Experiment 13 Qualitative Tests for Carbonyls; Unknown ... - myweb

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indicate the presence of an aldehyde or ketone. Record your results in your notebook. The color of the crystals,if any, is not indicative of an aldehyde or ketone but only that such a group is present.Test 2: Tollen’s TestThis test is selective for aldehydes. It is based on the fact that aldehydes can be oxidized to carboxylicacids while ketones can not. In the Tollen’s test, the aldehyde reduces Ag + , complexed with ammonia, to Ag 0(metallic silver) while it is oxidized to a carboxylic acid. Ketones do not undergo this reaction. When themetallic Ag 0 is produced it forms a silver mirror on the inner side of the test tube. In order for the mirror toform, the test tube must be very clean and without many scratches inside. The test tubes must be thoroughlyrinsed with water and soap. The reaction is shown in Figure 13.2.Figure 13.2 Silver(I) Oxidation of Aldehyes to Carboxylic AcidsORC Haldehyde++ 2 Ag(NH - 3 ) 2 OHH 2 OOR C O - ++NH 4+ 2 Ag 0 + NH - 4 OHcarboxylic acidsolid(ammonium salt)Procedure:We will do the Tollen’s test only twice, using a ketone for one test (either cyclohexanone or acetone)and an aldehyde for the other (use benzaldehyde).First prepare the Tollen’s reagent by adding 5 mL of 5% silver nitrate to 2 freshly cleaned medium sizedtest tubes. Add 3 drops of 10% sodium hydroxide to each test tube. Mix the solutions thoroughly. A browngrayprecipitate should form. To each tube add 10% ammonium hydroxide solution drop-wise, shaking afterthe addition of each drop, until the precipitate just dissolves.Add 2-3 drops of ketone to one test tube and 2-3 drops of aldehyde to the other one. Shake the tubes tomix them and allow them to stand without shaking for 10 minutes. Look for the formation of the silver mirror.Record your results in your notebook.Clean-up: To clean your tests tubes from the Tollen’s test you need to dissolve the silver in 20% nitricacid. This forms water-soluble silver nitrate. Add a few mL of 20% nitric acid solution to the test tube whichcontains the silver mirror and, using your test tube brush, dissolve all the solid material.Test 3: Benedict’s TestThis test is similar to the Tollen’s test but it uses cupric salts (Cu 2+ ) as the oxidizing reagent. These arereduced to copper I salts (Cu + ) as the aldehyde is oxidized to a carboxylic acid. Again, ketones do not react.Benedict’s solution is made by dissolving copper sulfate, sodium citrate, and sodium carbonate together inwater. The Cu 2+ cation is solubilized by the citrate. When the copper is reduced to form Cu + , it precipitates asbrick-red cuprous oxide.Procedure:Set-up six medium test tubes. We will do the Benedict’s test on cyclohexanol, cyclohexanone, acetone,benzaldehyde, tetrahydrofuran and ethyl acetate. Label the test tubes accordingly.Add 2 mL Benedict’s solution to each of the test tubes and then add 2-3 drops of test compound to eachtest tube. Heat the test tubes in boiling water for 10-15 minutes. Look for the formation first of a pale greencolor followed by the formation of the reddish precipitate of cuprous oxide. Record the results in yournotebook.2
Figure 13.3 Copper (II) Oxidation of Aldehydes to Carboxylic AcidsORC HaldehydeO OH OO+ Cu 2+ - O C CH 2 C CH 2 C ONa sodium carbonate, H 2 OO CR C O - Na +O - carboxylic acid(sodium salt)blue copper-citrate complex+Cu 2Ored solidTest 4: Chromic Acid Test (also called Bordwell-Wellman Test)This test is similar to the Tollen’s test and the Benedict’s test in that it distinguishes aldehydes fromketones on the basis of their ease of oxidation. In the chromic acid test we use chromic acid to oxidizealdehydes to carboxylic acids; ketones do not react with chromic acid. Chromic acid is prepared by mixingchromium trioxide with dilute sulfuric acid. The orange Cr 6+ cation is reduced to the blue-green Cr 3+ ion.Figure 13.4 Chromium (VI) Oxidation of Aldehyde to Carboxylic AcidORC Haldehyde+OH 2 Cr 2 OH 2 SO 4 7R C + CrOH2 (SO 4 ) 3orangecarboxylic acidblue-greenCr 6+ Cr 3+Procedure:Set-up six small test tubes in your test tube rack. We will test the same six compounds as in the 2,4-dinnitrophenylhydrazone and Benedict’s test (cyclohexanol, cyclohexanone, acetone, benzaldehyde,tetrahydrofuran and ethyl acetate). Add 1 mL of acetone to each tube and 2-3 drops of the test compound to thefirst test tube. Add 1 drop of the Chromic Acid reagent and shake vigorously using a small cork to stopper it.Record how long it takes for a color change (if any) to appear. Looking down the length of the upright testtube, resting on a white background, is the best way to judge color changes. Repeat with all of the testcompounds. Record the results in your notebook.Test 5: Schiff’s TestThe Schiff’s test is also used to discriminate between aldehydes and ketones. Aldehydes give a positivetest; ketones do not. Schiff’s reagent is made by adding the intensely colored triphenylmethane dye calledfuschsin to a solution of sodium bisulfite (NaHSO 3 ). The bisulfite reacts with the dye to produce a colorlesssolution. This colorless solution will then react with aldehydes – but not ketones – to produce a newtriphenylmethane dye that also has a brilliant purple color. This test is extremely sensitive and may give falsepositives. DO NOT RETURN USED REAGENT TO THE BOTTLE SINCE IT MAY BE CONTAMINATEDAND DO NOT TOUCH THE MEDICINE DROPPER OF THE REAGENT BOTTLE WITH YOURFINGERS. The reactions involved are shown in Figure 13.5.3
Page 1: Experiment 13Qualitative Tests for
Page 5 and 6: Figure 13.6 Iodoform ReactionROCCH
Page 7 and 8: Cool the test tube, first to room t
Page 9 and 10: Appendix 13.1 Infrared Spectra of C
Page 11 and 12: 2-Heptanonen-HeptaldehydeCyclohexan
Page 13: Acetophenonep-Tolualdehyde13

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