Classification Tests for Hydroxyl- and Carbonyl- Containing Compounds Reyes, K.O., Rivera, G.I., Samonte, A.A., Soliven, R.Y.*, Sotto, K.C.

2CMT, Faculty of Pharmacy, UST
Abstract Hydroxyl- or carbonyl- containing samples were given to the group for analysis. Hydroxyl group refers to a functional group containing OH- when it is a substituent in an organic compound whereas carbonyl group refers to a divalent chemical unit consisting of a carbon and an oxygen atom connected by a double bond. Hydroxyl group is the characteristic functional group of alcohols and phenols while carbonyl group is the characteristic functional group of aldehydes and ketones. The samples were analyzed through tests involving solubility of alcohols in water, Lucas Test, Chromic Acid Test (Jones Oxidation), 2,4-Dinitrophenylhydrazone (2,4-DNP) Test, Fehling¶s Test, Tollens¶ Silver Mirror Test, and Iodoform Test. Lucas Test differentiates primary, secondary, and tertiary alcohols. Chromic Acid Test is a test for oxidizables or any compounds that possess reducing property 2,4-DNP Test is a test for aldehydes and ketones. Fehling¶s Test and Tollens¶ Silver Mirror Test are tests for aldehydes. Iodoform test is a test for methyl carbinol and methyl carbonyl groups. When solubility of ethanol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol and benzyl alcohol was tested, only benzyl alcohol exhibited insolubility. Upon subjecting n-butyl alcohol, sec-butyl alcohol, and tert-butyl alcohol to Lucas Test, tert-butyl alcohol formed two layers, sec-butyl alcohol demonstrated slight turbidity and n-butyl alcohol produced a clear solution. Nbutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-butraldehyde, benzaldehyde, acetone, and acetophenone underwent Chromic Acid Test (Jones Oxidation). N-butyl alcohol, sec-butyl alcohol, n-butraldehyde, and benzaldehyde showed a positive result of green or blue-green solution. Fehling¶s Test, 2,4-dinitrophenylhydrazone (2,4-DNP) test, and Tollens¶ Silver Mirror Test were performed on acetone, acetaldehyde, n-butraldehyde, benzaldehyde, and acetophenone. All compounds produced a positive result of either a yellow or an orange precipitate when subjected to 2,4-DNP test. Acetaldehyde and n-butraldehyde are positive to Fehling¶s test forming a crude red precipitate and benzaldehyde demonstrated turbidity. Acetone and acetophenone produced a negative result of a clear blue solution under the same test. The samples produced a positive result of silver mirror except for acetone which produced a grayish-black solution and acetophenone which formed a gel-like precipitate. Lastly, Iodoform Test was performed on acetaldehyde, acetone, acetophenone, benzaldehyde, and isopropyl alcohol. All of the compounds exhibited positive result forming a yellow precipitate excluding benzaldehyde which formed a white suspended precipitate instead.

Introduction Hydroxyl group is used to describe the functional group ±OH when it is a substituent in an organic compound. Hydroxyl groups are especially important in biological chemistry because of their tendency to form hydrogen bonds both as donor and acceptor. This property is also related to their ability to increase hydrophilicity and water solubility. The hydroxyl group is especially predominant in the family of molecules known as carbohydrates. Hydroxyl group is the characteristic functional group of alcohols and phenols. Figure 1 Structure containing compound of a HydroxylAlcohols are characterized by one or more hydroxyl (íOH) groups attached to a carbon atom of an alkyl group (hydrocarbon chain). Alcohols may be considered as organic derivatives of water (H2O) in which one of the hydrogen atoms has been replaced by an alkyl group, typically represented by R in organic structures. Because of hydrogen bonding, alcohols tend to have higher boiling points than comparable hydrocarbons and ethers Alcohols, like water, can show either acidic or basic properties at the O-H group. With a pKa of around 16-19 they are generally slightly weaker acids than water, but they are still able to react with strong bases such as sodium hydride or reactive metals

depending on the ambient temperature. sec-butyl alcohol. They are very weak acids. also known as carbolic acid. C4H10O is a colorless liquid or white solid. and medicines. and picric acid. colorless. it is both an essential solvent and a feedstock for the synthesis of other products. and like alcohols. is a white. isopropyl alcohol. or drinking alcohol) is the second member of the aliphatic alcohol series. dyes. It is the simplest tertiary alcohol. colorless liquid that is soluble in 12 parts water and completely miscible with polar organic solvent such as ethers and other alcohols. detergents. or 2-butanol) is a flammable. Formerly used as an antiseptic. hygroscopic crystalline solid. Secondary alcohols are compounds in which the OH. Phenol itself (C6H5OH). C2H5OH. but made by acid hydrolysis of cumene hydroperoxide. pyrogallol. Phenols are aromatic compounds in which a hydroxide group is directly bonded to an aromatic ring system. cresol. phenol has more latterly been used to make bakelite and other resins. volatile. including scents. n-butyl alcohol. Alcohols have an odor that is often described as ³biting´ and as ³hanging´ in the nasal passages. grain alcohol. pure alcohol. and incompatible with strong oxidizers. or by fusion of sodium benzenesulfonate with sodium hydroxide. Ethanol. isolable from coal tar. and one of the four . Primary alcohols are those in which the hydroxyl group is attached to the carbon with only one carbon attached. In chemistry. clear liquid with a strong alcoholic odor.such as sodium. Figure 2 Structure of Ethanol N-butyl alcohol (also known as nbutanol. It is a clear. It is miscible with many organic solvents. 1-Butanol or 1-butyl alcohol) is a four carbon straight chain alcohol. 2-butyl alcohol. flavorings. Figure 4 Structure of sec-butyl alcohol Tert-Butanol. plastics. and rubbers. It burns with a smokeless blue flame that is not always visible in normal light. The hydroxylcontaining compounds used in the experiment are ethanol. The salts that result are called alkoxides.is attached to a carbon which has two other carbons attached. It is a volatile. and is miscible with water. There are three classifications of alcohols by the carbon to which the hydroxyl group is attached. form ethers and esters. tert-butyl alcohol. resorcinol. Ethanol has widespread use as a solvent of substances intended for human contact or consumption. It is a highly refractive compound which corrodes some plastics. colorings. Nbutanol is used as a direct solvent and as an intermediate in the manufacture of other organic chemicals. and benzyl alcohol. and drugs. and flammable liquid which is completely miscible with water and organic solvents. (also known as ethyl alcohol. Figure 3 Structure of n-butyl alcohol Sec-butyl alcohol with the formula CH3CH(OH)CH2CH3 (also known as secbutanol. The main phenols are phenol itself. Tertiary alcohols are compounds in which a hydroxyl group is attached to a carbon with three attached carbons.

used in the soap. the properties of aldehydes and ketones are determined by the behaviour of the carbonyl group. acyl halides. lacquers. paints. and quinones are also known collectively as carbonyl compounds. with a melting point slightly above 25 °C. other flavors and perfumes. Figure 7 Structure of Isopropyl alcohol Carbonyl group is a divalent chemical unit consisting of a carbon (C) and an oxygen (O) atom connected by a double bond. Like most alcohols. tert-Butanol is used as a solvent. It is a useful solvent due to its polarity. tert-butanol is more stable to oxidation and less reactive than the other isomers of butanol. anhydrides. especially for dissolving lipophilic contaminants such as oil. forming a new functional group with distinctive properties. It is often added to intravenous medication solutions as a preservative due to its bacteriostatic and antipruritic properties. It is also relatively non-toxic and evaporates quickly. as an oxygenate gasoline additive. It is also a precursor to a variety of esters. . Figure 6 Structure of Benzyl alcohol Isopropyl alcohol (also propan-2ol. It is a colorless. Isopropyl alcohol dissolves a wide range of non-polar compounds. It is unique among the isomers of butanol because it tends to be a solid at room temperature. Benzyl alcohol is used as a general solvent for inks. as a denaturant for ethanol. Aldehydes and ketones contain carbonyl groups attached to alkyl or aryl groups and a hydrogen atom or both. In carboxylic acids and their derivatives. where the alcohol carbon is attached to two other carbons. These groups have little effect on the electron distribution in the carbonyl group. Thus it is used widely as a solvent and as a cleaning fluid. The group is a constituent of carboxylic acids. perfume. isopropyl alcohol can be oxidized to acetone.isomers of butanol. as an octane booster for gasoline. and as an intermediate in the synthesis of other chemical commodities. Carboxylic acid (and their derivatives). As a tertiary alcohol. It is the simplest example of a secondary alcohol. or sulfur. the carbonyl group is attached to one of the halogen atoms or to groups containing atoms such as oxygen. which is the corresponding ketone. nitrogen. and quinones. is a colorless liquid with a mild pleasant aromatic odor. as an ingredient in paint removers. Benzyl alcohol is partially soluble in water (4 g/100 mL) and completely miscible in alcohols and diethyl ether. Being a secondary alcohol. ketones. Figure 5 Structure of tert-butyl alcohol Benzyl alcohol. and flavor industries. tert-Butanol is a clear liquid with a camphor-like odor. thus. amides. It is very soluble in water and miscible with ethanol and diethyl ether. 2-propanol is a common name for a chemical compound with the molecular formula C3H8O. C6H5CH2OH. and low vapor pressure. aldehydes. low toxicity. flammable chemical compound with a strong odor. it reacts with carboxylic acids to form esters. These atoms do affect the carbonyl group. and it is the characteristic functional group of aldehydes and ketones. and epoxy resin coatings. esters.

Benzaldehyde. a glucoside present in the kernels of bitter almonds and in apricot pits.Figure 7 Structure containing compound of a Carbonyl- Ketone compounds have important physiological properties. They are found in several sugars and in compounds for medicinal use. The aldehyde group is occasionally called the formyl or methanoyl group. Figure 8 Structure of Aldehyde Some of the carbonyl-containing compounds used in the experiment are benzaldehyde. Figure 9 Structure of Ketone An aldehyde is an organic compound containing a terminal carbonyl group. Some are very fragrant. Benzaldehyde is used in the preparation of certain aniline dyes and of other products. because the first aldehyde was prepared by removing two hydrogen atoms (dehydrogenation) from ethanol. The word aldehyde is a combination of parts of the words alcohol and dehydrogenated. It boils at 180°C. Acetaldehyde.. but is insoluble in water. Aldehydes are very easy to detect by smell. It is formed by partial oxidation of benzyl alcohol. by crushing the kernels or pits and boiling them in water.g. sodium hydroxide. . including perfumes and flavorings. e. They differ from aldehydes in that the carbonyl is placed between two carbons rather than at the end of a carbon skeleton. n-butraldehyde. is soluble in ethanol.. and the general formula for an aldehyde is R-CH=O. and others have a smell resembling that of rotten fruit. It is called oil of bitter almond. consists of a carbon atom bonded to a hydrogen atom with a single covalent bond and an oxygen atom with a double bond. sometimes simply called aldehyde. since it is formed when amygdalin. called an aldehyde group. e. such as carboxylic acids. Thus the chemical formula for an aldehyde functional group is CH=O. It is also prepared by oxidation of toluene or benzyl chloride or by treating benzal chloride with an alkali. including natural and synthetic steroid hormones. They are also distinct from other functional groups. and on oxidation forms benzoic acid. Organic acids are the result of the introduction of one oxygen atom to the carbonyl group (oxidation). This functional group. C6H5CHO (also known as benzenecarbonal) is a colorless liquid aldehyde with a characteristic almond odor. is hydrolyzed. glucose and hydrogen cyanide (a poisonous gas) are also formed.g. CH3CHO (also known as ethanol) is a colorless liquid aldehyde. Figure 10 Structure of Benzaldehyde Ketone features a carbonyl group (C=O) bonded to two other carbon atoms. It is soluble in water and ethanol. acetaldehyde. which have a carbonyl group bonded to a hetero atom. Molecules that contain an aldehyde group can be converted to alcohols by the addition of two hydrogen atoms to the central carbon oxygen double bond (reduction). acetone and acetophenone. esters and amides.

It is the simplest aromatic ketone. In industry. Fehling¶s Test.. This compound is the aldehyde derivative of butane. Chromic Acid Test (Jones Oxidation). This limits the test in general to Acetone (also known as propanone) is the organic compound with the formula (CH3)2CO. as well as a probe for the existence of the hydroxyl group. and Iodoform Test. trimethylolpropane. It is used as a reducing agent (e. and as a preservative. viscous liquid is a precursor to useful resins and fragrances. It is miscible with most organic solvents. aldehydes. solvents and polymers (such as 2-Ethylhexanol. mobile. Figure 13 Structure of Acetone . and ketones. antioxidants. Acetone is miscible with water and serves as an important solvent in its own right. This colorless. in the manufacture of synthetic resins and dyestuffs. primary alcohols do not give a positive result. Lucas Test. rubber accelerators. alcohols. Figure 11 Structure of Acetaldehyde Acetophenone is the organic compound with the formula C6H5C(O)CH3. flammable liquid with a characteristic sweetish smell is the simplest example of the ketones. polyvinyl butyral. Low molecular-weight compounds are generally limited to those with fewer than five carbon atoms.g.Acetaldehyde is made commercially by the oxidation of ethylene with a palladium catalyst. typically as the solvent of choice for cleaning purposes in the laboratory. textile auxiliaries. 2. This colourless. it is normally applicable only to alcohols that are soluble in the reagent. Tollens¶ Silver Mirror Test. nbutanol. Figure 12 Structure of n-Butyraldehyde The hydroxyland carbonylcontaining compounds were analyzed by utilization of different tests such as testing the solubility of alcohols in water. acetophenone is recovered as a byproduct of the oxidation of ethylbenzene. agrochemicals. n-butyric acid. Most organic compounds are not soluble in water with the exception of low molecular-weight amines and oxygencontaining compounds like alcohols.4-Dinitrophenylhydrazone Test. which mainly gives ethylbenzene hydroperoxide for use in the production of propylene oxide Figure 14 Structure of Acetophenone N-butyraldehyde (also known as butanal) is an organic compound with the formula CH3(CH2)2CHO. Lucas Test often provides classification information for alcohols. methyl amyl ketone). for silvering mirrors). Since the Lucas Test depends on the appearance of the alkyl chloride as a second liquid phase. It is a colourless flammable liquid that smells like sweaty feet. carboxylic acids. Substrates that easily give rise to cationic character at the carbon bearing the hydroxyl group undergo this test readily. It is also used as an intermediate to make pharmaceuticals. perfumery and flavors. Acetophenone can be obtained by a variety of methods. n-Butyraldehyde is used as an intermediate in the manufacturing plasticizers.

A drop of a liquid sample was placed into a small sample. whereas Tollens' reagent can be used to test for both aliphatic and aromatic aldehydes. The mixture was allowed to stand at room temperature. D. The rate of formation of the cloudy suspension or the formation of two layers were observed. If cloudiness resulted. sec-butyl alcohol. Solubility of Alcohols in Water Five test tubes were labelled accordingly and ten drops each of ethanol. acetone.0-ml of water. and tert-butyl alcohol. n-butyraldehyde. the alcohol is said to be soluble in water.4-Dinitrophenylhydrazone Test can be used to qualitatively detect the carbonyl functionality of a ketone or aldehyde functional group.4DNP Test) This test was performed on acetone. 5 drops of 2. C. and acetophenone. benzaldehyde. benzaldehyde. sec-butyl alcohol. acetaldehyde. The reagent was prepared by slowly adding a solution of 3 g of 2. If cloudiness resulted after the addition of 2. 50-mg or 2-3 drops of the sample was added to 1-ml of the reagent in a small vial or test tube and the mixture was shaken vigorously for a few seconds. 1 drop of liquid or a small amount of the solid sample was dissolved in 1-ml of acetone in a small vial or test tube. 1-ml of water was then added dropwise to the tube containing alcohol and the mixture was shaken thoroughly after each addition.4dinitrophenylhydrazine in 15-ml of concentrated sulphuric acid. and B. The mixture was then allowed to cool. 0. Lucas reagent was prepared by dissolving 16 g of anhydrous zinc chloride in 10-ml of concentrated hydrochloric acid. Methodology A. n-butyl alcohol. Chromic Acid Oxidation) detects the hydroxyl substituent that bearing at least one therefore oxidizable. . 2. Iodoform Test is a test for methyl carbinol (secondary alcohol with adjacent methyl group) and methyl carbonyl group. tert-butyl alcohol. n-butyraldehyde. tertbutyl alcohol. Chromic Acid Test (Jones Oxidation) This test was performed on n-butyl alcohol. sec-butyl alcohol. Fehling¶s Test and Tollens¶ Silver Mirror Test are used to detect aldehydes.monofunctional alcohols lower than hexyl and certain polyfunctional molecules. and benzyl alcohol were placed into the test tubes by the use of a Pasteur pipette. The total volume of water added was noted. The results were noted down. and acetophenone. Fehling's solution can only be used to test for aliphatic aldehydes.4-dinitrophenylhydrazone (or 2. 2 drops of 10% aqueous Potassium chromate solution and 5 drops of 6M sulphuric acid were added into the mixture.25-ml of water at a time was added continuously with vigorous shaking until a homogeneous dispersion results. while stirring to a mixture of 20-ml of water and 70-ml of 95% ethanol. The solution was then stirred and filtered. Lucas Test This test was performed on n-butyl alcohol. However. Test (Jones presence of a is on a carbon hydrogen.

3 drops of 2. acetone. Fehling¶s Test This test was performed on acetaldehyde. and acetophenone. and tert-butyl alcohol are all miscible with water with the exception of benzyl alcohol which exhibited insolubility. the solution was allowed ro stand for at least 15 minutes. It was noted that if Tollens¶ reagent is left unused for a period of time. and benzyl alcohol and their solubility in water. tert-butyl alcohol. If no reaction has occurred. This was avoided by neutralizing unused reagent with a little nitric acid and discarded afterwards. benzaldehyde. Fehling¶s reagent was prepared by mixing equal amounts of Fehling¶s A and Fehling¶s B. Fehling¶s B was prepared by mixing 35 g of Potassium sodium tartrate and 10 g of Sodium hydroxide in 100-ml water. E. The mixture was shaken and allowed to stand for 10 minutes. sec-butyl alcohol. the test tube was placed in a beaker of warm water (35-50 o C) for 5 minutes. acetophenone. only enough 2% ammonium hydroxide (concentrated ammonium hydroxide is 28%) was added drop by drop and with stirring to dissolve the precipitate. F. Adding excess ammonia will cause discrepancies on the result of the test. Tollens¶ Silver Mirror Test This test was performed on acetaldehyde.95% ethanol was added and well shaken. Fehling¶s A was prepared by dissolving 7 g of hydrated copper (II) sulfate in 100-ml of water. 3 drops of the sample to be tested was added in to the tube. and acetophenone. n-butyl alcohol. Next. sec-butyl alcohol. Results and Discussion Table 1 Solubility of Alcohol in Water Alcohol Condensed Structural Formula Amount of Water (in ml) needed to produce a homogeneou s dispersion Solubility Water in Ethanol N-butyl alcohol Secbutyl alcohol Tertbutyl alcohol Benzyl alcohol CH3CH2OH CH3CH2CH 2CH2OH 1 ml 2 ml 1 ml Miscible Miscible Miscible 1 ml Miscible N/A Immiscible Table 1 shows alcohols such as ethanol. G. Ethanol. Iodoform Test This test was performed on acetaldehyde. acetone. 1-ml of freshly prepared Fehling¶s reagent was placed into each test tube. nbutyraldehyde.4-DNP was added and if no yellow or orange precipitate formed. and isopropyl alcohol. The tubes were then placed in a beaker of boiling water and changes within 10-15 minutes were observed. acetone. Observations were recorded. Two drops each of the samples were then added. it may form explosive silver. mixed. The reagent was prepared by adding 2 drops of 5% Sodium hydroxide solution to 2-ml of 5% Silver nitrate solution and mixing thoroughly. Afterwards. Four test tubes with 1-ml of freshly prepared Tollens¶ reagent were prepared. The formation of a yellow participate was noted. 2 drops of each sample was placed into its own small vial or test tube. 20 drops of fresh chlorine bleach (5% Sodium hypochlorite) was slowly added while shaking to each test tube and then. n-butyraldehyde. benzaldehyde. benzaldehyde. n-butyl alcohol. .

tert-butyl alcohol immediately formed two layers. A compound with polar functional group is more soluble in water. Tert-butyl alcohol is the most soluble among the butanol derivatives because it has the most branching substituents present. Positive result is based on turbidity (alkyl chloride formation) and the rate of the reaction was observed. Ethanol has two carbon atoms. a secondary alcohol dissolves to give a clear solution (provided R does not have too many carbon atoms in the chain. Ethanol exhibits fastest solubility because it has only two carbon atoms as compared to the butanol derivatives having four carbon atoms. N-butyl alcohol and sec-butyl alcohol yielded a clear solution when subjected to Lucas Test whereas tert-butyl alcohol resulted to a cloudy immiscible suspension which eventually formed two layers. As stated. hence. while the other three all have four carbons since they are all derivatives of the alcohol. Reagents used include anhydrous ZnCl2 and HCl. Benzyl alcohol is immiscible with water because it is an aromatic alcohol. butanol. sec-butyl alcohol. the order of reactivity of the alcohols toward Lucas reagent is 3°>2°>1° because the reaction rate is much faster when the carbocation intermediate is more stabilized by a greater number of electron donating alkyl group bonded to the positive carbon atom. N-butyl alcohol was unreactive and is considered to be the primary alcohol. then form chlorides (cloudy solution) within five minutes. Generally. Secondary alcohols require 5-10 minutes before formation of second layer while primary alcohols are usually unreactive. One of which is number of carbon atom wherein the higher the number of carbon atoms. Hence. This means that the greater the alkyl groups present in a compound. and n-butyl alcohol. n-butyl alcohol. the faster its reaction would be with the Lucas solution. all alcohols are soluble in water except under C6. Lastly. There are different factors affecting solubility. Table 2 Reaction of Sample Compounds to Lucas Test Substance Condensed Structural Formula Reaction Inference n-butyl alcohol Sec-butyl alcohol Tertbutyl alcohol CH3CH2CH 2CH2OH Clear solution Clear solution Miscible Miscible Turbid solution and formation of two layers Immiscible The reaction of alcohols with halogen acids is a displacement reaction in which the reactive species is the conjugate acid of the alcohol R-OH2+. Ethanol is the most soluble alcohol followed by tert-butyl alcohol. -NH2. secondary. and tert-butyl alcohol are all miscible with water.The table shows that all alcohols are soluble in water except under C6. Table 2 shows the reaction of butanol derivatives to Lucas Test. CO2H) also tends to affect alcohol solubility in water. Tertiary alcohols form the second layer in less than a minute. the presence of polar functional groups (-OH. and as might be expected. is analogous to the replacement reactions of organic halides and related compounds with silver nitrate . sec-butyl alcohol. the more soluble (with the same number of carbons) it is. the more insoluble the alcohol is in water. Lucas Test differentiates primary. it is known to be a tertiary alcohol. Another factor is the branching of carbon chain in which the more branching present. ethanol.). Based on Table 2. Sec-butyl alcohol when subjected to Lucas test resulted to a clear solution although theoretically. and tertiary alcohols.

The effects of structure on reactivity in these reactions are closely related. Hydrogen bromide and Hydrogen iodide. a cloudy appearance of the mixture is observed within 5 minutes. and nbutyraldehyde resulted to a clear blue or green solution whereas tert-butyl alcohol. sec-butyl alcohol. This reaction is not a nucleophilic displacement comparable to that undergone by primary alcohols but rather proceeds by way of a carbonium ion intermediate. Secondary alcohols are intermediate in reactivity between primary and tertiary alcohols.and iodide ion. Thus. These are nucleophilicity orders to be expected in hydroxylic solvents. which have anions with nucleophilic reactivity increasing in that order. tert-butyl alcohol. Allyl alcohol. Although they are not appreciably affected by concentrated hydrochloric acid alone. on the one hand. Allyl chloride may be caused to separate by dilution of the mixture with ice water. acetone. benzaldehyde. and acetophenone to Chromic Acid test. it reacts rapidly with Lucas reagent with the evolution of heat. CHCH=CH2] As might be expected. primary alcohols do not react perceptibly with hydrochloric acid even in the presence of zinc chloride at ordinary temperatures. Reagent used includes 10% Potassium chromate and 6 M sulfuric acid. N-butyl alcohol. Table 3 Reaction of Sample Compounds to Chromic Acid Test Substance Condensed Structural Formula Reaction n-butyl alcohol Sec-butyl alcohol CH3CH2CH 2CH2OH Clear blue solution Clear blue solution Tert-butyl alcohol Clear yellow solution n-butyraldehyde Clear blue solution Benzaldehyde Clear green solution Acetone Clear yellow solution acetophenone Clear yellow solution Chromic Acid Test/Dichromate Test/Jones Test is a test for oxidizables or any compounds that possess reducing property (has an alpha acidic hydrogen. The acidity of the medium is increased by the addition of the anhydrous zinc chloride (a strong Lewis acid). sec-butyl alcohol. and the reaction rate is increased further. Table 3 shows the reaction of nbutyl alcohol. they react with it fairly rapidly in the presence of anhydrous . are increasingly reactive toward primary alcohols. and the primary carbonium ion is too unstable to serve as an intermediate in the carbonium mechanism. yields a carbonium ion that is relatively stable because its charge is distributed equally on the two terminal carbon atoms. chloride ion is too poor a nucleophilic agent to effect a concerted displacement reaction. on the other. Tertiary alcohols react with concentrated hydrochloric acid so rapidly that the alkyl halide is visible within a few minutes at room temperature. benzaldehyde. and acetophenone resulted to a clear yellow solution. although a primary alcohol. n-butyraldehyde. The high reactivity of tertiary alcohols is a consequence of the relatively great stability of the intermediate carbonium ion. a distinct layer is usually visible. and in about 10 minutes. acetone. CH2=CH-CH2OH [CH2=CHCH2+ + zinc chloride. at first as a milky suspension and then as an oily layer.

acetone. Table 4 Reaction of Sample Compounds to 2. benzaldehyde. Condensed Structural Formula Reaction Acetaldehyde Yellow precipitate Orange solution n-butyraldehyde Benzaldehyde Yellow precipitate Acetone Yellow precipitate acetophenone Orange precipitate 2.4-dinitrophenylhydrazine. The melting point of the solid should be checked to be sure it is different from that of 2. however. which is further oxidized to carboxylic acid. and acetophenone to 2. it may be desirable to carry out the reaction on the scale employed for the preparation of a derivative and to make an estimate of the yield.Primary.4-DNP Test Substance addition and elimination. A number of ketones. The test involves nucleophilic addition of NH2 to C=O and elimination of H2O. Positive result is the formation of a red-orange precipitate (conjugated carbonyl compounds) or yellow precipitate (non-conjugated carbonyl compounds). Primary.4-Dinitrophenylhydrazone (2. A tertiary alcohol is usually unreactive. A secondary alcohol reacts with chromic acid to yield ketone. Primary. Positive result exhibits a green or bluegreen solution.4DNP) test is a test for carbonyl groups It gives a positive result for aldehydes and ketones. 2. All the samples exhibited positive result because they all formed either a yellow or an orange precipitate. Its mechanism is condensation or The reaction of 2. n-butyraldehyde. If necessary. hence. n-butyl alcohol. as they may result to formation of another hydrazone. give dinitrophenylhydrazones that are oils. A further difficulty with the test is that certain allyl alcohol derivatives may be oxidized by the reagent to aldehydes and ketones. A primary alcohol reacts with chromic acid to yield aldehyde. this hydrazone derivative can be recrystallized from a solvent such as ethanol. Hence. which then give a positive result. which does not oxidize further. The precipitate may be oily at first and become crystalline on standing. Reagents used include 2. secondary alcohols and aldehydes will reduce the orange-red chromic acid/sulfuric acid reagent to an opaque green or blue suspension of Cr(III) salts in 2-5 seconds. If the dinitrophenylhydrazone appears to be formed in very small amount. secondary alcohols and aldehydes give a positive visible result. Most aldehydes and ketones yield dinitrophenylhydrazones that are insoluble solids. Solvents containing reactive carbonyl groups should not be used. Table 4 shows the reaction of acetaldehyde.4-DNPH with aldehydes and ketones in an acidic solution is a dependable and sensitive test. and n-butyraldehyde all formed either blue or green solutions. sec-butyl alcohol.4-DNP test proved that the samples are carbonyl-containing compounds and are either aldehydes or ketones.4-dinitrophenylhydrazine (MP 198oC). . secondary alcohols and aldehydes undergo oxidation and chromium undergoes reduction (from Cr+6 to Cr+3). Chromic acid test involves redox reaction. ethanol.4-DNP test. and H2SO4.

in particular turned from blue to muddy green then formed a crude red precipitate upon heating. They are both negative for Tollens¶ Silver Mirror test. a yellow dinitrophenylhydrazone may be assumed to be unconjugated. and benzaldehyde are aldehydes. Fehling¶s test involves redox reaction wherein aldehyde is oxidized to carboxylic acid and ketones do not undergo oxidation. n-butyraldehyde. n-butyraldehyde. NaOH ( Cu2+ in alkaline solution). Acetone resulted to a clear grayish-black solution while acetophenoe formed a gellike precipitate. Reagents include CuSO4. then. Table 6 Reaction of Sample Compounds to Tollens¶ Silver Mirror Test Substance Condensed Structural Formula Reaction Acetaldehyde Silver Mirror n-butyraldehyde Silver Mirror Condensed Structural Formula Reaction Benzaldehyde Silver Mirror Acetaldehyde Crude red precipitate Crude red precipitate n-butyraldehyde Acetone Clear grayishblack solution Gel-like precipitate Benzaldehyde Turbid solution. Conjugation with a carbon-carbon double bond or with a benzene ring shifts the absorption maximum towards the visible and is easily detected by an examination of the ultraviolet spectrum. These three sample compounds which exhibited positive result to Fehling¶s test are all aldehydes. Table 5 Reaction of Sample Compounds to Fehling¶s Test Substance exhibited positive result. Acetaldehyde. In general. However. . As shown in Table 5. since it may be due to contamination by an impurity. acetaldehyde. an orange or red color should be interpreted with caution. However. Dinitrophenylhydrazones of aldehydes or ketones in which the carbonyl group is not conjugated with another functional group are yellow. oily layer acetophenone Acetone Clear blue solution acetophenone Clear blue solution Fehling¶s Test is a test for aldehydes. The preparation of Tollens reagent is based on the formation of a silver diamine complex that is water soluble in basic solution.The color of a 2. The test proved that acetaldehyde. and benzaldehyde exhibited positive result of formation of silver mirror whereas acetone and acetophenone do not. acetaldehyde. and benzaldehyde Tollens¶ Silver Mirror test is a test for aldehydes. n-butyraldehyde. Copper is reduced (from Cu2+ to Cu+). Positive result is the formation of crude-red precipitate (Cu2O/cuprous oxide).4dinitrophenylhydrazone may give an indication as to the structure of the aldehyde or ketone from which it is derived. this shift is also responsible for a change in color from yellow to orange-red. As shown in Table 6.

the stable hydrate of trifluoroacetaldehyde gives a positive result. Modern Experimental Organic Chemistry. and isopropyl alcohol exhibited positive result. acetophenone. R. Reagents include 10% KI and NaClO. acetone. In some cases. Inc. New York: Van Hoffmann Press Acetone Yellow precipitate acetophenone Yellow precipitate Isopropyl alcohol Yellow precipitate Iodoform Test is a test for methyl carbinol (secondary alcohol with adjacent methyl group) and methyl carbonyl . Table 7 shows that among the sample compounds tested. as well as anaphthol and certain other phenols will give a positive result. however. John Wiley & Sons. Rinehart and Winston Shriner. Inc. and other aromatic amines.Tollens¶ Silver Mirror test involves reduction-oxidation reaction wherein aldehyde is oxidized to carboxylic acid and ketones do not undergo oxidation except alpha-hydroxyketone. Curtin. Formic acid. acyloins. Positive result is exhibited by the formation of yellow crystals or precipitate. John Wiley & Sons. Ralph Lloyd. hydroxylamine. hence the name ³silver mirror´ test. New York: Van Hoffmann Press Rodewald. the metal forms merely as a granular gray or black precipitate.. Ethanol and secondary alcohols with a methyl group attached to the same carbon as the ±OH group will also give a positive iodoform test. a-Alkoxy and adialkylamino ketones have also been found to reduce ammoniacal silver nitrate. Compounds with a methyl group next to a carbonyl group give a positive result with the iodoform (tri-iodomethane) test. L. New York: Holt. Silver is reduced from Ag+ to Ag0.to produce iodoform and carboxylic acid (2): Condensed Structural Formula Reaction Acetaldehyde Yellow precipitate White suspended precipitate Benzaldehyde References BOOKS Shriner. This is because the iodine oxidizes the alcohols to a carbonyl compound with a methyl group next to the carbonyl group. Roberts. diphenylamine. Table 7 Reaction of Sample Compounds to Iodoform Test Substance groups. When a methyl carbonyl compounds react with iodine in the presence of a base. The test often results in a smooth deposit of silver metal on the inner surface of the test tube. (1980). (1964). Systematic Identification of Organic Compound: A Laboratory Manual Fifth Edition. Systematic Identification of Organic Compound: A Laboratory Manual Sixth Edition. In addition. the hydrogen atoms on the carbon adjacent to the carbonyl group (a hydrogens) are subsituted by iodine to form tri iodo methyl carbonyl compounds which react with OH . acetaldehyde. The reaction is autocatalyzed by the silver metal and often involves an induction period of a few minutes. especially if the glass is not scrupulously clean. (1979). Fuson.

pdf. Retrieved September 19. In Encyclopædia Britannica.uniregensburg. 2010 from http://www.php.encyclopedia. 2010 from http://www. Retrieved September 19. 2010 from http://cameochemicals. Retrieved September 20. Retrieved September 19.html.WEBSITES Classification of Organic Compounds.com/EBchecked/to pic/13527/aldehyde.gov/chris/BT R. 2010 from http://www. 2010 from http://science.tutorvista.html. 2010 from http://www.de/Fakultaeten/nat_Fak_IV/Or ganische_Chemie/Didaktik/Keusch/DJodof-e. from Encyclopædia Britannica Online: http://www. Retrieved September 20. In Encyclopædia Britannica.com/topic/benza ldehyde.aspx. Retrieved September 19. from Encyclopædia Britannica Online: http://www. Phenol. 2010. (2010).britannica. 2010.htm. Carbonyl-containing Compounds.daviddarling. Carbon Compounds. Retrieved September 19.jrank. (2010).org/pages/198/Aldeh ydes.noaa. .britannica. Aldehydes. Hydroxyl Group.com/content/chemi stry/chemistry-ii/carboncompounds/acetone.info/encyclopedia /P/phenol. Benzaldehyde. Retrieved September 20. Aldehyde.com/EBchecked/to pic/279129/hydroxyl-group.

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