ORGANIC QUALITATIVE ANALYSIS Carry out the analysis based on following points, 1, Nature (solid/liquid) 2. Type (Acid/Phenolic/Base/Neutral) 3. Preliminary analysis (detection of saturation/unsauration & aliphatic or aromatic) 4, Detection of elements (Lassaigne’s tests for nitrogen, sulfur & halogens) 5. Detection of functional groups based on type and elements 6. Recording physical constants (melting/boiling point)oC gan*e Bim-Quderamue Anadyois oF uence Ps und 1, Nature of the compound: Determine the nature of given compound by visual analysis as solid or liquid. 2. Type determination of the compound: First determine the solubility of given compound in water. layer formation for liquid compound) b) Compound is water insoluble/immiscible (two layers are clearly observed for liquid compound) Test Observation Inference Compound in a test tube + a) Compound is water | Proceed with type water soluble/miscible* (no two | determination according to Table A Proceed with type determination according to Table B *For solids, ‘water soluble? phrase is used while for liquids, ‘water miscible’ phrase is used. Table A: Type deterinination of water soluble/miscible compounds. Test Observation Inference ‘Compound + 1 mL water, dissolve the compound and make water solution (WS). WS few drops on a small strip of blue litmus paper *Distinction between Acid or Phenolic (only ~— for observation a): Compound in test tube +NaHCOs a) Blue litmus turns red +i) Effervescence of COr *ii) No effervescence of COz Type of given compound is Acid or Phenolic* * Acid is confirmed *Phenolic is present ‘WS few drops on a small strip of red litmus paper b) Red litmus turns blue Type of given compound is Base ‘Conclusion: Type of given organic compound is~‘Table B: Type determination for water insoluble/immiseible compound Test ‘Observation Taference Compound in test tube +] a) Effervescence of CO2 and | Acid is present and confirmed NaHCOs solution, shake well | compound dissolves completely. Compound is reprecipitated/regenerated after addition of cone. HCI b) Compound is | Acid is absent insoluble/immiscible Compound in test tube +] a) compound dissolves | Phenolic is present NaOH solution, shake well | completely and reprecipitated/regenerated by conc. HC] ») ‘Compound is | Phenolic is absent insoluble/immiscible Compound in test tube + 1:1 fa) compound dissolves | Base is present HCI solution, shake well completely and reprecipitated/regenerated by 40% NaOH ») ‘Compound is | Base is absent insoluble/immiscible NOTE: If all the above tests for Acid, Phenolic and Base are absent, then type of given ‘compound will be Neutral. Conclusion: Type of given organic compound is —-——~ 6) 3, Preliminary tests: Test ‘Observation Taference Rea | Compound in test tube + Br [ a) Brown color of bromine | Unsaturated compound Saoe | in CC disappears (containing doubleftriple bond) may be present. b) Brown color of bromine | Saturated compound may be persists present. Compound in test tube +]a) Pink color of KMnOs | Easily oxidisable compound NavCOs + an KMnOs disappears may be present is alkaline KMnINOa, |) Pink color of KMn0s [Easily oxidisable compoundmay| persists pe absent.Place small quantity of fs) Sooty flame is observed | Aromatic compound present compound on copper gauze a and heat it on bumer (blue|b) Nosooty flame is | Aliphatic compound may be al flame) served present ion: Given organic acid / phenolic / basic / neutral (water insoluble / water insoluble/ water immiscible / water miscible compound may be a) Saturated / Unsaturated b) Easily oxidisable compound present / absent °) Aromatic / aliphatic WHOS, xD + Na a CN-, Was 7 Nak, Preparation of sodium fusion extract: In a sodium fusion tube take small quantity of sodium metal (avoid green portion, the metal piece should be shiny). Heat the metal piece on burner till it fuses (first it tums silvery shiny and then fuses). Allow to cool. Add small quantity of the compound to the fused sodium metal. Heat strongly on burner till bottom of the sodium fusion tube becomes red hot. In a porcelain dish take approximately 5-10 mL of distilled water and place hot sodium fusion tube in this water. Confirm that the tube gets broken after dipping in water. Boil the water in the dish and reduce the volume to 1 mL (while boiling, protect your face and eyes from water splashing by placing asbestos sheet in front of your eyes). This is called sodium fusion extract. oe 4. Element detection (Sodium fusion/Lassaigne’s tests): Test Observation Inference ‘Sodium fusion extract + | a) Green or blue color Nitrogen is present Coy FeSOs, heat well and add , (oy {dilute H2SO¢ b) No green or blue color Nitrogen is absent Sodium fusion extract _ +] a) Purple color is obtained __| Sulfur is present sodium nitroprusside/.. ncTibyto 1 | b)Nopurple color Sulfur is absent ‘Sodium fusion extract + conc. | a) White precipitate Halogens are present HNOs, heat well and add AgNO solution. b) No white precipitate Halogens absent .. as elements. ° Conclusion: Given organic compound contains C, H , (0), «. $, Determination of functional groups: A) For Acids — fests Observation Inference ‘Compétnd in a test. tube + | Effervescence of COz -COOH groups is present NaxCOs solution **Compound in a test tube + I | a) Green/blue coloration Penolic -OH functional group mL ethyl alcohol + neutral is present FeCl b)No green/blue coloration | Phenolicic -OH functional’ group is absent EdB) For Phenolics — Test ‘Observation Tnference Compound in a test tube + 1 [ a) Green/blue coloration Phenolic ~OH functional group mL ethyl alcohol + neutral is present FeCls 'b) No green/blue coloration Phenolic -OH functional group is absent ‘**Acid compound may contain Phenolicic -OH as functional group in addition to COOH (carboxylic acid) functional group, but for such a compound, main funetional group will be carboxylic acid (COOH). Such compounds where two or more functional groups are present are called bifunctional or multifunctional compounds. ©) For Base ~All organic bases are organic amines. These amines may be primary (1°), secondary (2) or tertiary (3°). Test Observation: Inference. Distinction between 1°, 2° and 3° amines ~ ‘Compound in a test tube + cone. HCl + NaNO> solution If observations a) and b) are negativethen, To above solution “add B — naphthol in NaOH solution (4- 5 drops) 2) Yellow colored precipitate If observation a) is negative then, b) Red colored solution is obtained ©) Orange dye stuff (orange colored thick precipitate) is obtained Secondary amine (2°) is present Tertiary (3°) amine is present Test for -NO2 (If base compound is bright yellow solid then this test is usually positive) Compound in a test tube + 1:1 alcohol + 2% CaCl solution + zinc dust. Heat this mixture strongly on burner. Filter this hot solution into freshly repared Tollen’s reagent a) A grey or black precipitate is obtained b) No grey or black precipitate Primary (1°) amine is present tule -NO> groups is present. Ue suk -NO2 groups is absent” 44) For Neutrals - Neutral compounds are divided based on presence of elements. 4) Neutral compounds containing C, H, (O) and N elements. strongly on burner. Filter this hot solution into freshly prepared Tollen’s reagent Test Observation Taference Test for -NOz a) A grey or black precipitate | -NOz groups is present Compound in a test tube + 1:1 | is obtained alcohol + 2% CaCl solution + zine dust, Heat this mixture | b) No grey or black precipitate | -NOz groups is absent Test for anilide group Compound in a test tube + cone. HCl + NaNO; solution. To above solution add 8 — naphthol in NaOH solution (4- a) Orange dye stuff (orange, colored thick precipitate) is obtained Anilide (NHCOR) group is present tube of turmeric paper 5 drops) b) No orange dye stuff. Anilide group absent Test for Amide (only for water soluble compound) Compound in a test tube + | a) Turmeric paper tums red | Amide (-NHCO) group is 10% NaOH solution, heat well | due fumes of ammonia present and place a moist turmeric paper on mouth of the test | b) No change in yellow color | Amide group absent Tollen’s reagent: 1 drop AgNOs +1 drop NaOH + ammonia till formed ppt dissolves (1-2 drops) ii) Neutral compounds containing C, H, (0), N and S elements. Test Observation Inference Test for Amide (only for water soluble compound) Complfitid'iin a test tube + 10% NaOH solution, heat well and place a moist turmeric paper on mouth of the test tube a) Turmeric paper tums red due fumes of ammonia b) No change in yellow color of turmeric paper Thioamide (NHC=S) group is present. Thioamide group absent Compound in a test tube + 1 mL water + 2 drops of FeCls solution a) Blood red coloration 'b) No blood red coloration Thioamide functional group is present Thioamide functional group is absentNeutral compounds containing C, H, (O) elements. 2,4-DNP reagent is positive) Silver mirror test. — Compound in a test tube + 1 mL of Tollen’s reagent. Shake well and warm on water bath, Test Observation Inference Test for carbonyl group Compound in a test tube + 1 | a) Yellow/orange/red colored | Carbonyl group of aldehydes mL ethyl alcohol + 2,4-DNP | precipitate obtained or ketone is present reagent b) No yellow/orange/red | Aldehyde/ketone group is precipitate absent _ < Test for aldehydes (if test for | a) A silver mirror gets | Aldehyde functional group is deposited on inner walls of the test tube b) No deposition of silver mirror is observed present. Aldehyde functional groups is absent. Test for ketone (only if test for 2,4-DNP is positive and test for aldehydes is negative) Compound in a test tube + few drops of sodium nitroprusside solution + NaOH solution, shake well. a) Red colored solution is obtained b) No red colored solution is observed Ketone functional group is present Ketone functional group is absent. Todoform test (only if ketone a) Yellow precipitate of Acetyl (CH3C=0) functional funetional groups test is | iodoform (CHb) separates out | group is present positive) — Compound in a test tube + 1] b) No yellow solid formation | Acetyl fimetional group is mL NaOH solution + 2 mL absent. iodine solution, warm on water bath, Test for ester (only if test for 2,4-DNP reagent is negative) Compound in a test tube + | a) Pink color of the solution | Ester group is present dilute NaOH (5%) + 1 drop of | gradually decreases and Phenolicphthalein indicator | disappears on gentle warming (thesolution should turn light | ina water bath pinkcolor). Warm the solution b) Pink color of the solution | Ester group is absent. gently on water bath. persists even after gentle ‘warming on water bath NOTE: If tests for 2,4-DNP reagent (aldehyde and ketone group)and for ester _ group are negative, then the compound is a hydrocarbon and contains no functional group.6. Determination of physical constants (MP/BP): The melting point of the compound needs to be determined. For this, we need dry and free flowing compound which can be filled in the capillary easily. Drying the compound under IR lamp is time consuming. We can press dry the ‘compound if it is wet or contains moisture. We will fill just sufficient compound in the capillary (one end is sealed and other end is open) so that we get an accurate physical constant. After filling the compound in the capillary, attach it with suitable thermometer (0 - 360 °C) with a thread. Cut excess thread as it may result in oil spurting while heating. Attach a Thiele’s tube such that its side arm is on either sides. Mount the thermometer correctly such that mereury bulb and bottom sealed end of the capillary are immersed in the oil. The open end of the capillary remains outside the oil level. The mounted thermometer should not touch the inner walls of the Thiele’s tube and the mercury bulb should reside exactly at the center of the tube. Also the thermometer should be parallel to the stand. Now the assembly is ready for recording physical constant, Heat the side arm slowly and allow the temperature to rise gradually. To record boiling point of a liquid, we fill small portion of the liquid in a sodium fusion tube and place a partially sealed capillary inside the liquid in inverted position (sealed end should be outside the fusion tube and open end should get immersed in the liquid). Then we tie the fusion tube to thermometer using a thread. ‘The melting point of a solid is recorded when solid just starts melting till complete melting takes place. It may be a range of 2-3 degrees. Never record melting point only at a particular temperature. As an example, a pure sample of benzoic acid would start melting at 120 °C and complete melting would take place at 122 °C. The melting point of pure sample of benzoic acid will be recorded as 120 - 122 °C. The boiling point of a liquid is recorded when vigorous bubbles start coming out from the inverted capillary till the liquid rises in the capillary. As an example, the pure sample of aniline will show vigorous bubbling at 182 °C and the liquid rise will occur at 184 °C, The boiling point of the pure sample of aniline will be 182 - 184°C. Result Table ‘Nature Type Elements Functional group(s) Physical constant (°C)