Identification of an Unknown

Experiment #9

Kayla Rhodes
Section #: A02
T.A.: Paul Mueller
Lab Partner: Kristen Reierson
11-18-09

Purpose:
The purpose of this experiment was to determine the structure of an unknown using the
chemical tests and spectroscopic data normally available in the organic laboratory. There isnt a
universal way of doing this, but a logical pathway needs to be developed in order to identify the
unknown structure. This lab encourages the discovery of such a pathway.
Experimental Procedure:
The unknown #2:033 and physical appearance of a light, yellow liquid were recorded
before conducting tests to identify the substance. The first tests conducted were solubility tests. A
.2 mL sample of the unknown was added to 3 mL of each solvent. The unknown was insoluble in
water, NaOH, and HCl. However, the unknown was soluble in H2SO4. Next, a micro-boiling
point of the sample was obtained with the micro-boiling point apparatus. A rapid, steady flow of
bubbles were seen from the capillary tube within the sample. This was followed by cessation of
the steady stream, and filling of the capillary tube with the unknown liquid. These events assisted
in the recording of the boiling point for this substance between 139 and 140C. Before moving
on to functional group tests, an IR was taken of the unknown sample to help determine which
tests would be necessary in identifying the unknown. The first test conducted was a
Bromine/CCl4 Test for the presence of Alkenes. A small sample of the unknown was dissolved in
2 mL THF. Then, a solution of 5% bromine in CCl4 was added dropwise, with shaking. An
instant discharge of the bromine color was observed, suggesting a positive test. The next test
conducted was the flame test for aromatic compounds. The unknown was placed on the tip of a
spatula, and burnt in the flame of a Bunsen Burner. A small amount of black smoke appeared,
indicating the presence of aromatic compounds. This positive test could not be replicated,

however, on subsequent tests. The next functional group tests conducted were done to verify the
presence of an aldehyde or a ketone. The 2,4-dinitrophenylhydrazine test required 2-3 drops of
the unknown be dissolved in a few drops of methanol. Then, 1 mL DNP reagent was added, and
the mixture shaken. A colored ppt was formed indicating the presence of an aldehyde or ketone.
From there the Tollens Test was done by first preparing the Tollens Reagent by adding conc.
Ammonia solution to 3 mL Tollens Solution A until the brown precipitate was redissolved. Then,
3 mL Tollens Solution B was added, followed by more conc. Ammonia solution. When the
mixture was almost clear again, .5 mL were added to 2-3 drops of the unknown. Neither a silver
mirror or black ppt were formed in the process indicating a negative test for the presence of
aldehydes. Since aldehydes were not present, a confirmation of a ketone indicated by the 2,4dinitrophenylhydrazine test was needed. The iodoform test was done to do so. For this test, 2-3
drops of the unknown were dissolved in a 1:1 mixture of THF:Water. Then 2-3 drops of 3M
NaOH were added, followed by 3 mL of iodine solution. The brown coloration did not disappear,
and a pale yellow ppt. did not form, indicating a negative test for methyl ketone. At this point,
the 2,4-dinitrophenylhydrazine test was repeated to confirm the negative results of the Tollens
and Iodoform tests. A colored ppt did not form, indicating a negative test for the presence of an
aldehyde or ketone. The next functional group test was the Hydroxyl Amine/Ferric Chloride Test,
which required adding 10 drops of a saturated ethanolic solution of hydroxylamine hydrochloride
to 2-3 drops of the unknown. Then, adding 10 drops of 20% ethanolic KOH. This mixture was
heated to boiling, and acidified with 5% HCl, followed by the dropwise addition of a 5% solution
of FeCl3. A deep purple coloration suggested the presence of an ester, but when the test was
repeated without using hydroxylamine hydrochloride the same deep purple was observed,
suggesting a phenol not an ester. The Chromic Acid and Lucas Tests were then performed for the

presence of an alcohol. The Chromic Acid Test required 1 drop of unknown be dissolved in 1 mL
of reagent grade acetone. To this, 1 drop chromic acid reagent was added, and the solution turned
a blue-green color indicating a primary or secondary alcohol. Adding 3 mL Lucas reagent to 0.5
mL unknown, and shaking for 15 sec. revealed no ppt after letting the solution stand for 5 min.
This was indicative of a primary alcohol. Five alcohols with boiling points within the ranges of
138 and 146C were submitted as possible structures of the unknown. This 1st attempt did not
contain any correct structures. The Iodoform Test was then repeated for the presence of a ketone
since alcohol was no longer a possibility. The test was positive for methyl ketone with a
disappearance of the brown coloration, replaced by a pale yellow ppt. A new list of structures
was submitted of ketones with boiling points ranging between 139 and 145C. The list contained
the correct structure believed to be 2,4-pentanedione (acetylacetone).
Results and Discussion:
1.) Unknown #: 2:033
2.) Physical Constants: The boiling point of the unknown was 139C. The microboiling point apparatus was used to determine the boiling point range, and suggested
a boiling point range of which I was very confident between 139 and 140C. The
same results were obtained with a second attempt to assure accuracy. This boiling
point range was helpful in identifying the correct structure of the unknown as 2,4pentanedione (acetylacetone) after further functional group testing.
3.) The solubility tests performed indicated a substance insoluble in water, NaOH, and
HCl. The unknown was, however, soluble in H2SO4 which is indicative of an oxygen
containing compound such as a ketone. These tests also eliminated the likelihood that
the unknown was a carboxylic acid or an amine, and therefore no tests were
performed to detect them.

4.) Functional Group Classification Test: The 2,4-Dinitrophenylhydrazine Test was

done to verify the presence of an aldehyde or a ketone as suggested by the IR
spectrum at 1707.65 cm-1. A colored ppt was formed indicating a positive test. To
further distinguish between the two functional groups the Tollens Test was conducted.
Neither a silver mirror or black ppt were formed in the process indicating a negative
test for the presence of aldehydes. The iodoform test was done to verify the suspected
ketone, but the brown coloration did not disappear and a pale yellow ppt. did not
form, indicating a negative test for methyl ketone. At this point, the 2,4dinitrophenylhydrazine test was repeated to confirm the negative results of the
Tollens and Iodoform tests. A colored ppt did not form, indicating a negative test for
the presence of an aldehyde or ketone. These negative tests combined with positive
tests for alkenes and aromatic compounds suggested the possibility of a phenol,
which was also indicated by a positive Ferric Chloride Test. The boiling point of the
unknown, however, was too low to be a phenol. The Alcohol tests were then
performed suggesting the presence of a primary alcohol. The boiling point range of
the unknown supported this possibility, and five possible alcohols were submitted for
the 1st attempt. These structures were incorrect, and since an aldehyde or ketone is
more clearly represented on the IR than an alcohol the Iodoform Test was repeated.
This time the brown coloration disappeared, and was replaced by a pale yellow ppt.
The test was positive for the presence of a methyl ketone, and the boiling point range
of 139-140C further supported the identification of the unknown as 2,4-pentanedione
(acetylacetone) with a boiling point of 139C.

5.) IR: The IR spectrum represents all of the functional groups that make up 2,4pentanedione (acetylacetone), but also a few impurities that were misleading in trying
to identify the unknown.
2,4-pentanedione (acetylacetone):
Frequency (cm-1)
1707.65
1726.65
2853.83 and 2961.48

Bond
C=O stretch
C=O stretch
CH stretch

Functional Group
Ketones
Saturated aliphatic
Alkanes

Impurities:
Frequency (cm-1)

Bond

Functional Group

1619.00

NH Bend

Primary Amines

3005.80

CH stretch

Alkenes, Aromatics

3414.25

OH stretch

Alcohols, Phenols

6.) NMR:
Position

Shift (ppm)

Integration

Multiplicity

Assignment

1 and 3

2.047

6H

Singlet

CH3

2.240

2H

Singlet

CH2

Conclusion:
1.) The information obtained from the solubility and functional group tests, as well as the
micro-boiling point allowed me to identify the unknown. The solubility tests
narrowed the unknown down to an oxygen containing compound. The Iodoform Test
suggested a methyl ketone and the boiling point range of 139-140C narrowed down
the possible ketones. The IR and NMR also supported the functional groups identified
in the unknown. These tests and spectra led to a confident identification of the
unknown as 2,4-pentanedione (acetylacetone).
2.) This experiment was a success. Through the use of chemical tests and spectroscopic
data, a logical pathway was developed. Positive tests suggested functional groups
present in the unknown as well as the impurities represented by the IR spectrum. The
boiling point was accurate and useful in narrowing down the possible ketones for
submission. The submissions contained the correct identity of the unknown, and were
further narrowed down to 2,4-pentanedione (acetylacetone) with a boiling point of
139C. The boiling point range of 139-140C supports this identification, and
suggests a successful experiment overall.
Appendix A: Calculations
N/A
Appendix B: Spectra
1.) 1H NMR attached
2.) IR attached
Appendix C: Data Sheet
Attached