LT-2024(AIIMS-CLASS NOTE) Part-I-CHEMISTRY ANALYTICAL CHEMISTRY Teaching points 1. Qualitative analysis * Cation analysis (group ItolV) sCu**, Pb, Fe Cr" AP" Ca’ + Anion analysis : [Carbonate and Bicarbonate sulphate and sulphide and Nitrate, Nitrite Halides except Flurides} Practical Organic chemistry : Detection andidentification of functional group [-OH, >c=0 [aldehyde and ketone}, carboxylic group, [alsohol and phenolic/amino and nitro group] + Test for Bimolecules « Testfor carbohydrates 1) Molisch’s test 2) Feshling's test and Benedict test 3)Tollen'stest 4) Barfoed's test 5)Seliwanaff's test 6)lodine test « Testfor olis and fats « Testor protein 1) Biuret test 2)Ninhydrintest 3) xanthoproteic test 2. Quantitative analysis * ACID, BASE and Theory of indicators + Titration and titration curves [Acid- Base ttrtion (simple, double)} 3. Preparation of some compounds Inorganic compounds : Mohr's salt, Potash Alum Organic compounds : Acetanilide, P-Nitroacetanilide, Aniline yellow, ladoform [Only Ag’. H; .2n?* Ni?’ NH},Mn” and MjLT-2024(AIIMS-CLASS NOTE) Part-I-CHEMISTRY ANALYTICAL CHEMISTRY INTRODUCTION Analysis always does not mean breaking of substance intoits ulitmate constituents. Finding out the nature of substance and identify of its constituents is also analysis and is known as qualitative analysis, Qualitative analysis of inorganic salts means the identification of cations and anions present in the salt of a mixture of salts. Inorganic salts may be obtained by complete or partial neutralisation of acid with base or vice-versa. In the formation of a salt, the part contributed by the acidis called anion and the part contributed by the base is called cation. For example, in the salts CuSO, and NaCl, Cu** and Na* ions are cations and SO? and Cl-ions are anions. Qualitative analysisis carried out on various scales. Amount of substance and employed in these is different. In macro analysis, 0.1 to 0.5 a of substance and about 20 mL of solution is used. For semimicro analysis, 0.05 a substance and ml. solution is needed while for micro analysis amount required is very small. Qualitative analysis is carried out through the reactions which are easily perceptible to our senses such as sight and smell ‘Such reactions involve: a) Formation ofa precipitate b) Change incolour c) Evolution of gas etc. ‘Systematic analysis of aninorganic saltinvolves the following steps i) Preliminary examination of solid salt and itssolution. ii) Determination of anions by reactions carried out in solution (wet tests) and confirmatory tests. ili) Determination of cations by reactions carried outin solution (wet tests) and confirmatory tests. Preliminary examination of a salt often furnishes important information, which simplifies further course of analysis. Although these tests are not conclusive but sometimes they give quite important clues for the presence of certain anions or cations. These tests can be performed within 10-15 minutes. These involve noting the general appearance and physical properties, such as colour, smell, solubility etc. of the salt. These are named as dry tests. Solubility of a saltin water and the pH of aqueous solutions give important information about the nature of ions present in the salt. If a solution of the salt is acidic or basic in nature then salt may be some carbonate or sulphide etc. Ifthe solution shows acidic nature then it may be an acid salt or salt of weak base and strong acid. In this case itis best to neutralise the solution with sodium carbonate before testing it for anions.LT-2024(AIIMS-CLASS NOTE) Partt-CHEMISTRY | QUALITATIVE ANALYSIS To detect one cation and one anion in the give salt from the following ions : Cations - Po", Cu”, As™,Al",Fe™ Mn’ Ni*,Co™, Ca”, Sr, Ba” Mg”,NH, e « ‘Arions- CO®,S*,80?-,NO;,NO;,CI-,Br-',PO}-.C,02 ,CH,COO™ y gf Unsolule sats tobe excudex), of a4 i Theory O Keo, 94 ‘Two basic principles of great use in the analysis are N i) the solubility product ane ii) the common ion effect When ionic product of a salt exceeds its solubility product, precipitation takes place. lonic product of salt is controlled by making use of common ion effect which you have studied in the textbook of chemistry. | (a). ANALYSIS OF ANIONS Pr ‘ary Test with Dilute Sulphuric Acid In this test the action of dilute sulphuric acid (procedure is given below) on the saltis noted at room temperature and on warming, Carbonate (CO? ), sulphide (S*), sulphite (SO: ), nitrite (NO, ) and acetate (CH,COO-) react with dilute sulphuric acid to evolve different gases. Study of the characteristics of the gases evolved gives information about the anions. Summary of characteristic properties of gases is given in Table 1 below. Fig : 1 Testing a Gas Table 1 : Preliminary test with dilute sulphuric acidL7-2024(AIIMS-CLASS NOTE) Part-1-CHEMISTRY Inference Observations GasEvoWved Possible Anion [A colouriess, odourless gas s evolved wih brisk Jetfervescence, which turns lime water milky. co; Carbobate (CO; ) [Cotourless gas wih the smell of rotioneggs is > Jevolved which turns lead acetate paper black. HS Sulphide (S*) [Cotourtess gas withthe a pungent smell, Ike _. Journing sulphur which turns aciifed potassium SO; Suiphite (SO; } lcichromate solution green, Brown fumes which turn acidified potassium NO, Witte (60,) iocide solution containing starch solution blue [CoTouriess vapours with smelf of vinegar (CH,COOH vapours (CH vapours turn bive litmus red Ps Aeatate, (CHsC00) Chemistry of Confirmatory Tests 1 Test for Carbonate ion [CO? | If there is effervescence with the evolution of a colourless and odourless gas on adding dil. H,SO, to the solid salt, this indicates the presence of carbonate ion. The gas turns lime water milky due to the formation of CaCO, Na,CO, +H,S0, ——+Na,SO, +H,0 + CO, Ca(OH), + CO, CaCO, +H,0 If CO, gas is passed in excess through lime water, the milkiness produced disappears due to the formation of calcium hydrogen carbonate which is soluble in water. CaCO, + CO, + H,0-—+Ca(HCO,), Test for Sulphate ion [S*] a) With warm dilute H,SO, a sulphide gives hydrogen sulphide gas which smells lke rotten eggs. A piece of iter paper dipped in lead acetate solution tums black on exposure to the gas due to the formation of lead sulphide which is black in colour. Na,S +H,SO, ——+Na,SO, +H,S (CH,COO), Pb+H,S— PbS. + 2CH,COOH b)_ Ifthe salt is soluble in water, take the solution of salt in water make it alkaline with ammonium hydroxide and add sodium nitroprusside solution. Ifit is insoluble in water take sodium carboante extract and add a few drops of sodium nitroprusside solution. Purple or violet colouration due to the formation of complex compound Na, [Fe(CN),NOS] confirms the presence of sulphide ion in the salt Test for Sulphite ion [S03 a) On treating sulphite with warm di of buming sulphur. Na,SO, +H,SO, —-Na,SO, +H,0+SO, 1,SO,,SO, gas is evolved which is suffocating with the smellL1-2024(A1IMS-CLASS NOTE) Part |-CHEMISTRY ‘The gas tums potassium dichromate paper acidified with dil.H,SO,, green. K,Cr,0, +H,SO, +380, —+K,SO, +Cr,(SO,),+H,O subhoietaroen) b) An aqueous solution or sodium carbonate extract of the salt produces a white precipitate of barium sulphite on addition of barium chloride solution, Na,SO, | BaCl, — »2NaCl + BaSO, This precipitate gives following tests. i) This precipitate on treatment with dilute HCI. dissolves due to decomposition of sulphite by cilute HCI. Evolved SO, gas can be tested. BaSO, +H,SO, —-BaSO, +H,0 +80, 2KMnO, + 3H,SO, ——-K,SO, +2MnSO, +3H,0 +510] SO, +H,0 +0] —+H,80, Test for Nitrite ion [NOz) a) On treating a soild nitrite with dilLH,SO, and warming, reddish brown fumes of NO, gas are evolved. Addition of potassium iodide solution to the salt solution followed by freshly prepared starch solution and acidification with acetic acid produces blue colour. Alternatively, a filter paper moistened with potassium iodide and starch solution and a few drops of acetic acid turns blue on exposure to the gas due to the interaction of liberated iodine with starch. i) 2NaNO, +H,SO, —+Na,SO, +2HNO, 3HNO, ——HNO, +2NO-+H,0 2NO+0,—— 2NO, own gee ii) NO, +CH,COOH—HNO, +CH,COO 2HNO, + 2KI+-2CH,COOH—+2CH,COOK + 2H,0-+2NO+1, |, + Starch ——Blue complex b) Sulphanilic acid — 1-napthylamine reagent test (Griss -llosvay test). On adding sulphanilic acid and 1-naphthylamine reagent to the water extract or acidified with acetic acid, sulphanilc acid is diazotised in the reaction by nitrous acid formed, Diazotised acid couples with 1-naphthylamine to form a red azo-dye. NO; + CH,COOH—-HNO, +CH,COOL7-2024(AIIMS-CLASS NOTE) Part-I-CHEMISTRY BH,CH,COO™ NeN-ooccH, ‘The test solution should be very dilute. In concentrated solutions reaction does not proceed beyond diazotisation Test for Acetate in [CH,COO-) a) Ifthe salt smells like Vinegar on treatment with dil. H,SO,, this incicates the presence of acetate ions. Take 0.1 g of salt in.a china dish and add 1 mL of ethanol. Then add about 0.2 mL of conc. H,SO, and heat. Fruity odour of ethyl acetate indicates the presence of CH,COO ion. 2CH,COONa +H,S0,——Na,SO, + 2CH,COOH CH,COOH +-C,H,0H—“CH,COOC.H, + H,0 (Paltyoour b) Acetate gives deep red colour on reaction with neutral ferric chloride solution due tothe formation ‘of complex ion which decomposes on heating to give iron (Ill) dinydroxyacetate as brown red precipitate. 6CH,COO” + 3Fe** +2H,0[Fe, (OH)2(CH,COO), |” + 2H” [Fe, (OH), (CH,COO), | +4H,O —+3|Fe(OH), (CH,COO)]}+3CH,COOH +H" ton daysronecette Test for Chloride ion (CH) a) Ifon treatment with warm conc. H,SO, the salt gives a colourless gas with pungent smell orand if the gas which gives dense white fumes with ammonia solution, then the salt may contain Cl ions and the following reaction occurs. NaCl+H,SO,— NaHSO, +, HCI osu, Hisogetnce nschnetDanae CSeesaae HCL+NH,——> NH,CIL7-2024(AIIMS-CLASS NOTE) Part-I-CHEMISTRY b) Ifa salt gives effervescence on heating with conc. H,SO, and MnO, and a light greenish yellow pungent gas is evolved, this indicates the presence of CI ions. MnO, + 2NaCl+2H,S0, —-Na,SO, +MnSO, +2H,0+Cl, ¢) Salt solution acidified with dilute HNO, on addition of silver nitrate solution gives a curdy white precipitate soluble in ammonium hydroxide solution. This indicates the presence of CI ions in the salt NaCl+ AgNO, NaNO, + _ AgCl ‘AgCl+-2NH,OH—+/Ag(NH, ), |. Dimnigenher d) Mixallittle amount of salt and an equal amount of solid potassium dichromate (K,Cr,O, )ina test tube and add conc. H,SO, to it. Heat the test tube and pass the evolved gas through sodium hydroxide solution. If a yellow solution is obtained, divide the solution into two parts. Acidify the first part with acetic acid and then add lead acetate solution. Formation of a yellow precipitate of lead chromate confirms the presence of chloride ions in the salt. This test is called chromyl chloride test. 4NaCI+K,Cr,0, + 8H,S0, —-2KHSO, Scie a AN@HSO, + 3H,0 C10, CI, + 4NaOH——-Na,CrO, + 2NaCl + 2H,0 (CH,COO), Pb +Na,CrO,, vero, +2CH,COONa Sedum Lesctromate cfomale (yen ros) Acidify the second part with dilute sulphuric acid add small amounts of amyl alcohol and then ‘mL of 10% hydrogen peroxide solution. On gentle shaking organic layer tums blue. CrO? ion formed in the reaction of chromyl chloride with sodium hydroxide reacts with hydrogen peroxide to form chromium pentoxide (CrO,) (See structure) which dissolves in amyl alcohol to give blue colour. CrO} +2H" +2H,0, — CrO, +3H,0 Test for Bromide ion [Br) Ion heating the salt with conc.H,SO, reddish brown fumes of bromine are evovled in excess, this indicates the presence of Br ions. The fumes get intensified on addition of MnO, Bromine vapours tum starch paper yellow. _—L7-2024(AIIMS-CLASS NOTE) Par-t-CHEMISTRY 2NaBr+2H,SO, ——-Br, + SO, +Na,SO, +2H,0 2NaBr +MnO, +2H,SO, ——Na,SO, +MnSO, +2H,0 a) Add 1 mL of carbon teterachoride \ichloroform (CHCI,)" and excess of freshly prepared chlorine water dropwise to the salt solution 7h water or carbonate extract neutralised with dilute HCI. Shake the test tube vigorously. The appearance of an orange brown colouration in the organic layer due to the dissolution of bromine in it, confirms the presence of bromide ions. 2NaBt + Cl, —+2NaCl+ Bry, ‘Acidity the sodium carbonate extract of the salt with dil. HNO, Add silver nitrate (AgNO,) solution and shake the test tube. A pale yellow precipitate is obtained which dissolves in ammonium, hydroxide with difficulty, NaBr + AgNO, NaNO, + ‘AgBr Test for lodide ion [H) If on heating the salt with conc.H,SO, deep violet vapours with a pungent smell are evolved, These turns starch paper blue and a violet sublimate is formed on the sides of the test tube, it indicates the presence of “ions. Some Hi, sulphur dioxide, hydrogen sulphide, and sulphur are also formed due to {the following reactions. Nal + 2H,SO, ——+Na,SO, +SO, +2H,0 +l, 1 +. Starch solution —Bluecolour ARE |-+H,S0, —NeaHSO, +HI 1 H,SO, —2H,0 +1, + SO, lal +4H,SO, 31, + 4H,O +S + 3Na,SO, 8Nal | 5H,SO,—_>4I, +H,S | 4Na,SO, +4H,0 (On adding MnO, to the reaction mixture, the violet vapours become dense. 2Nal-+MnO, +2H,SO, ——I, + MnSO, +Na,SO, +2H,0 b) Add 1 mLof CHCI, or CCI, and chlorine water in excess to the salt solution in water or sodium carbonate extract neutralised with dil HCland shake the test tube vigorously. Presence of violet colouration in the organic layer confirms the presence of iodide ions. 2Na(Cl.)—2naci lodine dissolvesin the organic solvent and solution becomes violet. @) Avy sodium carbonate extract ofthe sal ith di HNO, and edd of NH,OH confirms the presence ofiodide ions. Nal+AgNO,— _Agl_ +NaNO, hetL1-2024(AIIMS-CLASS NOTE) Part-I-CHEMISTRY 9. Test for Nitrate ion [NO,) a) fon heating the salt with conc. H,SO, light brown fumes are evolved then heat a small quantity of the given salt with few copper turnings or chips and conc. H,SO,. Evolution of excess of brown fumes indicates the presence of nitrate ions. The solution tums blue due to the formation of copper sulphate. NaNO, +H,S0,—-NaHS0, +HNO, 4HNO,, ©, 42,0 2NaNo, +44,SO, +3Cu—— 3CuSO, +Na,SO, + 4H,0+2NO Conner pate "bie! 2NO+0,—— 2NO, b) Take 1 mL ofan aqueous solution of the salt and add 2 mL conc. H,SO, slowly. Mixthe solutions thoroughly and cool the test tube under the tap. Now, add freshly prepared ferrous sulphate solution along the sides of the test tube dropwise so that it forms a layer on the top of the liquid already present in the test tuebe. A dark brown ring is formed at the junction of the two solutions due to the formation of nitroso ferrous sulphate (Fig, 2). Alternatively first ferrous sulphate is added and then concentrated sulphuric acid is added, oma vrark brown Fig. 2 : Formation ofbrown ring NaNo, +H,S0, ——>NaHSO, + HNO, 6FeSO, +3H,SO, +2HNO, —3Fe, (SO,), + 4H,0 +2NO FeSO, +NO—— |Fe(NO)|SO, +l ° + 2 AEA Fe (Ho) (n 3 N, Test for Sulphate and Phosphate < If no positive test is obtained in previous steps, then tests for the presence of sulphat and phosphate ions are performed. 1. Testof Sulphateions [SO] ‘Aqueous solution or sodkim carbonate extract othe salt acdifed with acetic acid on adition of barium sulphate insoluble in conc. HCI or conc. HNO. 10. alLT-2024(AIIMS-CLASS NOTE) Part-I-CHEMISTRY Na,SO, BaSO, +2NaCl b) Sulphate ions give white precipitate of lead sulphate when aqueous solution or soidum carbonate extract neutralised with acetic acid is treated with lead acetate solution. Na,SO, +(CH,COO),Pb———. PbSO, +2CH,COONa 2. Test for Phosphate ion [POS a) Addconc. HNO, and ammonium molybdate solution to the test solution containing phosphate ions and boil. A yellow colouration in solution or a canary yellow precipitate of ammonium phosphomolybdate. (NH,),(P(Mo,O.,),] is formed. Each oxygen of phosphate has been replaced by Mo,O,, group. 23HNO, NH, |P(Mo,0,,),|+ PNANO, +2°NH,NO, +12H,0 "(b)\ ANALYSIS OF CATIONS Examination of the Salt for Identification of Cz Preliminary Colour Test Colour Indicated Light green, Yellow, Brown 2 pe Blue 2 Bright green 2 Blue, Red, Violet Pink Light pink hin 2. DryHeating Test i) Take about 0.1 g of the dry satin a clean and dry test tube. ji) Heat the above test tube for about one minute and observe the colour pf the residue when itis hot and also when it becomes cold. Observation of changes gives indications about the presence of cations, which may not be taken as conclusive evidence (Table - 2) Table-2 : Inference from the colour of the salt in cold and on heating Colour when cold hot Cations: ue white {Green White ink ive 3. Flame Test The chlorides of several metals impart characteristic colour to the flame because they are volatile in nnon-luminous flame. This testis performed with the help of a platinum wire as follows i) Makea tiny loop at one end of a plantinum wire.sauing uasung fo aumy fo sauog : gT°T “BRT ao "pu so-Fumqum. fo RKP ahead NenOY amu pom 5794 J\\Grxarbasiprtane tio pp so. ‘SD JOY SD JON ‘aUOD aMIq aIPPIN (2) auet Berinpat todd ~~ “aoydoo ou 5 Sonn OO ON ysndind snounum-uoy 2 MO[AIq paqhiosap auv suey UasuNg ay} Jo syed a]qIstA AJOUTSIP 90r4.],L7-2024(AIIMS-CLASS NOTE) Part-I-CHEMISTRY ii) To clean the loop dipit into concentrated hydrochloric acid and hold it in a non-luminous flame (Fig.3). iii) Repeat step (i) until the wire imparts no colour to the flame, iv) Put2-3 drops of concentrated hydrochloric acid on a clean watch glass and make a paste of a ‘small quantity of the salt in it v) Dip the clean loop of the platinum wire in this paste and introduce the loop in the non-luminous (oxidising) flame (Fig.3) vi) Observe the colour of the flame first with the naked eye and then through a blue glass and identify the metal ion with the help of Tabl Fig.3 : Performing flame test Table-3: Inference from the colour of the saltin cold and on heating Colour of the flame Colour of the flame ‘observed bynakedeye | observed through blue glass | Inference \Green flame with [Same colour asobserved lblue centre withootgtass cu [Crimson red Purple se [Apple green Bluish green Ba’ [Brickred [Green ca Borax Béad Test This test is employed only for coloured salts because borax reacts with metal salts to form metal borates or metals, which have characteristic colours. i) Toperform this test make loop at the end of the platinum wire and heatit ina flametillitis red hot. ii) Dip the hot loop into borax powder and heat it again until borax forms a colourless transparent bead on the loop. Before dipping the borax bead in the test salt or mixture, confirm that the bead transparent and colourless. If itis coloured this means that, the platinum wire is not clean, ‘Then make a fresh bead after cleaning the wire. i) Dip the beadina small quantity of the dry salt and again hold itin the flame.LT-2024(AIIMS-CLASS NOTE) Part-I-CHEMISTRY ie Fig. 4 : Borax bead test (a) Heating in reducing flame (b) Heatingin oxidising tlame iv) Observe the colourimparted to the beadin the non - luminous flame as well as in the luminous flame while itis hot and when itis cold (Fig.4) v) Toremove the bead from the platinum wire, heat itto redness and tap the platinum wire with your finger. Fig 5) On heating, borax loses its water of crystallisation and decomposes to give sodium metaborate and boric anhydride. Na,B,O,.10H,O—-Na,B,0, +10H,0 Borex one WARK Na,B,0,_——- 2NaBO, + 8,0, wypmaaierae Boron On treatment with metal salt, boric anhydride forms imotaboraiact the metal which gives different colours in oxidising and reducing flame. For exampl8;in the casé of copper sulphate, following reactions occur. verninastons_, Mf Joo. .80 Exe0,, +80, ‘Two reactions may take placein the reducing flame i) The blue Cu(BO.), is reduced to colourless cuprous metaborate as follows: 2Cu(BO,), +2NaBO, + CH= _, 264BO, +Na,B,O, +CO or (ii) Cupric metaborate may be reduced to metallic copper and the bead appears red and opaque. 2Cu(BO,), + 4NaBO, +2C—"mHEM_.2Cy + 2Na,B,O, +2CO The preliminary identification of metal ion can be made from Table - 4 ora Fig.d : Kemoving borax bead,L7-2024(AIIMS-CLASS NOTE) PartI-CHEMISTRY Table 4 : Inference from the borax bead test Heating in oxidising Heating in reducing Inference ‘Colour of the salt head Colour of the salt bead oY [nhot [ncold Inhot Blue Vv. reer econague colourless oF Reddish brown [Violet 1 crey NE Light violet Ioht violet lout (Colourass Mn® [Yetow ellowish brows [ren Green Fe™ ‘The Separation and identification of various basic radicals into different group is mainly based upon six groups based on the increasing K,,, values of corresponding precipitating compounds. Table- 5 : Analytical ‘groups and their reagents Grp. | Group reagent | Cations Cations precipitated as 1. Dilwe HCL He", Ag’, PB HeyCle, AgC 2M) incold PCI, (PCI, is soluble in hot water, less in old water. H_/H,S inpresence HgS. POS. Bi,S, of 2 MHC! IM NH,CI* NH.OH Fe(OH), CHOW. AMOH), IN. H Sin basic CoS, NiS, MnS, ZnS medium, HS + NHOH V. NHCl+ NHOW Ba", Se*.Ca* | BaCO,, S100, HONH),CO, CO, Vi. Nospecific | Na®, K®, Me™ ero. Nesslr's NH, Fodids of Millon’s reagent base ammonical solution (Oxydimereure {Hel,) ‘ammonium iodide) ovis NHOW He Group I: Dilute HCI is added to the solution containing cations. Since the K,, values of the chlorides of group lis less than K., values of the chlorides of higher group, so only the chiorides of | groups are precipitated If the concentrated HCI is used, then [Cl° will increase, then the ionic product (Q,,) oftheir chlorides will increase, then chlorides of other group may be precipitated. Moreover, PbCI, is soluble in concentration HCL.(uum) Tod HN)BW foe i . qdd anym 2 & ID'HN pue HO'HN JO ia 8) eect eee (ONS 0288 | FOTHN Jo aouasaud ul ‘09' HN) 208) ‘eS ‘28 wW e761 TOT sng — suW ‘d peg Auig « Suz DAN : : L & yer Sop ‘SIN| pl & “gin uh aouasaid ul SH] IN ZUZ 2-09 UW Al ‘ua016 fai /uig — {HONS - + smunsteuerse now) BOTAN CHAN uysoig ysippay < (HO) ID'HN Jp a2uasaid ut HO"HN el ‘el 84 tM uoRnjos abueig —“sqs| \>+ PHN PHN abueio < ‘5°95 —_ MO|IaA —"5'sy “Sus i ea ‘dd unsig & sug : 59S" ¢.95' 5.5 eS" US 2,US ou WeH<—pH Isy Fo us‘("HN) (@piudins WNIUQUALY Quad) SUL sea aignjosut [5H TIP ul se’ s"H eePD ‘eo! ‘204d ‘25H 32ND (w) 20d z."6H .6y 1 samba Aono oy Wart “panjona si se6 wniuowwy yiqeay “(HO)eD 40 HORN HN 4L-2024(AIIMS-CLASS NOTE) Part-|-CHEMISTRY Group Il: H,S(a) is passed in an acidic medium to the solution containing cations. Since the K.,, values of the sulphides of group Il (~ 10 — 10 **) is ess than K,, values ofthe sulphides of higher gp. (> 10), so only the sulphides of group Il are precipitated. H,Sis a weak acid and its dissociation can be suppressed to get low [S*] such that ionic products of group Il sulphides are exceeded but not those of group Ill sulphides. This condition is achieved by passing H,Sin an acid medium so that H® (the common ion) suppress the dissociation of H.S. S—2H" +S? HCI—H® +.c1e Thus, the group Il sulphides are precipitated but not of other groups under these conditions because their K,, values are quite high. Note : Pb**is included in both groups | and Il. PbCl, is sparingly solublein dil HCL AnyPb** ion presentin group | filtrate will get precipitated as PbS in group Il Group Ill : Hydroxides of group Ill are precipitated by adding an excess of solid NHCI to these cations followed by the addition of excess of NH,OH. NH,OHis a weak base andis slightly ionised, whereas NH,CI being a strong electrolyte, t completely to givelarge |NH, NH,OH—=NH, +OH NH,CI—=NH, , 69 . Due fo commonion effect, the suppression of ionisation of NH,OH occurs and [OH] decreases appreciably. But even with this low [OH] ions, exceed the low value of the K,, of their hydroxides. Hence, only the hydroxides of group Ill get precipitated but not of other groups under these conditions because the K,,, of their hydroxides are quite high. Note . a [OH] wilbe high, and hence the Nafebkieass notite used in place of NH,OH, beings a strong base, b._AH,OH should be AB8E8'BHR SHBPSRHY AHCI otherwise common in absence of NH,Cl. Hence, hydroxides of other group willbe precipitatedosueffect would not occur ° pee and NaQH cannot be used in place of NH,Cland NH,OH. Both being strong ionises completely fo give high [OH]. NaCl cannot suppress the ionisation of NaOH. Therefore, hydroxides of other group will precipitate out, Moreover, AI(OH), and Cr(OH), are soluble in excess of NaOH because of the formation of aluminate and chromaterepectvely. = Group IV : Precipitation of sulphides of group IV occurs in presence of large excess of NH,OH. K,, of sulphides of group IV are sufficiently high. Therefore high concentration of S* ions as compared to that required in group Ilfor which K,, values are low. H,Sis weaklyionised as H,S——=2H" +S NH,OH——=NH, +S? +HLT-2024(AIIMS-CLASS NOTE) Part-I-CHEMISTRY Group Il: H,S(a) is passed in an acidic medium to the solution containing cations. Since the K.,, values of the sulphides of group Il (~ 10 — 10 **) is ess than K,, values ofthe sulphides of higher gp. (> 10), so only the sulphides of group Il are precipitated. Note : (|NH,),SO, cannot be uesed in place of NH,OH, because the sulphates of Ba, Ca and Sr. willget precipitated as white precipitate. Group V : The carbonates of group V are precipitated y adding (NH,),CO, solution to the solution of these cations in the presence of NH,CI and NH,OH. (NH,),CO, is a weak electrolyte that ionises slightly to give small (CO,* ions. (NH,), CO, —=2NH, +02 NH,Clisastrong electrolyte jonises almost completely to givelarge [NH,] . Due to the commonion effect, the dissociation of (NH,),CO, is suppressed and hence high [CO] decreases considerably.Buteven with thislow [CO | ions, the ionic products of these cations and [CO$-] ions exceed the low K,, values of their corresponding metal carbonates and thus get precipitated. Note : However, under these conditions, Ma Salts do not get precipitated a MgCO, since its K,, value is ‘comparatively high and thus requires a high |CO3_| ions for precipitation, The cabonates of Na, K and NH, are also not precipitated because they are quite soluble. The necessity of adding NH,OH arises due to the fact that (NH,),CO, solution usually contains a large amount of NH,HCO,, Thus, the cations of group V will orm not only insoluble carbonates but also soluble bicarbonates. As a result, the precipitation will not be complete. In order to convert NH,HCO,, NH,OH is always added. NH,HCO, +NH,OH——-(NH,}, CO, +H,O Note a _Na,CO, cannot be used inplace of (NH,),CO, because Na,CO, isa strong electrolytewhose ionisation cannot be suppressed by common ion effect. Therefore, the large |CO% | ions will also precipitate magnesium, b. Large excess of NH,CI [COP ions, to such atch WAP HSISt BOS dP LeERS SRSS PTB eatnes secu the ¢. The solution should be warmed and not boiled while precipitating group V radicals. Since warming decomposes the soluble bicarbonates (impurities) of Ca, Srand Ba into insoluble carbonates. Ca(HCO,), CaCO, +H,0 +CO, Boiling dissolves the insoluble carbonates as chlorides. CaCO, +2NH,CI—- CaCl, +-(NH,}, CO, 4. The group precipitates shouldbe cssolved in acetic acid. the preciptates are dissolved in trong acid like HCI or HNO., Ca will not get precipitated as calcium oxalate by adding ammonium oxalate because it is soluble in strong acid. H,SO, precipitates sulphates of Ca, Ba and Sr,Solution > Proceed with test for group I Toner Patobianed cm [i Solution, / Rescue) White ppt of AgCl, Hg5Cl,PDC] (Dissolve in hot water and filter) Dissolve in excess Solution PLC a SPs Fi, [ROAR Pb{HSO, Filtrate (Dissolves) (Dissolves) * Aqua Regia {[Cone. HNO, + Cone. HCI} (Ratio 1:3) | Aa(NH), “Cr une, / K.cr0, Ppt. reappears Ag,Cr,0.b due to (Brick red) neutralisation (Dissobves in ofNH, “agi Pty. KCN) (Brick yellow) (Dissolves in hypo, KCN) {K, Of[AQ(CN),]” and other is vary high it can dissolve even those salts with low ky) * AgCl - Dissolves in dil. NH, ‘AgBr - Partially soluble in i, NH, dissolved in concNH, ‘Agl - Partialy dissolves in concNH, [Pe(OH)° Pb” + Cr,0;" NHi(Q) and fier (bl, (aq) Dissolves anamnncy lack) (White) —— Dissolvesin| (Grey) aqua regia gal, cual yi a nCl(aq) Hal Ha 0) (Scarlet red) IaH As Chea) [evexces (wnitey KatHall(eq) (Soluble) snci,(aq) Hgt (elack) Flowchart 30.3: Systematic path for the analysis of group I radicalsGroup-II A (Copper Group) Chemistry of confirmatory tests of Group-II A cations 1. Test for Lead ion (Pb?*) Lead sulphide precipitate dissolves in dilute HNO,. On adding dil. H,SO,, and a few drops of alcohol to this solution a white precipitate of lead sulphate appears. This indicates the presence of lead ions. 3PbS + 8HNO, —>3Pb(NO,), + 2NO + 4H,0 + 38 PO(NO,), + H,SO, —»PbSO, + 2HNO, ‘The white precipitate dissolves in ammonium acetate solution on boiling. When this solution is acidified acetic acid and potassium chromate solution is added, a yellow precipitate of PbCrO,, is formed. On adding potassium iodide solution, a yellow precipitate of lead iodide is formed. PbSO, + 4CH,COONH, —>(NH,),{Pb(CH,COO),] + (NH,),SO, Ammonium tetraacetatoplumbate( 1) Pb?* + CrO,?> —»PbCr0, ; Pb* + 21> — Pbl, Lead chromate Lead iodide (Yellow precipitate) (Yellow precipitate) 2. Test for Copper ion (Cu?*) (a) Copper sulphide dissolves in nitric acid due to the formation of copper nitrate. 3CuS + 8HNO, —>3Cu(NO,), + 2NO +38 +4H,0 ‘Onbeating the reaction mixture for long time, sulphur oxidised to sulphate and copper sulphate is formed and the solution tums blue, A small amount of NOH precipitates basic copper sulphate which is soluble in excess of ammonium hydroxide due to the formation of tetraamminecopper (II) complex. $ +2HNO, —5H,SO, + 2NO 2Gu2* + S02 + INH, + 2H,O —>Cu(OH), CuSO, + 2NH,* ‘Cu(OH),,CuSO, + 8NH, —>2[Cu(NH,),]SO, + 20H” + SO Tetraamminecopper (II) sulphate (Deep blue) (b) The blue solation onacidification with acetic acid and then adding potassium ferrocyanide K ,{Fe(CN),] solution gives « chocolate colouration due to the formation of copper ferrocyanide ie. Cu,{Fe(CN),] [Cu(NH,),]SO, + 4CH,COOH —+ CuSO, + 4CH,COONH, 2CuSO, + K,[Fe(CN),] —+ Cu,[Fe(CN),] + 2K,S0, Potassium ‘Copper hexacyanoferrate (II) _hexacyanoferrate (11) (Chocolate brown precipitate)26 Group-II B (Arsenic Group) If group- II precipitate dissolves in yellow ammonium sulphide and the colour of thesolution is yellow, this indicates the presence of As*” ions. Ammonium thioarsenide formed on dissolution of s,S, decomposes with dil. HCl, and a yellow precipitate of arsenic (V) sulphide is formed which dissolves in concentrated ric acid on heating due to the formation of arsenic acid. On adding ammonium molybdate solution to the reaction mixture and heating, a canary yellow precipitate is formed. This confirms the presence of As** ions. As,S, + 3(NH,),S_ —> 2(NH,),AsS, +S Yellow ammonium sulphide 2(NH,),AsS, + 6HCI + As,S, + 3H,S + 6NH,CI 3As,S, + I0HNO, + 4H,O > 6H,AsO, + 10NO + 15S Arsenic acid H,AsO, + 12(NH,),MoO, + 21HNO, —> (NH,)\{As (Mo,0,,),] + 2INH,NO, +12H,0 Arsenic acid Ammonium Ammonium molybdate arsenomolybdate (yellow precipitate) (IV) Analysis of Group-III cations Ifgroup-II is absent, take original solution and add 2-3 drops of cone. HNO, to oxidise Fe°* ions to Fe* ions. Heat the solution for a few minutes. After cooling adda small amount of solid ammonium chloride (NH,C\) and an excess of ammonium hydroxide (NH ,OH) solution till it smells of ammonia, Shake the test tube. Ifa brown or white precipitate is formed, this indicates the presence of group-III cations. Confirmatory tests of group-III cations are summarised in Table 14 Observe the colour and the nature of the precipitate. A gelatinous white precipitate indicates the presence of aluminium ion (A1>"), Ifthe precipitate is brown in colour, this indicates the presence of ferric ‘Table 14 : Confirmatory test for Group-III cations Brown precipitate White precipitate Fe" ar Dissolve the precipitate in dilute HCI Dissolve the white precipitate in and divide the solution into two parts. dilute HCI and divide into two parts (@ [To the first part add potassium |(a)|To the first part add sodium ferrocyanide solution _[Potasium hydroxide solution and warm. A hexacyanoferrate (II)]. A blue white gelatinous precipitate soluble precipitate/colouration appears. in excess of sodium hydroxide solution is obtained (6) | To the second part add potassium |(b)| To the second part first add blue thiocyanate solution. A blood red litmus solution and then ammonium colouration appears. hydroxide solution drop by drop along the sides of the test tube. A blue floating mass in the colourless solution is obtained. eyChemistry of confirmatory tests of Group - III cations When original solution is heated with concentrated nitric acid, ferrous ion are oxidised to ferric ions. 2FeCl, + 2HCI + [0] —> 2FeCl, + H,O Their group cations are precipitated as their hydroxides, which dissolve in dilute hydrochloric acid due to the formation of corresponding chlorides. 1, Test for Aluminium ions (AP*) (a) When the solution containing aluminium chloride is treated with sodium hydroxide a white gelationus precipitate of aluminium hydroxide is formed which is soluble in excess of sodium hydroxide solution due to the formation of sodium meta aluminate. AICI, + 3NaOH —> Al(OH), + 3NaCl A\(OH), + NaOH —> NaAlO, + 2H,0 White gelatinous Sodium precipitate meta aluminate (b) In the second test when blue litmus is added to the solution, a red colouration is obtained due to the acidic nature of the solution. On addition of NH ,OH solution drop by drop, the solution becomes alkaline and aluminium hydroxide is precipitated. Aluminium hydroxide adsorbs blue colour from the solution and. forms insoluble adsorption complex named ‘lake’. Thus a blue mass floating in the colourless solution is obtained. The test is therefore called lake test. 2. Test for ferric ions (Fe**) Reddish brown precipitate of ferric hydroxide dissolves in hydrochloric acid and ferric chloride is formed. Fe(OH), + 3HCL —>(FeCl, + 3H,0 (a) When the solution containing ferric chloride is treated with potassium ferrocyanide solution a blue precipitate/colouration is obtained. The colour of the precipitate is Prussian blue. It is ferric ferro-cyanide. The reaction takes place as follows: 4FeCl, +PK{[Fe(CN),]] —> Fe,[Fe(CN),], + 12KCI ° Mpamsium ee ferrocyanide precipitate If potassium hexacyano ferrate (II) (i.e. potassium ferrocyanide) is added in excess then a product of composition KFe[Fe(CN),] is formed. This tends to forma colloidal solution (‘soluble Prussian blue’) and cannot be filtered. FeCl, + K,[Fe(CN),] KFe[Fe(CN),] (Soluble prussian blue} (b) To the second part of the solution, add potassium thiocyanate (potassium sulphocyanide) solution. The appearance of a blood red colouration confirms the presence of Fe** ions. Fe** + SCN- —+[Fe(SCN)]* Blood red colour 3KClTable 15 : Confirmatory test for Group - IV cations ‘White precipitate Flesh coloured precipitate (Zn) cn") Dissolve the precipitate in Dissolve the precipitate in | Dissolve the precipitate in aqua regia. dilute HCI by boiling. “Divide gifute HCI by boiling, then add | Heat the solution to dryness and cool the solution into two parts. | Sodium hydroxide solution in | Dissolve the residue in water and divide (a) To the first part add excess. A white precipitate is | the solution into two pars Sodium hydroxide solution | formed which tums brown on | (a) To the fist part of the solution add A white precipitate soluble | keeping ammonium hydroxide solution till it in excess of sodium becomes alkaline. Add a few drops of hydroxide solution dimethyl glyoxime and shake the test confirms the presence of tube. Formation ofa bright red pitta precipitate confirms the presence of (©) Neutralise the second part i ions. with ammonium hydroxide (b) Neutralise the'second part with solution and add potassium ammonium hydroxide solution. Acidity ferrocyanide solution. A it with dilute aeetie acid and add so bluish white precipitate potassium nitrite, A yellow precipitate appears ‘confirms the presence of Co” ions. ‘Chemistry of confirmatory tests of Group-TV cations Fourth group cations are precipitated as their sulphides. Observe the colour of the precipitate. A white colour of the precipitate indicates the presence of zinc ions, a flesh colour indicates the presence of manganese ions and a black colour indicates the presence of Ni** or Co” ions. 1, Test for Zine ion (Zn?*) Zinc sulphide dissolves in yxirgchloric acid to form zinc chloride. ZnS +2HCI HS (a) On addition of sodium) ‘ide solution it gives a white precipitate of zinc hydroxide, which is soluble in excess of NaOH solution on heating. This confirms the presence of Zn™ ions. ZnCl, + 2NaOH Zn(OH), | 2NaCl 2. Test for Manganese ion (Mn?) rv Manganese sulphide precipitate dissolves in dil. HCl on boiling. Onaddition of NaOH solution in excess, a white precipitate of manganese hydroxide is formed which turns brown due to atmospheric oxidation into hydrated manganese dioxide. MnS + 2HCl —» MnCl, + H,S MnCl, + 2NaOH —>Mn(OH), + 2NaCl (White precipitate) Mn(OH), + [0] —> MnO(OH), ° Hydrated manganese dioxide (Brown colour)3. Test for Nickel ion (Ni*) The black precipitate of nickel sulphide dissglves in aqua regia and the reaction takes place as follows: 2NO + 3S + 4H,0 After treatment With aqua regia nickel-chlorite's obtained which is soluble in water. When dimet! limethyl glyoxime isadded to the aqueous solution ofnicke| chloride, made alkaline, by adding NH OH solution, a brilliant mips, Ys + 0DMaT Ih NoMa), A d H,C H,C—C=N—OH aa YPN | +2NH,CI+2H,0 NiCl, + 2NH,OH H,C—C = N—OH S Cc 4 3) Hy eC “Y " “HC 0 \0 Complex of red colour (Stable form of complex) 4, Test for Cobalt ion (Co**) Cobalt sulphide dissolves in aqua regia in the same manner as nickel sulphide. When the aqueous solution ofthe residue obtained after treatment with aqua regia is treated with a strong solution of potassium nitrite after neutralisation with ammonium hydroxide and the solution is acidified with dil. acetic acid, a yellow precipitate of the complex of cobalt named potassium hexanitritocobaltate (III) is formed. CoS + HNO, + 3HCl —CoCl, + NOCI + S + 2H,0 CoCl, + TKNO, + 2CH, COOH 4K [Cot NO,),] + OKCl+ 2CH,COOK + NO + H,0 Potassium hexanitritocobaltate(III) (Yellow precipitate) (VI) Analysis of Group-V cationsGroup Ii filtrate ‘Add NH,OH and NH,CI, then pass H,S (excess) Residue Filtrate ZnS - dity white Move for group V Wns “ightPink |S pase sulphides CoS, Nis - black Add. dil. HCl, shake and filter Residue] Fitrate | Black ppt of Cost, NiS (MnCl, + ZnCl.) Dissolved in Boil (to remove any H,S dissolved) Yaqua regia ‘Add Br,/H,O + NaOH/filter NiCl,(aq.) CoCl,(aq)- |Add KNO, Evaporate |and filter to dryness Mno, v (Black brown) Residue Filtrate Nicl, CoCl, K[CONO,), _NiCl{aq) (ellow esidue) (Give residue) Dissolve in Vell (Green solution) cocn. HNO, A pansai Tums green tym pink then add PbO, (Potassium Turns\Green inwater in water ‘and heat Cobatinitrite) “in werer J excess|NH,OH HMfO, excess|NH,OH andldmg (Purple colour solution) N@2£RO2 andldmg Ni(dmg),t Nigdmg),t (Roy red cou) CH,COOH/aiLHCI (Rosy red colour) +K,{Fe(CN),] NH,OH+ ‘CH,COOH+ NHS + Zny{Fe(CN),) Pass HS ik (White) dirty white KNO, amyl alcohol aeet NH, K,ICo(NO,)) _ (NHYICO(SCN),] RPeeNel (Yellow ppt) (Blue colour in eect alcohol layer) Zn,K,{Fe(CN),), Flowchart 20.4: Bluish white ppt Suctematir nath for the analvcie af arewin IV radiealeV Group a’ S,G") \V Group fitrate. —> Boil off H,S then add (NH), solution Filter White ppt Filterate fA, 900, (a0) Disolejn CHACOOH and divide into three parts Aad test in sequence after removing the ppt Ls y [part +K,Cr0, part + (NHy)SO, Part + (NH,,0, (relow pot) \ { (Soluble in CH,COOH) White ppt White ppt Flowchart 5: fr thera cf group VacGROUP V (Ba (II), Sr (II), Ca (II) ‘Ammonium carbonate ppt. V group radicals in the form of carbonates.These carbonates are soluble in acetic acid, Table 30.24: Confirmatory test for group V radicals, Ba’ Test/Reagents Observation Ba(CH,COO), +K3CrO, —pBacro, + +2CH,COOK White ppt: Ba(CH,COO), + (NH,) 96, > Baso, 4 +2CH,COONH, B3(CH,COO), + (NH, )%%0, > BaC,0, 4 +2CH,COONH, oa White ppt. 57(CH,COO), +(NH,), SO, > S150, 4 +2CH,COONH, White ppt Sr(CH,COO), (NH, ), C0, > SrC,0, 4 +2CH,COONH, wore ppt : Calcium chlorate and calcium Ca(CH,COO), + (NH, ), C,04 > CaC,0, 1 +2CH,COONH, sulphate are soluble, White ppt VITH GROUP Table 30.25: Confirmatory test for group VI radical Mg* | Test/Reagents Observation Disodium hydrogen phosphate solution Mg? +NH, +HPO,2° ->Mg(NH,)PO, + Mg? +HP0,2° > MgHPO, + White crystalline ppt. is formed in presence of NH,CI prevent precipi of Mg(OH), and NH, soin white flocculent ppt ‘Ammonia solution Mg? +2NH,OH > Mg(OH), ¢ +2NH,° Mg(OH), —>Mg"? + 20H NHCl->NH,* +c; NH,’ +OH- > NH,OH(weakbase) White gelatinous ppt is sparingly soluble in water but readily soluble in ‘ammonium salts. NH,” ions ‘remove! OH” causing the hydroxide to dissolve more. Not possible with Nac. "Ammonium earbonate solution SMgi" +.6CO,?" + 7H,0 > 2MgCO, Mg(OH), SH,0 4 +2HCO,- NH," +CO,?> —NH, +HCO, Absence of NH,” salts tn the presence of NH,” salts no precipitation occurs, because the equilibrium is shifted towards the formation of HCO, ions. Ky of the ppt. being high K,, of pure MgCO, is110™), the concentration of carbonate ions necessary to produce a pt. is not attained 4-(4-Nitrophenyl azo resorcinol or Magneson | MgCl, + 2NaOH -> Mg(OH), + 2NaCl Magneson reagent = p-nitrobenzene-azo resorcinol, a dye stuff, absoibed over Mg(OH), to give a blue coloured lake. Ppt is dissolved in dilute HCI (min) +NaQH +0.5mI magneson-t reagent = Blue lakeTitan yellow (a water soluble yellow dyestuff) Deep red colour or ppt. Itis adsorbed by Mg(OH), Dissolve ppt. in dlHCfmin)+1 drop of NaOH soln (2M) + 1 drop titan | Deep red colour solution or ppt. yellow soln obtained. Ba’* andCa’* do not react but intensify the colour.L1-2024(AIIMS-CLASS NOTE) PartI-CHEMISTRY Il. QUANTITATIVE ANALYSIS Titration is the measurement of the volume of a solution of one reactant that is required to react completely with a measured amount of another reactant, As both the reactants are taken in the form of solutions and the titration is the measurement of volume of one solution that must be added to another solution til the reaction is complete, this method of quantitative analysis is, therefore, called volumetric analysis. Usually the concentration of one of the solutionsis known, (called standard solution) and it is desired to find the concentration of the other by titration. The apparatus used is shown in Fig, 8.2. Aknown volume of the solution is taken in the titration flask (with the help ofa pipette) and the other solution is taken in the burette which is graduated in cc's and has a stop-clock at the bottom to control the amount of flow into the flask. The solution to be titrated (taken in the flask) is called titrate and the solution with which the titration is to be done (taken in the burette) is called the titrant. The point at \which the required volume of one solution has been added to the other to exactly complete the reaction between the two is called end point or equivalence point. BURETTE | SOLUTION B stopcock : TITRATION (7 Fuask SOLUTION A Gey Figure 6 : Apparatus for titration There are many types of titrations such as redox titrations (involving oxidation and reduction), acid-base titrations (involving neutraisation), precipitation titrations (titrations (rg. NaCl vs AgNO), complexometric titrations (involving formation of complexes) but here we shall take up a brief discussion of acid-base titrations in aqueous solutions only. Theory of Indicators ‘An indicator'8 @ Substance which is used to determine the end pointin a titration. In acid base titrations organic substances are generally used as indicators. They change their colour within a contain pH range. The colour change and the pH range. The colour change and the pH range of common indicators are tabulated below.LT-2024(AIIMS-CLASS NOTE) Part-I-CHEMISTRY Table-7 Indicator purange Colour change IMetiyl orange [2-45 Pink to yellow [Methyl red aa-65 Red to yellow [Limos 5-75 Red to blue Phenclrad 68-85 Fellow to red [Phenoipnthaten [8.1 [Coloureless pink Theory of acid-base indicators (Ostwald's theory : According to this theory a) The colour changeis due to ionisation of the acid-base indicator. The unionised form has different colour than the ionised form. b) Theionisation of theindicatoris largely affected in acids and bases asitis either a weak acid or a weak base. In case, the indicator is a weak acid, its ionisation is very much lowin acids due to common H'ions while its fairly ionised in alkalies. Similarly, ifthe indicatoris a weak base, itsionisation islargein acids and lowin alkalies due to common OH-ions. Considering two important indicators phenolphthalein (a weak acid) and methyl orange (a weak base), Ostwald's theory can be illustrated as follows: Phenolphthalein : It can be represented as HPh. It ionises in solution to a small extent as HPh =H’ + Ph Colorless Pink Applying law of mass action, (Hh) (HPh} ‘The undissociated molecules of phenolphthalein are colourless while Ph ions are pink in colour. In presence of an acid, the ionisation of HPh is practically negligible as the equilibrium shifts to left hand side use due to high concentration of H" ions. Thus, the solution would remain colourless. On addition of alkati, hydrogen ions are removed by OH" ions in the form of water molecules and the equilibrium shifts to right hand side. Thus, the concentration of Ph ions increases in solution and they impart pink colour to the solution. Let us derive Henderson's equation for an indicator. Hin +H,0—H30+ In ‘Acid form’ “Base form’ + Conjugate acid-base pair In” )[H; 0] n= ae (Ky = Ionization constant of indicator) (Hj0]=K, x Hal in PH=~ logo (H5O]=~logig [K,]~ logy HUM) fin] {in} PH=pK,, +log,, L2} te +1810 Fay (Henderson's equation for indicator)LT-2024(AIIMS-CLASS NOTE) Part-I-CHEMISTRY Atequivalence point; (In-}=[HIn] and pH=pk,, Methyl orange : Itis a very weak base and can be represented as MeOH. Itisionisedin solution to give Me" and OH ions. MeOH == Me* + OH™ Yellow Red Applying law of mass action, x — Me" OH} [MeOH] In presence of an acid, OH" ions are removed in the form of water molecules and the above equilibrium shifts to right hand side. Thus, sufficient Me* ions are produced which impart red colour to the solution.On addition of alkali, the concentration of OH” ions increases in the solution and the equilibrium shifts toleft hand side, i.e., the ionisation of MeOH is practically negligible. Thus, the solution acquires the colour of unionised methyl ornage molecules, i.e., yellow. This theory also explains the reason why phenolphthalein is not a suitable indicator for titrating a weak base against strong acid. The OH" ions fumished by a weak base are not sufficient to shift the equilibrium towards right hand side considerably, ie., pH is not reached to 6.3. Thus, the solution does not attain pink colour. ‘Similarly, it can be explained why methyl orange is not a sutiable indicator for the titration of weak acid with ‘strong base. Selection of suitable indicator or choice of indicator ‘The neutralisation reactions are of the flowing four types i) A strong acid versus a strong base [Fig 7 (a)} ii) Aweak acid versus a strong base. [Fig.7 (b)] ill) A strong acid versus a weak base. [Fig.7(c)] iv) Aweak acid versus a weak base. [Fig.7 (d)] Inorderto choose a suitable indicator, itis necessary to understand the pH changes in the above four types of titrations. The change in pH in the vicinity of the equivalence point is most important for this purpose. The curve obtained by plotting pH as ordinate against the volume of alkali added as abscissa i known as neutralisation or titration curve. The titration curves of the above four types of neutralisation reactions are showin in Fig,7 (a), Fig.7 (b), Fig.7 (c), Fig.7 (4)(a5eq Buons pue pre xean) Se OF SEO SL OL SL OLS (25eq yeam pue ppe xa) Sh SE OF St oR SL OLS 0 ed ounennb is ( aseq eam pue pre 6u0Ns ) \weypoPPE oa HEH LOE MIEN Hm EO LOE SOLS 0, ed une ye ( 25eq 6u0ns pue pre 6uos) 4 ls wed uae in 0d upsLT-2024(AIIMS-CLASS NOTE) Part-I-CHEMISTRY In ech case 25 mL of the acid (N/10) has been titrated against a standard solution of a base (N/10). Each curve becomes almost vertical for some distance [except curve Fig.7 (d)] and then bends away again. This region of abrupt change in pH indicates the equivalence point. Fora particular titration, the indicator should be so selected that if changes its colour within vertical distance of the curve i) Strong acid vs. strong base : pH curve of strong acid (sy HCI) and strong base (say NaOH) is verticalover almost the pH range 4-10. So, the indicators phenolphthalein (pH range 8.3 to 10.5), methyl red (pH range 4.4-6.5) and methyl orange (pH range 3.2-4.5) are soluble for such a titration ii) Weak acid vs. strong base : pH curve of weak acid (say CH,COOH or oxalic acid) and strong base (say NaOH) is vertical over the approximate pH range 7 to 11. So, phenolphthalein is the suitable indicator for sucha titration i) Strong acid vs. weak base : pH curve of strong acid (say HClor H,SO, or HNO.) with @ weak base (say NH,OH)is vertical over the pH range of 4 to 7. So, the indicators methyl red and methyl orange are suitable for such a titration iv) Weak acid vs. weak base : pH curve of weak acid and weak base indicates that thereisnovertical part and hence, no suitable indicator can be used for such a titration. CONDUCTOMETRIC TITRATIONS The principle of conductomertrc titration is based on the fact that during the titration, one of the ions is replaced by the other and invariably these two ions differ in the ionic conductivity with the result that conductivity of the solution varies during the course of tiation. The equivalence point may be located graphically by pointing the change in conductance as a function of the volume of titrant added.LT-2024(AIIMS-CLASS NOTE) Part-I-CHEMISTRY ‘Some Typical Conductometric Titration Curves are 1 Strong Acid with a Strong Base, e.g. HCl with NaOH : Before NaOH is added, the conductance is high due to the presence of highly mobile hydrogen ions. When the base is added, the conductance falls due to the replacement of hydrogen ions by the added cation asH’ ions with OH" ions to form undissociated water. This decrease in the conductance continues till the equivalence point. At the equivalence point, the solution contains only NaCl. After the equivalence point, the conductance increases due to the large conductivity of OH" ions (Fig.9) ° T Fig. 9 Coductometric tration of a strong acid (HCI) vs. a strong base (NaOH) Weak Acid with a Strong Base, e.g. acetic acid with NaOH:: Initially the conductances low due to the feeble ionization of acetic acid. On the addition of base, there is decrease in conductance nat only due to the replacement of H’ by Na" utalso suppresses the dissociation of acetic acid due to common ion acetate. But very soon, the conductance increases on adding NaOH as NaOH neutralizes the un- dissociated CH,COOH to CH,COONa which is the strong electrolyte. This increase in conductance continues raise up to the equivalence point. The graph near the equivalence point is curved due the hydrolysis of salt CH,COONa. Beyond the equivalecnce point, conductance increases more rapidly with the addition of NaOH due to highly conducting OFF ions (fig.10) Fig, 10 : Coductometrc titration of a weak acid (acetic acid) vs. a strong base (NaOH)LT-2024(AIIMS-CLASS NOTE) Part-CHEMISTRY 3. Strong Acid with a Weak Base, e.g. sulphuric acid with dilute ammonia: Initially the conductance is high and then it decreases due to the replacement of H’. But after the endpoint has been reached the graph becomes almost horizontal, since the excess aqueous ammonia is not appreciably ionised inthe \- o T cme NH, 1.11 : Coductometrc titration of a strong acid (H,SO,) vs. a weak base (NH,OH) Weak Acid with a Weak Base : The nature of curve before the equivalence point is similar to the curve obtained by titrating weak acid against strong base. After the equivalence point, conductance virtually remains same as the weak base which is being added is feebly ionized and, therefor, is not much conducting (Fig.12) mot NH Conductance Fig. 12 : Coductometri titration of a weak acid (acetic acid) vs. a weak base (NH,OH) Mixture of a Strong Acid and a Weak Acid vs. a Strong Base or a Weak Base ‘In ths curve there are two break points. The first break point corresponds to the neutralization of strong acid. When the strong acid has been completely neutralized only then the weak acid starts neutralizing. The second break point corresponds to the neutralization of weak acid and after that the conductance increases due to the excess of OH ions in case of a strong base as the titrant. However, when the titrant is @ weak base, it remains almost constant after the end point similar to Fig. 12, 13)LT-2024(AIIMS-CLASS NOTE) Part-I-CHEMISTRY NH, OH OW) Conductance ont of base Fig. 13 : Coductometric titration of a mixture of a strong acid (HCl) and a weak acid (CH,COOH) vs. a strong base (NaOH) or a weak base (NH,OH) Ill, TESTS FOR FUNCTIONAL GROUPS IN ORGANIC COMPOUNDS TESTS FOR UNSATURATION Theory Organic compounds containing > C = C < and / or -C=C~ bonds are called unsaturated ‘compounds. These compounds undergo addition reaction with bromine water or the solution of bromine in carbon tetrachloride, chloroform or glacial acetic acid. Addition of bromine to an alkene results in the formation of vicinal dibromide. The reddish orange colour of the solution of bromine in carbon tetrachloride disappears on reaction with an alkene, The reaction is as follows, ja Ho=OH + Bes =e A be (colourless) Alkenes decolourise the neutral/alkaine KMnO, solution and vicind glycols are formed (Bayer's test). Reaction takes place as follows on 90H, = CH + ALO 2400; 19H, +208" + MnO, (purple) by Both the above reactions are used as tests for unsaturation. TEST FOR ALCOHOLIC (R-OH) GROUP Theory Alcoholic compounds on reaction with ceric ammonium nitrate give @ red colouration due to the formation of a complex. (NH), [CeINO,)» SROH—-+ {cetNO (ROH, + aNN4NO. Cenc ammoniire Rea complexL1-2024(AIIMS-CLASS NOTE) Part-I-CHEM ISTRY Distinction between primary, secondary and tertiary alcohols can be done on the basis of iodoform test and Lucas test. Ethanol and secondary alcohols which contain CH, —CH(OH)R group (lodoform reaction) give positive iodoform test. To carry out reaction, potassium iodide and sodium hypochlorite solutio are added to the compound in the presence of sodium hydroxide solution, Probably sodium hypochlorite first oxidses potassium iodide into potassium hypoiodite, which oxidises CH, ~CH(OH)R {group to CH,COR group and then iodinates tin the alkaline medium of the reaction mixture by replacing the a-hydrogen attached to the carbon atom adjacent to carbonyl group by iodine, lodoform is formed after cleavage of C=C bond. cncnon Lucas Test Lucas reagent contains zinc chloride and concentrated hydrochloric acid. This reagent reacts with primary, secondary and tertiary alcohols at different rates. Tertiary alcohols react almost instantantaneously, secondary alcohols react in about 1-5 minutes and primary alcohols react very slowly. The reaction may take 10 minutes to several days. Rewonsncr 2°, ro reactin/Slow reaction Rewonne: 82, Rene Rconsier #2, Rccieto Alcohols are solublein Lucas reagent but the formed alkyl halides are not solube. Therefore, formation of two layers in the reaction medium indicate the occurrence of the reaction Primary alcohols - Layers do not separate Secondary alcohols - Layers separate within 1-5 minutes Tertiary alcohols -Layers separateimmedately PHENOLIC (AR-OH) GROUP Theory ‘The-OH group attached directly to the ring carbon of an aromatic ring is called phenolic -OH group. Phenols are weakly acidic, therefore they are soluble in NaOH solution butat the same time they are not sufficiently acidic to be soluble is sodium hydrogen carbonate solution. Phenols give coloured ‘complex with neutral ferric chloride solution. For example, phenol gives a complex of violet colour as follows 6C,H,OH + FeCl, —+ [Fe(C,H,0),]" + 3HCI + 3H’ Violet complex Resorcinol, o-, m- and p-cresol give violet or blue colouration, catechol gives green colour which rapidly darkness. 1 and 2-Naphthol do not give characteristics colours. Phenols condense with phthalic anhydride in the presence of concentrated H,SO,, Phenol condeses to give phenolphthalein which ives a dark pink colour with NaOH solution. This. called phthalein dye test.LT-2024(AIIMS-CLASS NOTE) Part-I-CHEMISTRY on on a on cone. 450, > 5 my Excess NaOH. 7 1 ry (Cotoustess) (Pink) Table- 6 : Colours produced by some other phendic compoundsin phthalein dye test Compound | Colour ‘Compound Colour scaly blue takes - ol fo-creso ed [Catecr longer time 10 appear etresor Baan purple p-Cresol Nocolour ——_Resrcinot éreen fluorescent colour of fluorescein i ALDEHYDIC AND KETONIC GROUPS (—CHO and—C—) Theory Both aldehydes and ketones contain carbonyl group (>C = O) and commonly known as carbonyl compounds. Identification ofa aldehydes and ketonesis done by two important reactions of carbonyl group i.e. i) addition reaction on double bond of > C = O group and ii) oxidation of carbonyl group Addition reactions of derivatives of ammonia are important from the point of view of identification of carbonyl compounds. Addition is generally followed by elimination resulting in the formation of unsaturated compound. » PH no. = 04+RNH,—> > oc=NR >C=O+RNH—> Se (R= alkyl, aryl or C,H,NH etc.)L1-2024(AIIMS-CLASS NOTE) Part-I-CHEMISTRY ‘These reaction are catalysed by an acid or a base and do not occur under strongly acidic or basic conditions. Each reaction requires an optimum pH for its occurrence. Therefore, maintenance of pH is very important while carrying out these reactions. As far as oxidation is concerned, aldehydes are easily oxidised to carboxylic acids while ketones require relatively stronger oxidising agent. Distinction can be made between these two types of carbonyl compounds on the basis of difference in their reactivity Following tests are performed for the identification of aldehydic and ketonic groups. i) On reaction with 2, 4-dinitrophenylhydrazine (2, 4-DNP), they form the respective 2, 4-dinitropheny| hydrazones. 7 1. oie tal Oe at a ovo, no, sconmonmmmecne” — 24-Datmommsigenared enrbengt compound ‘These two carbonyl compounds (aldehydes and ketones) are distinguished on the basis of tests Using mild oxidising reagents, Ike Tollen’s reagent and Fehling’s reagent or Benedict's reagent. Tollen’s reagentis an alkaline solutions of silver cation complexed with tartarate and citrate ions respectively Fehiing’s reagent is freshly prepared by mixing equal amounts of Feshling's solution Aand Fehling’s ‘solution B.Fehling’s reagent deteriorates on keeping while Fehiing’s solutions A and B are quite stable. Fehling’s solution A is an aqueous copper sulphate solution while Fehling’s solution B is an alkaline ‘solution of sodium potassium tartarate (Rochelle's salt). The reagent contains Cu** ion complexed with tartarate ions. The structure of the complex is given below : or eno wee ng-87 Sopa nde —H [Body on6-0” o-cao Copper trarate complex Benedict modified the original Fehling’s test by using a single solution whichis more convenient for alkaline solution containing a mixture of copper sulphate and sodium citrate (2Na,C,H,0,.11H,0), Complex formation decreases the cupric ion concentration below that necessary for precipitation of cupric hydroxide. These two reagents oxidize aldehydes while ketones remain unaffected. The chemistry of these tests is as follows: RCHO+ 2Ag(NH,), +2OH" ——-2Ag+3NH, +H,O+RCOOH, From Tens een RCHO+2Cu’ (complexed)+50H ——+RCOO +Cu,0+3H,0 Fina’ soon However, aromatic aldehydes do not give positive Fehling’s test, In Benedict test also, Cu’"ions are reduced to Cu* ions in the same manner as in the case of Fehling’s reagent. Aldehydes also give pink colour with Schiff's reagent (the reagentis prepared by decolourising aqueous solution of p-rosaniline hydrochloride dye by adding sodium sulphite or by passing SO, gas). Ketones do not respond to this test.L7.2024(AIIMS-CLASS NOTE) Par-t-CHEMISTRY CARBOXYL GROUP (-COOH) Theory Organic compounds containing carboxyl functional groups are caled carboxylic acids, The term carboxyl, derivesits name from the combination of words carbonyl and hydroxyl because carboxylic functional group contains both of these groups(—C—OH). These acids tur blue litmus red and react with sodium hydrogencarbonate solution to produce effervescence due to the formation of carbon dioxide. This is a test that distinguishes caboxylic acids from phenols. RCOOH + NaHCO, —+ RCOONa + H,0 + CO, These react with alcohols in the acidic medium to produces esters. RCOOH + ROH Sst, RCOOR'+ H,0 Carboxylic Alcohol Ester acid ‘AMINO GROUP (-NH,) Theory Organic compounds containing amino group are basicin nature. Thus they easily react with acids to form salts, which are soluble in water. Both, aliphatic and aromatic amines are classified into three classes namely-primary(-NH,), secondary (-NH-) and tertiary (-N<), depending upon the number of hydrogen atoms attached to the nitrogen atom. Primary amine has two hydrogen atoms, secondary has one while tertiary amine has no hydrogen atom attached to nitrogen. i) Carbylamine test ‘Aliphatic as well as aromatic primary amines give carbylamine testin which an amineis heated with chloroform ReNH, + CHCI, +3KOH ——>RNC + 3KCL 51,0 (Coe) (ere) il) Azo dye test ‘Aromatic primary amines can be confirmed by azo dye test. Primary amine e.g. aniline reacts with nitrous acid generated in situ by the reaction of sodium nitrite with HCl at 0 ~5°C to produce diazonium salt. This couples with a-naphthol to give a scarlet red dye, which is sparingly soluble in water.L7-2024(AIIMS-CLASS NOTE) Part-I-CHEMISTRY VIL NITRO GROUP (-NO,) Mulliken and Barker's Test ‘About 0.5 9 of the nitro compound is mixed with few drops of ethanol (solvent) to form a homogeneous solution. NH,CI (0.5 g) and Zn dust (0.5 g) are added and heated carefully for 2 minutes. The mixture is allowed to stand for 3 minutes. Then itis filtered and the filtrate is divided into two parts. To one part, 2mL of Tollen’s reagent is added and warmed in a water bath. A black pracipitate of silver shows the presence of the nitro group. To another part, Fehling’s solution is added and boiled. A red precipitate of Cu,0 shows the presence of nitro group. Noe NHOH ZaINKEI, neta medium Prem iyrsyarine NHOH O 2paiNey QO warn NO + 2Ag) + 4NHy + 2H,0 Nitroso Black berwere No + 20u0 —> + CuO} + H,0 RedL-2024(AIIMS-CLASS NOTE) Part-I-CHEMISTRY IV, TEST FOR CARBOHYDRATES, FATS AND PROTEINS IN PURE FORM Tests for Carbohydrates Theory Carbohydrates are optically active polyhydroxy aldehydes, polyhydroxy ketones or compounds, which give these units as hydrolysis product. Starch, cellulose and sugars are the familiar examples of carbohydrates. Carbohydrates are classified on the basis of number of polyhydroxy aldehyde or ketone Units obtained from them on hydrolysis. Three broad classes are as follows i) Monosaccharides : These cannot be hydrolysed further to polyhydroxy aldehydes or ketones. i) Oligosaccharides : These yield 2-10 monosaccharide units on hydrolysis Common amongst these are disaccharides, which produce two monosaccharide units. ii) Polysaccharides : These yield large number of monosaccharide units on hydrolysis. Monosaccharides are further classified on the basis of number of carbon atoms and functional group present inthe. If a monosaccharide contains aldehydic group itis called aldose. fit contains keto {group itis called ketose. Carbohydrates of all classes give Molisch's test. Carbohydrates, which are sweet intaste, are called sugars. Glucose, fructose (fruit sugar) and sucrose (table sugar) are examples of sugars. Sugars are classified into two major categories : reducing sugars and non-reducing sugars, Reducing property of sugars is detected by the three tests namely Fehiling’s test, Benedict's test and Tollen’s tests, Theory of Molisch’s test (On adding concentrated sulphuric acid to the aqueous solution of carbohydrate containing alcoholic solution of 1-naphthol, a deep violet colour appears at the junction of the two liquids. Concentrated sulphuric acid hydrolyses glycosidic bonds of carbohydrate to give monosaccharides which are dehydrated to an aldehyde known as furfural which undergoes reaction with 1-naphthol to give a unstable condensation product of deep violet colour. This test may be given by some other organic compounds also. The following reaction takes place Fo Penton | RK ano, RCO sexapiniad PrattL-2024(AIIMS-CLASS NOTE) Part--CHEMISTRY Theory of test for reducing sugars Fehling’s test and Benedict test Black copper (lI) oxideis formed on heating a suspension of copper hydroxide in alkaline solution. CulOH), —, Cud +H,0 maar If some reducing agent is present in the reaction medium, then orange-red copper (I) oxide is precipitated. 2Cu(OH)2——> Cu,0 +2H,0 + [0] ‘Sree ea Reducing sugars contain aldehydic group or a-hydroxy ketonic group, therefore in alkaline medium reduce Cu ions. But if the reaction is carried out directly in the presence of an alkali then, copper (II) hydroxide ges precintated, To overcome this problem, coppe I ons are complexed with trate ions (Feshling's reagent) or citrate ions (Benedict's solution). Both the complex ions are soluble in alkaline medium and yield Cu’* ions in such a low concentration that solubility product of cupric hydroxide isnot reached Reducting sugars react with Fehling’s reagent according to the following reaction RCHO#2Cu** +50H—-RCOO- + Cu,0 +3H,0 ‘rebias) The discharge of blue colour due to Cu” ions and appearance of orange-red precipitate of CuO, indicates the reducing property of sugars. D-—Glucose + Cu” (citrate) ""°"""_.D—Gluconicacid+ Cu,O lomnge-edieoptt) D—Maltose + Cu” (tartarate)“"*""_.D —Maltobionicacid+ Cu,O (org adept) Fohing's Sucrose (disaccharide). »Noreaction ‘Sometimes, the cuprous precipitate comes down as yellow cuprous hydroxide, but on warming thisis converted to orange-red copper (I) oxide. In some cases, this reaction may be used as a quantitative analytical process for the determination of reducing sugars in blood and urine etc. All monosaccharides are reducing sugars. Disaccharides which contain a free hemi-acetal group (77 Jare also mild reducing sugars. Most naturally occuring disaccharides are reducing sugars ow (sucrose is an exception). Tollen’s test Tollen's reagent is ammoniacal solution of silver nitrate. A reducing sugar, reduces silver ion to metallic silver which gets deposited on the inner surface of the test tube in the form of silver mirror. The reaction occurs as follows RCHO+2/Ag(NH,),|’ +20H ——+2Ag+RCOONH, +H,0 +3NH,L1-2024(AIIMS-CLASS NOTE) Part-1-CHEMISTRY Theory of test to distinguish Monosaccharide from Disaccharide Barfoed's test The reagent is cupric acetate in acetic acid solution. It is weakly acidic and is reduced by only monosaccharides. Prolonged boiling may hydrolyse disaccharides and false positive test may be obtained. Monosaccharides react with this reagent within 5 minutes to give a brick red precipitate of copper (I) oxide. Disaccharides take a longer time to react because aldehyde function is masked in the acetal linkage. RCHO,, +2Cu”* ——RCCOH + Cu,O ‘The precipitate of cuprous oxide obtained isless dense andits colours brickredinstead of orange- re Test for Sucrose Hydrolysis the sucrose for performing the test by adding 5 drops of concentrated HCl to 5 mL of 1% sucrose solution and heating the mixture in the boiling water bath. Cool the mixture and add NaOH solution to obtain neutral or slightly alkaline solution. Perform the tests for reducing sugar and Seliwanoffs test given below with the hydrolysed prduct and record your resukits. Test to distinguish Ketose from Aldose Seliwanoff’s test Ketose dehydrate very rapidly under acidic conditions to give furfural, which reacts with resorcinol (1, 3-dihydroxy benzene) to give a coloured product. Ketohexoses give red colour and ketopentoses give blue-green colour. Aldoses take longer time to produce colour because under the same conditions, aldoses form furfural slowly, propbably because B elimination is required before dehydration to furfural. Therefore prolonged heating should be avoided. fen ben ty 2 Hon 2 don = tion Sr NN to. TO coloured1-2024(AIIMS-CLASS NOTE) Part-I-CHEMISTRY Theory of test for Polysaccharides (Starch) Starch gives blue colour with iodine solution due to the fomation of a complex known as starchiodide ‘complex. Starch is present in wheat, rice, maize, potatoes etc. Test for Oils and Fats Theory ‘These are the esters of glycerol and long chain fatty acids and are known as triglyoerides. Triglycerides which are liquids at room temperature are oils and those that are solids are called fats. Oils are of plantorigin and fats are of animal origin. Triglycerides in which three acyl groups are same are called simple triglycerides and a triglyceride in which three acyl groups are different is called mixed triglyceride. Many naturally occurring fatty acids contain two or threee double bonds. The fats from which these come are called polyunsaturated fats or oils, while oils are glycerides of unsaturated fatty acids. Fats and oils are insoluble in water. ‘On heating with potassium hydrogen sulphate, oils and fats give characteristic odour of acrolein. This is the testfor glycerol present either free or combined as an ester. On heating with potassium hydrogen sulphate, glycerol is dehydrated and acroleinis formed which has a pungent odour. The reaction is as follows CHO cH, l Heat, | GOH iso? FH + Ho CHLOH “CHO Tests for Proteins Theory Proteins are complex organic compounds containing nitragen and are made up of amino acids, Proteins are present in egg albumin, soya beans, pulses, fish, milk etc. Their presence can be confirmed by several tests. Due to the presence of characteristic side chains in them, certain amino acids exhibit typical colour reactions that form the basis for their identification. Proteins also respond o the colour reactions of amino acids, but can be distinguished from amino acids by biuret reaction, and coagulation reaction Biuret test for peptide bonds Alkaline copper sulphate reacts with compounds containing two or more peptide bonds to from complexes of violet colour, a ° and [Cu (NHCONHCONH),)” The name of the test comes from the name of the compound, biuret, which gives this test The reaction is not absolutely specific for peptide bond because many compounds containing two carbony| groupslinked through nitrogen or carbon atoms give a positive result1-2024(AIIMS-CLASS NOTE) Part-I-CHEMISTRY Ninhydrin reaction Ninhydrin is a powerful o Rhumann’s purple. izing agent and reacts with proteins to give a blue-violet compound called Note : Ammonia, primary amines, amoniacids and peptides also react with nihydrin, Xanthoproteic reaction ‘Aromatic groups of either the free aminoacid or protein, undergo nitration on heating with concentrated nitration on heating with concentrated nitric acid. The salts of these derivatives are orange in colour.LT-2024(AIIMS-CLASS NOTE) Part-I-CHEMISTRY V. PREPARATION OF SOME COMPOUNDS Aim To prepare double salts: ferrous ammonium sulphate (Mohr's salt and potash alum heory When a mixture containing equimolar proportions of potassium sulphate and aluminium sulphate or ferrous sulphate and ammonium sulphate is crystallised from its solution, a double salts formed. The formation of double salt may be shown as follows: be a a ee ON rv debates cee) eS feed mFS Ce edie ddl eee ied bees) Fe? anda ions undergo hydrolysis, therefore, while preparing aqueous solutions of ferrousulphate and aluminium sulphate in water, 2-3 mL dilute sulphuric acid is added to prevent the hydrolysis of these salts, Procedure a) Preparation of Double Salt : Potassium Aluminium Sulphate (Potash Alum) i) Take 10 mL ofdistiled water in a 50 mL beaker and heat itto about 40°C. Dissolve 6.6 g of aluminium Sulphate init and add about 0.4 mL of dilute sulphuric acid. ii) Weigh 2.4 g of powdered potassium sulphate and transfer it to the above solution, ii) Heat the solution with constant stirring fil potassium sulphate dissolves compeltely iv)Allow the solution to cool to room temperature slowly. v) On cooling, white crystals of potash alum separate out. vi) Decant the motherliquor and wash the crystals by gently shaking with 1 : 1 cold water and alcohol mixture vii) Filter the crystals, dry these between the folds of a filter paper and note the yield b) Preparation of Double Salt : Ammonium Ammonium Sulphate i) Dissolve 3.5 g of ferrous sulphate and 1.7 g of ammonium sulphate (weighed separately), in mL of distiled water contained in a 50 mL conical flask by heating. Add about 0.5 ml of dilute sulphuric acid to the flask and concentrate the solution by heating til he crystallization points reached. ii) Allow the mixture to cool to room temperature slowly. i) On cooling, ight green crystals of ferrous ammonium sulphate separate out iv) Decant the mother liquor and wash the crystals by shaking with very small amounts of 1:1 cold water and alcohol mixture to remove sticking mother liquor. v) Separate the crystals by filtration wash with alcohol, dry between the folds of a fiter paper and record the yield. Precautions a) Cool the solution slowly to get good orystals. Avoid rapid coaling, b) Do not disturb the solution while cooling. ©) Avoid prolonged heating while preparing crystals of ferrous ammonium sulphate, asit may oxidise ferrous ions to ferric ions and change the stoichiometry of the crystals.L7-2024(AIIMS-CLASS NOTE) PartI-CHEMISTRY Aim Toprepare acetanilide, Theory ‘The replacement of one hydrogen atom of the -NH, group of aniline by CH,CO— group in the presence of glacial acetic acid. Gives acetanilide. In the laboratory, acetylation is usually carried out with acetic anhydride. Acetyl chloride may also be used for the purpose of acetylation if acetic anhydride is not available. Acetylation with CH,COCI is usually carried out in the presence of pyridine. Procedure i) Take 5mL of aniline in a 100 mL round bottom flask and add acetylating mixture containing 5 mL acetic acid, Alternatively, you can use 5 mL of acetyl chloride and 5 mL of dry pyridine as the acetylating mixture. ii) Fir an air condenser on the mouth of the round bottom flask after adding a few pumice stones and yx the mixture gently for 10-15 minutes on.a sand ethanol. i) Cdl he weaciSe midore ond pour k Soave 1S0- 200K of ice cold water with string iv) Filter the solid, wash it with cold water and recrystallise a small amount of sample from hot water containing afew drops of methanol or ethanol. vv) Report the yield and the melting point of the compound. Precautions a) Handle acetic anhydride and acetyl chloride carefully as they causeiritation to the eyes and acety! chloride also strongly fumes in air. b) Store acetyichloride under dry conditions. ) Handle pyridine with extreme caution. Dispense tin an efficient fume cupboard and water disposable Glasses while using it d) Distil pyridine before use because it absorbs mioisture and the reaction does not take place under ‘moist conditions. e} Wash the sdid 2-3 times with cold water til the filtrate is neutral to litmus. #) Determine the melting point of perfectly dried and recrystallised sample. ALTERNATIVE METHOD FOR THE PREPARATION OF ACETANILIDE lf acetic anhydride of pyridine is notavailable then the following method can be used for the preparation of acetanilide. Procedure i} Take 1,mL of aniline ina dry boling tube, add 1 ml of glacial acetic acié to It and mix the two thoroughly ii) To the above mixture add 1 mL of acetyl chloride in lots (0.3 mL at a time). The mixture becomes IF the boiling tube becomes unbearable to touch, coolit under tap water. addition of whole amount of acety! chloride, heat the mixture for five minutesin a boiling water bath.L1-2024(AIIMS-CLASS NOTE) Pat-I-CHEMISTRY iv) Coo! the boiling tube and add ice-cold water (~ 10mL) into the tube with constant stirring v) Filler the acetanilide separated as white powder and wash with water fil fitrate is neutral to litmus. vi) Crystalise the crude acetanilide with hot water. White shining needle shaped are obtained. vii) Report the yield and melting point of the compound. Precautions a)!f aniline sampleistoo much coloured, distilit before carrying out the experiment, because yield is lowered with impure ariline. b) Use perfectly dry apparatus. )Donotinhale the vapours coming out during the addition of acetylchloride. aim To prepare p-nitroacetanilde. Theory -Nitroacetanilde is prepared by the nitration of acetanilide by using a mixture of conc. nitric acid and ‘cone. sulphuric acid as nitrating reagent. The mixture of the two acids release nitroniumion (NO; ),, which acts as an electrophile in the reaction. HNO, + 2H,S0, —-NO} +H,0 +2HS0, Nitronium ion attacks the benzene ring containing anilide group, mainly at the para position to give p nitrozcetanilide as a major product. Thisis an example of aromatic electrophilic substitution reaction. smcocr, 22 on J VS snicoen Cone. 1,50, ae A Acetanlide priueacetantie tar product) Procedure i) Dissolve 2 g of acetanilide in 2 mLof glacial acetic acid taken ina 100mL beaker. i) Add 4 mL of cone. H,SO, gradually with stirring to the above mixture. The mixture becomes hot and clear solutions obtained. Cool the reaction mixture in an ice bath maintained at 0-5°C. i) Add a cold mixture of 1.0 mLcone, HNO, and 1.0 mL conc. H,SO, to the viscous reaction mixture drop by drop with constant stirring, so that the temperature of the mixture does not rise above 10°C. iv) Remove the beaker from the ice bath and allow the reaction mixture to attain room temperature. Let itstand at room temperature for about 30 minutes. Stir the reaction mixture continuously and pouriton 100g of crushed ice. v) Stir the mixture well and filter the compound so obtained. vi) Wash the compound with cold water and dryit. vii) Recrystallise a small amount of the pale yellow solid from alcohol. Colourless crystals of p-nitroacetanilide are obtained. Yellow ortho-nitroacetanilide formed in the small amount remains WikABocerthithesviletlqQeing point ofthe pure compound. Precautions 2) Do not allow the temperature of the reaction mixture to exceed 10:C during addition of nitrating mixture. )Add mixture of concentrated nitric acid and sulphuric acid into the solution of acetanilide slowly and carefully.L1-2024(A1IMS-CLASS NOTE) Part-I-CHEMISTRY 4 Aim To prepare aniline yellow (p-amino-azobenzene} Theory p-aminobenzene can be prepared in a good yield by rearrangement reaction of diazoaminobenzene with a small quantity of aniline hydrochloride in the presence of aniline as solvent. The chemistry of mane omen Tie € S40 € Sm Cnn ZS, es fon yw ra res aay The above reactionis carried out onlyin weekly acidic conditions, Procedure i) Dissolve 3 g of finely powdered diazoaminobenzene in 7 mL of anilinein a 100ml corical flask. ii)Add 1.5 g of finely powdered aniline hydrochloride to the above mixture. ii) Warm the mixture with occasional shaking on a water bath at about 40-45°C, for a period of about one hour, iv) Remove the fiask from the water bath and allow the reaction mixture to stand at room temperature for about 30 minutes. v)Add 9 mL of glacial acetic acid diluted with an equal volume of water and shake the reaction mixture thoroughly to convert excess aniline to its acetate, which is water-soluble. vi)Allow the mixture to stand for 15 minutes with occasional stirring vii) Filter p-aminoazobenzene, wash with a litle cold water and dry between the folds of afiter paper. vii) Recrystallise a small portion of crude p-aminoazobenzene from carbon tetrachloride, ix) Report the yield and melting point of p-aminoazobenzene. Precautions a) Maintain the temperature of the reaction mixture at about 40-50°C. b) Wash the crude product with a small volume of water repeatedly. ©) Note the melting point of the perfectly dry sample. ANALTERNATIVE PROCEDURE FOR PREPARING ANILINE YELLOW Theory Aniline yellow can also be prepared by direct diazotisation and coupling as followed for pheny-azo-B- naphthol dye. However, coupling of the diazonium salt with aniline or any other aromatic amine is carried out in a weakly acidic mecium,L7-2024(AIIMS-CLASS NOTE) Part-I-CHEMISTRY Procedure i) Prepare a solution of benzene diazonium chloride using 2 mL of aniline according to the method Clesced forthe preparation of pheny-azo-B naphthol dye (see experiment 10.4) ii) Prepare a solution of 4 mLanilinein4 mL 1.0 MHCL ii) Add the cold solution of aniline hydrochloride slowly into the cold solution of benzene diazonium chloride iv) Filter the yellow compound and dry it between the folds of a filter paper. v) Recrystallise the smal amount of crude sample from carbon tetrachloride and report the yield and melting point. Aim To prepare iodoform. Theory CH,COCH, + 31. C1,cOcH, + 3H11 CI,COCH, + NaOH -+ CHT3 + CH,COONa Procedure Mass 5 grams of potassium carbonate K,CO,. Dissolve in 20 mL of distilled water, taken in an Erlenmeyer flask. Stir the mixture constantly to ensure the potassium carbonate is completely dissolved. ‘The mixture is then placed in a warm water bath, which is at about 75 to 80 degrees Celsius. Cool the solution when the reaction is complete. The yellow crystals formed is iodoform. Separate the iodoform from the mixture by filtration. Wash the iodoform with water. A small sample of the iodoform is recrystallized from alcohol. Dry the iodoform crystals.