Isabela Miguel March 14, 2019

Experiment 4: Identification of an Unknown through Qualitative Analysis 28A

Results
Unknown No. : 28A
Physical Properties of the Unknown:
Appearance: clear liquid
Odor: sweet, light rubbery, pungent smell. Somewhat fruity sweet.

Table 1. Solubility Test Results of the Unknown and Functional Group Standards.

Indications
5% NaOH

5% HCl (for water: indicate A for acidic, B for

H2SO4
water

Sample basic
For anything else: indicate X if
soluble)
No O or N atom,
toluene A X
cyclohexene A
t-butanol A X X
ethanol B X
acetone A X X X
ethyl acetate A X X
benzaldehyde A
unknown A

Table 2. Functional Group Test Results of the Unknown and Functional Group Standards.
A. Ignition, Bayer, Alcoholic Silver Nitrate Tests

Observations/Indications
Sample
Ignition Test Bayer Test Alcoholic Silver Nitrate
toluene + Yellow flame (sooty smoke) - No precipitate - No precipitate
cyclohexene - Yellow flame (non-sooty smoke) + Brownish precipitate - No precipitate
t-butanol - Yellow flame (no smoke) - No precipitate - No precipitate
ethanol - No flame - No precipitate - No precipitate
acetone - Yellow flame ( non-sooty smoke ) - No precipitate - No precipitate
ethyl acetate - Yellow flame ( non-sooty smoke ) - No precipitate + Precipitate
benzaldehyde + Yellow flame (sooty smoke) + Brownish precipitate - No precipitate
Yellow flame ( non-sooty smoke ) - No precipitate
unknown - - No precipitate
saturated

B. Lucas, Chromic Acid Tests, and Iron (III) Chloride Tests

Observations/Indications
Sample
Lucas Test Chromic Test Iron (III) Chloride
 toluene - Non-miscible, oily - Red orange precipitate - No change

cyclohexene - Dark yellow, cloudy - Yellow-green liquid - No change

Slight separation of 2 clear - - No change

t-butanol + Orange precipitate
(yellow-ish) layers
ethanol - clear - Blue green liquid - No change
acetone - clear - NA - No change
Clear(yellow-ish) w/ slight - Black-ish brown w/ - No change
ethyl acetate +
separation green tint precipitate
benzaldehyde - Cloudy-yellow formation + Red-brown precipitate + Red precipitate
- - Yellow from
unknown - Clear/ no separation Red-brown liquid
reagent

C. Hydroxamic Acid and Iodoform Tests

Observations/Indications
Sample
Hydroxamic Acid Test Iodoform Test
toluene - No precipitate, yellow liquid - Clear /cloudy, light yellow
cyclohexene - Brown solution - Clear light yellow
t-butanol - Dark yellow solution - Clear light yellow
Clear light yellow, w/dusting
ethanol - Yellow solution +
of precipitate
Clear w/ cloudy yellow
acetone - Yellow solution +
precipitate
Clear light yellow, w/dusting
ethyl acetate + Red-violet solution -
of precipitate
Clear light yellow, w/dusting
benzaldehyde - Yellow solution -
of precipitate
unknown - Dark red dusting of spots

D. 2,4-DNPH and Tollen’s Tests

Observations/Indications
Sample
2,4-DNPH Test Tollen’s Test
toluene + Little brown precipitate - Clear colorless liquid
cyclohexene + Orange precipitate + Silver mirror after heating
t-butanol - Orange solution - Pale yellow liquid
ethanol - Red-brown liquid - Golden liquid
acetone + Yellow precipitate - Golden liquid
ethyl acetate - Orange solution - Pale yellow liquid
benzaldehyde + Orange- yellow precipitate + Silver mirror w/o heating
unknown

Identity of the unknown : Isoamyl acetate

Postlab Questions

1. Summarize the results obtained from the unknown. Which tests gave positive/negative
results on the unknown sample? What do these results indicate?

The unknown was immiscible and characteristically oily in quality in all of the solubility tests
garnering a negative for water, 5%NaOH, 5%, and 5% HCl. Perhaps this is the true results given
the proper procedure, but this may also point to some possible errors that might have occurred
during the experimental process. The following tests such as the Ignition Test, Bayer Test,
Alcoholic Silver Nitrate test, Lucas test, Chromic test, Iron (III) Chloride, and Iodoform Test all
proved to have negative results on the unknown. The negative results, however, still point to
possible structures the unknown may have. Consider for example the Ignition test whose results
point to the unknown having a saturated structure. The negative Alcoholic Silver Nitrate test results
means the unknown has no halogen in the structure. The negative Bayer Test result point to an
aliphatic structure consisting of saturated single bonds while the negative Lucas test indicate a
structure without tertiary or secondary alcohols. The unknown also seems to not have any primary,
secondary alcohols or aldehyde, phenol or enol functional groups as indicated by the negative
Chromic acid test result and Iron (III) Chloride test. No yellow precipitates were observed during
the Iodoform Test, indicating the absence of methyl ketones and methyl carbinols.

2. Based on the indications of the different qualitative tests and the physical properties
of the unknown, what is the identity of the unknown sample?

Considering the lack of positives during the experimental procedures, identifying the
unknown relied on cancellation of unlikely candidates as well as a consideration of physical
properties. Based on the results gathered, the unknown could fall on either cyclohexane or Isoamyl
acetate. Both appear to be aliphatic in structure as well as saturated although the former appears to be
an aromatic ring while the other a carbon chain with an ester presence. Having performed either of the
tests that were not done would have indicated whether the unknown contained an ester or an aldehyde,
discriminating the identity of the unknown from cyclohexane. However, because these were not
performed, the identity of the unknown is ascertained from literature and the similar but slight
difference in odor. Both are clear liquids, however in terms of odor, the two have slight differences.
Cyclohexane can have a certain sweet, chloroform-like odor, while Isoamyl acetate is known to have
a pungent, fruity scent to it- which is the closest description observed of the unknown. Based on the
results and further analysis, isoamyl acetate may then the most probable identity of the unknown.

3. Can qualitative tests be used to ascertain unknown samples? Explain.

Qualitative tests can be used to ascertain unknown samples, given that the unknown is within
given test standards. The number and position of the functional groups is left unspecified, while the
mass or concentration of the elements also cannot be determined. However, their presence or absence
can be found out by reacting the unknown with various reagents systematically. Identifying the
exactly the unknown will be difficult to conclude due to the various kinds of information that is left
unknown such as the molecular formula and the structure of a compound, but it is still possible.
 4. What modern analytical techniques are available that provide the same information as
the qualitative tests? What are the advantages of these techniques over the qualitative
tests?
As mentioned earlier; qualitative tests may indicate the presence or absence of functional groups in an
unknown given the varied reactions when subjected to the different reagents. However, aside from
chemical properties, functional groups also have characteristic vibrations which give rise to
absorption at certain frequency range in the spectrum. Infrared Spectroscopy (IR Spectroscopy)
makes use of the measure of electromagnetic energy emitted by the vibration of covalent bonds to
graph the absorption bands of different functional groups. Nuclear Magnetic Resonance (NMR)
Spectroscopy on the other hand, improves the accuracy of the graph by using the concept of energy
transfer and magnetic spin of the nucleus of the molecules. In comparison to qualitative tests,
spectroscopy techniques give quick results, and given information on molecular conformation,
conformational exchange, phase change when trying to identify the functional groups in a compound

5. For each test, enumerate and explain why the standard tested positive.

References

National Center for Biotechnology Information. PubChem Database. Isoamyl acetate, CID=31276,
https://pubchem.ncbi.nlm.nih.gov/compound/31276 (accessed on Mar. 20, 2019)

Reusch W. Nuclear Magnetic Resonance Spectroscopy [Internet]. Michigan: Department of

Chemistry, Michigan State University; 2013 May 5 [cited 2019 Mar 20]. Available from:
https://www2.chemistry.msu.edu/faculty/reusch/virttxtjml/spectrpy/nmr/nmr1.htm

Reusch W. Infrared Spectroscopy [Internet]. Michigan: Department of Chemistry, Michigan

State University; 2013 May 5 [cited 2019 Mar 20]. Available from:
https://www2.chemistry.msu.edu/faculty/reusch/virttxtjml/spectrpy/infrared/infrared.htm

Yanza ER. Survey of Organic Chemistry Laboratory Manual. Quezon City: Department of Chemistry,
Ateneo de Manila University; 2014.