Qualitative Analysis of Unknown
Qualitative Analysis of Unknown
Qualitative Analysis of Unknown
Goal: To identify unknown #64 by comparing the results obtained in 1H NMR, 13C NMR, IR spectrogram,
solubility tests, melting point analysis, and five chemical classification tests with those of known compounds. .
water
STRONG BASE:
H 2O
0C 318C
(varies with concentration)
100C 1388C
(varies with concentration)
sodium hydroxide
(5% solution used) WEAK BASE: (5% solution used) STRONG ACID: (5% solution used) STRONG BASE:
NaOH
Na+ -OH
NaHCO3
50C
(varies with concentration)
851C
(varies with concentration)
HCl
HCl
36.461 g/mol
-114.8C
(varies with concentration)
-84.9C
(varies with concentration)
sulfuric acid
H2SO4
98.079 g/mol
10C
(varies with concentration)
337C
(varies with concentration)
hexane
POLAR APROTIC SOLVENT:
C6H14
86.18 g/mol
-96 -94C
(varies with concentration)
68-69 C (varies
with concentration)
dichloromethane
POLAR PROTIC SOLVENT:
CH2Cl2
84.93 g/mol
-96.7C -114C
(varies with concentration)
39.6C 78.37C
(varies with concentration)
ethanol
C 2H 6O C4H10O
diethyl ether
REACTS WITH 3, ALLYLIC, & BENZYLIC HALIDES TO FORM WHITE PPT:
-116.3C
34.6C
Silver Nitrate Test for 3, Allylic, & Benzylic Halides AgNO3 169.87 g/mol 212C 444C
(decomposes)
silver nitrate
ARYL HALIDE (negative halide control for silver nitrate test):
bromobenzene
BENZYLIC HALIDE (positive control for silver nitrate test):
C6H5Br
157.01 g/mol
30.8C
156C 198199C
benzyl bromide
C7H7Br
171.04 g/mol
3.9C
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nitric acid
ORGANIC SOLVENT (dissolves AgNO3 & halide):
HNO3
63.01 g/mol
42C
83C
95% ethanol
SOURCE OF FERROUS ION FOR FORMATION OF FERROUS HYDROXIDE:
C 2H 6O
46.07 g/mol
-114C
78.37C
Ferrous Hydroxide Test for Nitro Compounds Fe(NH4)2(SO4)2 284.05 g/mol (anhydrous) 100110C N/A
2M potassium hydroxide (in methanol) ACID THAT REACTS WITH KOH TO FORM HYDROXIDE ION: 2M sulfuric acid NITRO COMPOUND (positive control for ferrous hydroxide test):
KOH
KOH
56.1056 g/mol
406C
1327C
H2SO4
98.079 g/mol
10C
p-nitrotoluene
C7H7NO2
137.136 g/mol
53-54C
Baeyer Unsaturation Test for Non-Aromatic Alkenes & Alkynes REACTS WITH ALKENES & ALKYNES (nonaromatic) TO FORM BROWN PPT: KMnO4 158.034 g/mol
potassium permanganate
240C
N/A
(1% aqueous solution) CYCLOALKENE (positive control for Baeyer Unsaturation Test):
cyclohexene
ORGANIC SOLVENT (dissolves cyclohexene):
C6H10 C 2H 6O
-103.5C -114C
82.98C 78.37C
95% ethanol
2,4-Dinotrophenylhydrazine Test for Conjugated Aldehydes & Ketones REACTS WITH CONJUGATED ALDEHYDES & 198 KETONES TO GIVE AN ORANGE TO RED PPT: C 6H 6N 4O 4 198.14 g/mol 202C 2,4-dinotrophenylhydrazine (decomposes) CONJUGATED ALDEHYDE (positive aldehyde control for 2,4-dinitrophenylhydrazine test): C 9H 8O 132.16 g/mol -7.5C
N/AC
cinnamaldehyde benzophenone
248C
CONJUGATED KETONE (positive ketone control for 2,4-dinitrophenylhydrazine test): (in 1mL of 95% ethanol)
C13H10O
182.217 g/mol
47.9C
305.4C
Nitrous Acid Test for 1, 2, 3, & Aromatic Amines SOURCE OF NITRITE ION FOR FORMATION OF NITROUS ACID: NaNO2 68.9953 g/mol
sodium nitrate
271C (decomposes)
320C
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N-butylamine
AROMATIC AMINE [positive control for nitrous acid test (N2 bubbles) + diazo dye coupling reaction with -napthol (beige ppt)]:
C4H11N
73.14 g/mol
-49C
C6H5NH2
93.13 g/mol
-6.3C
aniline
2 ALIPHATIC AMINE [positive control for nitrous acid test (nitroso compound yellow oil/ppt): C 7H 9N 107.15 g/mol -57C
N-methylaniline
ACID (proton source for nitrous acid formation + prevents diazo dye coupling reaction): 2M sulfuric acid DIAZO DYE COUPLING REAGENT: H2SO4 98.079 g/mol 10C
337C
-naphthol
C10H8O NaOH
144.17 g/mol
123C
285C
(in 10% NaOH aqueous solution) BASE CATALYST FOR DIAZO DYE COUPLING REACTION:
sodium hydroxide
BASE CATALYST FOR DIAZO DYE COUPLING REACTION: 2.5% ferric chloride solution PHENOL [positive control for ferric chloride test (red, blue, purple, or green color change)]:
NaOH
39.9971 g/mol
318C
1388C
Ferric Chloride Test Reagents for Phenols FeCl3 162.2 g/mol (anhydrous) 306C (anhydrous) 315C (anhydrous decomposes) 181.7C
C 6H 6O
94.11 g/mol
40.5C
phenol
ORGANIC SOLVENT (dissolves phenol):
95% ethanol
SYMMETRICAL CARBOXYLIC ACID WITH DOUBLE BOND:
46.07 g/mol
-114C
78.37C
maleic acid
116.07 g/mol
135C
N/A
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Solubility Flowchart
Low MW amines Low MW carboxylic acids Low MW neutral soluble HCl soluble insoluble insoluble H 2 SO 4 insoluble BASES
NEUTRAL COMPOUNDS: Alkenes, alkynes, alcohols, ketones, aldehydes, nitro compounds, esters, ethers, amides
NaOH
INERT COMPOUNDS: Alkanes, alkyl halides, aromatic compounds STRONG ACIDS: Carboxylic acids & some phenols
soluble NaHCO 3
soluble
insoluble
Chemical Classification Tests 1. Silver Nitrate (Ethanoic) Test for 3, Allylic, & Benzylic Halides:
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Experiment #21: Qualitative Analysis to Identify Unknown #64: Maleic Acid 2. Baeyer Unsaturation Test for Non-Aromatic Alkenes & Alkynes
1 Aliphatic Amine
1 Aromatic Amine
2 Amine
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3 Aliphatic Amine
Aromatic Amine
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Ferrous Hydroxide Test for Nitro Compounds: 1. Added 1.5 mL of a 5% ferrous ammonium sulfate solution to test tube. 2. Added 1 drop of unknown #64 to test tube. Tapped to mix. 3. Added 1 drop of 2M sulfuric acid and then 1 mL of a 2M potassium hydroxide solution in methanol to test tube. Covered with parafilm & shook vigorously to mix. Noted an army green colored precipitate. 4. Unknown #64 had a negative ferrous hydroxide test suggesting that it is not a nitro compound. 2,4-Dinotrophenylhydrazine Test for Aldehydes & Ketones: 1. Added 5 drops of unknown #64 to a test tube. 2. Added 1 mL of 2,4-dinitrophenylhydrazine, covered with parafilm, and shook gently to mix. No precipitate formation noted. 3. Allowed test tubes to sit for 15 minutes and noted no changes. Gently heated test tubes #2 and #3 in a hot water bath for 10 minutes. Unknown #64 remained a golden yellow, clear liquid with no precipitate formation. 4. Unknown #64 had a negative 2,4-dinitrophenylhydrazine test suggesting that it is neither an aldehyde or a ketone. Nitrous Acid Test for 1, 2, 3, & Aromatic Amines: 1. Added 2 mL distilled water to a test tube labeled #1. 2. Added 8 drops of concentrated H2SO4 to same test tube. Then added 6 drops of unknown #64. Sulfuric acid provides the proton for nitrous acid formation and also keeps the diazo dye coupling reaction from occurring prematurely. 3. Added 2 mL of a 10% aqueous sodium nitrite solution to test tube #2, and dissolved 0.1 g -naphthol in 2 mL of aqueous 10% NaOH solution to test tube #3. The sodium nitrite will provide the nitrite ion to form nitrous acid. 4. Placed all 3 test tubes in an ice water bath at ~ 5C to stabilize the diazonium ion that can be formed by the reaction of 1 or aromatic amines with nitrous acid. 5. Added cold sodium nitrite solution dropwise to tube #1 and gently shook to mix. No precipitate, gas formation, or oily drops noted. 6. Poured half of the solution from test tube #1 into another test tube and allowed it to return to room temperature. No precipitate or gas formation noted. 7. Added 0.5 mL -naphthol drop by drop to the solutions that remained in the ice bath. No precipitate formation. No sign of azo-dye coupling reaction. 8. Unknown #64 had a negative nitrous acid test suggesting that it is not a 1, 2, 3, or aromatic amine. Ferric Chloride Test Reagents for Phenols: 1. Added a pea-sized amount of unknown #64 to a test tube. Dissolved in a small amount of ethanol. Covered with parafilm and shook gently to mix. 2. Added 7 drops of 2.5% ferric chloride solution to the test tube and shook gently to mix. No dramatic color change noted. 3. Unknown #64 had a negative ferric chloride test suggesting that it does not contain a phenol group.
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Characterization & Results: Various observations noted during the experiment are delineated in the
Procedures and Observations section above. The significant results of the solubility test and each of the six chemical classification tests are presented in the table below including findings related to unknown #64.
Physical Properties: Physical state: solid Color: white crystals ranging from small chunks to fine powder consistency Odor: very faint acidic odor Melting point: 134-137C Spectral Analysis: 1 H NMR: Showed a peak at 6.2ppm (consist with symmetrical alkene hydrogens). Peak for OH
hydrogens was off the scale of the spectrum at approximately 10 to 12ppm (consistent with aliphatic carboxylic acid hydrogens). See attached 1H NMR for analysis.
13
C NMR: Showed peaks at 135ppm (consistent with alkene carbons) and at 190ppm (consistent with
13
carboxylic acid carbons). See attached See attached IR spectrum for analysis.
IR spectrum: Showed deep depression in 3300 to 2500cm-1 range (consistent with carboxylic acid).
Solubility Test
Test Reagent H 2O 5% NaOH 5% NaHCO3 5% HCl Unknown # 64 Insoluble (white powder remains) Soluble (clear liquid no white powder) Soluble (clear liquid no white powder) Insoluble (white powder remains) Insoluble (white powder remains) Insoluble (white powder remains) Insoluble (white powder remains) Soluble (clear fluid no white powder) Insoluble (white powder remains) Results & Conclusions Not a low MW amine, low MW neutral compound, or low MW carboxylic acid Organic acid. Could be a carboxylic acid or phenol Strong organic acid. Could be carboxylic acid or a phenol. Not a neutral compound (alkene, alkyne, alcohol, ketone, aldehyde, nitro compound, ester, ether, or amide) Not an inert compound (alkane, alkyl halide, aromatic compound) Not a basic compound. Not a nonpolar compound Not a polar protic compound Compound is polar aprotic Not a nonpolar compound
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() no color change
Not a phenol
Conclusions: The experiment was completed per protocol with observations as noted. Specific results have
been presented in tabular format in the Results section. The solubility tests showed that unknown #64 was a polar aprotic compound and a strong organic acid. Using the solubility flowchart, it was determined that unknown #64 was a carboxylic acid or perhaps a phenol. Chemical classification tests showed that unknown #64 was an alkene or alkyne and that it was not a phenol; therefore, unknown #64 was determined to be a carboxylic acid with a double or triple bond. Both NMRs showed that the molecule was symmetrical with analysis presented on attached spectra. IR analysis showed a deep depression in 3300 to 2500cm-1 range that is consistent with a carboxylic acid. Melting point allowed for the identification of unknown #64 as maleic acid. UNKNOWN #64 is MALEIC ACID.
Post-Lab Questions: The information requested on the Results and Data sheet must be fully completed in
order to receive full credit.
Sources:
http://en.wikipedia.org/wiki/
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