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19 Apr 2012 4:30pm

Experiment #21: Qualitative Analysis to Identify Unknown #64: Maleic Acid

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. .

Physical Properties of Reagents:
Reagent Molecular Formula Structural Formula Solubility Tests POLAR PROTIC SOLVENT: Molecular Weight Melting Point Boiling Point

water
STRONG BASE:

H 2O

18.015 g/mol 39.9971 g/mol 84.007 g/mol

0˚C 318˚C
(varies with concentration)

100˚C 1388˚C
(varies with concentration)

sodium hydroxide
(5% solution used) WEAK BASE: (5% solution used) STRONG ACID: (5% solution used) STRONG BASE:

NaOH

Na+ -OH

sodium bicarbonate hydrochloric acid

NaHCO3

50˚C
(varies with concentration)

851˚C
(varies with concentration)

HCl

H⊕⊖Cl

36.461 g/mol

-114.8˚C
(varies with concentration)

-84.9˚C
(varies with concentration)

sulfuric acid

H2SO4

98.079 g/mol

10˚C
(varies with concentration)

337˚C
(varies with concentration)

(concentrated solution used) NONPOLAR SOLVENT:

hexane
POLAR APROTIC SOLVENT:

C6H14

86.18 g/mol

-96 – -94˚C
(varies with concentration)

68-69 ˚C (varies
with concentration)

dichloromethane
POLAR PROTIC SOLVENT:

CH2Cl2

84.93 g/mol

-96.7˚C -114˚C
(varies with concentration)

39.6˚C 78.37˚C
(varies with concentration)

ethanol

C 2H 6O C4H10O

46.07 g/mol 74.12 g/mol

(95% solution used) NONPOLAR SOLVENT:

diethyl ether
REACTS WITH 3°, ALLYLIC, & BENZYLIC HALIDES TO FORM WHITE PPT:

-116.3˚C

34.6˚C

Silver Nitrate Test for 3º, Allylic, & Benzylic Halides AgNO3 169.87 g/mol 212˚C 444˚C
(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

–30.8˚C

156˚C 198199˚C

benzyl bromide

C7H7Br

171.04 g/mol

–3.9˚C

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19 Apr 2012 4:30pm

Experiment #21: Qualitative Analysis to Identify Unknown #64: Maleic Acid
ACID THAT DOES NOT DISSOLVE SILVER HALIDES:

nitric acid
ORGANIC SOLVENT (dissolves AgNO3 & halide):

HNO3

63.01 g/mol

–42˚C

83˚C

95% ethanol
SOURCE OF FERROUS ION FOR FORMATION OF FERROUS HYDROXIDE:

C 2H 6O

46.07 g/mol

-114˚C

78.37˚C

Ferrous Hydroxide Test for Nitro Compounds Fe(NH4)2(SO4)2 284.05 g/mol (anhydrous) 100110˚C N/A

ferrous ammonium sulfate
(5% aqueous) BASE SOURCE OF HYDROXIDE ION FOR FORMATION OF FERROUS HYDROXIDE:

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

K⊕⊖OH

56.1056 g/mol

406˚C

1327˚C

H2SO4

98.079 g/mol

10˚C

337˚C 238˚C (flash point)

p-nitrotoluene

C7H7NO2

137.136 g/mol

53-54˚C

Baeyer Unsaturation Test for Non-Aromatic Alkenes & Alkynes REACTS WITH ALKENES & ALKYNES (nonaromatic) TO FORM BROWN PPT: KMnO4 158.034 g/mol

potassium permanganate

240˚C

N/A

(1% aqueous solution) CYCLOALKENE (positive control for Baeyer Unsaturation Test):

cyclohexene
ORGANIC SOLVENT (dissolves cyclohexene):

C6H10 C 2H 6O

82.143 g/mol 46.07 g/mol

-103.5˚C -114˚C

82.98˚C 78.37˚C

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 202˚C 2,4-dinotrophenylhydrazine (decomposes) CONJUGATED ALDEHYDE (positive aldehyde control for 2,4-dinitrophenylhydrazine test): C 9H 8O 132.16 g/mol -7.5˚C

N/A˚C

cinnamaldehyde benzophenone

248˚C

CONJUGATED KETONE (positive ketone control for 2,4-dinitrophenylhydrazine test): (in 1mL of 95% ethanol)

C13H10O

182.217 g/mol

47.9˚C

305.4˚C

Nitrous Acid Test for 1º, 2º, 3º, & Aromatic Amines SOURCE OF NITRITE ION FOR FORMATION OF NITROUS ACID: NaNO2 68.9953 g/mol

sodium nitrate

271˚C (decomposes)

320˚C

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19 Apr 2012 4:30pm

Experiment #21: Qualitative Analysis to Identify Unknown #64: Maleic Acid
1º ALIPHATIC AMINE [positive control for nitrous acid test (N2 bubbles)]:

N-butylamine
AROMATIC AMINE [positive control for nitrous acid test (N2 bubbles) + diazo dye coupling reaction with β-napthol (beige ppt)]:

C4H11N

73.14 g/mol

-49˚C

77˚C 184.13° C 194196˚C

C6H5NH2

93.13 g/mol

-6.3°C

aniline
2° ALIPHATIC AMINE [positive control for nitrous acid test (nitroso compound – yellow oil/ppt): C 7H 9N 107.15 g/mol -57˚C

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 10˚C

337˚C

β -naphthol

C10H8O Na⊕⊖OH

144.17 g/mol

123˚C

285˚C

(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

318˚C

1388˚C

Ferric Chloride Test Reagents for Phenols FeCl3 162.2 g/mol (anhydrous) 306˚C (anhydrous) 315˚C (anhydrous – decomposes) 181.7˚C

C 6H 6O

94.11 g/mol

40.5˚C

phenol
ORGANIC SOLVENT (dissolves phenol):

95% ethanol
SYMMETRICAL CARBOXYLIC ACID WITH DOUBLE BOND:

C 2H 6O Identity of Unknown #64 C 4H 4O 4

46.07 g/mol

-114˚C

78.37˚C

maleic acid

116.07 g/mol

135˚C

N/A

Reactions & Mechanisms:
Solubility Testing & Flowchart
The main rule of thumb for solubility and solvents is “like dissolves like” meaning that nonpolar compounds dissolve other nonpolar compounds while polar compounds dissolve other polar compounds. Additionally, solubility based on acid/base interactions depends on the acid/base strength of the compound to be dissolved as well as the solvent – strong acids can dissolve weak bases that cannot be dissolved in weak acids, strong bases can dissolve weak acids that cannot be dissolved in weak bases, weak acids dissolve strong bases, and weak bases dissolve strong acids. • Water (polar protic) – dissolves compounds with four or fewer carbons and also those containing oxygen or nitrogen; dissolves ionic compounds • 5% HCl (dilute acid) – dissolves basic compounds such as aliphatic amines that readily dissolve in acid to form soluble HCl salts in aqueous solution

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19 Apr 2012 4:30pm

Experiment #21: Qualitative Analysis to Identify Unknown #64: Maleic Acid
• • 5% NaHCO3 (weak base) – dissolves strongly acidic compounds Concentrated H2SO4 (strong acid) – dissolves weak bases that remain insoluble in weak acids including compounds with either nitrogen or oxygen that can be easily protonated by a strong acid leaving ions that are soluble in the solution media Hexane (nonpolar) – dissolves completely nonpolar organic compounds Dichloromethane (polar aprotic) – dissolves polar aprotic organic compounds Ethanol – dissolves polar protic compounds especially alcohols Diethyl ether – dissolves nonpolar organic compounds especially ethers

• • • •

Solubility Flowchart

soluble UNKNOWN COMPOUND H 2O insoluble

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

WEAK ACIDS: phenols

Chemical Classification Tests 1. Silver Nitrate (Ethanoic) Test for 3º, Allylic, & Benzylic Halides:

R–X + AgNO3 + HO–CH2CH3  R–OCH2CH3 + AgX(s) + HNO3

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19 Apr 2012 4:30pm

Experiment #21: Qualitative Analysis to Identify Unknown #64: Maleic Acid 2. Baeyer Unsaturation Test for Non-Aromatic Alkenes & Alkynes

3. Ferrous Hydroxide Test for Nitro Compounds

R–NO2 + 6 Fe(OH)2 + 4 H2O  R–NH2 + 6 Fe(OH)3 (s)) + MnO2 (s)

4. 2,4-Dinotrophenylhydrazine Test for Conjugated Aldehydes & Ketones

5. Nitrous Acid Test for 1º, 2º, 3º, & Aromatic Amines

1º Aliphatic Amine

1º Aromatic Amine

2º Amine

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19 Apr 2012 4:30pm

Experiment #21: Qualitative Analysis to Identify Unknown #64: Maleic Acid

3º Aliphatic Amine

Aromatic Amine

6. Ferric Chloride Test Reagents for Phenols:

Procedures & Observations:
Solubility Tests: 1. Added 1 mL of each of the following to different test tubes – water, 5% NaOH, 5% NaHCO3, 5% HCl, concentrated H2SO4, hexane, dichloromethane, ethanol, and diethyl ether. 2. Added a small amount of solid unknown #64. Unknown #64 was insoluble in H2O, 5% HCl, concentrated H2SO4, hexane, dichloromethane, and diethyl ether but soluble in 5% NaOH, 5% NaHCO3, and ethanol. Silver Nitrate (Ethanoic) Test for 3º, Allylic, & Benzylic Halides: 1. Added 0.5 mL of a 2% ethanolic AgNO3 to test tube. 2. Under the fume hood added 1 drop of unknown #64 to test tube. Covered test tube with parafilm. No white precipitate noted. 3. Placed the test tube in a hot water bath for 5 minutes. Noted the formation of a white precipitate in the test tube. 4. Allowed test tubes to cool. Then added 2 drops of dilute HNO3. The precipitate dissolved in the nitric acid. 5. Unknown #64 had a negative silver nitrate test suggesting that it is not a halide. Baeyer Unsaturation Test for Non-Aromatic Alkenes & Alkynes: 1. Added 5 drops of unknown #64 to a test tube.

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19 Apr 2012 4:30pm

Experiment #21: Qualitative Analysis to Identify Unknown #64: Maleic Acid
2. Slowly added 1% aqueous solution of potassium permanganate drop by drop while shaking the test tube to mix. Allowed the solution to sit for 5 minutes and observed a brown precipitate. 3. Unknown #64 had a positive Baeyer test suggesting that it has a non-aromatic alkene or alkyne group.

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 1º, 2º, 3º, & 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 β-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 ~ 5˚C to stabilize the diazonium ion that can be formed by the reaction of 1º 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 β-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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19 Apr 2012 4:30pm

Experiment #21: Qualitative Analysis to Identify Unknown #64: Maleic Acid
Melting Point, NMR, & IR Analysis: 1. Received 1H NMR and 13C NMR data from TA. See results section for analysis. 2. Performed melting point analysis. Melting point was 134-137°C. 3. Prepared KBr pellet per protocol. Ran IR spectrometry. See results section for analysis.

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: 134-137°C 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.

C NMR 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

Concentrated H2SO4 Hexane CH2Cl2 Ethanol Diethyl Ether

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19 Apr 2012 4:30pm

Experiment #21: Qualitative Analysis to Identify Unknown #64: Maleic Acid

Chemical Classification Tests:
Chemical Classification Test Silver Nitrate (Ethanoic) Test for 3º, Allylic, & Benzylic Halides: Baeyer Unsaturation Test for Non-Aromatic Alkenes & Alkynes Ferrous Hydroxide Test for Nitro Compounds 2,4Dinotrophenylhydrazine Test for Conjugated Aldehydes & Ketones Control(s) BENZYLIC HALIDE – (+) white ppt (insoluble in HNO 3 ) ARYL HALIDE – (–) white ppt (soluble in HNO3) NONAROMATIC ALKENE – (+) brown ppt NITRO COMPOUND - (+) rust color ppt CONJUGATED ALDEHYDE: (+) orange red ppt CONJUGATED KETONE: (+) orange ppt UNCONJUGATED ALDEHYDE/KETONE: (+) yellow ppt ---------------1º ALIPHATIC AMINE--------------(+) N2 gas: gas bubbles (+) azo dye: bright yellow ppt (with addition of β-naphthol) ---------------1º AROMATIC AMINE--------------(+) N2 gas: gas bubbles (when heated) (+) diazonium ion: beige ppt (+) azo dye: orange ppt (with addition of β-naphthol) ---------------2º AMINE--------------(–) N2 gas: no gas bubbles (+) nitroso compound: brown-yellow oily ppt (+) azo dye: orange ppt (with addition of β-naphthol) (+) Phenol: color change to dark purple Unknown #64 (–) white ppt (soluble in HNO3) (+) brown ppt (–) army green ppt (–) no ppt Identity of Unknown #64 Not a halide

Non-aromatic ALKENE or ALKYNE
Not a nitro compound Not a ketone or aldehyde

Nitrous Acid Test for 1º, 2º, 3º, & Aromatic Amines

(–) no ppt, no gas, no azo dye

Not a 1º, 2°, 3°, or aromatic amine

Ferric Chloride Test Reagents for Phenols:

(–) 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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Experiment #21: Qualitative Analysis to Identify Unknown #64: Maleic Acid
• • http://0.tqn.com/d/chemistry/1/0/9/9/1/silvernitrate.jpg http://www.sigmaaldrich.com/medium/structureimages/55/mfcd00000055.png http://wikipremed.com/image_science_archive_th/030101_th/197800_221px-Benzyl-bromideskeletal.svg_68.jpg http://www.trueknowledge.com/images/thumbs/180/250/fbceb9bcb7c448368d197871a777b00c.p ng http://www.inchem.org/documents/icsc/icsc/eics0932.htm http://www.chemistry.ccsu.edu/glagovich/teaching/316/qualanal/tests/dnp.html http://chemistry.gravitywaves.com/CHE301/Alkene%20Classification%20Tests.htm

• • • •

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