Principles Related to Practical Chemistry Croce © Detection of extra elements DETECTION OF ELEMENTS (NITROGEN, SULPHUR, HALOGENS) IN (Nitrogen, Sulphur, ORGANIC COMPOUNDS pees ecru RCAC COMPOUNDS ‘elements which may be present in organic compounds are oxygen, Nearer as hep ence nitrogen, halogens and sulphur. groups in organic compounds © The chemistry involved in Detection of Nitrogen, Sulphur, Chlorine, Bromine and lodine by the preparation of inorganic Lassaigne’s Test compeunds: Moe's salt ‘This testis mosly prefered to conf the oresenceof elements ike N i, Br, land S. In this test, salts fused with sodium metal to prepare its © The chemistry involved in water soluble salt called soda extract or Lassaigne's extract. the preparation of Organic are erate Preparation of Lassaigne’s Extract, prnitro acetanilide, aniline ‘To prepare soda extract, an small amount of organic compound is heated yellow, iodoform with dry sodium in a fusion tube, The red hot tube is crushed in distiled © The chemistry involved in the __ water and fered, the frate is known as Lassaigne’s extract. titrimetric exercises © Analysis of Cations © Analysis of Anions ‘The chemical reations of various elements with Na are as Na+C+N->NaCN © Chemical Principles involved 2N8+S>Na,S in the experiments: Na+XNaX Where Xmay be (Cl, Brorl) 3 Enthalpy of solution of If nitrogen and sulphur both are present in the compound then sodium cuso, thiocyanate is formed, a Enthalpy of GtNe a eee Na+C+N+S-> NaSCN ‘acid and strong base Formation of sodium thiocyanate is possible only when sodium metal is. OR reenter eer te present in litle amounts. ‘and lyophobic sols a Kinetle study of the reaction of iodide tons Sodium extract in a test tube is added with freshly prepared saturated with hydrogen peroxide solution of ferrous sulphate. A green precipitate of ferrous hydroxide is ae formed, Acidify the solution with dilute sulphuric acid and warm ferric chloride solution's added. A Prussian blue precipitate indicates the presence of nitrogen, Detection of Nitrogen Corporate Office : Aakash Tower, 8, Pusa Road, Now Delhi-110005, Phone : 011-476234862 Principles Related to Practical Chemistry EET 6NaCN + Fe(OH), > Na,|Fe(CN,)] +2NaoH rowan) 4Fe™ + 3IFe(CN), J“ Fe,|Fe(CN), , tron noma Detection of sulphur when nitrogen is not present ‘+ The sodium fusion extract is added with sodium nitroprusside, Exhibition of violet colour confirms the presence of. S*_+[Fe(CN),NO]* —»[Fe(CN),NOS] een! FCN NON Ee + Theextactis added with acotic acid and lead acetate is added tot. The appearance of black precipitate of lead sulphide confrms presence ofS. Pb? +S*—> Pos ook oe Test for Nitrogen and Sulphur when Present Together When both nitrogen and sulphur are present in an organic compound, sodium thiocyanate may be formed on fusion with sodium metal ‘Soda extract is acidified with dilute HCI, 2-3 drops of FeCl, is added to it. Appearance of blood red colouration Confirms the presence of both nitrogen and sulphur in the organic compound. FeCl, + 3NaSCN—> Fe(SCN), * 3NaCl Detection of Halogens To test halogens, first nitrogen and sulphur are removed in the form of HCN and H,S. For this soda extract is ‘added with few drops of conc. HNO, NaCN + HNO,—-»> NaNO, + HCN Na,S + 2HNO,—> 2NaNO,+H,S. {@) Now, AgNO, is added to the solution if a white pp. is formed which dissolved in excess of NH) then presence of chlorine is confirmed Ag'+cr—> Agcl mses ‘AgCl+ 2NH, —={AgINH,), JCI on, sole stem (b) Ifa yellow precipitate partially soluble in ammonium hydroxide solution is formed the presence of bromine is confirmed inthe organic compound. gt +B —» Ager ‘low (c) lodine ion forms dark yelow ppt that is insoluble in ammonia solution Ag’ +r—> Aal areetew es Layer test for bromine and iodine Soda extracts added with CCI, and chlorine water, appearance of range coloured layer confirms presence of Sr {and violet coloured layer incicates the presence of | Corporate Office : Aakash Tower, 8, Pusa Road, Now Delhi-110005, Phone : 011-47623456NET. Principles Related to Practical Chemistry 3 DETECTION OF FUNCTIONAL GROUPS Test for Alcoholic [R-OH] Group Ceric Ammonium Nitrate Test Alcoholic compounds on reaction with ceric ammonium nitrate give a red colouration due to the formation of a complex, (NH, ),[e(NO,),] +3ROH —> [Ce(NO, ), (ROH), }+ 2NH,NO, Lucastest Lucas reagent (2nCl, and cone. HCI): This reagent converts alcohols into the corresponding alkyl chorides. Zine chloride (a Lewis acid) increases the reactivity of alcohols with HCL {) 1" alcohol No reaction at room temperature. (i) 2 alcohol: Tubidty appears within an hour (i) 3" alcohot Turbidity appears immidiatoly lodoform Test This testis given by alcohols and carbonyl compounds having «-methyl groups such as Ct CO- groups respectively ‘Compound is heated with |, + Na,CO,/l, + NaOH/NaOlINalO, to give yellow iodoform. |,-CH(OH)- or CH, tees, cH co eH 51, cHO"_CHI, + HCOONA CH,CH,OH {A yellow precipitate of iodoform confirm the test. TEST FOR PHENOLIC [Ar - OH] GROUP Forric Chioride Test Phenols form violet coloured complex with freshly prepared FeCl, solution 60,H,OH+ FeCl, —> [Fe(C,H,0), | + SHO1+ 3H” Resorcinol, o-, m-and p-cresol give violet or blue colouration, catechol gives green colour which rapidly darkens, ‘Vand 2-Naphthol do not give characteristics colours. Phthalein Dye Test, Phenols condense with phthalic anhydride in the presence of concentrated H,SO,, Phenol condenses to give phenolphthalein which gives a dark pink colour with NaOH solution. Ths is called phthalein dye test. oH “0. o Ot I ¢ (Colours) (Pin) Corporate Office : Aakash Tower, 8, Pusa Road, Now Delhi-110005, Phone : 011-476234864 Principles Related to Practical Chemistry EET Wl TEST FOR ALDEHYDIC AND KETONIC GROUPS (-CHO AND —C -) 2,4-Dinitrophenylhydrazine test (2,4-DNP test) This testis performed by both aldehydes and ketones. 2,4-Dinitrophenylhydrazine reacts with aldehydes and ketones to give 2,4-dinitrophenylhydrazones. The colour of the product is yellow and red for aldehydes and ketones respectively RR’ drogen or akyl Tests to Distinguish Aldehydes and Ketones: Schif's test, Fehling’s test and Tollen’s test are given by aldehydes only. So, the carbonyl compounds which take part in 2,4-DNP test as well as give positive Fehling test, Schiff's test and Tollen's test contain aldehydic group while ketones give negative results in the above tests, i.e, Schiff test, Febling's test and Tollen’s test. Preparation of Fehling’s Reagent: Fehiing Reagent is a mixture of freshly prepared Fehling solution A and Fehling solution 8. Fehling solution A is an aqueous solution of copper sulphate while Fehling solution B is an alkaline solution of sodium potassium tartarate (Rochelle's sal) We mix the two solution just before the reaction as Fehling reagent (mixture) is not stable while separately Fehling Aand B are quite stable. Fehling reagent (mixture) contains complex of copper with tartarate fons as fotows o-ex0 ‘| j bg ae a | 0-0-0 operas complex CCupric ions oxidises aldehydes into carboxylic acid and orange red precipitate of Cu,0 is formed while the ketones remain unaffected. The important point to note here that aromatic aldehydes do not give positive Fehling Test. RCHO + 2Cu2"(complexed) + SH” ——» RCOO™ + Cu,0 + 3H,0 Fonings soon Benedict solutions the modified form of Fehling solution where a single solutionis used. tis an alkaline solution containing a mixture of copper sulphate and sodium citrate (2Na,C,H,0, 11H,0).Itis more stable than Fehling solution and canbe stored fora longer duration. Schifts Tost Schiff's reagent is prepared by decolourising an aqueous solution of p-rosaniline hydrochloride dye by adding sodium sulphte to itor by passing SO, gas in it, Apink colouration on adding Schif’s reagent tothe compound indicates the presence of aldehyde group. Tollens'Test Preparation: n the freshly prepared siver nitrate solution (~2 %) afew drops of sodium hydroxide solution is added to obtain a dark brown precipitate of silver oxide. Further ammonium hydroxide solution is added to iin Grop-wise manner to dissolve the precpiate. The obtained solution is termed as Tollen’ reagent. Corporate Office : Aakash Tower, 8, Pusa Road, Now Delhi-110005, Phone : 011-47623456NET. Principles Related to Practical Chemistry 5 Test ‘An aqueous or an alcoholic solution of the organic compound is added to the Tollen’s reagent and heated. Formation ofa layer of sliver metal on the inner surface of the test tube (silver mirror) indicates the presence of an aldehyde, RCHO + 2{Ag(NH, ),]’ + 20H" —> 2Ag + 3NH, +H,0 + RCOONH, From Tales eapent TEST OF CARBOXYL GROUP [-COOH] ‘Sodium Hydrogencarbonate Test Litmus Test Bue Litmus tus red when a drop of carboxylic acid is added to Imus solution’ paper. Sodium hydrogencarbonate Test: if an organic compound containing carboxylic acid group is added to the ‘aqueous solution of sodium hydrogen carbonate, the carbon dioxide gas is evolved with brisk effervescence, RCOOH + NaHCO, + RCOONa +H,0+CO, Ester Test (Organic compound containing carboxylic acid group when added to alcohols in acidic medium then a compound with fruity sweet smellis formed BSQOH, + ROH SHEL RoQOR’+H,0 TEST FOR AMINO GROUP (-NH,) Carbylamine Test When a primary aliphatic or aromatic amine is heated with chloroform in the presence of alkali, a foul smelling ‘compound (Isocyanide/ carbylamine) is formed. RNH, +CHCI, +3KOH——» R—NC_ +3KCI+3H,O yl isocyarie Ale cay amine PhNH, + CHCl, + 3KOH ——» Ph - NC + 3KCI+3H,0 ‘Note: Secondary and Tertiary amines do not give positive carbylamines test. Solubility Tost ‘Due to the basic nature of amino group, amtines react with acids to form salts which are soluble in water. Hence: ‘can be used asa test for the amino group. C,H_NH, +HCI—> C,H,NH,CI- (inn core oubien ame) Azo Dye Test Itis a well-known test to identify primary aromatic amines and commonly used confirmatory test for it. The test involves the following two steps: + Diazotisation: Reaction of primary aromatic amine with NaNO, and HCI at 0°C-5°C to produce diazonium chloride Om. neo, C)- ier Benzene diazonium chloride Corporate Office : Aakash Tower, 8, Pusa Road, Now Delhi-110005, Phone : 011-476234866 Principles Related to Practical Chemistry EET + Coupling Reaction: On addition of beta naphthol to diazonium salt, coupling reaction take place to form a scarlet coloured dye which is sparingly soluble in water. “2 (> " Ore Onur» [Nephi [-Naphthal azo-dye (Scarlet red ‘The formation ofa scarlet red dye confirms the presence of aromatic primary amine. CHEMISTRY INVOLVED IN THE PREPARATION OF INORGANIC COMPOUNDS Both Mohr's salt and Potash Alum are double salts: Potash Alum: Crystallisation of an equimolar mixture of potassium sulphate and aluminium sulphate results in the formation of potash alum K,S0, + Al,(SO,), + 24,0 —> K,SO, Al,(SO,),: 24H, of 2KAKSO,),'12H,O (Pate ater) Mohr’s Salt: Crystalisation of an equimolar mixture of ferrous sulphate and ammonium sulphate results in the formation of Mohr's sat (Ferrous ammonium salts) FeSO, + (NH,),S0, + 6H,O —>FeSO,(NH,),S0,-6H,O Forot rnin sd Preparation of Double Salt: Potassium Aluminium Sulphate (Potash Alum) ‘+ Aluminium sulphate with dilute sulphuric acd is dissolved in 10 mL of distilled water. ‘+ Assmall amount of powdered potassium sulphate is added and mixture is heated and then cooled to room temperature, ‘+ White crystals of potash alum gets separated on cooling. ‘© Crystals are washed with mixture of cold water and alcohol and then dried, Preparation of Double Salt: Ferrous Ammonium Sulphate ‘+ Ferrous sulphate and ammonium sulphate are taken in 2: 1 ratio and dissolved in minimum amount of distlled water ‘* Few drops of dilute sulphuric acid is added to the solution and itis concentrated by heating tilthe crystallisation points reached. ‘* Oncooling, light green crystals of ferrous ammonium sulphate are obtained which are washed with a mixture ‘of cold water and alcohol followed by drying. Chemistry involved in the prepar jon of following organic compounds. 4. Acetanilide prnitro acetanilide 2. 3. Aniline yellow 4. lodoform 1 Preparation of Acetanilide: Acetanide is prepared from aniline by replacement of one H-atom from -NH i ‘group with acetyl group (-C-CH,) using glacial acetic acid Corporate Office : Aakash Tower, 8, Pusa Road, New Dolh-110005, Phone : 011-47623456NEET. 2 Principles Related to Practical Chemistry 7 + Acetylation of aniline can be done using acetic anhydride or acetyl chloride, ‘Note: This reaction is carried out in the presence of strong base than amine like pyridine, which removes HCI so formed and shifts the equilibrium towards forward direction Procedure! + Aniline is taken in a round bottom flask and mixed with acetic anhydride and glacial acetic acid facetylating mixture] + Anair condenser on the mouth of the round bottom flask is filed after adding pumice stones and refluxing the mixture gently on a sand bath + Next step is cooling the reaction mixture and pouring it slowly in ice cold water with stirring. + After cooling next step is fitering the solid, washing it with cold water and recrystallizing a small amount ‘of sample from hot water containing a few drops of methanol and ethanol. Preparation of p-nitro acetanilide: Formation of p-itro acetanilide follows electrophilic aromatic substitution reaction in which nitronium ion (NO}) acts as.an electrophile + In this reaction, the acetanilide reacts with ritrating reagent (mixture of cone. nitric acid and conc. sulphuric acid) to get p-nitro acetanilide as major product. 9 1 Note: ~AH-C-ck, group of acetanilide acts as an electron donating group to benzene ring through +M effect which directs the incoming electrophile (NO) to the ortho and para position, Formation of electrophile (NO): NO} is produced by transfer of proton (from sulphuric acid) to nitric acid as folows: f 4 Stop-ti: 1-G1No, = H,0 + fio, + Acetanilide is itself prepared using acetylation of aniline. Ne nucoct, nicoch, = ete Ye Procedure! + Acotanilde is dissolved in glacial acetic acid and taken in a beaker. ‘+The above mixture becomes hot and clear solution is obtained when cone. H,SO, is added. + Cold mixture of cone. HNO, and cone. H,SO, stirring is added to the above mixture drop by drop with constant Corporate Office : Aakash Tower, 8, Pusa Road, Now Delhi-110005, Phone : 011-47623486Principles Related to Practical Chemistry EET + Alter removing the beaker from ice bath mixture is allowed to attain room temperature, + The mixtures stived and the compound obtained is fitered + After drying, recrystallise a small amount ofthe pale yellow solid from aleohol. + Colourless crystals of p-nitroacetanilide are obtained 3. Preparation of Aniline yellow: The reaction of diazonium salt with aniline forms p-aminoazobenzene (yellow dye). This reaction follows electrophilic substitution reaction and known as coupling reaction, Oe Om Oe Om + Finely powdered Diazoaminobenzene and aniline are dissolved in a conical flask + Powdered aniline hydrochloride is added to the above mixture. + The mixture is heated on a water bath for approximately 1 hour. + Temperature of mixture is lowered in the next step by allowing it to stand at room temperature. + Excess aniline is converted toits acetate by adding glacial acetic acid and water to the mixture ‘Allow the mixture to stand for 15 minutes with occasional string Inthe next step, p-aminoazobenzene is fitered, washed with litle cold water and dried. Inthe last step, a small portion of crude p-aminoazobenzene is recrystallised from carbon tetrachloride. 4. Preparation of lodoform: lodoform (CH) is a pale yellow crystalline solid having a characteristic odour. It is used asa mild antiseptic and disinfectant. lodoform can be prepared by treating any organic compound containing CH,CH(OH}- group (e.g, ethanol, 2-propanol, 2-butanol) or CH,CO- group (e.9., propanone, 2-butanone) with iodine in presence of sodium hydroxide. in the laboratory, tis usually prepared from either ethanol or propanone. The chemical reactions involved are (a) With Ethanol 2NaOH +1, Nal + Nal+ HO CH,CH,OH + NaOl + CH,CHO + Nal + H,0 (CH,CHO + 3NaOl -»1,CCHO + 3NaOH L,CCHO + NaOH CHI, + HCOONa (b) With Propanone (CH,COCH, + 3Na0! > CH,COCI, + 3NaOH (CH,COCI, + NaOH CHI, +CH,COONa Acids and Bases Acids and bases are popular chemicals which react with each other to form salt and water. Acidic substances are usually identified by their sour taste. An acid is basically a molecule which can donate an H’ ion and can remain energetically favourable after aloss of H’. Acids are known to turn blue litmus red. Bases, on the other hand, are characterized by a bitter taste and a slippery texture, Abase that can be dissolved inwater is referred to as an alkali. Bases are known to turn red litmus blue. Corporate Oca : Aakash Tower, 8, Pusa Road, New Delhi-110005, Phone : 011-47623456NET. Principles Related to Practical Chemistry 9 + The Arrhenius theory of acids and bases states that “an acid generates H’ ions in a solution whereas a base produces an OH ion ints solution” +The Bronsted-Lowry theory defines “an acid as a proton donor and a base as a proton acceptor” + Finally, the Lewis definition of acids and bases describes “acids as electron-pair acceptors and bases as lectron-pair donors” pH of Acids and Bases In order to find the numeric value of the level of acidity or basicity of a substance, the pH scale (wherein pH stands for ‘potential of hydrogen’) can be used. The pH scale is the most common and trusted way to measure how acidic or basic a substance is. A pH scale measure can vary from 0 to 14 at 25°C, where O is the most acidic and 14 is the most basic a substance can be. Another way to check if a substance is acidic or basics to use litmus paper. There are two types of litmus paper available that can be used to identify acids and bases - red litmus paper and blue litmus paper. Blue litmus paper turns red under acidic conditions and red litmus paper turns blue under basic or alkaline conditions. Indicators in Acid Base Titration ‘Acid base indicators are sensitive to pH change. For most acid base titrations, its possible to select indicators Which exhibit colour change at pH close to the equivalence point, We will discuss here about only two indicators - phenolphthalein and methyl orange, Phenolpthalei Phenolpthalein is a weak acid, therefore it does not dissociate in the acidic medium and remains in the unionised form, which is colourless. Heh = HY + Pho lonised and unionised forms of phenolphthalein are given below QF cx = o ma Cc, a i Z So 8 o (Cores act (Pat abat In the acidic medium, equiliorium lies to the left. In the alkaline medium, the ionisation of phenolphthalein increases considerably due to the constant removal of H” ions released from HPh by the OH ions from the alka ‘So the concentration of Ph ion increases in the solution, which imparts pink colour tothe solution. Heh = HY+ Phe NaOH = —» Nat + OH" Hi +H —> H,0 For a weak acid vs strong alkal titration, phenolphthalein is the most suitable indicator. Ths is so because the last drop of added alkali brings the pH of the solution in the range in which phenolphthalein shows sharp colour change. Corporate Office : Aakash Tower, 8, Pusa Road, Now Delhi-110005, Phone : 011-4762348610 Principles Related to Practical Chemistry NEET Methyl orange Methyl orange is a weak base and is yellow in colour in the unionised form. Sodium salt of methyl orange is represented as follows: Nou, The anion formed from the indicator is an active species, which on accepting a proton (.e acting as Bronsted Lowry base) changes from the benzenoid form to the quinonoid form. The quinonoid form is deeper in colour and thus is responsible forthe colour change at the end point. Ths is ilustrated inthe following manner: cH, ou, sXe XY os Soi Nox Now, Benzenoid form ofthe anion Quinonoid form ofthe anion (Yellow in colour) (Pinkish red in colour pH Range of Indicators, ‘sno, ] Nameof | Colourinaci Colourin | Working pH range indicator medium | basic Medium | of indleators 1. Mathyr orange Orange red Yetow 37045 2. [Methyl red Red Yelow 421062 3._[Phenotred Yellow Red 620082 % | Pherobhihaien | Gotourlese Pink B2t0102 (HPn) Acid-Base Titration ‘An acid-base titration is an experimental technique used to acquire information about a solution containing an acid orbase. Important points of titration: (Titration is always possible in two opposite nature solutions. (i.e. one is acidic and other is basic), (i) Forany titration only that indicators suitable if their working pH range is in pH range of titration. (il) Atthe end point of titration, number of equivalents of acids and bases are equal (W) Atthe equivalence point, nature of solution depends on the type of titration, SAISB - )at25°C SAWB - WAsB - WAWB = - ~—_—Acidic/Basic ‘No. | Type of titration | pH range of tivation ‘SAISE 3-11 ‘Allinleators (MeOH, HPh ete) 2 SAWE 327 Methyl orange (MeOH) and methylred wars 711 Phenolphthalein (HPA) {) Strong acid-strong base titration: In the titration of HCI with NaOH, the equivalence point lies in the pH range of 3-11. Thus, methyl orange, methyl red and phenolphthalein willbe suitable indicators. Corporate Office : Aakash Tower, 8, Pusa Road, Now Delhi-110005, Phone : 011-47623456NET. Principles Related to Practical Chemistry | 14 (li) Weak acid-strong base titration: In the titration of CH,COOH with NaOH the equivalence point ies between and 11, Hence, phenolphthalein (8.2— 10.2) willbe the suitable indicator. Weak base-strong acid titration: Inthe titration of NH,CH (weak base) against HCI (strong acid), the pH at equivalence point lies between (3 - 7). Thus, methyl orange (3.1 ~ 4.6) or methyl red (4.2 ~ 6.2) will be suitable indicators. (Iv) Weak acid-weak base titration: In the titration of a weak acid (CH,COOH) with weak base (NH,OH) the pH at the equivalence point is about 7, .e., lies between 6.5 and 7.5 but no sharp change in pH is observed in these titrations. Thus, no simple indicator can be employed for the detection of the equivalence point Titrimetric Analysis (Redox Reactions) ‘reaction, which involves simultaneous oxidation and reduction is called a redox reaction. The titrations involving redox reaction are called redox titrations, In acid-base titrations, indicators which are sensitive to pH change are used to identity the end point. Similarly, in redox titrations there is a change in oxidation potential ofthe system. The indicators used in redox reactions are sensitive to change in oxidation potential. The ideal oxidation-reduction Indicators have an oxidation potential intermediate between the values for the solution being titrated and the titrant and these show sharp readily detectable colour change. 1, Titration —ttis a process of quantitative analysis which is carried out by determining the volume of standard solution which is required to react quantitatively with known volume ofa solution to be determined, Titrant—A.reagent of known concentration (standard solution) in the titration, Titrand ~The substance being titrated is termed as titrand, Titration curve —A plot of pH vs millilitres of trant showing the manner in which pH changes vs mililtres of titrant during an acid-base titration, 5, Equivalence point — The point at which just an adequate reagent is added to react completely with a substance, Titration of oxalic acid solution against potassium permanganate solution The titration of KMnO, vs Oxalic acd is a good example of the oxidation - reduction reaction. KMnO, solution is considered a strong standard oxidizing agent and H,C,0, strong reducing agent. + Forthe experiment, lt 0.1 M standard solution of oxalic acid ito be propared The formula ofhydrated rystaine oxalic aca 00H boon and is molar mass is 126 It 126g of oxalic acids present in one lr of he soliton tis known as one 24,0 12 molar (1.0 M) solution. Forthe preparation of one litre of 0.1 M oxalic acid solution, we require “py =12.6 9 of hydrated oxalic acid Following reactions occur during the titration Reduction half reaction: MnO; +52” + 8H* —>MIn** + 4H,0]x2 Oxidation half reaction: C,0% — 260, +2615 2NInO; +5C,0% +16H' ——>2Mn** +10C0, + 8H,0 Here, MnO; is reduced tohin® and C,02~ is oxidised to CO,. The oxidation number of carbon in C,0- changes from +3 to +4, ‘The strength of the unknown solution in terms of molarity may be determined by the following equation, = nM, 0 Corporate Office : Aakash Tower, 8, Pusa Road, Now Delhi-110005, Phone : 011-4762348612 Principles Related to Practical Chemistry NEET For oxalic acid vs potassium permanganate titration: 2, (the number of electrons lost per formula unit of oxalic acd in a balanced equation of hatf cell reaction) 1,5, (the number of electrons gained per formula unit of potassium permanganate inthe balanced equation of half cell reaction) M, and M, are the molarties of oxalic acid and potassium permanganate solutions used inthe titration. V, and V,are the volumes of oxalic acid and potassium permanganate solutions. ‘On putting the value of n, and n, in equation () we get Number of equivalents of oxalic aci 2M.V, 5M,V, w Number of equivalents of KMnO, 2M, We can calculate the molarity of potassium permanganate solution by using equation (i) strength of the solution isgivenby Strength = Molarity x Molar mass lone of the reactants has some characteristic intense color, then no external indicator is added forthe indication ‘of completion of reaction. For example, KMnO,, which has an intense violet color. As soon as the reaction ‘complete, only one extra drop of KMnO, from burette is capable of changing the color ofthe solution, n of ferrous ammonium sulphate (FeSO,(NH,),50,-6H,0) against potassium permanganate Ferrous ammonium sulphate also acts as a reducing agent inthe titration against potassium permanganate, ‘To prepare 0.05 M standard solution of ferrous ammonium sulphate, following steps are followed + Weigh 4.9000 g of ferrous ammonium sulphate and transfer it into a 250 mL measuring flask through a funnel + Transfer the solid sticking to the funnel with the help of distilled water into the flask and add dilute H,SO, into the flask drop wise to get the clear solution and shake the flask til the substance dissolves. Following reaction occur during the titration Reduction half reaction: MnO; +86" + 8H" Mn + 44,0 Oxidation half reaction: _Fe®* —>Fe"" +e°}x5 MnO; +5Fe® +8H* ——9Mn® « SFe™ + 4H, ‘The oxidation number of iron in Mohr's salt is +2. ron is oxidised during the reaction and its oxidation number changes from +2to +3, From the overall balanced chemical equation, itis clear that 1 mole of potassium permanganate react with 5 moles of Mohr's salt, Molarity of KMInO, x Volume of KMnO, No.of moles of KMnO, 1 Motarity of Mohr's salt Volume of Mahr's salt No. of moles of Monr's salt 5 Molarity of Mohr's salt Volume of Mohr's saltxt Therefore, Molarty of KMnO, ‘Volame of KMS Proliminary tests of the Salt for Identification of Cations 4. Colour Test Colour of the salts give useful information about metal ions. Corporate Office : Aakash Tower, 8, Pusa Road, Now Delhi-110005, Phone : 011-47623456NEET. Principles Related to Practical Chemistry 13 Characteristic colours of some metal ions Colour ations: Light green, Yall Brown Fo* Fe Blue coe 1 Bright gre NE 1 Blue, Red, VIEL PINE or ight pink nin 2, Dry Heating Test ‘Observe colour ofthe salt in hot and cold conditions. Colour when cold] Colour when hot Taferenee. Blue White [or Green Dirty white or yellow Fer White "allow Za Pink Blue com 3, Flame Test Metal salts impart characteristic colour to the flame test. Platinum wire is used to perform the test. Inference from the flame test Colour ofthe Colour ofthe fame | Terence ‘flame observed by | observed through blue glass naked oye Green fame with | Same colour as cbserved CF blue centre without glass (Crimson red Purple 3 ‘Apple green Blush goo Ba Bick red Green ca 4. Borax Bead Test Borax reacts with metal salts to form metal borates which have characteristic colour. Coloured salts are ‘considered for this test. Inference from the borax bead test Heating in oxidising (non Heating in reducing luminous) flame {Juminous) fame Inference Tolour ofthe salt bead Colour of th salt bead ncoid Ta hot Tncoid Ta hot Blue ‘Green. Rad opaque | Colours cr Reddish brown | Violet Gea Gre NE Lgntvelst [Light vt | Colourass | Covouriss Mer Yellow Yellowish brows_[ Green Green Fe 5, Charcoal Cavity Test ‘On heating metal carbonates in a charcoal cavity, the carbonates are converted to metal oxide, which are coloured residues. Sometimes metal oxides are converted to metal on carbon reduction within the charcoal cavity, Inference from the charcoal cavity test ‘Observations Tnference Yellow reside wen fot and grey metal wher Com Por While esidue wilh the adour of gave Ase Brown residue cr ‘Yellow residue when hot and white whan old Zam 6. Cobalt Nitrate Test If the residue in the charcoal cavity is white, cobalt nitrate testis performed. (i) The residue is treated with few drops of cobalt nitrate solution, (i) Heat the mixture with the help of a blow pipe and observe the colour of the residue. Corporate Office : Aakash Tower, 8, Pusa Road, Now Delhi-110005, Phone : 011-4762348614 Principles Related to Practical Chemistry NEET ‘Onheating, cobalt nitrate decomposes into CoO, which gives a characteristic colour on reaction with metal ‘oxide present in the charcoal cavity. 2CoINO,), Hs 2600 + 4NO, +0, ‘C00 +2n0 > Co0:2n0 ‘ron ‘CoO +MgO > Co0-MgO (C00 1-Al,0, -» C00-Al,0, Wet Tests for Identification of Cations In the first step, prepare the clear aqueous solution of the salt. This is called original solution. Cations of different groups with group reagent have been depicted in the table given below. Group reagents for precipitating ions. Group _| Cations™ ‘Group Reagent Group 7e_| NA Nore GroupT [Po Dike HOT Group PRC Aa FOS gas W presence ofa ACT Group AP Fe NFOW m presence of NFCT Group-W | CORN Min, Za= | Fos ta presence oT NHLOH Group [BaF SE Ca TNF pCO a presence of NFLOF Gm [Mo None ‘To identity metal cations, these are precipitated from the original solution by using the group reagents according to the flow chart given below: Original Solution Dil, Ho! Precpitate, Group | Ino procpteo is obtaines {Pb")} as chloride pass HS gas], Precpitate, Group I Ino precipitate, take orginal solution (Po cu", as”) Heat wih cone. HNO, ss tuiptiien cool and add sod NH,CI + NH,OH| solution in excess Precetate, Group I Irn precptate (Fo, A") as hydroxides Pass Hs Precitata Group ly Ifo preciptate, tke original solution (CoP NE Mat, 2) ‘Add NH,OH and as sulbhides| solid (NH), CO, Procite, Group V Ifo precipitate, ake orgina (ee", Sa") Solin to tsi Group Wi, 38 carbonates a (0). Analysis of Group-zero cation (NH; ion) ‘Small amout of salts treated with few drops of sodium hydroxide solution and then heated. there is smell (of NH, this indicates the presence of ammonium ions, Corporate Office : Aakash Tower, 8, Pusa Road, Now Delhi-110005, Phone : 011-47623456NET. Principles Related to Practical Chemistry 15 Confirmatory Tests for NH ion (a) Ammonia gas evolved by the action of sodium hydroxide on ammonium sats reacts with hydrochloric, acid to give ammonium chloride, which is visible as dense white fume, (NH,),SO, + 2NaOH > Na,SO, + 2NH, + 2H,0 NH, + HCI NH,CI (White fumes) (b) On passing the gas through Nessler's reagent, a brown precipitate of basic mercury(I) amido-iodine is, formed ‘2KaHal; +NHs +3KOH > HgO:Hg(NH, I+ 7Kl+2H,0 oy etna (W) Analysis of Group-| cations Lead is precipitated as lead chloride in the first group. The precipitate is soluble in hot water. 41, To the hot solution, potassium iodide solution is added, a yellow precipitate of Pbl, is observed which confirms the presence of Pb’ ions. PoC, +2Ki> — Pbl, +2KC! (at soul) Yeton eat This yellow precipitate is soluble in boiling water and reappears on cooling as shining crystals. 2. To the hot solution, potassium chromate solution is added which results in a yellow precipitate of lead chromate. This confirms the presence of Pb ions. PbCl, +K,CrO,-> PbCrO, +2KCI (estan) Meier Lead chromate is soluble in hot sodium hydroxide solution, PbCrO, + 4NaOH = Na, [Pb(OH), |i Na,CrO, Sedu a ‘yeep 3. Addition of alcohol followed by treatment with dilute H,SO, solution gives white precipitate of PBSO,. PbO, +H,SO, > PbSO, +2HCI (vine peta) Lead sulphate is soluble in ammonium acetate solution due to the formation of tetraacetoplumbate(|I) PbSO, + 4CH,COONH, — (NH,)a[Pb(CHjCOO),] + (NH, },80, tensor (ll) Analysis of Group-Ii cations If group-1 metal cation is absent, add few mL of water to the same test tube, Warm the aqueous solution and pass H,S gas for few minutes and shake the test tube. Ifa precipitate is observed, this indicates the presence of group-II cations. Pass excess of H,S gas to the solution for complete precipitation. 1. Confirmatory test for Lead ion (Pb*) Lead sulphide precipitate is dissolved in dilute HNO, .To iti. H,SO, and a few drops of alcohol is added to solution, a white precipitate of lead sulphate appears. This indicates the presence of lead ions. 3PbS + BHNO, — 3Pb (NO,), + 2NO + 4H,0 +38, Pb{NO.), + H,S0,-PbSO, + 2HNO, Corporate Office : Aakash Tower, 8, Pusa Road, Now Delhi-110005, Phone : 011-4762348616 Principles Related to Practical Chemistry NEET 2. Confirmatory test for Copper ion (Cu) {@) Copper sulphide precipitate dissolves in nitric acid due tothe formation of copper nitrate 3CUS + BHNO, -> 3CuINO,), + 2NO + 38 + 44,0 (On heating the reaction mixture, sulphur obtained is oxidised to sulphate resulting information of ‘copper sulphate and the solution tums blue. Addition of small amount of ammonium hydroxide, precipitates basic copper sulphate which fs soluble in excess of ammonium hydroxide solution due tothe formation of deep blue tetraamminecopper l) sulphate S+2HNO, + H,SO, + 2NO 20u* + SOF +2NH, +2H,0 Cu(OH}, "CuSO, +2NHy CulOH), CuSO, + 8NH, —> 2[CUINH, ),|S0, + 20H + $02" ‘Teanmasctppe (0) eat [Deepets) (©) Addition of acetic acid to the blue solution followed by treatment with K,[Fe(CN), gives a chocolate colouration due tothe formation of copper ferrocyanide. {CuINH,)]$0, # 4CH,COOH + CuSO, + 4CH,COONK, 26180, + KyfF{CN] > CUJFELEN),] + 26,80, sa (ean {V) Analysis of Group-til cations, If group-I is absent, take original solution and add few drops of cone. nitric acid and heat to oxidise Fe* ions to Fe™ ions, After cooling add a small amount of solid ammonium chloride and excess of ammonium hydroxide solution and shake the test tube till small amount of NH, arises. If brown or white precipitate is formed, this indicates the presence of group-III metal cations, Group III metal cations are precipitated as their hydroxides, which dissolve in dilute hydrochloric acid due to the formation of corresponding metal chlorides. 1. Confirmatory test for Aluminium ions (AP*) ‘Aqueous solution of AICI, is treated with sodium hydroxide, a white gelatinous precipitate of aluminium hydroxide is formed which is soluble in excess of sodium hydroxide solution due to the formation of sodium aluminate, AICI, + NaOH > AI(OH), + 3NaCl Al(OH), + NaOH — NaAlO, + 2H,0 White gelatinous Sodium respite aluminate 2. Confirmatory test for ferric ions (Fe) Ferric hydroxide the reddish brown precipitate, dissolves in hydrochloric acd and fetic chloride i formed Fe(OH), + 3HCI-> FeCl, + 3H,0 (@) Ferric chloride solution, on treatment with potassium ferrocyanide solution resulsin ablue precipitate! ‘colouration. Itisferi fert-cyanide, which is prussian blue in colour. “AF eC, + 3K, [Fe(CN)g] — Fey[Fe(CNy ly + 12KCl Patan Prussian be ‘oronce eerie (©) To the second part, add potassium thiocyanate solution. The appearance of a blood red colouration confirms the presence of Fe™ ions. Fe 4 SCN" > [Fe(SCN)F* Corporate Oca : Aakash Tower, 8, Pusa Road, New Delhi-110005, Phone : 011-47623456NET. Principles Related to Practical Chemistry 17 (V) Analysis of Group-lV cations. I Group-lis absent, H,S gas is passed in the solution of group-Il for afew minutes. Ifa precipitate appears (white or black) then the group-1V cations are present, Fourth group cations are precipitated as their sulphides. A white colour of the precipitate indicates the presence of zinc ions while black colour indicates Ni ions. 41. Confirmatory test for Zinc ion (Zn) The precipitate, Zin sulphide dissolves in hydrochloric acd to form zinc chloride. ZnS + 2HCI-> ZnCl, + H,S {@) Aqueous solution of ZnCl, on reaction with sodium hydroxide solution 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 Zn(OH), +2NaOH > Na,Zn0, +2H,0 (b) When potassium ferrocyanide solutions added tothe solution after neutralisation by NH,OH solution, white precipitate of zinc ferrocyanide is formed ‘2zZnCl, + KglFe(CN)s] -» ZnglFe(CN),] + 4KCI 2. Confirmatory test for Nickel ion (Ni*) Nickel sulphide dissolves in aqua regia. 3NIS + 2HNO, + 6HCI > 3NICI, + 2NO + 3S + 4H,0. When dimethyl glyoxime is added to the aqueous solution of nickel ehorde and is made alkaline by adding NH OF soluton a brilantredprecptat obtained 7 Hw ° 0 peek bao norg=te ow eS aa Hc—C=N—OH o™ Complex of rc colour (Stab form af compos) (V1) Analysis of Group-V cations If group-1V cations are absent then take original solution and add a small amount of solid NH,CI and an ‘excess of NH,OH solution followed by solid ammonium carbonate (NH,),CO,, Appearance of white precipitate indicates the presence of group-V cations. ‘The Group-V cations are precipitated as their carbonates which dissolve in acetic acid due tothe formation of corresponding acetates, 1. Confirmatory test for Barium ion (Ba) {@) Precipitate BaCO,, on treatment with acotic acid followed by addition of K,CrO, results in yellow precipitate of barium chromate. BaCO, + 2CH,COOH + (CH,COO), Ba+ H,0+ CO, (CH,COO), Ba+K,CrO, > BaCrO, +2CH,COOK ‘senumonromate {yeti precise) (b) Flame test ~ It gives apple green colour to the flame test. Corporate Office : Aakash Tower, 8, Pusa Road, Now Delhi-110005, Phone : 011-4762348618 Principles Related to Practical Chemistry NEET 2. Confirmatory test for Calcium ion (Ca”) (@) Group V precipitate is dissolved in acetic acid which is then treated with ammonium oxalate. A white precipitate is obtained which confirms Ca* ion. CaCO, + 2CH,COOH ~ (CH,CO0), Ca+ H,0+ C0, (CH,COO), Ca+(NH,}, C0,» (COO), Ca +2CH,COONH, Armani" Calomoabte ‘raite” ieee) (©) Flame test - Calcium imparts brick red colour to the lame. (Vit) Analysis of Group-MI cations If group-V is absent then perform the test for Mg ions. Confirmatory Test for Magnesium fon (Mg”) {@) If group-V is absent the solution may contain magnesium carbonate, which is soluble in water in the presence of ammonium salts because the equilibrium is shifted towards the right hand side. NHj +COf =2NH, +HCO; “The concentration of carbonate ions required to produce a precipitate is not sufficient to the given solution Disodium hydrogenphosphate solution is added and the inner wall ofthe test tube is scratched with a glass rod, appearance of white crystalline precipitate of magnesium ammonium phosphate confirms the presence of Mg" ions. Mg? +Na,HPO, > Mg(NH,)PO, +NH,OH+2Na’ +H, ‘Analysis done to understand the nature of the substance and to identiy its constituents is termed as Qualitative analysis. Constituents of inorganic salts are cations and anions. In the qualitative analysis of inorganic salts, we identify cations and anions present in sat orn the mixure of salts. Qualitative analysis is carried out through the reactions in which we can easily identify the changes by some of the physical observation like: (2) Evolution of gas (b) Change in colour (c) Formation of a precipitate For the systematic analysis of an inorganic salt, we follow the following steps: {Preliminary examination of sold salt and its solution, {i Determination of anions by reactions carried out in solution (wet tests) and confirmatory tests. (ii) Determination of cations by reactions carried outin solution (wet tests) and confirmatory tests, Preliminary examination of a sats not conclusive but generally it gives quite important hints for the presence of certain anions or cations and simplifies the process of analysis. Preliminary tests are termed as ‘dry test’ and include to observe the general appearance and physical properties like colour, odour, solubility et The first step in the qualitative analysis of a salt includes identification of anions present initand we proceed with preliminary tests followed by confirmatory analysis. Gases evolved in the preliminary tests with dil. H,SO,/dil HCl and cone. H,SO, help t identify the presence of acid radicals (anions). Corporate Oca : Aakash Tower, 8, Pusa Road, New Delhi-110005, Phone : 011-47623456NEET. Principles Related to Practical Chemistry 19 SYSTEMATIC ANALYSIS OF ANIONS Itincludes two steps 1-preliminary examinations 2-confirmatory tests, Preliminary Examinations with dilute sulphuric ace (SalvMixture of sats + dl. H,S0,) Tnference Observations Gas evolved | Possible Anion Evolution of colourless, odourless gas wih} COs Carbonate brisk effervescence. This gas tums lime water 2 mig (cof) Evolution of colourless gas with the smell of | FAS Sulphide (S rotten eggs. This gas tums lead acetate paper black. Brown fumes are evolved which turn acidified | Nz Wire (NO3) potassium iodide solution containing starch solution blue. Preliminary examination with concentrated sulphuric acid (Galtmixture of salts + conc. H,SO,) Taference Observations Gasivapours evolved Pungent emel ofa colpuTess gas ks observed Tgwes Cr ‘orange, (OFT dense white fumes when a rod cipped in NH.OH i brought near the mouth ofthe tel ube Reddish brown gas along wih a pungent odour evawea. | Brsvapours | Brome, TOF] (On eating the reaction mixture with Sold MnO, soliton acguires red colour and intensity ofredish gas ‘nereases. ‘Violet coloured sublmate gets deposited on the ses oftest_| vapours | —Todide, 7) {ube duo the evolston of voll vapours, These vapours get dense on addon of MnO; to the reaction mature, Evalulion brown fumes which oes dense on heating wih NOr va copper ming minors stan scare le aout Nate, (N03) Chemistry of Confirmatory Tests 1. Testfor Carbonate ion [CO] (On adding dilute sulphuric acid to the solid salt, there is the evolution of a colourless and adourless gas with brisk effervescence. This shows the presence of carbonate ion. Evolved gas turns lime water milky due to the formation of Caco, Na,CO, + H,SO, -+Na,SO, + H,0+ 00, Ca(OH), + CO, Caco, +H,0 Milkiness disappears on passing excoss of CO, through lime water due to formation of soluble Ca(HHCO, CaCO, +60, +H,0->CalHHCO,), 2, Testfor Sulphide fon [$4] a) With warm dilute sulphuric acid, sulphide salt gives hydrogen sulphide gas which can easily be identined by its rotten egg like smell \When this gas is passed on a filter paper dipped in lead acetate then the paper tus black due to the formation of lead sulphide. Na,S+H,S0,-»Na,S0, +H,S (CH,COO),Pb+H,S—» PbS +2CH,COOH Corporate Office : Aakash Tower, 8, Pusa Road, Now Delhi-110005, Phone : 011-4762348620 Principles Related to Practical Chemistry NEET (b) Check solubilty of satin water: If salt is water soluble then take its aqueous solution, make it alkaline by adding ammonium hydroxide solution and add sodium nitroprusside solution toi If salt is water insoluble then take its sodium carbonate extract“and add sodium nitroprusside solution to it Purple (or violet) coloured complex compound Na,[Fe(CN),NOS| is formed which confirms the presence of sulphide ion in the salt 'Na,S+Na,{Fe(CN).NO] -> Na,|Fe(CN), NOS] Sek riepnaie Papel Sodium carbonate Extract: Mix salt with 3-part sodium carbonate and add distilled water to it. Boil the mixture for 10 minutes and fiter. Fitrate is known as sodium carbonate extract. 3. Test for Nitrite ion [NO3] (@) When solid salt containing nitrite anion is heated with dil. sulphuric acid, reddish brown fumes of NO, gas are evolved (0) 2NaNO, + H,80, + Na,SO, +2HNO, 3HNO, > HNO, + 2NO + ‘2NO+0, > 2NO, Brown gis Inte salt solution, f potassium iodide alowed by freshly prepared starch solution is added andaciifcation with acetic acid is done then blue colouration confirms nitit ion. The same test can also be done by taking a iter paper moistened with potassium iodide and starch solution anda few drops of acetic acid When the evolved gas comes in contact with that fiter paper, i tums blue due tothe interaction of liberated iodine with starch (i) NO; ~CH,COOH > HNO, = CH,COO- 2HNO, + 2KI+2CH,COOH ~> 2CH,COOK+2H,0+2NO +1, |, + Starch -> Blue complex {b) Sulphanilic acid -1-naphthylamine Reagent Test (Griss-losvay test) ‘Take nite salt and acidified with acetic acid and add it to sulphanlic acid and ‘-naphthyamine Acidification of nitrite sat will form nitrous acid which leads to diazotization of sulphanilic acid, Diazotised acid couples with 1-naphthylamine to form red coloured azo-dye. Ne + CH,COOH—>HNO, + CH,COO- it,cH,c00" N=N-ooccH, ba be SO,H NH ‘-Naphthy| amine Red azo.dye ‘The test solution should be very dilute. In concentrated solutions reaction does not proceed post diazotisation Corporate Office : Aakash Tower, 8, Pusa Road, Now Delhi-110005, Phone : 011-47623456NET. Principles Related to Practical Chemistry | 24 4. Testfor Chloride ton (Cr) Chloride anion inthe salt can be identified by following ways {@) Evolution ofa colourless gas with pungent smell, on treatment with warm cone. sulphuric acid. When ‘evolved gas s passed in ammonia solution then gives dense white fumes. NaCl+H,S0,-> NAHSO, +, | HCL vices ‘Ca HCLINH, > NHCI ‘wns himes) {b) Evolution of light greenish yellow gas with effervescence on treatment with MnO, and conc. H,SO, MnO, +2NaCl+2H,SO, -»Na,SO,+MnSO, +2H,0+Cl, (c) Acidify the salt solution with dilute nitric acid and add silver nitrate to it. A curdy white precipitate which is soluble in ammonium hydroxide solution is obtained, NaCl+ AgNO, NaNO, + — AgCl (wires) 'AgCl+-2NH,OH -» [Ag(NH,)_]Cl +H,0 Banmnesive() (4) Chromyl Chloride Test: A litle amount of salt is mixed with an equal amount of solid potassium dichromate and a few drops of cone. sulphuric acid, Evalved gas is passed through sodium hydroxide solution, Obtained yellow coloured solution is divided into two parts: First partis acidified and lead acetate is added tot, Formation of yellow precipitate oflead chromate confirms the presence of chloride ions in salt “ANaCl-+K,C1,0; + 6H,S0, -» 2KHSO, + 2Cr0,Clp+ 4NaHSO, +3H,0 (ene) CrO,C}, + 4NaOH —>Na,CrO, + 2NaCl+ 2H,0 (CH,COO), Pb+Na,CrO, > PbCIO, +2CH,COONa ‘en (i) Second partis acidified with dilute sulphuric acid. Further addition of amy! alcohol followed by 10% hydrogen peroxide solution tums the organic layer blue. Reason for the Blue Colouratior Cr0,* ions formed in the reaction mixture react with NaOH and H,O, to form chromium pentoxide (CrO,), Formed CrO, gets dissolved in amy! alcohal to give blue colour, 9 age Ded CrOZ 42H" +2H,0, > CrO, +3H,0 o ‘o ate seve of event mice (Gutlerty structure) Corporate Office : Aakash Tower, 8, Pusa Road, Now Delhi-110005, Phone : 011-4762348622. Principles Related to Practical Chemistry EET 5. Test for Bromide ion (Br-) Presence of bromide ions can be identified by the evolution of brown fumes of bromine on heating the salt with cone, sulphuric acid, Evolution of fumes gets intense on addition of MnO, to reaction mixture, Starch paper turns yellow when comes in contact with these bromine vapours. 2NaBir + 2H,SO, -» Br, + SO, +Na,SO, +2H,0 2NaBr + MnO, + 2H,SO, »Na,SO, + MnSO, + 2H,0 + Br, Further confirmation of Br ions can be done as follows: (@) Take the salt solution in water or take its sodium carbonate extract and neutralize it with dilute HCl Prepare a mixture of carbon tetrachloride or chloroform and freshly prepared chlorine water and add to the water extract or sodium carbonate extract of salt in dropwise manner. Brown colouration in organic layer shows the presence of bromide ions, 2NaBr + Cl, + 2NaCl + Br, (b) Acidifiad sodium carbonate extract of the saltis taken and silver nitrate solution is added to it. Formation of yellow precipitate (soluble in ammonium hydroxide) shows the presence of bromide ions. NaBr+AgNO, >NaNO,+ —_ AgBr Serene, (Pateysow poco) 6. Test for lodide lon (1) {@) Evolution of violet coloured vapours of iodine with @ pungent smell on heating the salt with cone. sulphuric acid shows the presence of iodide ions. Addition of MnO, to the reaction mixture intensify the evolution of violet vapours. These vapours tums starch paper blue and leave violet sublimate on the sides of test lube. 2Nal + 2H,SO, + Na,SO,+SO,+2H,0+1, 2Nal + MnO, + 2H,SO, |, + MnSO, + Na,SO, + 2H,O |, + Starch solution -» Blue colour ‘Along with iodine vapours some Hi, SO,,, H,S and Sulphur's also formed Nal+H,S0,-> NaHSO, + HI 2HI+H,S0, + 2H,0 +1, + SO, 6Nal + 4H,SO, + 31, + 4H,O + S + 3Na,SO, 8Nal + SH,SO, ->4I, +H,S + 4Na,SO, + 4H, (0) Take the salt solution in water or take its sodium carbonate extract and neutralize it with dilute HCl Prepare a mixture of carbon tetrachloride or chloroform and freshly prepared chlorine water and add to the water extract or sodium carbonate extract in dropwise manner. Violet colouration in organic layer shows the presence of iodide ions. (Iodine is soluble in organic solvents) 2Nal + Cl, -> 2NaCl + |, Acidified sodium carbonate extract ofthe salt is taken and silver nitrate solution is added to it, Formation ‘of yellow precipitate (insoluble in ammonium hydroxide) shows the presence of iodide ions Nal+AgNO,;-> — Agl_ +NaNOs sveronde (veto pees) ) Corporate Oca : Aakash Tower, 8, Pusa Road, New Delhi-110005, Phone : 011-47623456NET. Principles Related to Practical Chemistry 23 7. Testfor trate ion (NO5] (a) When nitrate salt is heated with conc. sulphuric aci, light brown fumes are evolved. Excess of brown fumes are evolved when salt is heated with few copper turnings and cone. sulphuric acid. The colour of the solution also turns blue due to the formation of copper sulphate, NaNO, +H,S0, > NaHSO,+HNO, 4HNO, + 4NO, +0, +2H,O ‘2NaNO, + 4H,SO, +3Cu-» 3CuSO, +Na,SO, + 4H,O+2NO phate ‘2NO+0,-> 2NO, rom es) Brown Ring Test {b) Small amount of aqueous solution ofthe salt is mixed with freshly prepared ferrous sulphate solution and ‘cone, sulphuric acid is added slowly to It along the sides of the test tube. It results in the formation of a ‘dark brown ring atthe junction of the two solutions due to the formation of nitroso ferrous sulphate. NaNO, +H,S0, >NaHSO,+HNO, 6FeSO, +3H,S0, +2HNO, ~>dFe,(S0,), +4H,0+2NO FeSO, +NO _[Fe(NO}ISO, vetoes ‘Alternatively, first conc. sulphuric acid can be mixed with aqueous salt solution in a dropwise manner land add freshly prepared ferrous sulphate solution to it along the sido of the test tube post cooling the ‘mixture. twill also form a brown coloured ring 8. Testof Suiphato ions [S02] If salt neither reacts with dilute sulphuric acid nor with cone. sulphuric acid, then it may contain sulphate anions. The following confirmatory tests are done in this case: (a) Awhite precipitate of barium sulphate is formed when an aqueous solution or sodium carbonate extract of the salts acidified with acetic acid and mixed with barium chloride, Precipitate of barium sulphate is insoluble in cone. HCI or cane. HNO,. 'Na,SO,+BaCl, > BaSO, +2NaCI Banumsuheie (inopreaptat) {(b) A white precipitate of lead sulphate is formed when an aqueous solution or sodium carbonate extract of the satis neutralised with acetic acid and treated with lead acetate solution, 'Na,SO, +(CH,COO),Pb-> PbSO, +2CH,COONa teeta) (0) Chemical principles involved in enthalpy of solution of CuSO, Generally reactions in lab are carried out at atmospheric pressure so heat changes observed during these reactions are enthalpy changes. The relationship between enthalpy change and temperature is given by formula. Corporate Office : Aakash Tower, 8, Pusa Road, Now Delhi-110005, Phone : 011-4762348624 Principles Related to Practical Chemistry EET where V = Volume of the solution. d= Density of the solution C, = Heat capacity AT = Change in temperature Calorimeters are the vessels that are used to measure the heat changes. Thermochemical reactions are generally carried out in beakers placed in thermos flask or thermally insulated boxes. Use of metallic calorimeters is not preferred for measuring thermochemical changes because of tendency of metals to react, with substances. So stainless steel or gold plated copper colorimeters can be used. The amount of heat ‘absorbed by calorimeter, tharmameter and stirrer during the measurement af heat change is called calorimeter constant. Glass is a material with low thermal conductivity, for such materials calorimeter constant for that partis found which is in direct contact with reaction mixture, Ithias been observed that when calorimeter is made up of low thermal conductivity material, maximum heat is absoreed by area in direct contact with liquid. In order to determine the calorimeter constant, specified volume of hot water at particular temperature is mixed with specified volume of water contained in the calorimeter at room temperature. Heat absorbed by calorimeter and cold water is equal to heat released by hot water, this is according to law of conservation of energy. So the equation can be written as AH, + AH, =—AH, AH, = Enthalpy change of calorimeter, stirrer and thermometer (calorimeter constant) AH, = Enthalpy change of cold water AH, = Enthalpy change of hot water In thermochemical measurement, mostly aqueous solutions are mixed, So water act as medium for which temperature change is due to chemical reactions taking place in solution, ‘The sum of enthalpy changes taking place as either gain or loss of energy in the calorimeter must be zero. Therefore AH, + 4H, + 4H, + 4H, =0 AH, = Enthalpy change of reaction In these reactions, the product of density and heat capacity of solutions, dC, = 4.1814 J.mL~ K~, Enthalpy of solution is defined as amount of heat released or absorbed when one mole ofa solute is dissoved in such a large quantity of solvent that there is no heat change on further dilution, () Chemical principles involved i enthalpy of neutralisation of strong acid and strong base During neutralisation reaction H” ions furnished by acid combines with OH" furnished by base combines to form H,0. This reaction is always exothermic ast involves bond formation between H’ and OH. Enthalpy of neutralisation is defined as amount of heat released when 1 mole H' ions combines with 1 mole of OH-and forms water H'(aq) + Haq) $H,0(). 4,4 aH is enthalpy of neutralisation. If both the acid and base undergoing neutralisation reaction are strong, then 57 ki of heat is released forthe formation of 1 mole of H,O. So A,,,,H for strong acid and base is 87 ki mot ve Ifany one of the acid or base is weak orifboth of thom are weak, then some amount of heat releasedis used for ionisation of the acid or base or both of them and heat released is less than 57 kJ mat’ {lll) Chemical principles involved In preparation of lyophilic and lyophobic sols A colloidal solution is a heterogeneous system in which one phase (dispersed phase) is dispersed as very fine particles in another system (dispersion medium). Colloidal particles are so small that they remain ‘suspended in medium. Generally, size of colloidal particles ranges from 11000 nm. A colloidal system having solid and liquid as dispersed phase and dispersion medium respectively are called sol. Based on the nature of interaction between dispersed phase and dispersion medium, there are two type of colloidal sol First is lyophilic sol also known as liquid loving sol and second is Iyophobic sol means liquid hating sol. Corporate Oca : Aakash Tower, 8, Pusa Road, New Delhi-110005, Phone : 011-47623456NET. Principles Related to Practical Chemistry 25 Lyophilc sol can be prepared by mixing the two phases together. Example of lyophilic sol are Egg albumin, starch and gum. Lyophabic sol cannot be prepared directly by mixing. They can only be prepared by special methods. Examples of lyophobic sols are freshly prepared ferric hydroxide, aluminium hydroxide, arsenic ‘sulphide etc. Lyophilic sols are more stable than Iyophobic sols. Lyophilic sols are also called reversible sols because if dispersed phase and dispersion medium has separated, the sol can be reconstituted simply by mixing. This is not the case with Iyophobic sol, so Iyophobic sol are called irreversible sol. Therefore, lyophobic sol need stabilising agents for their preservation. Two factors responsible for the stability of sol are ‘charge and solvation ofthe colloidal particles by the solvent. Lyophilic sols are stabilized due to solvation of colloidal particles by dispersion medium while stability of Iyophobie sol is due to charge on colloidal particles. The charge on the colloidal particles prevents coagulation ‘of colloidal particles and helps them to remain in medium. The charges can be negative or positive. Starch ‘and arsenious sulphide are negatively charged sol. Addition of FeCl, to excess of hot water leads to formation ‘of positively charge sol while negatively charged sol of hydrated ferric oxide is formed when ferric chloride Is added to NaOH solution, (WV) Chemical principles involved in ki at room temperature, jc study of the reaction of iodide ns with hydrogen peroxide ‘The reaction between hydrogen peroxide and iodide ion in acidic medium can be represented as: 2Haq) +H,0, (I) + 2H (aq) — |(9) + 2H,0() Ir has been oxidised to |, so the above reaction shows oxidising nature of H,0,-On addition of calculated ‘amount of sodium thiosuiphate in presence of starch solution, the released |, reacts with thiosulphate and is reduced back t I, til all the thiosuilphate ions are oxidised to tetrathionate ions. 1b{g) + 28,03 (aq) —> $,0%-(aq) + 2 (aq) \When all he thiosulphate ions are consumed, the concentration of Iodine released in the reaction of H,O, with increases rapid to a point where login forms intense blue complex wit starch, The time required to ‘consume a fixed amount of thiosulphate can be reproduced. As the time for the appearance of coloris noted, the reaction is also referred as clock reaction. EXERCISE 1, The group reagent for the test of alcohols is (1) Cericammonium nitrate (2) Schiffs reagent 3) Hinsberg’s reagent (4) Bromine water 2. The following two compounds | and Il can be distinguished by using reagent on 0 coon Ho. ” door (@) aq.NaHco, (©) Neutral FeCl, () Bue timus soliton (@) HeuznCI, anhydrous (1) fa)or(c) (2) (b)or(d) (3) (d)or(a) @) (c)or(a) Corporate Office : Aakash Tower, 8, Pusa Road, Now Delhi-110005, Phone : 011-4762348626 Principles Related to Practical Chemistry NEET 3. Which of the following compound will not react with | OH"? ° ° c-cH, a H,-cH,-cHO 8 (4) CH,-cHO 4. Which ofthe fotiowing will not give positive test with CHCI/KOH? (1) CH,-CH,-NH-CH, @) CH,-CH,-CH,—NH, he, oH, e (@) cHy-cH-NH, 5. Apositive carbylamine testis given by (1) NJN-dimethylaniine Q) 24-dimethylaniline (3) N-methylo-methylaniline 4) N-methylaniine 6. The Hinsberg's method is used for (1) Preparation of primary amines (2) Preparation of secondary amines (3) Preparation of tertiary amines (4). Separation of amine mixtures 7. Which of the following would produce effervescence with sodium bicarbonate? i sou con 0 or @ Os oH On No, 8 (4) Alofthese No, 8. Acompound is heated with zine dust and ammonium chloride followed by addition of the Tollens’ reagent. Formation of silver mirror indicates the presence of following group ° () -cHo @ 4 @) -No, @ -NH, 8. Inthe Lassaigne's test, one ofthe organic compounds gave red colour with FeCl,, Compound can be (1) Nas (@) NH,CSNH, 6) HCl (4) Nacn 410. Lassaigne's test is used in qualitative analysis to detect (1) Nitrogen @) Sulphur 8) Chlorine (@) Allofthese Corporate Office : Aakash Tower, 8, Pusa Road, Now Delhi-110005, Phone : 011-47623456NEET. Principles Related to Practical Chemistry 27 11. The compound that does not give a blue colour in Lassaigne's testis () CH,-NH, @) CH,CONH, (@)_NH,-NH, 4) CH,-NO, 412. Nitrogen containing organic compound when fused with sodium metal forms: (1). Nano, (2) Nac (3) NaNH, (@) Naco, 18. The sodium fusion extract of an organic compound on acidification with acetic acid and addition of lead acetate solution gives a black precipitate. The organic compound contains (1) Nitrogen (2) Halogen (3) Sulphur (4) Phosphorus 14, Match the compounds given in colurnn - | withthe reagents (which can distinguish the compounds) given in column = Il Column-t ‘Column-tl (A) [CH=-H CH C-CH, [(P) | Totans’ reagent 3 3 L uw (| NO: ocr (@ | wNaoH yw 0 jlo e (9) | Lucas reagent i i (CH,-CH-CH,, CH.-C-CH, 0 a (©) [CH=CH C-H CH=C-H 5) | Neutral Fecls 3 ° I 1 Choose the correct code (1) (A), (B)- (8). (©) -(9, (0) - (@) 2) (A)-(P).(B)- (a) (C)- (9. (0) (8) @)_ (A) (6). (8) (@). (©) - (9, (0) -() 4) (A)-(4). 8)- (0). (C)- (8). (0)-(0 15. Observe the following compound and select +ve and -ve test respectively. () NaHCO, v0. )NaHeO, OL. —{i2aone jwzaowe (ii) Lucas reagent LU) Lucas reagent, () tee @ +45 @ -+- () --+ Corporate Office : Aakash Tower, 8, Pusa Road, Now Delhi-110005, Phone : 011-4762348628 Principles Related to Practical Chemistry NEET 16. Which ofthe following amine does not react with Hinsberg's reagent? (1) CH,CHNH, (2) (CH,CH),.NH (8) (CHCH)N @) Allof these 17. Lassaigne's test for the detection of nitrogen wil alin the case of a 10 ©pweom 2 Seeman, oN «© (Owe, 18. Anorganic compound with 68.9% of C and 4.92% of H, is aromatic and gives CO, with NaHCO,.. The organic compound is oH “ee a or on @ Goon °® @ HAWK, 8 Goon 19. Which ofthe folowing reagents may be used to distinguish between phenol and benzoic acid? (1). Aqueous NCH (2) Tallens'reagent (8) Hinsberg's reagent (4) Neutral FeCl, 20, Among the following the one that gives postive lodoform test upon reaction with |, and NaOH is (1) CH,CH,CH(OH)CH,CH, (2) C\H,CH,CH,OH @) ‘CH,-eH-cHy (8) PhCH(OHCH, 44-08 21. Inconversion of 2-butanone to propanoic acid which reagent is used. (1) DIBAL-HIH,O (2) Fehling’s reagent (8) NaOH,1JH® (@) Tollens' reagent 22, Silver mirror testis given by which one of the following compounds? (1), Acetaldenyde (2) Acetone (8) 2-Butanone (4) Benzophenone 23. On heating an aliphatic primary amine with chloroform and ethanolic potassium hydroxide, the organic ‘compound formed is (1) analkanol @) anakanediol (3) an alkyl cyanide (4) an alkyl isocyanide 24. lodoform can be prepared from all except (1) Ethyl methyl ketone @ Isopropylalcoho! (3) 3-Methy-2-butanone (@)_Isobuty! alcoho! 25, The formula mass of Mohr's salt is 392. The iron present in itis oxidised by KMnO, in acidic medium. The equivalent mass of Mohs salt is: (1) 392, @ 316 @) 278 @) 186 Corporate Office : Aakash Tower, 8, Pusa Road, Now Delhi-110005, Phone : 011-47623456NEET. Principles Related to Practical Chemistry 29 28. How many moles of acidfied FeSO, can be completely oxidised by one mole of KMnO,? ) 10 @5 @. 2 27. Whats the strength in g per lire of solution of sulphuric acid, 12 mi of which neutralise 15 ml of Ni0 sodium hycroxide solution? (1) 3.218 @ 289 @) 289 (@) 6.125 28. 25 ml of N/10 caustic soda solution exactly neutralises 20 mL of an acid solution containing 7.875 g of acid per lite. The equivalent mass of the acid will be 2 @ (3) 6 @) 91 29. Asample of Na,CO,_H,O weighing 0.62 gis added to 100 mL of 0.1 N sulphuric acd. The resting solution be (At mass H = 1, C= 12, 0= 16, Na=23, S= 32) (1) Weakly acidic (2) Basic (@) Neutral (4) Strongly acidic 30, How many grams of NaHCO, are required to neutralise 1 mL of 0.0902 N an acid? (1) 84x 1029 @ 151079 @) 758% 109 () 107x109 31. 1 mol H,SO, will exacly neutralise @) 2mole otammonia (&) 1 molofBa(OH), (c) 0.5molofBa(OH), (@) 2mol of KOH (1) (@only (2) (@)and(b)only ® (@)and (cy only (8) (2), (o)and (6) only 32. How many moles of MnO; ions willreact with 1 mole of ferrous oxalate in acidic medium? “ @ ) ® 33, KNInO, reacts with oxalic acid according o the equation, 2MnO; + 5C,02 + 16H" -» 2Mn#* + 10C0, + 8H,O Hero, 20 mL of 0.1 MKMnO, is equivalent to: (1) 120ml of 025MH,C,0, @) 150mL0f0.1MH,C,0, (2) 5omLof0.1MH,C.0, (@) 50 mi of 0.2MH,C,0, 34, Inan oxidation-reduction, MnO; ion is converted to Mn, whatis the number of equivalents of KMnO, (mol. wt.= 168) present in 250 mL of 0.04 M KMnO, solution? (1) 002 @) 0.05 @) 0.04 (@) 007 Corporate Office : cash Tower, 8, Pusa Road, New Delhi-110005, Phone : 011-47623456