(APUR CLASSES _ORG, BASIC/ PURIFICAITS B.S. (PG. IT 4. What Is the criteria of determining purity of an organic compound? A Ana Neing point, boiling point and refractive indox are generally used as the criteria of purly Of 20 rgante compound. This s because each pure compound possesses & distinct set of physical properti (es it from other compounds 2, Name the different methods used for the purification of organic compounds A eae ivost common methods used for the purification of organic compounds are : (i) Crystallization (i) Sublimation (ii) Distillation (iv) Differential extraction (v) Chromatography. ‘3, What is the principle of obtaining the pure organic compound and the impurities in a ¢ in the solubilities of the compound an A. CRYSTALLIZATION: is based on the differencs Suitable solvent. The impure compound is dissolved in a solvent in which itis sparingly soluble at room temperature but appreciably soluble at higher temperature. The solution is concentrated to get nearly a saturated solution, On cooling, the pure substance crystallizes out and is removed by filtration, 4. Describe the method, which can be used to separate two compounds with different solubilities in a solvent table solvent. he impurities ina Wved in a solvent in which it is sparingly fe solution is concentrated to es out and is removed by x. A, Crystallization method is used. The impure compound is dissoh luble at higher temperature. The soluble at room temperature but appreciably sol get nearly a saturated solution. On cooling, the pure substance crystallize filtration. +t be satisfied by a suitable solvent in the recrystallization method? 5, What conditions mus! A. A suitable solvent is one which fulfils the following conditions: {in the form of crystals on {i) Itdissolves the substances on heating and readily allows it to separate out cooling. (ii) teither does not dissolve the impurities at all or dissolves them to a very small extent. {iii) It does not react chemically with the substance. 6. How will you separate sugar from a mixture of sugar and common salt? ‘. Sugar mixed with common salt can be separated by using ethy! alcohol as a solvent. Sugar dissolves in ethyl alcohol but common salt does not. 7. Explain the process of sublimation with example. weap inethod is used to purify those solids which sublime readily and contain non-volatie impurities. For qrampte, naphthalene on heating is converted to vapours without passing through the intervening liquid State. The vapours on cooling yield crystals of the pure naphthalene. 4. Name a method used for separating a mixture of iodine and sodium chloride, thloride because iodine sublime readily. A. Sublimation is used to separate iodine and sodium cl 9" How will you separate the camphor from mixture of urea and camphor ? Bee wixture contains a solid which sublime readily (camphor) and non-sublimable impurities (urea). So, sublimation is used to separate the components of this mixture, to.avoiimture contains calcium sulphate and camphor. Name a suitable method of separation of the ‘components of this mixture. ‘A. Gamphor is sublimable while calcium sulphate is non-sublimable. Therefore, sublimation technique is used for the separation of these two from the mixture. 41.Suggest a suitable technique of separating naphthalene fro kerosene present in a mixture. A. Naphthalene is high sublimable compound. Therefore, ‘sublimation is used for separating naphthalene from kerosene. 42.What are the esser A. The essential con pressure. a 43. What is the principle of Distillation? ‘This important method is used to separate to boil. that its vapour pressure should be equal to the atomospheric intial conditions fora liquid dition for a liquid to boi A. DISTILLATION: ant F Volatile liquids from non-volatile impurities beh ng points. d difference in their boiling 7 are cooled an itures. The vapours 7 8 Peatferent temperatures. Te VAP er areas Liquids having sufficient Liquids having different the liquids so formed are col separated b’ distillation. . 1a aepe re tnethod is most appropriate in the separation of ether A. Distillation is used to separate the ether from Jr example- 45.When do we use fractional distillation Girerences ‘im polling points of differ Pe the fractional distillation is used if the mixture are passed through @ small. In this technique, the vapours of aliquid mee the mouth of the round bottom TAT int condonse 1 higher boring, fining of petroleum. he liquid with Vapours of ie aint This is used in the fe ith lower boiling po! as.exetain Mie principle of steam distillation: boiling points vaporize lected separately. chloroform (D.P. 334K) (b.p. 308K) from toluene (P-P- 383 K)? rent liquid of a mixture Is Very ronatina column fited over id parison to the vapours of HaulKAPUR CLASSES ORG, BASIC/ PURIFICAITON /Ni G.S.KAPUR (PG. IIT-D) A. This technique is applied to substances which are steam volatile and are immiscible with water. In steam distillation, steam from a steam generator is passed through a heated flask containing the liquid to be distilled. The mixture of steam and the volatile organic compound is condensed and collected. The compound is later separated from water using a separating funnel. In steam distillation, the liquid boils when the sum of vapour pressure due to the organic liquid (Ps) and that due to water (P:) becomes equal to the atmospheric pressure (p). i. p= Pi+ Po. Aniline is separated by this technique. 17,How would you separate the aniline (CcHsNH,) from urea 7 A. Aniline is steam volatile and is sparingly soluble in water, while urea is non-volatile. Therefore, steam distillation is used. 18.How are high-boiling liquids, or liquids which decompose at or below their normal boiling points, distilled OR what is the principle of distillation under reduced pressure? A. DISTILLATION UNDER REDUCED PRESSURE: This method is used to purify liquids having very high boiling points and those which decompose at or below their boiling points. Such liquids are made to boil at a temperature lower than their normal boiling points by reducing the Pressure on their surface. A liquid boils at a temperature at which its vapour pressure is equal to the external pressure. The Pressure is reduced with the help of a water pump or vacuum pump. Glycerol can be separated by using this technique, 19.Explain the technique of differential extraction giving an example. A. DIFFERENTIAL EXTRACTION : When an organic compound Is present in an aqueous medium. It is Separated by shaking it with an organic solvent in which it is more soluble than in water. The organic folvent andthe aqueous solution should be immiscible with each other so that they form two distinct ‘The organic solvent is later removed by distillation or by evaporation to get back the compound. Differential extraction is carried out in a separating funnel. For example, benzoic acid can be extracted from a water solution using benzene. 20.What is the basic principle of chromatography ? ‘A. The method is based on the differential adsorption of the various components in a mixture on a suitable adsorbent by using suitable solvent known as eluent. 21.Describe the method of column chromatography. A. Chromatography is based on the differential adsorption of different compounds present in the mixture on a suitable adsorbent, e.g. alumina, silica gel and so on. In column chromatography, a suitable adsorbent is packed in a column to act as a stationary phase. The mixture is dissolved in a suitable solvent to act as a mobile phase. The solution is poured on the top of the column, Different solutes are adsorbed in different parts of the adsorbent column. They are then eluted out by @ suitable solvent. The weakly adsorbed compound willbe elutd first and the one that i strongly adsorbed later. : 22.Name the adsorbent used in colurn chromatography. A. The adsorbent used in the column chromatography is a slurry of solid alumina (Al,Os). 23.What do you understand by the stationary phase and the moving phase in paper chromatography ? ‘A. Chromatography paper contains water trapped in it, acts as the stationary phase. The solvent which rises up the paper by capillary action and flows over the spot act as a mobile or moving phase. 24.Explain the principle of paper chromatography. A. Paper chromatography is type of partition chromatography which is based on continuous differential partitioning of components of a mixture between stationary and mobile phase: 25.Name three different types of chromatography ? ‘A. The different types of chromatography are: (i) Column chromatography (ii) Paper chromatography (iil) Thin layer chromatography (TLC 26.What are the advantages of using the chromatography method over other methods of separation ? ‘A. Advantages of using chromatography oves other methods of separation are as follows: (i It is used to ‘separate the complex mixture of substances. (ii) it is also used in biology to separate the plant pigments. (iii) t is more accurate and efficient. _ i 27.Name the method to separate the amino acids. Name the substance which is used to detect the amino acid. A, Thin layer chromatography is used to detect and separate the ar solution is used to detect the amino acids. 7 28.The Ry values of A and B in a mixture determined by TLC in a solvent mixture are DGS sve ® 42 respectively. If the mixture is separated by the column chromatography using the same solvent ‘a mobile phase, which of the two components, A or B, will elute fi . A. The relative adsorption of each component of the mixture is expressed in terms of ts retention factor (Ra Distance moved by the substance from base line / Distance moved by the solv 10 acids, The substance ninhydrin wvMi Ee ORG. BASIC/ PURIFIGAITON /N3 G.S.KAPUR (PG. IIT-D) ue of Ais more than R value of B, component & is adsorbed or revsines Moke the plate. as Ral of Ais ore har jaw nth clurn slowly using the Sang Soh ce 1h sulptance (component A) is retained more near the top and the less adsorb substance [Component 8) elute first from the column. 2aWnich method is most appropriate in the separat plants (ii) Petroleum into useful fractions. 1 {y Fractional distiition (i) Steam distillation (Ii) Fractional distillation, '30.What is fractional crystallization ? EL 20.na is aystallization is a process used to separate the organic solids which have very small difference in their solubilities in a given solvent. QUALITATIVE ANALYSIS. halogen, oxygen and phosphorus in addition to carbon and KAPUR CLASSES ion of (i) methanol and propanone (ji) Essential oils in Organic compounds contains nitrogen, sulphur, hydrogen. 4. How will you qualitatively detect the presence of carbon and hy relevant equations. asa satiydrogen are detected by strongly heating @ mixture of the organic compound and cupric cate. ‘The carbon present is oxidised to carbon dioxide (tested by lime water) and hydrogen to water (tested by anhydrous CuSO.). Ct 2CuO——> CO,+2CU — COz+ Ca(OH): —> CaCOs (White ppt.) + H:0 2H+CuO——> H;0+Cu _4H,0 + CuSO,(white}—>CuSO.5H20 (blue) 2. Discuss the chemistry of Lassaigne's test. X. Nitrogen, sulphur and halogens in the organic compounds are detected by Lassaigne’s test. These Glements are covalently bonded in organic compounds and have to be first converted into the ionic form, This is done by the fusion of an organic compound with sodium metal. In his way sodium cyanide, sodium sulphide and sodium halides are formed. [Organic compound containing C, H, O, N,$ halogens] +Sodium——> | NaCN + NaxS + NaX (X= Cl, Br, XI} 3. Why is an organic compound fused with sodium for testing nitrogen, sulphur and phosphorus ? ‘A. The organic compound is fused with sodium which converts these elements from their covalent forms into the ionic form. Na+C+N———> NacN 2Na+S——> NaS 4. Write the chemical equations involved in the detection of nitrogen present in an organic compound. ‘A. We detect nitrogen in the organic compound as NaCN. The reactions involved in this test are as follows: GNaCN + FeSOx-> Nax[Fe(CN)d (Sodium ferrocyanide) + NasSOx ‘3Nas{Fe(CN)s] + 2Fex(SO,)s —> Fea[Fe(CN}e]s (Prussian blue)+ 6Na2SOx '5, Discuss the principle of estimation of sulphur an organic compound, ‘A. We detect the sulphur in the organic compound as NaS. Lassaigne’s solution is acidified with acetic acid and lead acetate solution is added to it. A black precipitate of lead sulphide indicates the presence of sulphur. w NazS + Pb (CHsCOO)2 ———-> PbS (Black ppt.) + 2CHsCOONa ‘Second test for sulphur is sodium nitroprusside test, with which the sodium fusion extract gives a violet colour. Nas + Nao [Fe(CN)s(NO)] —> NaddFe(CN)s(NOS)] sodium nitroprusside violet colour 6. Why jis it necessary to use acetic acid and not sulphuric acid for acidification of sodium extract for testing sulphur by lead acetate test ? A. We use sulphuric acid for acidificiton, then on adding lead acetate, lead sulphate will precipitate Huidition of aveti¢ acid for acidification also increases the precipitation of PbS due to common ion eet, Tet neh astan would you draw ifthe Lassaigne’s extract gives a blood red colour with FeCl? Write the relevant chemical equations. , |A, Blood red coloration with FeCl indicates the presence of sulphur and niregen together Compound. Sodium thiocyanate is formed during fusion due to insufficient sostum. SNUSCN + FeCl, —--> 3NACI + Fe(SCN)s Ferric thiocyanate (blood red colour) i in an organic compound. 7 jscuss the principle of estimation of halogens in an organic corpse cy and NasS, famY- \ydrogen in an organic compound? Give all in organic Now add 8. A. A portion of the Na extract is boiled with conc. ‘AgNO; solution followed by NH.OH. NaX + AgNO -——> AgX + NaNOs. ‘AgX: if white ppt soluble in NH,OH indicates Cr if yellow ppt sparingly soluble in NHAOM ro jel insoluble in NH.OH indicates 7 9. Why n ne acid ‘duded to sodium extract before adding Gait sree oF es D. Witte acid ts added to sodium extract to decompoer 62 hydrogen cyanide and hydrogen sulphide, resPerive'Y” NaCN + HNO: ——> NaNO> + HCNT sess 40.Will CCl give white precipitate es Br a er eating rasunpniae (i presen Jon for your answer. G.S.KAPUR (PG. IIT-D) 'd which cannot give free med. KAPUR CLASSES. ORG, BASIC/ PURIFICAITON /N4. ‘A. No precipitate will be formed. Tetrachloromethane is a covalent compoun chloride CI~ions in solution to react with Aq" ions. Therefore, no precipitate Is £0 CClx+ AGNOs > No white precipitate 41.Discuss the principle of estimation of phosphorus pres ‘A. In the test for phosphorus, the compound is heated with phosphate which gives a yellow precipitate with nitri A yellow precipitate of ammonium phosphomolybda organic compound. 5Na;0; + 2P ——> 2NasPOx + 2Na,O Na,PO, + 3HNO) ~> HPO« HsPO, + 12(NHa):MOOs + 21HNOs > (NH,)sPO«, 12Mo0; (Yellow ppt.) + 21NHd QUANTITATIVE ANALYSIS 4. How would you quantitatively determine the presence of carbon and hyd A.A known mass of the organic compound is heated in a current of di presence of CuO till all the carbon is oxidised to CO, and all the hydrogen is Let the mass of organic compound De m pg. mass of water and carbon dioxide produced be m, and m, g respectivel: 12~ 1m, «100 +3NaNOs NO} + 12H,0 gen in an organic compound? roger gn vee tom CO2) I” the ised to HO. Percentage of carbon= Percentage of hyarogen 1, 2. Give an expression for the estimation of (a) halogen present (b) S(c)P in an organic compound by Carius method A Let the mass of orgarnic ‘compound taken =m «= Mass of Agx formed = m, & 1 mol of Agx contains 1 mol of 7 Mass of halogen in mg of Agx atomic mass of X =m, molecular mass of AZ Percentage of halogen. atomic mass of Xx Mm, x10O molecular mass of Agot =m Let the mass of organic compound taken = m g and the mass of barium sulphate formed = m,g 32xm, x100 233xm 62m, x100 222.xm where. 222 u is the molar mass of Mg,P,07. Tr. the mass of organic compound taken, m,. the mass of Mg,P,0, formed and 62, the mass of two phosphorus atoms present in the compound Mg,P,0;. In what form do we estimate nitrogen in Dumas method? ’, Dumas method: The nitrogen containing organic compound, wh it ide i Etmosphere of carbon dioxide, yields free nitrogen ine heated With Copper oxide in an ‘Addition to carbon dioxide and water. GiHNe + (2x + yl2) CUO —> xGOr + yi2H20 + 2/2Np + (2x4yl2] \Cu The mixture of gases so produced is collected over an at aN i absorbs carbon dioxide. Nitrogen is collected in the upper part ofthe ube ones yaroxiae WHICH Hence in the Dumas method, we estimate the nit Ginvogen gas at STP. 'rogen present in the organic compound as V mL of Percentage of sulphur: Percentage of phosphorus = pe 28xVx100 Percentage of nitrogen = 22400xmAPUR POTD) KAPUR CLASSES ORG, DASIC/ PURI IGAIION (M6 4, What Is the role of aquooun notution of potassium hydro ise me Darna met A. Tho mixture of gains produced In Du arto ti 1b per art on ne 1 dioxide mothod contain hydroxide to absorbs eat . Give chemistry of Kjoldaht Kietdaht's motto thn compe Nitrogen in the compound gots ¢ The t oa ath epee ot wei nyciron 1 is absorbed in an excons of standard xolution of wuiphuate wet, He aman dotormined by oxt saa pene! woqiunied 190 OACMO ing a gat Wray catty cnet spate ae at attr the aborpuon of amenla Wy Teri standard alkall solution. Th ference betwen the initial amount of wed taken ae action gives the amount of acid roactod with ammonia, 2NaON Organic compound + H,80.—-> (NHy}8O4 > NayfhOx + 2NHs # 2440 2NHy + HsSO4——> (NH) 80+ The mi ompound taken» m gram olanty. M4 takont = Vm nlarity M uned for tration of excess of Hy8O«# Vi Mb . In What form is nitrogen estimated in the Kjoldaht's method? “In Kjeldaht's method, wo estimate nitrogen as ammonta ga. For which type of compounds, Kjoldaht's mothod is not applicable? Kjeldaht's method is not applicable to compounds containing quinoline or DNA and RNA, and the compounds containing nitro and dlazo(-NeN- can not be changed into ammonium sulphato 8, A welding fuel gas contains carbon and hydrogen only. Burning a small sample of iin oxygen gives 3:38 carbon dioxide, 0.690 «of wator and! no othor products. A volume of 10.0 L. (measured at STP) of this welding gas is found to weigh 11.6 g. Calculate molar mass, EF and MF of the ga: 9. An organic acid contains C,H and O, 4.4.21 mg sample of acid is completely burned. It gives 6.21 mg of carbon dioxide and 2.64 mg of water. What is the mass percontage of each element in the acid. 40.An organic compound contains 69% carbon and 4.8% liydrogen, the remainder being oxygen. Calculate ‘the masses of carbon dioxide and water produced when 0.20 ¢ of this substance Is subjected to complete combustion. 11.0n heating 0.1248 g of the organic substance with HNO; and BaCh, we get 0.1292 g of BaSOx. Find the percentage of sulphur in the organic substance. 42.In the estimation of sulphur by Carius method, 0.468 g of an organic sulphur compound afforded 0.668 g of barium sulphate. Find out the percentage of sulphur in the given compound. 43.‘In sulphur estimation, 0.167 g of an organic compound gave 0.4813 g of barium sulphate. What is the percentage of sulphur in the compound? 44.An organic substance weighing 0.2388 g containing chlorine was heated with strong HNOs and AgNOs in a ‘sealed tube. The weight of dry AgC! obtained was 0.3046 g. Calculate the percentage of chlorine in the ated sulphuric 46rd ite te fronted with 0 oni sulphate >e ated ammonia Gass cod 18 nor mnonia prod nitrogen in the ring, like pyridine or group as this nitrogen pape substance. 45. 0.3780 g of an organic chloro compound gave 0.5740 g of silver chloride in Carius estimation. Calculate the percentage of cltlorine present in the compound, 46.In Carius method of estimation of halogen, 0.16 g of an organic compound gave 0.12 g of AgBr. Find the percentage of bromine in the compound. 47Heating 0.751 g of an organic compound containing phosphorus, with conc. HNOs in the Carius tube followed by reaction with magnesia mixture gives MgNH4POx, this on ignition left a residue of Mg:P:07 weighing 1.2646 ,ealeulate the percentage of phosphors in Dorgane compound, 48.In.a Dumas method for estimation of nitrogen, 0.3 g of an organic cor Collected at 300 K. temperature and 716 mm pressure, eppeen eve oO nt ot eionen Calculate the percentage composition of nitrogon in the compound. (Aqueou 7 18.01€ got an organic compound on Kjetdahlising produced enough aumvon to be neutralized by 30 cn of 0.126 M H,S0s. Calculate the percentage of nitrogen in the organic compound, 20.During estimation of nitrogen present in an organic compound by Kjeldahl’ Pond Sorihe compound in Keldahr's estimation of nronon, recared 40 et ai #801 Find out the percentage of nitrogen in the compound, 21.A sample of 0.60 g of an organic compound was treated according to Kjoldaht’ Ae ope oer ttre a ee Tema for neutralisation. Find the percentage composition of nitrogen in the compound. 22, Give three points of differences botween inductive effect and resonance effect. A.__ Inductive effect osonance e TH Use o-electrons {a) Use W- electrons or lone pair of electrons {ii) Move up to 3-carbon atoms (b) All along the length of conjugated system i) Slightly displaced electrons _(c) Complote transfer of electrons weve a