Ceric nitrate test

Suggest a chemical test that would allow you to distinguish between tert-butyl alcohol and 1-butanol, both of which give a positive ceric nitrate test. 

Chemical Tests. A positive ceric nitrate test (Qiapter 9) should confirm the presence of the alcohol grouping. The ignition test may be used to establish that the material is an aliphatic species. The phenyl or a-naphthylurethane derivative may also be prepared to further characterize the alcohol (Chapter 9). 

Chemical Tests. The ignition test should indicate that this compound is an aliphatic species. Does your result confirm this fact Perform the ceric nitrate test to demonstrate the presence of the —OH group and the Lucas test to demonstrate that a secondary alcohol has been prepared. If you were required to prepare a solid derivative of this alcohol, which one would you select It may be of interest to determine the solubility of this product in water, ether, concentrated sulfuric, and 85% phosphoric acids. Do your results agree with what you would predict What test(s) would you perform to establish that one of the starting reagents was an aldehyde ... 

Compound A (C7H14O) burned with a yellow, nonsooty flame and did not decolorize a bromine-methylene chloride solution. It did give a positive 2,4-dinitrophenylhydrazine test, but a negative Tollens test. Treatment of the compound with lithium aluminum hydride followed by neutralization with acid, produced compound B, which gave a positive Lucas test in about 5 min. Compound B also gave a positive ceric nitrate test. The NMR spectrum for compoimd A... 

Chemical Tests. Several chemical tests (see Chapter 9) may also be used to establish that an alcohol has been formed by the reduction of a ketone. Perform the ceric nitrate and 2,4-dinitrophenylhydrazine test on both the starting ketone and the alcohol product. Do your results demonstrate that an alcohol was obtained You may also wish to prepare a phenyl- or a-naphthylurethane derivative of the cyclohexanol. Before the development of chemical instrumentation, the formation of solid derivatives was used extensively to identify reaction products. 

The ceric nitrate and/or the Jones oxidation test for the alcohol. 

Note. A few less common alcohols cannot be detected by the ceric ammoniiun nitrate test because of interference, e.g. by the amino-group in an amino-alcohol. 

These are oily liquids, soluble in water, insoluble in ether, and strongly alkaline. The amino-group interferes with the ceric ammonium nitrate test for the alcohol function. 

Ethyl 2,4-diphenylimidazole-5-carboxylate and aq. KOH refluxed 1.75 hrs. with removal of the condensate until a test with ceric nitrate reagent shows the absence of ethanol 2,4-diphenyloxazole-5-carboxylic acid. Y ca. 100%. D. L. Aldous, J. L. Riebsomer, and R. N. Castle, J. Org. Ghem. 25, 1151 (1960). 

Qualitative. The classic method for the quaUtative determination of silver ia solution is precipitation as silver chloride with dilute nitric acid and chloride ion. The silver chloride can be differentiated from lead or mercurous chlorides, which also may precipitate, by the fact that lead chloride is soluble ia hot water but not ia ammonium hydroxide, whereas mercurous chloride turns black ia ammonium hydroxide. Silver chloride dissolves ia ammonium hydroxide because of the formation of soluble silver—ammonia complexes. A number of selective spot tests (24) iaclude reactions with /)-dimethy1amino-henz1idenerhodanine, ceric ammonium nitrate, or bromopyrogaHol red [16574-43-9]. Silver is detected by x-ray fluorescence and arc-emission spectrometry. Two sensitive arc-emission lines for silver occur at 328.1 and 338.3 nm. 

J. Lamond, Analyst 74, 560—61(1949) [Small quantities of alcohol in ether may be detd after extracting it from ether by water, followed by testing the aqueous extract by means of ceric ammonium nitrate. The following reaction takes place, producing the red coordination product ... 

Ceric ammonium nitrate To 1 to 2 ml of 5% ceric ammonium nitrate add 10 drops of the compound to be tested. A change to an orange/red color is indicative of an alcohol (detection limit, 100 mg compounds tested, C, to C10). 

Alcohols Ceric ammonium nitrate Dichromate test Iodoform test Lucas test Positive for all alcohols Positive for 1° and 2° alcohols negative for 3° alcohols Positive for all alcohols of the general formula CH3CH(OH)R Immediate reaction for 3°, allylic or benzylic alcohols slower reaction (2-5 min) for 2° no reaction for 1° alcohols... 

Wear face shield, goggles, laboratory coat, and nitrile rubber gloves. Cover spill with a 1 1 1 mixture by weight of sodium carbonate or calcium carbonate, clay cat litter (bentonite), and sand. Using a plastic shovel, scoop into a pail of water in the fume hood (about 66 mL/g). Cautiously add aqueous 5.5% ceric ammonium nitrate (4 volumes per volume of aqueous solution) and stir for an hour. If the solution remains orange, an excess of ceric ammonium nitrate is present and the azide has been completely destroyed. The solution can be washed into the drain with at least 50 times its volume of water.6,7 The solid residue is treated as normal refuse. A spot test for checking if azide is completely destroyed is as follows Place a drop of the test solution in the depression of a spot plate and treat with 1 or 2 drops of dilute hydrochloric acid. Add a drop of ferric chloride solution and gently heat the spot plate. A red color indicates hydrazoic acid and incomplete decomposition. 

Wear eye protection, laboratory coat, and nitrile rubber gloves. In the fume hood, behind a shield, cautiously add silver azide to a large excess of cold ceric ammonium nitrate solution (about 66 mL/g azide) with agitation sufficient to provide suspension of all solids. Cool the reaction. When reaction is complete (see spillage disposal for test for completeness of reaction), wash solution into the drain with water.7 Large amounts of silver salts may be worth recovering. 

Assay Dissolve about 0.4 g of sample, accurately weighed, in 20 mL of 16 100 sulfuric acid, add 5 mL of 85% phosphoric acid, dilute with approximately 50 mL of water, and immediately titrate with 0.1 N ceric sulfate, using orthophenanthroline TS as the indicator. Perform a blank determination (see General Provisions), and make any necessary correction. Each milliliter of 0.1 N ceric sulfate is equivalent to 5.585 mg of Fe. Chloride Heat 100 mg of sample, accurately weighed, with 25 mL of water and 2 mL of nitric acid until the sample dissolves. Cool, dilute to 100 mL with water, and mix. Take 10 mL of this solution, and dilute to 30 to 40 mL with water. Proceed as directed in the Chloride Limit Test under Chloride and Sulfate Limit Tests, Appendix IIIB, beginning with add 1 mL of silver nitrate TS... . Any turbidity produced does not exceed that shown in a control containing 20 pig of chloride (Cl). 

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