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Geography

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Ambuj Singh
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Page tof 19 (CPP - SANKALP_POC-PHLVIL CPP PRACTICAL ORGANIC CHEMISTRY INTRODUCTION The identification of organic compounds differs from that of the inorganic salts in the respect that inorganic salt analysis is very systematic while there is no such systematic scheme for the analysis of organic ‘compounds. However, the following operations are generally useful forthe identification of unknown organic ‘compounds: (0) Protiminary tests (2) Physical state (0) Colour (©) Odour (6) Ignition test (e) Saturation test (6) Solubility (ll) Detection of elements. (li) Detection of functional groups (iv) Determination of metting or boling point and. (v) Preparation of derivatives (if any) QUALITATIVE ANALYSIS IN ORGANIC CHEMISTRY DETECTION OF ELEMENTS Organic compounds consist mainly of carbon, hydrogen and oxygen. Hence, detection of these elements are not necessary. In addition to the above elements, organic compounds often contain nitrogen, halogens, and sulphur. Hence identification of organic compounds means detection of nitrogen, halogens and sulphur only. (a) Lassaigne’s test (for nitrogen, sulphur and halogens) Nitrogen, sulphur and halogens are generally detected by this test. Cut a small piece of sodium metal with a knife, press it between the folds of a filter paper to wipe out the kerosene oil and transfer to a fusion tube. Add a litle of the organic compound. Heat the fusion tube first gently and then strongly to dull-red. Continue heating for some time and then immerse the hot tube into 15-20 mi distilled water. The tube ‘must be broken into pieces. Grind the whole mass thoroughly and then filter. Use this fiterate for testing the presence of nitrogen, sulphur and halogens in the organic compound. ‘The following reactions occur when sodium is fused with an organic compound. Carbon and nitrogen from the organic compound react with sodium to form sodium cyanide. Na+C+N——> NaCN Halogen and sulphur present in the organic compound react with sodium to form sodium halide and ‘sodium sulphide respectively. Na +X —> NaX (X= Cl, Br, 1) 2Na +S ——> NaS When nitrogen and sulphur both are present, sodium thiocyanate is formed, Na+C+N+S —> NaCNs. ‘These substances being soluble are extracted with water and identified. (0) For Nitrogen: The following reactions take place when the filtrate is treated first with ferrous sulphate solution, then with ferric chloride and finally with excess of dilute sulphuric acid, 2Na + 2H,O ——> 2NaOH + He FeSO, +2NaOH ——> Fe(OH), + Na:SO, Fe(OH), + 2NaCN ——> Fe(CN)2 + 2NaOH THITIEE LCS Huse, Serapriga Vihar ear Hx Ras Tes Terminal New Dei 16, FR 6515990, OB6SIO2, GBS, Pax: SII Page 20119 (CPP -SANKALP._POC-PH.VI Fe(CNp + 4NaCN ——> Na[Fe(CNd Sodium ferrocyanide 3Na\[Fe(CN] + 4FeCl, ——> Fes[Fe(CNh + 12NaCI ferricferrocyanide (prussian blue) {An intense blue colouration is produced due tothe formation of Prussian blue Hydrazine (NH.NH), Benzene diazonium salts do not give Lassiagne's test of nitrogen (i) For sulphur (a) NaS + Nas{Fe(CN).NO] —> Nae[Fe(CN):NOS] sodium sulpho nitroprusside (violet colour) (b) Na:S + (CHsCOO):Pb ——» PDSL + 2CH;COONa lead sulphide (black) For halogens: (@) NaCN + HNO, —> NaNO, + HCN NaCl + AgNO, —» AgCll + NaNO, ‘Curdy wiite ppt. soluble in alkali NaBr + AgNO; —> Agr! + NaNO, pale yellow / off write pot. partially soluble in alkali Nal + AgNO; ——> AglL + NaNO; bright yellow ppt. insoluble in alka Before adding AgNO, solution, the fitrate is boiled with conc. HNO to decompose NaCN present. Otherwise, a white precipitate wil be formed even in absence of halogen. In this test acidity a little sodium extract with dil. HNO or dil. HSO, and add CHCl, or CCl, and excess of chlorine water. If organic layer becomes yellow or brown, bromine is present and if Violet, iodine is present. Chlorine is not detected by this test. CS; can also be used. 2NaBr + Cl, —> 2NaC! + Bre CHCl, + Br2 —> Yellow or brown layer 2Nal + Cly —> 2NaCl + I CHCl, +p —> Violet layer (lv) For nitrogen and sulphur: (when both are present) (a) C+N+S —™ yNaCNS 3NaCNS + FeCl, ——> Fe(CNS)s + 3NaCl ferric thiocyanate (red colour) (b) NaCNS + HCl —+ HCNS + Naci thiocyanic acid 4HCNS + Co(NOs)2 —» HeICo(SCN).] + 2HNOS ccobalti-thiocyanic acid (blue) Biolstein’s test Many organic compounds containing halogens impart a green colour to the Bunsen flame when heated on a Copper wire. The green colour is developed due to the formation of volatile halides of copper. However, urea (H:NCONH,) and thiourea (H:NCSNH.) do not contain halogens even then they given Biclstein’s test. Fluorine is unable to respond this test as it is volatil DETECTION OF FUNCTIONAL GROUPS Detection of functional groups is an important step in the analysis of organic compounds. It largely depends (on the correct determination of the constituent elements. (a) Tests for carboxylic group (— COOH) (i) Litmus test: Place a small quantity of the organic compound or its aqueous solution on a piece of ‘moist blue litmus paper. Ifthe paper turns red, carboxylic group may be present. THITIEE LCS Huse, Serapriga Vihar ear Hz Raa Tes Terminal New Dei 16, FR 6515990, OBGSIO2, GSA, Pax: SII Page 30f 19 (CPP - SANKALP_POC-PHLVIL (ij Sodium Bicarbonate test: Add a small quanity of the organic compound to about '5 ml sodium bicarbonate solution taken in a test-cube. Compound dissolves with brisk effervescences. COOH + NaHCO; ——» RCOONa + H,0 + COT Take a small quantity of the organic compound and add 4-5 mi of alcohol in a test-tube. Add a few H p-Rosaniline hydrochloride Schif's reagent (colourless) ce Ks HSO:H © C) 7 + RCHO.H,SO: NHSO;H (Pink colour) (li) Fehling’s test: Mix equal volumes of Fehling's (A) and Fehling’s (B) solution in a test-tube. Add a ‘small amount of the organic compound and boll for some time. A red precipitate of Cu,0 is obtained, RCHO + 2Cu0 ——+ RCOOH + Cu,04 Red (ii) Tollen’s test: Take about 5 mi of Tollen's reagent in a test-tube. Add a small quantity of the organic ‘compound and heat on a water bath. A shining silver mirror is formed on inner walls of the test-tube. CHO + 2[Ag(NHs),JOH + HO ——> RCOONH, + NH +2NH.OH + 2AgL ‘Tollen's reagent Silver mirror (iv) Benedict's test: Take 4-5 mi of Benedict's reagent in a test-tube. Add a few mi of the organic ‘compound (or a solution prepared in alcohol or water). Heat the mixture to boiling. Formation of red precipitate indicates the presence of aldehydes. RCHO + 2Cu(OH), * NaOH ——> Cu,0 + RCOO Na’ + 3H.0 (6) Tests for kotonic group ( ll (i) Ketones, unlike aldehydes, do not restore the pink colour of Schif's reagent nor do they reduce Febling’s solution or ammoniacal silver nitrate solution. However, they form crystalline precipitate with 2,4-dinitro phenylhydrazine and also with sodium bisulphite reagent. 02 NO; RL RL C= 0+ H,NHN- NO, —> (C= NHN- NO: R’ TFITIEE Td, ICES House, Seroopriga Var far Hur Rha Bus Terminal New Debi 16, Pr OS1S949, GBOSTBZ, GBSHTOD, Pax 519942 age 4ot 1 CPP. SANKALP_POC-PHAN R K An R” So.Na (Bisulphite ation compound) (li) Sodium nitroprusside test: Treat 1 mi of the organic compound with 1 ml of freshly prepared solution of sodium nitroprusside followed by excess of NaOH solution. A wine-red colour is obtained, Xe 0+ NaHSO; —> R (i) Litmus test: Place a trace of the organic compound on the moist biue litmus paper. It tus red. (li) Neutral FeCl, test: When phenols are treated with neutral ferric chloride solution, they form coloured complexes. The colour of the complex may be violet, red, blue or green. This is a characteristic reaction of compounds having enolic group. (=C-OH). All enols respond to this test (iil) Anine Dye test: Dissolve a little aniline in dilute hydrochloric acid, cool in ice-cold water and add aqueous solution of sodium nitrite dropwise. To this cold solution, add organic compound already dissolved in sodium hydroxide solution. A red or orange precipitate is obtained. NaNO, + HCl ——> HNO, + NaCl Benzeneiazonium Phenol p-hydroxy azobenzene (dye) {iv) Phthaloin test (Fluorescein test): Heat gently some organic compound and phthalic anhydride with a few mil of conc. sulphuric acid in a test-tube. Pour the heated mixture to about 50 mi of water taken in @ beaker and then add sodium hydroxide solution til it became alkaline. A beautiful pink or purple colour appears. OO". O° C=0 +H,0 | | o-t6 € Son ont 7 IN K ow 2nv0t a, a (pink or purple) (¥) Bromine water test: Take aqueous or alcoholic solution of the organic compound in a test-tube. Add excess of bromine water. A yellowish white precipitate is obtained. TFITIEE Td, ICES House, Seroopriga Var far Hur Rha Bus Terminal New Debi 16, Pr OS1S949, GBOSTBZ, GBSHTOD, Pax 519942 Page Sof 19 (CPP - SANKALP_POC-PHLVIL OH Bi + 3Br —> Phenol Br (2,4,6-tribromophenol) (vi) Ceric ammonium nitrate test: Treat a few drops of the ceric ammonium nitrate with 3-4 ml hot ‘aqueous solution of the organic compound. A green or brown precipitate is obtained (NH,),{Ce(NOs)e] + 2CcHsOH —> [Ce(NOs)s(CeHsOH),] + 2NH,NOs phenol ‘green or brown ppt. (vil) Liebermann’s test: Take a litle amount of the compound and fuse with a few crystals of NaNO» in a test-tube. Cool the test-tube and add 1 ml conc. H:SO,. A deep green colour is obtained which changes to pruple, to blue and finally, when poured into large excess of water, to red. When a lttie NaOH solution is added to the aqueous solution, the same green, purple or blue colour reappears, a s{_ on ne of Indophenol (red) Indophenol (blue) (©) Tests for alcoholic group (—OH) Alcohols may be considered as neutral compounds. They are soluble in water or dioxane. (Sodium test: Take 3-4 mi ofthe organic compound in atest-tube. Add a thin slice of sodium metal A brisk effervescence due to the evolution of hydrogen takes place. (Organic compound should be free from water) 2ROH + 2Na ——» 2RONa + H.t Ester test: Warm the given liquid with acetic acid in presence of sulphuric acid. A fragrant smell Indicates the formation of ester. ROH + CHsCOOH — 2, RCOOCH, + H,0 Alcohols give crystalline esters with 3,5-dinitrobenzoy! chloride, These esters have sharp melting points and can be used for testing a given alcohol. NO» NO: oO NO: NO; Oxidation test: Take some organic compound, 5 ml of K;Cr20; solution and 2-3 ml of conc. HzSO,, in a test-tube, Heat the test-tube after fiting a delivery tube. The distillate is passed into another test-tube containing water. Test the aqueous solution of the distilalte for aldehyde group. A positive test indicates the presence of primary alcoholic group in the given compound, RCH,OH —®> RCHO + H,0 (Corie ammonium nitrate test: Shake a few drops of ceric ammonium nitrate with ‘ml ofthe organic compound. A red colour is produced (Phenols give a green or brown colour) 2ROH + (NH,)o{Ce(NOs}s] —» [Ce(NOs).(ROH):] + 2NH.NOs Distinction between primary, secondary and tertiary alcohols TFITIEE Td, ICES House, Seroopriga Var far Hur Rha Bus Terminal New Debi 16, Pr OS1S949, GBOSTBZ, GBSHTOD, Pax 519942 Page 6 0f 19 (CPP - SANKALP_POC-PHLVIL Lucas test: Add 3-4 drops of alcohol to 2 mi of Lucas reagent (anhydrous ZnCl, + conc. HCl) in a test-tube. ‘Shake the mixture and allow to stand at room temperature. If a cloudy precipitate is obtained immediately then itis a tertiary alcohol, if obtained after 2-3 minutes then itis a secondary alcohol, while no cloudy precipitate even after long standing means itis a primary alcohol. ee @ R-OH + ZnCh => R-O ZrCkh —> R—“> RCI H [Zn(OH)Ch]- () Tosts for primary aminos(-NH,) () Carbylamine test: Heat the organic compound with alcoholic KOH and chloroform in a test-tube. A highly offensive smell is evolved due to formation of isocyanides, RNH2 + CHCl + 3KOH ——> R-N 5 C + 3KCI + 3H,0 This testis applicable to aliphatic and aromatic primary amines. (li) Dye tost: This test is applicable only for aromatic primary amines. Dissolve a small amount of the ‘organic compound in dil. HCI. Cool it in ice-cold water. Add cold solution of sodium nitrite with constant shaking and then add fi-naphthol prepared in NaOH solution. An orange-red dye is obtained. NaNO, + HCl > HNO, + NaCl oe S € Spas ino, — CV Son ano H OH ce OF Q- Ort ) Cy -naphthot (Orange-red dye) Distinction between Primary, Secondary, Territory amines () Hinsberg Test Hinsberg reagent is benzene sulfonyl! chioride 1° anines reacts with Hinsberg Rat. to form a complex which is soluble in alkali due to the presence of acidic hydrogen i moi’ \ —s i t H ary ° 2° amines reacts with Hinsberg Rgt. to form a complex which Is insoluble in alkali due to absence of acidic hydrogen (soluble in alkali) TFITIEE Td, ICES House, Seroopriga Var far Hur Rha Bus Terminal New Debi 16, Pr OS1S949, GBOSTBZ, GBSHTOD, Pax 519942 Page 7 of 19 (CPP - SANKALP_POC-PHLVIL (insoluble in alkali) 3* amines do not react with Hinsberg Rat. due to absence of replaceable hydrogen. i mon oC) ee °) I Re Nitrous Acid (HNO.) Test 1° amines on reaction with HNO» Le. NaNO. + dil. HCI produces brisk effervescences. If confirms the presence of 1° aliphatic amines. 2! amines no reaction with HNO; ie., NaNO; + dil HC! gives yellow oily drops. It is given by both 2° aliphatic and 2° aromatic amines, For 3° amines: Original solution of amine + HNO; (NaNO; + dil. HC!) ‘Shake Well No reaction indicates Formation of green or the presence of 3° brown colored salt aliphatic amines. Confirms the presence of 3° aromatic amine, Note:- 1° Aromatic amines on reaction with HNO: forms diazonium salts which on reaction with - naphthol produces red or orange-red dye. Tests for secondary amines (-NH-) Lieberman's nitroso test: Dissolve some organic compound in 3 ml of cone. HCI and then add 2-3 ml Cf water. Coo! the solution in ice-cold water and then add 3-4 ml of cold dilute NaNO> solution. A white or yellow emulsion is produced. Take 4-5 drops of the above emulsion in a test tube. Add 4-5 drops of Phenol and conc. H.SO,. A blue colour develops. Addition of water changes blue colour to red which again changes to blue on adding NaOH solution. (h) Tests for nitro group (i) Reduction test: Take a small amount of the organic compound in a test-tube, Add a few ml of conc, hydrochioric acid and one or two pieces of granulated zinc or tin. Heat the mixture gently for few minutes. Decant the clear liquid into a test-tube. Cool it in ice-cold water and then add cold dilute solution of sodium nite, Pour this cold solution into an alkaline solution of f-naphthol. An orange-red dye is obtained. This testis applicable ony to aromatic nitro compounds. Zn + 2HC] —> ZnCl. + 2[H] CCoHzNO> + 6H] —> CoHeNH, + 21,0 NaNO. + HCI —> HNO. + NaCl GaHsNHa + HNO. + HCI —> C,H.N:CI + 21,0 TFITIEE De, ICES House, Seroopriga Var far Hur Ras Bus Terminal New Debi 16, Pr OS1S949, GBOSTBZ, GOSHTOD, Pax 519942 Page 8 of 19 (CPP - SANKALP_POC-PHLVIL naphthol (Phenyl az0 B-naphithol dye) Mullikon's test: Take a small amount of the organic compound in test-ube. Add a few ml of water 0 alcohol, 1 mi of calcium chloride or ammonium chloride solution and then a pinch of zine dust. Boll the mixture for few minutes. Cool and then fier. Treat this fitrate with ammoniacal siver nirate solution. A grey or black precipitate is obtained. 2n+ 2,0 —» Zn(OH) + 21H] ‘CeHsNO2 + 4[H] ——> CeHsNHOH + H-0_ CoH:NHOH + Ag,0 —> CoHeNO + H,0 + 22g! Grey This testis also applicable for aromatic nitro compounds. Test for Carbohydrates (—) (Cone. H2S0, Test: Carbohydrates on reaction with conc. H2SO, immediately charred and the solution becomes black. It can be easily observed in lab where the wooden selves are black because of the reaction between cellulose and conc. H:SO. Molisch’s Test: An original solution of carbohydrate is mixed. with Molisch’s Reagent and itis rapidly shaken. Now addition of conc. H,SO, on the side wall of test tube produces reddish violet ring at the junction of two liquids and it confirms the presence of carbohydrates. Notes: Molisch’s Rat. is 20% solution of a-napthol in alcohol or in 10% solution in chloroform. Test for Unsaturation Unsaturated compounds (containing double or triple bonds) can be easily defected by the following two test. () Bre—Water Test Nod + watttoy et Po \ * enctbotce l | r Br (Colouress) Br Br + 28r,(H,0) > —¢—G¢— Br Br (Colouriess) (i) Baeyer's Test Baeyer's Rot —> Cold dilute KMnO, / OH” \_/ fe / oN S22 The light pink colour disappears que to formation of glycols TFITIEE Td, ICES House, Seroopriga Var far Hur Rha Bus Terminal New Debi 16, Pr OS1S949, GBOSTBZ, GBSHTOD, Pax 519942 Page 9 of 19 (CPP - SANKALP_POC-PHLVIL ‘Note: (1), Benzene and other aromatic compounds do not give above test for unsaturation despite having three double bonds. NNote:- (2) Terminal and Non-terminal alkynes can be distinguished by the following tests. jitter R—C= Cag’ R—c=c—H—| Lee sR—c=Cou'L —itt2r-> No Reaction mr R—c=c_r—_| |e, No Reaction QUANTITATIVE ELEMENTAL ANALYSIS ‘After determining the constituent elements of an organic compound, the next step is to determine their ‘amounts by quantitative methods. The methods usually involve combustion, oxidation etc. of an organic ‘compound so that they may change into such inorganic compounds as can be estimated either by volumetric or gravimetric method, ESTIMATION OF CARBON AND HYDROGEN LLiebig’s Combustion Method: A weighed amount of the compound is heated in a current of dry air free from carbon dioxide or pure oxygen till the carbon of the compound changes to CO, and hydrogen into water. Carbon dioxide and water thus formed are trapped in a suitable apparatus and weighed. C+#2Cu0 —+ CO, +2Cu 2H+ CuO —> H.0+Cu The percentage composition is then calculated. 12x100y sw and percentage of hydrogen = 2 Percentage of carbon 9° ow ESTIMATION OF NITROGEN () Duma’s Method: In this method the organic compound is heated with copper oxide strongly. Carbon, hydrogen and sulphur are oxidized to CO;, HO and SO; respectively, while nitrogen is set free ‘These gases are passed through a nitrometer containing 30% KOH solution. Carbon dioxide and sulphur dioxide are absorbed, steam condenses and nitrogen collects by the displacement of KOH solution. From the volume ofthe collected ritrogen, the percentage of nitrogen is calculated. + Cu0 > x00, + ¥H0+ ZN: + Cu GH\Ne-+ CuO O02 + LHO+ FNr+ Oi 28 Volume of N, at NIP Porcentage of Ritrogen = R400 ~ Weight of substance: 100 Kjeldahl's Method: The principle of this method is that when an organic compound containing nitrogen is heated with concentrated sulphuric acid, the nitragen is converted into ammonium sulphate, The resulting solution on treatment with excess of sodium hydroxide solution gives off ‘ammonia. Ammonia is then absorbed in excess of standard sulphuric acid. The amount of ammonia land hence the amount of ritrogen is determined by finding the amount of acid neutralized by back titration of the residual acid with a standard alkali solution. From this the percentage of nitrogen is calculated. 100 Percentage of nitrogen = Weight of nitrogen x 100 _ Peele 99°" ™ Weight of substance O14 N eV 100 Ww TFITIEE Dd, ICES House, Seroopriga Var far Hur Ras Bas Terminal New Debi 16, Pr 6515949, GBOSTBZ,GBSHTOD, Pax 519942 Page 10 of 19 (CPP - SANKALP_POC-PHL-VIL Kjeldahi’s method fails to detect nitrogen from azo compounds (-N = N-), ° t ‘Azoxy (-N=N-) , nitroso (-NO) compounds and nitrogen present in pyridine ring. ESTIMATION OF HALOGEN () Carius Method: The compound containing halogen is heated with fuming nitric acid in a sealed tube (Carus tube) in presence of silver nitrate. Carbon and hydrogen present are oxidized to carbon dioxide and water. The halogens react with silver nitrate to give the preciptate of silver halide. The Preciptate is collected, washed, dried and weighed. ie _weight 0 Molecular weight of silver halide” W_ 0 100 Percentage of halogen ESTIMATION OF SULPHUR ‘The compound is heated with fuming ritric acid. Sulphur present is oxidized to sulphuric acid, Barium chioride solution is added. The precipitate of barium sulphate is obtained. It is collected, washed, dried and weighed. *% of Sulphur Weight of BaSO, Atomic weight _of Sulphur __ 100 Molecular weight of BaSO, Weight of Organic compound CPP - SANKALP_POC-PH.VIL Platinichloride method for determining molecular weight of organic bases Organic. bases (e.g. amines) form insoluble salts known as platinichlorides when treated with hydrochloroplatinic acid [HaPtCle]. These salts are represented by the general formula B,H,PtCls, where B is one equivalent of the base. These salts on ignition leave a residue of metalic platinum. ‘The base is dissolved in HCI and a solution of platinic chloride PtCl, is added. The yellow crystalline salt that separates out is filtered, washed and dried. A known weight of the dried salt is ignited is a crucible, Calculation Let X; g of the platinichloride leave on ignition Xe g of platinum. X29 Of Pts left by X; g of the salt on ignition. 195 g (At. weight of Pt is lett by = ) arte sat on ten Molecular weight of the salt x, Ay 195 % Molecular weight of HaPICl, = 410 Equivalent weight of base B = Ba4PtCl, “H,PICl, _\% It the acidity of the base is n, then Molecular weit = |{ Xet95|-410 x2 ttm [2 sg 12 of 19 (CPP - SANKALP_POC-PHLVIL 2x weight of compound x 22400 volume of vapour given by substance at NIP 100 x K, x weight of substance ‘AT, x weight of solvent Where K;= Molal freezing point depression constant AT; = Depression in freezing point 100 x K, x weight of compound ‘AT, = weight of solvent where K, = Molal boiling point elevation constant ATi, = Elevation of balling point Molecular weight Molecular weight THITIEE LCS Huse, Serapriga Vihar ear Hx Ras Tes Terminal New Dei 16, FR 6515990, OB6SIO2, GBS, Pax: SII 1g 13 of 19 (CPP - SANKALP_POC-PHLVIL CPP PRACTICAL ORGANIC CHEMISTRY EXAMPLE 1 0.25 g of an organic compound on combustion gave 0.495 g of CO; and 0.2026 g of H,0. Calculate the percentage of carbon and hydrogen in the compound. SoLuTion Given weight ofthe substance = 0.25 g Weight of CO; formed = 0.495 g Weight of H.0 formed = 0.2025 g 44 g of CO, are formed from 12 g of carbon. 0406 formes torn 12 0485 cation 120.495 Now 0.25 g of the substance contains g carbon. 120.498 %100 440.25 Since 18 g of H.0 are formed from 2 g of hydrogen 0.2025 g H.0 are formed from 2 0.2025 g hycrogen 210.2028 ryerogen 20.2025 100 0.25%18 100 g of the substance contains =54.559 Now, 0.25 g of the substance contains 100 g of the substance contains 9% of carbon = 54.55 ° of hydrogen = 9.09 = 9.09 g hydrogen Exams 2 0.159 g of an organic compound gave 14.01 cc of nitrogen at 19°C and 719.5 mm pressure by Duma’s ‘method. Calculate % of nitrogen in the organic compound. Given: Aqueous tension of water = 11.5 mm of Hg at 19°C. SoLuTioN ‘Aqueous tension at 19°C = 11.5 mm We know, PM. PaMe 7 oT (719.5-11.5)x14.01_760xV,_at_NTP. (273+19) 273, Vp. at NTP = 708214015273 7 760x292 Now, 22400 cc of Ne at NTP weigh 28 g 28 1 oc of Neat NTP weigh 75059 708%14.01%273 4. . 28x70B%14.01x273 760292 22400760292 28708 14.01x273 22400760292 28708 x14.01x273%100 22400760 x 2920.159 0.159 g of the compound contains. 100 g of the compound contains Percentage of nitrogen = 9.6% = 9.60 g of nitrogen EXAMPLE 3 0.69 g of an organic compound after heating with concentrated sulphuric acid was distilled with excess of NaOH. Ammonia liberated was passed into 100 cc of N HCI solution. The excess of the acid noutralized 80 cc of N NaOH. Calculate the percentage of nitrogen in the compound. SowuTion 80 cc of N NaOH = 80 cc of N HCI = Volume of residual acid THITIEE LCS Huse, Serapriga Vika lear Hz Raa Tes Terminal New Dei 16, FR 6515990, OB6SIO2, BSAC, Pax: SII 1g 14 of 19 (CPP - SANKALP_POC-PHLVIL ‘Volume of acid neutralized = (100-80) co N = 20 cc of NHCI= 20 cc of N NH Now, 1000 cc N NH = 14 g of nitrogen 20.cc N NH, = 14*20 000 9 o Nitrogen 1004 14%20%100 100 g of the substance contains =eO=— Percentage of nitrogen = 40% Exampur 4 0.26 g of an organic compound on heating with fuming nitric acid and silver nitrate gi silver bromide. Calculate the percentage of bromine in the compound. sousnon Nom, Agr > Br or (108+80) g = 809 188 g of AgBr give 80 g of bromine. 031 got Ader ve 22.1031 = 0.131 tome Now, 0.26 g of the substance give 0.1319 g bromine. 100 g ofthe substance gave 91318100 59,7 Percentage of bromine = 50.7 EXAMPLE 5: 40 g of an organic compound gave 0.60 g of barium sulphate after Carius method. Find out the percentage of sulphur in the compound. SowuTion Since, BaSO; =S 2339 329 238 g of BaSO, gives 32 g of sulphur. 060918880, gies 22 «0609 sph = 0082 sani Parcentage of suprur= 2022, 100 = 0.208% EXAMPLE 6 0.167 g of the silver salt of a monobasic organic acid left on ignition 0.108 g of silver. Calculate the molecular weight of the acid. SoLuTiON Weight of Ag salt = 0.167 g and weight of Ag left = 0.108 g. 0.167 , 0.108 Equivalent weight of acid = 167 - 108 + 1 = 167 107 = 60 Molecular weight of the acid = 60 x 1 (basicity) = 60 The weight of Ag salt that would leave 108 g of silver EXAMPLE 7. Calculate the molecular weight of a monobasic base, 0.298 g of whose platinichloride left 0.0975 g of platinum on ignition. SoLuTion Weight ofthe platinichloride = 0.298 g (X;) and weight of platinum = 0.0975 g (X). 0.298 0978" 195-419_ 596-410 186 2 2 2 Molecular weight of the base = 93 « 1 (acidity) = 93 Equivalent weight of the base THITIEE LCS Huse, Serapriga Vihar ear Hx Ras Tes Terminal New Dei 16, FR 6515990, OB6SIO2, GBS, Pax: SII Page 15 of 19 (CPP - SANKALP_POC-PHLVIL EXAMPLE 8 ‘A mono acid organic base on analysis gave the following results: 0.10 g of the base gave 0.28 g of CO; and 0.075 g of water and 0.20 g of the base gave 31.32 ml Nz measured at 15°C and 760 mm, 0.30 g of the platonic chloride left on ignition 0.093 g of platinum. What is the molecular formula of the base? SoLuTion ‘The molecular formula is derived as follows (a) Calculation of % of elements 12, 0.28 n= 120.28 199 = 76.36% eof carbon = TEx EFT %100 = 76.36 2 0.075 4% of hydrogen = 2 100 = 8.33% werogen = 80.10 28 Volume of Ny at_NTPx100 % of nitrogen = 26. Volume _of Ny _at_NTP%100- nilrogen = 32400 " Weight of organic compound 2831.32 100 9 oF nitrogen = Tocog 7 13:05% Calculation of relative number of each atom c= 1638 2636; 4 = 53 28.33 and N= 19:8 =0.90 2 4 4 Calculation of simplest rato 635 7 y= 833

200, +y2H40 4 mole of C4 ives = 0.05 a mo of CO; O05x=0.08 0.05, 05 THITIEE LICE Huse, Serapriga Vika ear Hz Raa Tux Terminal New Dei 16, FR 6515990, OBGSIO2, GSA, Pax: SLID 1g 16 of 19 (CPP - SANKALP_POC-PHLVIL Now, 1 mole of CH, gives = % mol of H.0 0.05 mol of CH, will give = 0.05 5 mol of #10 0.05 ¥ =0.10 2 4 Hence, the hydrocarbon is CH. 6x1.12 _ Weight of 1.12 litre CH, at STP = 455% ‘Also, CH, + 20: —> CO, + 20 1 mol of CH requires 2 x 32 g oxygen 0.05 mol of CH, requires 2 x 32 x 0.05 = 3.2.g COs CH, requires 02 = 3.2.9 08g Exampue 10 ‘An organic compound, A containing C, H, N and O, on analysis gives 40.32% carbon, 9.59% hydrogen and 19.18% nitrogen. A on boiling with NaOH gives off NH, and a salt which on acidification gives a monobasic nitrogen free acid B. The silver salt of B contains 59.67% silver. Deduce the structures of A and B. SoLuTion Percentage of oxygen = 100 ~ (49.2 +9.59 + 19.18) = 21.91, Parcentage composition c 49.32 2 Elements ‘Atomic weight | Relative No. of atoms | Simplest ratio 49.12 ay 4a 2 137 259 90 358 1 137 N 1918 18.1837 137, ia7 ° 21.91 a7 a 137. H 9.59 Fence empirical formula of A= C3H;NO Because A, gives NH; on boiling with NaOH, it can be an amide. Now, silver salt of B, has 59.67% silver. (100 108) } Hence equivalent weight of acid = fence equivalent weight of acid = | “> ~ 107 = 74 Molecular weight of monobasic acid = 74 x 1 = 74 Molecular formula of acid = CH,O; ‘Structural formula of acid B is C;HCOOH. Molecular formula of amide = C,H;NO. Hence structural formula of amide (A) is CHCONH,. tee THITIEE LCS Huse, Serapriga Vihar ear Hx Ras Tes Terminal New Dei 16, FR 6515990, OB6SIO2, GBS, Pax: SII Page 17 of 19 SANKALP_POC-PHAVIL Objective Problems 1 The percentage of sulphur in the organic compound, when 0.2595 g of a sulphur containing organic compound in 2 quantitative analysis by Carius method yielded 0.35 g of barium sulphate is, (@) 14.52% (b) 16.52% (c) 18.52% (a) 19.52% ‘A compound containing 80% carbon and 20% hydrogen is likely to be (@) CoH (b) CaH_OH (0) Cate (a) CHls ‘Aniline, chloroform and alc. KOH on heating gives (a) Phenyl isocyanide (b) Phenyi cyanide (c) Chlorobenzene (4) Phenol 1f 0.228 g of silver salt of dibasic acid gave a residue of 0.162 g of silver on ignition, then molecular weight of the acid is (a) 70 (b) 80 (©) 90 (a) 100 Methyl ketones are usually characterized through (@) Tollen's test (0) lodoform test (c) Schiff test (d) Benedict's test CICH;COOH is heated with fuming nitric acid in the presence of AgNOs in a Carius tube. After fitration and ‘washing a white precipitate is obtained. The precipitate is (@) AgNO; (0) AgO (c) AgCl (@) CICH;COOAg Which of the following is used for separating aniline from nitrobenzene? (a) Na,CO, (b) HC (e) NaHCO, (@) Nac The compound that does not give a blue colour in Lassaigne's testis, () Aniline (0) Giycine (e) Hydrazine (@) Urea The Lassaigne's extract is boiled with dil. HNO; before testing for halogens because (a) Silver halides are soluble in HNOs, (b) NaS and NaCN are decomposed by HNOs. (C) AgeS is soluble in HNOs, (8) AgCN is soluble in HNOs, 0.2 g of an organic compound on complete combustion produces 0.18 g of water, then the percentage of hydrogen in the compound is @s (o) 10 fe) 18 (a) 20 In which ofthe following compounds, nitrogen cannot be tested by Lassaigne’s test? (@) CoHeNHe (b) NHeNHs.H2O—(c) CHsCONHp (a) CeHsNOe When a ritrogen containing organic compound is strongly heated with conc. H:S0., the product is (@) HNO; (b) (NH):SO, (e) NH (a) Ne To determine the weight of a halogen in organic compound, the compound is heated with fuming HNO; in presence of (a) Ag {b) AgNO; (c) Ag,COs (a) AgsSO, ‘Ammixture of o-nitrophenol and p-nitrophenol can be separated by (a) Sublimation (b) Steam disilation (©) Fractional crystalization (8) Distilation In Lassaigne’s test for nitrogen the blue colour is due to the formation of (a) Ferric-Ferro cyanide (b) KalFe(CN),] (c) Nas{Fe(CN)e) (@) Nacn Nitrogen is estimated by (@) Liebigmethod —(b) Carius method (c) Duma's method (4) None of these ‘An organic compound is found to contain C = 39.9%, H = 6.7%, O = 53.4%. Its empirical formula is (a) CHO (b) CHO, (c) CHO; (a) CHO ‘Which ofthe following compounds will give blood red colour in the Lassaigne’s test for nitrogen? (a) (NH2).C = 0 (0) HaN(CsH,)SO3H__(C)_CoHsSO3H (@) CHC TFITIEE De, ICES House, Seroepriga Var ar Hur has Bas Terminal, New Deki 16, Pe 6515949, GB6SIBZ,GBSHTOD, Pax 519942 Page 18 of 19 (CPP - SANKALP_POC-PHLVIL 73. 20. In Kjeldah's method, nitrogen elements estimated as (@) No (@) NO (c) NHs (a) No; 0.10 g of an organic compound containing phosphorus gave 0.222 g of Mg:P.0;. Then the percentage of phosphorus in itis (a) 62 (b) 62 to) 31 @ 3 ‘A gaseous hydrocarbon has 85% carbon and vapour density of 28. The possible formula of the hydrocarbon willbe (@) CsHe (b) CoH (0) Catt, (A) CaHy The silver salt of a monobasic acid on ignition gave 60% of Ag, The molecular weight ofthe acid is (a) 37 (b) (©) 73 (a) 77 0.1914 g of an organic acid is dissolved in about 20 mi of water. 25 ml of 0.12 N NaOH is requited for the complete neutralization of the acid solution. The equivalent weight of the acid is (a) 65 (b) 64 (©) 638 (a) 625 If empirical formula of an organic compound is CH.0 and its 6.02 x 10 molecules weight 60 g, then it can be (@) CHSOH (0) CaH-OH (¢) HCOOH (a) HCOOCH, If the percentage of nitrogen in an organic compound is 12.6% then how much of the organic compound should be taken so as to produce 50 mi of Nz at 300 K and 715 mm pressure (Aqueous tension = 15 mm)? (@) 04199 (©) 0.1499 (c) 09149 (a) 0.941g Answer Key Objective Problems 2 3. 4 7. 8 9. 12. 13. 14. 17. 18. 19. 22. 23. 24, Subjective Problems 1 ‘A dibasic organic acid containing 26.66% of carbon and 2.22% of hydrogen, gave a silver salt containing 71.05% of siver. What is the molecular formula of the acid? Give its structural formula also. ‘A dibasic organic acid gave the following results on analysis, 0.2496 g of acid gave 0.3168 g of CO; and 0.0864 g of H.0. 0.1092 g of acid is exactly neutralized by 21 mi N/10-NaOH. Calculate the molecular formula of the acid 0.177 g of a dibasic acid gave on combustion 0.2642 g CO; and 0.081 g H.O. 0.2988 g of its silver salt left 0.1944 g of silver on ignition. Write structural formula of its possible isomers. What experiment would you Perform to assign it a definite formula? ‘An organic compound contains 69.4% C, 5.8% H. A sample of 0.303 g of this compound was analyzed for nitrogen by Kjeldahl method. «The ~~ ammonia evolved was absorbed in 50 mi of 0.05 M H.SO,, The excess acid required 25 mi of 0.1 M NaOH for neutralization. Determine ‘molecular formula of the compound, fits molecular mass is 121. Draw possible structures of this compound. 0.0663 g of an organic compound gave 0.0621 g of carbon dioxide and 0.0381 g of water. 0.0980 g of the same compound gave 0.4860 g of barium sulphate. In a vapour density determination, 0.205 g of the substance displaced 52.6 ml of air over water at 293 K and 773 mm of Hg pressure, The vapour pressure of water is 17 mm of Hg at 293 K. What is the molecular formula of the compound? ‘A sample of 0.22 g of a volatile compound containing carbon, hydrogen and chlorine yielded 0.195 g CO2 and (0.0804 g water on combustion in oxygen. 0.120 g of the compound occupied a volume of 37.24 ml at 105°C and 768 mm of Hg pressure. Calculate the molecular formula of the compound, TFITIEE Td, ICES House, Seroopriga Var far Hur Rha Bus Terminal New Debi 16, Pr OS1S949, GBOSTBZ, GBSHTOD, Pax 519942 Page 19 of 19 (CPP - SANKALP_POC-PHLVIL 7. 10.57 mg of an organic compound gave on combustion 1.08 mi of nitrogen, measured at 19.5°C and 7335 ‘mm of pressure. Find the percentage of the nitrogen in the compound. Given: Vapour pressure of water at 195°C is 17.8 mm. 66 mg of an organic compound containing phosphorus gave 11 mg of MgzP20; by the usual analysis. Calculate the percentage of phosphorus in the compound, The _quantative analysis of a well known broad spectrum antibiotic says that it contains 57.49%, H = 5.39%, N = 8.39%, S = 9.58%. If each molecule of the antibiotic contains one atom of sulphur, deduce the molecular formula of the antibiotic. ‘A monoacid base contains 53.3% carbon, 15.5% hydrogen and 31.2% nitrogen. 1.0 g of the chloroplatinate of the base gave 0.39 g of platinum. What is the molecular formula of the base? ‘Answer Subjective Problems CaO, H-O-C-C-O-H 2. CaHLO. oO Molecular formula: CsHsOx Possible structures: ‘OOH fh - COOH daa) CH; ~ COOH coon Suecinie acid Methyl malonie acid Can be distinguished by decarboxyation Molecular formula = nC;H;NO = C;H;NO. Structure HO. NH? CaHeS: 6 GH.Cl; 11.229 8. 51.20 CH ysNeSOx 10. CH)N tee THITIEE LCS Huse, Serapriga Vihar ear Hx Ras Tes Terminal New Dei 16, FR 6515990, OB6SIO2, GBS, Pax: SII

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