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C H E M I S T R Y

Q.B. ON STOICHIOMETRY AND REDOX-3

C-39, LAJPAT MARG, C-SCHEME, JAIPUR 0141-2377707, 2328182

STOICHIOMETRY AND REDOX -3

Exercise I
Q1. 125 mL of a solution of tribasic acid (molecular weight = 210) was neutralized by 118mL of decinormal NaOH solution and the trisodium salt was formed. Calculate the concentration of the acid in grams per litre. 25cc of a solution of oxalic acid required 29cc of .098 normal sodium hydroxide for complete neutralization. What is the number of grams of anhydrous oxalic acid per litre of the solution? What volume of exactly decinormal oxalic acid solution could be made from 500cc of this solution? Calculate the normality of the solution obtained by dissolving 500cc of gaseous hydrogen chloride in 660 cc of water, the gas being measured at 20oC and 750 mm pressure. (Assume no change in volume during the dissolution of the gas.) Upon heating one litre of N/2 HCl solution, 2.675g of hydrogen chloride is lost and the volume of solution shrinks to 750 ml. Calculate (i) the normality of the resultant solution (ii) the number of milliequivalents of HCl in 100 mL of the original solution. For the standardization of a Ba(OH)2 solution, 0.2g of potassium acid phthalate (m.wt. 204.2g) weighed which was then titrated with Ba(OH)2 solution. The titration requires 27.80mL Ba(OH)2 solution. What is the molarity of base? The reaction products include BaC8H4O4 as only Ba containing species. Calculate the number of gm. of borax, Na2B4O7.10H2O, per litre of a solution of which 25cc required 15.6 cc of N/10 hydrochloric acid for naturalization, methyl orange being used as indicator. In aqueous solution, borax hydrolyses according to the equation: Na2B4O7 + 7H2O = 2NaOH + 4H3BO3 The liberated boric acid is a weak acid and is without effect on methyl orange. A solution containing 4.2 g of KOH and Ca(OH)2 is neutralized by an acid. If it consumes 0.1 equivalent of acid, calculate composition of sample in solution. (K=39, Ca=40) 10mL of 0.2N HCl and 30mL of 0.1N HCl together neutralize 40 mL of a solution of NaOH which is also neutralized exactly by a solution of 0.61g of an organic acid. Find the equivalent weight of organic acid. 1g sample of washing soda was dissolved in 50ml of 1.0M HCl. The excess acid required for neutralization 21.13mL of 1.018M Ba(OH)2. Compute the degree of hydration of washing soda. 1.575g of oxalic acid (COOH)2 . xH2O are dissolved in water and the volume made upto 250mL. On titration 16.68mL of this solution requires 25mL of N/15 NaOH solution for complete neutralization. Calculate x. 10g CaCO3 were dissolved in 250mL of M HCl and the solution was boiled. What volume of 2M KOH would be required to reach equivalence point after boiling? Assume no change in volume during boiling. A definite amount of NH4Cl was boiled with 100mL of 0.8N NaOH for complete reaction. After the reaction, the reactant mixture containing excess of NaOH was neutralized with 12.5mL of 0.75N H2SO4. Calculate the amount of NH4Cl taken. 25mL of a solution of Na2CO3 having a specific gravity of 1.25g ml-1 required 32.9 mL of a solution of HCl containing 109.5g of the acid per litre for complete neutralization. Calculate the volume of 0.84N H2SO4 that will be completely neutralized by 125g of Na2CO3 solution. 1g of impure Na2CO3 is dissolved in water and the solution is made upto 250mL. To 50 mL of this made up solution, 50mL of 0.1N HCl is added and the mixture after shaking well, required 10mL of 0.16N NaOH solution for complete neutralization. Calculate % purity of the sample of Na2CO3. 0.4609gm of moist specimen of sodium nitrate was heated with an excess of caustic soda and about 3gm of Devarda's alloy, whereby the nitrate was quantitatively reduced to ammonia. The ammonia was boiled off and absorbed in 80cc of N/10 hydrochloric acid. The excess of hydrochloric was finally titrated and required 31.65cc of 0.098 N sodium hydroxide solution. What was the percentage of sodium nitrate in the specimen? A sample containing 0.4775g of (NH4)2C2O4 and inert materials was dissolved in water and made strongly alkaline with KOH, which converted NH4+ to NH3. The liberated ammonia was distilled into

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C-39, LAJPA T MARG , C-SCHEME, JAIPUR, RAJASTHAN. PH # 0141-2377707, FAX- 2328182

STOICHIOMETRY AND REDOX -3

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exactly 50.0mL of 0.05035M H2SO4. The excess H2SO4 was back titrated with 11.3 mL of 0.05035M NaOH. Calculate : (a) percent of N (b) percent of (NH4)2C2O4 [Mol. wt. of (NH4)2C2O4 = 124. 10 and at. wt. of N=14.0078] 5gm of a double sulphate of iron and ammonia was boiled with an excess of sodium hydroxide solution and the liberated ammonia was passed into 50cc of normal sulphuric acid. The excess of acid was found to require 24.5cc of normal sodium hydroxide for naturalization. Calculate the percentage of ammonia (expressed as NH3) in the double salt. 6gm of a mixture of ammonium sulphate and ammonium chloride was made up to 1000cc with water. 25cc of this solution was boiled with 50cc of N/10 sodium hydroxide until no more ammonia was evolved and it was then found that the excess of sodium hydroxide required for naturalization 24.3cc of N/10 hydrochloric acid. What was the percentage of ammonium chloride in the mixture? A 10.0g sample of "gas liquor" is boiled with an excess of NaOH, and the resulting ammonia is passed into 60cm3 of 0.90N H2SO4. Exactly 10.0 cm3 of 0.40N NaOH is required to back titrate the excess sulfuric acid (not neutralized by the NH3). Determine the percent ammonia in the "gas liquor" examined. A sample containing amino acid alanine, CH3CH(NH2) COOH plus inert matter is analyzed by the Kjeldahl method. A 2g sample is digested, the NH3 is distilled and collected in 50.0mL of 0.150M H2SO4, and a volume of 9.0 mL of 0.100 M NaOH is required for back titration. Calculate the percent alanine in the sample.

Exercise II

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A small amount of CaCO3 completely neutralized 52.5 mL of N/10 HCl and no acid is left at the end. After converting all calcium chloride to CaSO4, how much plaster of paris can be obtained? A sample of Na2CO3 was found to contain Na2SO4. 1.25g of this sample was dissolved in water and made upto 250ml, 25ml of this solution required 20ml of N/10 H2SO4 for exact neutralization. Find the percentage of Na2SO4 in the original sample. 2.013g of a commercial sample of NaOH containing Na2CO3 as an impurity was dissolved to give 250ml solution. A 10ml portion of this solution required 20ml of 0.1N H2SO4 for complete neutralization. Calculate % by weight of Na2CO3. 10ml mixture of H2SO4 and HCl was completely neutralized with 16ml of N/8 NaOH. The 20ml of the same mixture precipitated 0.3501g BaSO4 in presence of excess of BaCl2. What is the amount of HCl in one litre mixture? 0.5g of fuming H2SO4(oleum) is diluted with water. The solution requires 26.7mL of 0.4N NaOH for complete neutralization. Find the % of free SO3 in the sample of oleum. A sample of fuming sulphuric acid containing H2SO4, SO3 and SO2 weighing 1.00g is found to require 23.47mL of 1.00N alkali for neutralization. A separate sample shows the presence of 1.50% SO2. Find the percentage of "free" SO3, H2SO4 and "combined" SO3 in the sample. 6g mixture of NH4Cl and NaCl is treated with 110mL of a solution of caustic soda of 0.63N. The solution was then boiled to remove NH3. The resulting solution required 48.1mL of a solution of 0.1N HCl. What is % composition of mixture? Calculate the number of gm(a) of hydrochloric acid, (b) of potassium chloride in 1 litre of a solution, 25cc of which required 21.9cc of N/10 sodium hydroxide for naturalization and another 25cc after the addition of an excess of powdered chalk, required 45.3cc of N/10 silver nitrate for the complete precipitation of the chloride ion. What is the concentration of a solution of sodium carbonate (expressed as gm. of anhydrous sodium carbonate per litre), 25cc of which required 18.3cc of 0.12N sulphuric acid for neutralization, phenolphthalein being used as an indicator? When the salt, KNaC4H4O6 . 4H2O (molecular weight 282) is ignited, there is a residue of sodium carbonate and potassium carbonate. A gram of this salt gave a residue which required 63.8cc of N/10 hydrochloric acid for neutralization, methyl orange being used as indicator. Calculate the percentage purity of the salt.

C-39, LAJPA T MARG , C-SCHEME, JAIPUR, RAJASTHAN. PH # 0141-2377707, FAX- 2328182

STOICHIOMETRY AND REDOX -3 Q11.

2gm of mixture of hydrated sodium carbonate Na2CO3 . 10H2O, and sodium bicarbonate was dissolved

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in water and made up to 250 cc. 25 cc of this solution was titrated, using methyl orange as indicator, and 22.5cc of 0.087N HCl were required for naturalization. Calculate the percentage of sodium bicarbonate in the mixture. What is the concentration of a solution of orthophosphoric acid(gm H3PO4 per litre), 25cc of which required 18.8cc of N sodium hydroxide for naturalization in the presence of phenolphthalein as indicator? 25mL of a 0.107M H3PO4 was titrated with 0.115M solution of NaOH solution to the end point identified by the colour change of the indicator, bromocresol green. This required 23.1mL. The titration was repeated using phenolphthalein indicator. This time, 25mL of same H3PO4 solution required 46.8mL of same NaOH solution. What is the coefficient 'n' in the equation. H 3PO4 + nOH- nH2O + [H(3-n)PO4]n- for each reaction? A mixture containing Na2CO3, NaOH and inert matter weights 0.7500g. When the aqueous solution is titrated with 0.5000N HCl, the colour of the phenolphthalein disappears when 21.00mL of the acid has been added. Methyl orange is then added and 7.00 mL more of the acid is required to give a reddishorange colour to the solution. Find the percentage composition of the sample. 25.0cm3 of a solution containing Na2CO3 and NaOH required 10cm3 of 1.0M H2SO4 for neutralization when phenolphthalein was used as the indicator. Whereas when methyl orange was used, it required 15cm3 of the same acid for neutralization. Calculate the masses of Na2CO3 and NaOH per dm3 of the solution. Calculate (i) the number of gm. of anhydrous sodium carbonate, (ii) the number of gm. of sodium bicarbonate, present together in one litre of a solution. 25cc of this solution required 11.8cc of N/10 hydrochloric acid for naturalization when phenolphthalein was used as indicator and 31.0cc of N/10 hydrochloric acid when methyl orange was used as indicator. 10gm. of mixture of sodium acid oxalate, NaHC2O4, and sodium oxalate, Na2C2O4, was heated to a constant weight and gave 6.120gm of sodium carbonate. If another 10gm of the same mixture were dissolved in water and made up to 1000cc and 25cc of this solution were titrated against N/10 NaOH with phenolphthalein as indicator, what volume of the sodium hydroxide solution should be required? 5.832gm of a mixture of anhydrous sodium carbonate and sodium bicarbonate was dissolved in water and made up to 1 litre. 25cc of this solution required for naturalization 8.1cc of 0.109N HCl, phenolphthalein being used as indicator. When methyl orange was the indicator, 25cc of the solution required 23.9cc of N/10 HCl for neutralization. Calculate by two independent methods the percentage of sodium carbonate in the mixture. Sodium sesquicarbonate has the formula, Na2CO3 . NaHCO3 . 2H2O Calculate its equivalent as an alkali when it is titrated against hydrochloric acid in the presence of (a) phenolphthalein, (b) methyl orange, as indicator. Hence calculate the number of gm of the salt per litre of a solution, 25 cc of which required 28.3 cc of 0.11N hydrochloric acid for neutralization, methyl orange being used as indicator. 25cc of a solution containing hydrochloric acid and orthophosphoric acid required 18.6cc of decinormal sodium hydroxide for neutralization using methyl orange as indicator, and 23.7cc of the same alkali using phenolphthalein. What are the weights of hydrochloric acid and phosphoric acid per litre of the solution? What weight of sodium hydroxide would be required to convert the acid in 1 litre of the solution into sodium chloride and trisodium phosphate?

Exercise III
Q1. Q2. How many mL of 0.1N HCl are required to react completely with 1g mixture of Na2CO3 and NaHCO3 containing equimolar amounts of two? [IIT 71, 74] 0.50g of mixture of K2CO3 and Li2CO3 required 30mL of 0.25N HCl solution for neutralization. What is % composition of mixture? [REE 88]

C-39, LAJPA T MARG , C-SCHEME, JAIPUR, RAJASTHAN. PH # 0141-2377707, FAX- 2328182

STOICHIOMETRY AND REDOX -3 Q3.

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1.20g sample of Na2CO3 and K2CO3 was dissolved in water to form 100mL of a solution. 20mL of this solution required 40mL of 0.1N HCl for complete neutralization. Calculate the weight of Na2CO3 in mixture. If another 20 mL of this solution is treated with excess of BaCl2, what will be the weight of precipitate? [REE 97] 1g of mixture of Na2CO3 and K2CO3 was mole made upto 250mL is aqueous solution. 25mL of this solution was neutralized by 20mL of HCl of unknown concentration. The neutralized solution required 16.24mL of 0.1N AgNO3 for precipitation. Calculate (a) the % of K2CO3 is mixture. (b) conc. of HCl in g/litre (c) molarity of HCl. [IIT 96] A sample of magnesium was burnt in air to give a mixture of MgO and Mg3N2. The ash was dissolved in 60 meq of HCl and the resulting solution back titrated with NaOH. 12 meq of NaOH were required to reach the end point. An excess of NaOH was then added and the solution distilled. The ammonia released was then trapped in 10 meq of second acid solution. Back titration of this solution required 6 meq of the base. Calculate the percentage of magnesium burnt to the nitride. [REE 98, 7] 1g of a mixture containing equal number of moles of carbonates of two alkali metals, required 44.4 ml of 0.5N HCl for complete reaction. The atomic weight of one metal is 7, find the atomic weight of other metal. Also calculate amount of sulphate formed on quantitative conversion of 1.0g of the mixture in two sulphates. 5mL of 8N HNO3, 4.8mL of 5N HCl and a certain volume of 17M H2SO4 are mixed together and made upto 2litre. 30 mL of this acid mixture exactly neutralizes 42.9mL of Na2CO3 solution containing 1g of Na2CO3 . 10H2O in 100mL of water. Calculate the amount of sulphate ions in grams present in the solution. [IIT 85] During acidity (remember the "ENO" ad.?:-), HCl concentration in stomach rises from a normal of 8 x 10-2M to 0.1M HCl. One digene tablet (an antacid) contains 334 mg of active component, NaAl(OH)2CO3, which produces NaCl, AlCl3, CO2 and H2O on neutralization. What percentage of tablet should be sufficient to return the molarity to normal if your stomach contains 300mL of the acid. 3.6g of Mg is burnt in limited supply of oxygen. The residue was treated with 100mL of H2SO4 (35% by mass, 1.26g mL-1 density). When 2.463L of H2 at 760 mm Hg at 27oC was evolved. After the reaction, H2SO4 was found to have a density of 1.05g mL-1. Assuming no volume change in H2SO4 solution. Find (i) % by mass of final H2SO4 (ii) % by mass of Mg converted to oxide 2 litres of air, measured at NTP were shaken with 50cc of N/50 barium hydroxide, the carbon dioxide in the air being converted quantitatively into barium carbonate. The residual barium hydroxide was titrated against N/50 oxalic acid of which 33.2cc were required for naturalization, phenolphthalein being used as indicator. Calculate the percentage by volume of carbon dioxide in the sample of air. In Pettenkoffer's method, 50cc of a solution of barium hydroxide was run into a bottle of capacity 2560cc, which was then quickly stoppered and well shaken. It was found that the residual barium hydroxide required 58.4cc of N/50 oxalic acid (phenolphthalein indicator). In a separate titration 50cc of the barium hydroxide solution 63.2cc of N/50 oxalic acid for neutralisation. What value for the percentage by volume of carbon dioxide in air is given by these results? When 1g of KNaC4H4O6 . 4H2O is ignited, the residue obtained required 31.8mL of 0.2M HCl for complete neutralization. What is % purity of salt? The saponification no. of fat or oil is defined as the no. of mg of KOH required to saponify 1g oil or fat. A sample of peanut oil weighing 1.5763g is added to 25mL of 0.4210M KOH. After saponification is complete, 8.46mL of 0.2732M H2SO4 is needed to neutralize excess of KOH. What is the saponification no. of peanut oil? 0.454gm of a mixture of ammonium sulphate and sodium sulphate gave 0.773gm of barium sulphate on treatment with barium chloride. When 0.454gm of the mixture is boiled with 40cc of 0.1N sodium hydroxide until no more ammonia is evolved, how many cc of 0.1N hydrochloric acid will be required to neutralize the excess of sodium hydroxide?

C-39, LAJPA T MARG , C-SCHEME, JAIPUR, RAJASTHAN. PH # 0141-2377707, FAX- 2328182

STOICHIOMETRY AND REDOX -3

Q15(a). 50 ml of water sample required 10 ml of N/50 HCl for complete neutralisation. Calculate the temporary hardness of water. (b) 200 ml of this water was then boiled with 100 ml N/50 soda reagent. After boiling the volume was again made to 200 ml and the solution was filtered. 25 ml filtrate required 8.2 ml of N/50 HCl for complete neutralisation. Calculate the permanent hardness in ppm. Q16. A 100 ml sample of hard water is passed through a column of the iron exchange resin H2R. The water coming off the column require 15.17 ml of 0.0265 M NaOH for titration. What is the hardness of water in ppm of Ca2+. A sample of water has its hardnesss due to only CaSO4 when this water is passed through an anion exchange resin, SO42 ions are replaced by OH. A 25 mL sample of water so treated requires 21.58 mL of 103 M H2SO4 for titration. What is the hardness of water in ppm of CaSO4. Assume dwater = 1 g/ ml. A sample of hard water contain 96 ppm of SO42 and 183 ppm of HCO3 with Ca2+ as only cation. How many moles of CaO will be required to remove HCO3 from 1000 kg of this water? If 1000 kf og this water is treated with the amount of CaO calculated above, what will be the concentration (in ppm) of residual Ca2+ ions (assume CaCO3 is completely insoluble in water). If Ca2+ ions in one litre of the treated water are completely exchanged with hydrogen ions, what is the concentration of H+ ions. [JEE 97, 5] *****

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C-39, LAJPA T MARG , C-SCHEME, JAIPUR, RAJASTHAN. PH # 0141-2377707, FAX- 2328182

STOICHIOMETRY AND REDOX -3

Exercise I
Q1. 6.608 g/litre Q4. 0.0176M Q9. 10 Q13. 470 mL Q17. 8.67 Q20. 62.8% alanine Q6. 11.92 g/litre Q10. 2 Q14. 90.1% Q18. 56.2%

Answers
Q2. 5.116 g/litre, 568.4 cc Q3. 0.0311 Q7. 35%, 65% Q11. 25 mL Q15. 90.4% Q4. (i) 0.569N, (ii) 50 Q8. E = 122 Q12. 3.78g Q16. 13.1%, 57.8%

Q19. weight% of NH3 is sample = 8.5%

Exercise II
Q1. 0.381 g Q5. 20.77% Q2. 15.2% Q3. 2.63% Q4. 1.816 g/litre Q6. H2SO4 = 35.4%, SO2 = 1.5%, SO3 = 3.1% combined SO3 = 28.89% Q8. 3.198 g HCl/litre, 6.974 g KCl/litre Q12. 36.85 g/litre Q13. 1, 2

Q7. % of NH4Cl = 57.5%, % of NaCl = 42.5% Q9. 9.31 g/litre Q10. 90.0%

Q11. 56.7%

Q14. % of NaOH=37.33%, % of Na2CO3=49.47% Q15. Na2CO3= 40 x 10-2mol, NaOH= 40 x 10-2mol Q16. (i) 5.003 g/litre, (ii) 2.486 g/litre Q19. 9.38 g/litre Q17. 12.57cc Q18. 64.2%, 64.5%

Q20. 1.971 g HCl/litre, 2.000 g H2PO4/litre, 4.608 g NaOH/litre

Exercise III
Q1. 157.8 mL Q2. 96%, 4% Q3. 0.5962 g, 0.394 g Q5. 27.27% Q6. 23, 1.3996 g Q10. 0.188% Q7. 6.528 g Q11. 0.043% Q4. (a) 60%, (b) 2.9638 g/litre, (c) 0.0812 Q8. 64.67% tablet Q12. 89.67% Q16. 80.4 ppm

Q9. (i) 28%, (ii) 33.33% Q13. 209.8 Q17. 117.4 ppm Q14. 5.79 cc

Q15(a) 200 ppm; (b) 344 ppm

Q18. 1.5, 40 ppm, 2 x 103 mol

C-39, LAJPA T MARG , C-SCHEME, JAIPUR, RAJASTHAN. PH # 0141-2377707, FAX- 2328182

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