Experiment 7: Qualitative Analysis

Eric Sprys

213 Organic Chemistry II Laboratory

4/26/2018
INTRODUCTION:

Sometimes in chemistry an unknown molecule is given and must be identified. A way of

identifying an unknown molecule is by using a qualitative analysis. There are many different

ways to do a qualitative analysis but one of the main points of doing an analysis is to determine

the functional groups in the molecule. When the functional groups are known the type of

molecule will be known (ex. Ester, alcohol, carboxylic acid) and the structure of that molecule

can then be determined. Some tests that can be used in qualitative analysis are Jones test, DNP

test, melting point range, IR, and NMR. Many of these test can be used together to determine

the identity of an unknown molecule. In the lab and in industry scientists can use a qualitative

analysis harmful substances in water supplies and chemicals that may be present at crime

scenes.

During a qualitative analysis a Jones test (chromium trioxide test) can be used to

determine the presence of 1°/2° alcohols and aldehydes. In a test tube the unknown molecule

is dissolved and Jones reagent is added. If the test is positive the solution will become a blue

green color within 5 seconds. A positive test will mean there is a 1°/2° alcohols or aldehydes

present. The jones test uses chromium trioxide to oxidize primary alcohols and aldehydes to

carboxylic acids and secondary alcohols to ketones. In the real world the Jones test is used in

breathalyzers that test drivers to see if they are drunk.

One other important test that can be used in a qualitative analysis is a DNP test (2,4-

dinitrophenylhydrazine). The structure of DNP can be seen in Figure 1. This test looks for to see

if there is an aldehyde of ketone present in the unknown molecule. For a DNP test the unknown

molecule is dissolved in a test tube and DNP is added. A positive test will be shown as an
orange/yellow precipitate being formed in the solution. The positive test will mean that there is

either a ketone or aldehyde present in the unknown molecule. This reaction is a condensation

reaction because as the DNP reacts with the ketone or aldehyde there is a loss of water. A DNP

test does not show positive for carboxylic acids or esters because these carbonyls have a less

electrophilic carbon. The less electrophilic carbonyl carbon will not react with the DNP so no

reaction will take place. The purpose of this experiment was to determine the identity of the

unknown molecule through the use of a Jones test, DNP test, IR, and proton NMR.

Figure 1. The structure of DNP.

DISSCUSION:

An unknown liquid was acquired from the instructor. The liquid was said to be a 1°

alcohol, 2° alcohol, 3° alcohol, hydrocarbon, ketone, aldehyde, or ester. The first test done to

determine the identity of the liquid was a Jones Test. The Jones test was used to determine if

the liquid was a primary/secondary alcohol or and aldehyde. A positive Jones test is

represented by an opaque blue green solution and represents 1° alcohol/aldehydes becoming

carboxylic acids or 2° alcohols becoming ketones. One drop of my solution was dissolved in

acetone. Jones reagent was then added and the result was an opaque brown liquid. This was a

negative result for the Jones test meaning the molecule was not a 1°/2° alcohol or an aldehyde.
The results from this test can be seen in Table 1 with the X marking what the molecule cannot

be.

The next test to be done was a DNP reagent test. A DNP test looks for the presence of a

ketone or aldehyde in the unknown sample. A positive DNP test can be seen as an orange

precipitate being formed. This precipitate comes from a primary amine reacting with the

carbonyl group of a ketone or aldehyde to form an insoluble imine product. One drop of the

unknown liquid was dissolved in ethanol and the DNP reagent was added. The result was a clear

orange liquid with no precipitate present. This was a negative result for the DNP test and

showed that the unknown molecule was not an aldehyde or a ketone. The results from this test

can be seen in Table 1.

Table 1. The test results from the three tests showing what the unknown molecule cannot be.
Alc 1°, 2° Alc 3° Hydrocarbon Ketone Aldehyde Ester
Jones Test x x

DNP Test x x

IR x x x x x

Table 2. The frequencies and functional groups taken from the IR run on the acetanilide.
Frequency cm-1 Bond Functional Group

3015 =C-H stretch Alkenes

 2916 C-H stretch Alkanes

1607 N-H bend Amines

1471 C-C stretch Aromatics

1374 C-H rock Alkanes

An infrared spectroscopy (IR) was taken on the unknown liquid and the spectrum can be

seen in Figure 2. The major peaks from the spectrum are represented in Table 2 along with the

corresponding functional groups. The first peak was at 3015 cm-1 and represented a =C-H

stretch that is present in alkenes. The second peak at 2916 cm-1 corresponded to a C-H stretch

that is presents in alkanes. This peak would be expected in an organic molecule because organic

molecules are mostly made up of carbon and hydrogens. The third peak at 1607 cm-1

corresponded to a N-H bend that is present in amines. An amine was not a possible

identification for the molecule because an amine was not one of the seven molecules that the

unknown molecule could be. The peak may have been misinterpreted and the peak could be a

C-C stretch (in-ring) that is present in aromatics because that frequency is just 7 cm -1 away from

the peak. The next peak was at 1471 cm-1 and corresponded to a C-C stretch that is present in

aromatics. The final peak at 1374 cm-1 corresponded to a C-H rock that is present in alkanes.

From the Jones test and the DMP test a determination was made that the molecule could be a

3° alcohol, hydrocarbon, or ester. If the molecule was a 3° alcohol there would have been a

broad peak at 3500 cm-1 and if the molecule was a ester there would have been a sharp peak at

1700 cm-1.The IR narrowed the possibilities down so the unknown molecule could only be a
hydrocarbon. This was because the IR showed no functional groups that would be present in a

3° alcohol or an ester. The IR did however show functional groups that could be present in a

hydrocarbon possible with an aromatic ring present in the hydrocarbon.

Figure 2. The spectrum produced from the IR taken on the unknown substance.

Figure 3. Spectrum from the NMR of the unknown molecule.

 Knowing that the unknown molecule was a hydrocarbon from the information gathered

from the Jones test, DNP test, and IR the structure of the hydrocarbon was then determined

using a proton NMR. The NMR spectrum for the unknown molecule can be seen in Figure 3.

The spectrum showed 2 peaks with the one farthest downfield (peak A) being at 6.7 PPM. The

peak was a singlet with an integration of 1. The second peak (peak B) was at 2.2 PPM was a

singlet and had an integration of 3. After a while attempting to make a molecule with current

integration it was determined that the integration was set wrong and needed to be multiplied

by 3. This made the integration for peak A 3 and made the integration for peak B 9. Peak A was

determined to be a benzene ring with 3 substituents coming off of the ring. This was because

the peak had a chemical shift that represented an aromatic ring. The ring was known to have 3

substituents attached because there were 3 hydrogens attached to the other 3 carbons on the

ring. These hydrogens were all equivalent and that is why all the hydrogens showed up in one

peak. With an integration of 9 peak B was determined to be three methyl groups coming off of

the benzene ring. The peak was a singlet so there were no adjacent hydrogens to any of the

groups and this makes sense because there are no hydrogens attached to a carbon on an

aromatic ring with a substituent also attached. All the hydrogen were equivalent in the three

methyl groups because all the hydrogens showed up in one peak. This made the methyl groups

alternate on the carbons of the benzene ring. The alternation made all the hydrogens

equivalent to each other. With all the information from the Jones test, DNP test, IR, and NRM

put together the unknown molecule was determined to be 1,3,5-trimethylbenzene. The

structure of 1,3,5-trimethylbenzene can be seen in Figure 4.

Figure 4. The structure of the unknown molecule (1,3,5-trimethylbenzene C9H12).

CONCLUSION:

A qualitative analysis was done on an unknown liquid using a Jones test, DNP test, IR

and NMR. The first test done to the unknown liquid was the Jones test. The molecule was

negative for the Jones test showing that there was not a 1°/2° alcohols or aldehydes present. The

next test that the unknown liquid was put through was the a DNP test. The test showed a

negative result so the unknown molecule was not a ketone or aldehyde. The IR spectrum showed

that the molecule was not a ester or 3° alcohol because if the molecule was a 3° alcohol there

would have been a broad peak at 3500 cm-1 and if the molecule was a ester there would have

been a sharp peak at 1700 cm-1. The IR did however show that alkanes, alkenes, and aromatics

were all functional groups that were present in the molecule. The molecule was determined to be

a hydrocarbon through the process of elimination of all the other functional groups. A proton

NMR was then used to determine the structure of the unknown hydrocarbon. The NMR spectrum

showed two peaks that were both singlets. The peak farther downfield had an integration of 3

and corresponded to a tri-substituted benzene ring. The other peak (peak B) had an integration of

9 and corresponded to three equivalent methyl groups. The methyl groups alternated on the

carbons of the benzene ring so that all the hydrogens would be equivalent. The final structure of
the molecule was determined to be 1,3,5-trimethylbenzene and the structure can be seen in

Figure 4. The experiment was a success because the unknown molecule was identified using a

Jones test, DNP test, IR, and NMR.

 REFRENCES

Lou, J., Zhu, L., Ma, Y., & Li, L. (2007). Ferric(III) Nitrate Supported on Kieselguhr: A New

Reagent for Selective Oxidation of Alcohols. ChemInform,38(11).

doi:10.1002/chin.200711038