Organic Qualitative Analysis

Physical Properties, Chemical tests and Infrared Spectroscopy to Identify:

Unknown Halide
Hydrocarbon Alcohol References:

(primary, secondary, tertiary)

(alkane, alkene, aromatic) (primary, secondary, tertiary)

Slayden, S., Stalick, W.; 2010, Catalyst - Organic Chemistry Laboratory Manual, GMU Print Services Pavia, D., Lampman, G., Kriz, G, Engel, R, 2010, A Small Scale Approach to Organic Laboratory Techniques, 3nd ed, Cengage Learning
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Organic Qualitative Analysis

Purpose: Become familiar with a combination of physical and chemical tests for characterizing classes of organic compounds. To use these tests plus Refractive Index and IR to identify an unknown. Classes: Compounds without a Carbonyl group or Nitrogen group

Alkanes
Alkenes Alkynes Aromatics Alkyl (1o, 2o, 3o) & Aryl Halides Alcohols (1o, 2o, 3o)

C-C
C=C CC C=C R-X R-OH

Note: Tests for carbonyl based compounds (Aldehydes & Ketones) will be presented next semester
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Organic Qualitative Analysis

The Tests Compound Classes Test Solubility Relative to H2O & H2SO4 Density Relative to H2O Beilstein (Flame) Silver Nitrate/Ethanol Sodium Iodide/Acetone Bromine/Methylene Chloride KMnO4 (Baeyer Test) Ignition Acetyl Chloride Lucas Test Chromic Acid

Compound Class All All Halides Alkyl & Aryl Halides Alkyl & Aryl Halides Unsaturated C=C CC Unsaturated C=C CC Aromaticity C=C Alcohols Alcohols Alcohols

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The Tests Test References (Pavia (3rd ed) GMU Version or Pavia Main text as indicated) Test Page No. Solubility Relative to H2O & H2SO4 p. 453-458 Density Relative H2O p. 717-719 Beilstein (Flame) p. 459-460 Silver Nitrate/Ethanol P. 460-461 Sodium Iodide/Acetone p. 158 Pavia Main Text Bromine/Methylene Chloride p. 464-466 KMnO4 (Baeyer Test) p. 466-467 Ignition p. 467-468 Acetyl Chloride p. 585 Lucas Test p. 585 Chromic Acid p. 586-487
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Elements

of the Experiment Week One Boiling Point & Purification (Simple Distillation) Physical Characteristics of Unknown Solubility Relative to Water & Conc H2SO4 (Just the unknown) Page 453

Density relative to Water (Just the unknown) Refractive Index (unknown only) Temperature Correction for Refractive Index Beilstein Test (Halides) Page 459 Ignition Test (Aromaticity) Page 467

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Organic Qualitative Analysis

Elements

of the Experiment Week Two Silver Nitrate/Ethanol Alkyl & Aryl Halides p. 460 Sodium Iodide/Acetone Alkyl & Aryl Halides Note: This experiment is not in the GMU Pavia text, but is in the regular hard cover Pavia Text p. 158 Bromine/Methylene Chloride Unsaturated C=C CC p. 465 KMnO4 (Baeyer Test) Unsaturated C=C CC p. 466 Acetyl Chloride Alcohols p. 485 Lucas Test Alcohols p. 485 Chromic Acid Alcohols p. 486 IR Spectra p. 851

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General Notes Dangerous Chemicals Acetyl Chloride, Conc H2SO4 Use Gloves, Goggles, and Lab Coat (Buttoned) Use a test tube rack from cabinet Use medicine droppers from equipment set Pasteur pipettes are not available Make sure to wash and dry the medicine dropper and test tubes for each test

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General Notes

The Beilstein (flame) Test for Halides and the Ignition test for Aromaticity with be done in the hood with the assistance of the instructor Record the results of the chemical tests in a 5-column table created in the prelab template (see slide 11) Use simple, direct language to describe your test. It is very important to describe an observation completely Ex. The Unknown was soluble in water Be sure to obtain a good positive result for each test; repeat the test until a good positive result is obtained
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Testing Sequence for Knowns & Unknown The boiling point, solubility, refractive Index, flame test, and IR should indicate the general class of the unknown compound Halogen, Hydrocarbon, Alcohol Test your unknown against all the reagents Test each of the known samples against only those tests that are applicable to the class of compounds to which the known belongs Note: See table on page 57 of Slayden Lab Manual For each test, set up a sufficient number of test tubes to accommodate the unknown and as many knowns specified in the table on page 57 Add test reagent Add compound to be tested; shake mixture Heat reaction mixture as specified in test directions
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The Report Each Test is a Procedure and must be set up with: A Title Materials & Equipment, including reagents, known and unknown compounds, test tubes Procedure Description in bullet format Test Results include a 5-column table (see next slide) containing the name of the compound, your observations, and an indication of whether a result for a givent compound was positive or negative relative to the compound tested and the test applied Summary All results summarized in a paragraph Analysis & Conclusions Arguments showing how your results support your identification of the unknown
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Suggested table for recording Qualitative Organic test results (Create your own, dont copy)
Compound Observation (Rm Temp) Observation 50oC Observation Was Result 100oC Expected?

Unknown
Known #1 Known #2 Known #3

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Organic Qualitative Analysis

Solubility Test (Water (H2O) and Conc Sulfuric Acid (H2SO4)

Only the unknown is to be tested for solubility in Water and Concentrated Sulfuric Acid

Water

Compounds with <5 Carbons containing O, N, S are soluble Compounds with 5-6 Carbons containing O, N, S are borderline (slightly soluble) Branching Alkyl chains result in lower melting/boiling points and increased solubility Increase N, O, S to Carbon ratio increases solubility
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Solubility Test (Water (H2O) and Conc Sulfuric Acid (H2SO4)

Conc H2SO4 Solubility Compounds containing N, O, S can be protonated in Conc H2SO4 and thus are considered soluble. Alkenes (C=C) Alkynes (CC) Ethers (C-O-C) Nitroaromatics (Nitrobenzene) Amides Alcohols (R-OH) Ketones Aldehydes Esters
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Solubility Test (Water (H2O) and Conc Sulfuric Acid (H2SO4)

Water & Conc H2SO4 Solubility Not soluble Alkanes Aromatic Hydrocarbons Alkyl Halides Aromatic Halides

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Organic Qualitative Analysis

Relative Solubility & Density

Procedure Water & H2SO4 Note: Solubility & Density test is performed only on the Unknown

Place about 2 mL of Distilled Water or Conc H2SO4 in a test tube

Add 3-5 drops of the compound to be tested

Shake vigorously Solubility is indicated by a single clear liquid, i.e. no bubble or additional layers Production of a gas, a change in color, and/or a change in temperature indicates a chemical reaction; thus, solubility
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Relative Solubility & Density (Cont)

Procedure Water & H2SO4 (Cont)

Density relative to water of an insoluble compound is indicated by where the insoluble compound settles: top bottom (less dense) (more dense) suspended (similar density) Solubility of a hydrocarbon in water indicates 4 or less carbons

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Organic Qualitative Analysis

Beilstein Test

(General for Halides)

Procedure Bend small loop in the end of piece of copper wire. Heat loop in Bunsen Burner After cooling Liquid sample: dip wire in sample. Solid sample: dip wire in water then sample. Heat wire Compound first burns with yellow flame. After burning for a few seconds, a green flame is produced if a halogen is present Does not differentiate between Chlorine, Bromine, or Iodine Weak color could indicate present of impurities in a non-halide sample
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Silver Nitrate in Ethanol Test

(Sn1 for Halides)

Does not distinguish between Chloride, Bromine, or Iodine Sn1 (nucleophilic substitution) reactions depend on: Weak Nucleophile (NO3) Polar Solvent (Ethanol) Compounds equipped with good leaving groups (H2O, CL, Br, I) The Halide (leaving group) is replaced with the nitrate nucleophile forming an insoluble white precipitate The degree of precipitate formation is dependent on the relative stability of the compound and the resulting Carbocation that forms in the reaction Benzyl Allyl > Tertiary (3o) > Secondary (2o) > Primary (1o) > Methyl > Vinyl > Aryl (Aromatic)
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Silver Nitrate in Ethanol Test

(Sn1 for Halides)

The Test

Add 1 to 2 drops of liquid sample (or 5 drops of solid sample dissolved in Ethanol) to 2 mL of 2% Ethanoic Silver Nitrate Positive test cloudy to heavy white precipitate depending on relative stability of Carbocation

Allyl, Benzyl, Tertiary Halides give white precipitate at room temperature Primary & Secondary Alkyl Halides test positive (usually cloudy ppt) when heated (100oC) Aromatic and many Vinyl Substituted Halides do not give positive tests
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Organic Qualitative Analysis

Sodium Iodide in Acetone (Sn2 for Alkyl Halides)

Sodium Iodide is soluble in Acetone, but Sodium Chloride and Sodium Bromide are not soluble

The Iodide ion is an excellent Nucleophile A Lewis Base with a pair of unshared electrons that seeks a positive part of an atom
Acetone is a non-polar solvent

Alkyl Chlorides and Bromides would react with the Sodium Iodide in an Sn2 reaction in which the Chloride & Bromide ions are replaced with the Iodine atoms
The reaction equilibrium is continuously forced to the right as the NaCl & NaBr precipitate in acetone As the reactivity of the Halide becomes less reactive (Benzyl and Aromatic) precipitation ceases
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Sodium Iodide in Acetone (Sn2 for Alkyl Halides)

Relative Halide reactivity for an Sn2 reaction is the opposite of an Sn1 reaction, that is: Vinyl > Methyl > Primary (1o) > Secondary (2o) > Tertiary (3o) > Allyl Benzyl Aryl (Aromatic) Note: Aryl (Aromatic) Halides are unreactive for both Sodium Iodide (Sn2) and Silver Nitrate (Sn1) tests

Primary Alkyl Halides will give an immediate precipitate at room temperature Secondary Alkyl Halides will give a cloudy precipitate when heated to 50oC and then cooled Tertiary Alkyl Halides will also give a precipitate when heated to 50oC and then cooled

Aryl Halides, like Chlorobenzene, will not give a precipitate, even after heating
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Sodium Iodide in Acetone (Sn2 for Alkyl Halides)

The Test

Add 6-8 drops of sample to 2mL of the 15% Sodium Iodide (NaI) in Acetone solution and shake gently Positive Test is a white or cloudy white precipitate If a precipitate forms but disappears with mild shaking, the instructor may suggest adding additional sample

Record the observed results at room temperature

If no precipitate forms, heat solution in a water bath (maximum 50oC) for 1 minute and cool solution to room temperature

Observe results
Record results for both room temperature and at 50oC

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Organic Qualitative Analysis

Bromine in Methylene Chloride (Simple Multiple Bonds)

Addition reaction of Bromine (Br2), a red liquid, to a compound containing a double or triple bond produces a colorless Dibromide

The double (or triple bond) must be sufficiently electron-rich to initiate the reaction. Therefore, minimal electron withdrawing groups (Deactivators), such as Carboxyl Groups attached to molecule, would hinder the reaction Unsubstituted Aromatic compounds do not react with the Bromine reagent Even if the ring has substituted activating groups (donate electrons to the ring) the reaction would be a substitution and not an addition
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Bromine in Methylene Chloride

The Test

If sample is a solid, add 50 mg of a solid sample to 1 mL Methylene Chloride in a test tube If sample is a liquid, add 2 mL of liquid sample directly to test tube

Add 2% Bromine solution (Br2 & Methylene Chloride) dropwise to the test tube and shake solution
The test is positive for presence of double or triple bonds if 5 drops of Bromine decolorize the solution If HBr is evolved, the test is negative indicating a substitution reaction, instead of an addition reaction, i.e., there are no double or triple bonds present
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Potassium Permanganate (Baeyer) Test
(double or triple bonds)

Potassium Permanganate (KMnO4) is an oxidizing agent.

It has a Purple color Following the oxidation of an unsaturated compound, the Permanganate ion is reduced to Manganese Dioxide (MnO2), a brown precipitate Note: Other easily oxidized compounds Aldehydes, some Alcohols, Phenols, and Aromatic Amines should be accounted for in your analysis

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Organic Qualitative Analysis

Potassium Permanganate (Baeyer) Test
(double or triple bonds)

The Test

Dissolve 25 mg a solid sample or two drops of a liquid sample in 1-2 mL of one of the following solvents:

Water (if soluble, skip Ethanol & Dimethoxymethane)

95% Ethanol (if soluble, skip Dimethoxymethane)

1,2-Dimethoxymethane

Slowly add 1% aqueous solution Potassium Permanganate, drop by drop, while shaking (usually just one drop works) If the purple MnO4-1 ion is reduced to Manganese Dioxide (MnO2), a brown precipitate, the test is positive for double or triple bonds, but not Aromatic rings
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Ignition (Aromaticity)
(=C-H bonds in Aromatic rings)

The Test

In a hood, place a small amount of the compound on a spatula and place it in the flame of a Bunsen burner Positive test is a sooty yellow flame

Note: The Sooty flame usually comes off fairly quickly. Look for it moving quickly away and upward from the yellow/blue flame area

Positive test is indicative of a high degree of Unsaturation and is probably Aromatic

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Organic Qualitative Analysis

Acetyl Chloride (Alcohols)

Acid Chlorides react with Alcohols to form esters Acetyl Chloride forms Acetate esters This test does not work well with solid alcohols Phenols also react with Acetyl Chloride and should be eliminated prior to testing for Alcohols Amines also react with Acetyl Chloride to produce heat and also should be eliminated prior to testing

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Organic Qualitative Analysis

Acetyl Chloride (Alcohols)

The Test

Cautiously add 10-15 drops of Acetyl Chloride, drop by drop, to about 0.5 mL of liquid sample Positive test is evolution of Heat and Hydrogen Chloride (HCl) gas

Addition of water will sometimes precipitate the ester, further confirming the test

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Organic Qualitative Analysis

Lucas Test (Alcohols)

Primary Alcohols dissolve in reagent giving clear solution

Secondary Alcohols produce cloudiness after about 3-5 minutes. May need to heat slightly
Tertiary, Benzylic, and Allylic alcohols produce immediate cloudiness; eventually, an immiscible Alkyl Halide separates into a separate layer

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Organic Qualitative Analysis

Lucas Test (Alcohols)

The Test

Reagent Conc HCL + Anhydrous Zinc Chloride

Lucas test does not work well with solid alcohols Place 2 mL Lucas Reagent in small test tube.

Add 3-4 drops of liquid sample; shake vigorously

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Organic Qualitative Analysis

Chromic Acid (Alcohols)

Chromic Acid (Cr+6) oxidizes Primary and Secondary Alcohols to Carboxylic Acids and Ketones, respectively

Chromium (+6) is reduced to Chromium (+3)

The color change is from orange to green Tertiary Alcohols do not react with Chromic Acid Distinguish Primary & Secondary Alcohols from Tertiary Alcohols

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Organic Qualitative Analysis

The Reaction

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Organic Qualitative Analysis

Chromic Acid (Alcohols) (Cont)

The Test

Dissolve one drop of liquid sample or 10 mg of solid sample in 1 mL pure Acetone

Add 1 drop of Chromic Acid reagent

Blue green color appears in less than 2 seconds for Primary and Secondary Alcohols

Tertiary Alcohols do not produce blue-green color within 2 seconds and solution remains orange

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