OBJECTIVE To distinguish unknown solution based on the characteristic of aldehyde and ketones.

INTRODUCTION Aldehydes and ketones share the carbonyl functional group which features carbon doubly bonded to oxygen. In the case of ketones there are two carbon atoms bonded to the carbonyl carbon and no hydrogens. In the case of aldehydes there is at least one hydrogen bonded to the carbonyl carbon; the other attachment may be to a carbon or a hydrogen. In all cases the carbon(s) that are attached to the carbonyl group may be aliphatic (not part of an aromatic ring) or aromatic (part of an aromatic ring). Since they share the carbonyl group, aldehydes and ketones share much of their chemistry, but they are different enough to be considered different classes of compounds. This situation is similar to that of alcohols and phenols which both share the -OH group. Aldehydes and ketones both undergo a reaction type known as nucleophilic addition. Under less acidic conditions, in this type of reaction a nucleophile (a species that can donate a pair of electrons, in other words a Lewis base) donates a pair of electrons toward the carbonyl carbon forming a single bond to it. At the same time the double bond between the carbonyl carbon and oxygen becomes a single bond as one bonding pair of electrons in the double bond moves to become an unshared pair on the oxygen. The oxygen now has one bond to it and it holds three pairs of unshared electrons, so it has a negative charge. Consequently, the oxygen picks up a proton from somewhere (possibly one that was attached to the nucleophilic atom that attacked the carbonyl carbon) and becomes an -OH group. Under more acidic conditions the results are pretty much the same, but the sequence in which they happen is more or less reversed. In this case, a proton (from an acid) attaches itself to one of the unshared pairs of electrons on the oxygen. The carbonyl group now has a +1 charge and is very inviting to even a weak nucleophile. So, a nucleophile attacks the carbonyl carbon forming a bond and the doubly bonded oxygen of the carbonyl becomes an -OH, as before.

LITERATURE REVIEW Chemical Properties: Aldehydes are easily oxidized a fact due to the presence of the hydrogen attached to the carbonyl group (this is not present in ketones, which are less easily oxidized). Oxidation of aldehydes yields carboxylic acids. Even air will oxidize an aldehyde (eq 1).

Other weak oxidizing agents can bring about this reaction. One of these is Tollens' reagent, a basic (OH-) solution of the silver complex ion, Ag(NH3)+. The reaction produces metallic silver (Ag0), which often forms a shiny "mirror" on the sides of the container (eq 2).

Tollens' reagent is used to detect the presence of aldehydes. A solution of Benedict's reagent can also oxidize aldehydes. This solution consists of a basic (OH-) solution of copper(II) citrate (whose complex composition cannot be represented by a simple formula):

The conversion of the clear, blue copper(II) citrate to insoluble, reddish copper(I) oxide indicates a positive test. The reaction occurs not only with simple aldehydes but also with "reducing sugars" such as glucose. Structure and Physical Properties of Aldehydes and Ketones: Aldehydes and ketones both contain the C=O or carbonyl group. Aldehydes have at least one hydrogen bonded directly to the C=O whereas ketones always have two alkyl groups attached to the C=O.

Because they contain the polar carbonyl group, aldehydes and ketones are polar compounds. However, they cannot form hydrogen bonds one to another, as do alcohols. Therefore, the boiling points of aldehydes and ketones are less than those of alcohols of similar molecular weight, but greater than those of hydrocarbons of similar molecular weight. The solubility of aldehydes and ketones in H2O is significant if they contain less than five carbons. This is because hydrogen bonds to the water molecules are formed. Acetaldehyde (ethanal, CH3CHO) and acetone are miscible with water in all proportions.

CHEMICALS REQUIRED Known: cyclobenzene, benzaldehyde Unknown: Unknown A, Unknown B (both aldehyhde/ketones) TEST REAGENTS: 2,4- dinitrophenlyhydrazine Chromic acid test reagent (Jones reagent) Tollens test reagent APPARATUS: Warm water bath Beaker Glass rod Ice bath Pastuer pipet Bunsen burner Filter paper Test tubes

PROCEDURE 2,4 DINITROPHENLYHYDRAZINE:

A solution of 1 or 2 drops or 30 mg of unknown was added in 2 mL of 95% ethanol to 3 mL of 2,4-dinitrophenylhydrazine reagent. Vigorously shake, and if no precipitate forms immediately, allow the solution to stand for 15 minutes. Complications Some ketones give oils which will not solidify. Some allylic alcohols are oxidized by the reagent to aldehydes and give a positive test. Some alcohols, if not purified, may contain aldehyde or ketone impurities.

Jones (Chromic Acid) Oxidation Test for Aldehydes:

Dissolve 10 mg or 2 drops of the unknown in 1 mL of pure acetone in a test tube and add to the solution 1 small drop of Jones reagent (chronic acid in sulfuric acid). A positive test is marked by the formation of a green color within 5 seconds upon addition of the orange-yellow reagent to a primary or secondary alcohol. Aldehydes also give a positive test, but tertiary alcohols do not.

Complications Aldehydes are better characterized in other ways. The color usually develops in 5-15 seconds.

Tollens Test for Aldehydes

Add one drop or a few crystals of unknown to 1 mL of the freshly prepared Tollens reagent. Gentle heating can be employed if no reaction is immediately observed. Tollens reagent: Into a test tube which has been cleaned with 3M sodium hydroxide, place 2 mL of 0.2 M silver nitrate solution, and add a drop of 3M sodium hydroxide. Add 2.8% ammonia solution, drop by drop, with constant shaking, until almost all of the precipitate of silver oxide dissolves. Don't use more than 3 mL of ammonia. Then dilute the entire solution to a final volume of 10 mL with water.

Complications The test tube must be clean and oil-free if a silver mirror is to be observed. Easily oxidized compounds give a positive test. For example: aromatic amine and some phenols.

RESULT Ketones 2,4 dinitrophenlyhydrazine Chromic Acid test Light Yellow precipitate Dark, brown precipitate Grey solution Silver ppt. appear Benzaldehyde Orange color precipitate Black precipitate Black solution Silver ppt. appear Unknown A Orange color precipitate Black precipitate No changes Unknown B Orange color precipitate Black precipitate Black ppt.

Tollens Test Tollens Test (after heating)

Silver ppt.

No change

After certain test it show that Unknown B is most likely is an aldehyde and Unknown A is most likely a ketones.

DISCUSSION 2,4-Dinitrophenylhydrazine test: This test uses an organic reactant, 2, 4 - dinitrophenylhydrazine, to distinguish the carbonyl compounds (aldehydes and ketones) from the non-carbonyl compounds (the alcohols). The 2,4- dinitrophenylhydrazine reagent is a translucent yellow solution, but in the presence of a carbonyl compound, a yellow-colored precipitate will form.

Tollens reagent: Aldehydes are also oxidized by Tollens reagent, a substance that contains Ag +1. The silver ion is, concomitantly, reduced to metallic silver. Silver ion is a weak oxidizing agent; aldehydes are very easily oxidized and are essentially unique in being able to reduce silver ion to silver metal.

Jones Reagent: Aldehydes are oxidized by chromic acid, ketones are not. When an aldehyde is oxidized by orange-brown chromic acid the chromic acid is reduced to Cr+3, which is green. Consequently, chromic acid can distinguish between aldehydes and ketones.

CONCLUSION From the experiment we conclude that the Unknown B is an aldehyde and the Unknown A is ketones. QUESTIONS 1. Using chemical tests, how would you distinguish among 2-pentanone, 3pentanone and pentanal? Sodium bisulphate test: 2-pentanone being a methyl ketones when treated with saturated solution of sodium bisulfate gives a white precipitate of 2-pentanone sodium bisulphate addition compound whereas 3-pentanone does not. CH3CH2CH2COCH3 + NaHSO3 CH3CH2CH2-C(OH)(SO3Na)-CH3 (2-pentanone sodium bisulfate addition compound) OH and SO 3Na are present on the same carbon. CH2CH2COCH2CH3 + NaHSO3 No reaction Only pentanal will give a positive Tollens test and only 2-pentanone will give a positive iodoform test. Tollens reagent (silver mirror test) is use as a test for aldehyde, which are oxidized to carboxylic acids. The iodoform test is a qualitative

chemical test for the detection of ketones and aldehydes carrying an alpha methyl group. 3-pentanone will give negative results in both these tests. 2. Draw the structure of two geometric isomers, C5H8O, that give a positive iodoform test.

REFERENCES Aldehyde and ketones . Retrieves on November 2011 from http://www.wellesley.edu/Chemistry/chem211lab/Orgo_Lab_Manual/Appendix/Classific ationTests/aldehyde_ketone.html Addition of 2,4-Dinitrophenyl hydrazine to Aldehydes and Ketones. Retrieves on November 2011 from www.demochem.de/D-DNPH-e.htm BLOCH, D. R. (2006). organic chemistry demystified. USA: McGraw Hill. Carbonyl Reactivity. Retrieves on November 2011 from www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/aldket1.htm Skoog, D. A., West, D. M., Holler, F. J., & Crouch, S. R. (2004). Fundamental of Analytical chemistry. USA: Cengage learning.