MADURAI KAMARAJ UNIVERSITY PSY Niza isa] (University with Potential for Excellence) ‘s 3 Cal Madurai - 625 021. DIRECTORATE OF DISTANCE EDUCATION B.Sc., Chemistry PAPER - II Inorganic Semimicro Qualitative Analysis PRACTICAL - I www.mkudde.org 5023 UCHELO1Printed At Vimala Note Book Copies - 500 Fresh Print 2014B.Sc. Degree Course Subject: Chemistry Dear Students, We welcome you to the B.Sc. Chemistry course. This self instructional material (SIM) contains the systematic procedure for the qualitative analysis of inorganic salt mixture. The procedure has been presented ina simple and an easy way for you to understand the chemistry behind the analysis. We hope you are aware of your responsibility to become successful in this course and evolve as a proficient graduate in chemical science. We assure you of our help through learning materials and personal contacts. Department of Chemistry, Directorate of Distance Education List of contributors: Dr. P. Gurusamy S. Nagarajan (Reviewer) Associate professor Associate professor Department of Chemistry Department of Chemistry Sri, SRN, M. College Sri. S. R .N .M. College Sattur-626 203 Sattur -626 203.Course: B. Se Subject: Chemistry Objectives: To enable the graduates to Acquire skills to identify the acidic and basic radicals. To gain knowledge about the principles behind the practical Syllabus: Analysis of a mixture containing two anions of which one is an interfering anion — and two cations (semi micro method). I. Anion : carbonate, sulphate, nitrate, chloride, bromide, oxalate, borate and phosphate. IL. Cation : ammonium, lead, bismuth, copper, aluminum, zine, manganese, cobalt, nickel, barium, calcium, magnesium. References: 1. Venkateswaran, V. Veerasamy, R. Kulandaivelu A.R., Basic principles of Practical Chemistry, 2” edition, New Delhi, Sultan Chand & sons (1997). Distribution of marks: Maximum marks: 100 35 Passing minimun Record = 10 marks Viva voce = 10 marks 20 x 4 radicals = 80 marksInstructions to students The chemistry laboratories give students the opportunity to perform experiments that hemistry laboratory can be a place of discovery and learning, However, by the very nature of explore important chemical concepts through systematic procedures. The laboratory work, it can be a place of danger if proper precautions are not followed. Beware that lab chemicals can destroy personal possessions. Work carefully and follow the given instructions. Attire + Confact lenses are not allowed. Various fumes may accumulate under the lens and cause serious injuries or blindness. Wear goggles. + Students must be present in fully covered dress with closed toe shoes for laboratory classes. 4 Students should bring laboratory manual and Record note book for all laboratory classes + Long hair must be tied back. Conduct 4 Food and drink, open or closed, should never be brought into the laboratory or chemical storage area. 4+ Never use laboratory glassware for eating or drinking purposes. 4 Never taste anything, Never directly smell the source of any vapor or gas. Keep your hands away from your face, eyes, mouth, and body while using chemicals. 4 Do not engage in practical jokes or boisterous conduct in the laboratory. Never run in the laboratory. 4 No unauthorized experiments are to be performed. Learn where the safety and first-aid equipment are located. ‘> Notify the instructor immediately in case of an accident. + The use of personal audio or video equipment is prohibited in the laboratory, +» Always wash your hands before leaving lab.Proper Handling of Chemicals and Equipment + Consider all chemicals to be hazardous unless you are instructed otherwise “Excess reagents are never to be returned to stock bottles. If you take too much, dispose of the excess. ‘ Many common reagents, for example, alcohols and acetone, are highly flammable. Do not use them anywhere near open flames. ‘> Abways pour acids into water. If you pour water into acid, the heat of reaction will cause the water to explode into steam, sometimes violently, and the acid will splatter. Ifchemicals come into contact with your skin or eyes, flush imme diately with copious amounts of water and consult with your instructor. “Never point a test tube or any vessel that you are heating at yourself or your neighbor. Clean up all broken glassware immediately. 4 Never leave burners unattended. Turn them off whenever you compete the experiments. ¢ Be sure that the gas is shut offat the bench rack when you leave the lab. + Beware of hot gss--it looks exactly like cold glass. + Do not leave the laboratory without permission. “* Keep the work place clean and organized. % Keep work area neat and free of any unnecessary objects. Do not block the sink drains with debris. * + Thoroughly clean your laboratory work space at the end of the laboratory session, 4 Never pour chemical wastes into the sink drains or waste-baskets. ° Phce chemical wastes, filter paper, and paper towels in appropriate waste containers Before leaving the laboratory + All the chemical containers must be closed and returned to their designated places. + Ensure that your work place is neat and clean, Wash your hands.SYSTEMATIC PROCEDURE FOR INORGANIC SEMIMICRO QUALITATIVE ANALY S. EXPERIMENT OBSERVATION INFERENCE No 1 PRELIMINARY TESTS: Green, May be Nickel Color of the substance is noted. Blue May be copper Colorless Absence of copper, Cobalt, Nickel 2 | FLAME TEST: Allittle amount of the substance is | Bright green May be Copper or taken in a watch glass and few borate drops of concentrated hydrochloric acid are added and made into paste, The paste is Presence of Barium taken in a glass rod and| Pale green introduced into the flame, The color of the flame is noted Presence of Brick red Caleium 3 CALCIUM FLUORIDE TEST: The substance is mixed with little calcium fluoride and conc. sulphuric and made into paste in a watch glass The paste is introduced into the flame by means of glass rod. The color of the flame is noted. Deep green color Presence of borateTEST FOR CARBONATE: Few drops of dilute hydrochloric acid are added to substance taken ina test tube. Colorless gas is evolved with brisk Effervescence. Presence of carbonate TEST FOR OXALATE: Substance + manganese di oxide +dil. sulphuric acid and warm. Colorless gas is evolved with brisk effervescence. Presence of oxalate ‘ACTION OF CONC. SULPHURIC ACID: Reddish brown Presence of nitrate ‘A little of the substance is | vapors are or bromide warmed with few drops of cone. | evolved sulphuric acid in a dry test tube ‘ACTION OF CONC. Reddish brown Presence of SULPHURIC ACID AND MANGANESE DI OXIDE: Substance +a pinch of manganese di oxide + cone. sulphuric acid and warm the contents. vapor is evolved Greenish yellow gas is evolved with pungent smell. bromide Presence of chloride COPPER TURNINGS TEST: Substance + copper turnings+few drops of conc. sulphuric acid and warm the contents. Reddish brown gas is evolved and the solution tums pale Green Presence of Nitrate. ETHYL BORATE TEST Substance + few drops of ethyl alcohol + few drops of cone. Sulphuric acid. Warm the contents and ignite the vapours in the flame Bums with a green edged flame Presence of Borate.10 AMMONIUM MOLYBDATE TEST : Substance + few drops of cone. nitric acid, heat and cool the contents. Then add few drops of ammonium molybdate solution. Canary yellow ppt. Presence of Phosphate, 1 ‘CHROMYL CHLORIDE TEST: Little quantity of the substance is taken in a dry test tube and a pinch of Potassium dichromate and few drops of cone, sulphuric acid are added and heated. The red orange vapour produced is passed into water. Yellow solution is got. To this few drops of acetic acid and lead acetate are added, Yellow ppt is got Presence of Chloride. 12 SODIUM HYDROXIDE TES A little of the substance is heated with few drops of sodium hydroxide solution Colorless gas with smell of ammor is evolved which gives white dense fumes with a glass rod dipped in cone. hydrochloric acid. Presence of Ammonium ion PREPARATION OF SODIUM CARBONATE EXTRACT: A Small quantity of the substance is taken ina semimicro_ boiling tube + thrice the quantity of anhydrous sodium carbonate + 5 ml of distilled water. Boil the contents for about 10 minutes. It is then cooled and centrifuged. The centrifugate is known as sodium carbonate extract and it is used to conduct the following tests. Check your progress 1. Why do you see effervescence when testing for carbonate?S.No. EXPERIMENT OBSERVATION INFERENCE, VER NITRATE TEST A little of the extract is acidified with dil. nitric acid till there is no bubbles. It is then boiled and few drops of silver nitrate soln. is added. White curdy ppt soluble in NH,OH. Pale yellow ppt partly soluble in NH.OH, Presence of Chloride, Presence of bromide, BARIUM CHLORIDE TEST A litle of the extract is acidified with dil hydrochloric acid till effervescence stops. It is then boiled and few drops of barium chloride solution are added A White ppt insoluble in all mineral acid is got Presence of sulphate. BROWN RING TEST The extract is acidified with dil, sulphuric acid till there is no effervescence and then mixed with with few drops of freshly prepared ferrous sulphate solution, To this mixture conc. sulphuric acid is added carfully along the sides without shaking the test tube. Brown ring is formed at the junction of the liquids. Presence of nitrate. CALCIUM CHLORIDE TEST The extract is acidified with acetic acid till there is no effervescence. It is boiled and few drops of calcium chloride solution are added. A white pptis obtained Presence of oxalateThe ppt is dissolved dil. sulphuric acid and the contents are warmed. Now few drops of dil. potassium permanganate solution are added Pink color is decolorized Presence of oxalate, Check your progress 2. What is the chemistry behind the brown ring test for nitrates? Check your progress 3. Why the pink color of permanganate decolorizes? ELIMINATION OF INTERFERING ANIONS AND PREPARATION OF ORIGINAL SOLUTION ELIMINATION OF OXALATE: If oxalate is present, a pinch of the substance is roasted in a C about 10 minutes, The roasted residue is then dissolved in dilute hydrochloric acid and centrifuged. ‘The residue if any is analyzed for lead. The centrifugate is used for the analysis of second group and so on. ELIMINATION OF BORATE: ina dish for A Pinch of the substance is taken in a china dish and few drops of concentrated hydrochloric acid are added. It is then evaporated to dryness. This pro: ss is repeated for 3 times. The residue is dissolved in dil, hydrochloric acid and centrifuged. The residue if any is analyzed for lead. The centrifugate is used for the analysis of second group and so on. ELIMINATION OF PHOSPHATE: Phosphate has to be eliminated only after the TI Group separation, The centrifugate from the II group is boiled to expel hydrogen sulphide gas and then few drops of ammonium chloride and zirconium chloride ( or zirconium nitrate) are added. It is then centrifuged. The residue is 5 Check your progress 4. What are called interfering anions?Check your progress 5. What is Nessler’s reagent? discarded. The process is repeated until no white ppt is obtained by the addition of zirconyl chloride. The centrifugate is used for the analy III Group and so on. is of SYSTEMATIC ANALYSIS OF CATIONS TEST FOR AMMONIUM ION: A little quantity of the mixture is taken in a centrifuge tube. One ml of distilled water is added and shaken well. It is then centrifuged .To the centrifugate few drops of sodium hydroxide and an excess of NESSLER'S REAGENT is added. A brown precipitate shows the presence of AMMONIUM ION. IDENTIFICATION OF GROUPS EXPERIMENT | OBSERVATION INFERENCE To the original solution a few drops of dil. hydrochloric | White ppt is go. Presence of Group I acid is added and centrifuged. The centrifugate is | Black or brown ppt. Presence of Group It heated, Hydrogen sulphide gas is passed and centrifuged. The cenirifugate from the above is boiled. Few drops of ammonium chloride | white ppt Presence of Group IIT and excess of ammonium hydroxide are added and centrifuged.The above centrifugate is Boiled, cooled and hydrogen Sulphide gas is passed and centrifuged. White ppt or flesh colored ppt or Black ppt Presence of Group IV The centrifugate is boiled and cooled. Few drops of ammonium chloride, ammonium hydroxide and Ammonium carbonate are added and centrifuged. White ppt Presence of Group V The centrifugate from group V is concentrated by boiling. Few drops of cone. nitric acid are added and evaporated {ill no more fumes are evolved. The residue is extracted with water To the solution few drops of ammonium hydroxide and an excess of Sodium phosphate solutions are added, shaken and the sides of the test tube are rubbed with a glass rod, White crystalline ppt. Presence of Mg Check your progress 6, What is common and different with the reagents used for Il and IV groups?ANALYSIS OF GROUP I METALS ‘The ppt obtained in group 1 is boiled with 5 ml of water and centrifuged while hot. The centrifugate is divided into 2 portions. 1) To the first portion, few drops of acetic acid and few drops of potassium chromate are added. LEAD. Yellow ppt is got-PRESENCE OF 2) To the second portion, few drops of potassium iodide solution are added. Yellow ppt is got. This ppt is heated with 10 ml of water and cooled, Golden yellow spangles appear - PRESENCE OF LEAD. ANALYSIS OF GROUP II METALS [Pb, Bi, Cu] ‘The GROUP II residue is washed with water and boiled with 2 drops of dil. nitric acid and 2 drops of dil. sulphuric acid and centrifuged. RESIDUE CENTRIFUGATE This is boiled with a few drops of ammonium acetate solution and divided into 2 parts. To one part, added 2 drops of potassium chromate solution, Yellow ppt-presence of lead. To another portion, potassium. lodide solution is added. To the centrifuate, ammonium hydroxide is added in excess and centrifuged RESIDUE, CENTRIFUGATE Residue is dissolved in Minimum amount of dilute hydrochloric acid and divided into 2 parts. To the first part, little water is added. White turbidity Presence of BISMUTH. To one portion of the centrifugate, few drops of acetic acid and few drops of Potassium ferro cyanide are added. Brown color ppt- presence of copperThe yellow ppt obiained is boiled with 10 ml of water — Golden yellow spangles — presence of lead. To the second part, little amount of thiourea and few drops of dil. nitric acid are added. Yellow color — presence of bismuth, ANALYSIS OF GROUP I METALS [Al] The third group ppt is boiled with about Sml of water and little sodium peroxide till the liberation of oxygen stops. It is diluted and centrifuged. A portion of the centrifugate is acidified with dil. hydrochloric acid. Ammonium hydroxide solution is added in excess and allowed to stand for few minutes. White gelatinous precipitate — presence of aluminium. ANALYSIS OF GROUP IV METALS [Ni, Co, Zn, Mn] ‘The IV Group ppt is washed with water and shaken with 1 ml of dil. HCL and 4ml of water. The mixture is then centrifuged. Check your progress 7. Can you draw the Structure of N-DMG complex? RESIDUE CENTRIFUGATE This is dissolved in cone, hydrochloric acid and a erystal of potassium chlorate is added and evaporated to dryness in a china dish. The mass is dissolved in little water and divided into 3 parts Hydrogen sulphide is boiled off and sodium hydroxide solution is added in excess and centrifuged, RESIDUE CENTRIFUGATETo the first part, 2 drops of ammonium chloride, 4 drops of ammonium hydroxide and 4 drops of Potassium ferricyanide solutions are added. Reddish brown color or ppt — presence of cobalt. To the second part, Little solid ammonium thio cyanate is added followed by a few drops of amyl alcohol and ether .It is shaken well. Blue layer-presence of Cobalt To the third part, 2 drops of ammoniumchloride 4 drops of ammonium hydroxide and 4 drops of dimethyl glyoxime Solutions are added. Rosy red ppt-presence of kel. White ppt tuning brown is got. This is shaken with a pinch of sodium bismuthate and 2 to 4 drops of dilnitric acid. Pink — Color- presence of Manganese. This is divided into 2 parts. To one portion Hydrogen sulphide gas is passed. White ppt - presence of Zine. The ppt is dissolved in cone. nitric acid and few drops cobalt nitrate solutions are added. A’ filter paper is dipped in this solution and burnt Green ash is got-presence of Zinc ‘The second partis acidified with acetic acid and 2 drops of potassium ferrocyanide solution is added. White ppt is got-presence of Zine. 10ANALYSIS OF GROUP V METALS [ Ba, Ca, Sr] The V GROUP ppt is dissol acid, Potassium ved in warm act chromate solution is added in slight excess, boiled and centrifuged. RESIDUE CENTRIFUGATE Yellow residue is got. This is made in to a paste with cone. hydrochloric ‘id and flame test is conducted. Pale green color-presence of Barium Toa portion of centrifugate few drops of ammonium hydroxide and 4 drops of ammonium oxalate solution are added. White ppt-presence of Calcium. TEST FOR MAGNESIUM To the original solution, add solutions of ammonium chloride, ammonium hydroxide and di sodium hydrogen phosphate, White pp — Presence of Magnesium. Check your progress 8, Why do you see a white ppt when you add sodium hydrogen phosphate to.a solution of Mg?* ions? a