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Q.l A sample of calcium carbonate contains impurities which do not react with a mineral acid.

When 2 grams of the sample were reacted with the mineral acid, 375 ml of carbon dioxide were obtained at 27C and 760 mm pressure. Calculate the % purity ofthe sample of CaC03? Q. 2 One gram of an alloy of aluminium and magnesium when heated with excess of dil. HCl forms magnesium chloride, aluminium chloride and hydrogen. The evolved hydrogen collected over mercury at 0C has a volume of 1.2 litres at 0.92 atm pressure. Calculate the composition of the alloy. Q.3 10 gm of a mixture of anhydrous nitrates of two metal A & B were heated to a constant weight & gave 5.531 gmofa mixture ofthe corresponding oxides. The equivalent weights ofA&B are 103.6&31.8 respectively. What was the percentage of Ain the mixture. Q. 4 Sulfur dioxide is an atmospheric pollutant that is converted to sulfuric acid when it reacts with water vapour. This is one source of acid rain, one of our most pressing environmental problems. The sulfur dioxide content of an air sample can be determined as follows. A sample of air is bubbled through an aqueous solution of hydrogen peroxide to convert all of the SO, to H,S04 H2O2 + so2 > H2SO4 Titration of the resulting solution completes the analysis. In one such case, analysis of 1550 L of Los Angeles air gave a solution that required 5.70 ml of 5.96 x 10 3M NaOH to complete the titration. Determine the number of grams of SO, present in the air sample. Q.5 A mixture of FeO and Fe203 is reacted with acidified KMn04 solution having a concentration of0.2278 M, 100 ml of which was u sed. The solution was then titrated with Zn dust which
3+ of

the solution to Fe- The Fe2

converted Fe of FeO & Fe A

+ required 1000 ml of 0.13 M K2Cr0? solution. Find the %

Q.6 50ml of a solution, containing 0.01 mole each NaC03, NaHC03 and NaOH was titrated with NHC1. What will be the titre readings if (a) only Ph is used as indicator. (b) only MeOH is used as indicator from the beginning (c) MeOH is added after the first end point with Ph. Q.7 A 0.517g sample containing Ba(SCN), was dissolved in a bicarbonate solution. 50.0 mL of 0.107 N iodine was added, and the mixture was allowed to stand for five minutes. The solution was then acidified, and the excess L was titrated with 16.3 mLof0.0965M sodiumthiosulphate. Write a balanced equation forthe oxidation of SCN" into S0 42 and HCN. Calculate the percent Ba(SCN)2 in the sample. Q.8 An acid solution of a KRe04 sample containing 26.83 mg of combined rhenium was reduced by passage through a column of granulated zinc. The effluent solution, including the washings from the column, was then titrated with 0.10 N KMn04. 11.45 mL ofthe standard permanganate was required for the re-oxidation of all the rhenium to the perrhenate ion, Re04~. Assuming that rhenium was only element reduced. What is the oxidation state to which rhenium was reduced by the Zn column. (Atomic mass of Re = 186.2)

Q.9 The element Se, dispersed in a 5.0 ml sample of detergent for dandruff control, was determined by suspending the sample in warm ammonical solution that contain 45.0 ml of0.020 M AgN03. 6Ag+ + 3Se(s) + 6NH3 + 3H20 > 2Ag,Se(s) + Ag2Se03 (s) + 6NH4+ The mixture was next treated with excess nitric acid which dissolves the Ag2SeO, but not the Ag,Se. The Ag+ from the Ag2Se03 and excess AgN03 consumed 16.74 mi of 0.0137 N KSCN in a Volhard titration. How many milligrams of Se were contained per millilitre of sample.

Q.10 Chrome alum K^SC^. Cr^SO^. 24 H20 is prepared by passing S02 gas through an aqueous solution ofK2Cr207 acidified with dilute sulphuric acid till the reduction is complete. The alum is crystallized followed by filtration/centrifiigation. If only 90% of the alum can be recovered from the above process, how much alum can be prepared from 10kg ofK2Cr207? Give the number of moles of electrons supplied by SO, for reducing one mole of K2Cr,0?. Q.ll A substance of crude copper is boiled in H,S04 till all the copper has reacted. The impurities are inert to the acid. The SO, liberated in the reaction is passed into 100 mL of 0.4 M acidified KMn04. The solution of KMn04 after passage of S02 is allowed to react with oxalic acid and requires 23.6 mL of 1.2 M oxalic acid. If the purity of copper is 91%, what was the weight of the sample. Q.12 A1.87gm. sample of chromite 0re(Fe0.Cr,03) was completely oxidized by the fusion of peroxide. The fused mass was treated with water and boiled to destroy the excess of 2 peroxide. After acidification the sample was treated with 50ml. ofO. 16MFe +. In back titration 2.97 ml of0.005M barium dichiomate was required to oxidize the excess iron (II). What is the percentage of chromite in the sample? Q.13 25 mL of a solution containing HCl was treated with excess of M/5 K10 3 and KI solution of unknown concentration where I2 liberated is titrated against a standard solution of 0.021 M Na,S,03 solution whose 24 mL were used up. Find the strength of HCl and volume of KI0 3 solution consumed. Q. 14 A lOg sample of only CuS and Cu2S was treated with 100 mL of 1.25 M K,Cr,Or The products
3 2+

and SO,. The excess oxidant was reacted with 50 mL of Fe2

obtained were Cr 4 , Cu + solution. 25 ml of the same Fe2+ solution required 0.875M acidic KMn04 the volume of which used was 20 mL. Find the % of CuS and Cu,S in the sample,
2 4

Q.15 H20, is reduced rapidly by Sn +, the products being Sn + & water. H202 decomposes slowly at room temperature to yield 02 & water. Calculate the volume of O, produced at 20C & 1.00 2 atm when 200g of 10.0 % by mass H,0, in water is treated with 100.0 ml of 2.00 M Sn +& then the mixture is allowed to stand until no further reaction occurs. Q.16 0.6213 g of sample contains an unknown amount ofAs,03. The sample was treated with HCl resulting in formation ofAsCl3(g) which was distilled into a beaker of water. The hydrolysis reaction is as follows ASC13 + 2H20 -> HAsO, + 3H++ 3C1~. The amount ofHAsO, was determined by titration with 0.04134 MI2, requiring 23.04 mL to reach ihe equivalence point. The redox products in the titration were H3As04 and I . Find the amount of KMn04 needed to oxidize As in As,03 to its maximum possible oxidation state in acidic medium. Q.17 A sample of steel weighing 0.6 gm and containing S as an impurity was burnt in a stream of O,, when S was converted to its oxide SO,. SO, was then oxidized to S04~~ by using H20, solution containing 30ml of 0.04 M NaOH. 22.48 ml of0.024 M HCl was required to neutralize the base remaining after oxidation. Calculate the % of S in the sample. Q.18 3.6 g of Mg is burnt in limited supply of oxygen. The residue was treated with 100 mL of H,S0 4

(3 5% by mass, 1.26 g mL"1 density). When 2.463 L of H2 at 760 mmHg at 27C was evolved". After the reaction, H,S04 was found to have a density of 1,05 g mL" 1. Assuming no volume change in H2S04 solution. Find (i) % by mass of final H,S04 (ii) % by mass of Mg converted to oxide (iii) mass of oxygen used. (Mg = 24, S= 32) Metal reacts with acids to displace H,gas Q.19 A1 Ogm mixture of Cu2S and CuS was treated with 200 ml of 0.75 M Mn04" in acid solution, 2 2 producing S02, Cu + & Mn +. The S02 was boiled off and the excess MnO; was titrated with 2+ 175 ml of 1M Fe solution. Calculate the % CuS in the original mixture. Q.20 3.3 gm of a sample of Anhydrous CuS04 was dissolved in water and made to 250ml. 25 ml of this solution after taking usual precautions was treated with a little excess of KI solution. A white ppt. of Cu,I2 and iodine was evolved. The iodine so evolved required 24.6 ml of hypo solution containing 20gm of (Na2S203 5H20) per litre. What is the purity of CuS04 solution. Q.21 A certain sample of coal contained some iron pyrite (FeS 2) - a pollution causing impurity. When the coal was burned iron(II) was oxidised and S02 was formed. The S02 was reacted with NaOH when sodium sulphite and water was formed. On a particular fay 10 3 kg of coal was burned and it required 4 litres of 5M NaOH for the treatment of S0 2. What was the percentage of pyrite in the coal. What was the percentage of sulphur in the coal.
2+

can be titrated withMn0

Q.22 In the presence of fluoride ion, Mn 4", bothreactants being converted to a complex ofMn(III). A 0.545 g sample containing Mn304 was dissolved and all manganese 2 was converted to Mn +. Titration in the presence of fluoride ion consumed 31.1 ml of KMn04 that was 0.117 N against oxalate. (a) write a balanced chemical equation for the reaction, assuming that the complex is MnF4~. (b) what was the % of Mn304 in the sample? Q.23 Calculate the % of Mn02 in a sample of pyrolusite ore, 1.5 g which was made to react with lOg. 2 of Mohr's salt (FeS04.(NH4)2S04. 6H20) and dilute H2S04. Mn02 was converted Mn +. After the reaction the solution was diluted to 250 ml and 50 ml of this solution, when titrated with 0.1 N K2Cr207, required 10 ml ofthe dichromate solution. Q. 24 1.4 g of a complex [Co(NH3)J Cl3 was treated with 50 mL of 2N NaOH solution and boiled. Ammonia gas evolved was passed through 50 mL of IN H2S04. After the reaction was over, excess acid required 37.2 mL of0.5 NNaOH. Calculate (i) The percentage of ammonia in the sample, (ii) The value of x in the formula.

EXERCISE III

Q. 1 Amixture of two gases, H2S and S02 is passed through three beakers successively. The first 2 beaker contains Pb + ions, which absorbs S2~ forming PbS. The second beaker contains 25 ml of0.0396 NI2 to oxidize S02 to S042 . The third contains 10 ml of 0.0345 N thiosulphate solution to retain any I2 carried over from the second absorber. A 25 / gas sample was passed

through the apparatus followed by an additional amount of N2 to sweep last traces of S02 from first and second absorber. The solution from the first absorber was made acidic and treated with 20ml of0.0066 M K,Cr207 which converted S2 " to SO,. The excess dichromate was reacted with solid KI and the liberated iodine required 7.45 ml of0.0345 N Na2S203 solution. The solutions in the second and third absorbers were combined and the resultant iodine was titrated with 2.44 ml of the same thiosulphate solution. Calculate the concentrations of S02 and F^S in mg/L of the sample. Q.2 Chromium exists as FeCr204 in the nature and it contains Fe0 950 & other impurity. To obtain pure chromium from FeCr204, the ore is fused with KOH and oxygen is passed through the mixture when K2Cr04 and Fe203 are produced. 2 g of ore required 270 mL of 02 at STP for complete oxidation of ore. K,Cr04 is then precipitated as BaCr04 after addition of a Barium 3 salt. To remaining solution 10 mL of 1 M K,Fe(CN) g is added when Fe + ions react with it to form KFe[Fe(CN)6], often called 'Prussian Blue'. To determine excess of K4Fe(CN)6 in
2+

is added when all the K

solution 7mL of 0.2 N of Fe Calculate the percentage ofFe095 O.

4Fe(CN)6 is precipitated as K2Fe[Fe(CN)6],

Q.3 2g of chromite ore sample was mixed with enough potassium carbonate and potassium chlorate and fused. The reaction that occurred was: 6FeCr204 + 12K2C03 + 7KCI03 -> 3Fe203 + 12 K2Cr04 + 7KC1 + 12C02 The fused mass was cooled and extracted with 2N sulphuric acid. This was filtered and thoroughly washed. The filterate and washings were collected in a 500 ml. Volumetric flask. When all the soluble portion of the fused mass was extracted, 100 ml of 1M solution of ferrous ammonium sulphate were added and the solution made to 500ml. An aliquot of 25ml was titrated with potassium dichromate solution, prepared by dissolving 0.98 g of dried potassium dichromate in distilled water in a 250ml volumetric flask. The titration required 32.5 ml of this solution. Calculate the percentage of chromium in the sample of the ore. Q.4 One gram of a moist sample of a mixture of KCI0 3 and KC1 was dissolved in water and made upto 250 mL. 25 ml of this solution was treated with S0 2 to reduce chlorate into chloride and the excess S02 was boiled off. When the total chloride was precipitated, 0.1435 g of AgCl was obtained. In another experiment 25mL of the original solution was treated with 30 mL of 0.2N solution of FeS04 and unreacted FeS04 required 37.5 mL of 0.08 N solution of an oxidizing agent for complete oxidation. Calculate the molar ratio of chlorate and chloride in 2 the given mixture. Fe + reacts with CI03~ according to the equation.
2 3

CI03" + 6Fe + + 6H+ -> CI" + 6Fe + + 3H20 Also calculate the mass per cent of moisture present in the moist sample. Q.5 A steel sample is to be analysed for Cr and Mn simultaneously. By suitable treatment the Cr is oxidized to Cr2072- and the Mn to Mn04-. A lO.OOg sample of steel is used to produce 250.0 mL of a solution containing Cr2072" and Mn04~. A 10.00 mL portion of this solution is added to a BaCL, solution and by proper adjustment of the acidity, the chromium is completely precipitated as BaCr04; 0.0549 g is obtained. A second 10.00 mL portion of this solution 2+ requires exactly 15.95 mL of 0.0750M standard Fe solution for its titration (in acid solution). Calculate the % of Mn and % of Cr in the steel sample.

Q.6 25 ml from a stock solution containing NaHC03 and Na2CQ3 was diluted to 250 ml with C02 free distilled water. 25 ml of the diluted solution when titrated with 0.12 MHC1 required 8 ml., when phenolphthalein was used as an indicator. When 20 ml of diluted solution was titrated with same acid it required 18 ml whenmethly orange was used as an indicator. Calculate concentration of NaHC03 in the stock solution in gm/litre and in mole / litre. To 100 ml of the stock solution how much NaOH should be added so that all bicarbonate will be converted into carbonate? Q.7 1.16 g CH3(CH2)n COOH was burnt in excess air and the resultant gases (CO, and H20) were passed through excess NaOH solution. The resulting solution was divided in two equl parts. One part requires 5 0 mL of 1 N HCl for neutralization using phenolphthalein as indicator. Another part required 80 mL of IN HCl for neutralization using methyl orange as indicator. Find the value of n and the amount of excess NaOH solution taken initially Q.8 A2.50g sample containing As205 and Na2HAs03, and inert material is dissolved and the pH is adjusted to neutral with excess NaHCO,. The As(III) is titrated with 0.150 Ml, solution, requiring 11.3 mL to just reach the end point. Then, the solution (all the arsenic in the +5 state now) is acidified with HCl, excess KI is added, and the liberated I, is titrated with 0.120 MNa2S203, requiring 41.2 mL. Calculate the per cent As,05 and Na,HAsO, in the sample? Q.9 A 0.141g sample of a phosphorus containing compound was digested in a mixture of HNO. and H2S04 which resulted in formation of C02, H20 and H,P04. Addition of ammonium molybdate yielded a solid having the composition (NH4)3 P04. 12 Mo03. The precipitate was filtered , washed and dissolved in 50.0 mL of 0,20 M NaOH: (NH4)3P04. 12 MO03 (S) + 260H" -> HP042" + 12Mo042~ + 14H20 + 3NH3(g) After boiling the solution to remove the NH3, the excess NaOH was titrated with 14.1 mL of 0.174M HCl. Calculate the percent of phosphorus in the sample. Q.10 An accurately weighed 3.15 gm of H2C,04 2H20 was dissolved in water to make 500 ml solution. A warmed 20ml of this solution acidified with H,S04 required 18ml of a KMn04 2 3 solution for complete oxidation. Then 10ml solution containing 1 g ion / litre of Fe + & Fe + together free from CI ions or other ions which interfere in KMn0 4 titration, was diluted 10 fold with water. 20 ml of this diluted solution required 9.5 ml of the above KMn04 solution 3 for complete oxidation in H,S04 medium. Determine the amount of Fe + ion in gin/litre of original solution.
2

Q.ll A 1.65 gm sample ofFeS, was oxidized by excess oxygen & the products were SO, and Fe +, The SO, gas produced was passed through an acidified solution of 40ml Ba(MnO 4)2 2 produced S04~~ & Mn +. The excess permagnate was diluted to 100 ml & 10 ml of it was treated with excess KI & iodine produced req. 0.05 M 5 ml hypo solution producing S 4062". In a separate titration the 25 ml of same solution of permagnate under alkaline condition when treated with KI produced I, that required 20 ml of 0.05 M hypo solution producing 6 S40,2 & Mn +. Calculate the % of FeS2 in the sample.

Q.12 3 Occ of a solution containing 9.15gm of a salt KxHy (C,0 Jz nH,0 per litre required 27cc of 0.12 N NaOH for neutralization. The same quantity of solution was also found to require 36cc of 0.12 N KMn04 solution for complete oxidation. Calculate X, Y, Z and n. 13 Reducing sugars are sometimes characterized by a number RCu, which is defined as the number of mg of copper reduced by 1 gm of sugar, in which half reaction for the copper is Cu2' + OH > Cu,0 + H20 It is sometimes more convenient to determine the reducing power of a carbohydrate by an indirect method. In this method 43.2 mg of the carbohydrate was oxidized by an excess of K3(Fe(CN)6). The Fe(CN)64" formed in this reaction required 5.29 ml of0.0345 N CefSO^ for reoxidation to Fe(CN)63. Determine the RCu value for the sample. Q.14 12.0 g of an impure sample of arsenious oxide (acting as acidic oxide) was dissolved in water containing 7.5g of sodium bicarbonate and resulting solution was diluted to 250 ml. 25 ml of this solution was completely oxidized by 22.4 ml of a solution of iodine. 25ml of this iodine solution reacted with same volume of a solution containing 24.8g of hydrated sodium thiosulphate (Na2S203-5H,0) in one litre. Calculate the percentage of arsenious oxide in the sample. Also report the % purity of NaHC03.