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INTERMEDIATE CHEMISTRY INTERMEDIATE CHEMISTRY BY T. M. LOWRY, C.B.E., M.A., P-Sc, F.R.S. LATE rROT^SSOR OF PHYSICAL CHEMISTEV IN THE UNIVERSIT^ ^^ CAMBRIDGE AND A. C. CAVELL, M.A., B.Sc SENIOR SCIENCE WiStER. AT UPPINGHAM. £.GH.Q^^ FIFTH EDITION t^ •? MACMILLAN AND CO., LIMITED ST. MARTIN'S STREET, LONDON 1949 COPYRIGHT First Edition, 1936. Second Edition, 1939. Revised and reprinted, 1941. Tliird Edition, 194g. Eevised and reprmted^ 1944. EeprinFed, 1945, 1946. Fourth Edition, 1946, Fiftli Edition, 1947. Revised and reprinted, 1949. / PRINTED IN GREAT BRITAIN PREFACE The purpose of the present volume is to provide a complete text-book of chemistry for Intermediate and Higher School Certificate Examinations. It therefore includes under one cover sections on General and Theoretical, Inorganic and Organic, Analytical and Physical Chemistry. In prepar- ing it, the books already written by the senior author, either alone or in collaboration, have been drawn upon, especially as regards the figures and illustrations, so far as they were suitable for this purpose. The inorganic section (Parts I to' III) has been completely reconstructed, however, and bears only a remote resemblance to Lowry's " Inorganic Chemistry " ; the four chapters on inorganic analysis (Part IV) and the whole of the section on " Principles of Organic Chemistry " (Part VI), with the ex- ception of some of the organic preparations, are new ; only the physical section (Part V), therefore, resembles at all closely those portions of Lowry and Sugden's " Class-book of Physical Chemistry " which have been adapted with relatively little change for their present use. The planning of an " Intermediate Chemistry " differs in many impor- tant respects from that of an elementary or of an advanced text-book. Thus, in writing .a book for the stage which immediately follows Matric- ulation, it may be assumed that the reader is already familiar with the great classical discoveries of the composition of air and of water, of the •" changes of weight which accompany the burning of chalk to lime and of metals to their calces, and in general with the main facts of chemical combination and decomposition, including the observations of Davy and Faraday on electrolysis. Historical details, which may again become important in a more advanced study, need not therefore be stressed so strongly at the intermediate stage. On the theoretical side, it may be assumed that the atomic and molecular theories have been expounded in the closing stages of the Matriculation or School Certificate course, and that the reader understands, at least in general terms, the meaning of chemical formulae and the significance of chemical equations, so that these can be used freely from the very beginning. In these circumstances, it is a convenient and logical procedure to begin by setting out the theore- vi PREFACE tical conceptions in terms of which the facts of chemistry are now ex- pressed. Recent discoveries in the field of atomic and molecular physics are also in place, so far as they tend to increased orderliness and simpli- city. In particular, the introduction of atomic numbers is obviously essential; and even at this early stage there is much to be gained, and nothing to be lost, by contrasting the processes of electron transfer and electron sharing as alternative methods of forming chemical compounds from their elements. One other point of contrast i j important. The early stages in the study of chemistry are necessarily concerned mainly with the non-metals, and usually include only a fragmentary survey of the much larger range of the metals. By contrast, the intermediate student may conveniently under- take the systematic study of the typical elements in the sequence laid down in the periodic classification, dealing first with the alkali metals, as ele- ments which readily lose an electron, and finishing with the halogens, as elements which readily accept an electron, in order to acquire the con- figuration of an inert gas. This reversal oi the usual sequence has the advantage that the metals occupy the earlier pages, whilst the non- metals come up again for review only after their influence on the metals has been discussed. The transitional elements are described after the typical elements, but in a sequence of valencies which is not the same as the sequence of atomic numbers. The organic section, under the title " Principles of Organic Chemistry," includes the subjects prescribed in the new syllabus recently issued by the University of London. In harmony with the title, detailed descrip- tions of preparations and properties of organic compounds have been excluded, in principle, from the text, and transferred to the Experiments ; but the underlying theories have been discussed more fully than has been customary hitherto, even in advanced text-books of organic chemistry. Thus we have cited Lapworth's interpretation of the cyanhydrin reaction, and Robinson's explanation of the contrast between the unsaturation of olefines and of ketones, not merely because we accept them as true, but because they are too simple and clear to be overlooked, even in an elementary course of organic chemistry, at least when (as in the present instance) some knowledge of the structure of matter and of the electronic theory of valency can be assumed. Teachers who may be interested in these recent developments in the theory of organic chemistry will find the materials which inspired this section of our work in a book on " Physical Aspects of Organic Chemistry " by Dr. W. A. Waters, to which the senior author contributed an introduction and some portions of the text. PREFACE vu Experiments numbered from i to 190 are an important feature of the book. They have survived the test of use in school classes, and it is believed that they will be of real value in practical work. They include a series of preparations, which are attached to those paragraphs to which they are most closely related ; but tables for use in qualitative analysis, and detailed instructions for volumetric and gravimetric analysis, have been placed together in Part IV of the book. Since the book is intended to be used in the laboratory as well as in the classroom, it has been provided with a water-proofed cover. Typical questions have been collected and classified into sections corresponding to successive groups of chapters, so that the reader may be able to test his progress in knowledge at convenient stages. Solutions have been given to some of the problems in organic chemistry set in recent Scholarship Examinations. More than fifty new figures have been prepared for the present volume, and many more have been modified or redrawn for the sake of greater clearness. All temperatures are expressed in centigrade degrees. In conclusion, we wish to express our indebtedness to Sir Richard Gregory ior expert advice and helpful sympathy; to Messrs. J. V. S. Glass and P. W. Goddard for valuable suggestions in the composition of the inorganic section ; to Messrs. Imperial Chemical Industries for the prints used in preparing a diagram of the Gaillard tower, and for assist- ance in the preparation of certain other figures ; to the Old Chemistry Department at the University of Oxford for permission to reproduce Experiments 10, 47 and 48 ; to Prof. J. R. Partington for permission to reproduce Figs. 57 and 85 ; to Dr. S. F. Boys for data (in part not previously published) in reference to the absolute configurations of valeric, lactic and tartaric acids ; to Mr. R. P. Ayres of Leys School, Mr. F. E. Hague of Culford School, and Mr. A. J.V. Gale for reading the slip-proofs and paged proofs of the book ; to numerous pupils at Leys, Winchester and Uppingham who have tried out the experiments and helped in the correction of proofs, and finally to the Boards of Examiners whose questions we quote. The authors will welcome information as to errors which may have escaped detection during numerous readings of the proofs. T. M. LOWRY A. C. CAVELL June 1936, PREFACE TO T H E SECOND EDITION T H E subject matter has bee^n thoroughly revised and brought up to date in the second edition of this book. New sections have been added on the electrochemical series and adsorption indicators, and extensive alterations have been made to a number of the experiments, especially in the organic section, by the insertion of fuller and improved details. The junior author wishes to take this opportunity of expressing his great sorrow at the death of Prof. T. Martin Lowry, whose sympathetic collaboration was invaluable in the production of^ the original issue of this book. 1939 A. C. CAVELL PREFACE TO T H E F I F T H EDITION SEVERAL sections of Parts I and II have been revised and extended in the hght of recent work on the structure of matter and the formulae of inorganic compounds. In addition, modern developments in organic chemistry, such as the chlorination and nitration of paraffins, the polymerisation of olefines, and the application of resonance to the structure of compounds, have been described. Minor changes have also been made in other parts of the book where these seemed desirable, and some of the diagrams have been redrawn. A. C. CAVELL 1947 CONTENTS PART I. GENERAL AND THEORETICAL CHAPTER PACK L T H E ATOMIC THEORY - - - - - - - i II. CHEMICAL EQUIVALENTS - - - - - - 7 I I I . T H E MOLECULAR THEORY - - - - - - 14 IV. T H E DETERMINATION O F ATOMIC WEIGHTS - - - 20 V. T H E STRUCTURE OF MATTER - - - - - - 24 VI. T H E ELECTRONIC THEORY OF VALENCY - - - - 34 V I I . F O R M U L A E AND EQUATIONS. EQUIVALENTS OF COM- POUNDS - - 4 2 V I I I . CLASSIFICATION O F THE ELEMENTS - - - - 51 PART II. TYPICAL E L E M E N T S I X . T H E INERT GASES 63 X. H Y D R O G E N , WATER AND HYDROGEN PEROXIDE - - 67 X I . T H E ALKALI METALS . - _ . . . - . go X I I . M E T A L S O F T H E ALKALINE EARTHS - - - - i i i X I I I . BORON AND ALUMINIUM - . - - . . - 125 X I V . CARBON AND SILICON - - - - - - - 136 XV. T I N AND LEAD . . . . . . . . - . 163 X V L N I T R O G E N - - - - •- - - - 174 X y i l . PHOSPHORUS - - - - . . . . . 205 X V I I l . ARSENIC, ANTIMONY AND BISMUTH .. . . . 219 X I X . O X Y G E N - - • • - 230 X X . SULPHUR - - •• 243 X X I . T H E HALOGENS - . - • • . . - . . 267 ix CONTENTS PART III. TRANSITIONAL ELEMENTS CHAPTER XXII. THE TRANSITIONAL ELEMENTS - - - XXIII. THE COINAGE METALS . - - - XXIV. THE MERCURY GROUP . . . . XXV. NICKEL AND COBALT XXVI. IRON - - - - - XXVII. CHROMIUM AND MANGANESE .' . . 301 308 330 342 350 364 PART IV. ANALYSIS XXVIII. QUALITATIVE ANALYSIS OF A PURE SUBSTANCE ' - - 377 XXIX. QUALITATIVE ANALYSIS OF MIXTURES . . . 399 XXX. VOLUMETRIC ANALYSIS _ 412 XXXI. GRAVIMETRIC ANALYSIS 436 XXXII. ORGANIC ANALYSIS . . . . . . . 445 PART V. PHYSICAL CHEMISTRY XXXIII. THE GASEOUS STATE 453 XXXIV. LIQUEFACTION AND THE LIQUID STATE . . . 470 XXXV. THE SOLID STATE . - . - . - - 490 XXXVI. SOLUTIONS - - 495 XXXVII. OSMOTIC PRESSURE - 507 XXXVIII. MOLECULAR WEIGHTS IN SOLUTION . . . . 516 XXXIX. T H E PHASE RULE 530 XL. THERMOCHEMISTRY . 548 XLI. CHEMICAL EQUILIBRIUM 554 XLXI. VELOCITY OF CHEMICAL CHANGE . . . . 571 XLIII. THE MECHANISM OF CHEMICAL CHANGE . . . 583 XLIV. ELECTROLYSIS AND ELECTROLYTIC DISSOCIATION - 593 XLV. APPLICATIONS TO ELECTROLYTES OF THE LAW OF MASS ACTION - - 614 XLVI. THE COLLOIDAL STATE 641 CONTENTS xi PART VI. P R I N C I P L E S O F ORGANIC CHEMISTRY CHAPTER PAGE X L V I I . G E N E R A L PRINCIPLES . - - - • . . - 651 X L V I I I . PARAFFINS - - - . . . - - . - 661 X L I X . O L E F I N E S - - . . . . . . . 668 L. A C E T Y L E N E 674 LI. T H E ALCOHOLS - - . . . . . . - 677 L I I . ALDEH-iTDES AND KETONES - 6 8 9 L I I I . CARBOXYLIC ACIDS . - . . - . - 709 LIV. E T H E R S AND ESTERS - - - - . , - 720 LV. P O L Y H Y D R I C ALCOHOLS - - - - . . . 734 LVI. H Y D R O X Y ACIDS AND DICARBOXYLIC ACIDS - - . - 742 L V I I . A M I N E S , AMIDES AND AMINO-ACIDS - . . . 759 L V I I I . C Y A N I D E S AND NITRITES - 766 L I X . AROMATIC HYDROCARBONS - - - - - - 771 L X . AROMATIC ALCOHOLS, ALDEHYDES, KETONES AND CARB- OXYLIC ACIDS - - - - - - - - - 785 L X I . P H E N O L S AND AROMATIC AMINES - - ' - - - 791 QUESTIONS -^ 803 A N S W E R S TO QUESTIONS . . - , , . 856 I N D E X . . . . - . - . . • 861 LIST OF EXPERIMENTS NUMBER PAGE 1. Conservation of mass during precipitation - - - - - 5 2. Conservation of mass in combustion of phosphorus . . . 5 3. Conversion of silver into silver chloride . . . - . 5 4. Analysis of cupric and cuprous oxides 6 5. Equivalent of tin by the S3mthesis of stannic oxide - - - 12 6. Analysis of calcium carbonate 13 7. Equivalent of magnesium or zinc by displacement of hydrogen - 13 8. Equivalents of potassium, chlorine and silver by analysis of potassium chlorate 13 9. Decomposition of water by sparking 78 10. Preparation of hydrogen peroxide 85 11. Thermite process - - - - 131 12. Preparation of aluminium chloride 133 13. Preparation of potash alum - ,- - - - - - 134 14. Adsorption by charcoal ' .- - - 140 15. jPreparation of carbon monoxide - - - - - - - 142 16. Volumetric composition of carbon dioxide . . . - - 146 17. Preparation of silicon tetrafluoride 160 18. Preparation of nitric oxide (first method) 190 19. Preparation of nitric oxide (second method) - - - . 190 20. Estimation of nitrogen as nitric oxide 202 21. The glow of phosphorus , . . . , . - . 208 22. Preparation of phosphine 209 23. Preparation of phosphonium iodide 210 24. Preparation of phosphorous oxide - - - - - - 211 25. Preparation of phosphoric oxide - - - - - - - 212 26. Preparation of phosphoric acid 213 27. Preparation of phosphorus trichloride 216 28. Preparation of phosphorus pentachloride 217 29. Marsh's test,for arsenic - - - 221 30. Volumetric composition of ozone . . . . - - 237 31. Estimation of carbon dioxide in air (Pettenkofer's method) - - 241 32. Preparation of prismatic sulphur - - - - - - - 246 33. Volumetric composition of hydrogen sulphide . - . . 251 34. To illustrate the lead chamber process 258 35. Volumetric composition of hydrogen chloride . - - . 283 36. Preparation of potassium chlorate . . . - - - 288 37. Preparation of potassium perchlorate - - - - - - 289 38. Preparation of bromine from potassium bromide - - - - 291 39. Preparation of hydrogen bromide (first method) - - - - 293 40. Preparation of hydrogen bromide (second method) - - - 293 41. Sublimation of iodine 296 42. Preparation of hydrogen iodide - . . - - - - 298 43. Preparation of iodic acid - 300 44. Fehling's solution = " 315 xiii xiv LIST OF EXPERIMENTS NUMBER PAGE 45. Preparation of cuprous chloride 316 46. Preparation of cuprammonium sulphate 319 47. Preparation of chloropentammine cobaltic chloride - - - 349 48. Preparation of sodium cobaltinitrite 349 49. The rusting of iron 3^7 50. Preparation of ferrous ammonium sulphate 359 51. Hydrolysis of ferric chloride 360 52. Preparation of chromium 365 53. Preparation of chromic oxide . . . . . . . 367 54. Preparation of chrome alum 367 55. Preparation of chromic acid . . . . . . . 368 56. Preparation of chromyl chloride 370 57. Preparation of potassium perinanganate 374 58. Estimation of a mixture of hydroxide and carbonate, or of bicar- bonate and carbonate 416 59. Estimation of the percentage of ammonium sulphate in lawn sand 417 5o. Estimation of nitrogen in potassium nitrate by reduction to ammonia - . . . - . . . . . ^jg 61. Determination of the solubility of hydrogen sulphide in water - 420 62. Determination of the percentage purity of a specimen of arsenious oxide - - - - - - - - - - - 421 6$. Estimation of available chlorine in bleaching powder. (lodometrie method) - - - - - 422 64. Estimation of available chlorine in bleaching powder. (Arsenite method) 422 65. Determination of available oxygen in pyrolusite - . - - 424 65. Estimation of copper in crystalline copper sulphate - - • 425 57. Analysis of a mixture of hydrogen peroxide and persulphuric acid 427 68. Estimation of calcium in marble 428 69. Estimation of the equivalent of potassium - - - - - 431 70. Estimation of silver in coinage - - , - - - - - 432 71. Estimation of the hardness of tap-water by Clark's method - - 434 72. Determination of temporary and permanent hardness of tap-water by Hehner's method - , 435 73. Estimation of silver in an alloy - . - . . . . 438 74. The percentage of chlorine in rock salt . . . . . 439 75. Estimation of iron in ferrous ammonium sulphate - - - 439 76. Estimation of aluminium in potash alum 440 77. Estimation of copper in blue vitriol . . . . . . 440 78. Estimation of zinc in calamine 441 79. Estimation of barium in hydrated barium chloride - - - 441 80. Estimation of lead in lead nitrate . . . . . . 442 81. Estimation of sodium in a mixture of sodium nitrate and sodium chloride 442 82. Estimation of soluble sulphates as barium sulphate - - - 442 83. Gravimetric estimation of magnesium . . . . . . 443 84. To determine the percentage of phosphorus in microcosmic salt - 444 85. The detection of elements in organic compounds . - - . 443 86. Determination of the equivalent of an organic acid . - - 446 87. Estimation of carbon and hydrogen . - - - . - 447 88. Estimation of nitrogen by combustion . . . . . . 449 89. Determination of the density of air - - - - - - 464 90. Density of carbon dioxide 464 91. Relative densities of oxygen, nitrogen and air by diffusion - - 468 LIST OF EXPERIMENTS xv NUMBER PAGE 91A. Measurement of vapour densities by Dumas' method - - 469 giB. Measurement of vapour densities by Victor Meyer's method - 469 92. Observation of critical phenomena - 482 93. Measurement of vapour-pressure. Barometric method - - 483 94. Determination of the melting-point. Capillary tube method - 494 95. Determination of the freezing-point. Method of cooling - - 494 96. Separation and analysis of air dissolved in water . . - 505 97. Absorption coefficient of oxygen in water 505 98. Steam-distillation - - - - - - - - - 506 99. Osmosis through parchment paper 514 100. Preparation of a semipermeable membrane of copper ferrocyanide 514 101. Measurement of osmotic pressure - - - _ _ . ^15 102. Preparation of a liquid semipermeable membrane - - - 515 103. Determination of lowering of vapour-pressure by Menzies' method 525 104. Determination of molecular weights by lowering of vapour- pressure. Dynamical method - 516 105. Determination of molecular weights by elevation of the boiling-point 527 106. Determination of molecular weights by the freezing-point method 528 107. Determination of the transition-point of sulphur by the dilatometer method 545 108. Solubility curve for Glauber's salt - - - - - - 546 109. Determination of the transition temperature of Glauber's salt - 547 n o . Freezing-point diagram for a binary mixture - . - - 547 111. Heat of neutralisation of sodium hydroxide by acids - - - 552 112. To illustrate qualitatively the effect of concentration on the posi- tion of an equilibrium - - - - - - - - ^67 113. Partition of bromine between carbon disulphide and water - - 568 114A. To determine the molecular formula of benzoic acid in toluene - 569 114B. To determine the formula of the cuprammonium ion - - 570 115. Equilibrium in the interaction of alcohol and acetic acid - - 570 116. The decomposition of oxalic acid - - - - ' - - 580 117. Saponification of ethyl acetate - - - - - - - 581 118. Order of the reaction between potassium persulphate and potassium iodide . . . ^ ^82 119. Influence of temperature on the rate of oxidation of hydrogen iodide by hydrogen peroxide - - - - - - - ^go 120. Catalysis of the decomposition of hydrogen peroxide by haemase 591 121. Rate of hydrolysis of methyl acetate in the presence of acids - 592 122. Conductivity of aqueous solutions of acetic acid - - - - 609 123. Titration, using conductivity as an indicator - - - - 611 124. Determination of the solubility of barium oxalate - - - 611 125. Transport number for silver nitrate - , - - . . . 612 126. Demonstration of movement of hydrogen ion - - - - 613 127. Preparation of buffer solutions - - - - - - - 638 128. Working range of indicators - - - - . . . 638 129. Measurement of the hydrolysis of sodium acetate - - - 639 130. Determination of the solubility-product of potassium bromate - 639 131. Solubility-product of silver acetate - - - - - - 639 132. Catalytic activity of acids of different strength - - - . 639 133. Hydrolysis of urea hydrochloride - 640 134. Preparation of colloidal platinum - - 648 135. Preparation of colloidal arsenious sulphide - - - - 648 136. Preparation of colloidal aluminium hydroxide - - - - 649
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