Qualitative Analysis of Alcohols, Aldehydes, and Ketones

2012, Sharmaine S. Cady East Stroudsburg University

Skills to build:

Using qualitative tests to identify an alcohol Using qualitative tests to identify an alcohol as primary,
secondary, or tertiary Using qualitative tests to identify an aldehyde Using qualitative tests to identify a ketone Using a flow chart to identify an unknown alcohol, aldehyde or ketone

Introduction Alcohols, aldehydes, and ketones are organic molecules that have recognizable oxygen-containing functional groups. These functional groups react differently with various reagents. An unknown structure may be identified as an alcohol, aldehyde, or ketone by performing a set of reactions and noting the results. Further testing can distinguish an alcohol as primary, secondary, or tertiary Alcohols are a class of organic compounds which contain the -OH functional group covalently bonded to carbon. An alcohol may be represented as a water molecule in which one of the hydrogens is replaced with a hydrocarbon R group. Like water,

alcohols are polar; however, their polar character decreases as the size of the nonpolar R group increases. Alcohols can be further classified as primary, secondary, or tertiary:
CH3
CH3 C HO CH3 CH3

H2 C HO CH3

C HO H

CH3

primary

secondary

tertiary

Qualitative Analysis of Alcohols, Aldehydes, and Ketones

Alcohols which have one R group bonded to the carbon attached to the -OH functional group are primary (1); two R groups are secondary (2); three R groups are tertiary (3). In the above examples, R is a methyl group, but any aliphatic or aromatic group may be bonded to the hydroxyl carbon. All three classes of alcohols are capable of hydrogen-bonding in the pure state or to other alcohol molecules because the -OH functional group is always present. Alcohols also have the ability to hydrogen bond with water; however, their solubility decreases as the size of the R group and their hydrocarbon-like character increases.
Aldehydes and ketones are classes of organic compounds in which oxygen is covalently joined to a carbon atom by a double bond. The carbon and oxygen are collectively referred to as a carbonyl group. Ketones differ from aldehydes by replacement of a hydrogen with an R group. Consequently, aldehyde functional groups are always found at the end of hydrocarbon chains.
O C R O C H R O C R

carbonyl group

aldehyde

ketone

The geometry around the carbon atom of a carbonyl group is different from the tetrahedral geometry of sp3- hybridized carbon atoms attached to -OH functional groups. The presence of the double bond results in sp2 hybridization on the carbon and a trigonal planar arrangement of atoms. Oxidation of Alcohols Alcohols undergo several types of chemical reactions. The most important reaction alcohols undergo is oxidation to carbonyl compounds. Primary alcohols are oxidized to aldehydes, which themselves are sensitive to oxidation to carboxylic acids. Oxidizing agents convert secondary alcohols to ketones, and tertiary alcohols lack the ability to undergo oxidation. The following reactions show the expected products for different alcohols with the Jones reagent, a solution of chromic acid (H2Cr2O7) prepared by dissolving CrO3 in concentrated H2SO4. The chromic acid serves as the oxidizing agent as it changes from an oxidation number of +6 to +3. In the reactions, R represents the remaining hydrocarbon groups (methyl, isopropyl, etc.) on the carbon.
O 3 R CH2 OH + 4 CrO3 + 6 H2SO4 3 R C OH + 2 Cr2(SO4)3 + 9 H2O

1 alcohol
R 3 R CH OH + 2 CrO3 + 3 H2SO4 3 R R C

blue-green ppt.

O + Cr2(SO4)3 + 6 H2O

2 alcohol

blue-green ppt.

Qualitative Analysis of Alcohols, Aldehydes, and Ketones

R R C R OH + CrO3 + H2SO4 No Reaction

Lucas Test for Alcohol Classification Alcohols also react to form alkyl halides, in which the intermediate is a carbocation. Carbocations can be primary, secondary, or tertiary:
H + C H H + C R R + C R

Stable intermediates form faster than unstable ones. The order of stability of carbocations is 3>2>1; hence, tertiary alcohols react faster than secondary alcohols, which react faster than primary alcohols. The reactions may be written
ZnCl2 R CH2 OH + HCl R CH2 Cl + H2O

1 alcohol
R R CH OH + HCl

clear after 5 min

ZnCl2 R R CH Cl + H2O

2 alcohol
R R C R OH + HCl

cloudy reaction within 3-5 min

ZnCl2 R R C R Cl + H2O

3 alcohol

cloudy reaction within 1 min

where ZnCl2 in concentrated HCl is referred to as the Lucas reagent. Tertiary alcohols produce a cloudy suspension immediately; secondary alcohols turn the reaction mixture cloudy within 3-5 minutes; and primary alcohols do not react under these conditions. The cloudiness results from the insolubility of the alkyl halide in the reaction mixture.

Qualitative Analysis of Alcohols, Aldehydes, and Ketones

Oxidation of Aldehydes Similar to alcohols, aldehydes and ketones differ in their ability to be oxidized. As noted previously, aldehydes can be oxidized to carboxylic acids. Ketones, which lack a hydrogen bonded to the carbonyl group, cannot be oxidized. The following reactions show the expected products aldehydes, and ketones with the Jones reagent.
H 3 R C O + 2 CrO3 + 3 H2SO4 2 R O C OH + Cr2(SO4)3 + 3 H2O

aldehyde
R R C O + CrO3 + H2SO4

blue-green ppt.

No Reaction

ketone

2,4-Dinitrophenylhydrazine (2,4-DNP) Test for Aldehydes and Ketones Aldehydes and ketones undergo a condensation reaction with 2,4-dinitrophenylhydrazine to produce yellow to orange precipitates as products. Alcohols do not undergo this reaction. Note the condensation reaction involves the removal of water with loss of the carbonyl oxygen.
R C O H + O2N H2N N H NO2 R C N H N H NO2 O2N + H2O

aldehyde
R C O R + O2N H2N N H NO2

yellow-orange precipitate
R C N R N H NO2 O2N + H2O

ketone

yellow-orange precipitate

In this experiment the above chemical reactions will be used to qualitatively identify alcohols, aldehydes, and ketones. The flow chart on the following page shows how an unknown may be identified as an aldehyde, ketone, or primary, secondary, or tertiary alcohol. Not all tests may need to be performed before an identification can be made. Table 1 summarizes expected results with each test.

Qualitative Analysis of Alcohols, Aldehydes, and Ketones

Alcohols, Aldehydes, Ketones 2,4-dinitrophenylhydrazine

alcohols

none

yellow ppt.

ketones, aldehydes

Jones reagent

blue-green ppt. aldehyde

none ketone

Jones reagent none blue-green ppt.

Lucas test cloudy < 1 min 3-5 min

3o

1o, 2o

3o

none 1o

2o

Table 1. Summary of Results + positive negative * not applicable Lucas Test Jones Compound 2,4-DNP Room Test Test temperature 50 C Aldehyde + + + * *

Ketone 1 alcohol 2 alcohol 3 alcohol

* +

Qualitative Analysis of Alcohols, Aldehydes, and Ketones

Experimental Methods and Materials

Safety considerations
Wear suitable protective clothing, gloves, and eye/face protection!

You should read the online MSDS for: tert-Amyl Alcohol 1-Butanol 2-Butanol tert-Butyl Alcohol 2,4-Dinitrophenylhydrazine 2-Heptanone Hydrochloric Acid Jones Reagent 2-Pentanol 1-Propanol Propiophenone Salicylaldehyde p-Tolualdehyde Zinc Chloride

Qualitative Analysis of Alcohols, Aldehydes, and Ketones

2, 4-Dinitrophenylhydrazine test 2, 4-Dinitrophenylhydrazine is used to distinguish aldehydes and ketones from alcohols. Clean and thoroughly rinse with distilled water five test tubes. Label a test tube for formaldehyde, acetone, absolute ethanol, isopropyl alcohol, and tertbutyl alcohol. Add 10 drops of each compound to its labeled test tube. Add 5 drops reagent grade ethanol to each test tube. Add 10 drops 2, 4dinitrophenylhydrazine to each test tube. Record your results. The presence of a yellow to orange-red precipitate is a positive test. Chromic acid test (Jones reagent) The chromic acid test may be used to distinguish an aldehyde and primary and secondary alcohols from ketones and tertiary alcohols. Clean and thoroughly rinse with distilled water five test tubes. Label a test tube for formaldehyde, acetone, absolute ethanol, isopropyl alcohol and tert-butyl alcohol. Add 5 drops of each compound to its test tube. Add 10 drops reagent grade acetone to each test tube. Add 2 drops of the Jones reagent to each test tube. Stir to mix the contents of each test tube. Allow the solutions to stand for 1 minute. Record your results. The appearance of a blue-green color or precipitate is a positive result. Lucas test The Lucas test is used to distinguish between primary, secondary, and tertiary alcohols. Clean and thoroughly rinse with distilled water three test tubes. Label a test tube for absolute ethanol, isopropyl alcohol, and tert-butyl alcohol. Add 5 drops of the compound to its labeled test tube. Add 15 drops Lucas reagent to each test tube. If no reaction has occurred after 5 minutes, heat the test tube in a 50C water bath for 5 minutes. Record your results. The immediate formation of a white cloudy suspension is a positive test for a tertiary alcohol. The appearance of the cloudy layer after 5 minutes or heating is a positive test for a secondary alcohol. If no cloudiness is observed after heating, the alcohol is primary.

Identification of unknown Obtain an unknown sample from your instructor. Mark the letter or number on your report sheet. Using the flow chart and Table 1, identify your unknown as a 1, 2, or 3 alcohol, aldehyde, or ketone. Determine the refractive index to identify which alcohol, aldehyde, or ketone is your unknown. If necessary, correct the refractive index.

Qualitative Analysis of Alcohols, Aldehydes, and Ketones

UNKNOWN POSSIBILITIES 1-butanol 1-propanol 2-butanol 2-pentanol tert-butyl alcohol salicylaldehyde p-tolualdehyde 2-heptanone propiophenone tert-amyl alcohol

References Pasto, D. J.; Johnson, C.R.; Miller, M. J. Experiments and Techniques in Organic Chemistry; Prentice Hall: Upper Saddle River, NJ, 1992, pp 306, 324, 328-331.

Laboratory Report Using the flow chart, describe how you classified your unknown. Explain how you identified your unknown compound. Give the structure of the unknown. Give the chemical reaction for each known compound that undergoes a positive reaction.