!Answer!: Fe_{3}O_{4}.
45. If an element has 98 for its atomic weight, and after reduction with stannous chloride could be oxidized by bichromate to a state corresponding to an XO_{4}^{-} anion, compute the oxide, or valence, corresponding to the reduced state from the following data: 0.3266 gram of the pure element, after being dissolved, was reduced with stannous chloride and oxidized by 40 cc. of K_{2}Cr_{2}O_{7}, of which one cc. = 0.1960 gram of FeSO_{4}(NH_{4})_{2}SO_{4}.6H_{2}O.
!Answer!: Monovalent.
46. Determine the percentage of iron in a sample of limonite from the following data: Sample = 0.5000 gram. KMnO_{4} used = 50 cc. 1 cc.
KMnO_{4} = 0.005317 gram Fe. FeSO_{4} used = 6 cc. 1 cc. FeSO_{4} = 0.009200 gram FeO.
!Answer!: 44.60%.
47. If 1 gram of a silicate yields 0.5000 gram of Fe_{2}O_{3} and Al_{2}O_{3} and the iron present requires 25 cc. of 0.2 N KMnO_{4}, calculate the percentage of FeO and Al_{2}O_{3} in the sample.
!Answer!: 35.89% FeO; 10.03% Al_{2}O_{3}.
48. A sample of magnesia limestone has the following composition: Silica, 3.00%; ferric oxide and alumina, 0.20%; calcium oxide, 33.10%; magnesium oxide, 20.70%; carbon dioxide, 43.00%. In manufacturing lime from the above the carbon dioxide is reduced to 3.00%. How many cubic centimeters of normal KMnO_{4} will be required to determine the calcium oxide volumetrically in a 1 gram sample of the lime?
!Answer!: 20.08 cc.
49. If 100 cc. of pota.s.sium bichromate solution (10 gram K_{2}Cr_{2}O_{7} per liter), 5 cc. of 6 N sulphuric acid, and 75 cc.
of ferrous sulphate solution (80 grams FeSO_{4}.7H_{2}O per liter) are mixed, and the resulting solution t.i.trated with 0.2121 N KMnO_{4}, how many cubic centimeters of the KMnO_{4} solution will be required to oxidize the iron?
!Answer!: 5.70 cc.
50. If a 0.5000 gram sample of limonite containing 59.50 per cent Fe_{2}O_{3} requires 40 cc. of KMnO_{4} to oxidize the iron, what is the value of 1 cc. of the permanganate in terms of (a) Fe, (b) H_{2}C_{2}O_{4}.2H_{2}O?
!Answers!: (a) 0.005189 gram; (b) 0.005859 gram.
51. A sample of pyrolusite weighing 0.6000 gram is treated with 0.9000 gram of oxalic acid. The excess oxalic acid requires 23.95 cc. of permanganate (1 cc. = 0.03038 gram FeSO_{4}.7H_{2}O). What is the percentage of MnO_{2}, in the sample?
!Answer!: 84.47%.
52. A solution contains 50 grams of KHC_{2}O_{4}.H_{2}C_{2}O_{4}.2H_{2}O per liter. What is the normal value of the solution (a) as an acid, and (b) as a reducing agent?
!Answers!: (a) 0.5903 N; (b) 0.7872 N.
53. In the a.n.a.lysis of an iron ore containing 60% Fe_{2}O_{3}, a sample weighing 0.5000 gram is taken and the iron is reduced with sulphurous acid. On account of failure to boil out all the excess SO_{2}, 38.60 cubic centimeters of 0.1 N KMnO_{4} were required to t.i.trate the solution. What was the error, percentage error, and what weight of sulphur dioxide was in the solution?
!Answers!: (a) 1.60%; (b) 2.67%; (c) 0.00322 gram.
54. From the following data, calculate the ratio of the nitric acid as an oxidizing agent to the tetroxalate solution as a reducing agent: 1 cc. HNO_{3} = 1.246 cc. NaOH solution; 1 cc. NaOH = 1.743 cc.
KHC_{2}O_{4}.H_{2}C_{2}O_{4}.2H_{2}O solution; Normal value NaOH = 0.12.
!Answer!: 4.885.
55. Given the following data: 25 cc. of a hydrochloric acid, when standardized gravimetrically as silver chloride, yields a precipitate weighing 0.5465 gram. 24.35 cc. of the hydrochloric acid are exactly equivalent to 30.17 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 pota.s.sium 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 apat.i.te weighing 0.60 gram is a.n.a.lyzed 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 a.n.a.lysis of a sample of steel weighing 1.881 grams the phosphorus was precipitated with ammonium molybdate and the yellow precipitate was dissolved, reduced and t.i.trated 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 t.i.trate the iodine liberated from an excess of pota.s.sium 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 a.n.a.lyzed sample of stibnite containing 70.05% Sb is given for a.n.a.lysis. A student t.i.trates 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 a.n.a.lysis shows the sample to contain 70.32% Sb. Calculate the true normal value of the iodine solution, and the percentage error in the a.n.a.lysis.
!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 pa.s.sed into pota.s.sium iodide and the liberated iodine is t.i.trated 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 t.i.trated?
!Answer!: 26.22 cc.
65. In the determination of sulphur in steel by evolving the sulphur as hydrogen sulphide, precipitating cadmium sulphide by pa.s.sing 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 t.i.trated 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. a.r.s.enite 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 pa.s.sed into CdCl_{2} solution, the acidified precipitate being t.i.trated 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%.