An Introductory Course of Quantitative Chemical Analysis, Henry P. Talbot [chrome ebook reader txt] 📗

cc. of KHC_{2}O_{4}.H_{2}C_{2}O_{4}.2H_{2}O solution. How much water must be added to a liter of the oxalate solution to make it exactly 0.025 N as a reducing agent?

!Answer!: 5564 cc.

56. Ten grams of a mixture of pure potassium tetroxalate (KHC_{2}O_{4}.H_{2}C_{2}O_{4}.2H_{2}O) and pure oxalic acid (H_{2}C_{2}O_{4}.2H_{2}O) are dissolved in water and diluted to exactly 1000 cc. The normal value of the oxalate solution when used as an acid is 0.1315. Calculate the ratio of tetroxalate to oxalate used in making up the solution and the normal value of the solution as a reducing agent.

!Answers!: 2:1; 0.1577 N.

57. A student standardized a solution of NaOH and one of KMnO_{4} against pure KHC_{2}O_{4}.H_{2}C_{2}O_{4}.2H_{2}O and found the former to be 0.07500 N as an alkali and the latter exactly 0.1 N as an oxidizing agent. By coincidence, exactly 47.26 cc. were used in each standardization. Find the ratio of the oxalate used in the NaOH standardization to the oxalate used in the permanganate standardization.

!Answer!: 1:1.

58. A sample of apatite weighing 0.60 gram is analyzed for its phosphoric anhydride content. If the phosphate is precipitated as (NH_{4}){3}PO{4}.12MoO_{3}, and the precipitate (after solution and reduction of the MoO_{3} to Mo_{24}O_{37}), requires 100 cc. of normal KMnO_{4} to oxidize it back to MoO_{3}, what is the percentage of P_{2}O_{5}?

!Answer!: 33.81%.

59. In the analysis of a sample of steel weighing 1.881 grams the phosphorus was precipitated with ammonium molybdate and the yellow precipitate was dissolved, reduced and titrated with KMnO_{4}. If the sample contained 0.025 per cent P and 6.01 cc. of KMnO_{4} were used, to what oxide was the molybdenum reduced? 1 cc. KMnO_{4} = 0.007188 gram Na_{2}C_{2}O_{4}.

!Answer!: Mo_{4}O_{5}.

60. What is the value of 1 cc. of an iodine solution (1 cc. equivalent to 0.0300 gram Na_{2}S_{2}O_{3}) in terms of As_{2}O_{3}?

!Answer!: 0.009385 gram.

61. 48 cc. of a solution of sodium thiosulphate are required to titrate the iodine liberated from an excess of potassium iodide solution by 0.3000 gram of pure KIO_{3}. (KIO_{3} + 5KI + 3H_{2}SO_{4} = 3K_{2}SO_{4} + 3I_{2} + 3H_{2}O.) What is the normal strength of the sodium thiosulphate and the value of 1 cc. of it in terms of iodine?

!Answers!: 0.1753 N; 0.02224 gram.

62. One thousand cubic centimeters of 0.1079 N sodium thiosulphate solution is allowed to stand. One per cent by weight of the thiosulphate is decomposed by the carbonic acid present in the solution. To what volume must the solution be diluted to make it exactly 0.1 N as a reducing agent? (Na_{2}S_{2}O_{3} + 2H_{2}CO_{3} = H_{2}SO_{3} + 2NaHCO_{3} + S.)

!Answer!: 1090 cc.

63. An analyzed sample of stibnite containing 70.05% Sb is given for analysis. A student titrates it with a solution of iodine of which 1 cc. is equivalent to 0.004950 gram of As_{2}O_{3}. Due to an error on his part in standardization, the student's analysis shows the sample to contain 70.32% Sb. Calculate the true normal value of the iodine solution, and the percentage error in the analysis.

!Answers!: 0.1000 N; 0.39%.

64. A sample of pyrolusite weighing 0.5000 gram is treated with an excess of hydrochloric acid, the liberated chlorine is passed into potassium iodide and the liberated iodine is titrated with sodium thiosulphate solution (49.66 grams of pure Na_{2}S_{2}O_{3}.5H_{2}O per liter). If 38.72 cc. are required, what volume of 0.25 normal permanganate solution will be required in an indirect determination in which a similar sample is reduced with 0.9012 gram H_{2}C_{2}O_{4}.2H_{2}O and the excess oxalic acid titrated?

!Answer!: 26.22 cc.

65. In the determination of sulphur in steel by evolving the sulphur as hydrogen sulphide, precipitating cadmium sulphide by passing the liberated hydrogen sulphide through ammoniacal cadmium chloride solution, and decomposing the CdS with acid in the presence of a measured amount of standard iodine, the following data are obtained: Sample, 5.027 grams; cc. Na_{2}S_{2}O_{3} sol. = 12.68; cc. Iodine sol. = 15.59; 1 cc. Iodine sol. = 1.086 cc. Na_{2}S_{2}O_{3} sol.; 1 cc. Na_{2}S_{2}O_{3}= 0.005044 gram Cu. Calculate the percentage of sulphur. (H_{2}S + I_{2} = 2HI + S.)

!Answer!: 0.107%.

66. Given the following data, calculate the percentage of iron in a sample of crude ferric chloride weighing 1.000 gram. The iodine liberated by the reaction 2FeCl_{3}+ 2HI = 2HCl + 2FeCl_{2} + I_{2} is reduced by the addition of 50 cc. of sodium thiosulphate solution and the excess thiosulphate is titrated with standard iodine and requires 7.85 cc. 45 cc. I_{2} solution = 45.95 cc. Na_{2}S_{2}O_{3} solution; 45 cc. As_{2}O_{3} solution = 45.27 cc. I_{2} solution. 1 cc. arsenite solution = 0.005160 gram As_{2}O_{3}.

!Answer!: 23.77%.

67. Sulphide sulphur was determined in a sample of reduced barium sulphate by the evolution method, in which the sulphur was evolved as hydrogen sulphide and was passed into CdCl_{2} solution, the acidified precipitate being titrated with iodine and thiosulphate. Sample, 5.076 grams; cc. I_{2} = 20.83; cc. Na_{2}S_{2}O_{3} = 12.37; 43.45 cc. Na_{2}S_{2}O_{3} = 43.42 cc. I_{2}; 8.06 cc. KMnO_{4} = 44.66 cc. Na_{2}S_{2}O_{3}; 28.87 cc. KMnO_{4} = 0.2004 gram Na_{2}C_{2}O_{4}. Calculate the percentage of sulphide sulphur in the sample.

!Answer!: 0.050%.

68. What weight of pyrolusite containing 89.21% MnO_{2} will oxidize the same amount of oxalic acid as 37.12 cc. of a permanganate solution, of which 1 cc. will liberate 0.0175 gram of I_{2} from KI?

!Answer!: 0.2493 gram.

69. A sample of pyrolusite weighs 0.2400 gram and is 92.50% pure MnO_{2}. The iodine liberated from KI by the manganese dioxide is sufficient to react with 46.24 cc. of Na_{2}S_{2}O_{3} sol. What is the normal value of the thiosulphate?

!Answer!:: 0.1105 N.

70. In the volumetric analysis of silver coin (90% Ag), using a 0.5000 gram sample, what is the least normal value that a potassium thiocyanate solution may have and not require more than 50 cc. of solution in the analysis?

!Answer!: 0.08339 N.

71. A mixture of pure lithium chloride and barium bromide weighing 0.6 gram is treated with 45.15 cubic centimeters of 0.2017 N silver nitrate, and the excess titrated with 25 cc. of 0.1 N KSCN solution, using ferric alum as an indicator. Calculate the percentage of bromine in the sample.

!Answer!: 40.11%.

72. A mixture of the chlorides of sodium and potassium from 0.5000 gram of a feldspar weighs 0.1500 gram, and after solution in water requires 22.71 cc. of 0.1012 N silver nitrate for the precipitation of the chloride ions. What are the percentages of Na_{2}O and K_{2}O in the feldspar?

!Answer!: 8.24% Na_{2}O; 9.14% K_{2}O.

GRAVIMETRIC ANALYSIS

73. Calculate (a) the grams of silver in one gram of silver chloride; (b) the grams of carbon dioxide liberated by the addition of an excess of acid to one gram of calcium carbonate; (c) the grams of MgCl_{2} necessary to precipitate 1 gram of MgNH_{4}PO_{4}.

!Answers!: (a) 0.7526; (b) 0.4397; (c) 0.6940.

74. Calculate the chemical factor for (a) Sn in SnO_{2}; (b) MgO in Mg_{2}P_{2}O_{7}; (c) P_{2}O_{5} in Mg_{2}P_{2}O_{7}; (d) Fe in Fe_{2}O_{3}; (e) SO_{4} in BaSO_{4}.

!Answers!: (a) 0.7879; (b) 0.3620; (c) 0.6378; (d) 0.6990; (e) 0.4115.

75. Calculate the log factor for (a) Pb in PbCrO_{4}; (b) Cr_{2}O_{3} in PbCrO_{4}; (c) Pb in PbO_{2} and (d) CaO in CaC_{2}O_{4}.

!Answers!: (a) 9.8069-10, (b) 9.3713-10; (c) 9.9376-10; (d) 9.6415-10.

76. How many grams of Mn_{3}O_{4} can be obtained from 1 gram of MnO_{2}?

!Answer!: 0.8774 gram.

77. If a sample of silver coin weighing 0.2500 gram gives a precipitate of AgCl weighing 0.2991 gram, what weight of AgI could have been obtained from the same weight of sample, and what is the percentage of silver in the coin?

!Answers!: 0.4898 gr.; 90.05%.

78. How many cubic centimeters of hydrochloric acid (sp. gr. 1.13 containing 25.75% HCl by weight) are required to exactly neutralize 25 cc. of ammonium hydroxide (sp. gr. .90 containing 28.33% NH_{3} by weight)?

!Answer!: 47.03 cc.

79. How many cubic centimeters of ammonium hydroxide solution (sp. gr. 0.96 containing 9.91% NH_{3} by weight) are required to precipitate the aluminium as aluminium hydroxide from a two-gram sample of alum (KAl(SO_{4}){2}.12H{2}O)? What will be the weight of the ignited precipitate?

!Answers!: 2.26 cc.; 0.2154 gram.

80. What volume of nitric acid (sp. gr. 1.05 containing 9.0% HNO_{3} by weight) is required to oxidize the iron in one gram of FeSO_{4}.7H_{2}O in the presence of sulphuric acid? 6FeSO_{4} + 2HNO_{3} + 3H_{2}SO_{4} = 3Fe_{2}(SO_{4}){3} + 2NO + 4H{2}O.

!Answer!: 0.80 cc.

81. If 0.7530 gram of ferric nitrate (Fe(NO_{3}){3}.9H{2}O) is dissolved in water and 1.37 cc. of HCl (sp. gr. 1.11 containing 21.92% HCl by weight) is added, how many cubic centimeters of ammonia (sp. gr. 0.96 containing 9.91% NH_{3} by weight) are required to neutralize the acid and precipitate the iron as ferric hydroxide?

!Answer!: 2.63 cc.

82. To a suspension of 0.3100 gram of Al(OH){3} in water are added 13.00 cc. of aqueous ammonia (sp. gr. 0.90 containing 28.4% NH{3} by weight). How many cubic centimeters of sulphuric acid (sp. gr. 1.18 containing 24.7% H_{2}SO_{4} by weight) must be added to the mixture in order to bring the aluminium into solution?

!Answer!: 34.8 cc.

83. How many cubic centimeters of sulphurous acid (sp. gr. 1.04 containing 75 grams SO_{2} per liter) are required to reduce the iron in 1 gram of ferric alum (KFe(SO_{4}){2}.12H{2}O)? Fe_{2}(SO_{4}){3} + SO{2} + 2H_{2}O = 2FeSO_{4} + 2H_{2}SO_{4}.

!Answer!: 0.85 cc.

84. How many cubic centimeters of a solution of potassium bichromate containing 26.30 grams of K_{2}Cr_{2}O_{7} per liter must be taken in order to yield 0.6033 gram of Cr_{2}O_{3} after reduction and precipitation of the chromium?

K_{2}Cr_{2}O_{7} + 3SO_{2} + H_{2}SO_{4} = K_{2}SO_{4} +
Cr_{2}(SO_{4}){3} + H{2}O.

!Answer!: 44.39 cc.

85. How many cubic centimeters of ammonium hydroxide (sp. gr. 0.946 containing 13.88% NH_{3} by weight) are required to precipitate the iron as Fe(OH){3} from a sample of pure FeSO{4}.(NH_{4}){2}SO{4}.6H_{2}O, which requires 0.34 cc. of nitric acid (sp. gr. 1.350 containing 55.79% HNO_{3} by weight) for oxidation of the iron? (See problem No. 80 for reaction.)

!Answer!: 4.74 cc.

86. In the analysis of an iron ore by solution, oxidation and precipitation of the iron as Fe(OH){3}, what weight of sample must be taken for analysis so that each one hundredth of a gram of the ignited precipitate of Fe{2}O_{3} shall represent one tenth of one per cent of iron?

!Answer!: 6.99 grams.

87. What weight in grams of impure ferrous ammonium sulphate should be taken for analysis so that the number of centigrams of BaSO_{4} obtained will represent five times the percentage of sulphur in the sample?

!Answer!: 0.6870 gram.

88. What weight of magnetite must be taken for analysis in order that, after precipitating and igniting all the iron to Fe_{2}O_{3}, the percentage of Fe_{2}O_{4} in the sample may be found by multiplying the weight in grams of the ignited precipitate by 100?

!Answer!: 0.9665 gram.

89. After oxidizing the arsenic in 0.5000 gram of pure As_{2}S_{3} to arsenic acid, it is precipitated with "magnesia mixture" (MgCl_{2} + 2NH_{4}Cl). If exactly 12.6 cc. of the mixture are required, how many grams of MgCl_{2} per liter does the solution contain? H_{3}AsO_{4} + MgCl_{2} + 3NH_{4}OH = MgNH_{4}AsO_{4} + 2NH_{4}Cl + 3H_{2}O.

!Answer!: 30.71 grams.

90. A sample is prepared for student analysis by mixing pure apatite (Ca_{3}(PO_{4}){2}.CaCl{2}) with an inert material. If 1 gram of the sample gives 0.4013 gram of Mg_{2}P_{2}O_{7}, how many cubic centimeters of ammonium oxalate solution (containing 40 grams of (NH_{4}){2}C{2}O_{4}.H_{2}O per liter) would be required to precipitate the calcium from the same weight of sample?

!Answer!: 25.60 cc.

91. If 0.6742 gram of a mixture of pure magnesium carbonate and pure calcium carbonate, when treated with an excess of hydrochloric acid, yields 0.3117 gram of carbon dioxide, calculate the percentage of magnesium oxide and of calcium oxide in the sample.

!Answers!: 13.22% MgO; 40.54% CaO. 92. The calcium in a sample of dolomite weighing 0.9380 gram is precipitated as calcium oxalate and ignited to calcium oxide. What volume of gas, measured over water at 20°C. and 765 mm. pressure, is given off during ignition, if the resulting oxide weighs 0.2606 gram? (G.M.V. = 22.4 liters; V.P. water at 20°C. = 17.4 mm.)

!Answer!: 227 cc.

93. A limestone is found to contain 93.05% CaCO_{3}, and 5.16 % MgCO_{3}. Calculate the weight of CaO obtainable from 3 tons of the limestone, assuming complete conversion to oxide. What weight of Mg_{2}P_{2}O_{7} could be obtained from a 3-gram sample of the limestone?

!Answers!: 1.565 tons; 0.2044 gram.

94. A sample of dolomite is analyzed for calcium by precipitating as the oxalate and igniting the precipitate. The ignited product is assumed to be CaO and the analyst reports 29.50% Ca in the sample. Owing to insufficient ignition, the product actually contained 8% of its weight of CaCO_{3}. What is the correct percentage of calcium in the sample, and what is the percentage error?

!Answers!: 28.46%; 3.65% error.

95. What weight of impure calcite (CaCO_{3}) should be taken for analysis so that the volume in