Unknown Liquid Compounds by the Means of Simple
Distillation
A clean distillation flask and a clean receiving flask were massed. A mixture of two unknown
liquids was obtained and the readily observable characteristics of the mixture were recorded.
Next, the distillation apparatus was assembled and the top of the distillation flask was insulated.
The flask was gently heated until the temperature readings of the vapor phase in the distillation
flask stabilized and the first drops of the lower boiling product (LB) started to distill in the
receiving flask. Heating was continued for only three minutes and terminated as another
significant rise in temperature was observed. After the heat was removed, the distillation flask
was cooled down to the room temperature. The masses of the distilling flask, the receiving flasks
and the products were recorded and the percent recovery for each isolated product was
determined.

After the distillation, 2.00 mL of the LB were transferred to a test tube. The thermometer probe
was clamped with the tip of the probe submerged in the liquid sample. After the addition of the
boiling stones the sample was set on an aluminium block on a hot plate and heated slowly until it
boiled. The sample was allowed to boil for 1 minute before its boiling range was recorded.
The same procedure was followed with the 2.00 mL of the higher boiling temperature liquid.
To determine densities of the liquid products, two clean 1 mL volumetric flasks and their
stoppers were massed, filled with the LB and HB unknowns to the meniscus and then massed
again. The samples were then discarded in a waste container.
24

Lab 3 Liquid-Liquid Extraction of two Solid Unknowns

An unknown mixture of two solids was obtained and massed and the readily observable
characteristics of the mixture were recorded. The mixture completely dissolved in 50.0 mL of
dichloromethane. The solution was then transferred into a separatory funnel and 20.0 mL of
1.0 M NaOH solution was added to the funnel. The extraction was done by gently inverting and
swirling the funnel for 30 seconds. During the procedure, the stopcock was vented several times
to relieve the pressure buildup in the funnel. The separatory funnel was then returned to the ring
stand. After the two components separated, they were poured into two labelled beakers. The
organic phase was then poured back to the separatory funnel and extracted with another 20.0 mL
of NaOH. After the second round of the extraction, the aqueous phase was combined in one
beaker and the organic phase in another.
Next, 10.0 mL of 6 M HCl was added to the aqueous phase. After the formation of acidic
precipitate the beaker was put into ice water bath for about 10 minutes. The aqueous phase was
then vacuum filtered for another 10 minutes. While vacuuming it was rinsed with cold water.
After the filtration the crude solid was transferred onto a watch glass and dried in the oven for 20
minutes. The dried solid was then transferred to a labelled vial and sealed with the parafilm.
The organic phase was treated with MgSO4 until a snow storm effect14was observed while
swirling the flask. The organic phase was then vacuum filtered and placed in a rotary evaporator.
The remaining solution was then transferred to a massed, labelled vial.
Lab 4 Purification of the Extracted Unknowns by Recrystallization Technique

1414 Chemistry 231 Laboratory Manual, 2015

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First, 51.0 mL of recrystallization solvent (ethanol) was gently heated in a covered beaker until it
started to boil. The minimal amount of the hot ethanol was then added to the beaker holding the
crude carboxylic acid (RCOOH). Next, more solvent was added until the acid dissolved. The
solution was then immediately taken away from the hot plate and allowed to slowly cool to the
room temperature. After it cooled, the solution was then placed in an ice water bath. A small
amount of ethanol was also cooled in an ice bath. Next, the mixture was vacuum filtered on a
Buchner funnel and rinsed with cooled ethanol for 10 minutes. Recrystallized RCOOH was then
transferred to a massed watch glass and dried in the oven for 20 minutes. The acid was then
removed from the oven and massed before being placed in the waste container. Similar
procedure was followed for the neutral organic compound (RZ). The recrystallization solvent
used for the purification of RZ was also ethanol, but the purified product was massed
immediately after the vacuum filtration, without being placed in the oven at 110 C.
Two melting point samples were prepared for each pure unknown solid and their melting points
were recorded in Table 2.
Lab 5 Mass Spectroscopy
A mass spectroscopy sample was prepared for the two compounds in the mixture of liquids
(LB and HB, unknown #6) and the two compounds in the mixture of solids (R-COOH and R-Z,
unknown #18). Each sample was then placed in a Hewlett-Packard 5890 Series II gas
chromatograph with a 5971 Series mass detector to produce a mass spectrum that was later used
in the characterization and analysis of the unknown compounds along with the IR spectra and the
1

H/13C NMR spectra.

26

Lab 6 Infrared Spectroscopy (IR)

An IR sample was prepared for the two compounds in the mixture of liquids (LB and HB,
unknown #6) and the two compounds in the mixture of solids (R-COOH and R-Z, unknown #18).
Each sample was then placed in a Nicolet Avatar 360 spectrometer to produce an IR spectrum
that was later used in the characterization and analysis of the unknown compounds along with
the mass spectra and the 1H/13C NMR spectra.
Lab 7 Nuclear Magnetic Resonance Spectroscopy (1H NMR and 13C NMR)
The 1H NMR and 13C NMR samples were prepared for the two compounds in the mixture of
liquids (LB and HB, unknown #6) and the two compounds in the mixture of solids (R-COOH
and R-Z, unknown #18). Each sample was then placed in Bruker Avance 300 MHz NMR
spectrometer to produce 1H NMR and 13C NMR spectra that were later used in the
characterization and analysis of the unknown compounds along with the mass spectra and the IR
spectra.

27

References:
1,5,7,20

Chemistry 231 Laboratory Manual; DePaul University: Chicago, IL, 2015

4,6,8,9,10,11,12,13

Gorzynski-Smith, J. Organic Chemistry, Ed. 4; McGraw-Hill: New York, 2014; pp

96-533.

Jackson, R.; Bavel, C. Solar Distillation of Water from Soil and Plant Materials: A Simple
Desert Survival Technique. Science. 1965, 149, 1377-1379.

16-19

Sigma Aldrich. http://www.sigmaaldrich.com/united-states.html accessed (March 10, 2015)

Zubrick, J., W. Distillation. The Organic Chem Lab Survival Manual A Students Guide to
Techniques, Ed. 9; Wiley: USA, 2014; pp 165-171.

28

Appendices
Calculations:
All masses seen in Table 1 and Table to were determined using the mass by difference technique.
To obtain the mass of the isolated LB liquid (Table 1), the mass of an empty receiving flask was
subtracted from the mass of that same flask containing isolated product.
Mass LB=M receivingflask product ( g)M empty receiving flask ( g )
Mass LB=79.5706 ( g )74.3244 (g)
Mass LB=5.2463(g)

Because both the receiving and the distillation flask were initially massed without the stoppers
and identification of the correct stopper for each flask was not possible later in the process, the
average mass of the two stoppers used was calculated and included in the initial masses of the
empty receiving and distilling flasks.
Avg stopper mass=Mas s stopper 1 ( g)+ Mas s stopper 2 (g)
Avg stopper mass=19. 2873 ( g )+19.5822 ( g )
Avg stopper mass=19.4348(g)

29

The percent recovery for the crude solid products was obtained by dividing the mass of the crude
component by the total mass of the original mixture and by multiplying it by a hundred percent.
Crude RZ recovery=

Mass crude RZ (g)

100( )
Masstotal ( g)

Crude RZ recovery=

1.1176( g)
100( )
4.2474 (g)

Crude RZ recovery=26.313( )

Similarly, the percent recovery for the pure products were obtained by dividing the mass of the
purified components by the total mass of the original mixture and by multiplying it by a hundred
percent.
Pure RZ recovery =

Mass pure RZ ( g)
100( )
Masstotal (g)

Pure RZ recovery =

0.8154(g)
100()
4.2474(g)

Pure RZ recovery =19.20()

The total percent recovery for both crude and pure compounds was calculated by adding the
recovery values for the original components.
Total pure recover y (RZ+ RCOOH )=RZ ( ) + RCOOH ( )
30

Total pure recover y (RZ+ RCOOH )=19.20 ( ) +0.275( )

Total pure recover y (RZ+ RCOOH )=19.48( )

The densities of the liquid products (Table 1) were determined by dividing the masses of small
samples of LB and HB by their volume, equal to 1.00 mL.
d unknow nlower BP =

Mass of sample ( g)
Volume of the sampe(mL)

d unknow nlower BP =

0.7956( g)
1.00(mL)

d unknow nlower BP =0.796(

g
)
mL

31