Procedure for systematic identification of Organic Compounds In the identification of organic compounds, the following steps should be followed systematically Haphazard methods will lead to wrong results, waste of chemicals and time. As far as possible stick to the relative amounts reagents mentioned in the procedure. Use of excess of chemicals will not always give the desired results. When you are using volatile and inflammable solvents like ether and benzene, keep the test-tube away from flame. 1. Physical Examination: a) State- Solid/liquid b) Colour- white/colourless / yellow /red/dark c) Odour- Characteristic odour/odourless. 2. Ignition test: Experiment Two or three drops of the given liquid or a small pinch of the given solid is taken in a spatula and heated, till the substance catches fire and burns 3. Bromine Water Test: Observation a) The compound burns liberating lot of smoke b) White fumes are liberated c) A voluminous porous, black residue is left behind Inference The compound is aromatic and /or unsaturated Compound may be urea Compound may be carbohydrate Compound+ 1drop of bromine water. Shake well Reddish brown colour of bromine is discharged or faded Reddish brown colour is not discharged Compound may be unsaturated or a phenol or amine or an amide or an aldehyde Compound is none of the above OR Compound+1-2 drops of 1% Pink colour is discharged KMnO4 Solution. Shake well It is an easily oxidizable compound like an unsaturated compound or a phenol or an amine or an aldehyde Pink colour is not discharged The Compound is none of the above. White ppt soluble in NH4OH Pale yellow ppt sparingly soluble in NH4OH Chlorine is present Yellow ppt insoluble in NH4OH Iodine is present Test for Halogens: (1) 2ml of stock solution +10-15drops of conc. HNO3 Boil, cool and add silver nitrate solution (2) 2 ml of stock solution +Cl2 water +CCI4 shake well. (3) Beilstein’s test for halogens: Dip a clean and fresh copper wire in the substance and hold it in the blue flame of a Bunsen burner 6. Solubility Test: Bromine is present Bromine is confirmed a) Orange red globule b) Violet globule A green flame is observed Iodine is confirmed Halogen is present in the compound The Purpose of this test is to find out the correct group to which the organic compound belongs. For this purpose different solvents are tried and the solubility of the compound is determined. This gives the group and the probable functional groups in that group. Then classification reactions for that particular solubility group are carried out to find out the exact functional group. The solute and the solvent should be used in a proper proportion to judge solubility. For this purpose 2-3 drops of the unknown liquid or about 0.2g of the unknown solid, about 5ml of the solvent is added and shaken well. The unknown liquid is said to be soluble in a solvent if, a) b) c) d) Two separate layers are not formed Oily drops are not seen Emulsion is not observed A homogeneous solution is formed with or without change of colour or liberation of heat. On mixing a liquid with a solvent (e.g. benzyl alcohol and conc. H2SO4) if a solid if formed, that compound has reacted with the solvent and hence it belongs to that group of the solvent The unknown solid is said to be soluble in a solvent if it dissolves completely in it to form a homogenous solution. Note: 1) If the compound is insoluble in water, solubility in ether should not be tested 2) To try ether and conc. H2SO4 as solvents, the test tube must be completely dry. 3) If the compound contains nitrogen, and it is insoluble in water and 5% HCI, it belongs to VII group. Then solubility in NaOH and conc. H2SO4 should not be carried out. Solubility Table Soluble in ether Group Compoun ds Insoluble in ether ( Nitrogen may be present) Soluble in Soluble In 5% HCI 5% NaOH (Nitrogen Is Present) Soluble in cold conc H2SO4 I II III IV V Many low mol wt. compounds and Resorcinol Amides and carbohydrate s e.g. Urea Glucose Amines e.g. Aniline O,m,p Toluidines. Monomethyl Aniline Dimethyl aniline Carboxylic acids and phenols e.g. Benzoic alcohol, Salicylic acid Pehnol O,m,pcresols Alcohols Aldehydes Ketones and esters e.g. Benzyl alcohol, Benzaldeh yde Acetophen one Methyl & Ethyl Benzoates Insoluble in cold conc H2SO4 ( Halogen may be present) Nitrogen is present and compound is insoluble in water and 5%HCI VI Aromatic hydrocar bonds and their halogen derivativ es e.g. Toluene Biphenyl Naphthal ene, Chlorobe nzene, Benzyl Chloride VII Amides and nitro compound s Benzamid em Nitrobenzene mdinitroBenzene, P-Nitro toluene 4. Physical Constants: If the given compound is a solid, determine the melting point. Note down the temperature when the substance in the capillary tube has just melted If the given compound is a liquid, determine the boiling point. See that the bulb of the thermometer is just a little bit below the level of the side arm of the distillation flask. Note down the constant temperature when about half of the liquid has distilled out. This is the observed boiling point. Since boiling point decreases by one percent for every 1,000ft. Altitude above sea level, at Bangalore a correction of 3.5% is to be added to the observed B.P. to get the correct B.P. Correct B.P. = observed B.P. +3.5% correction. 5. Lessaigne’s Test (Sodium fusion test) or Elementary Analysis: The purpose of this test is to find out the presence or absence of nitrogen, sulphur and halogens in the given organic compound. A piece of metallic sodium is taken on a filter paper by means of a spatula. It is pressed between the folds of the filter paper and dried. It is then introduced into a dry sodium fusion tube. The tube is held by a pair of tongs and waved over a flame once or twice till the sodium becomes a silvery white button. The fusion tube is cooled in air. A small quantity of the given organic substance is introduced into it and the tube is heated intermittently. Sodium reacts with nitrogen, sulphur and halogens to form the respective sodium compounds, namely sodium cyanide, sodium sulphide and sodium halide. The fusion is complete when a black fused mass is formed in the fusion tube. Now the fusion tube is heated strongly till it becomes red hot. It is then plunged into about half a test tube of distilled water taken in a mortar. Two more fusions are carried out similarly and these fusion tubes are also dropped into the same mortar. Using a pestle, the fused mass with glass is crushed. The mixture as such is taken in a small beaker and boiled. The purpose of boiling is to extract the fused mass to the maximum extent. The hot mixture is filtered. The filtrate called ‘Stock solution’ is used as follows to detect nitrogen sulphur and halogens. Experiment Test for nitrogen: Observation A blue or a green coloured solution or a ppt Inference Nitrogen is present 2mlof stock solution+Freshly prepared ferrous sulphate Solution +2 drops of NaOH. Boil, cool and add excess of dil H2SO4 Test for sulphur 2ml of stock solution +2or 3 drops of sodium nitro prusside indicator Sulphur is present Violet coloured solution OR Sulphur is present 2ml of stock solution +acetic acid + lead acetate solution Black ppt 7. Classification reactions: Depending on the solubility group to which the organic compound belongs, classification reactions of the particular group are carried out to detect the functional group. For example, if the compound belongs to IV group, tests for carboxylic acid and phenolic compounds are conducted. 8. Preparation of a suitable solid derivative: To confirm the identification of the functional group, a suitable solid derivative having a M.P. between 500 and 2500C is prepared, filtered, washed, dried and the melting point is determined. CLASSIFICATION REACTIONS FOR I GROUPOF THE SOLUBILITY TABLE: Compounds belonging to this group are soluble in water and also in ether. Reactions for phenolic compounds are carried out. Experiment 1) Compound dissolved in water+ a few drops of neutral ferric chloride solution. 2) Compound + water + bromine water dropwise. Shake well 3) Phthalein Test: Compound in a dry test tube +1/2 its quantity of phthalic anhydride + 2 drops of conc. H2SO4. Heat till a dark red coloured mixture is formed. Pour the mixture into a beaker containing cold water. Add excess of NaOH solution and stir. Observation Inference A violet coloured solution. It is a phenolic compound Reddish brown colour of bromine water is discharged It is a phenolic compound Yellow coloured solution is formed Phenolic compound is confirmed A double coloured (green and red) solution is obtained The given compound may be resorcinol Preparation of derivative, Dibenzoate. Take about one gram of the given compound in a 100ml. Stoppered conical flask. Add about 15 to 20ml. of 5% NaOH solution. Shake well. Add about 2ml. of benzoyl chloride in excess as can be recognised by its odour and irritating action. Cool the flask if lot of heat is liberated. Pour the contents of the flask into a beaker of cold water. Filter the dibenzoate derivative at the pump. Wash with water and dry. CLASSIFICATION REACTIONS FOR II GROUP OF THE SOLUBILITY TABLE: Compounds of this group are soluble in water but insoluble in ether. Such substances are 1. Amides like urea 2. Carbohydrates like glucose. IF the elementary analysis shows the absence of nitrogen, it canbe concluded that amides are absent and tests for carbohydrates should be directly carried out. Reaction of amides: Experiment 1) Compound +5ml of 4 N NaOH solutions. Boil and expose a wet red limus paper to the vapour. Expose a glass rod dispped in HCi to the gas 2) Biuret test: The given compound is heated in a dry test tube till all ammonia is expelled in the form of white fumes. The solid melts and then solidifies. On cooling, to the white residue a few drops of NaOH solution and a drop of copper sulphate solution are added Observation Inference Red litmus paper turns blue. Dense white fumes It is an amide A purple or violet colour is seen The given substance is urea. 1. Compound+Conc. H2SO4 Heat A black product is formed It is a carbohydrate 2. Compd. +NaOH solution boil well Yellow coloured solution first formed turns brown It is a Carbohydrate A violet ring is formed It is a carbohydrate A red ppt if formed It is a reducing sugar Reactions of Carbohydrates: 3. Molisch Test Solution of compound in water+(alpha) Naphthol colution in alcohol+conc. H2SO4 carefully down the sides of the test tube 4. Compound+ Fehling’s solution ( Mix equal volumes of Fehling’s A and Fehling’s B Solution) Heat for a few minutes 5. Silver Mirror Test Experiment Observation Inference Compound+ Tollen’s Reagent (To 2ML. of silver nitrate solution, add a few drops of NaOH solution. A brown ppt is formed. Add enough NH4OH just to dissolve the ppt to form a colourless solution.) Heat by placing the test tube in a beaker containing hot water or by direct heating without shaking the test tube The test tube appears silvery white from outside It is a reducing sugar 6. Osazone Formation: It is a reducing sugar Compound dissolved in water+phenyl hydrazine. Heat the test tube in a beaker containing boiling water. Preparation of derivatives: A. For amides(ex. Urea)- nitrate derivative Dissolve a little urea in water taken in a test tube. Add Conc. HNO3 dropwise till a white crystalline ppt appears. Filter the ppt, wash with minimum quantity of water and dry B. For Carbohydrates (ex. Glucose)—Osazone derivative. The yellow crystalline solid formed inreaction(6) for Carbohydrates is the osazone of the sugar. It is filtered, washed and dried. CLASSIFICATION REACTIONS FOR III GROUP OF THE SOLUBILITYTABLE Compounds belonging to this group contain nitrogen. They are insoluble in water, but dissolve in 5% hydrochloric acid. Such compounds are Primary amines- aniline and o,m,p- toluidines Secondary amines- monomethyl aniline Tertiary amines- dimethyl aniline. Experiment Observation 1. Compound in a dry test tube+acetyl chloride drop by drop 2. Compound +2ml of glacial acetic acid +2ml of acetic anhydride. Heat and pour the mixture to cold water or dil NaOH solution taken in a beaker A vigorous reaction takes place with the evolution of heat Inference It may be ap – or a s- amine but not a t- amine. OR A solid is formed 3. Compound in a dry test tube + a few drops of benzoyl choloride 4. Cabylamine Test: Compound +alcoholic KOH solution+ chloroform. Heat the mixture and pour into water and feel the smell A vigorous reaction takes place with the liberation of heat and a solid is formed It may be p- or s-amine but not tamine A foul smell 5. Diazotisation and coupling reaction: a. Compound + di HCL. Cool the test tube in ice water for 2 minutes b. Cool a solution of sodium nitrite in water, in ice water for 2 minutes. The compound must be a pamine Pale blue or yellow coloured solution Mix the two solutions(a) and (b) It is a p-amine OR Yellow oily drops It is a s-amine OR Green ppt It is a t-amine A red dye is formed To the above mixture of (a) and (b) add an ice cold solution of β naphthol in NaOH solution P-amine is confirmed Derivatives: (a) Acetyl or benzoyl derivatives of p-and s-amines: To the compound taken in a dry test tube, add acetyl chloride or benzoyl chloride drop wise. A vigorous reaction takes place in cold itself. Lot of heat is liberated and a solid if formed. Pour the reaction mixture into water or dil NaOH solution. Filter the solid derivative and dry. (b) Preparation of p-bromo derivative of t-amine: To the compound taken in a test tube, add a solution ofbromine in glacial acetic acid and warm. Filter the p-bromo derivative which separates out on cooling. Wash and dry. CLASSIFICATION REACTIONS FOR IV GROUP OF THE SOLUBILITY TABLE: Compounds belonging to this group are insoluble in water and 5% HCI. But they are soluble in 5% NaOH. Such substances are carboxylic acids and phenolic compounds. E.g. Benzoic acid, Phenol, o, p, m-cresols, phenolic acids ( salicylic acid) Reactions of Carboxylic acids. Experiment 1. Compound+water+a piece of blue litmus paper. Shake well. 2. Compound +5% sodium bicarbonate solution. 3. Esterification: Compound +3-4 drops of ethyl alcohol +2-3 drops of conc. H2SO4. Heat and pour the mixture into beaker contining water. Add a little NaOH soln to neutralize the solution 4. Formation of acid amides: Compound in a dry test tube+ A small quantity of phosphorus pentachloride. Heat slightly. Cool. Add liquor ammonia to the mixture carefully. Reactions of Phenols: Observation Inference Blue limus paper turns red It is an acidic compound Slow effervescence takes place on the surface of the solid. It is a carboxylic acid Sweet fruity odour It is a carboxylic acid A vigorous reaction takes place and a white solid is formed It is a carboxylic acid 1. Compound+ water+2-3 drops of neutral ferric chloride solution. 2. Compound+Bromine water dropwise. Shake Violet or pink or dirty green coloured solution It is a phenolic compound Reddish brown colour is discharged and a white or pale yellow ppt is formed It is a phenolic compound Colour less solution turns pink or blue in NaOH medium It is a Phenolic compound (Exception-p-cresol) 3. Phthalein Reaction: Compound in a dry test tube+half its quantity of phthalic anhydride + 2-3 drops of conc. H2SO4. Heat the test tube till a homogeneous red coloured mass is formed. Pour the mixture into water taken in a beaker. Add NaOH solution in excess Derivative: (a) Amide derivatives of carboxylic acids: Take the given compound in a dry test tube and add phosphorus pentachloride. Heat and cool the liquid product. Add liquor ammonia dropwise carefully. A Vigorous reaction takes place with the liberation of heat and white solid is formed. (b) Preparation of acetyl derivative of salicylic acid(aspirin) Take the given compound in a test tube. Add acetic anhydride (2ml) and glacial acetic acid (2ml). Heat and pour the mixture into dil NaOH solution taken in a beaker. Filter the white solid which separates out, wash and dry. (c) Preparation of benzoate derivative of phenol, m-cresol and p-cresol: Add about one test tube of 5% NaOH to about 2ml of the phenol taken in a 100ml stoppered conical flask. Add about 2ml of benzoyl chloride dropwise with vigorous shaking. Destroy any excess of benzoyl chloride by the addition of excess of NaOH solution. Cool, filter the precipitate, wash and dry. (d) Preparation of picrate derivative of O-cresol and m-cresol: Prepare strong solution of cresol in about 3ml of benzene and picric acid in about 3ml of benzene separately. Mic the two solutions and evaporate to dryness near the window. Yellow crystalline solid separates Out. CLASSIFICATION REACTIONS FOR V GROUP OF THE SOLUBILITY TABLE Compounds belonging to this group do not contain nitrogen. They are insoluble in water, 5% HCI & 5% NaOH. But they are soluble in cold con. Sulphuric acid, with the evolution of heat or change of colour. Such compounds are. Alcohols- Benzyl alcohol AldehydesBenzaldehyde Ketones _ Acetophenone. Esters- Methyl benzoate and ethyl benzoate. Experiments Test for alcohols: 1. Compound (3-4 drops) in a dry test tube + a piece of dry sodium 2. Acetylation: 3-4 drops of the compound +2=3 drops of acetyl chloride or acetic and anhydride and 2-3 drops of glacial acetic acid. Warm the solution and pour into water taken in a beaker. Add NaOH solution to neutralise the solution Observation Inference A vigorous reaction takes place and sodium quickly dissolves It is an alcohol A pleasant smelling solution is obtained It is an alcohol Test for aldehydes and ketones: 1. Compound +phenyl hydrazine 2. Compound +2.4 dinitro phenyl hydrazine 3. 2-3 drops of compound +5ml of 40% sodium bisulphate solution. Shake vigorously for a few minutes 4. Compound+2-3 drops of Schiffs reagent. Shake well in cold/ 5. Compound + Tollen’s reagent. Heat the test tube in a beaker Yellow solid is formed It is an aldehyde or a ketone Orange red solid is obtained It is an aldehyde or a ketone A crystalline think white ppt is obtained It is an aldehyde or a Ketone A rose red coloured solution is obtained It is an aldehyde The test tube appears silvery white from outside It is an aldehyde containing hot water or by direct heating without shaking the test tube 6. Compound + a few drops of sodium nitro prusside +NaOH solution in excess. Shake well 7. Compound+ twise the quantity of m-dinitrobenzene +NaOH solution in excess. Shake well. 8. Iodoform Reaction: Compound +Iodine solution + excess of NaOH solution. Shake well. Warm if necessary A red coloured Solution It is a ketone A pink or violet colour is developed; this fades away gradually It is a ketone A yellow ppt is formed It is a methyl ketone Test for esters: 1. Odour of the compound Sweet fruity Odour 2. Compound + 20% sodium jhydroxide A white precipitate is formed solution. Boil for about 10 minutes. Cool and add excess of dil H2SO4. 3. Compound + 2-3drops of ethyl alcohol. Shake. Add about 0.2g hydroxylamine hydrochloride + about 5ml of 2N NaOH solution. Boil gently; cool Add 1-2 drops for neutral ferric chloride solution and excess of dil HCI A violet or deep reddish brown colour is seen 4. Compound + dil NaOH + Pink colour gradually disappears Phenolphthalene and warm with shaking It may be an ester It is an ester It is an ester It is an ester Preparation of derivatives: (A) Benzoic acid from benzyl alcohol. Take a mixture of a few drops of benzyl alcohol and about 5ml of 10% sodium carbonate Solution in a 100ml concial flask provided with a one holed cork carrying a long glass tube which serves as a condenser. Heat the solution and add about 15ml of saturated solution of potassium permanganate slowly till a light pink colour remains. Boil for a few more minutes. Filter off brown ppt of managanese dioxide. Add dil H2SO4 to the filtrate till the solution is acidic. On cooling benzoic acid separates out as a white solid. Filter, wash and dry. (B) Preparation of phenyl hydrazone derivative of benzaldehyde and acetophenone: To about 5ml of phenyl hydrazine taken in a test tube add a few drops of glacial acetic acid and a few drops of benzaldehyde or acetophone. Shake well. Filter off the yellow ppt. of the phenyl hydrazone. Wash and dry. (c) Preparation of benzoic acid from methyl and ethyl benzoates: To about 2ml of methyl or ethyl benzoate taken in 100 ml concial flask provided with a one holed cork carrying a long glass tube, add about 25 ml of 20% NaOH solution. Boil for about 10-15 minutes. Acidify with HCI and cool. Filter off the precipitate of benzoic acid, wash and dry. CLASSIFICATION REACTIONS FOR VI GROUP OF THE SOLUBILITY TABLE Compounds belonging to this group do not contain nitrogen. They are insoluble in water, 5% HCI 5% NaOH and cold conc. H2SO4 such compounds are Aromatic Hydrocarbons- Toluene, Naphthalene and biphenyl. Aromatic Halides- Chlorobenzene and benzyl chloride. Experiment Observation Inference 1. 2 to 3 drops of the liquid or a small pinch of the solid +5 ml. of fuming H2SO4. Heat strongly with carefully shaking Compound dissolves to form a homogeneous solution. It is an aromatic compound 2. Small quantity of substances as above+5 ml of dimethyl sulphate. Heat the solution strongly with shaking Compound dissolves to form a homogeneous solution It is an aromatic compound A white turbid mixture is formed It is an aromatic compound Add NH4OH to the mixture The following reaction is carried out only if the presence of chlorine in the given compound has been established by elementary analysis. Compound + silver nitrate solution+5ml of ethyl alcohol. Shake well. White ppt Chlorine atom is in the side chain No ppt Chlorine atom is attached to the aromatic nucleus Preparation of Derivatives: A. Benzzoic acid from toluene: For procedure, see the method of preparation of benzoic acid from benzyl alcohol in V group. Use toluene instead of benzyl alcohol. B. Pictrate derivative of naphthalene: To a strong solution of naphthalene in about 3 ml of benzene add a stron solution of picric acid in about 3ml of benzene. Mix the two solutions. Evaporate the solution to dryness near the window to get the solid. C. Preparation of nitro derivatives for biphenyl, chlorobenzene and benzyl chloride. Take the compound in a test tube and add a mixture of 3ml. of fuming nitric acid and 3ml of conc. Sulphuric acid, Boil with shaking for about 5 minutes. Add one or two drops of the mixture to a little ice water taken in another test tube. If a yellow solid separates out, nitration is complete. If a yellow emulsion is formed nitration is incomplete and the mixture must be heated for a few more minutes. Finally, pour the mixture into ice water. Filter off the yellow solid, wash and dry. CLASSIFICATION REACTIONS FOR VII GROUP OF THE SOLUBILITY TABLE Compounds belonging to this group contain nitrogen. They are insoluble in water and 5% HCI. Such compounds are, Amides- Benzamide Nitro compounds- Nitrobenzene , mdinitrobenxene, p-nitrotoluene Experiment Test for amides Compound + excess of 2N NaOH solution. Boil well and expose a wet red litmus paper to the vapours; also expose the vapours to glass rod dipped in HCI. Cool the solution and add excess of HCI Observation Inference Red Litmus paper turns blue Dense white fumes A white solid separates out It is an amide A red dye is formed The original compound is a nitro- compound An ash-grey coloured ppt is formed It is a nitro compound Tests for nitro compounds: 1. Compound (3-4 drops or a small pinch of solid) + Tin or Zinc bits + conc HCI. Boil well with shaking till the yellow compound has dissolved completely to form a colourless solution. Filter the hot solution. Cool the filtrate first under tap and then in ice. To this, add an ice cold solution of sodium nitrite in water and then an ice cold solution of β-naphthol in NaOH 2. Mullikan and Barker’s reaction: Compound + alcohol+ concentrated solution of calcium chloride + zinc dust. Boil and filter. Filtrate +Tollent’s reagent 3. Janowsky’s reaction: Compound+acetone+NaOH Pale yellow coloured solution. Shake well solution Violet or pink coloured solution Preparation of derivatives: A. Benzoic acid from benzamide: It is a mononitro compound It is a dinitro compound To a little benzamide taken in a test tube, add about 5ml of 50 % H2SO4. Boil well and pour the mixture into ice water taken in a beaker. Filter off the precipitated benzoic acid, wash and dry. B. Preparation of M-dinitrobenzene from nitrobenzene: To about 3ml of nitrobenzene, add about 3 ml of fuming HNO3 and 3ml of conc- H2SO4. Boil for about 5 minutes with shaking. Pour the mixture into ice water. Filter off the yellow solid, wash and dry. C. Preparation of derivative from m-dinitrobezene Prepare a strong of m-dinitrobenzene in 3ml of benzene. To this add a strong solution of naphthalene in 3ml of benzene and mix well. Concentrate and cool the solution or evaporate the solution to dryness near the window to get the derivative. D. Preparation of p-nitrobenzoic acid from p-nitro toluene: For procedure, see method of preparation of benzoic acid from benzyl alcohol in V group. Use pnitro toluene instead of benzyl alcohol.