ve Lathate fathethei o " (hatiothett Habe nif dade tet alee . 4 * Pr se) det a icatelgaat tater wiabaitate Gatsts silepaaat Ha secel ened eyet rer erst rrr rt ated Hedied tts inten a4 ae aed il nits 4 n arte via doll ait ni{vite feptiettad sihwiie det wh aii 4 4 fs aaitghattotial tate tater aif datietaite pa ttatla le ten Lathede fae bade ate (la jaigelle alekathe indy yo jatiathy de ile piadellatadat’s byte Ay M4 sitallet see { defiatini sfls ie hott vet) hg Bin Boe th U Galiadabed tbarida (hells a\foihe ayedatiell ainda ere H wis ibe Galley hadallege dethet Y ea fairl site te balla ident data de Mog athriba ll foiaite’l steloteisy lah e viele Asia faite tededette te ahelsdedatad elatell taieieee fail la lete wie: Bedebeds J yi baie abating of ate fails a y=eds iste dh dit ite arbi Mi i i nay t ie i ut tated? io bbed i i dated adodette da dndadanatteiketl i datnitndad aint! tal iats jaited ail atte te be adatiade ‘ dadabad vdsiade dae th gaitemiatt auananadeil ad top walla’ shots bed others ha te betelha tet ; Hedetettetsita te’ ihe te deitaiadetanass® Hated etaihy ¢ otiel ae! Theledaliaite Ato hehalet Hatatlahat statateds the! taliitallal ty of ay ri "ee i ‘tie alts wer * 4 isteny a le uy aM laifette abel aheihe athena Hehed a4 sitalherts ra eseal Weehe Me ‘ Veit rH hinds tie i “sib toe t ledelie heonedg dail Gohadadgiletets als Wiatate Py at be Dera ay ne pik sitadedy Ted eiiaiels ia ete tad ine On 4 etelintn tate tal Ria edathedaily ie Latiell ite Se belated on ritintieitatia att Wikete ds aie ] ty ( othcthy Tale fa tiaty iia A ath a ) tagagettsi rate tates ahadeda ints aided ie tet sjaitaa {ig Posies sith aa a delgeeitin ti » ‘ tein ty Peet eed preepreteen (| Aeteas fase Takeda ther aay baba Dh sGenatanauad se aeHabs oth f htdibsbeeeat Hy ares aiqlegale wig Gieiawo ned vtsdsdaee MASHER, devin Ms ae it aye tates aly Hoey aye i ayadaent Ge “f aia es went rh quand beg ate gaw Mf qingaat seasons gt ele fecatit ais ae aeaesns athe wastes i wile ga ‘ Sr Gadeken aaeasts Wate pedtaena ted igs lagaieds Godt edauaitig da teens pais tegen Pheaacdeas isgagedeetyt aieuen ait is , ene 1 bt; dea leds aged bade . agate RAS ay ive yeaa catty 19 cele OP etek bt ptrt ated 4 Gagetee dad ; ianegoa gedaan 498 ‘ eae ga dsaageys ys 4 ait patil siedanzetlt wa jail gana (anent fasdtganganird’ : 4 sailed Yee iteqedn Gedney cate ailaliatted ey Eat ited Beit igh see sive a we ana bie LW 4 Pile bate / Nebo dangiea Sianga aqeterali 4 sad r pariee preety i tate 4 ween ated hagent® veges at de ade Qedere caksueastall a taste He alin lg Ef | JOURNAL AND PROCEEDINGS OF THE ROYAL SOCIETY OF NEW SOUTH WALES FOR 1941 (INCORPORATED 1881) es VOLUME LXXV Parts I-IV — EDITED BY THE HONORARY SECRETARIES THE AUTHORS OF PAPERS ARE ALONE RESPONSIBLE FOR THE STATEMENTS MADE AND THE OPINIONS EXPRESSED THEREIN SYDNEY PUBLISHED BY THE SOCIETY, SCIENCE HOUSE GLOUCESTER AND ESSEX STREETS Issued as a complete volume. July 3. 1942. CONTENTS. VOLUME LXXV Part 1* Art. I.—Presidential Address. By A. P. Elkin, M.A., Ph.D. (Issued July 4, 1941) Art. II.—The Effect of the Synthetic Gistrogens, Stilbcestrol and Hexcestrol] on the Pouch and Scrotum of Trichosurus vulpecula. By A. Bolliger, Ph.D., and A. J. Canny, M.B., B.S. (Issued July 4, 1941) “ite oe a ie i ae Gs Art. III.—Magnetic Studies of Coordination Compounds. Part V. Binuclear Copper Derivatives of Diphenyl Methyl Arsine. By D. P. Mellor, M.Sc., and D. P. Craig, B.Sc. (Issued July 4, 1941) cn i a “e ae Ae as Art. IV.—Progressive Rates of Tax in Australia. By H.S.Carslaw, Se.D., LL.D. (Issued August 18, 1941) Cs we a A Me ie ais ape is se Part II+ Arr. V.—Clarke Memorial Lecture. The Climate of Australia in Past oe By C. A. Sussmilch, F.G.S. (Issued September 11, 1941) cee m Art. VI.—An Examination of the Essential Oils Distilled from the Tips and Normal Cut of Hucalyptus polybractea. By Philip A. rye M.Sc., and Thomas B. Swanson, M.Se. (Issued September 11, 1941) ai ‘ ae A ae ae Art. VII.—The Jurassic Fishes of New South Wales. By R. T. Wade, M.A., Ph.D. (Issued September 11, 1941) ue an Ae 4A as Art. VIII.—Remarks on Goodness of Fit of Hypotheses and on Pearson’s y Test. By D. T. Sawkins, M.A. (Issued September 11, 1941) a Part III i Art. IX.—Permian Blastoids from New South Wales. By Ida A. Brown, D.Sc. (Issued October 27, 1941) ie , ah a “he ee ve ArT. X.—Bryozoa from the Silurian and Devonian of New South Wales. By Joan Crockford, B.Sc. (Issued November 27, 1941) .. ae pil ie ae ArT. XI.—A Note on Determinations of Physiological Specialisation in Flax Rust. By W. L. Waterhouse, M.C., D.Se. ot D.1.C., and I. A. Watson, B.Sc.Agr., Ph.D. (Issued November 27, 1941) ap ge Ss a a wh Art. XIJ.—The Thiamin (Vitamin B,) Content of the Urine of Trichosurus vulpecula. By A. Bolliger, Ph.D., and C. R. Austin, M.Se., B.V.Se. (Issued November 27, 1941) Art. XITI.—The Chemistry of Bivalent and Trivalent Rhodium. PartI. A Qualitative Study of Trivalent Rhodium Salts; and the Properties of Some Rhodous Salts. By F. P. Dwyer, M.Sc., and R. S. Nyholm, B.Sc. (Issued January 9, 1942).. Art. XIV.—The Chemistry of Bivalent and Trivalent Rhodium. Part II. Hexacovalent Complexes of Rhodous Halides with Diphenylmethylarsine. By F. P. Dwyer, M.Sc., and R.S. Nyholm, B.Se. (Issued January 9, 1942) Ee a a a * Published August 27, 1941. + Published September 23, 1941. t Published March 17, 1942. MAR - 3 1948. Page. 1 21 27 31 47 65 dA 85 96 104 115 118 122 127 1V CONTENTS. Part IV* Page. Art. XV.—Radial Heat Flow in Circular Gplindaes with a General wna Condition. II. By J. C. Jaeger, M.A., D.Sc. (Issued April 22, 1942) Be -. 130 Art. XVI.—The Chemistry of Bivalent and Trivalent Rhodium. Part III. Compounds of Rhodic Halides with Tertiary Arsines. By F. P. Dwyer, M.Sc., and R. S. Nyholm, B.Se. (Issued April 21, 1942) Ws Sid ca ae ae ate mt .. 140 Art. XVII.—The Triassic Fishes of New South Wales. By R. T. Wade, M.A., Ph.D. (Issued April 22, 1942) a a ot as oe .- 144 Art. XVIII.—Studies on the Cultivation of the Tung Oil Tree, Aleurites fordi. Part II. Study of a Heavy Yield of Fruit Obtained on the North Coast of New South Wales. By A. R. Penfold, F.A.C.1., F.C.S., F. R. Morrison, A.S.T.C., A.A.C.I., and S. Smith- White, B.Sc.Agr. (Issued | April 22, 1942) oe 148 Art. XIX.—The Stereochemistry of Some Metallic Complexes, with Special Reference to their Magnetic pee eee and the Cotton Effect. By D. P. Mellor, M.Sc. (Issued April 21, 1942) #2 ae Age i ae ou) DBF ArT. XX.—On the Frequency of the Primes. By F. A. Behrend. (Issued May 15, 1942) 169 TirtLeE Pace, ContTeNTs, NoTIcES, PUBLICATIONS wn sae aA at ans ae 1 OFFICERS FOR 1941-42... ate is Rye a Be ee aa: os son ey ae List oF MEMBERS, AWARDS OF MEDALS, ETC. Bee ns ae i a RE ix ABSTRACT OF PROCEEDINGS te fe ae am a a Bs ee Minmare. <3 | PROCEEDINGS OF THE SECTION OF GEOLOGY ae ay ate sie Fy ‘s.\) Se PROCEEDINGS OF THE SECTION OF INDUSTRY be A A bag oie we | InDEX TO VoLUME LXXV ne a Ve Be bie ute ae a ..XXXill * Published July 3, 1942. NOTICES. Vv NOTICE. Tue Roya Society of New South Wales originated in 1821 as the “ Philosophical Society of Australasia’; after an interval of inactivity, it was resuscitated in 1850, under the name of the ‘‘ Australian Philosophical Society ’’, by which title it was known until 1856, when the name was changed to the “‘ Philosophical Society of New South Wales ”’; in 1866, by the sanction of Her Most Gracious Majesty Queen Victoria, it assumed its present title, and was incorporated by Act of the Parliament of New South Wales in 1881. TO AUTHORS. Authors should submit their papers in typescript and in a condition ready for printing. All physico-chemical symbols and mathematical formule should be so clearly written that the compositor should find no difficulty in reading the manuscript. Sectional headings and tabular matter should not be underlined. Pen-illustrations accompanying papers should be made with black Indian ink upon smooth white Bristol board. Lettering and numbers should be such that, when the illustration or graph is reduced to 5 inches in width, the lettering will be quite legible. On graphs and text figures any lettering may be lightly inserted in pencil. Photo- micrographs should be rectangular rather than circular, to obviate too great a reduction. The size of a full page plate in the Journal is 5 x 7? inches, and the general reduction of illustrations to this limit should be considered by authors. When drawings, etc., are submitted in a state unsuitable for reproduction, the cost of the preparation of such drawings for the process-block maker must be borne by the author. The cost of colouring plates or maps must also be borne by the author. Further particulars regarding the preparation of manuscripts are contained in the ‘“ Guide to Authors,”’ which is obtainable on application to the Honorary Secretaries of the Society. FORM OF BEQUEST. S be yur ath the sum of £ to the Royat Society or New SoutH WaALxss, Incorporated by Act of the Parliament of New South Wales in 1881, and I declare that the receipt of the Treasurer for the time being of the said Corporation shall be an effectual discharge for the said Bequest, which I direct to be paid within calendar months after my decease, without any reduction whatsoever, whether on account of Legacy Duty thereon or otherwise, out of such part of my estate as may be lawfully applied for that purpose. [Those persons who feel disposed to benefit the Royal Society of New South Wales by Legacies, are recommended to instruct their Solicitors to adopt the above Form of Bequest. |] aval PUBLICATIONS. The following publications of the Society, if in print, can be obtained at the Society’s Rooms, Science House, Gloucester and Essex Streets, Sydney. Transactions of the Philosophical Society, N.S.W., 1862-5, pp. 374, out of print. Vols. I-xI Transactions of the Royal Society, N.S.W., 1867-1877 3s Vol. xIl Journal and Proceedings ae a 1878, pp. 324, price 10s. 6d. > xu y 30 Ns Re ve 1879, ,, 255, Ls » XIV > > 53 1 ee SSO. se eos i" %9 XV 39 96 a 50 Ls 1881, ,, 440, ys >» XVI 39 49 ne a Si5 188253. 32:05 sa Ms XVII 4 i us ie Pe) ABSS. ag on Bees in os XVIII a su hi + Bo 1884, ,, 224, it » xIx 2) 39 ae a a 1885, ,, 240, a >» xx >» i 3 a a 1886, ,, 396, x >» XXI 5 By as 35 Ae 1887, ,, 296, ee Rs xXx Ya a iy so 5 1888, ,, 390, AG %9 XXII 5 55 ae a oe 1889, ,, 534, of » XXIV oD 19 99 4: a 1890, ,, 290, He 29 XXV Ag ne oe np 189i 5,, 348, ar >» XXVI d» 99 >» Op 53 1892, ,, 426, av %» XXVII sa He RE if a 1898, ,, 530, a »» XXVIT ap Se 5a 3 i 1894, ,, 368, Bo » XXIX a S KA Me Ry 1895, ,, 600, an ” XXX o> 9 2 ne <3 1896, ,, 568, bis o XXXI nh ae tA a ut 1897, ,, 626, a Be XXXII BA i mn “A “ 1898. <5. 476, sis » XXXII 53 a m a 4% 1899, ,, 400, a 56 XXXIV ie AN Ae Me ae 1900, ,, 484, ss » XXXV ve as aH a Br, 19015 15400 Dol, aA > XXXVI 99 5 54 "6 Be 19025055) Dol, ss A 1e-€.0.6f0 cs uA A Me Bf 1903, ,, 663, Ag >, XXXVIII 5 nS s a} ae 1904, ,, 604, »» XXXIX 3 35 Bs ay we 1905, ,, 274, 5h >» XL 50 56 rs 5 As 1906, ,, 368, AF om XLI a i a5 an is WSO%s. s5u) OCs a 58 XLII a A Be iss of 1908, ,, 598, i 3 XLII ie > ne i 55 1909, ,, 466, i >> XLIV 56 os 5 ae Pe WOTOS as LO Ay »» XLV 36 55 an os a TOUT Gl, 5 fe XLVI AP F 3 A Ne NON. eer o 50 XLVII Be 35 me ws 3 1913. ols; 55 29 XLVI es ae 5 Hes ae 1914, ,, 584, oh > XLIX BA He a5 = nt 1915, ,, 587, 8 » L 56 6 zy Ee . 1916, ,, 362, 5% 9 LI 50 56 Be os My 1917, ,, 786, re »» LIL 56 of ts 4 ‘5 1918, ,, 624, 45 » LIII Di 50 .s _ ae 1919, ,, 414, yi » LIV Ao ae ae ae an 1920, ,, 312, price £1 Is. ” LV 5¢ 5b be * AS 1921 3) 418, A >» LVI 5 30 Li # ws 1922 SZ, ae »» LVI 5 +5 A if igi TO23 ei We BAI i >» LVIII 50 53 “e ne 1924, ,, 366, R 7 LIX a Me ag ae we 1925, ,, 468, 56 » Lx 56 55 Ho ie He 1926, ,, 470, 3 >» LXI 50 . 8 be 45 1927, ,, 492, 5 re LXII 90 Hb 5 Ae ie 1928, ,, 458, 5 » LX 36 30 ss a - 1929, ,, 263, 3 o LXIV 86 5 Ae as ss 1930, ,, 484, ie » LXV 7 99 a > Ay 1931, ,, 366, sa » LXVI 53 5 ap fe 5S 19322 725) (GOL: ie »» LXVII 3 50 5 “ie ae 193330 .40 UL, Le >» LXVUI 3 50 5 aE Aa 1934, ,, 328, Bp 2 LXIxX 9 » ne ue Bs 1935, ,, 288, Sy. ” Lxx 33 Ae Br Ss ai 1936, ,, 528, a Re LXXxI AS a ws We ne 1937, ,, 708, o9 29 LXXIL Ie) 9 +) be) >> 1938, oe) 396, 99 29 LXXI 29 29 99 Le) i) 1939, oe) 344, 99 be) LXXIV >> oe) 29 29 ” 1940, 9° 658, ed 29 LXXV 29 29 29 99 29 1941, 29 224, 99 Royal Society of New South Wales OFFICERS FOR 1941-1942 Patrons: His EXcELLENCY THE GOVERNOR-GENERAL OF THE COMMONWEALTH OF AUSTRALIA, THe LORD GOWRIE, V.c., P.c., G.C.M.G., C.B., D.S.O. His EXcELLENCY THE GOVERNOR OF NEw SoutH WALES, THE LORD WAKEHURST, «.c.m.c. President : D. P. MELLOR, m.sc. Vice-Presidents : H. S. HALCRO WARDLAW, D.sc., F.A.C.1. | E. H. BOOTH, M.c., D.Sc., F.Inst.P. W. L. WATERHOUSE, m.c., D.sc.agr., Pror. T. G. ROOM, m.a.* D.1.C3, F.L.S. | E. J. KENNY, M.aust.1.M.M. Honorary Secretaries : Pror. A. P. ELKIN, .a., Ph.p. | C. ANDERSON, .a., D.Sc. Honorary Treasurer : A..R. PENFOLD, F.A.c.1., F.c.s. Members of Council: Pror. V. A. BAILEY, M.a., D.Phil., F.1nst.P. EK. J. KENNY, M.Aust.1.M.m. A. BOLLIGER, Ph.D., 4.A.c.1. E> LIONS, B:Sc.,; Ph-D., A.1.0.7 G. H. BRIGGS, p.sc., Ph.D., F.Inst.P. W. H. MAZE, m.sc. IDA A. BROWN, pD.sc. G. D. OSBORNE, pD.sc., Ph.p. W. R. BROWNE, pD.sc. A. CLUNIKES ROSS, B.sc., F.c.a. (Aust.). Pror. C. E. FAWSITT, D.sc., Ph.p. * Resigned August 27, 1941. j Elected September 18, 1941. RE a LIST OF THE MEMBERS OF THE Royal Society of New South Wales as at March 1, 1942 P Members who have contributed papers which have been published in the Society’s Journal. The numerals indicate the number of such contributions. t Life Members. Elected. 1938 P 2 (|tAlbert, Adrien, Ph.p. Lond., B.Sc. Syd., a.t.c. Gt. B., Commonwealth Research Fellow in Organic Chemistry, University of Sydney ; p.r. “‘ Green- | knowe,”’? Greenknowe-avenue, Potts Point. 1935 tAlbert, Michel Francois, ** Boomerang,’’ Billyard-avenue, Elizabeth Bay. 1898 Alexander, Frank Lee, Surveyor, 21 George-street, Parramatta; p.r. 154 William-street, Granville. 1941 Alldis, Victor le Roy, u.s., Registered Surveyor, Young, N.S.W. 1905 en Anderson, Charles, M.A., D.Sc. Hdin., c.M.z.s., 17 Towns-road, Vaucluse. (Hon. Secretary.) (President, 1924.) 1909 Pat Andrews, Ernest C., B.a., Hon. Mem. Washington Academy of Sciences and of Royal Society of New Zealand, No. 4, *“‘ Kuring-gai,”’ 241 Old South Head- road, Bondi. (President, 1921.) 1930 Aston, Ronald Leslie, B.sc., B.E. Syd., M.Ssc., Ph.D. Cantab., A.M.I.E.Aust., Lecturer in Civil Engineering and Surveying in the University of Sydney ; p-r. 24 Redmyre-road, Strathfield. 1919 1 eat Aurousseau, Marcel, B.sc., 16 Woodland-street, Balgowlah. 1935 Back, Catherine Dorothy Jean, m.sc., The Women’s College, Newtown. 1924 Pt Bailey, Victor Albert, M.A., D.Phil., F.Inst.P., Professor of Experimental Physics in the University of Sydney. 1934 Piet Baker, Stanley Charles, M.sc., F.Inst.p., Teacher of Physics, Newcastle Technical College, Islington ; p.r. 8 Hewison-street, Tighe’s Hill, N.S.W. 1937 Baldick, Kenric James, B.Ssc., 19 Beaconsfield-parade, Lindfield. 1919 Bardsley, John Ralph, 76 Wright’s-road, Drummoyne. 1939 Pel Basnett, Elizabeth Marie, m.sc., 36 Cambridge-street, Epping. 1933 Bedwell, Arthur Johnson, Eucalyptus Oil Merchant, ‘‘ Kama,’ 10 Darling Point-road, Edgecliff. 1926 Bentivoglio, Sydney Ernest, B.Sc.agr., c:o Tooth & Co. Limited, Sydney ; p-r. corner of The Crest and Rosebery-road, Killara. 1940 Betty, Robert Cecil, 67 Imperial-avenue, Bondi. 1937 Pe 6 Birch, Arthur John, m.sc., 15 Hilltop-road, Headington, Oxford, England. 1923 Birks, George Frederick, Wholesale Druggist, c/o Potter & Birks Ltd., 15 Grosvenor-street, Sydney; p.r. 42 Powell-street, Killara. 1916 Birrell, Septimus, 74 Edinburgh-road, Marrickville. 1920 Bishop, Eldred George, Manufacturing and General Engineer, 37-45 Myrtle- street, Chippendale ; p.r. 17 Thompson-street, Clifton Gardens. 1939 P—2 Blake, George Gascoigne, M.I.E.E., F.Inst.P., ‘‘ Holmleigh,’’ Cecil-avenue, Pennant Hills. 1933 PeV8 Bolliger, Adolph, Ph.p., Director of Research, Gordon Craig Urological Research Laboratory, Department of Surgery, University of Sydney. 1926 ley Booker, Frederick William, m.sc., c/o Geological Survey, Mines Department, Sydney. 1920 P 9 Booth, Edgar Harold, M.c., p.sc., F.Inst.Pp., New England University College, Armidale. (Vice-President.) (President, 1935.) 1939 Bosworth, Richard Charles Leslie, m.sc., p.sc. Adel., Ph.D. Camb., F.A.C.1., F.Inst.P., c/o C.S.R. Co., Pyrmont; p.r. 41 Spencer-road, Killara. 1922 Bradfield, John Job Crew, c.M.c., D.sc. Eng., M.E., M.Inst.C.E., M.Inst.E.Aust., Barrack House, 16 Barrack-street, Sydney ; p.r. 23 Park-avenue, Gordon Bl MAR - 3 1048 x Elected. 1938 1940 1919 1935 1941 1913 1940 1940 1898 1926 1919 1940 1940 1938 1903 1913 1933 1940 1913 1935 1935 1940 1938 1941 1940 1940 1940 1940 1940 1920 1913 1933 1940 1919 1909 1940 1941 192] 1940 1935 1940 1890 1919 Ped 2 P2t P 23 1 P 4 P 4 P 19 PZ ledae)| Po Pind Piel Pipl des P38 Bie _ Breckenridge, Marion, B.sc., Department of Geology, University of Sydney ; r. 28 Junction-road, Hornsby. Brigden, Alan Charles, B.sc., 22 Kelso-street, Enfield. Briggs, George Henry, D.sSc., Ph.D., F.Inst.P., Officer-in-Charge, Section of Physics, National Standards Laboratory of Australia, University Grounds, Sydney; p.r. 13 Findlay-avenue, Roseville. Brown, Ida Alison, D.sc., Lecturer in Paleontology, University of Sydney. Brown, Samuel Raymond, A.c.a. Aust., 87 Ashley-street, Chatswood. Browne, William Rowan, D.sc., Assistant-Professor of Geology in the Univer- sity of Sydney. (Vice-President.) (President, 1932.) Buckley, Daphne M. (Mrs.), B.sc., 4 Sharland-avenue, Chatswood. Buckley, Lindsay Arthur, B.sc., 4 Sharland-avenue, Chatswood. ‘tBurfitt, W. Fitzmaurice, B.A., M.B., Ch.M., B.Sc. Syd., F.R.A.C.S., ““ Radstoke,”’ Elizabeth Bay. Burkitt, Arthur Neville St. George, M.B., B.sc., Professor of Anatomy in the University of Sydney. Burrows, George Joseph, B.sc., Lecturer and Demonstrator in Chemistry in the University of Sydney. Cane, Reginald Frank, M.sc., A.A.c.1., National Oil Pty. Ltd., Glen Davis, N.S.W. t Callanan, Victor John, B.se., 17 Wheatleigh-street, Naremburn. tCarey, Samuel Warren, D.Sc., Practising Petroleum Geologist, c/o Australasian Petroleum Co., Port Moresby. Carslaw, Horatio Scott, Sc.D., LL.D., F.R.S.E., Emeritus Professor of Mathe- matics, University of Sydney, Fellow of Emmanuel College, Cambridge ; Burradoo, N.S.W. Challinor, Richard Westman, F.I.C., A.A.C.1., A.S.T.C., F.C.S. ; p.r. 54 Drumalbyn- road, Bellevue Hill. (President, 1933.) Chalmers, Robert Oliver, a.s.tT.c., Assistant (Professional) in Mineralogy, Australian Museum, College-street, Sydney. Chambers, Maxwell Clark, B.sc., c/o J. and E. Atkinson Pty. Ltd., 469-75 Kent-street, Sydney. ; Cheel, Edwin, 40 Queen-street, Ashfield. (President, 1931.) Churchward, John Gordon, B.Sc.Agr., Ph.p., 1 Hunter-street, Woolwich. Clark, Sir Reginald Marcus, k.B.E., Central Square, Sydney. Clarke, Ronald Stuart, Bp.a., 28 Beecroft-road, Beecroft. Clune, Francis Patrick, Author and Accountant, 15 Prince’s-avenue, Vaucluse. Cohen, Max Charles, B.sc., Box 2248 U, G.P.O., Melbourne. Cohen, Samuel Bernard, M.Sc., A.A.C.1., 9 Boonara-avenue, Bondi. Colditz, Margaret Joyce, B.sc., 9 Beach-street, Kogarah. Cole, Edward Ritchie, s.sc., 14 Barwon-road, Lane Cove. Cole, Joyce Marie, B.sc., 14 Barwon-road, Lane Cove. Collett, Gordon, B.sc., 49 Liverpool-road, Summer Hill. Cooke, Frederick, c/o Meggitt’s Limited, Asbestos House, York and Barrack- streets, Sydney. Coombs, F. A., F.c.s., Instructor of Leather Dressing and Tanning, Sydney Technical College; p.r. Bannerman-crescent, Rosebery. Corbett, Robert Lorimer, Managing Director of Robert Corbett & Co. Ltd., Manufacturing Chemists, Head Office, 379 Kent-street, Sydney. Cortis-Jones, Beverly, m.sc., St. Andrew’s College, Newtown. Cotton, Frank Stanley, p.sc., Chief Lecturer and Demonstrator in Physiology in the University of Sydney. Cotton, Leo Arthur, M.A., D.Sc., Professor of Geology in the University of Sydney. (President, 1929.) Cox, Morris Edward. Craig, David Parker, Research Scholar, 62 Springdale-road, Killara. tCresswick, John Arthur, A.A.C.1., F.c.S., Production Superintendent and Chief Chemist, c/o The Metropolitan Meat Industry Commissioner, State Abattoir and Meat Works, Homebush Bay; p.r. 101 Villiers-street, Rockdale. Crockford, Joan Marian, B.sc., 219 Victoria-road, Gladesville. Culey, Alma Gertrude, M.sc., 37 Neirbo-avenue, Hurstville. | Dadour, Anthony, 25 Elizabeth-street, Waterloo. Dare, Henry Harvey, M.E., M.Inst.c.E., M.I.E.Aust., 14 Victoria- street, Roseville. | de Beuzeville, Wilfred Alex, Watt, J.P., “ Mélamere,” Welham-street, Beecroft. P 21 y xi Dick, James Adam, o.m.c., B.A. Syd., M.D., O.M. Hdin., F.R.c.8. Hdin., Col. A.A.M.C., Comr. Ord. St. John, Medical Practitioner, ‘‘ Catfoss,’’ 148 Belmore-road, Randwick. {Dixson, William, ‘“‘ Merridong,’’ Gordon-road, Killara. Doherty, William M., F.1.c., F.A.c.1., 30 Hampden-road, Pennant Hills. Donegan, Henry Arthur James, 4.S.T.c., A.A.c.1., Analyst, Department of Mines, Sydney ; p.r. 18 Hillview-street, Sans Souci. Dulhunty, John Allan, B.sc., Geology Department, University of Sydney ; p.r. 10 Tusculum-street, Potts Point. Dupain, George Zephirin, 4.A.C.1., F.c.S., Director Dupain Institute of Physical Education and Medical Gymnastics, Manning Building, 449 Pitt-street, Sydney; p.r. “‘ Rose Bank,” 158 Parrmaatta-road, Ashfield. Dwyer, Francis P. J., m.sc., Lecturer in Chemistry, Technical College, Sydney. Earl, John Campbell, D.sc., Ph.p., Professor of Organic Chemistry in the University of Sydney. (Vice-President.) (President, 1938.) Eastaugh, Frederick Alldis, a.R.S.M., F.1.c., Professor in Engineering Tech- nology and Metallurgy in the University of Sydney. Elkin, Adolphus Peter, m.a., Ph.D., Professor of Anthropology in the University of Sydney. (President, 1940.) Emmerton, Henry James, B.sc., 41 Nelson-street, Gordon. English, James Roland, t.s. A..F. Enright, Walter John, B.A., Solicitor, High-street, West Maitland ; p.r. Regent- street, West Maitland. Esdaile, Edward William, 42 Hunter-street, Sydney. Evans, Silvanus Gladstone, 4.1.4.4. Lond., A.R.A.1.A4., 6 Major-street, Coogee. Farnsworth, Henry Gordon, Government Stores, Harrington-street, Sydney ; p.r. “‘ Rothsay,’’ 90 Alt-street, Ashfield. Faull, Norman Augustus, c/o National Standards Laboratory, University Grounds, Chippendale. Fawsitt, Charles Edward, D.sc., Ph.D., Professor of Chemistry in the University of Sydney. (President, 1919.) Fiaschi, Piero, 0.B.E., v.D., M.D. Columbia Univ., p.p.s. New York, M.B.c.S. fing., L.R.c.P. Lond., 178 Phillip-street, Sydney. Finch, Franklin Charles, B.sc. Finnemore, Horace, B.Sc., F.1.c., Reader in Pharmacy in the University of Sydney. Firth, Francis Williamson, Elliotts and Australian Drug Ltd., O’Connell- street, Sydney. Firth, John Clifford, B.sc., ‘‘ Avoca,’’? Huntley’s Point-road, Gladesville. Fisher, Robert, B.sc., No. 4 Flat, 11 French-street, Maroubra. Fisk, Sir Ernest Thomas, K.B., F.Inst.R.E., A.M.1.E. Aust., Chairman of Directors, Amalgamated Wireless (Australasia) Ltd., Wireless House, 47 York-street, Sydney ; p.r. 16 Beaconsfield-parade, Lindfield. Flack, Arthur Charles Allenby, B.sc., High School, Broken Hill. Fletcher, Harold Oswald, Assistant Paleontologist, Australian Museum, College-street, Sydney. {Foreman, Joseph, m.R.c.s. Hng., u.R.c.P. Hdin., ““ The Astor,” Macquarie-street, Sydney. Forman, Kenn. P., M.1.Refr.z., c/o Westinghouse Sales & Rosebery, Dunning- avenue, Waterloo ; p.r. Taren Point-road, Taren Point. Foy, Mark, c/o Geo. O. Bennett, 133 Pitt-street, Sydney. Franki, Robert James Anning, B.Sc., 891 New South Head-road, Rose Bay. Freney, Martin Raphael, B.sc., McMaster Laboratory, Sydney. Garretty, Michael Duhan, m.sc., Chief Geologist, North Broken Hill Ltd., Broken Hill, N.S.W. Gascoigne, Robert Mortimer, 5 Werona-avenue, Killara. Gibson, Alexander James, M.£E., M.Inst.C.E., M.I.E.Aust., Consulting Engineer, 906 Culwulla Chambers, 67 Castlereagh-street, Sydney; p.r. “ Wirruna,” Belmore-avenue, Wollstonecraft. Gillis, Richard Galvin, 27 Kia Ora, 453 St. Kilda-road, Melbourne, S.C.2. Goddard, Roy Hamilton, F.c.a. Aust., Royal Exchange, Bridge-street, Sydney. xl Hlected. 1936 1940 1938 1934 1880 1892 1940 1905 1936 1937 1934 1923 1929 1934 1919 1940 1935 1938 1918 1936 1928 1916 1930 1919 1919 1941 1935 1936 1938 1923 1940 1909 1935 1930 1911 ro bd oo P15 P16 Goulston, Edna Maude, B.sc., Demonstrator in Micro-Chemistry in the Uni- versity of Sydney ; p.r. 83 Birriga-road, Bellevue Hill. Graves, John Nevil, B.sc., 96 Wentworth-street, Randwick. Griffiths, Edward on B.Se., AA.C.E3 A-1.05 Chief Chemist, Department of Agriculture ; p.r. 151 Wollongong-road, Arncliffe. Hall, Norman Frederick Blake, mM.sc., Chemist, Council for Scientific and Industrial Research (Tobacco Section), Dept. of Organic Chemistry, University of Sydney; p.r. 154 Wharf-road, Longueville. tHalligan, Gerald Harnett, L.S., F.G.S., Retired Civil Engineer and Hydro- grapher, “ The Straths,” Pacific Highway, Killara. Halloran, Henry Ferdinand, u.s., 153 Elizabeth-street, Sydney. Hanlon, Frederick Noel, B.sc., Geologist, Department of Mines, Sydney ; p.r. 4 Pearson-avenue, Gordon. Harker, George, D.Sc., F.A.C.1.; p.r. 75 Prospect-road, Summer Hill. Harper, Arthur Frederick Alan, M.Sc., A.Inst.P., Physics Department, The University, Sydney. Harradence, Rita Harriet, M.Sc., Research Scholar, c/o Dyson Perrins Laboratory, Oxford University, Oxford, England. Harrington, Herbert Richard, Teacher of Physics and Electrical Engineering, Technical College, Harris-street, Ultimo. Harrison, Travis Henry John, D.Sc.agr., D.1.c. London, Commonwealth Fruit Officer, Australia House, Strand, London, England; p.r. 41 Queen’s Gardens, Ealing, W.5, London. Hawley, J. William, J.p., Financial Agent, 4 Castlereagh-street, Sydney ; p.r. 12 King’s-road, Vaucluse. Hayes, William Lyall, a.s.tT.c., A.A.c.1., Works Chemist, c/o Messrs. Wm. Cooper & Nephews (Aust.) Ltd., Phillip-street, Concord ; p.r. 21 Wandella-avenue, Roseville. Henriques, Frederick Lester, 208 Clarence-street, Sydney. Heselton, Thomas William, B.sc., c/o Munition Laboratories, Maribyrnong, Victoria. Hewitt, Frank Rupert, 7 Tindale-road, Artarmon. Hill, Dorothy, M.sc. Q’ld., Ph.D. Cantab., Geological Research Fellow, University of Queensland, Brisbane. Hindmarsh, Percival, M.A., B.Sc.Agr., Principal, Hurlstone Agricultural High School, Glenfield. Hirst, Edward Eugene, A.M.1.E., Vice-Chairman and Joint Managing Director, British General Electric Co. Ltd.; p.r. “‘ Springmead,”’ Ingleburn. Hirst, George Walter Cansdell, B.sc., A.M.1.E. (Aust.), A.M.Inst.T.; p.r. “ St. Cloud,’ Beaconsfield-road, Chatswood. Hoggan, Henry James, A.M.I.M.E. Lond., A.M.1.E. Aust., Consulting and Designing Engineer, “‘ Lincluden,”? 81 Frederick-street, Rockdale. Holmes, James Macdonald, Ph.D., F.R.G.S., F.R.S.G.S., Associate Professor of Geography in the University of Sydney. Hoskins, Arthur Sidney, Engineer, Steel Works, Port Kembla; postal address, P.O. Box 36, Wollongong. Hoskins, Cecil Harold, Engineer, c/o Australian Iron & Steel Ltd., Kembla Building, 58 Margaret-street, Sydney, Box 3375 R, G.P.O. Howard, Harold Theodore Clyde, B.sc., Principal, Wollongong Technical High School, Wollongong. Howarth, Mark, Grange Mount, Bull-street, Mayfield, Newcastle, N.S.W. Howie, Sir Archibald, K.B., M.t.c., 7 Wynyard-street, Sydney. Hughes, Gordon Kingsley, B.S¢., Lecturer in Chemistry, University of Sydney. tHynes, Harold John, D.Sc., B.Sc.Agr., Biologist, Department of Agriculture, Box 36a, G.P.O., Sydney ; p.r. “‘ Belbooree,’’ 10 Wandella-avenue, Rose- ville. Johns, Thomas Harley, 130 Smith-street, Summer Hill. Johnston, Thomas Harvey, M.A., D.Sc., C.M.Z.S., Professor of Zoology in the University of Adelaide. (Cor. Mem., 1912.) Joplin, Germaine Anne, B.Sc., Ph.D., Geological Department, University of Sydney; p.r. 18 Wentworth-street, Eastwood. Judd, William Percy, 123 Wollongong-road, Arncliffe. Julius, Sir George A., Kt., B.Sc., B.E., M.I.Mech.E., M.1.E.Aust., Culwulla Chambers , Castlereagh-street, Sydney. Elected. 1935 | 1935 1940 1924 1934 1896 1940 1920 1939 1936 1924 1934 1936 1920 1940 1929 1940 1940 1906 1927 1940 1939 1940 1940 1940 1906 1891 1932 1927 1940 1924 1926 1935 1941 1912 1929 1940 1928 1940 1940 1940 1941 1922 1934 1915 3 a Pp 3 P 54 Pak ped Pork 2 pot P 16 P 25 xii Kelly, Caroline Tennant (Mrs.), “ Eight Bells,’’ Castle Hill. Kelly, Francis Angelo Timothy, ‘“‘ Hight Bells,’ Castle Hill. Kennard, William Walter, 9 Bona Vista-avenue, Maroubra. Kenny, Edward Joseph, Geological Surveyor, Department of Mines, Sydney ; p-r. 17 Alma-street, Ashfield. Kerslake, Richmond, A.8.T.C., A.A.C.I., Industrial Chemist, c/o Australian Paper Mfrs. Ltd., Macauley-street, Matraville; p.r. 55 Harold-street, Matraville. King, Sir Kelso, x.B., Underwriter, 117 Pitt-street, Sydney. King, Leonard Esmond, 161 Nelson Bay-road, Bronte. Kirchner, William John, B.sc., A.a.c.1., Manufacturing Chemist, c/o Messrs. Burroughs Wellcome & Co. (Australia) Ltd., Victoria-street, Waterloo ; p-r. 18 Lyne-road, Cheltenham. Lambeth, Arthur James, “ Yeronga,’’ Wylde-street, Potts Point. Leach, Stephen Laurence, B.A., B.Sc., A.A.c.I., P.O. Box. No. 21, Concord. Leech, Professor Thomas David James, B.Sc., B.E. Syd., Professor of Engin- eering, Auckland University College, Auckland, N.Z. Leech, William Dale, Californian Institute of Technology, Pasadena, California, U.S.A. Lemberg, Max Rudolf, D.Phil., Biochemist, Royal North Shore Hospital ; p.r. 12 de Villiers-avenue, Chatswood. Le Souef, Albert Sherbourne, 3 Silex-road, Mosman. Lincoln, Gordon James, 15 Turner-avenue, Haberfield. Lions, Francis, B.Sc., Ph.D., A.I.c., Department of Chemistry, University of Sydney ; p.r. 31 Chesterfield-road, Epping. Lipson, Menzie, Chemist, C.S.I.R., 5 Phillip Court, Latimer-road, Rose Bay. Lockwood, William Hutton, B.sc., Institute of Anatomy, Canberra, A.C.T. Loney, Charles Augustus Luxton, M.Am.soc.Refr.E., National Mutual Building, 350 George-street, Sydney. Love, William Henry, B.Sc., Ph.p., Lecturer in Physics, University of Sydney. Luciano, Albert Anthony, 16 Arthur-street, Bellevue Hill. Maccoll, Allan, M.sc., 76 Springdale-road, Killara. Maccoll, Mrs. Margaret Elphinstone, B.A., B.Ec., 76 Springdale-road, Killara. McGrath, Brian James, 40 Mooramie-avenue, Kensington. McGregor, Gordon Howard, 4 Maple-avenue, Pennant Hills. McIntosh, Arthur Marshall, “‘ Moy Lodge,’ Hill-street, Roseville. tMcKay, R. T., L.s., M.mst.c.z., Eldon Chambers, 92 Pitt-street, Sydney. McKie, Rev. Ernest Norman, B.A. Syd., St. Columba’s Manse, Guyra. McMaster, Sir Frederick Duncan, kt., ‘* Dalkeith,’’ Cassilis, N.S.W. Malone, Edward E., 45 Norton-street, Randwick. Mance, Frederick Stapleton, ‘“‘ Binbah,’’ Lucretia-avenue, Longueville. Mathews, Hamilton Bartlett, B.A., F.1.S., F.C.I.v., Box 2968 NN, G.P.O., Sydney. Maze, Wilson Harold, B.sc., Lecturer in Geography, University of Sydney. Melville, George Livingstone, Managing Director, Federal Machine Co. Ltd., Loftus-street, Arncliffe. Meldrum, Henry John, B.A., B.Sc., Lecturer, The Teachers’ College, University Grounds, Newtown ; p.r. 98 Sydney-road, Manly. Mellor, David Paver, m.sc., Lecturer and Demonstrator, Chemistry Depart- ment, University of Sydney ; p.r. 35 Oliver-road, Roseville. (President.) Mercer, Edgar Howard, McMaster Laboratory, Parramatta-road, Glebe. Micheli, Louis Ivan Allan, m.sc., Ph.p., Research Chemist, c/o Colonial Sugar Refining Co., Pyrmont. Millership, William, m.sc., Chief Chemist, Davis Gelatine (Aust.) Pty. Ltd., 15 Shaw-avenue, Earlwood. Mills, James Edward, M.sc., Ph.D., 16 Smith-road, Artarmon. Morris, Benjamin Sydney, 22 Kelso-street, Enfield. Morrissey, Matthew John, B.A., Aa.s.t.c., Auburn-street, Parramatta. Morrison, Frank Richard, 4.a.c.1., F.c.s., Assistant Chemist, Technological Museum, Sydney. Mort, Francis George Arnot, Manufacturing Chemist, 16 Grafton-street, Woollahra. Murphy, Robert Kenneth, pDr.ing., Chem.Eng., A.S.T.C., M.I.Chem.E., A.A.C.I., Lecturer in Charge of Chemistry and Head of Science Department, Sydney Technical College. Xiv Elected. 1940 1923 1930 1932 1935 1938 1920 1940 1940 1935 1903 1913 1921 1928 1920 1933 1940 1938 1935 1938 1919 1896 1921 1918 1938 1927 1918 1893 1935 1940 1922 1919 Pitz 1 Saye ea | Murray, Alban James Moore, B.sc., 54 Sydney-road, Willoughby. Murray, Jack Keith, B.a., B.sc.agr., Principal, Queensland Agricultural College, Gatton, Queensland, and Professor of Agriculture in the University of Queensland. Naylor, George Francis King, M.A., M.Sc., Dip.Ed., Assistant Director, Australian Institute of Industrial Psychology, 12 O’Connell-street, Sydney; p.r. ** Kingsleigh,’’ Ingleburn, N.S.W. Newman, Ivor Vickery, M.Sc., Ph.D., F.R.M.S., F.L.S., Department of Biology, Victoria University College, Wellington, N.Z. Nicol, Phyllis Mary, m.sc., Sub-Principal, The Women’s College, Newtown. Noble, Norman Scott, D.Sc.agr., M.Sc., D.1.c., Secretary, Linnean Society of N.S.W., Science House, Gloucester-street, Sydney. {Noble, Robert Jackson, M.sc., B.Sc.Agr., Ph.D., Under Secretary, Department of Agriculture, Box 36a, G.P.O., Sydney; p.r. 32a Middle Harbour-road, Lindfield. (Vice-President.) (President, 1934.) Norrie, Jack Campbell, B.sc., 28 Ray-road, Epping. Nyholm, Ronald Sydney, B.sc., 77 Bland-street, Ashfield. O’Connell, Rev. Daniel J. K., s.3., M.sc., F.R.A.S., Riverview College Observatory, Sydney. tOld, Richard, ‘‘ Waverton,’ Bay-road, North Sydney. Ollé, A. D., F.c.s., A.A.c.I., ‘“ Kareema,’’ Charlotte-street, Ashfield. Osborne, George Davenport, D.sc., Ph.D. Camb., Lecturer and Demonstrator in Geology in the University of Sydney. Parsons, Stanley William Enos, Analyst and Inspector, N.S.W. Explosive Department; p.r. Shepherd-road, Artarmon. Penfold, Arthur Ramon, F.A.C.1., F.C.8., Curator and Economic Chemist, Technological Museum, MHarris-street, Ultimo; p.r. 67 Park-avenue, Roseville. (Hon. Treasurer.) (President, 1935.) Penman, Arthur Percy, B.E. Syd., Mining Engineer, 10 Water-street, Wahroonga. Pettingell, William Walter, B.sc., 28 Conder-street, Burwood. Phillips, Marie Elizabeth, B.sc., 20 Kardinia-road, Clifton Gardens. Phillips, Orwell, 55 Darling Point-road, Edgecliffe. Pickard, Una Annie Frazer, B.Sc., Microscopist, 5 Malvern-avenue, Croydon. Poate, Hugh Raymond Guy, m.B., chm. Syd., F.R.c.Ss. Hng., u.R.c.P. Lond., F.R.A.C.S., Surgeon, 225 Macquarie-street, Sydney; p.r. 38 Victoria-road, Bellevue Hill. tPope, Roland James, B.A. Syd., M.D., Ch.M., F.R.C.S. Hdin., 185 Macquarie- street, Sydney. Powell, Charles Wilfrid Roberts, F.1.c., A.A.c.I., Company Executive, c/o Colonial Sugar Refining Co., O’Connell-street, Sydney ; p.r. “* Wansfell,”’ Kirkoswald-avenue, Mosman. Powell, John, Director, Foster Clark (Aust.) Ltd., 17 Thurlow-street, Redfern ; p.r. “ Elgarth,’”’ Ranger’s-road, Cremorne. Powell, John Wallis, A.s.T.c., A.A.c.I., Managing Director, Foster Clark (Aust.) Ltd., 17 Thurlow-street, Redfern. Price, William Lindsay, B.E., B.sc., Teacher of Physics, Sydney Technical College ; p.r. 8 Wattle-street, Killara. Priestley, Henry, M.D., Ch.M., B.Sc., Professor of Biochemistry, Faculty of Medicine, the University of Sydney. Purser, Cecil, B.A., M.B., Chm. Syd., ‘‘ Ascot,’’ Grosvenor-road, Wahroonga. tQuodling, Florrie Mabel, B.sc., Demonstrator in Geology, University of Sydney. Ralph, Colin Sydney, 87 Ballandella-road, Toongabbie West. Raggatt, Harold George, D.sc., Geological Adviser to the Commonwealth of Australia, Census Building, Canberra, A.C.T. Ranclaud, Archibald Boscawen Boyd, B.Sc., B.E., Lecturer in Physics, Teachers’ College, The University, Sydney. a bo P 16 XV Randall, Harry, Buena Vista-avenue, Denistone. Rayner, Jack Maxwell, B.sc., F.Inst.P., Physicist to the Department of Mines, Sydney; p.r. 125 William-street, Granville. Reid, Cicero Augustus, 19 Newton-road, Strathfield. Richardson, Henry Elmar, Chemist, Chase-road, Turramurra. Ritchie, Ernest, B.sc., 6 Military-road, North Bondi. Roberts, Richard George Crafter, Electrical Engineer, ‘“‘ Lameroo,’’ Church Point, N.S.W. Robertson, Rutherford Ness, B.sc. Syd., ph.p. Cantab., Flat 4, 43 Johnston- street, Annandale. Robinson, Albert Jordan, Managing Director, 8. T. Leigh & Co. Ltd., Raleigh Park, Kensington. Room, Thomas G., M.A., F.R.S., Professor of Mathematics in the University of Sydney. Rosenbaum, Sidney, 44 Gilderthorp-avenue, Randwick. Ross, Allan Clunies, B.Ssc., F.c.A. Aust., Chartered Accountant Aust., 544 Pitt-street, Sydney ; p.r. The Grove, Woollahra. (Member from 1915 to 1924.) Ross, Jean Elizabeth, B.Sc., Dip.Ed., 5 Stanton-road, Haberfield. Royle, Norman Dawson, M.D., ch.m., 185 Macquarie-street, Sydney. Sarroff, Carlyle Joseph. Savage, Clarence Golding, Director of Fruit Culture, Department of Agriculture, Sydney. Sawkins, Dansie Thomas, m.A. Syd., B.A. Camb., Reader in Statistics, The University, Sydney ; p.r. 60 Boundary-street, Roseville. Scammell, Rupert Boswood, B.Sc. Syd., A.A.c.1., F.c.s., c/o F. H. Faulding & Co. Ltd., 98 Castlereagh-street, Redfern ; p.r. 10 Buena Vista-avenue, Clifton Gardens. Scott, Reginald Henry, B.sc., 154 Highfield-road, Camberwell, Vic. Selby, Esmond Jacob, pDip.com., Sales Manager, Box 175 D, G.P.O., Sydney. Sellenger, Brother Albertus, Sacred Heart College, Glenelg, S.A. Sherrard, Kathleen Margaret Maria (Mrs.), m.sc. Melb., 43 Robertson-road, Centennial Park. Sibley, Samuel Edward, Mount-street, Coogee. Sheahan, Thomas Henry Kennedy, B.sc., Chemist, 2 Edward-street, Gordon. tSimpson, R. C., Lecturer in Electrical Engineering, Technical College, Sydney. Slade, George Hermon, B.sc., Director, W. Hermon Slade & Co. Ltd., Manu- facturing Chemists, 23 Rosebery-avenue, Rosebery; p.r. “ Raiatea,”’ Oyama-avenue, Manly. Smith, Eric Brian Jeffcoat, 1 Rocklands-road, Wollstonecraft. Smith, Thomas Hodge, Australian Museum, College-street, Sydney. Southee, Ethelbert Ambrook, 0.B.E., M.A., B.Sc., B.Sc.Agr., Principal, Hawkes- bury Agricultural College, Richmond, N.S.W. Spencer-Watts, Arthur, “‘ Araboonoo,’’ Glebe-street, Randwick. Stephen, Alfred Ernest, F.c.s., c/o Box 1158 HH, G.P.O., Sydney. Stephens, Frederick G. N., F.R.C.S., M.B., Ch.M., 135 Macquarie-street, Sydney ; p.r. Captain Piper’s-road and New South Head-road, Vaucluse. {Stewart, J. Douglas, B.v.Ssc., F.R.C.v.S., Emeritus Professor of Veterinary Science in the University of Sydney; p.r. “‘ Berelle,’’ Homebush-road, Strathfield. (President, 1927.) Stokes, Edward Sutherland, m.B., chm. Syd., p.p.H. Irel., Medical Officer, Metropolitan Board of Water Supply and Sewerage, 341 Pitt-street, Sydney ; p.r. 15 Highfield-road, Lindfield. Stone, Walter George, F.S.T.C., A.A.C.I., Senior Analyst, Department of Mines, Sydney; p.r. 14 Rivers-street, Bellevue Hill. Stroud, Richard Harris, ‘‘ Dalveen,’’ corner Chalmers and Barker-roads, Strathfield. {Sullivan, Herbert Jay, Director in Charge of Research and Technical Depart- ment, c/o Lewis Berger & Sons (Australia) Ltd., Rhodes; Box 23, P.O., Burwood ; p.r. “‘ Stonycroft,” 10 Redmyre-road, Strathfield. {Sussmilch, C. A., F.G.S., F.s.T.c., Consulting Geologist, 11 Appian Way, Burwood. (President, 1922.) {Sutherland, George Fife, a.p.c.sc. Lond., Assistant Professor of Mechanical « Engineering in the University of Sydney. Xvi Elected. 1920 1941 1941 1915 1935 1939 Ue) 1923 1935 1923 1940 1932 1940 1921 1935 1933 1903 1940 1919 1913 1921 I? ay) Sutton, Harvey, 0.B.E., M.D., D.P.H. Melb., B.Sc. Oxon., Professor of Preventive Medicine and Director, School of Public Health and Tropical Medicine, University of Sydney ; p.r. “ Lynton,’’ 27 Kent-road, Rose es Suvoroff, Victoria, B.sc., Chief Chemist and Metallurgist, c/o G. E. Crane & Sons, Pty., Burwood: road, Concord. Swanson, Thomas Baikie, m.sc. Adel., Lecturer in Chemistry, New England University College, Armidale. Taylor, Brigadier Harold B., M.c., D.Sc., F.1.C., F.A.C.1., Second Government Analyst, Department of Public Health, 93 Macquarie-street, Sydney ; p.r. 44 Kenneth-street, Longueville. Tennant, Thomas Henry, Manager, Government Stores Department; p.r. 2 Borrodale-road, South Kensington. Thomas, Mrs. A. V. M., 12 Clifton-avenue, Burwood. Thorne, Harold Henry, m.a. Cantab., B.Sc. Syd., F.R.A.S., Lecturer in Mathe- matics in the University of Sydney ; p.r. 55 Railway-crescent, Beecroft. Tindale, Harold, General Manager, The Australian Gas Light Company, Haymarket, Sydney. Tommerup, Eric Christian, M.sc., A.A.c.1., P.O. Box 97, Atherton, North Queensland. Toppin, Richmond Douglas, a.1.c., 231 Weston-road, Rozelle. Tow, Aubrey James, M.sc., No. 5, “‘ Werrington,’’ Manion-avenue, Rose Bay. Trikojus, Victor Martin, B.Sc., D.Phil., New Medical School, University of Sydney; p.r. 97 Beresford-road, Bellevue Hill. Vernon, James, Ph.D., A.A.C.I., Chief Chemist, Colonial Sugar Refining Co., 1 O’Connell- street, Sydney. Vicars, Robert, Marrickville Woollen Mills, Marrickville. Vickery, Joyce Winifred, m.sc., Demonstrator in Botany, University of Sydney ; p-r. 17 The Promenade, Cheltenham. Voisey, Alan Heywood, m.sc., Lecturer in Geology and Geography, New England University College, Armidale. Vonwiller, Oscar U., B.Sc., F.Inst.P., Professor of Physics in the University of Sydney. (President, 1930.) Wade, Robert Thompson, M.A., Ph.D., 2 St. John’s Court, Hunter-street, Parramatta. Walkom, Arthur Bache, pD.sc., Director, Australian Museum, Sydney; pr. 45 Nelson-road, Killara. (Member from 1910-1913.) Wardlaw, Hy. Sloane Halcro, p.sc. Syd., F.a.c.1., Lecturer and Demonstrator in Physiology in the University of Sydney. (President, 1939.) tWaterhouse, Gustavus Athol, D.Sc., B.E., F.R.E.S., F.R.Z.S., 39 Stanhope-road, Killara. Waterhouse, Leslie Vickery, B.z. Syd., Mining Engineer, Shell House, Car- rington-street, Box 58 CC, G.P.O., Sydney; p.r. 4 Bertha-road, Neutral Bay. Waterhouse, Lionel Lawry, B.E. Syd., Lecturer and Demonstrator in Geology in the University of Sydney. Waterhouse, Walter L., M.c., D.Sc.Agr., D.I.C., F.L.S., Reader in Agriculture, University of Sydney; p.r. ‘‘ Hazelmere,’’ Chelmsford-avenue, Lindfield. (Vice-President.) (President, 1937.) Watson, Irvine Armstrong, Ph.D., B.Sc.Agr., Assistant Lecturer, Faculty of Agriculture, University of Sydney. Watt, Robert Dickie, m.a., B.Sc., Professor of Agriculture in the University of Sydney ; p-r. 64 Wentworth- road, Vaucluse. (President, 1925.) Wearne, Harold Wallis, 6 Collingwood-street, Drummoyne. Welch, Marcus Baldwin, B.Sc., A.1.c., Senior Research Officer, Forestry Com- mission of N.S.W., 96 Harrington- street, Sydney. Wellish, Edward Montague, M.A., Associate- ‘Professor of Applied Mathematics in the University of Sydney ; p.r. 15 Belgium-avenue, Roseville. Wenholz, Harold, B.Sc.Agr., Winector of Plant Breeding, Department of Agri- culture, Sydney. tWhite, Charles Josiah, B.Sc., Lecturer in Chemistry, Teachers’ College, Uni- versity Grounds, Newtown. ; White, Douglas Elwood, m.sc., D.Phil., Chemistry Department, The University, Melbourne. Wiesener, Frederick Abbey, M.B., Ch.M., D.O.M.S., Ophthalmic Surgeon, 143 Macquarie-street, Sydney; p.r. Jersey-road, Strathfield? ai ae Si Elected. 1920 1940 1935 1940 1935 1936 1906 1916 1921 1939 1914 1931 1915 1912 1915 1922 Pye Pl EP t2 Xvi Williams, Harry, A.1.c., A.A.c.1., Frog’s Hall Cottage, Aldham, Essex, England. Willison, Alan Maynard, m.sc., 3 Stanley-street, Randwick. Wilson, Ralph Dudingston, M.sc.agr., Biological Branch, Department of Agriculture, Sydney. Wogan, Samuel James, 34 Neich-parade, Burwood. Wolstenholme, Edmund Kay, ‘‘ Petarli,’’ New South Head-road, Double Bay. Wood, Harley Weston, M.Sc., A.Inst.P., F.R.A.S., Assistant Astronomer, Sydney Observatory ; p.r. 4 Ormond-street, Ashfield. Woolnough, Walter George, D.sc., F.G.S., “* Callabonna,’’ Park-avenue, Gordon. (President, 1926.) Wright, George, Company Director, c/o Farmer & Company Limited, Sydney ; p.r. ““ Wanawong,” Castle Hill, N.S.W. Yates, Guy Carrington, Seedsman, c/o Arthur Yates & Co. Ltd., 184 Sussex- street, Sydney; p.r. Boomerang-street, Turramurra. HoNnoRARY MEMBERS. Inmited to Twenty. Chapman, Frederick, A.L.S., F.R.S.N.Z., F.G.S., “‘ Hellas,” 50 Stawell-street, Kew, E.4, Victoria. Hill, James P., D.sc., F.R.S., Professor of Zoology, University College, Gower- street, London, W.C.1, England. Lyle, Sir Thomas Ranken, K.B., C.B.E., M.A., D.Sc., F.R.S., “‘ Lisbuoy,”’ Irving- road, Toorak, Melbourne, Victoria. Maitland, Andrew Gibb, F.a.s., ‘‘ Bon Accord,’’ 28 Melville-terrace, South Perth, W.A. Martin, Sir Charles J., c.M.G., D.Sc., F.R.S., Roebuck House, Old Chesterton, Cambridge, England. Thomson, Sir Joseph J., 0.M., M.A., D.Sc., F.R.S., Nobel Laureate, Master of Trinity College, Cambridge, England. Wilson, James T., M.B., ch.m. Edin., F.R.S., Professor of Anatomy in the Uni- versity of Cambridge ; p.r. 31 Grange-road, Cambridge, England. OBITUARY 1941-1942. Elected. 1894 Richard Thomas Baker. 1935 Leon Macintosh Ellis. 1891 Edward George Noble. 1918 Carl Gustaf Sundstrom. THE REV. W. B. CLARKE MEMORIAL FUND. The Rev. W. B. Clarke Memorial Fund was inaugurated at a meeting of the Royal Society of N.S.W. in August, 1878, soon after the death of Mr. Clarke, who for nearly forty years rendered distinguished service to his adopted country, Australia, and to science in general. It was resolved to give an opportunity to the general public to express their appreciation of the character and services of the Rev. W. B. Clarke “ as a learned colonist, a faithful minister of religion, and an eminent scientific man.” It was proposed that the memorial should take the form of lectures on Geology (to be known as the Clarke Memorial Lectures), which were to be free to the public, and of a medal to be given from time to time for distinguished work in the Natural Sciences done in or on the Australian Commonwealth and its territories; the person to whom the award is made may be resident in the Australian Commonwealth or its territories, or elsewhere. The Clarke Memorial Medal was established first, and later, as funds permitted, the Clarke Memorial Lectures have been given at intervals. CLARKE MEMORIAL LECTURES. Delivered. 1906. ‘“‘The Volcanoes of Victoria,” and ‘“‘The Origin of Dolomite’’ (two lectures). By Professor E. W. Skeats, D.Sc., F.G.S. 1907. ‘‘ Geography of Australia in the Permo-Carboniferous Period’”’ (two lectures). By Professor T. W. E. David, B.A., F.R.S. ‘The Geological Relations of Oceania.’”> By W. G. Woolnough, D.Sc. ‘“* Problems of the Artesian Water Supply of Australia.” By E. F. Pittman, A.R.S.M. ‘“The Permo-Carboniferous Flora and Fauna and their Relations.” By W. 8. Dun. 1918. ‘‘ Brain Growth, Education, and Social Inefficiency.”” By Professor R. J. A. Berry, M.D., F.R.S.E. 1919. ‘' Geology at the Western Front,” By Professor T. W. E. David, C.M.G., D.S.O., F.R.S. 1936. ‘‘The Aeroplane in the Service of Geology.” By W. G. Woolnough, D.Sc. (THIS JOURN., 1936, 70, 39.) 1937. ‘‘ Some Problems of the Great Barrier Reef.’’ By Professor H. C. Richards, D.Sc. (THIs JouRN., 1937, 71, 68.) 1938. ‘‘The Simpson Desert and its Borders.”” By C. T. Madigan, M.A., B.Sc., B.E., D.Sc. (Oxon.). (THis Journ., 1938, 71, 503.) 1939. ‘‘ Pioneers of British Geology.” By Sir John S. Flett, K.B.E., D.Sc., LL.D., F.R.S. (THis Journ., 1939, 73, 41.) 1940. “The Geologist and Sub-surface Water.” By E. J. Kenny, M.Aust.I.M.M. (TuIs JouRN., 1940, 74, 283.) 1941. ‘‘ The Climate of Australia in Past Ages.” By C. A. Sussmilch, F.G.S. (THis Journ., 1941, 75, 47.) AWARDS OF THE CLARKE MEDAL. Established in memory of The Revd. WILLIAM BRANWHITE CLARKE, m.a., F.R.S., F.G.S., etc. Vice-President from 1866 to 1878. The prefix * indicates the decease of the recipient. Awarded. 1878 *Professor Sir Richard Owen, K.C.B., F.R.S. 1879 *George Bentham, C.M.G., F.R.S. 1880 *Professor Thos. Huxley, F.R.s. 1881 *Professor F. M‘Coy, F.R.S., F.G.S. 1882 *Professor James Dwight Dana, LL.p. 1883 *Baron Ferdinand von Mueller, K.c.M.G., M.D., Ph.D., F.R.S., F.L.S. 1884 *Alfred R. C. Selwyn, LL.D., F.R.S., F.G.S. 1885 *Sir Joseph Dalton Hooker, 0.M., G.c.s.1., C.B., M.D., D.C.L., LL.D., F.R.S. 1886 *Professor L. G. De Koninck, m.p. 1887 *Sir James Hector, K.C.M.G., M.D., F.R.S. Kix Awarded. 1888 *Rev. Julian E. Tenison-Woods, F.G.S., F.L.S. 1889 *Robert Lewis John Ellery, F.R.S., F.R.A.S. 1890 *George Bennett, M.D., F.R.c.S. Hng., F.L.S., F.Z.S. 1891 *Captain Frederick Wollaston Hutton, F.R.s., F.G.S. 1892 *Sir William Turner Thiselton Dyer, K.C.M.G., C.I.E., M.A., LL.D., Sc.D., F.R.S., F.L.S. 1893 *Professor Ralph Tate, F.L.s., F.G.S. 1895 *Robert Logan Jack, LL.D., F.G.S., F.R.G.S. 1895 *Robert Etheridge, Jnr. 1896 *The Hon. Augustus Charles Gregory, C.M.G., F.R.G.S. 1900 *Sir John Murray, K.C.B., LL.D., Sc.D., F.RB.S. 1901 *Edward John Eyre. 1902 *F. Manson Bailey, cC.M.G., F.L.s. 1903 *Alfred William Howitt, D.Sc., F.G.S. 1907 *Professor Walter Howchin, F.a.s., University of Adelaide. 1909 *Dr. Walter E. Roth, B.a. 1912 *W. H. Twelvetrees, F.G.s. 1914 Sir A. Smith Woodward, LL.p., F.R.s., Keeper of Geology, British Museum (Natural History), London. 1915 *Professor W. A. Haswell, M.A., D.Sc., F.R.S. 1917 *Professor Sir Edgeworth David, K.B.E., C.M.G., D.S.0., M.A., SC.D., D.Sc., F.R.S., F.G.8. 1918 *Leonard Rodway, c.m.c., Honorary Government Botanist, Hobart, Tasmania. 1920 *Joseph Edmund Carne, F.G.s. 1921 *Joseph James Fletcher, M.A., B.Sc. 1922 *Richard Thomas Baker, The Crescent, Cheltenham. 1923 *Sir W. Baldwin Spencer, K.C.M.G., M.A., D.Sc., F.R.S. 1924 *Joseph Henry Maiden, 1.s.0., F.R.S., F.L.S., J.P. 1925 *Charles Hedley, F.u.s. 1927 Andrew Gibb Maitland, F.a.s., ‘‘ Bon Accord,” 28 Melville Terrace, South Perth, W.A. 1928 Ernest C. Andrews, B.A., F.G.S., 32 Benelong Crescent, Bellevue Hill. 1929 Professor Ernest Willington Skeats, D.sc., A.R.C.S., F.G.S., University of Melbourne, Carlton, Victoria. 1930 =‘ L. Keith Ward, B.A., B.E., D.Sc., Government Geologist, Geological Survey Office, Adelaide. 1931 *Robin John Tillyard, M.A., D.Sc., Sc.D., F.R.S., F.L.S., F.E.S., Canberra, F.C.T. 1932 Frederick Chapman, A.L.S., F.R.S.N.Z., F.G.S., Melbourne. 1933. Walter George Woolnough, D.sc., F.G.s., Department of the Interior, Canberra, F.C.T. 1934 *Edward Sydney Simpson, D.Sc., B.E., F.A.C.1., Carlingford, Mill Point, South Perth, W.A. 1935 George William Card, a.R.s.mM., 16 Ramsay-street, Collaroy, N.S.W. 1936 Sir Douglas Mawson, Kt., 0.B.E., F.R.S., D.Sc., B.E., University of Adelaide. 1937 J. T. Jutson, B.sc., LL.B., 9 Ivanhoe-parade, Ivanhoe, Victoria. 1938 Professor H. C. Richards, p.sc., The University of Queensland, Brisbane. 1939 OC. A. Sussmilch, F.a.s., F.s.T.c., 11 Appian Way, Burwood, N.S.W. 1941 Professor Frederic Wood Jones, M.B., B.S., D.Sc., F.R.S., Anatomy Department, University of Manchester, England. AWARDS OF THE SOCIETY’S MEDAL AND MONEY PRIZE. Money Prize of £25. Awarded. 1882 John Fraser, B.a., West Maitland, for paper entitled ‘“‘ The Aborigines of New South Wales.”’ 1882 Andrew Ross, m.D., Molong, for paper entitled ‘‘ Influence of the Australian climate and pastures upon the growth of wool.” The Society's Bronze Medal and £25. Awarded. 1884 W. EK. Abbott, Wingen, for paper entitled ‘‘ Water supply in the Interior of New South Wales.” 1886 S. H. Cox, F.c.s., F.c.s., Sydney, for paper entitled ‘‘ The Tin deposits of New South Wales.” 1887 Jonathan Seaver, F.c.s., Sydney, for paper entitled ‘“‘ Origin and mode of occurrence of gold-bearing veins and of the associated Minerals.”’ 1888 Rev. J. E. Tenison-Woods, F.G.s., F.L.S., Sydney, for paper entitled ‘‘ The Anatomy and Life-history of Mollusca peculiar to Australia.” 1889 Thomas Whitelegge, r.R.m.s., Sydney, for paper entitled ‘‘ List of the Marine and Fresh- water Invertebrate Fauna of Port Jackson and Neighbourhood.”’ O Awarded. 1889 Rev. John Mathew, m.a., Coburg, Victoria, for paper entitled *“‘ The Australian Aborigines.” 1891 Rev. J. Milne Curran, F.c.s., Sydney, for paper entitled ‘“‘ The Microscopic Structure of Australian Rocks.” 1892 Alexander G. Hamilton, Public School, Mount Kembla, for paper entitled ‘“‘ The effect which settlement in Australia has produced upon Indigenous Vegetation.” 1894 J. V. De Coque, Sydney, for paper entitled the ‘‘ Timbers of New South Wales.” 1894 R. H. Mathews, u.s., Parramatta, for paper entitled “‘ The Aboriginal Rock Carvings and Paintings in New South Wales.”’ 1895 C. J. Martin, D.sc., M.B., F.R.S., Sydney, for paper entitled ‘‘ The physiological action of the venom of the Australian black snake (Pseudechis porphyriacus).”’ 1896 Rev. J. Milne Curran, Sydney, for paper entitled ‘‘ The occurrence of Precious Stones in New South Wales, with a description of the Deposits in which they are found.” AWARDS OF THE WALTER BURFITT PRIZE. Bronze Medal and Money Prize of £50. Established as the result of a generous gift to the Society by Dr. W. F. Burritt, B.A., M.B., Ch.M., B.Sc., of Sydney. Awarded at intervals of three years to the worker in pure and applied science, resident in Australia or New Zealand, whose papers and other contributions published during the past three years are deemed of the highest scientific merit, account being taken only of investigations described for the first time, and carried out by the author mainly in these Dominions. Awarded. 1929 Norman Dawson Royle, M.D., ch.m., 185 Macquarie Street, Sydney. 1932 Charles Halliby Kellaway, M.c., M.D., M.s., F.R.c.P., The Walter and Eliza Hall Institute of Research in Pathology and Medicine, Melbourne. 1935 Victor Albert Bailey, M.A., D.Phil., Associate-Professor of Physics, University of Sydney. 1938 Frank Macfarlane Burnet, m.p. (Melb.), ph.p. (Lond.), The Walter and Eliza Hall Institute of Research in Pathology and Medicine, Melbourne. 1941 Frederick William Whitehouse, D.sc., Ph.p., University of Queensland, Brisbane. AWARDS OF LIVERSIDGE RESEARCH LECTURESHIP. This Lectureship was established in accordance with the terms of a bequest to the Society by the late Professor Archibald Liversidge. Awarded at intervals of two years, for the purpose of encouragement of research in Chemistry. (THis JourNAL, Vol. LXII, pp. x-xiii, 1928.) Awarded. 1931 Harry Hey, c/o The Electrolytic Zine Company of Australasia, Ltd., Collins Street, Melbourne. 1933. W. J. Young, D.sc., M.sc., University of Melbourne. 1940 G. J. Burrows, B.Sc., University of Sydney. : 4 ; se URN. “FOR i 1941 Be ya hy Ra ANCORPORATRD 1881) a Cee | Re { oe VOL. LXXV eae ‘ ; ia : ee a 4 avery Pee nee Bea! | Pie es morph By, ee 3 “THE HONORARY SECRETARIES = sd le 7p st pep aH fhe bre Wy AM Ps 3 U 2 5 os IL. ithe Effect of the Synthetic arog Stilbeestrol ah Hee cute nthe and Scrotum of Trichosurus vulpecula. » Ph. D., cn e as J.C a BS. (Issued ee & hee . 5 oe III. _ Mapes Stndies An Dooraenee Comp pounds. : ae of eee 1 Methy 7 oie By) preys Ss. Carslase, Se.D D., »ULD. i eee A shy : 48 nae | » interests A “have hg Pe PRESIDENTIAL ADDRESS By ProFessor A. P. ELKIN, M.A., Ph.D. (Delivered to the Royal Society of New South Wales, April 3, 1941) . CONTENTS. Part I. THe Royat Socrety. Page. The Past Year ite ae Ae ve es na fas 1 The Function of the Royal Society ae a, x ae ie a me 3 Part II. Science, SocieTY AND EVERYMAN: SCIENTISTS, THE PROPAGANDISTS OF SCIENCE. The Royal Society and Anthropology .. 4 The Subject of this Address 5 Science and Everyman : 6 Government Administration and Seience hs ee es ay Ee wee 7 Scientists and Secrets 8 Scientists and Social Duty sole ee is me ie ve 9 Race Propaganda and the World Siewntion SR sae i: Aa ae 1] ** Half-Castes ’’, Biology and Prejudice : ae a ap Fi 14 Anthropology a the Administration of Net aces a ae sits as 15 Scientific Study of our own Society .. ie ap re He 16 a 17 Science, Education and Everyman se ae ae ae a ne ane 19 Part I. THE ROYAL SOCIETY. THE PAST YEAR. A feature of the past year in the Society’s history has been the large number of members elected, namely sixty-two—the result for the most part of the efforts of one or two members. In the name of the Society I heartily welcome them and trust that they will continue “ to run the race that is set before them ’’, in the fellowship of our Society ever pushing further away the boundaries of knowledge. During the year we lost eight members by resignation and six by death. Our present membership stands at 307. One of the very pleasant duties of the President—a duty which is usually a surprise to the newly-elected occupant of the chair—is to be official visitor to the New South Wales Observatory and in that capacity to attend a meeting of the Board of Visitors. I was fated to be the last of a series of Presidents who enjoyed the privilege of attending this meeting, with the late Mr. J. Nangle, a Past-President of our Society and Government Astronomer, as host, secretary and inspirer. Mr. Nangle and the two scientific members of his staff were performing very important work for science and the nation, indeed, for the world—for obviously there can be no boundaries to astronomy: the heavens are for all, even though the earth be partitioned out. As you know, Mr. Nangle, even before retiring from the position of Director of Technical Education, offered his services as Honorary Astronomer, and A—April 3, 1941. , oy a! {QFre. " AR Ni 2, A. P. ELKIN. fortunately his offer was accepted. As it may not be possible for any person with the requisite qualifications to accept the position now under the same conditions, I am sure that I am speaking for you all in asking the Government to make such financial provision as will ensure the appointment of a Government Astronomer of distinction and the maintenance of an adequate staff for the continuation of the valuable work which is now in progress at the Observatory. On my own and your behalf I sincerely thank the members of the Council and of the various committees and the office staff for their ready help and good work during the year; in particular, I thank the executive officers for the zeal with which they have performed their never-ending, though honorary, tasks— Mr. A. R. Penfold, Official Secretary ; Mr. Welch, Honorary Treasurer; and Dr. C. Anderson, Editorial Secretary ; also Mr. D. P. Mellor, who assisted the Editor, and Professor Earl, our Honorary Librarian. Nor do I forget the good work done by the Chairmen and Honorary Secretaries of Sections. Finally, I express my appreciation of the goodwill shown me by the members of the Society during my term of office. The following statistics reveal some of the activities of the Society and its office-bearers. During the year there were nine general meetings, with an average attendance of fifty-three, at which forty papers were read; eleven Council meetings, with an average attendance of fourteen out of eighteen members. The executive officers kindly met me in consultation ten times, and there were eight meetings of special committees to deal with such matters as finance, rules, the appointment of Clarke Memorial Lecturer and Medallist and the Liversidge Lecturer. Four Popular Science Lectures were arranged, and were well attended. The Society appreciates very much the help thus given by the lecturers: Phyllis M. Kaberry, M.A., Ph.D. (July 18, “An Inland People of New Guinea ”’), A. R. Woodhill, B.Sc.Agr. (August 15, “ Insects and Disease in War-time, with Special Reference to Mosquito Biology ’’), R. N. Robertson, B.Sc., Ph.D. (September 19, ‘“‘ Energy for Living ’’), A. R. Penfold, F.A.C.I., F.C.S. (October 17, ‘““ Romances of Chemistry—Coal Stockings and Glass Ties ’’). The ninth Clarke Memorial Lecture was delivered on June 14 by Mr. E. J. Kenny, and was entitled “ The Geologist and Sub-surface Water ’’, and the Liversidge Research Lecture on October 31 by Mr. G. J. Burrows, B.Sce., on the subject ‘‘ Organic Arsenicals in Peace and War’”’. This was the third Liversidge Research Lecture delivered under the auspices of our Society. As in previous years, your Council has endeavoured to make the general meetings of interest to all members. The highly specialised papers have been presented usually in very brief form, leaving time at three meetings for informative lecturettes (“‘ Highlights of a Recent World Tour’’, by Mr. A. R. Penfold ; ‘“Submarine Canyons ”’, by Dr. G. D. Osborne; “‘ The Early History of Wire- less ’’, by Mr. G. G. Blake), and at another meeting for an explanation of exhibits (Ethnological by Professor A. P. Elkin and Glass Textiles by Mr. A. R. Penfold). In addition, almost the whole of the general meeting in August was devoted to a symposium on Potassium which had been organised by Mr. D. P. Mellor. The Lecture Hall was full. Prepared papers were read by G. de Vahl Davis, B.Sc.Agr., “The Commercial Potash Situation in Australia’”’?; D. P. Mellor, M.Sc., “Some Aspects of the Chemistry of Potassium, with Special Reference to Potential Sources in Australia’; N. H. Parbery, D.Sc., “ Potassium in Soil’’?; and R. N. Robertson, B.Sc., Ph.D., “ Potassium in Plants’. Mr. de Vahl Davis also showed a film entitled ““The Mining and Manufacture of Potash in Europe ’’. A number of persons present contributed to the discussion. Because of the importance of the subject, especially during the present inter- national situation, the papers, together with the contributions made in the PRESIDENTIAL ADDRESS. 3 discussion, were later printed as a booklet and distributed to members and others interested. To sum up, at five out of the nine general meetings about half of the time (in one case, almost all) was devoted to subjects of general interest. At a sixth, the annual general meeting, all papers were read by title only to make time for elections and the hearing of the Annual Report and the President’s Address. Thus, at only three meetings was the whole of the time—apart from formal business—expended on the reading and discussion of specialist-researches. Tf less time still were to be devoted to the latter purpose, it would mean that in most cases the papers would have to be read by title only. This would be a possible plan if they were read in full and discussed at previous section meetings, through which experience they might emerge with useful amendments. But it may be that the process would not stop there, for most sciences tend to be departmentally specialised, so that we might have subsections of sections. As against this, no doubt members like to hear at general meetings the results obtained by fellow members in their latest researches. The upshot is that we must seek a balance in the agenda of our general meetings, and, of course, as scientists, be not afraid to experiment with that agenda. FUNCTION OF THE ROYAL SOCIETY. Our Society has a threefold function: (1) In the first place, the Society exists to encourage research in all departments of science, art, literature and philosophy. It does this by providing a means of publishing worthy papers and an opportunity for discussing such papers and also subjects of scientific importance, and by awarding honours in the form of medals, money prizes and lectureships. These awards have been made possible by gifts from the late Professor Liversidge and Dr. Walter Burfitt and by the fund raised sixty years ago aS a memorial to the late Reverend W. B. Clarke. For a period, too, 1882-1896, the Society, from its own current funds, awarded on, fourteen, occasions a substantial money prize, combined on, twelve occasions with a bronze medal, as a reward and encouragement for research in various scientific fields. The award was actually made in each case for a particular paper. I suggest that when, the financial position justifies the Society in so doing some such award as this should be renewed without limitation of the field of research. In addition, the Society would welcome benefactions to enable it to increase its power of encouraging, and indeed of assisting research, not only by the awards of prizes, but also by making grants and awarding fellowships. Apart from such benefactions, the Society can do little more than at present, namely maintain, the Journal and library and meet necessary and, incidentally, very moderate administrative expenses. To enable it to do this, your Council depends on the Government grant, for which we are all very thankful, on members’ subscriptions, and on the income derived from the Society’s limited amount of capital investment. With regard to the discussion of research results, as I have already suggested, the formation of more sections might be encouraged ; for example, in Chemistry and Sociology. In this connection the Council regretfully accepted during the past year the dissolution of the Physics Section which, after fifteen and a half years of useful work, prepared the way for the formation in Sydney of a branch of the Institute of Physics. (2) The second function of our Society is to give all members an opportunity for becoming acquainted as soon as possible with the results of recent research ; in, other words, to enable specialists in the various branches and also what may be called “lay members” to keep abreast of scientific advances in general. This is the object of the general meetings, with their brief explanations and AA—April 8, 1941. 4 A. P. ELKIN. discussions of papers and lecturettes. The informal talks during supper can also help in this direction. (3) The final function of the Society is its “ popular ’ work—the passing on, in acceptable form of scientific knowledge to the general public. At present, we rely mainly on four or five public lectures a year given in, an honorary capacity by experts. I believe we would be rendering service to the community by expanding this part of our work, if we had the funds—a subject to which I will return, in a later section of this address. If we could not do this directly, we should try to do so indirectly, that is by urging, inspiring, assisting and co- operating with other scientific and educational groups to spread scientific knowledge and the scientific attitude. In concluding this part of my address, I express regret that owing to the present time of international strain which affects each one of us, the Annual Dinner was not held. Your Council at first planned to hold it, but as the weeks passed by I formed the opinion that our Society should refrain from any function, the purpose of which was solely pleasurable, and with this opinion both the executive officers and later the Council expressed agreement. Incidentally, the dinner was not held during the war of 1914-18. Our next dinner (and may it soon be held) will celebrate the cessation of hostilities and the dedication of the energies of scientists to their share of the work of rehabilitation of society on a peace basis. ¢ 3 Parr If. SCIENCE, SOCIETY AND “ EVERYMAN ” OR SCIENTISTS, THE PROPAGANDISTS OF SCIENCE. THE ROYAL SOCIETY AND ANTHROPOLOGY. The Presidents of the Royal Society have come hitherto from many depart- ments of science—agriculture, astronomy, botany, chemistry, engineering, geology, mathematics, physics, physiology, statistics, veterinary science and zoology. It is interesting to notice that while all these subjects are of vital importance to man if he is to understand the universe in which he finds himself, none of them are directly concerned with the phenomenon of man himself as a thinking and social being. In 1940, however, you drew your President from the field of the social sciences, a term that is coming into vogue, in particular from anthropology—and more precisely from social anthropology, which is sociology writ wide and large. This is not the first recognition given by our Society to anthropology. Many papers on the subject have been published in our Journal, especially between 1890 and 1910.1 The Society’s money prize was awarded in 1882 (John Frazer), 1889 (Reverend John Mathew) and 1894 (R. H. Mathews) for papers on the Australian Aborigines, and three of the recipients of the Clarke Memorial Medal, A. W. Howitt (1903), W. E. Roth (1909) and Baldwin Spencer (1923), whatever other accomplishments could be credited to them, will live in the annals of Australian science for their contributions to our knowledge of the Australian Aborigines. The election of a social anthropologist, however, to the very honourable position of President of the Royal Society of New South Wales in these latter days is very significant. Wittingly or unwittingly, in so doimg you have 1From 1870-1889, 12 papers; from 1890-1899, 23 papers; from 1900-1909, 18 papers ; from 1910-1940, 9 papers. PRESIDENTIAL ADDRESS. 5 expressed what I think is one of our greatest needs today—the scientific study of human society ; that is, the endeavour to ascertain, the principles of. social structure not only in itself but also in relation to culture and change, to under- stand the laws of social and cultural change and to clarify the relation of society to the individual, his thoughts, feelings and actions. I cannot take time here to develop this point further, but must content myself with saying that sociology can be and must be as scientific in its methods, techniques and objectives as any other science, pure and applied. THE SUBJECT OF THE ADDRESS. Until 1900 the annual address to the Society was termed the Anniversary address, and up to 1880 was delivered by a Vice-President of the Society. The Governor, who was President of the Society, was spared this task. From 1881 to 1900, the address was delivered by the President, who, however, was no longer the Governor, the latter having been made ex officio Honorary President of the Society by a rule adopted in 1879, and Vice-President on, a revision of the rules in 1901. But be he President or Vice-President who delivered the annual address, he was generally somewhat perplexed regarding its subject matter. As one put it forty years ago: “ There comes the important question as to what rightly constitutes the subject matter of the presidential address: whether it should be a retrospect of the scientific work of the year, an announcement of something new in science, a history of science brought to date, a discussion of some ‘ burning question ’, or merely a dissertation on some particular subject passing in the mind of the President.’ Fortunately there is no rule governing the matter of the address, nor indeed is there a rule that one should be inflicted on the President and members. Tradition, however, steps in and prevents him from escaping its preparation and constrains a quorum to be present during its delivery. Tradition, too, is the main factor in determining the general outlines of the address. Almost all have contained brief references to events of interest and significance in the life of the Society during the preceding year, including the year’s register of obituary notices of members, a necrology, as three Presidents aptly termed it. For many years too, the address included a survey of the year’s advances in all departments of science the world over— an, undertaking which grew more formidable each year until at last, in the first decade of this century, in face of the increased specialisation within each science, and of the great growth of scientific work in country after country, the President wisely shrank from the task; instead, he confined himself either (a) to unburdening himself of some thoughts which came, “‘ perhaps unbidden’’, to his mind during the year, or (b) to giving a survey of research, discovery and applica- tion within his own specialised sphere of work, and/or (¢) presenting the results of a definite piece of research carried out by himself. The addresses for the last thirty years have tended towards the establishing the third as a tradition, though it is sometimes combined with the second. Fortunately, however, this has not quite scotched the urge of an occasional President either to devote the whole of his address to “ unburdening his mind ”’, or else to making his survey of specialised scientific advance the basis for some degree of “‘ unburdening ”’. In other words, all scientists cannot all the time keep within the academic cloisters and the laboratory, but are constrained to speak directly to the general public or to the government on matters of practical significance arising out of their special studies. It is good that this is so, and may the tradition of this Society never be set against such breaking forth from the scientific cocoon ! “ Science for the sake of science ”’ is a noble motto to be observed during research, although “ science for the sake of business ”’ or “ of war” is not unknown. But im ahy case, science was made for man and not man for science. It has come into being for the use of man; it is a means by which he learns to understand 6 A. P. ELKIN. and adapt himself better to and even use his total environment—material, human, and social. Life is the task, and science one of the means by which man performs that task. SCIENCE AND EVERYMAN. It is a chastening thought to realise that science, aye and scientists too, mean, very little, usually nothing, to the average man. It is true that the latter has gained from the scientists’ discoveries, which underlie the telephone, radio, motor car, aeroplane, electric sweeper, the “ talkies ’ and so on, but to “ Every- man ”’ the great majority of these things mean no more than the magic lantern, and steam engine did to people of other days. The present generation grows up quite accustomed to them. I am concerned, however, not so much with the material benefits bestowed by science as with man’s attitude to the world, to life in the world, and the problems related thereto. One social scientist ventured to predict that with increasing scientific knowledge—psychological and sociological as well as natural—the cohesion of society would be ensured and man would live a moral life without any reference to religious sanctions and the sphere of the contingent with which these are interrelated. ‘““ Psychology ”’, he said, “ will in the future enable us to construct a truly - scientific scheme of education and child training. If in the distant future biology should show us how to breed a better race, science will-ultimately give man a new self .. ..The social sciences may be expected to yield up the secrets of social order and progress and thus enable man to perfect his social system. Meanwhile, there need be no fear that, if men cease to believe in God, they will straightway prepare to go to the devil .. .. The moral code based on the mandates of God yields slowly but surely to one based on, the mandates of science, but the new morality is doubly strong. It not only makes its own appeal to the human reason and the desire to live long and well, but it has back of it the same social sanction which compels conformity everywhere.’? This author has obviously very great faith in the logical character of man’s conduct—at least in the far distant future ; his is a vision of a future which he desires. But I doubt whether the facts allow us so to dream, and those facts are human beings as they are and as they have been. Most of our behaviour is based not on scientific knowledge and logical deductions therefrom, but is non-logical, arising from our desires and from the attitudes which we have imbibed from, or which have been inculeated in us by, our society or by some group within that society. It is all too easy to say that we are living in a scientific age ; we are living in an age in which there are very many scientists and in which much practical use is being made of scientific research, but the comparatively many scientists are but a very small minority of the population, and again, a very small minority of the latter has any worthwhile appreciation of science or of the scientific attitude to life and its problems. In spite of school curricula, of scientific subjects in the Leaving Certificate and of popular science on the radio, you will be fortunate to find in a township, or indeed in many suburbs, apart from scientific teachers and workers, more than half a dozen individuals who know anything about scientific method, scientific attitude or “scientific mandates’. The proceedings of scientific bodies is not considered news by the papers. Moreover, a very strong proof that our age is not scientific is provided by the flourishing existence of Christian science and astrology, the former with its refusal to face unpleasant phenomena, and the latter with its removal of human responsibility for decision to the accident of birth in relation to the stars—a witness to the gullibility of human beings. Then there is British Israelitism, with its convenient proofs from the 2F. H. Hankins, An Introduction to the Study of Society, pp. 596-7. PRESIDENTIAL ADDRESS. 7 Great Pyramid and the Bible, or Jehovah’s Witnesses with their effective salesmanship of their propagandist literature. Probably few if any of the members of our Society are interested in these and similar cults, but hundreds of thousands of citizens are keenly interested in them and many more nibble at the baits which are extended. These cults are mostly paying concerns and in some cases are organised on an immense scale. But if the social disciplines of psychology, anthropology and history, and the natural sciences of astronomy and biology really contributed to the stock-in-trade of the average man, this would not, or at least should not, be so. In other words, the scientific knowledge and attitude possessed by a few is unknown to, or ignored by, very many who are therefore the mental, social and financial prey of strange cults and superstitions. In the face of the contingencies of life, of the unknown and of disasters, they return to the primitive or the medizeval—to astrologer, anthroposophist, ‘““ medicine-man healer ’’, or the soothsayer whether he use the stars, the pyramid, the Bible or the séance. What is the explanation of this phenomenon? Some say it is a sign of the general neurosis which has overtaken, our age, itself the result of the vast speeding up of the pace of life—the consequence of mechanical advance. Others say it is the fault of the churches for not giving people a saner attitude when faced with life’s difficulties and disasters, or they blame the education system, which is said to be concerned overmuch with preparing children to make a livelihood, instead of equipping them to recognise and meet squarely and sanely the problems of life as they arise and to solve them consciously and logically. But scientists and scientific bodies must acknowledge that they themselves have not done all that they should have done. The age is not scientific because the scientists have persuaded neither the authorities—political, administrative and educational—nor the people generally that they should and can be scientific, that science provides not only a content of knowledge and a means of increased efficiency and pleasure, but also an attitude to life. GOVERNMENT ADMINISTRATION AND SCIENCE. Another sign of this failure is the lack of appreciation by governments of the co-operation which they could receive from scientists—an unfortunate fact about which much has been heard since the threat and outbreak of this war. Scientists and scientific bodies when offering their services have been nonplussed when told that there was nothing for them to do. The members of one scientific group were told to get in touch with their respective air-raid wardens—advice which takes us to the root of the trouble. It is not merely that Cabinet ministers think that everything possible is no doubt being done by the experts in the various government departments, or (as is sometimes said) that these latter do not welcome outside assistance, but that ministers and departmental heads are usually typical examples of “Everyman ’’, that is, they have no more grip of the significance of science for human thought and well-being than the latter. Therefore, in face of the scientists’ offer of service, they are genuinely nonplussed, for do they not hold the usual opinion that the scientist—professor or not— spends all his time in his laboratory, like a chrysalis in its cocoon, and has no understanding of practical affairs? Moreover, government and administrative heads, knowing their own power, believe that all contingencies and problems can be met by administrative efficiency—by additional administrative officers, if necessary. And so persons renowned for their business acumen and adminis- trative abilities are appointed to this or that service, often irrespective of the content or specialty of the particular department. A good administrator is held to be a person who not only can grip all the details of a particular department and task in a few months, but also can understand the problems associated with it, be these human or scientific. Of course, good administrators are required CH A. P. ELKIN. for public affairs in both peace and war, but apart from the fact that some scientists are good administrators, the really good administrator for many departments of life these days should be one whose training has taught him to understand the scientific attitude, to appreciate the relation of scientific experi- ment and discovery to national welfare, and, when confronted with important problems, to be prepared to call upon the scientific resources and potentialities of scientists engaged in the particular sphere which is in question. This, of course, would be done most simply through the organised scientific bodies such as our own, the Australian National Research Council, and any nation-wide register of scientists which is in existence. Such help would then be used in collaboration with the Council for Scientific and Industrial Research and the departmental scientific experts. A very sad feature of that most interesting recent Penguin Special, Science mm War (1940), is the revelation of the small degree in which science and scientists were being used in England quite recently in the war effort, and of the inefficiency and serious consequences which followed from this state of affairs. It is stated that the group of scientists who still stand outside war work and who include some of the most powerful minds in science, “ has no knowledge, except in the most general terms, of the problems by which the country is faced’’. Unfortunately too, those scientists who sit on government advisory boards and committees or conduct extra-mural war work in their laboratories, seem unable to do more than agree with government decisions, instead of challenging them when necessary in the name of science. Various examples are given in this book of the way in which science could help the war effort if it could be effectively heard and used. Thus: “there is little dcubt that geographic and economic knowledge and the assistance of great modern developments in mathematics could lead, in a minimum of time, to a revolution in strategy far greater than that introduced by Napoleon ’”’. Again, in air warfare, while many problems have been dealt with effectively by science, “‘ others could be if government departments were willing to carry out proposals based on scientific study ”’ ; and with regard to bomb shelters, the scientific approach, which is briefly summarised, was made outside official circles before the war and “ its application was strenuously resisted by the government department concerned’. Other examples are provided by the camouflage methods—an extraordinarily con- vineing instance of the ineptitude of the existing system where science is concerned, by the provision of food in war time and go on.? The picture is becoming less gloomy, thanks to the course of the war and much agitation on the part of scientific bodies. In Australia, the Commonwealth Government is becoming gradually seized with the necessity for making a survey of available manpower and resources, which could be used wherever and whenever required in the present national emergency—but so far it has been a piecemeal process instead of being part of a planned unitary scheme. In addition, advisory panels have been set up, including, or consisting of scientists, and a number of individual non-Government scientists are working on war problems under the auspices of various government departments. SCIENTISTS AND SECRETS. Incidentally, a matter of some psychological importance arises in connection with this. Scientists whose services are used to assist the war effort on panels or in research, not only become acquainted with and contribute technical processes of a secret nature; in addition they are supplied with confidential information regarding the seriousness of the war itself or the country’s situation with reference to this or that vital necessity, so that they may be fully seized 8 Science in War, pp. 12-13, 35, 43, 91. PRESIDENTIAL ADDRESS. 9 with the significance and importance of their work. Needless to say, they will not discuss such information with any person, outside their particular panel or board; but they are not so accustomed to possessing secret information of vital significance as are for example members of the diplomatic service and father confessors. This is as it should be, because normally there is nothing confidential about the objects, methods or results of scientific research, all of which are displayed for the benefit and interest of all who desire to use them. But in the war situation a good deal of emotional tension is apt to be created— a tension which occasionally breaks, and reference is made, possibly in the course of discussion, to one’s possession of confidential information, though details are not mentioned, with the effect that one’s arguments may seem irresistible. This is quite understandable, for scientists, in spite of cartoons, are hormal human, beings, “‘ of like passions ’’ with other men. In certain critical circum- stances all of us are apt to be less than scientific and to appeal to the emotions rather than to an array of facts carefully observed or experimentally tested. But in the realm of what might be termed vital information, unless the cards can be put on the table, let them be kept in the table drawer, with the drawer shut. No references should be made to what cannot be disclosed. This applies of course not only to scientists, but to governments and national leaders, all of whom should give to one another and to people at large definite information only, be it good or bad ; this can be faced and dealt with. But they should not make suggestions of possible national “‘ time-bombs ”’ about which they know something but can reveal nothing except a feeling of anxiety. It is the duty of administrations, together with the help of scientists when necessary, to render those ‘‘ time-bombs ” harmless, be they economic, military or international, or else to prepare as fully as possible for the explosions. The cohesion and unity of society which is so important in time of war depends, like the success of a scientific experiment, on a positively formulated plan based on all available knowledge. Such knowledge must be shared out on a basis of cooperation in the tasks to be accomplished. But cohesion is weakened by creating emotional tensions on the basis of suggested but concealed knowledge regarding national difficulties, handicaps and possible disasters. And since the psychological and sociological principles involved are well established, scientists will not only observe them in their own work and attitudes in time of national crisis, but will ask the governments also to bear them in mind. SCIENTISTS AND SOCIAL DUTY. This brings me again to my theme that if scientific societies and scientists possess knowledge and understanding which would make for the welfare, cohesion, and progress of society, or prevent disintegration of society or the confusion of its individual members, then those scientists are as citizens bound to do their utmost to press their knowledge on both government and people. We should not sit aloof adopting the attitude that if the country does not want our knowledge or help it can leave it. In doing this we become morally responsible for the continuation of unsatisfactory conditions, or for disasters which could have been avoided had our knowledge been used. It may be that some scientists are temperamentally unsuited for the necessary propaganda work which is involved, and that persons who are not themselves research workers but who do appreciate the practical and national significance of science, are better fitted for it. Against this, however, is the fact that the scientific Specialist can speak with authority, and if he possess the necessary patience and persistence, eventually he will be heard. In any case, scientific societies, such as our own, could undertake this essential national work in which they would be guided by their own expert committees or sections. Suppose for example that 10 A. P. ELKIN. immunisation against some epidemic diseases such as diphtheria were regarded as of sufficient importance and effectiveness to justify a campaign to ensure its voluntary universal practice, then such a society aS our own might well set up an, expert committee of medical scientists and chemists to examine the evidence, and if this committee reported against the practice, the fact should be com- municated to the authorities as well as to the public. If, however, the report justified the practice, the Society, in addition to informing the health authorities of its finding, might well support their campaign by arranging for a public symposium, popular lectures, wireless talks, newspaper articles and pamphlets, in all of which the scientific basis and proof as well as the statistical results of the practice would be set forth. Such action on the part of a disinterested and purely scientific body would be of great support to the health authorities’ campaign, and could not be dismissed as a mere fad of the health department. Of course, such scientific body would carefully avoid all political entanglements. I have mentioned immunisation as an example because so many people are still worried about it and, with regard to diphtheria, there has been a campaign, against it. The subject is of national importance, and therefore a scientific body would be doing a national service by endeavouring to get a scientific attitude adopted by the public towards it, and by spreading a knowledge of the facts. As another example, I could refer to the danger of overcrowding of civilians or soldiers in camps without satisfactory precautions against uncleanli- ness, with the consequent risk of typhus or other epidemic diseases, aS was pointed out in one of our popular lectures during the past year.* In this case, if events warranted such action, our Society, probably through a select committee, should back up the efforts of the specialist by putting the scientific facts before the Government and the particular administrative department (military, works or other). At the same time it should make the public conversant with them so that public opinion would be ready for, and indeed weculd ask for, the necessary administrative action. Examples could be taken from other spheres: biology, agriculture, astronomy, physics, and so on. The suggestion of this line of social propagandist action for such a society as our own, is evolutionary, not revolutionary. The object of our Society, as expressed in its Act of Incorporation, is to encourage studies and investigations in science, art, literature and philosophy, to which is added in Rule 1 the significant words, “‘ especially on such subjects as tend to develop the resources of Australia ’’. Moreover, in the course of its history it has adopted the plan of holding popular lectures as a means of disseminating to the man in the street, in understandable form, the results and importance of specialist-research. The suggestion is that we and all scientific bodies do more of this, and also when circumstances demand, press our knowledge and attitude on governments and people alike—if necessary with the persistence of the importunate widow. Certainly we should not adopt the “ take it or leave it ’’ attitude. We are citizens, and our best contribution must be through our specialised disciplines, not merely to be stored in learned journals steadily mounting until our articles have reached the century mark, but also, if the material be appropriate, to be added to the life and thought of “‘Everyman’’. Scientific groups belong to the body politic and are not only concerned with the academic pursuit of science and occasionally with related issues such as the exportation of fossils and the preservation of fauna and flora ; they must also watch over and contribute to the well-being of society as a whole whenever their special knowledge enables them to do so. If the public is being misled by dangerous propaganda and is mistaken on significant 4A. R. Woodhill, ‘‘ Insects and Disease in War-time, with Special Reference to Mosquito Biology ’’, Royal Society of N.S.W. Popular Lecture, August 15, 1940. PRESIDENTIAL ADDRESS. 11 matters and we know the facts, then we must make those facts known. At times, scientists must be propagandists. Needless to say the term propaganda as I use it here contains no suggestion of misrepresentation, but means, as in the dictionary definition, the dissemination of principles and knowledge so that these may bear fruit in the life of man and society. Misrepresentation may be used in propaganda, but not by scientists. On the other hand propaganda of the false can be counteracted most effectively by propaganda of the true. RACE PROPAGANDA—AND THE WORLD SITUATION. Let me now illustrate my theme with a subject from the anthropological sphere, namely “‘ propaganda and the concept of race’’. The idea had grown up—especially a century or more ago—of “ the complete separateness of certain populations ’’, and this was exploited by propagandists who discussed racial questions for national or political ends. But physical anthropologists have known for decades that there is no sharp grouping between the races of mankind, that is if the term race be used in its only valid sense, as a biological concept, without any reference to culture in general, or language in particular. It is interesting to notice that the first investigator to maintain that human, races formed a continuous system with distinguishable parts but no abrupt divisions was a German, J. F. Blumenbach,? whose work has obviously been ignored in propounding official racial theories in modern Germany. All recent research confirms Blumenbach’s contention. Apart from the ideal conceptions we have of the four main divisions of mankind (or major sub-species) into European or Caucasian, Mongol, Negroid and Australoid, the division into biological races, that is the inheritance of group characteristics, is a statistical matter, for so-called races both shade off into and overlap one another. We have fairly clear pictures of such ideal types (or minor sub-species) as Nordic, Alpine and Mediterranean, but we find few pure examples of these types, the result of diversity in prehistoric and early historic times, of migration, of intermarriage, and of the influence of environment on, certain physical features. Thus, if we pass from Scandinavia and Finland south to the Sahara, where shall we draw the various racial divisions, or if we travel from Ireland east to Siberia and Japan, will our task be any easier? The fact is that there is no population in Europe today which can be sharply divided off from neighbouring peoples on the basis of racial distinctions. On our journeys we pass through various nations, or countries as we frequently call them, but as the result of the study of such significant biological features as head-form, body height, hair form and colour, skin and eye colour and blood grouping, we realise that such unity as each nation possesses is not the consequence of its supposed unitary racial origin, but is a cultural factor, built up during the course of history. Even Germany, while possessing a number of blondes in its population, is the outstanding example of a national European group consisting of a number of sections which differ markedly in their physical characters. Likewise, while there is, or was, a French nation, there is no French race. Conversely, some peoples think they are racially quite distinct from their neighbours, when there is no such distinction, but only a marked difference in language and, possibly, in other cultural ° His works on the subject were published in Germany in 1775 and 1795, and translated for and published by the Anthropological Society of London in 1865 under the title of ‘“* The Anthrop- ological Treatises of Johann Friedrich Blumenbach”’. Vide T. K. Penniman, A Hundred Years of Anthropology, pp. 55—6, 373, and G. M. Morant, ‘‘ Racial Theories and International Relations ”’, Journal of the Royal Anthropological Institute, London, Vol. LXIX, p. 153. Vide also F. H. Hankins, An Introduction to the Study of Society, pp. 93-6, for further reference to Blumenbach and a discussion of overlapping of races. Also C. 8. Coon, The Races of Europe, 1939, pp. 251-96, for a similar but more recent discussion. 12 A. P. ELKIN. elements. For example in 1939 the Finnish Government announced that the Finns had neither national nor racial affinity with Russia, and that the Finns are Nordic in character. But “the evidence of physical characters shows unequivocally that Finns and white Russians are closely allied, and it fails entirely to indicate any line of division between them which might be correlated with a national or linguistic frontier’. Again, the Czechs of Bohemia regard themselves as Slavonic and used to dream of a union of all the Slavonic peoples of Europe, but racially they are closely allied to the neighbouring peoples of Germanic speech and “ this racial bond is much more intimate than that between, the populations of western and eastern Germany on the one hand or those between the Czechs and many Slavonic peoples on the other”. The Slavonic characteristics of the Czechs are cultural rather than racial (biological), the result of an historical accident—their conversion to Christianity from the Hast. Had this influence come to them from the West, they would have become Teutonic in culture and speech.’ The point is that race is not related to nationhood or culture either logically or biologically, but only through the happenings of history. We must bear in mind and indeed promulgate the following facts : (1) A nation may consist of more than one race. (2) The same race may constitute part of more than one nation. (3) In every or almost every case some groups of people in neighbouring nations are closely related racially, and that as far as Hurope is concerned, any war between national groups is in some degree or other racially a “ civil ” war. (4) While a racial group possesses distinctive hereditary traits in spite of variations around the particular racial type, racial types are relative and in a state of flux and, in characteristic features, shade off into one another ; therefore to speak of a nation as a pure race, or indeed of a race as being pure, is in almost every case biological and racial nonsense. This applies, of course, to the Nazi doctrine that the Germans are pure Nordics. (5) The so-called “‘ race consciousness ’’ of which we hear at times and which implies that a people possess a feeling of unity and of distinction from other peoples because its members share a common descent, is a pure fiction. There may be a strong national consciousness, based on contiguity, historical continuity and community of economic and political life, but this national group may ultimately be made up of individuals or even small groups sprung from several racial sources. Consciousness of community is an historical accomplishment, not a racial inheritance; and it is this, not race, which is the basis of true nationhood. (6) Another baseless fiction is the doctrine of Nordic supremacy, that is to say that a certain racial group, distinguished by fair hair, blue eyes and tall stature, was by reason of something in, its biological inheritance the creator and organiser of all civilisations, and is the only hope of the future. The foundation of the doctrine appeared in the work of Count Arthur de Gobineau, who in 1853 declared that the fundamental factor in the development and decay of civilisation 6G. M. Morant, ‘“ Racial Theories and International Relations’’, Journal of the Royal Anthropological Institute, Vol. LXIX, p. 161. Also C. 8. Coon, The Races of Hurope, 1939, pp. 359-67, 568 and maps, pp. 176—7, 294-5. 7G. M. Morant, op. cit., p. 161. The War and Democracy, by various authors, 1914, p. 70. C.S. Coon, op. cit., pp. 560-2 and map, pp. 294-5. Professor Coon writes that zoologically the Czechs are descendants of early Slavic immigrants who, like all Slavs, were primarily Nordic. But the Czechs changed in form during the centuries until from the point of view of measurements they became Alpine in head and face, while their colour is as fair as in the case of most Southern Germans. PRESIDENTIAL ADDRESS. ies is racial, and that if the fundamental racial constitution be engulfed among other races to such an extent that it ceases to exert the necessary influence, both the people and civilisation will die out. In 1895 H. 8. Chamberlain maintained that ‘“ the Teutonic stock was the real creator of present-day civilisation and our best hope for the future ’.8 The use made of this false theory by Nazi Germany is well known, and just as well known to students is the fact that the doctrine is politically inspired and not anthropologically based. Germany is not a pure race—even, with all the Jews ejected—and as we have seen, racial groups shade off into one another; moreover, civilisation is built up by the experience and contributions of many races and nations. There are valuable cultural crossings and diffusions, as well as racial crossings and immigrations. But, of course, the Nordic theory or any similar theory of racial superiority, appealing as it does to a people’s vanity, can be used with great effect in unifying a people and arousing enthusiasm for some cause, be it the spread of German, kultur as in the last war, or the spread of Nazism today. As one writer puts it, “‘ in adopting beliefs regarding racial theories, most people are prepared to become followers of a cult; few will show any inclination to become students of a science ’’.® I am drawing your attention to these anthropological facts and principles not merely because of their importance and interest, but because they have not entered into the working mental equipment of the public (voters) or governments in our own, country or the world at large, and because scientists, to wit anthrop- ologists, must bear the blame for this. The ideas which people hold regarding race, nation and culture are usually so nebulous that they can be easily swayed by astute propaganda; moreover, racial preaching is apt to grip peoples’ imagination and stir their enthusiasm in a remarkable and indeed overpowering manner, for it appeals both to man’s interest in his past and to pride in his future. A somewhat inoffensive example is provided by British Israelism. But the same cannot be said of the Aryan racial propaganda of Germany, nor indeed of the ridiculous plea made by Professor Carmelo Midulla for the recognition of an “ Aryan and Mediterranean ’”’ type as the Italian national “ archetype ”’, which incidentally is said to approximate in measurements to the statues of Apollo Belvedere and of Venus (of Cyrene and Venus Anadyomene). This plea could be none other than an attempt to bolster up national pride, political in intent, for scientifically it is absurd both as regards the method of selecting individuals and of striking averages in the measurements, and also in the use of the term Aryan-Mediterranean, which is apparently a blanket term used to cover either two distinct divisions of mankind or else a linguistic and a racial grouping. No doubt it is meant to convey the idea that the Italian Mediterranean people are to be distinguished from other peoples of Mediterranean, stock, such as the Jews, Arabs and Abyssinians, and to be affiliated with that supposed Aryan race which not only originated the basic Aryan tongue but also alone possesses the powers to develop a truly advanced culture. At least this would show that the Italians are fit partners for Hitler.!° Of course, anthropologists knew quite well that these theories were ill- founded and were propounded for political and national aims. F. H. Hankins, for example, examined and exposed them in his Racial Basis of Civilization 8T. K. Penniman, A Hundred Years of Anthropology, pp. 84 and 126. Fora full examination of the theory, vide F. H. Hankins, The Racial Basis of Civilization. 9G. M. Morant, op. cit., p. 158. 10 Strictly speaking too, Aryan is a linguistic term and has no reference to race ; but Hitler and apparently this Italian professor also use for their own purposes the old mistaken idea that race can be determined by language—by linguistic origin; thus an Aryan people is one which speaks and is sprung from Aryan-speaking ancestors. Italy consists mainly of Mediterranean peoples, but the Alpine racial type and to a less extent the Nordic type is found in northern Italy. With regard to Midulla, vide ‘*‘ Aryan and Mediterranean Anthropometry ”’, by C. Suffern, Man, December, 1939, pp. 199-200. 14 A. P. ELKIN. (1926), and more recently A. C. Haddon and Julian Huxley provided a most helpful survey of the racial make-up of Europeans in their book We Huropeans (1935). And students in the few anthropological classes in the British Empire and in the somewhat greater number in America also became acquainted with the facts, but the knowledge was not broadcast and impressed on the general public—on “‘ Everyman”. And what is worse, when the propaganda regarding racial distinctions which was broadcast before the war, especially in Europe, was doing much to embitter international relations, anthropologists did not make any effective protest. They knew the facts, they recognised or could have recognised the hollowness of some continental theories and their political motive, and they should have tried by means of public lectures, pamphlets, newspaper articles and wireless talks to expose the fallacies and broadcast the truth in their own and other tongues, and should have done so tirelessly. It is true that if this campaign had been successful, the Nazi propagandists might have found some alternate theme to serve their purpose, but to make the other side shift its ground through the exposure of inherent fallacies is to cause at least some degree of lack of confidence and loss of equilibrium. In any case, the duty of anthropologists was clear, but it was not performed. The principal reason for this failure was no doubt the doctrine that scientists should not interfere in political and practical affairs, although they might criticise them learnedly within the academic precincts and in esoteric publications.!! Let us hope that when this war is over and boundaries in Europe and North Africa and perhaps elsewhere have to be arranged anthropologists (and historians too) will be summoned, or will persist in being summoned, to the pertinent international committees, and will ensure that there be no confusion cf race with culture or of either with nation, and that all divisions of populations on so-called racial grounds be very carefully examined before being made the basis of continuing or of establishing national boundaries. ‘* HALF-CASTES ”’, BIOLOGY AND PREJUDICE. An example of the confusion of biological inheritance with cultural factors comes from our own country—a confusion arising from ignorance. It refers to the people of mixed European and Aboriginal blood in Australia, often called “ half-castes ’’, irrespective of the proportion of Aboriginal and European ancestry in each case. We frequently hear it said, even in high places, that these folk inherit the vices of both races. But the word vice has reference only to standards of behaviour and is solely of cultural significance. Some Aborigines are vicious according to Aboriginal moral standards, just as some Europeans are vicious according to European standards. There is no evidence, however, to show that half-castes should in some remarkable way inherit vices from their two parents which possibly the latter did not exhibit. Nor indeed is there any evidence to show that moral standards or vice and virtue are biologically inherited. On the one hand moral standards are evolved during a society's history, and on the other hand vice and virtue are accomplishments developed during an individual’s history as the result of training and reaction to his environment—home, society, economic conditions etc. They are cultural phenomena. With regard to half-castes it is sufficient to say that if any of them exhibit the vices of both races it is because they belong culturally to neither. They have not learnt the standards and sanctions of Aboriginal society and, being treated as outcasts by us, they have neither received the same early training aS we, nor any real assurance of an effective place in our 11 The responsibility of anthropologists in this particular has been elaborated by Dr. G. M. Morant in The Races of Central Hruope (1939) as well as in his article ‘‘ Racial Theories and Inter- national Relations ”’, Journal of the Royal Anthropological Institute, Vol. LXTX, 1939, pp. 151-62. PRESIDENTIAL ADDRESS. 15 social and economic order, with the result that in some cases they throw restraint to the winds or become resentful and suspicious. The point is that their so-called vices are culturally determined, and the responsibility is ours even more than theirs. This criticism of half-castes is related to our colour prejudice, which again is a cultural attitude developed and possessed by British folk, but not by some other European peoples. It is not innate nor biologically founded, and incidentally is by no means strong enough to prevent miscegenation between, British men and Aboriginal women. The antipathy is sometimes rationalised on the basis that the half-castes are not well washed, live in dirty conditions and are not educated, and so we prefer not to admit them to our schools, hospitals and churches. These assertions are true in a number of cases, but they can be overcome with patience, water, training and fellowship. Anthropologists, knowing that the objections to half-castes are cultural and not biologically founded, must say so, especially to the general public, and thus clear the ground for an honest tackling of the “ half-caste ’’ problem in this continent. ANTHROPOLOGY AND THE ADMINISTRATION OF NATIVE RACES. My next illustration of the theme that science must make itself effective in the life and thought of people is taken from a related sphere which should be of interest to all of us—the administration of native races—for we in Australia are directly concerned with our Aborigines and the natives of Papua, the Mandated Territories of New Guinea and Nauru, and in a less degree with all the native races of the British Empire. Good administration as distinct from repression and slavery is not based simply on a knowledge of what a native people can do for us or of what we can derive from its country, but (a) on an understanding of that people’s social and religious organization, (b) on the conviction that it possesses a pattern of culture which has been built up in the course of its history and which serves it more or less well in adjusting itself to environment and to the changes which occur in the course of time, and (c) on a study of the facts and problems of cultural and “ racial ’’ contact and of change. Now these three prerequisites of good administration are the special concern of social anthropology. A few administrators and missionaries had realised these facts, even though “through a glass darkly ’’, but it is only the specialised work of trained social anthropologists during the past three or four decades which has enabled us to understand the life of primitive societies; and, incidentally, to evaluate the commonly held clichés, not all inoperative today, such as the savage is magic- ridden, weighed down by superstitions and overwrought by fear; he has no law, and yet is helpless in the power of tradition and consequently is ultra-con- servative ; he cannot adapt himself to our culture, but is a member of a child-race and must be treated as a child; and so on. As a result of research, we no longer regard the so-called savage as a queer individual with a number of strange beliefs and quaint and maybe horrible customs which it is interesting to record, before his old ways have been com- pletely changed, or he and his fellows have ceased to exist upon the earth. This is the view of the collector—the museum-exhibit attitude. Instead, we now have a living and dynamic approach, sometimes called functional. We look at primitive society as a living whole, the present stage in an historical process. This society, just as in the case of a civilised society, consists of its individual members grouped in various ways on the bases of contiguity (locality), kinship, age, sex, economic pursuit, religious cult and one or more social interests. Thus there are families, kinship groups, occupational groups, sex and age groupings and cult groups. Clans, moieties, social ranks, castes and political groups are 16 A. P. ELKIN. found in some primitive and other societies.12. The actual forms and numbers of these groups depend on historical happenings and conditions, such as the environment, the economic situation (food supply aad possibilities of developing arts and crafts), the size of population, contact with other peoples and cultures, and the rise of leaders. But the point is that the various groups of any one society function together, and society’s task is to maintain a state of equilibrium— not necessarily static—a condition which will be reflected in the lives of its individual members, for each one is a member of several if not of all the different types of groups in his society, religious, occupational, sex, age, kinship, clan, family and locality. He has several loyalties, and on the working out of a system of loyalties depends not only his own mental and social well-being but also the well-being of society. Of course, tradition helps in this. Thus life, even in a primitive society (Papuan or other) is a social task which has relation to the history and culture of that society and none other. Society, however, as this reference to culture reminds us, is not only a grouping of human beings in various ways, enabling them to live and reproduce their kind in an orderly way. It is also the means by which an heritage of culture is built up, preserved, modified, added to and handed on from generation to generation. In this process the various groups in a society have their particular.functions and, in turn, are themselves built up and modified by the culture. Culture is society looked at from its time aspect. It is the accepted way of dealing with the problems of the environment and of life in general, and includes the social, economic, scientific, esthetic and religious institutions and the intellectual and emotional attitudes which have been adopted and modified and handed down during the society’s history—a process which is continuous. Moreover, as the history of any particular society is its own history, so its culture, which is an historical process of adaptation, is peculiar to it. The society’s structure, culture and history constitute a dynamic unity. As a result, a modification of the culture must cause some change in the social structure (that is, the groups and their mutual relations), and, conversely, a change in fundamental social forms such as the family, clan, social ranks or local grouping, brings with it a change in culture and the associated modes of behaviour. In either case, such change causes some alteration in the society’s course as set by experience in the past. If the change, whether it originate within or without the society, constitute too great a break with the past, and in the adjustment to the total environment, a social and cultural revolution results, with its conse- quent disintegration. This may be only temporary, or else so fundamental that cohesion is not recovered. In the case of some peoples, too, depopulation follows. Unless structural and cultural changes can be linked on to the past and accepted by individuals as their own decisions, psychological and sociological disasters ensue. Such are some of the principles which are established by a study of society and change—which indeed have been revealed by happenings in both the primitive and civilised worlds during the past hundred years. Therefore, seeing in, the first place that the contact of civilised peoples with peoples of primitive cultures, through settlers, missionaries and administrators, has caused and must cause such revolutions in the lives of the primitive peoples concerned ; and in the second place that social anthropologists are aware of the consequences which must follow, it is surely their bounden duty to do more than academically analyse the situations and record the results of their investigations. They must also endeavour to constrain the governments, administrations and missionary organisations to accept and act on sociologically determined results 12 Vide A. P. Elkin, Society, the Individual and Change, Lecture I, especially pp. 15-30. 13 Tbid., Lecture II, especially pp. 49-53. PRESIDENTIAL ADDRESS. 7 and principles, and at the same time they must proclaim the latter without ceasing to ‘Everyman’, for in the final analysis he is the government, administration and missionary society. Once again, it is a case of social propaganda, and the specialist must be the propagandist. I have found this to be so with regard to the Aboriginal problem in Australia. In this problem, as in all problems of racial and cultural contact, principles of humanitarianism and justice are evoked, but by themselves are frequently—sometimes correctly—attributed to a sentimentality divorced from knowledge. But a campaign based on sociological analysis of the situation, and on, an understanding of the cultures and of the process and effects of change is quite another matter. In a democratic country it must eventually succeed. In this, as in all spheres of human, activity, knowledge and understanding must triumph, even against vested interests or indifference. This, of course, is the fundamental reason why the victory of democracy is so essential in the present war. I therefore suggest that social anthropologists, with the support of those scientific societies which are in a position to evaluate their results, should set themselves the twofold task, first, of disseminating amongst the public generally a knowledge of the established facts and principles regarding native peoples and their cultures and the problem of “ racial ’’ contact, and, in the second place, the task of constraining the governments, administrations and missions which are concerned with the Aborigines and the peoples of New Guinea and Papua, always to base their policies and actions on these facts and principles, for sociological science can, be applied in such spheres just as chemistry and physics are applied in industry. SCIENTIFIC STUDY OF OUR OWN SOCIETY. But, as I have implied, what is true of primitive societies is true also of civilised societies, including our own. Structure, culture and history are interrelated, and change is ever upon us, arising from within or without, or both. The immediate cause of such change may be economic, social, political, religious or ethical in nature. Moreover, a change in one sphere will usually cause changes in, other spheres. Possibly the greatest and most effective as well as the most disturbing change these days is the phenomenon of war. This is not the reaction of an instinct of pugnacity to an appropriate stimulus. It is the result of an act or a series of acts of decision which are made by a number of persons for the purpose of attaining some desired end or maintaining the status quo. But as war is a communal, that is national, effort, the leaders of the nation have to obtain, the co-operation of “‘ Everyman ’’, and this means propaganda, whether in, democratic or totalitarian countries. While the propaganda may seem to be more thorough or even ruthless in the latter countries, the changes which are wrought in democratic countries by war measures, including propaganda, are relatively greater. We tend, and indeed endeavour, to become in practice totalitarian, or at least a planned unit, while at the same time remaining, as far aS possible, politically democratic. This implies an important social change, which, if it lasts long, will modify the very structure of our society, made up as it is in no small measure of semi- or almost completely independent groups (employers, investment companies, labour organisations, religious groups, etc.); and such change will have repercussions in the economic, social and political life. Indeed, the very organisation for war inaugurates or accentuates changes which cannot be arrested—changes in the relation of the individual to society, in the position of women, in the balance of the sexes, and in population figures, while war itself raises important problems in the spheres of ethics and 18 A. P. ELKIN. religion.14 As a consequence of war, the social, economic, political, ethical and religious aspects of a nation’s life and structure receive severe shocks : equilibrium is disturbed, and the course of history is altered. In other words, society, which is continually in a process of change, is hurled by a “ total ’’ war almost headlong into a vortex of change. This is vital to us, and hence we hear already of planning for reconstruction after the war—but let us remember that this cannot be reproduction of the pre-war life. If the transition to peace conditions and the building of a “‘ new world ” are not to be fraught with disaster, we must do more than think in terms of economics or administration. We must see whether there be any laws revealed in social structure, cohesion and change, and if the sociologists tell us that there are, as they will, then ascertain in what way those laws are functioning in our own society and rest not until schemes of reconstruction take full account of them. Once again constructive propaganda is required, and social anthropologists and sociologists must be the propagandists. They must show those in authority that they have a practical and essential contribution to make to the ordering, changing and reconstruction of society, and convince the governments that this contribution should be used. At the same time they must disseminate the sociological outlook to ‘“‘ Everyman, ’’, so that it will become natural for those in authority to seek and use the help of this social science whenever important changes are contemplated. This task will not be easy, for in Australia we have up to the present ignored sociology. There is no chair or lectureship in sociology in any of our universities, though an introduction to it is included in the Anthropology II course at the University of Sydney. But sociology should be provided for in all our universities and secondary schools. Surely it is important to know and understand our own, society and our individual relations to it—even though instruction in some other subject has to be omitted: mathematics for some children, Latin or ancient history for others, and so on! The opinion has recently been expressed by a Cabinet Minister that we should have in this State a university department of rural sociology. I agree, provided that it is associated with a department of sociology in general. May they both be established in the near future ! In this connection it is interesting to notice that while there are only a few university departments of sociology in western Europe, the smaller and ‘* newer ”’ countries in south-eastern Hurope seem more willing to accept sociology and to provide it with the opportunity to justify its existence. ‘“‘ Very intense teaching and research in sociology ”’ existed in the former state of Czechoslovakia, where there were three departments of sociology (Prague, Brno and Bratislava). Rumania exhibits an “ exceptional understanding for sociology ” ; a quite new school of sociological method and thought had been built up in the department of sociology in the Bucharest University, and special attention is paid to rural sociology. Finally, there are six universities and colleges in Yugoslavia in which there are departments of sociology, all recently established.1® If by chance we are overwhelmed by the great development of sociological teaching and research in America, in, schools, colleges and universities, with its various specialisations (urban, rural and Negro), let us look at these small countries, take heart, make a beginning, and go forward. 14 On this section, vide A. P. Elkin, Society, The Individual and Change, Lecture III, especially pp. 70-91. 15 Nicholas Mirkowich, ‘‘ Beginnings of Rural Sociology in Yugoslavia”’, Rural Sociology, Vol. V, No. 3, September, 1940, pp. 351-4. PRESIDENTIAL ADDRESS. 19 SCIENCE, EDUCATION AND EVERYMAN. My theme has been that there are occasions when scientists must be propagandists so as to ensure that their special knowledge is used by the com- munity and its leaders, in peace and war ; and in the refrain after each example I have pointed out that the general public, “‘ Everyman ’’, as much as the leaders must be the object of this campaigning. Now obviously this would not be necessary if during the years at school every boy and girl (“ Everyman ”’ junior) were inspired with the scientific attitude to the problems presented by life, and in simple form with those scientific results which should form the mental stock-in-trade of “‘Everyman’’. Let me enlarge a little: while selected (or self-selected) children will always be encouraged to study one or more scientific subjects (chemistry or other) to the Intermediate or Leaving Certificate standard, all children should be given, some idea of the ground covered by the chief scientific disciplines, of the attitude and methods adopted by scientists and finally some idea of the most significant results of each of these sciences for the life of “‘ Every- man’. For example, from the introduction to astronomy could be drawn an appreciation, of the concept of order in the universe as well as some under- standing of the marvels of the sky, and above all, an inkling, if not a grasp, of the absurdity of astrology; from physiology could be derived not only enlightenment regarding procreation and its wonder, but also such knowledge regarding illness and disease that the phantasy of Christian science and the shallowness of ‘“‘ medical ’”’ quackery will be seen through in advance; from anthropology could be learnt facts about the human races, nations and cultures which will engender an understanding of, and respect for, other peoples, the facts, too, that war is not inevitable in the sense of springing from man’s biological make-up, and that mixed bloods do not inherit vices of both their constituent races; and so on from sociology, psychology, zoology, botany and physics. Of course, the teaching would be graded for primary, intermediate and leaving forms in, schools, but if done in an intelligent way would add much knowledge, interest and balance to the life of ““ Everyman’’. Eventually, too, as a result those in authority in the State and in industry would possess the scientific attitude and would know and be expected to know the value of science. More- over in this way society would be fulfilling its task of handing on to successive generations the results of its experience—not only the experience of trial and error in practical life, but also the experience of the scientist, which is gained through trained observation and the search for natural laws, through experiment and research. But the imparting of the scientific attitude and the dissemination of scientific knowledge should not terminate with the close of school. The churches do not confine their efforts at indoctrination to the Sunday school, nor the Communists to their youth organisations. Education is a life-long process, and if science is worth while, its specialists should from time to time impart to “ Everyman ”’ Senior, in aS widespread and understandable a manner as possible, the significant results of their special research, as well as a better understanding of the fields and methods of their own, branches of science. Finally, as I have tried to show throughout this address, it is their duty to “ speak ’’ out when by impartation of their assured knowledge needed warning or help can be given to both govern- ment and people alike. Of course, this contact with “ Everyman” implies the co-operation of learned societies, universities, newspapers, publishers and _ broadcasting commissions and companies. Learned societies, such as our own, and the universities are doing a little by arranging popular lectures. Publishers are for financial reasons naturally hesitant, and so the provision of special publication ‘funds is required. Newspapers and broadcasting authorities could do much more than they do. “‘ Everyman ”’ is really much more intelligent than many 20 A. P. ELKIN. newspapers and broadcast programmes would lead us to believe. Regular articles and talks on their own, subjects by specialists with some facility for writing and speaking respectively—in, all newspapers and over all broadcasting networks—would do much good, such articles and lectures to cover all scientific fields, including the social disciplines, and to be concerned with methods and approaches, as well as with descriptions of inventions and processes. In these various ways, during school and adult life, we will eventually reach the stage when, we can truthfully speak of a scientific age. Needless to say, I do not imply that the only scientific research which counts is that which can be seen to bear on definite technical and social problems. Ultimately, no doubt, all scientific research does so bear, but in the meantime scientists will do their research in many cases solely to extend the boundaries of knowledge and to understand better the world and man’s relation to it. But even so such knowledge and understanding is for “‘ Everyman ’—it belongs to society, and must be woven into its culture. In the long run all knowledge affects living, for knowledge is life, and the scientist is not a miser, hoarding up his knowledge, but one who shares it willingly, though not ostentatiously. It is the welfare of society and the good of “‘ Everyman ” which are fundamental, and to that welfare and that good scientists constitute one contributing group, and one of no little value. Its talents must not be hidden, but invested in the life of the nation. And who are the investors? Surely none other than scientists themselves. We must remember, however, that science does not provide the only attitude and equipment with which “‘ Everyman ”’ lives or necessarily will live in this world, meeting its problems and experiencing success and failure, joy and sorrow. Science gives knowledge and knowledge power, but our knowledge is still very far from complete and therefore our power is limited. And out of his ignorance and weakness ‘““ Everyman ”’ seeks other sources of enlightenment and strength— concerning the validity of which there will be differences of opinion for a long time, perhaps always. Moreover, as Sir James Frazer reminded us at the end of his twelve-volume search for the significance of the “‘ Golden Bough ’’, “‘ the history of thought should warn, us against concluding that because the scientific theory of the world is the best that has yet been formulated, it is necessarily complete and final . . . it may hereafter be superseded by some more perfect hypothesis, perhaps some totally different way of looking at the phenomena, of which we in this generation can form no idea.’’ In the meantime, let scientists be one group which will say tc “ Everyman ” ‘*T will go with thee And be thy guide; In thy most need To go by thy side.” THE EFFECT OF THE SYNTHETIC G&STROGENS, STILBAESTROL AND HEX@STROL ON THE POUCH AND SCROTUM OF TRICHOSURUS VULPECULA. By A. BOLLIGER, Ph.D., and A. J. CANNY, M.B., BS. (With Plate I.) (Manuscript received, April 17, 1941. Read, May 7, 1941.) In previous communications": *) it has been shown that the pouch and the scrotum of the common Australian phalanger or possum (Trichosurus vulpecula) show marked reactions towards the administration of the esters of naturally occurring oestrogens. In the present communication it will be shown the synthetic cestrogens such as stilbcestrol (4: 4’ dihydroxy-a, 6-diethyl stilbene) and hexcestrol (4: 4’ dihydroxy-a, 6-diethyl dibenzyl), which have no direct chemical relationship to the naturally occurring cestrogens, have a similar action. (A) THE ACTION OF STILBGSTROL AND HEXQGSTROL ON THE POUCH. The well developed pouch of Trichosurus vulpecula has recently been described.“ Furthermore, it has been demonstrated that the administration of estradiol benzoate and cestradiol dipropionate as well as cestrone produce hypertrophy of the muscle situated in the lips of the pouch and secretion of pigment within the pouch. With larger doses a marked contraction of the pouch was produced. Experimental. Two fully grown female phalangers were injected with an oily solution of Stilbcestrol, three with stilbcestrol dipropionate, and two with hexeestrol. Before injections were begun these animals had pouches of varying sizes, a factor which depended upon whether the animal was in cstrus or had had a young recently. Generally speaking, they all responded to the injections with the different artificial cestrogens in a similar manner. The lips of the pouch became markedly thickened, and the cavity of the pouch decreased in size. The three animals which received the dipropionate of stilbcestrol succumbed with signs and symptoms indicative of renal failure within a fortnight of the commencement of the experiment. The remaining four survived for an indefinite period. Although these animals lost weight during the period of immediate action of the drug, they subsequently increased in size and weight till they were both larger and heavier than at the beginning of the experiment. Three of these experiments will be given in detail. Expervment S1. The fully grown phalanger weighing 1-9 kg. which was used in this experi- ment had had a young one approximately a year ago. At the commencement of the experiment (8.8.40) its pouch appeared to be in a state of ancestrus. It was about 1 cm. in depth and prac- tically dry. One day after the injection of 0-9 mg. of stilbcestrol intramuscularly, the lower margin of the pouch was found to be thickened. The right nipple, to which the young had previously been attached, and its mammary gland, appeared to be more prominent than before. B—May 7, 1941. 22 BOLLIGER AND CANNY. There was also a slight suggestion of moisture in the previously dry pouch. The next day (10.8.40) the depth of the pouch was only about 0-5 cm. The lips were puckered and definitely thickened, particularly caudad. For the next three days similar conditions prevailed. The depth of the pouch became almost negligible and the lips remained thickened and firm. The right mammary gland was now a plaque-like structure of about 1 cm. in diameter and the nipple was definitely larger and firmer when compared with the conditions existing before the experiment began. There was only a slight increase in pigment within the pouch. A week after the injection (15.8.40). the depth of the pouch had increased again to 1-0 em. and coloured threads of hair provided evidence of pigment secretion on the right nipple. The lips were still thicker than at the commencement of the experiment. Some days later (20.8.40) another injection of 0:9 mg. of stilbcestrol was given. The response of the pouch seemed to be more marked than after the first injection, and two days after this administration of stilbcestrol the lips were found to be very thick and definite small droplets of fresh pigment were found here and there in the interior of the pouch. The right nipple and mammary gland were very firm. For about ten days the depth of the pouch was decreased as it had been after the first injection, then it increased to about 2-0 cm., but the muscles situated in the lips of the pouch remained prominent. Five weeks after the first injection an intramuscular dose of 1-0 mg. of stilbcestrol dipropionate was given. The effect was essentially the same as that following the administration of free stilbcestrol but seemed to be rather more intense and of slightly longer duration. After its contraction the pouch increased again and about seven weeks after this last injection this organ had a depth of 4-0 cm. This large pouch was found to persist for another three months. The animal itself, after an initial loss of weight of 0-2 kg. during the period of injections, weighed 2-4 kg. at the termination of the experiment. The phalanger, therefore, showed a gain of weight amounting to 0-5 kg. compared with its initial weight. Experiment S3. The animal used in this experiment was a mature female which about one month previously had lost a pouch young of some 12 cm. in length. Involution of the pouch was incomplete when the experiment began. Its depth was 4-5 cm. and its maximum width 8:0 cm. Some dried pigment was present on the slightly moistened surface of the pouch. An intramuscular injection of 1-5 mg. of stilboestrol was given (4.9.40). Four and a half hours after the injection the lips of the pouch were taut and the interior was very wet. On the following day the lips were still tense and appeared to be thickened. The depth of the pouch had decreased to 3-5. Five days after the beginning of the experiment (9.9.40) the thickened lips had assumed a cord-like form. At this stage the depth of the pouch was about 3-0 cm. and its maximum width 5:0 ecm. On this day a second dose of 1-5 mg. of stilbcestrol was injected. Within the next 24 hours (10.9.40) the pouch became very moist and more pigmented and its depth decreased to 2:5 cm. Two days later (12.9.40) the lips of the pouch were puckered and the depth was only 1-5 cm. On the 13.9.40 it had become about 0-5 cm. deeper. The depth continued to increase during the next few days till it was again 4:5 cm. Another injection of 1-5 mg. stilbcestrol was then given (16.9.40). The subsequent changes in the pouch were essentially the same as those fcllowing the earlier injections and a minimum depth of 2-5 cm. was reached three days after this last injection. The pouch then enlarged again and reached a depth of 4-5 cm. two months after the last injection. This large pouch persisted for another two months while the animal was under observation. At the beginning of the experiment, the animal weighed approximately 2:0 kg. Shortly after the injections had been concluded the animal weighed 1-7 kg. After this it slowly increased in weight and three months after the last injection the animal weighed 2-6 kg. Experiment S5. This experiment was executed for the purpose of ascertaining if the opening of the pouch moved its position while the pouch itself was undergoing contraction. For this purpose the hairs covering the lower abdomen of a mature female (S85) were removed. Then two straight lines were drawn across the abdomen with silver nitrate at right angles to the long axis of the pouch opening and touching its upper and lower ends. After the lines became visible they were photographed and the animal then was injected with 2 mgm. of stilbcestrol dipropionate (3.10.40). The pouch, which measured only 1-0 cm. in depth before the commencement of the Se THE EFFECT OF THE SYNTHETIC GQ&STROGENS. 23 injection, contracted considerably and was found to measure only 0-3 cm. in depth four days after the administration of the stilbcestrol. The lines drawn with silver nitrate which were originally straight had now become slightly bent in such a fashion that the apex of the curve lay on the mid-line and was pointing cephalad. This seemed to indicate that the lips of the pouch had been pulled cephalad. (B) THE ACTION OF STILBGSTROL AND HEXGSTROL ON THE SCROTUM. In a previous communication’) it has been reported that in immature male phalangers injected with “ cstroform”’ (B.D.H.) brand of cstradiol benzoate, the testes and epididymes leave the prepenile scrotum and become situated under the skin near the inguinal area. This process was called testicular ascent. In older but still sexually immature animals this reaction was slower and less complete, and only after the administration of large and ultimately lethal doses of cestrogens could a complete unilateral ascent be obtained. In sexually mature animals the testes remained confined to the scrotum even after the administration of very large doses of cestrodiol benzoate. However, in one case it was observed that the left testicle, although still completely confined to the scrotal sac, became tightly wedged in the very short scrotal neck. In the present communication it will be shown that the synthetic cestrogens stilbcestrol and hexcestrol exert a similar action. Observations additional to those already published in connection with the naturally occurring hormones will also be related. Experimental. Two sexually mature males and one sexually immature male were injected with stilbcestrol. Four sexually mature specimens were injected with stilbcestrol dipropionate and one with hexeestrol. In all these experiments there was noted a Shortening of the scrotal neck. In experiments of sufficient duration and after the administration of a sufficiently large dosage a decrease in size of the testicles as well as the cessation of spermatorrhcea’) was observed. In the case of a fully grown but sexually immature male (851) complete bilateral testicular ascent was obtained after injection of stilbcestrol. Subsequently the scrotum reformed, the testicles descended, and spermatozoa appeared in the urine. This particular experiment and another will be given in full detail. Experiment S51. This experiment was conducted over a period of six months. Before the beginning of the injections the bodyweight of the animal was 2:0 kg. and on the examination of the urine no spermatozoa were observed. Only one urine examination was performed before injections were begun. The testicles appeared to be of about normal size but the neck of the ' scrotum measured only about 0-5 cm. when extended, giving the scrotum the appearance of a sessile structure. Over a period of three weeks the animal was injected with a total of 4-5 mg. of stilbcestrol averaging about 1:5 mg. per week. After the injections were completed the weight of the animal had decreased to 1-6 kg. It was drinking large amounts of water and it was swollen around the eyes as if edematous. About three weeks after the cessation of the injection the health of the animal had improved considerably. Its testicles, however, were only about 3/5 of their original size, but the scrotal neck was still very short and practically absent. One month after the last injection it appeared as if the right testicle was beginning to leave the scrotum, and a week later the right testis had completely ascended and became lodged under the abdomina! skin, while the left testicle was still in the scrotum. In another week the left testicle had also left the scrotum and was situated under the abdominal skin. At this stage the testes and epididymes appeared to be elongated as compared with their original form, which was almost spherical in appearance. The empty scrotal sac had completely collapsed, forming an area of wrinkled skin flush with the abdominal wall (Fig. 1). Demarcating the scrotal area semi-lunar folds faintly suggesting a rudimentary pouch were sometimes observed. At this stage the 24 BOLLIGER AND CANNY. animal weighed 1-9 kg. and appeared to be in reasonably good health. The urine contained no spermatozoa and was also free from casts, which had been noted in previous weeks. This state of complete testicular ascent persisted for one month. Then the left testicle began to bulge out again into the scrotal skin and a fortnight later the left testis had gone back completely into the scrotum (23.12.40). By this time the right testis began to show signs of imminent descent, which was completed within another week. At this juncture the scrotum formed a sessile structure possessing a maximum diameter of about 4-3 cm. The width of each testis, which was with its epididymis again assuming an almost spherical shape, was about 1-7 em. The skin of the reformed scrotum was thin and soft like that of a newborn baby. This status, which was very similar to the one existing before the injections were begun, persisted up to the end of the sixth month of this experiment. Up till then no spermatorrhea was observed at any time, although the animal must have reached the age of sexual maturity several months previously. On standing the urine took on a dark brown colour as is generally observed to a varying degree in this species. On the hairless skin around the scrotum the secretion of a brown pigment similar to that seen in the pouch of the female was noted. This secretion oceurred directly in front of, and particularly behind, the scrotum over a rounded area of about 4 em. diameter. In the seventh month of the experiment the appearance of spermatozoa in the urine was noted. At first they did not seem to be numerous and frequently they were deformed, but a few days later they became numerous and with a few exceptions appeared to be normal. On several occasions a few of the spermatozoa were found to be motile. At this stage the weight of the animal was 2-4 kg. Kaperiment H50. This animal of 2-3 kg. of bodyweight received injections of 2 mg. cf hexcestrol twice a week over a period of four weeks. Spermatorrhcea was present before the injections were begun and persisted during the first two weeks. After this no further spermatozoa were observed in the urine. Before the experiment was begun the scrotal neck measured 5 cm. in length, whilst the maximum diameter of the scrotum was 4:0 cm. Four days after the first injection (8.12.40) the scrotal neck had decreased in length by about 1-0 cm. and after six days this organ had diminished to half its original length. Four weeks after the first injection the scrotal neck had almost completely disappeared and the scrotum became a sessile structure. The testes had considerably diminished in size and consequently the maximum width of the scrotal sac had been reduced to 2:5. cm. After the termination of the injections the maximum diameter of the scrotal sac slightly increased again to 3-0 cm. The scrotal sac appeared to be thickened and had a felt-like texture for a period of about two weeks after the injections had been terminated. During the same period the animal lost weight and its bodyweight diminished to 1-7 kg. The animal remained in this poor condition for about a month, the only change being a lengthening of the scrotal neck to about 2-5 cm. Then it began to increase in weight and three and a half months after the beginning of the experiment the phalanger had reached again its original weight (2-3 kg.), the scrotal neck now measured 4-0 cm. in length, and the maximum diameter of the scrotal sac was also 4-0 cm. (Fig. 3). Spermatozoa reappeared in the urine although in comparatively small numbers. Within another fortnight they became as numerous as they were before the experiment was started. DISCUSSION. These experiments indicate that the synthetic cstrogens (stilbcstrol and hexcestrol) act very much like the esters of the naturally occurring cestrogen cestradiol as far as the pouch and the scrotum of Trichosurus vulpecula are concerned. Medium and large doses bring on a contraction of the pouch, which is accompanied by hypertrophy and contraction of the pouch muscle. In the male the neck of the scrotum becomes shortened, and in young animals which may be fully grown, though not yet sexually mature, the testes and epididymes may actually leave the scrotum and become situated under the skin near the abdominal ring, while the scrotal sac atrophies. ~ THE EFFECT OF THE SYNTHETIC Q&STROGENS. 25 The present experiments with synthetic cestrogens bring out certain points which enlarge our concept of the action of cestrogens on the phalanger. For example, the marked shortening of the long scrotal neck, which is due to a shortening of cremaster muscle in sexually mature males, though observed, had not been emphasised before. This reaction is undoubtedly similar to that observed in younger animals where actual testicular ascent occurred but where primarily only a very short scrotal neck was present. In the older specimens with a scrotal neck of 4 or more centimetres in length considerable contraction (approx. 4 cm.) has to occur before the testes are close to the abdominal skin as observed in our experiments. On the other hand, in the case of the sessile scrotum of the younger animal, a similar or even a smaller contraction would pull the testicles out of the scrotum and bring them under the skin in front of the abdominal ring. Similar action should be expected in the case of the compressor mamma, which is the female homologue of the cremaster in the male. This may well be the case, because, when the pouch diminishes in size under the action of the cestrogens, there is also a slight but definite movement of the mammary glands cephalad. For example, in a large pouch the mammary glands are situated practically over the pelvic girdle. In the case of a marked contraction they may be situated near the anterior end of the marsupial bone. In view of this observation it seems most probable that the cremaster in females (compressor mamme) may undergo a process of shortening as in males and may assist in the contraction of the pouch, which apparently is brought on by all the muscles connected with this organ. Post mortem examination of the cremaster in males and females treated with cestrogens suggests that this muscle has shortened and thickened. By tracing the distortion of lines drawn on the abdominal wall it has been shown that the pouch opening moves cephalad when the pouch muscles contract. Such a displacement of the opening in relation to the floor of the pouch would increase the depth of the organ. The observed decrease in the depth of the pouch cannot to any extent be accounted for by changes in the relative positions of the opening and the floor except in so far as the floor moves cephalad to a greater degree than does the opening. In addition to this conception of cestrogenie action on the cremaster of males and females several other points became more clearly defined in the course of this present study. Previously testicular ascent had been produced by persistent administration of cestrogens, and with the exception of a very young male that had small but numerous injections all the animals died as a result of the experi- ments. The fate of the ascended testes following cessation of the treatment was, therefore, not observed. In the present investigation it was noted that some time after the administration of the drugs was suspended the testicles returned to the scrotum. These observations are another example of the antagonism between cstrogenic substances and the male sex hormone, testo- Sterone. The former cause shortening of the scrotal neck with contraction of the cremaster muscle, while testosterone produces an elongation of the scrotum associated with lengthening of the cremaster.‘® All the animals treated lost weight while the injections were given and for some time afterwards. This, in part, may have been due to the renal insufficiency produced in these animals and not due to the growth-hindering action of cestrogens. However, those animals which survived for one month after the injections had ceased not only made up the weight lost previously, but they all became heavier than they were before the injections were begun. This group of animals was definitely heavier than a control group of similar phalangers which was kept in the laboratory on the same diet for a similar time. It is realised 26 BOLLIGER AND CANNY. that the group of animals under discussion is rather a small one ; notwithstanding this fact, these animals treated with stilbcestrol and hexcestrol did not exhibit any growth-inhibiting reaction, but on the contrary their growth has, if anything, been stimulated by these hormones. The increase of pigment in the pouch was less pronounced than in experiments with natural cestrogens. In spite of frequent association with males none of the female phalangers which had been injected with artificial cestrogens has subsequently become pregnant. Restoration of spermatogenesis in the males was shown by the reappearance of spermatozoa in the urine. SUMMARY. In the female of Trichosurus vulpecula stilbcestrol and hexcestrol produced hypertrophy of the pouch muscle and contraction of the pouch. In the male, cessation of spermatorrhca, shortening of the neck of the scrotum, and decrease in size of the testicles are the most obvious reactions, but all of them are reversible. In the younger animals testicular ascent occurs, and in one experiment on an apparently fully grown, though sexually immature male, complete testicular ascent was obtained. Some time after the injections. were terminated the testicles descended again into the scrotum and became of normal size. This was accompanied by restoration of spermatogenesis. These findings, which are similar to those observed after the administration of esters of oestradiol, have been discussed, and the shortening of the cremaster of males and females has been recognised as a manifestation of cestrogenic activity. ! ACKNOWLEDGMENT. The authors wish to thank Mr. G. K. Hughes for preparing the hexcestrol used in this investigation. REFERENCES. {) Bolliger, A., and Carrodus, A.: THis JouRNAL, 1940, 73, 218. 2) Bolliger, A., and Carrodus, A.: Austral. New Zealand Journ. Surg., 1939, 9, 155. ‘3) Bolliger, A., and Canny, A. J.: Med. Journ. Austral., 1941, 697. (4) Bolliger, A., and Carrodus, A.: Med. Journ. Austral., 1938, 1118. (5) Bolliger, A., and Carrodus, A.: Med. Journ. Austral., 1940, 368. DESCRIPTION OF PLATE [. Fig. 1.—Experiment $51. Complete testicular ascent three months after beginning injections with stilbcestrol. Note the collapsed scrotal sac and the elevations on the abdominal skin lateral to it indicating the new positions of the testicles. Fig. 2.—Experiment 851. Redescended testes five and a half months after beginning the injections with stilbcestrol. Note the thinness of the scrotal sac. Fig. 3.—Experiment H50. Three months after cessation of hexcestrol injections the scrotal neck has been restored to its previous length. At this stage the appearance of the scrotum is the same as before the experiment commenced. The scrotum had to be held in this extended position to prevent voluntary retraction. The Gordon Craig Research Laboratory, Department of Surgery, and the Department of Pathology, The University of Sydney. Si é Journal Royal Society of N.S.W., Vol. LXXV, 1941, Plate I o ath ‘ n . wes MAGNETIC STUDIES OF COORDINATION COMPOUNDS. PART V. BINUCLEAR COPPER DERIVATIVES OF DIPHENYL METHYL ARSINE. By D. P. MELLOR, M.Sc., and D. P. CRAIG, B.Sc. (Manuscript received, April 21, 1941. Read, May 7, 1941.) In order to explain the isomerism of two copper derivatives of diphenyl methyl arsine, first described by Burrows and Sanford, the following structures have been proposed.) oe II _AsMePh heleise be cane 2 cn OSS Bite RE a 2 Phe Vat Wh PhoMeAs*” “~cl-—~ “~AsMePh2 PhoMeAs—~” “ cl “ AsMePho The Tete The isomerism depends essentially upon the difference in stereochemical properties of cuprous (Cu!) and cupric (Cull) copper. Four covalent bonds to Cul are always tetrahedrally arranged as in CuCl. Quadricovalent Cul, on the other hand, is characterised by square coordination, as in CuCl,2ZH,O. There is no reason to believe that cupric copper forms other than predominantly covalent bonds in (I) and (II), since the extent of the covalent character of the bonds is determined largely by the electronegativity of the atoms attached to the metal. As arsenic is less electronegative than oxygen, the conditions for forming covalent bonds with Cu in (I) and (II) are just as favourable as in CuCl,2H,O. Up to the present, the main evidence for the existence of copper in the two valency states in the above compounds has rested upon chemical analysis: the composition of each form corresponds to the empirical formula Cu,Cl,(Ph,MeAs);. On account of its significance in regard to the constitution of these compounds it was thought worth while to check the existence of the two valency states by means of magnetic measurements. A satisfactory check of this kind will not, of course, prove the correctness of the proposed structures in the way that a complete X-ray crystal analysis would. Because, however, it is very unlikely that complete analyses of such complicated structures will be carried out for some time to come, the most promising line of attack on the constitution of these compounds lies in the accumulation of as much indirect evidence as possible. The magnetic properties of copper compounds which have been extensively studied by Sugden may be summarised as follows: Cuprous compounds are diamagnetic, a fact which is taken to mean that the cuprous atom contains no unpaired electrons. Cupric compounds on the other hand are always para- magnetic, with moments ranging between 1-7 and 1-9 Bohr magnetons, that is, the cupric atom contains one unpaired electron. Thus if formule I and IT are correct, each molecule should contain one unpaired electron. EXPERIMENTAL. The main objects of these additional notes on the preparation of the compounds are (1) to draw attention to certain significant colour changes which occur in the course of the preparations, 28 MELLOR AND CRAIG. and (2) to specify more definitely the conditions for obtaining the blue form free from the brown. To make the brown form, diphenyl methyl arsine (1 mol.) was slowly added to an alcoholic solution of cupric chloride (1 mol.). The dark brown colour of the alcoholic cupric chloride solution slowly disappeared owing to the almost complete reduction of the cupricion. On allowing the solution to stand about 12 hours the brown colour reappeared, owing to aerial oxidation of some, at least, of the cuprous copper. To make the blue form, cupric chloride dihydrate (1 mol. 12:2 gm.) was dissolved in 50 ml. of boiling alcohol and diphenyl] methy] arsine (1 mol. 17-5 gm.) was then added drop by drop over ten minutes. The resulting pale brown solution was kept between 50° and 60° for 45 minutes. Sufficient aqueous alcohol (2 parts alcohol : 5 of water) was then added to bring the total volume of the solution up to 800 ml. This volume of aqueous alcohol was found to be sufficient to hold up the white cuprous compound (CuPh,MeAsCl). At this stage the solution was water white. If air were excluded from it no colour change occurred, but on allowing the solution to come freely into contact with the air it slowly developed a blue colour closely resembling that of cupric sulphate, and, after about 24 hours, crystals of the blue form began to separate. Once again the marked colour change indicates aerial oxidation of part, at least, of the cuprous copper. Chemical analysis and magnetic measurements show that only part of the cuprous copper is oxidised. As already pointed out,‘?) both forms can be recrystallised from nitrobenzene. The appear- ance of the blue form when recrystallised from nitrobenzene is somewhat altered. Instead of being a sky blue it takes on a more greenish hue, presumably because it separates in smaller crystals. Examination of the pleochroism of the two sets of crystals under a polarising microscope and chemical analysis show that they are the same substance. Since the compounds were previously analysed for Cu, Cl and As only, it was decided to check and extend the analyses to all constituents. The following results were obtained : Cu Cl As . H = a OM Blue form* (from aqueous alcohol) .. bie ae (ors oh : | Bier fomns (from nitrobenzene) fe os 13-8 10-5 22-0 44-7 | 4-0 ibis Goa a ae he ae fey |) Load 10-8 22-1 i | — Ene one 3 ue =v We lene 10-6 | 22-3 || 44-9 | ioere Brown ferent C0 pe ee geo |? too renee ae There is no doubt that the two forms have the same composition. This evidence, in conjunction with molecular weight determinations, makes it clear that the two compounds are isomeric. The low results for carbon are very puzzling and as yet no explanation for them can be suggested. One possibility that suggested itself, but which was finally excluded, was that an arsine oxide might have been formed and coordinated with copper. Residues left after the separation of crystals of both the blue and brown forms invariably yielded, on long standing, flaky white crystals of (C,H;),CH,AsO. This substance, if present in the copper complexes, could account for low carbon. There is, however, no evidence that it is present. On passing dry ammonia over the blue and brown = - Microanalyses carried out by Dr. G. Burger of the EY OrENy of Adelaide. + Analysis by Burrows and Sanford. : Calculated for Cu,Cl,(Ph,MeAs),: Cu=13-1%, Cl=10-9%, As=23:3%, .H=4-0%, C=48-8%. t In order to test whether the blue form is a hydrate of the brown, weighed amounts of the blue form both in the coarsely crystalline and very finely powdered form were exposed over P,O; in vacuo for two weeks. At the end of this time, although the finely powdered sample had become brown, no change in weight could be detected. ~ MAGNETIC STUDIES OF COORDINATION COMPOUNDS. 29 copper complexes it was slowly absorbed with the simultaneous expulsion of the arsine, which on account of its low volatility remained with the copper ammonia complex formed. By treating the residue (from the ammonia treatment) with methyl iodide and then extracting with ether, the arsine could be recovered as the methiodide.* Magnetic Measurements. Although a fairly large tube was employed in these measurements, the change in weight ot the substance due to the magnetic field was rather small on account of the large diamagnetic contribution of the molecule. Because of this the accuracy of the measurements is not high. As a check on the measurements, copper phthalocyanine, a substance which also has a high molecular weight and hence a large diamagnetic contribution, was measured. Its moment was found to be 1-72 Bohr magnetons, a value which agrees very well with that obtained by Klemm ')(1-73). As amatter cf interest, measurements were also made on the complex copper cyanide Cu,(CN,)(NH3;)3,") the molecule of which should contain one unpaired electron. The experimental results are summarised in Table 1. TABLE l. : aa et Tee | Molar Susceptibility. | Magnetic Moment Substance. sie wiles | u (Bohr Magnetons). | i 1. Copper phthalocyanine we Oe ay 890 de2 2. Cu,Cl,(Ph,MeAs), (blue). .. ui on 830 | 1-79-(1-5) 3. Cu,Cl,(Ph,MeAs), (brown) .. .. we 812 | 1-78 4. Cu,(CN),(NH;), vs ae ie ae 1195 | 1-78 Some specimens of the blue form gave low results for the magnetic moment (uw=1-5) but no satisfactory explanation could be found for these figures. The higher value quoted in the table refers to a specimen recrystallised from nitrobenzene. Magnetic moments were calculated on the assumption that the compounds followed Curie’s Law. The following calculated diamagnetic corrections (x 10°) were used: 1.-338, 2.-515, 3.-515, 4.-125. DISCUSSION. It can be seen that the results of the magnetic measurements are consistent with the formulations IJ and II for the two isomers, but further work will be needed before these constitutions can be considered as established. So far, all attempts to elucidate the structures by experiments on the fission of the binuclear complexes with various reagents have failed. The transformation of one isomeric form to the other, which takes place fairly readily, can be pictured as occurring in a very simple way—namely, by the transfer of an electron from the Cu! to Cut. This transfer would be accompanied by such changes in bond orientation about the copper atoms as would be determined by their new valency states. It is interesting to note that Mann and Purdie‘*) have recently described a compound very similar to (I) and (II). The compound, dibromobistripropy] arsine-u-dibromopalladium mercury (III) is similar in the sense that it contains two metal atoms about which four covalent bonds are directed to the corners of a square and a tetrahedron respectively. The similarity extends to the fact that (IIT), like (I) and (II), undergoes dissociation in solution, but an important * Unpublished experiments with B. S. Morris. 30 MELLOR AND CRAIG. difference arises in regard to the possibilities of isomerism. IJIsomerism of the type observed with the copper compounds cannot occur with (III). This is related to the fact that in the former the two metal atoms are uni- and bivalent respectively, whereas in the latter both metal atoms are bivalent. PraAs Br AsPrs Ore ar 1 Hg Tae Br—_ pp “Br lift. SUMMARY. Magnetic measurements show that the molecule of each form of Cu,Cl,(Ph,MeAs), contains one unpaired electron. This is consistent with the structures previously proposed for these isomers. REFERENCES. (4) G. J. Burrows aud E. P. Sanford: Turis JourAt, 1935, 79, 182. (2) —D. P. Mellor, G. J. Burrows and B. 8. Morris: Nature, 1938, 141, 414. (3) W. Klemm and L. Klemm: Journ. ftir prakt. Chem. N.F., 1935, 145, 82. (4) Treadwell and Girsewald: Zeit. fiir anorg. Chem., 1904, 39, 84. (5) KF, D. Mann and D. Purdie: Journ. Chem. Soc., 1940, 1230. Chemistry Department, University of Sydney. PROGRESSIVE RATES OF TAX IN AUSTRALIA. By H. 8S. CARSLAW, Sc.D., LL.D. (With 15 text-figures.) (Manuscript received, March 25, 1941. Read, May 7, 1941, INTRODUCTORY. Heavy expenditure on war purposes has made the Federal Government obtain from income tax a much larger revenue. As the State taxes on income are far from uniform, and the Federal tax must be the same throughout Australia, the Federal authorities are seriously hampered at all points of the seale, and not least in their dealings with high incomes. It seems clear that the present position with regard to taxation of incomes cannot continue. Both Federal and State Income Tax Schedules are based upon a progressive rate of tax whose principle is little understood. It may be helpful in present circumstances to give a simple and critical exposition of the system and of its use by Federal and State authorities. Only elementary mathematics is employed, but with the aid of mathematics a little more advanced the matter could be put more concisely and naturally. PROGRESSIVE RATES IN FEDERAL TAXES. 1. The simplest form of tax is that in which the rate is constant; e.g. 6 pence in the £. Next comes a graduated tax of which the following may be taken aS an example: On so much of the Income as | The Rate of Tax | per £ shall be | Sa dt Does not exceed £500 .. Re! 0 6 Exceeds £500 but does not Becood: £1, 000 0 8 Exceeds £1,000 but does not exceed £1,500 |: 0 10 Exceeds £1,500 but does not exceed bie | iG Exceeds £2,000 .. ne : Lie? Let the amount of the tax on an income of £# be T pence. Then 7 =6x7, when 0<%#%<500. T =6 x 500 +8(2#—500), when 500 Common difference 2a’. and the x,th £ pays [a’(2x,—1)-+b’] pence. J] _pax +l y Mig. 3.” There is a flat rate 2a’7,-++b’ on the excess over £x7,. It will be seen that the amount of the tax on an income of £z is given by the area bounded by the line HP,P,P,, the ordinate at x, and the axes. When 0 7,600 = the axes of x and y, and the. < ordinate at any point 2, a represents the amount of the E | tax on an income of £7; % and the tax on the «th £, & when « does not exceed ‘20 “A 7,600, is given by _ the < (ow) pc Income in £. 4 Absentees are not allowed an exemption. PROGRESSIVE RATES OF TAX IN AUSTRALIA. 37 Unfortunately, in dealing with property income, Knibbs introduced com- plexities of a mathematical kind.® For the first £546 of taxable income, the formula for R was of a type similar to that for earned income; the amounts paid by each successive £ formed an arithmetical progression. From £546 to £2,000 each successive £ paid just a little more than the preceding £, but the progression was not arithmetical. Here his “curve of the second degree ”’ entered. From £2,000 to £6,500 each successive £ paid just a little more than the preceding. Here his “curve of the third degree’ came in. Every £ of the excess over £6,500 paid 60 pence, this being the amount paid by the 6,500th £. There seems no doubt that Knibbs could have got all he needed by breaking up the interval into three parts, in each of which a different arithmetical pro- eression was used, as described in §4. A ready reckoner was issued by the taxation authorities showing the amount of the tax on any income. Without its help the taxpayer would have been quite ignorant of what he had to pay. When income was derived partly from personal exertion and partly from property, the rate on the earned income was that for an earned income of the whole amount, and that on the property income also that for a property income of the whole amount. ‘This principle is to be understood as applying below to both State and Federal incomes of this kind unless otherwise remarked. 8. These rates of tax remained the basic rates for Federal income tax from 1915-16 till 1930-31. They were altered from time to time by certain percentages, sometimes over the whole income range, sometimes only over parts of the range. For some years there was a Special Property Tax at a flat rate. In this way the gradual progressions of the original formule were interfered with; and for this as well as other reasons a new scale of rates was devised for the year 1931-32. The person responsible on that occasion was Professor Giblin. Knibbs’s curves were dropped. The Integral Calculus had no longer to be used in determining the amount of the tax. The linear rate R=ax-+b remained the characteristic feature of the formule for both kinds of income. The new scales can be stated as follows: Harned Income. (i) If the taxable income does not exceed £6,900, R=3 + ae (ii) If the taxable income exceeds £6,900, on the first £6,900, R=3 4A =46-125, and on the excess over £6,900 the rate of tax per £ is 90d. Property Income. (i) If the taxable income does not exceed £500, R=3 +in5: (ii) If the taxable income exceeds £500 but does not exceed £1,500, 14% ec “T 000° (iii) If the taxable income exceeds £1,500 but does not exceed £3,700, 23% 7 pel ieee a 4a 13 000" (iv) If the taxable income exceeds £3,700, on the first £3,700, 23 x 3,700 Sa/) I a aia AT Nhe R=43+ 2,000 47 +3, and on the excess over £3,700 the rate of tax per £ is 90d. _° For these, reference can be made to a paper by Carslaw in The Economic Record, Vol. 7 (1931), entitled ‘“‘ The Federal Income Tax Acts, 1915-1931’. C—May 7, 1941. 38 H. S. CARSLAW. These scales® are represented on Fig. 8. That for earned income is the familiar type with the amounts paid by each successive £ up to the 6,900th forming an arithmetical progression with a common difference 0-0125d. The flat rate on the excess is determined by the amount paid on the last £ of the progression. In the scale for property income it will be noticed that # is continuous at £500 and £1,500. The discussion in §5, though given for the case of only two intervals, applies also to any number. The gradient in the interval 500 to 1,500 is steeper than that in the interval 1 to 500. This explains the jump up at 500 in the amounts paid by the adjacent £’s and the formule (1) and (11) show that this is as much as 2d., whereas the common difference in the pro- gression from 1 to 500 is 0-02, while that in the interval 500 to 1,500 is 0-028. Again at 1,500 there is a jump down of nearly 4d. These awkward breaks at the 500th £ and at the 1,500th are a blot on this scale. Indeed it is surprising that it was allowed to remain the basic rate from 1931-32 till 1939-40, with percentage 80 changes over the whole range from time to time as the revenue needs demanded more or less. Ae It is also rather astonishing that a simpler means of dis- criminating between the two kinds of income has not even 40 yet been adopted by the Federal authorities. There is much to be said in favour of the method used in England. A certain pro- portion is deducted from the total of the earned income, but this deduction must not exceed a certain sum. When the earned 20 Rate of Tax in pence per £. 0 BOO NWO! A alee Bee income has been reduced in Income in £. this way and the deductions, as Fig. 8 provided in the regulations, have been made from each _ class of income, the two are treated alike ; their sum forms the taxable income and the rates of tax refer to the taxable income without any further distinction as to the way,in which it is composed. 9. For the year 1939-40 the Federal Parliament passed two Income Tax Acts. The Income Tax Act (No. 1) 1940, of May, anticipated the budget for the year, which was placed before the new Parliament in November. The Federal Treasurer, then Mr. Spender, in introducing the measure, made some reference to the “‘ income tax technique ” adopted by the Commonwealth and the rates of tax designed by Sir George Knibbs. He was bold enough to assert’ that ‘‘ for some considerable time the Commonwealth led the world on methods of income taxation and other countries followed. In particular, most of the Australian States followed the Commonwealth lead, improved on the principle, and adapted it to their own needs.” This praise seems to me somewhat excessive 6In Fig. 8 and later figures, the upper of the two graphs refers to Property Income. 7 Commonwealth of Australia, Parliamentary Debates, 15th Parliament, 2nd Session, p. 604 . (1940). PROGRESSIVE RATES OF TAX IN AUSTRALIA. 39 and with regard to the so-called improvements the States made on the principle there will be something to say later. The scheme embodied in Schedules [ and II of the Income Tax Act (No. 1) 1940 was influenced by the incidence of the State taxes on income. “‘ This practical limitation of Federal income taxation ”’, said the Treasurer,’ “‘ causes difficulties at present, but not of a serious order.’’ Six months later his successor, Mr. Fadden, had a different tale to tell. The scale of rates can be put briefly as follows: Earned Income. When 0<2%<500, R=5. 500— , 1,000 i < OLDER SERIES oo-o" ig, 1. eS THE CLIMATE OF AUSTRALIA IN PAST AGES. 49 structures give evidence of the climatic conditions under which they were formed ; many sedimentary rocks also contain the fossilised remains of once living animals and plants, and some of these afford evidence of the climatic conditions existing at the time they were alive. It is not necessary to describe here all of these evidences in detail; such deseription can be found in all geological text books, but they will be referred to later briefly when necessary. In my discourse it will be necessary to refer to the various subdivisions of geological time; these are given in Text-figure 1. From the above table it will be seen that there are five primary subdivisions called eras, and that each of these is divided into a varying number of sub- divisions called periods, and that these latter are further divided into epochs. The classification given is not a complete one, but is sufficient for our present purpose. The actual length of time in years represented in this chart will vary from 100 to 1,800 millions of years, according to the factors used in computing it; the longer period is probably nearest to the truth. It is usual in discussing past variations of climate to refer them to our existing climate as being a normal one, and to look upon the colder and warmer periods of the past as being abnormal, but this is not necessarily correct, as some geologists consider our present climate to be abnormal, and the world to be still in one of the inter-glacial epochs of the last great Ice-age. In discussing the probable climates of the various geological periods it will be assumed that Australia as a continent has always occupied its present position with regard to the equator, but this also is not necessarily correct, because there is one school of geologists which considers that all of the continents have in the past changed their relative positions from time to time, and are in fact still doing so. If this view were correct it is obvious that, if in one of the past geological periods Australia had occupied a position far to the south of that now occupied, it would have had a climate much colder than that of today without any necessary alteration in the climate of the world as a whole. This belief in drifting continents is not, however, held by all geologists, and we will assume for our present purpose that the position, of Australia as a whole has remained constant throughout geological time. THE ARCHAOZOIC ERA. Rocks of this age occur over very wide areas in Australia, particularly in. Western, Australia, South Australia, and the Northern Territory; they are, however, so much metamorphosed and altered that such of their original characters as might have given evidence of the climatic conditions under which they were laid down have been largely obliterated. These conditions are not: peculiar to Australia, but exist also in all other parts of the world where strata, of this age occur. There does occur, however, on the Kanowna Goldfield of Western Australia, a series of conglomerates belonging to the Yilgarn series which are not much altered, and T. W. E. David has given it as his opinion that they may have had a flurio-glacial origin. and show evidence, therefore, of a cold climate at the time they were being deposited. This view has, however, not been, accepted by Western Australian geologists. Such evidence is not limited to Australia ; there occurs in central Canada a similar series of conglomerates. apparently of similar age, which A. P. Coleman definitely considers to have had a glacial origin and which he has called the Timiskamian or Sudbury Boulder conglomerates, and with these there has been found in many localities beds of varve-like shales showing seasonal banding. In India also there occur the Darwar conglomerates, considered by Foote to be similar in character and age to those of Canada. There appears to be some evidence, therefore, of a world- 50 Cc. A. SUSSMILCH. wide refrigeration of the climate during some part of the Archxozoic Era, in which Australia may Wee participated. THE PROTEROZOIC ERA. Rocks of the Proterozoic age are very widespread in Australia, particularly so in Western, Central, and South Australia. The Proterozoic formations of Western Australia have been divided into an older division, called the Mosquito Creek Series, and a newer division called the Nullagine Series. The older series consists mainly of schists, phyllites and jaspers, with some thick beds of dolomitic limestone, and the presence of the limestone beds and the fact that some of them are dolomitised suggests that at the time of their deposition the climate was warm to hot, but in the absence of recognisable fossils this evidence is not altogether conclusive. The Nullagine Series outcrops extensively in the Pilbarra District, and here they have at their base a series of coarse conglomerates ranging up to 500 feet in thickness ; no definitely glacially striated boulders have yet been obtained from these beds, but T. W. E. David) considered that they may have had a fluvio-glacial origin. Above these conglomerates thick beds of limestone occur, but they have not yet yielded any fossils. In Central Australia the Nullagine Series contains many very thick beds of limestone, some of which contain an abundance of fossil marine plants (Algw#) which have been referred to the Cryptozoa; these algal limestones extend over very wide areas, and it has been suggested that they indicate at least a mild, if not a warm, climate at the time of their deposition. In South Australia the Upper Proterozoic strata are known as the Adelaide Series and they have been fully described by W. Howchin™ ; he has subdivided them as follows (in descending order) : — pond . The Brighton, limestone. . Banded siliceous limestones. . Tapley’s Hill ribbon slates with occasional pebbles of quartzite. . Impure dolomitic limestones. The Sturtian Tillite. Quartzites and claystones. . The Blue Metal limestones. . The Upper Phyllites. The Torrens Limestone. . Phyllites, slates and shales. . The Basal Beds (conglomerates, grits and sandstones). These beds have an aggregate thickness of about 13,000 feet. The most interesting feature of this section is the Sturtian Tillite, which ranges up to 1,500 feet in thickness ; it is a typical glacial till containing numerous glacial erratics ranging individually up to 10 feet in diameter, and striated and facetted pebbles are common. Some thin lenticular beds of a gritty limestone occur interstratified in the Tillite. Howchin originally considered these beds to be of Cambrian age, but they are now generally accepted as being of Upper Pro- terozoic age. Howchin considers that the Sturtian Tillites were laid down on the sea floor by floating ice, but that the snow-fields were not very far distant, as many of the erratics appear to be identical with certain older rocks outcropping immediately to the south and west of the glacial beds. He has traced these glacial beds northwards to Hergott in Lat. 29° 40” South. gia THE CLIMATE OF AUSTRALIA IN PAST AGES. 51 From this northern area D. Mawson, has,‘ in the foothills of the Flinders Range, measured the following section : Thickness. 13. Glacial Series—tillites, conglomerates and quartzites me 800 feet + 12. Caleareous Series—algal limestone with some sandstone and shale .. a 3,200 ,, 11. Arenaceous and Argillaceous ‘beds - 2,700 ,, 10. Dolomitic marble x = a m: 1,000 _,, 9. Chocolate shales: a 350 ,, 8. Limestones, including algal, ‘dolomite, and oolitic varieties, with some shale bands .. 450, 7. Oolitic limestones 1 ; 560, 6. Limestones with shaly and clayey layers 950 ,, 5. Dolomitic limestone .. £30. ©, 4, Algal limestones - ie ee 120 ,, 3. Calecareous shales and limestones a - 500 =z, 2. Laminated shales op e ye 790s, 1. Glacial and fluvio- oc beds ¥ *: 1,000 ,, Total ms m v - me LDR OLOty 5 Mawson, calls this series of strata the Munyallina Beds and correlates them with the Adelaide Series from near Adelaide already referred to. In describing the lower glacial horizon, Mawson states: “ At the base of the section, is a glacial and fluvio-glacial formation which includes true tillites; near the base the boulders are dominantly basic lavas derived from the underlying formation, and also large blocks of dolomitic limestone also from the underlying formation ; a couple of hundred feet above the base the boulders include quartzite, granite and quartz-porphyry ranging up to 3’ 6” in diameter, and pebbles have been found exhibiting glacial strie ’’. Mawson states further, “ some of the beds are obviously glacially transported and accumulated and that it is quite obvious that, during the time the beds were being deposited, land ice existed in this region and as the glacial beds are followed immediately and conformably by an undoubted series of marine strata, the land over which the ice travelled was not much above sea-level; a glacial climate is therefore indicated’. This lower glacial horizon is separated from the upper one by a thickness of over 10,000 feet of strata, mainly limestones, and many of these contain marine alge such as Girvanella, Collenia and Mawsonella. Mawson, considers that these algal lime- stones are indicative of a warm climate and comes to the conclusion that “* the climatic record is a remarkable one varying from severe glacial to probably warm arid conditions and again glacial within the period of deposition, of these beds’. Mawson correlates the topmost glacial bed with the Sturtian Tillite of the Adelaide Series, and, if this is so, possibly the lowest glacial bed may be the equivalent of the conglomerates (possibly fluvio-glacial) which occur at the base of the Nullagine Series of Western Australia. W. G. Woolnough‘” has also described some of the Proterozoic strata of the Flinders Range and has recorded evidence of aridity of climate in the red colour of some of the sedimentary rocks, the presence of sun-cracks, and in certain other features. The glacial beds of the Adelaide Series are known, to outcrop over an area 450 miles long in a north-south direction and 200 miles long in an east-west direction, where they extend into the Broken Hill district of New South Wales, and over this large area not only are the tillites very thick but the glaciers or ice-sheets must have extended down to sea-level, and as already pointed out 52 Cc. A. SUSSMILCH. extended northwards to Lat. 29° 40’ South, one must conclude therefore that the climate of Australia in the Upper Proterozoic was very cold and remained so for a considerable time. It is interesting to note that this refrigeration of the climate was not limited to Australia, because glacial beds of similar age, the Numee Tillites, occur in South Africa, extending there also to Lat. 29° S.; and glacial beds have also been found from such widely separated localities as Utah, U.S.A., Simla in India, and the Yangtse Cafion in China (the latter may be of Lower Cambrian age). This widespread occurrence of glacial beds in both Northern and Southern hemispheres indicates a worldwide refrigeration of the climate in Upper Pro- terozoic times, a refrigeration, even more pronounced than that of the recent Pleistocene Ice age, when, land ice only reached as near the equator as Lat. 38° as against Lat. 29° of the earlier era. THE CAMBRIAN PERIOD. Marine strata of Cambrian age occur in South Australia immediately overlying the Adelaide Series described in the last section, and these strata extend as a broad belt northwards through Central Australia and western Queensland and thence into the Northern Territory. These Cambrian strata contain an abundance of the fossils of once-living marine animals including trilobites, brachiopods, pteropods and gasteropods, but the most important of the fossils belong to an extinct group of organisms called the Archeocyathine. These animals in their skeletal structures, which are calcareous, have some resemblance to both sponges and corals, and like the latter they built extensive reefs much like existing coral reefs. The Archzocyathine had become extinct by the close of the Cambrian period, and we have therefore no direct knowledge as to the climatic conditions under which they lived, but from their close resemblance to the reef-building corals it is considered that, like them, they lived in warm tropical seas, and if this assumption is correct, Australia down to its southern margin must have had a warm tropical climate in Cambrian times ; the other fossils found in the Cambrian rocks do not oppose this view. This extinct group of organisms has also been found as fossils in the Antarctic continent as well as at various localities in the Northern Hemisphere, and this suggests that not only Australia, but practically the whole world had a much warmer climate in Cambrian times than it has today. In some parts of South Australia the topmost beds of the Cambrian System consist of cross-bedded red sandstones interstratified with chocolate-coloured Shales and some thin beds of limestone; W. Howchin™ has suggested that there is a strong probability that these strata accumulated under arid or even semi-desert conditions for the following reasons: (a) the prevailing red colour of the rocks; (b) many of the limestones are oolitic or nodular with wavy and concentric structures that appear identical with surface travertine that is forming today in the drier parts of Australia; (c) the newest members consist of red, friable, cross-bedded sandstone closely resembling wind-blown sand dunes. These conclusions, of course, would apply only to the limited area in which these strata now occur. THE ORDOVICIAN PERIOD. The evidence of climatic conditions of this period in Australia are not very definite. Strata of this age are widespread, particularly in Victoria, New South Wales, and Central Australia. In the first two States the strata consist mainly of marine shales and sandstones, and the contained fossils consist almost entirely of graptolites, an extinct group of hydrozoa. These animals inhabited the surface waters of the ocean, and we find them preserved in abundance in THE CLIMATE OF AUSTRALIA IN PAST AGES. 53 Ordovician, strata all over the world ; they therefore had a very wide geographical range. The group became extinct in the next geological period (Silurian), and they afford therefore no direct information as to the climatic conditions under which they lived. The Ordovician strata of Central Australia do not contain fossil graptolites, but have yielded an abundance of other marine fossils such as brachiopods, mollusca and trilobites; these also are not very definite climatic indicators. There is, so far as we know, an entire absence of reef- building corals in Australia, although they were living in other parts of the world, and their absence, together with the extinction of the Archeocyathine, might possibly suggest cooler conditions. In the Northern Hemisphere, on the other hand, limestones of Ordovician age containing fossil reef-building corals are abundant, and, aS these extend as far north as Baffin Island, they indicate a tropical climate extending well into the Arctic region at that time. It seems probable, therefore, that the climate of Australia in Ordovician, times was still warm, although perhaps not quite so warm as it had been in Cambrian times. THE SILURIAN PERIOD. For this period the rocks yield quite definite evidence as to the nature of the climate, as we find an abundance of limestones of Silurian age crowded with the remains of once-living reef-building corals ; such coralline limestones occur in a broad belt of strata extending from Tasmania northwards through Victoria, and New South Wales to the Chillagoe district of north Queensland ; and it would appear that what was then the eastern coast of Australia was as that time fringed with coral reefs along its whole length. As reef-building corals ae ee Upper Silurian Sea : Heavier Sedimentanon ay, fe Mitta Mitta Geanticline LY, ‘ v by This Geanticline became submerged i in many places during part of Upper Silurian Time of Xe Fig. 2.—Areas in Australia in which fossil corals of Silurian age occur. (Compiled by E. C. Andrews.) 54 Cc. A. SUSSMILCH. are abundant in our present day seas, we know something about the conditions necessary for them to flourish. These conditions include the following: (a) the temperature of the sea-water must not fall below 68° F.; (b) the water must not exceed 240 feet in depth; (ec) the sea-water must be in general free from the presence of much mechanical sediment such as mud and sand. All of these conditions exist along the coast of Queensland today and we find a continuous belt of coral reefs extending from Cape Yorke southwards nearly to the latitude of Brisbane. South of this point no coral reefs exist for the one and only reason that the temperature of the sea-water there is too low for their requirements. The fact that coral reefs in Silurian times flourished in Tasmania, some 1,200 miles south of their present habitat, indicates a considerably warmer climate than that of today. . The Northern Hemisphere affords even more striking evidence, as coralline limestones of this age exist well into the Arctic regions. We can say, therefore, without hesitation, that the climate of Australia was definitely tropical during the Silurian period, just as it was in other parts of the world. THE DEVONIAN PERIOD. The warm conditions of the Silurian period continued into the succeeding Devonian period, because we find coralline limestone of Middle Devonian age occurring so far south as Victoria (the Buchan and Bindi Limestones). The sea disappeared from Victoria at the end of Middle Devonian times, but in New South Wales there was in the Upper Devonian a very extensive transgression of the sea which extended from the present south coast north-westwards into the Cobar district ; this was a shallow sea and in it were deposited coarse sedi- ments for the most part such as sandstone and conglomerates with some shales ; in some localities the prevailing red colour of the beds and other factors suggest semi-arid conditions of climate. This Upper Devonian sea was inhabited by an, abundance of marine life, principally brachiopods and pelecypods, and there were also humerous marine fish. The presence of an abundance of the fossil stems of land plants in some of these marine beds indicates that the land in places supported an abundant vegetation, so that the climate could not have been, semi-arid everywhere. The absence of reef-building corals in these Upper Devonian, strata suggests that the climate may have become somewhat less tropical than it appears to have been earlier in the period. THE CARBONIFEROUS AND PERMIAN PERIODS. As the climatic conditions of these two periods appear to have been very similar, it will be convenient to consider them together. ‘sellog oUTIep, IOMO'T ‘UBIULIOd IOMO'T 000‘€—-00¢‘T ‘soseyg prlojroyyny pue Aoprey | O&Z ‘SounsvoyT [BOD IOMO'T ‘Vy UOoZLIOFZ [RIOR WIG 000‘E-00G‘T ‘(qaed aoddn ut so1yea19 . jeroeys yqIm) oseyg ud}xuvig ‘q uozWIOoFR [eryy ye 00F (o4B10ULOTSUOD ‘gollog oulrey, t9ddq ‘UBIULIOG S[PPTIN UvBIULLOg BIIMJOY AIA) o8B4Ig soIN] 000‘€-00¢‘T ese SuLIq(Iny soinsveyy [Vop s9ddq ‘uetulleg i1sddq “700 "SsuUoZILO FT 1DI0D7H ay, Huraywnorpur sap mM Yynog man fo pUIsIq wang swajuNn ey? fo swashy uniisaq pun snosafvuoqwog ay) [0 suorsimipqnys ‘| WIaV, 1, ah? THE CLIMATE OF AUSTRALIA IN PAST AGES. 57 placed tentatively in the Upper Carboniferous epoch, which, if correct, would mean that they followed the Kuttung sedimentation without any marked time break ; much geological field work has been, done in various parts of Australia since then and many geologists are now of the opinion that these beds are of Lower Permian age, and that there is consequently a very definite time break between, the close of the Kuttung epoch and the laying down, of the Lochinvar Beds; even if this be so the time break represented, that is the time break between, glacial horizons 2 and 3, would probably be of no greater magnitude than, that which exists between some of the other glacial horizons, say, for example, that between horizons 4 and 5, which are both within the Permian system and which are separated by nearly 4,000 feet of strata, including both marine beds and fresh-water beds (the Lower Coal Measures) ; we may therefore still consider that both the Carboniferous and Permian, glacial beds belong to one great climatic epoch. The Lochinvar Beds begin with a series of glacial beds (3rd glacial horizon) followed by a thickness of 2,400 feet of marine strata, which constitute the lower part of the Lower Marine Series. (d) The Lower Marine Series. The lower part of this series has just been referred to as the Lochinvar Beds ; immediately above these are the Allandale conglomerates, containing some glacial erratics (4th glacial horizon), and these in, turn are followed by some 1,500 to 2,000 feet of marine strata containing an abundance of marine fossils, but no reef-building corals. (e) The Lower or Greta Coal Measures. This is a series of fresh-water strata some 230 feet in thickness containing two important coal seams, one of which reaches a thickness of 30 feet of coal. An abundance of fossil plants (the Glossopteris flora) is associated with these strata. The presence of this fresh- water series with its coal seams and fossil plants between two glacial series (horizons 4 and 5) indicates a marked but temporary warming up of the climate, in other words a typical interglacial epoch. (f) The Upper Marine Series. This follows conformably upon, the Lower Coal Measures and consists of marine strata ranging up to 6,000 feet in thickness. Two glacial horizons occur in this series; the lowest of these (horizon, 5A) is situated in the upper part of the Branxton Beds, where many large glacial erratics have been, found scattered through the marine beds; these include boulders of limestone containing Silurian corals and boulders of quartzite containing Devonian brachiopods. Such rocks occur in situ at the present day in, the Blue Mountains on what was the western shoreline of the upper marine sea in Permian times. It is obvious that at this time land ice reached sea-level, broke away as icebergs which melted as they floated across this sea, dropping their load of morainic material on the sea bottom. Some 500 feet above these beds are the Bolwarra Conglomerates (glacial horizon 5B); this is a typical marine glacial boulder bed crowded with glacial erratics and is the highest and last of the glacial beds of the Carboniferous-Permian Series. The boulders found in horizon 5A and 5B consist in general or rocks quite different to those found in the Kuttung glacial horizons and must have come in the main from a different source; they cannot be redistributed material from the Kuttung glacial beds. Those parts of the Upper Marine Series above the Bolwarra Conglomerates show no evidences of glacial conditions, but there is no change in the marine life occurring in them as fossils. (g) The Upper Coal Measures. This is a fresh-water series ranging up to 6,000 feet and including many coal seams; these strata contain an abundance of fossil plants similar for the most part to those found in the Lower Coal Measures. In one locality many small fossil insects have been found. In some beds, particularly just above some of the coal seams, many fossil trees occur ranging 58 Cc. A. SUSSMILCH. up to eighteen inches in, diameter, showing that at times the land was covered with fairly dense forests. All of these facts indicate that glacial conditions had ceased and the climate had become warmer, but not necessarily tropical; R. J. Tillyard, who has described the fossil insects from this series, considered that their small size indicated that the climate was still somewhat rigorous. Both terrestrial and marine glacial beds of Permian age occur in Tasmania ; at Wynyard, on the north coast, the glacial beds are 1,500 feet thick and contain erratics up to five feet in diameter, and they rest upon, glacially striated pave- ments; the strie have a NNE trend indicating that the ice was moving in that direction. Both the Allandale and the Branxton glacial horizons are represented in Tasmania. ‘Terrestrial glacial beds are also widespread in Victoria and South Australia; in the latter State they range up to 900 feet in, thickness and in both States extensive glaciated pavements underlie these beds ; there is some uncertainty as to whether these glacial beds of Victoria and South Australia are to be correlated with the Carboniferous or Permian glacial beds of New South Wales, but there is no question that they are of Upper Paleozoic age. In Western Australia marine glacial beds exist over very extensive areas occurring near the base of the Permian formations of that State, and in the Kimberley district they extend northwards to Lat. 18° S. In Queensland, also, marine glacial beds of Permian age extend well into the tropics. These glacial formations of Carboniferous and Permian age appear to have their greatest development in the south-eastern parts of Australia. In New South Wales there were at least five important glacial epochs as follows : Glacial Horizon. Thickness. 5B Bolwarra Conglomerate ee ie ee: 40 feet Marine strata ee me bi 2 500 sé, 5A Branxton Erratic horizon .. oe * i aes Marine strata a Bei) ‘a 2,000 _ i, Lower Coal Measures os a 100-230 ___,, Marine strata ; us: 1,300%- > 4 Allandale Beds with glacial ‘erraties a 2hO) ie Marine strata a 2,400 ,, 3 Lochinvar glacial beds if me 300 4, (?) Unconformity representing part of Upper Carboniferous time. 2 Main glacial stage of the Kuttung Series... 4,700 ,, Volcanic state of the oe Series - .. ¢ “2500s 1 Varved shales < - £60" Wollarobba Conglomerates ‘and tuft with some striated pebbles .. he < “2,005 It will be noted that great thicknesses of strata separate most of these glacial horizons from one another; for example there are over 3,900 feet of strata between, horizons 4 and 5 and 2,400 feet of strata between horizons 3 and 4. If an unconformity exists between horizons 2 and 3, a considerable thickness of strata might be missing there. As the thickness of strata between horizons 5A and 5B is only 500 feet, these two might be considered as belonging to one horizon. It would seem, therefore, that during the Carboniferous and Permian periods there were five epochs of heavy glaciation separated from one another by four quite long interglacial epochs. This does not necessarily mean that glacial conditions disappeared entirely from Australia during these interglacial epochs, but that the ice fields must have become much restricted during such periods. In the case of the interglacial period between horizons 4 and 5, with its coal measures and thick coal seams, glacial conditions probably almost ceased at that time. THE CLIMATE OF AUSTRALIA IN PAST AGES. 59 Besides these major oscillations of climate during this period, the detailed section of the Kuttung Series indicates also minor oscillations ; as has already been shown, there are in the Main Glacial series of the Hunter River district at least four horizons of tillites and varve shales separated from one another by moderate thicknesses of non-glacial strata, indicating successive advances and retreats of the ice-sheets. Conclusive evidence exists, therefore, that throughout the greater part of the Carboniferous and Permian periods great ice-sheets existed in Australia, and that during the Kuttung epoch land ice existed as far north in Queensland as Lat. 30° S., and that during Permian, time drifting ice deposited morainic material as far north as Lat. 18° S., and, as these occurrences extend much nearer to the equator than similar deposits of Pleistocene age, the refrigeration of the climate in, Upper Paleozoic time must have been, greater than, that which occurred in the last great Ice Age, when no land ice appears to have occurred nearer to the equator than Lat. 40°. It is important to note that glaciation was not limited to the Australian, continent in Upper Paleozoic times ; similar glacial deposits of this age are also found in Africa and South America over large areas, and in the Northern Hemi- sphere extensive deposits have been found in India, while limited deposits occur in the United States near Boston, and also in England and Germany in Europe. The Upper Paleozoic refrigeration of the climate was therefore worldwide, but the areas affected by the glaciation appear to have been much more extensive in the Southern than in the Northern Hemisphere. THE TRIASSIC AND JURASSIC PERIODS. The available evidence suggests that during these two periods the geological history was very similar and it will be convenient therefore to consider them together. At the close of the Permian period important earth movements took place which brought about a general uplift of the land of moderate amount, accom- panied by a complete retreat of the epicontinental seas which had covered such large areas during the Permian period. As a result, at the beginning of the Triassic period the Australian continent extended further seawards in most parts than it does today. This was particularly the case along its eastern margin, where it extended some considerable distance across what is now the Tasman Sea; this eastern extension, which has since disappeared beneath the sea, has been called Tasmantis. Some of the Permian fresh-water lakes in which the Upper Coal Measures had been, deposited still continued as such into the Triassic period, and new lakes developed ; thus by the beginning of the Jurassic period very extensive areas in eastern, Australia were covered by such lakes. The largest of these has been, called Lake Walloon ; it extended from the coast in south-eastern Queens- land, westward into central Australia, covered parts of northern New South Wales and extended from there northwards to the present Gulf of Carpentaria ; its area must have been at least 300,000 square miles. In these Triassic-Jurassic lakes a fairly thick series of fresh-water strata was deposited and in many places valuable coal seams are included, such as the Ipswich coal measures of Queens- land and the Gippsland Coal Measures of Victoria. The fresh-water strata have yielded an abundance of fossil land plants, as well as fossil insects, Amphibia, fish and reptiles. Many fossil insects have been obtained at Ipswich in Queens- land, including many dragon-flies; they have been described by R. J. Tillyard, and from their nature and the large size of many of them he inferred that they indicated a warm climate. The remains of reptiles found in Queensland belong to an, extinct group of large individuals called Dinosaurs, and these also indicate at least a mild climate ; one of these, Rhetosaurus, was about 40 feet in length. 60 Cc. A. SUSSMILCH. No marine strata of Triassic or Jurassic age have been found in Australia, except a limited area of Jurassic marine strata in north-west Australia. The evidence of the land animals and plants found, however, suggests that the climate during these two periods was at least as warm as, and probably warmer than, it is today. This is supported by the evidence from the Northern Hemi- sphere, where in Upper Triassic times coral reefs extended into Alaska (Lat. 60° N.), some 2,000 miles north of the present day limit of reef-building corals. While the evidence from the Northern Hemisphere in general suggests a warm climate, it also indicates that some marked oscillations took place, but it was never very cold. Professor Neumayer, of Vienna, as a result of his study in 1883 of a group of cephalopods called the Ammonites and their distribution, concluded that the earth in Jurassic times had clearly marked equatorial temperate and cool polar climates, agreeing in the main with the present occurrences of the same zones. THE CRETACEOUS PERIOD. At the close of the Jurassic period an invasion of the sea took place from the north and converted most of the area previously occupied by Lake Walloon into an arm of the sea. This extensive epicontinental sea extended southwards into northern New South Wales and south-westwards into northern South Australia ; it possibly extended also as far southwards as the Great Australian Bight and thus completely divided the Australian continent into two parts This sea brought with it an abundant marine fauna, now found as fossils in the strata deposited in it. From a study of these fossils F. W. Whitehouse has concluded that the water was comparatively cold, his reasons being as follow : (1) The fauna contains no reef-building corals, no Rudistid lamellibranchs, no equatorial types of Ammonites, and no large types of Foraminifera. (2) Angular fresh felspars occur throughout the Roma and Tambo series of the Lower Cretaceous. (3) Ice-borne erratics, some of which show faint glacial striz, occur as dropped boulders indenting the underlying Cretaceous Shales at Stuart Range in South Australia and at White Cliffs in New South Wales. (4) Pseudomorphs in opal after glauberite are numerous at White Cliffs ; these resemble the Glendonites associated with glacial erratics found in the marine sediments of the Middle Permian of New South Wales. This evidence of cold climate receives support from the finding of terrestrial glacial deposits ip South Australia by W. G. Woolnough and T. W. E. David.®) These deposits occur in the Flinders Range between latitudes 26° 25’ S. and 30° 25’ S., that is near the southern margin of the Cretaceous sea; they have been traced over an area of about 40,000 square miles. E. J. Kenny has recorded the presence of glacial erratics in the Lower Cretaceous marine strata of the Tibooburra district of New South Wales, where they are associated with typical marine fossils of that age. The existence of probable glacial beds of a similar age has been reported from Great Britain, Iceland, Spitsbergen and South Africa, so that a cold climate appears to have been worldwide at this time; it is not considered, however, that it was so pronounced as that of Upper Paleozoic time. THE TERTIARY PERIOD. The first three subdivisions of the Cainozoic era, which are called the Eocene, Miocene and Pliocene periods respectively, are frequently grouped together and referred to as the Tertiary period ; and we will follow that practice here. At the close of the Cretaceous period important earth movements took place which appear to have brought about a complete disappearance of the THE CLIMATE OF AUSTRALIA IN PAST AGES. 61 epicontinental seas and fresh-water lakes which had covered such large areas in that period. Just what happened during the Eocene period we do not know, as no rocks of this age have yet been found in Australia. Towards the close of the Eocene period a subsidence began, in the southern parts of Australia accom- panied by considerable transgression of the sea along the present southern margin of the continent ; this subsidence continued throughout the Miocene and PRESENT Ula —_— ee INCREASING RAINFALL DECREASING RAINFALL Recession of desert RECENT sandhills; \ degrading of Chernozems \ Formation of desert and coastal sandhills; formation of lime and gypsum soil pans. River Terraces < PLEISTOCENE Older Alluvial Deposits — present eS more than one maximum. Non - siliceous limestones Later Lateritic Soils Ture Later PLIOCENE Siliceous Limestones Temperat _ Seasonal Rains mo" Earlier Lateritic Soils Uniform Rains Earlier MIOCENE = Siliceous Limestones. Fig. 3. Generalised curves to interpret the more important climatic changes in Queensland since Miocene times. The centre line represents present-day conditions. The continuous curve assesses rainfall values. The broken line is a general temperature curve. In both curves the cusps to the left represent values higher than at present; cusps to the right are lower values. (After Whitehouse.) 62 Cc. A. SUSSMILCH. Pliocene periods and considerable thicknesses of marine strata were deposited. These strata contain an abundance of marine fossils, mostly polyzoa and mollusca ; some fragmentary remains of whales and sharks have also been found. Reef-building corals are rare, but one genus has been found in the Miocene strata of Table Cape in Tasmania, and from this occurrence T. W. E. David) has suggested that the sea there must have been at least 10° F. warmer than it is today, and states further that towards the close of the Pliocene period the evidence suggests that the seas were getting steadily colder. Fresh-water deposits, mainly river deposits, of Miocene and Pliocene age have been found at many localities in the eastern half of Australia, extending from Queensland to Tasmania and as far west as South Australia, and many of these fossils appear to be very closely related to, and in some cases “ identical ”’ with, plants occurring in our present day “ brush ”’ forests (rain-forests), now growing in those eastern parts of Queensland and New South Wales where there is a fairly hot climate with a high rainfall. The wide distribution of this type of vegetation in Tertiary time suggests, therefore, a warm moist climate as far south as Tasmania and extending westwards into regions which are now too arid to support such a vegetation. The evidence both from the marine animals and the land plants therefore indicates a climate somewhat warmer and certainly moister than that of today, and this view is supported by evidence from other parts of the world. Possibly in Upper Pliocene times a cooling of the climate began, which culminated in the great ice age of the following Pleistocene period. In Text-figure 3 is shown a diagram prepared by Dr. F. W. Whitehouse showing oscillations of the climate of western Queensland extending from the Miocene period down to the present day ; this is based on variations in the nature of the rocks and soils formed during the periods represented. It shows variations in, rainfall as well as temperature, but the curves representing the rainfall do not seem to have any definite relation to the general curve representing the temperature. . THE PLEISTOCENE PERIOD. Very pronounced earth movements took place in Australia at the close of the Tertiary period as a result of which our present mountains and tablelands. were elevated to their present positions. Prior to this uplift most of the con- tinent appears to have been low-lying with only occasional isolated hills and short narrow ridges rising above the general level. The production of that great belt of tablelands (the Australian Cordillera) which now exists along the whole of the eastern margin of the continent, and ranges up to 4,000 feet or more in altitude, must naturally have had some modifying influence on, the climate locally, but this could not have had any very profound influence on the climate of Australia as a whole. Similar mountain-making movements took place simultaneously in many other parts of the world, and such great mountain ranges aS the Alps, Himalayas, Rocky Mountains and Andes were elevated at this time. Following soon after this great mountain-making epoch, but not necessarily resulting from it, there developed a very pronounced refrigeration of the climate throughout the world, which produced one of the world’s great ice-ages. Great ice-Sheets came into being, ultimately covering some 12,000,000 square miles of the earth’s surface; in Europe these extended southwards to London and Berlin, and in North America southwards to Cincinnatti in the Mississippi Valley. Glaciation occurred also in the Southern Hemisphere and affected considerable areas in South America, New Zealand and Australia. During this glacial period a considerable lowering of the snow-line took place which varied in amount from place to place, but which averaged about 4,000 feet. THE CLIMATE OF AUSTRALIA IN PAST AGES. 63 The area submerged under ice in Australia was quite small. About one- half of Tasmania was covered and on the west coast the glaciers extended almost down to sea-level, and the ice ranged up to 1,500 feet in thickness ; peat beds occurring in, some of the tillites suggests interglacial epochs. On the continent of Australia the glaciation was limited to the small area of the Kosciusko Table- land which projects above the 5,000 feet level. The snow-line in this region is today at an elevation of about 8,000 feet, and in Pleistocene times it was lowered to about 5,000 feet ; no other part of the mainland reaches this elevation, apart from the tops of a few isolated peaks, and these are too small in area to have allowed of sufficient accumulation of snow to form glaciers. T. W. E. David states that in the Kosciusko region?) a small ice-sheet formed early in Pleistocene times, and towards the end of the period, as the cold became less intense, this split up into small valley glaciers, and these finally disappeared not less than about 20,000 years ago. The reason why Australia, as a whole, was so little affected by the Pleistocene glaciation is that it does not project sufficiently far to the south. In the Northern Hemisphere all the areas glaciated, except some of the high mountains, lay on the poleward side of Lat. 40° N., whereas in, Australia the only part lying on the poleward side of the corresponding south latitude is Tasmania. Because of the very much larger area occupied by the ice-sheets in Europe and North America, these regions display a much more complete record of the glacial conditions than Australia. The Alpine region of Europe gives evidence of at least four distinct advances of the ice, separated from one another by very definite interglacial epochs during which the climate was at least as warm as, perhaps a little warmer than, it is today.; one of these interglacial epochs continued for such a long period of time that the ice-sheets may have almost entirely disappeared for a considerable period of time, only to advance again, however, during the next glacial epoch. In North America there were no less than five separate advances of the ice-sheets. Various estimates have been made as to the length of time occupied by the Pleistocene ice-age; these estimates vary from 300,000 years to 1,000,000 years. A. P. Coleman” gives as his considered opinion, a period of from 600,000 to 700,000 years, and also concluded that the last ice-sheet began to retreat some 25,000 to 35,000 years ago. Two large areas are today still submerged under great ice-sheets ; these are the Antarctic continent and the island of Greenland, representing an area of nearly 6,000,000 square miles ; many of the high mountain ranges also support large glaciers. In all of these regions the ice today is steadily retreating. Both Antarctica and Greenland have had mild climates in past geological periods and consequently some geologists consider that the great ice-age is not yet finished, and that at the present time we are living in an interglacial epoch. In some of the Pleistocene terrestrial deposits of Australia there have been found the bones of some extinct marsupials some of which were much larger than any living representatives of this group of vertebrate animals. These ~ have been, found not only in the coastal regions where there is today a relatively good rainfall, but also in some of the very arid regions of Central Australia. From Lake Calabonna in the northern part of South Australia almost complete skeletons of an extinct marsupial, Diprotodon, somewhat like a wombat in general form but almost as large as a rhinoceros, have been found; and for herds of these large slow-moving animals to have existed these regions must have had a much better rainfall then than they have now. SUMMARY. From the evidence given it will be obvious that very marked changes in, the climate of Australia have taken place since the beginning of geological 64 Cc. A. SUSSMILCH. time ; the more important of these are shown, diagrammatically in. Fig. 1. On the right-hand side of this diagram the vertical line indicates the present-day climate, while the dotted line indicates the variations, the curves to the left indicating the colder periods, whereas those to the right indicate the warmer periods. It will be noticed that very definite colder periods occurred during (a) the Upper Proterozoic era, (b) the Carboniferous-Permian periods, (¢) the Cretaceous period, (d) the Pleistocene period. It is worthy of note that each of the great glaciations occurred at or near the close of the Proterozoic, Paleozoic, Mesozoic and Cainozoic eras respectively. On the other hand the definitely warmer periods, which were relatively longer, appear to have started at the beginning of each era and continued through several periods until interrupted by the oncoming colder period towards the close of the era. These facts suggest that the average climate of the. past has been warmer than that of today. The changes of climate shown in this diagram may be referred to as the major ones; in addition there were changes of a second order, such as the ' interglacial epochs which took place, for example, during the Carboniferous- Permian, glacial period, each of which must have lasted quite a long time. There were oscillations also of a third order, such as those indicated in the diagram in, Fig. 3, and superimposed on, these again may have been even less important changes. Another feature that should be noticed is that the climatic changes which Australia has suffered appear to correspond in, general with those which occurred simultaneously in other parts of the world, indicating a control which was worldwide in its operation. It is not proposed to discuss here the possible causes of these changes of climate ; many theories have been advanced, but none have yet met with general acceptance, and it may be said that this is still one of the unsolved problems of geology. | ACKNOWLEDGMENT. I desire to thank the University of Queensland for permission to make use of text-fig. 3, prepared by Dr. F. W. Whitehouse. REFERENCES. {) Coleman, A. P.: Ice Ages, Recent and Ancient. Macmillan.and Co., London, 1926. ® David, T. W. E.: Explanatory Notes, Geological Map of Australia, Australasian Medical Publishing Co. Ltd., Sydney, 1932. ‘) David, T. W. E., and Sussmilch, C. A.: Upper Paleozoic Glaciations of Australia, Bull. Geol. Soc. of America, Vol. 42, p. 481. . ‘) Howchin, W.: Geology of South Australia. R. E. E. Rogers, Government Printer of South Australia, 1918. (5) Mawson, D.: The Munyallina Beds, a Late Proterozoic Formation, Trans. Roy. Soc. of S. Aust., Vol. LVIII, 1934. ‘6) Whitehouse, F. W.: The Climate of Queensland since Miocene Times, University of Queens- land, Department of Geology, Vol. 2, No. 1, 1940, p. 62. ‘7) Woolnough, W. G.: The Geology of Flinders Range in the Neighbourhood of Wooltana Station, Journ. Roy. Soc. of N.S. Wales, Vol. LX, 1926. ‘8) Woolnough, W. G., and David, T. W. E.: Cretaceous Glaciation in Central Australia, Q.I.GS., Volo EXO Part 3. pjo22. AN EXAMINATION OF THE ESSENTIAL OILS DISTILLED FROM THE TIPS AND NORMAL CUT OF EUCALYPTUS POLYBRACTEA. By Puiniep A. BERRY, M.Sc., and THOMAS B. SWANSON, M.Sc. (Manuscript received, May 8, 1941. Read, June 4, 1941.) The examination of the oils obtained by monthly distillation of (a) growing tips and (b) old leaf of #. eneorifolia showed marked differences between, the two series (Berry, Macbeth and Swanson, J.C.S., 1937, 1443). The yield of oil from the growing tips increased during the period of active growth, accompanied by a pronounced increase in terpene content, while oils from old leaf showed only slight variation from month to month. The association of l-« and /-6 phel- landrene in (a) with /-phellandral, /-4-isopropyl- A?-cyclohexen-1l-one (termed eryptone, J.C.S., 1938, 1409) and cuminal was discussed in connection with the biogenetic relationship of these constituents. Since L. polybractea has been, shown, to contain the same three carbonyl constituents (Penfold, J.C.S., 1922, 121, 266; Cahn, Penfold and Simonsen, ibid., 1931, 1366 ; Berry, Macbeth and Swanson, tbid., 1937, 986), it was decided to examine oils distilled monthly from the tips of this species and also from the normal growth, to see if a similar relationship occurred. Messrs. J. Bosisto & Co. Pty. Ltd. kindly collected the material and carried out the monthly distilla- tions of the oils (Tables I and IJ). Only slight differences occurred between the two series. The variations in the monthly oils from the young tips were remarkably small; alcohols ranged from 1:9% to 5:6%, aldehydes and ketones from 2-2°% to 3-7%, cineole from 87:2% to 92-0%, and terpenes, etc., from 2:2% to 7:2%. No evidence of a Seasonal variation, in the composition of the oils from the young tips was apparent. Unfortunately, the climatic conditions during the period of the investigation were most unfavourable and undoubtedly adversely affected the formation of oil. It is during the months October to January that the most pronounced variations in the oils are likely to occur. The rainfall for the year 1938 was only 7 inches (average annual 17-87 inches), while the excessively hot summer of the year 1938-1939 was also an important factor. One leading distiller recorded that the drought had caused the leaves to wither and turn yellow. We hope at a later date to examine the oils over a normal season and see if any appreciable variation occurs in the oils from the growing tips. It was decided, however, to carry out a more detailed investigation of Several samples of the oils to see if relevant differences could be observed and to identify the aldehydes and terpenes present. The results of a detailed examination of four of the samples of oil have been Summarised in Table ITI. In the oils examined, the high boiling carbonyl constituents have been identified as a mixture of (-phellandral, l-cryptone (l-4-isopropyl- A 2-cyclo- hexen-1l-one) and cuminal. Insufficient material was obtained for the accurate estimation, of the relative proportions of cuminal, cryptone and phellandral. The total amounts recovered varied from 25% to 60% of the amount present as indicated by the hydroxylamine estimation. Associated with these carbonyl H—June 4, 1941, BERRY AND SWANSON. 66 cNHH IN © Meeks +H CO x: “JUILIYIG Aq ‘040 ‘souod oy, 0:66 0-16 é: 16 F-06 2-16 0-06 Gc: 68 0-68 9-88 0-88 P-2£8 6° L8 €-248 % “pouyvW [OSe19-O Aq 9foouly N NAN iO HH OO GD oO N oNOMHO OM + 19 ANMNOA A AN A o . ‘OHO se poqze[no[eD souojey pure sopAqeply 1e40L, Sl evencomecs N CAPONE DMD H 19 ODD OD OM COLO HOD SH OD ON o | ° 08 T H° T @) sv poqyenoreg s[oyool[W RIOD Ome DO DB O dH “OnIeA 14S" 3 aT 0] U014BYO YW oyloeds °G-GT/G- ST AYIABLD oygtpeds “PLPITA 990UII19g YRS or) oO as Vo) 88/F/6% 88/F/F “PeTtlasid SOAVIT 68/8/63 68/6/ZS 68/T/E% 88/Z1L/8% 8g/LT/0E 8e/0T/9% 8&/6/8% 8g/8/TE 88/2/13 88/9/62 88/G/SZ 88/F/LS 88/E/0E “TOQuUINN VOUd1OJOY ‘eoqoeiqAfod “q fo Ayuo sduyz ay} woul pajusy ‘| XIAVI, SLO apnig ay} fo sashjvup 67 ESSENTIAL OILS DISTILLED FROM EUCALYPTUS POLYBRACTEA. oOo nN kk © OO eH eH ett A SO re GN eH! Het! On “QUILOYIG Aq ‘0490 ‘souodig Ty, Ste ash j=) or) DBOnaArs Oo Ne) Kt ie) “pouyela [OS919-O Aq 9[oIulD 1D rb © a NN AN pr OOnNht AA HOON {0418 Rg) se poqeno[e9 souojayy pur sopAyeply TROL . Onsrie 9 se peqe[no[eg s[Oyoory TROL, rm me Ne) oOo & re ine) ao © AOOrmms tH HHO OS $8-0- o-0— 10= O1LIZ ZO-O+ 83-0+ OL-0+ #0-0+ 61-0+ 18-0+ WS Ve 60: 0+- 66-07 u014B)0% oyloadg OOEG- OOE6- 166: F8c6° 98G6- C86: ZLB6- 8126: ZLZ6- FFE °G-GT/G-GT AYABIN) oyioedg 0 0 0 0 0 0) 0) OL-0 ap) H \iealisbimlime! ina i =! i! “PLLA 99¥YUII10 6EF/9 6E/F/¢ 68/€/8 68/8/2 68/Z/% 6E/G/L 6¢/T/1T 68/T/OL 86/S1/2 8/Z1/9 8s/TL/¢s S8/TL/% 88/0T/2 88/0T/9 8e/6/2 8¢/6/9 R¢/8/E 8e/L/F 8g/¢/TS 8E/G/% 8e/8/TS PAIRS SSS “polltgsid SOAVOT 6€/¢/6Z 6E/Z/ZE 6/1/G% 8/Z1/8% 8¢/T1/08 8¢/01/9% 8¢/6/8% 8¢/8/TE 88/2/23 88/9/62 88/9/92 88/F/L3 88/8/8z qu) SOABOT *LoquIn NT VOUIIOJOY ‘INQ [DWsaWWUMOD JOULLOAT ‘BayoVIqATOd “Wy wWouf paz/Yysig sproQ apnsy 9y2 fo Sashjnup ‘II TH4VL 68 BERRY AND SWANSON. TABLE III. Phellandral Ketone and Approximate} Percentage Percentage Cuminal Percentage Terpene Terpene Percentage Oil in Crude Mixture of and and Cymene Percentage Number. Oil. (Percentage | Phellandral Cymene Cymene in Cymene (Actual in Crude in in Oil. Rotation Terpene in Oil. Recovery.) Oil.) Mixture. (Actual [o],)- Fraction. (Actual Recovery.) Recovery.) roe iL, Normal cut 0:52 0:74 5 PAO. +13:°3 46-7 1:0 28/3/88. Growing tips 0-59 0-40 12 5-2 4+11°5 38°7 2-0 gee: Normal cut 0-90 1:11 34 4-0 +9-0 29-0 1:2 BASE Growing tips 0:50 0:42 6 4:1 +11:8 21:5 0:9 25/5/38. : compounds is a dextro-rotatory terpene which has not yet been identified, but which definitely contains no appreciable amount of phellandrene. In this connection it is of interest to note that during the investigation of the oils distilled from the tips of HL. cneorifolia, dextro-rotatory terpene fractions were obtained from some of the winter oils (i.e. after growth had ceased). These responded only slightly to the test for phellandrene. A further investigation of this terpene will be carried out. Cymene is present in the oils in association with the terpene and constitutes approximately from 20-50% of the terpene fraction. Some evidence was obtained of the presence of keto-phenols in the oil. As will be seen from Tables I and II, cineole constitutes approximately 90% of every sample, the range over 26 samples being 86 -2°, to 92%, a remark- ably uniform result. Alcohols were also present, but no further work has been done on them. METEOROLOGICAL DATA. RAINFALL. Inglewood, Victoria. Average Monthly and Annual Rainfall. (In Inches.) Years. Jan. | Feb. | Mar. | April. | May. | June. | July. | Aug. | Sept. | Oct. | Nov. ; Dec. | Year. 51 years of record | 0:97 | 1-02 | 1:1 1-30 | 1-99 | 2°22) 1-73") 1-9 1:67 | 1-48 | 1-18 | 1:20 | 17-87 1937 ie .. | 1-74 | 0-60 | 0-19 | 1-31 | 1-10 | 0-67 | 0-34 | 1:59 | 0:96 | 3-17 | 0-23 | 1-138 | 13-03 1938 ae .. | 0:74 | 0:56 | 0-09 | 0-63 | 0-21 | 1-64 | 1-97 | 0-57 | 0-19 | 0-05 | 0°36 — 4 OL 1939 a .. | 0-93 | 4:86 | 0:40 | 3:03 | 2:84 | 2:53 | 1:34 | 2:29 | 0-93 | 1:63 | 3:06 | 0-32 | 24-16 TEMPERATURE. Bendigo, Victoria (the nearest town recording these details). Average Mean Maximum Monthly Temperature. Years. Jan. | Feb. | Mar. | April. | May. | June.| July. | Aug. | Sept. | Oct. | Nov. | Dec. | Year. 75 years of record 85:4 | 85:2 | 79-2 | 70-0 | 61:4 2 | 54:0 | 57-2 | 62-4 | 69-2 | 76: 81: 69-8 1937 oe .. | 78:3 | 84-2 | 79-9 | 68-2 | 60°5 | 56-4 | 54-6 | 60-3 | 63-2 | 71-6 | 80-9 | 80-0 | 69-8 1938 ies .. | 82:1 | 81-7 | 81:7 | 73-5 | 66-4 | 538-6 | 58-4 | 57-2 | 64-2 | 74-6 | 80-2 | 82-7 | 70:9 1939 ste .. | 91°6 | 86°38 | 77:0 | 67-8 | 62:2 | 53-2 | 5 54: 60:8 | 67-0 | 70: 77° 68-4 ESSENTIAL OILS DISTILLED FROM EUCALYPTUS POLYBRACTEA. 69 EXPERIMENTAL. Distillations. The distillations were carried out by Messrs. J. Bosisto & Co. Pty. Ltd. at their Richmond factory from material collected at Inglewood (Victoria). The leaves (average weight about 150 lb.) were delivered at Richmond the day after cutting, and the oil distilled as soon as possible by steam distillation. The time of distillation was 3} hours. The crude oils were analysed without further rectification, cineole being determined by the o-cresol method ; alcohols (cal- culated as C,)H,,0) by difference between the ester value of the oil and the ester value after acetylation ; aldehydes and ketones by the hydroxylamine method ; and terpenes by difference. Aldehydes and ketones were calculated as C,)H,,0, in conformity with our work on FL. cneorifolia oils (Joc. cit.). The ester values have not been calculated in terms of a particular ester, since the individual values are comparatively low ; the figures for terpenes, etc., therefore include esters. Examination of Individual Oils. As the method of separation and identification of the various constituents was the same for each oil, it will be sufficient to describe the general method, and a typical result. The following are the results for oil No. 5. The methods used for the separation of the various constituents are described previously (Berry, Macbeth and Swanson, loc. cit.). Crude oil, 1,007 gm. Extracted with 500 ml. of 35% Na,SO,;. Unabsorbed cil 994 gm. [a]p —1-2. Ketone recovered 9:0 gm., [a]p —43°. Identified by preparation of p-nitro- phenylhydrazone, m.pt. 168° C. (recryst. from MeOH); m.pt. undepressed by admixture with same derivative of authentic /-cryptone (l-4-isopropyl cyclohexen-1-one). The unabsorbed oil, after drying with anhydrous magnesium sulphate, weighed 911 gm., and was then distilled under a pressure of 2 mm., through a 50 cm. rod and disc column with the following result : Specific Specific Fraction. Weight. Temperature. Pressure. Gravity. Rotation 15°/15°. [a], g mi mm 1 116 40-44 y 0:9227 +1:43 2 or ay vs 468 44-48 2, 0:9239 +0:97 a Re oo ae 180 48-49 3 0:9258 +1:08 Still residues <6 130 — — 09649 —1-50 Loss .. cre Ae 17 | When treated as described before the still residues gave 7:1 g. of aldehyde A, [a]pn —31-3, and 3:0 g. aldehyde C, [«]n —40-2. These two aldehydes were mixed in alcoholic solution and treated with boiling 35% sodium bisulphite solution (Penfold’s separation). From the solid cake was obtained 4-0 g. aldehyde, [«]p +0. This gave a p-nitro-phenylhydrazone m.pt. 192-1938° C., recryst. from MeOH, which gave no depression of m.pt. when mixed with an authentic specimen of cuminal p-nitro-phenylhydrazone. The aldehyde oxidised rapidly in air, and after purification and recrystallisation from dil. acetic acid, the acid so obtained melted at 117° C. (cuminic acid). From the bisulphite solution of the above separation was obtained 3:0 g. aldehyde, [a]p —66-7°. This gave a 2:4 dinitro-phenylhydrazone, m.pt. 201-202°C., recryst. from ethyl acetate; mixed m.pt. with authentic /-phellandral derivative showing no depression. The remainder of the aldehyde was oxidised to the corresponding unsaturated acid, m.pt. 144° C., recryst. from aqueous MeOH; [a]p —103 (c., 2:05 in MeOH), which are the constants for l-phellandric acid. Twenty per cent. of the combined terpene fraction, treated as described before, with the modification that it was mixed with twice its volume of petroleum ether before shaking with resorcinol solution, gave 7:3 g. of terpene and cymene. This had [«]p -+9-0 for the mixture and gave no precipitate in petroleum ether solution when treated with nitrous acid at 0° C., 70 BERRY AND SWANSON. thus indicating absence of phellandrene. From this was obtained 2-1 g. of cymene, optically inactive, which on oxidation with hot aqueous potassium permanganate gave the characteristic p-hydroxyisopropyl benzoic acid, m.pt. 156-157° C. Separation of Phenols, etc. The crude oil was shaken twice with 40 c.c. of 5% NaOH, and twice with 50 c.c. of water. The combined extracts were shaken with ether to remove adhering oil and then acidified with 3N sulphuric acid in the presence of ether. After drying and removal of ether the alkali-soluble fractions were recovered. To attempt a separation of these fractions, the above material was dissolved in ether and shaken with 5% sodium carbonate solution (‘Trikojus and White, Proc. Royal Soc. N.S.W., 1932, 66, 279). From the ether an oil was recovered, and by acidification and extraction of the sodium carbonate solution in the usual way with ether a second oily fraction was obtained. Neither fraction as prepared above gave definite colour reactions characteristic of australol (Earl and Trikojus, Proc. Royal Soc. N.S.W., 1925, 59, 301) or “‘ Tasmanol ”’ (loc. cit.) with alcoholic ferric chloride, and an attempt to prepare the benzoate of the portion soluble in NaOH only, yielded a non-crystalline gum. Both the fraction soluble in sodium carbonate solution and the fraction soluble in sodium hydroxide solution were examined to determine if they contained any of the keto-phenols reported by Reuter (Jour. and Proc. Aust. Chem. Inst., 1938, 5, 291). It was noticed that the fraction soluble in NaOH gave a blue-green colour with alcoholic ferric chloride and reacted with 2: 4 dinitro-phenylhydrazine to give a precipitate, m.pt. 125° C. The fraction soluble in sodium carbonate gave no precipitate with the above reagent and appeared to be chiefly a mixture of liquid acids. This result would appear to confirm that of Reuter (loc. cit.) that keto-phenols are present in the oil of this species. We wish to thank Professor A. K. Macbeth, who suggested this investigation, and under whose direction it was carried out; also Bosisto & Co. Pty. Ltd. for collecting the material and distilling the oils. One of us (T.B.S.) is indebted to the Commonwealth Government for a Federal Research Grant which enabled him to complete the work. Johnson Chemical Laboratories, The University of Adelaide. New England University College, Armidale, N.S.W. THE JURASSIC FISHES OF NEW SOUTH WALES. By R. T. WADE, M.A., Ph.D. (With Plates II, III and 8 Text-figures.) (Manuscript received, April 23, 1941. Read, June 4, 1941.) THE COLLECTIONS. In 1895 the Geological Survey of New South Wales published a description by Smith Woodward of a collection, of fossil fishes from a locality near Talbragar Creek, north of Gulgong, New South Wales.” The greater part of this collection, and one made by the late John Mitchell are housed in the Australian Museum, Sydney. In 1936 and 1939, with some financial assistance—now gratefully acknow- ledged—from the Council for Scientific and Industrial Research, I was able to visit the field and collect not only specimens of most of the recorded species, but also several specimens of a new Macrosemiid. LOCALITY AND AGE. The fossils were found at Farr’s Hill, Uarbry Road, about 16 miles from Gulgong, but the beds are best approached from the Mudgee-Cassilis road, through Bobadean Station, situated about 3 miles from Farr’s Hill. The age of the beds is discussed by J. A. Dulhunty.™ THE CENOGENOIDEI. Under this head are grouped the fishes Atheolepis, Archwomene, and Aphnelepis of Smith Woodward.) He provisionally assigned = numerically. We Hence the total frequency is approximately (27) 2(% 1) ant 8 te — Aon Ae ua VPn cas with limits of integration as shown above. n eee sek ee Since S(x) =0 we have t,4/m,+tov/met .. .-+tnr/mn=0 ....-.-- -- (7) 1 Take (n—1) new variables, viz. el ee te Ma oda ge, Us /M,+Met....+tmn_1 (6, +te/me+ +tn_1vVm : —2 and V,, Vg,----Un_2 forming an orthogonal set so that ‘8 (02) an (Cee u Oh dine ct (Oh n From (7) and (8), %/N —mp=tnr/mMn, tn? =(;- 1) -—2 ad n n 1 v2 n-2 Hence S(t?)= 8 tovn(d —1) opt + SEOs Ri een Aen ae eee) 1 ty Pn Pint A The jacobian is +1. Hence the integral (6) becomes {fee A(/+/Pn) - 1 Bd Bea aa | ee tone far Af 27 /2t with appropriate limits corresponding to those of (6). Therefore v //pn, V1,----Un_»g are statistically independent standard normal variates. We may examine these (n—1) variates by various methods, including the two methods referred to at p. 85. n 2 First we may say that the sum of their squares, which by (9) is S (=) 1 n 2 at IS & Y¥n_3", le. that (5) is a Gamma variate o(" 2 whose c.f. from a 1 41) E.P., pp. 215, 230. 90 GOODNESS OF FIT OF HYPOTHESES AND PEARSON’S y? TEST. oO n—1 3 SS el : particular value u to oo is ean: ria du. By putting 4y? for | Bal (pees 2 u, this integral takes the form in which it was originally written in 1900 by Karl Pearson. But, as pointed out at p. 85, there are also (n—2) Beta variates (or corresponding ¢ variates) to be examined before we can be satisfied ae the “goodness of fit’ of the hypothesis which may be indicated by the ;? test alone. Secondly, we may proceed by the more direct method illustrated at pp. 85, 86, and in order to do so it is necessary to specify all members of the orthogonal set. aaa Re Rests i2e AS % = (41M HH Met -- -» +tn_1V/Mn_1) 4/N —my rie es we may choose vp=—ky(Crtrs/myt .. .. +tp_1+/mn_1) where 0=¢rmr+mMyi4+----+Mp_1 and ky=(Cr*My +Mriy + tee +mn_1)7?. 0) Now replacing ty by #;/4/my and briefly writing S(x) for S (as), we have fe SON Ja =| Se - “Go mse For the first of the standard ae roe we ee from (7) and (8) Be REL eS VPn WV Pn(N —mn) VNPodn Already my has been referred to one of the larger cells and we may now refer m,, M,, .--- to those cells which show the more questionable values of a/4/m. From (10) it appears that when there are many cells, as in the following -1 (10) where @n=1— pn .: -- >). (2) n— example, v, does not differ greatly from 7,/ 4/M, as Hi S (ms) is usually small ; likewise for further early members of the orthogonal cob The following table (p. 91) is based on results of 1,000 observations made at Greenwich of the Right Ascension, of Polaris, tabulated i in Whitaker and Robin- son’s Calculus of Observations, 1924, p. 174. The first three cells, also the last two, as there given are combined, so that for no cell is m less than 25. As the parameters of the normal curve ‘fitted to the data, viz. mean 0-06, standard deviation 1-2, are evidently not derived from these particular observations, the number of statistically independent standard normal variates arising from the fitting is one less yoru the number of cells considered. The table shows the usual 2 calculation of 8(— —}, also the values of =e — om) and of the earlier members of the ae set. : From the 5th column the value of y,,)2 as usually computed is 14:1. As the frequency of larger values is about 0-17, the observed value is regarded by the usual reasoning as not lying at a “ high level of significance ”. (It will be seen in §IIT that this reasoning is not valid, and that the observed value really lies at an even lower level of significance than thus appears.) 2). b>), pareou. T. SAWKINS. 91 (1) (2) (3) (4) (5) (6) (7) (8 (9) Chosen Ai! x (1 x ae Order of a m x ™m Pa \\ a any x” aa v Cell. f/m 39 34:0 5:0 0:74 0-1 5:5 0:94 43 45-3 —2°3 0-12 —3:0 | —0-45 74 81:8 —7°8 0:75 —0:-1 —8:°5 | —0:-94 126 121-5 4-5 0-17 5:0 0-46 150 153°8 —3:8 0:09 —4:5 | —0-36 ia 168 166-2 1-8 0-02 2-5 0-19 0-22 148 147-6 0:4 0-00 1:0 0-08 2 129 111-9 Ly 2-62 17-5 1-65 1-58 78 72-4 5:6 0°43 0-1 6-0 0-70 33 38°4 —5°4 0-76 —0:-1 —6:0 | --0°97 1 12 27-1 | —15-1 8:40 1-0 --15:5 | 2-98 |—3-01 1000 1000-0 0-0 14:1 1-0 0-0 In column (7) the value of x’, the mean deviation used in Chesnais expression (6), is found by increasing the observed deviation numerically by 4 and forcing this result to the nearest half unit, except in the case of the largest cell, chosen aS No. 11, which is adjusted so that S(u ‘)=0. In column (9) three of the ten independent standard normal variates an shown, these being more than enough to show that the inference from the value of y,,)? is quite misleading. The value of v), derived from cell 11, is =0:22. From / (166 -2 x 0 -8328) —15-5 4/27-1(—2-5+15-5) Silane a a7 © 10001662271 (1 Sue =—3-01, and so does not greatly differ from x’,/1/m,, as anticipated. Now the frequency with which a set of ten statistically independent s.n.v. contains one or more members as large numerically as 3-01 is 1—(0-9974)!9= 1 —(1 —0-0026)!°—0-026 approx. So in spite of the y? test the normal curve with the above parameters fits this set of observations badly. The argument of the last paragraph will be made quite conclusive if we consider for the suspected cell, viz. cell 1 in the chosen order, the range 13 to 41 and so exclude the observed number 12. The corresponding value of v, is then —2-89 instead of —3-01. To include the observed number 12 we must increase the range of v, beyond +2-89; the frequency with which one or more among a set of ten s.n.v. take values beyond this range is 0:04. Hence the fit is bad. A case when there are several cell numbers whose combined presence makes the fit suspect is aS shown in the table on p. 92. Here in cells 1, 2, 3 (chosen order) the observed number is brought nearer by one to the mean number for the cell; «’ and v are computed as above and equation (10), n=] 2 2 — as usually. As 8 =13-2, a value of y,)? which is exceeded with the frequency 0-2, the fit is held by the usual reasoning to be tolerably good. On the other hand, there are three among ten independent s.n.v. numerically exceeding 1-75, an event with the frequency 0:04. So the fit is bad. 92 GOODNESS OF FIT OF HYPOTHESES AND PEARSON’S y? TEST. Chosen Observed | Considered ac’ a Order. Number. | Number. ™m a’ 4/m v ™m 39 39 34-0 5:5 0-94 0-74 43 43 45-3 —3:0 —0:45 0-12 3 65 66 81-8 —16°5 —1-82 —1-78 3°45 126 126 121-5 5:0 0-45 0-17 150 150 153-8 —4-5 —0-36 0-09 11 168 167 166-2 1-5 0-12 0-13 0-02 149 149 147-6 2-0 0-16 0-01 2 132 131 111-9 19-5 1-84 1-87 3-62 78 78 72-4 6-0 0-71 0-43 33 33 38-4 —6-0 —0:97 0:76 1 17 18 27-1 —9-5 —1-82 —1-84 3-76 Total af 1000 1000 1000-0 0-0 13-2 In a large number of cases the goodness of fit can apparently be well judged 2 by inspection of the column 2’/,/m without computing v, or S (7): III. CONFIDENCE RANGES. Exception was taken in SII to the practice of considering a single tail of a skew distribution such as that of y,)” in estimating the “ significance ’ of an observed value. It is proposed now to show that this practice is fallacious. A confidence range is defined as a range of values of the variate such that every possible value of the variate within this range has a greater frequency than every possible value without this range. If the frequency curve is drawn for a continuous distribution fading on both sides of its mode, any parallel to the variate axis cutting the curve gives two values of the variate 7,, 7, at which the frequency densities are equal, and the range of values from «, to x, is a confidence range, whether the curve is symmetrical or not. In a positive J-shaped distribution the range of values up to any value x is a confidence range. Let us first consider the estimation of significance in the case of a discrete variate. Suppose that a variate used to form a judgment of the validity of an hypothesis which may be true or false, takes only integral values (#) with D. T. SAWKINS. 93 frequencies (f) aS shown in the adjacent table. Successive confidence ranges are 8 (single value), 8 and 9, 8 to 10, 8 to 11, 7 to 12, 7 to 13, etc. Suppose a single experiment or trial 2x f leads to the value 8. Only one value can occur. Whatever the frequency of the value 8, the governing considera- ~~ tion is that it has a greater frequency than any other value. 6 0-02 Hence our confidence in the hypothesis is not at all disturbed. 7 0-08 Suppose the experiment gives the value 7. Although this 8 0-25 value occurs in the long run in only 8 per cent. of such experi- io 0-22 ; ; ; 0-18 ments, values which occur more frequently, viz. those in the ll 0-10 confidence range 8 to 11, occur in only 75 per cent. of trials. 12 0-08 This confidence range then is not very exhaustive, for values 13 0-05 outside it occur in as many as 25 per cent. of trials. As 7 If 0-02 occurs in the long run not less frequently than any other of these outside values, its occurrence on this occasion would not commonly be regarded as very surprising. Total 1-00 If the experiment leads to the value 12, no more and no less doubt is engendered than by the occurrence of 7. Either value may be said to lie at the “‘ 0-25 significance level ”’. But, using one end of the distribution, it is often said that as values as high as or higher than 12 have the frequency 0-15, therefore 12 is at the “0-15 significance level’’. The implication is that the frequency 0-15 supports the hypothesis while the remaining 0-85 is against it. The fallacy lies in thus setting 7 against 12 whereas these two values have equal frequencies, in setting 6 against 12 whereas 6 has the lower frequency, and so on. Likewise it is argued that as values as small as or smaller than 7 occur with a cumulative frequency of 0:10, so 7 is at the “0-1 significance level’”’. Both statements are false, the correct statement being that either 7 or 12 is just outside the 0-75 confidence range, or that either lies at the “ 0-25 significance level ”’. In the case of a continuous J-shaped distribution such as that of y,? or of x5”, in which the frequency density is greatest at the value zero of the variate and continually diminishes as the value of the variate increases, the range from 0 to any value of the variate is obviously a confidence range, and the total frequency of values exceeding that value may validly be referred to as the “ significance level ’’ corresponding to that value. But this is not valid for a continuous distribution which fades at both ends. For example, in a standard normal distribution, values exceeding +1-96 have the frequency 0-025; values from —1-96 to +1-96 form a confidence range with total frequency 0-95 ; values outside this range have the frequency 0-05; and either +1-96 is correctly said to lie at the 0:05, but not the 0-025, “‘ significance level ’’. In a symmetrical distribution the limiting values of any confidence range are equal and opposite; but in a skew distribution, when one limit is given its companion, is not found so readily. The frequency density at the value wu of the Gamma variate 4 49?=c(5) is Fert 8 If 14 is an observed value of X10" and so 7 is the corresponding observed value of ¢(5), it can be found (con- veniently with a slide rule having a log-log scale) that the f.d. at 2 is about the same as at 7 and thus that 4 to 14 is a rough confidence range for 7492. The frequency of values of y4)2<4 is about 0:05, and of values +14 about 0-17. Hence either 4 or 14 is at the 0-22 significance level. For sums of squares of larger numbers of statistically independent s.n.v. Such a8 yz)", the error in estimating “‘ significance’? from one end of the ‘“ probability integral ’’ continues to be important—if importance is to be a9) E.P., p. 217. 94 GOODNESS OF FIT OF HYPOTHESES AND PEARSON’S y? TEST. measured by the current demand for great accuracy in these matters. For example, the values 18-5 and 40 of y9? have about the same f.d. and form a confidence range. On reference to a table of yg? it is sometimes said that 40 is at the 0-10 significance level nearly, and that 18-5 is at the 0-05 level nearly, whereas either is at the 0-15 significance level, and this gives a quite different basis for either confidence or doubt. In the same way it follows that the widely used tables of the Variance Ratio (Fisher’s 2 and e?4 or Ff tables)” in which, for example, the “‘ upper and lower 5 per cent. points ’’ correspond to the two tails of the same Beta distribution,‘ are liable to the same kind of misinterpretation. For example, when the argu- ments of these tables, n, and n,, have equal values, then instead of “5 per cent.”’ we should read “10 per cent.” But when n,n, it will be clear from the preceding paragraphs that we shall often need to use a multiplier larger than 2 to convert to a true significance level the apparent level derivable from these tables. We may now test the efficacy of the device of using opposite cell numbers in producing confidence ranges by applying the analysis of y? in §IT to a simple binomial frequency distribution. A supposedly random sample of 103 individuals is drawn from a very large population in which the proportions of black and white are said to be 10 per cent. and 90 per cent. The sample is found to contain 15 black and 88 white. Here there are two cells only and m,=10-3, m,=92-7; 1/m, and 1/./m, are O(0-1). We (tentatively) neglect this order. By (11) the frequency with which «, ranges from 14 to its opposite number 7 (the sum of these being the nearest integer to 2m,) is to be found approximately by taking 7,=—14-5—10:3, xv’,=4:0, and therefore xv’,—=—4-:0, whence we have opposite values of the ee 4-0 1/M oo 3+/1:03 | will just exclude the observed value 15. From the normal table the frequency of values in this range is 0-811 and of values outside it 0-189. Examining the frequencies of individual values in the appended table of (0:9+0-1)!°3, we see that 7 to 14 is a true confidence range, and also that values outside this range have the frequency 0-101+0-88=0-189. For another example, suppose a sample of 102 contains 16 black. Here m,=10-2 and from the opposite numbers 15 and 5 we find a’,=—5-5; the S.n.v. has the range +1:815, and the frequency of values outside this range is 0-070. Comparing this with the binomial table of (0-9-+0-1)!° we find that 5 to 15 is a true confidence range and that the frequency of values outside it is 0-021+0-046=0-067. (In this case one would be disposed to doubt either the technique of sampling or the reputed proportions.) In these examples the small cell has a mean number as low as 10 nearly, while the large cell, postulated for the argument of §II, is only moderately large, its mean number being about 90. Yet the device of opposite numbers provides results which are approximate enough for practical statistical purposes. HExcep- tions occasionally occur near the centre of the binomial distribution; for example, the opposite numbers 9 and 12 in a sample of 103 do not form a true confidence range. This would tend to make the reasoning uncertain in the case of several small cells showing observed numbers very near to the mean numbers. These binomial examples may, of course, also be solved by forming the value of y,*, which gives a solution equally critical with that already found, for here there is but one s.n.v. to be considered. Thus in the first case, the $.0.V. =-+1-314 to determine a confidence range which (14) Fisher and Yates, ‘‘ Statistical Tables ’’, Oliver and Boyd, 1938, pp. 30, 31. 15) .P., pp. 236, 237. —— D. T. SAWKINS. 95 frequency with which the number in cell (1) is outside the range from 14 to its opposite number 7 is approximately the frequency with which y,? exceeds (4-0) (4:0)? (4-0)? 10°3 © 92-7 10°3x0-9 x,” table,“ or, as it is the f. with which the s.n.v. is outside the range =1-726. This frequency may be found from the aa from the normal table as already computed. /10°3 x 0-9 Table of Binomial Distributions. (0-9-+0-1)1 (0:9-+0-1)10 (0-9+0- 1) j (0-9+0-1)15 % ub f ip ii 2 2 2 2 1 3 6 5 5 4 4 16 14 13 12 5 34 32 29 26 6 60 54 52 47 7 89 83 80 74 8 115 109 107 102 9 130 127 125 122 10 132 131 131 130 11 120 122 123 125 12 Se) 103 105 108 13 74 us 82 86 14 51 56 58 63 15 33 37 38 43 16 19 22 23 26 17 11 12 118) 15 18 3) 6 i! 8 19 2 3 4. + 20 1 2 2 2 21 l 1 1 1 22 — — — 1 Total Ets 1000 1000 1000 1000 6) Yule and Kendall, Theory of Statistics, 1937, p. 535, Appendix, Table 4B. P i 4 ot <— \ —— emer II ‘ i 5 ; —- 5; i on y \ * ' i) a e y ‘ EDICAL PUBL _ A tye, NER M N LASIA ‘AUSTRA ER Oe & Mm Be ate th ot Ake i . a eS PART I A ae AND PROCEEDINGS | Pade? vom. ene core i es eh a j 3 . if = | i: ee : FOR Baie cad Caetngs | oe oy EAE "(INCORPORATED 4881) PART III (pp. 96 to 129) oe VOL. LXXV ee ain 1g Papers: read in August, September and October, - ae wees with Plates IV-VI_ Py Ba 4s te oR TS ee i . : Ce - ‘ ise =< R dub EDITED BY THE. HONORARY SECRETARIES — AEONIAN INSFF ° wag 30.1543 NA STIONA C puses™ : BAL. SEDNEY a "PUBLISHED BY THE SOCIETY, SCIENCE HOUSE | GLOUCESTER AND ESSEX STREETS y 1942 u Pe Art. XIV.—The Chemistry of aacaient” ‘ond aiivelouy® Rhodium. Part ‘ L fe CONTENTS. : : Part III oe «ae Ar. IX. LUpaanan Blastoids aa New South Wales. eonaae October 27, egos Ihe eters ie Balan ent pay eae es aon ae ART. gee from the Silurian and Devonian oe New South Wales. By Joan _ Crockford, B. ES (Issued November: 27, 1941.) ae oe a ae Ph.D. _(issued | November 27, 1941. ). ; Cet ae kg A. Bolliger, Ph. D., and c. R. Austin, MSe, BYSe. November 27, 1941.) .. .. os Togtbranone tic Cua em sen meer vats ae ArT. XIII —The Chemistry of Bivalent ‘and rivalent: ‘Bhoditin® ; vans “st ey, Qualitative Study of Trivalent Rhodium Salts; and the Properties of. ‘Some Rhodous Salts. By F, he Se _ Dwyer, M.Sc., ae pe 8. aM ener, Be i aes oh ener 1942.) eM aey Zi tone yi ahs Roe PORT we gene gh nee I au mayen Care cri a ne Sa es Bs 7 ee ie = Hexacovalent Complexes of Rhodous Halides with Pipheny inet a Oh Cas es Dwyer, cine and R. ae eee B.Sc." dae baci ie f : ft it : i 2 ~ . ‘ j + , x / 7 ‘ % i oo f oe e nee ¢ % hay hat . . : ; é oo Ph pene ‘i oy ‘ ¢ alge re : gi 4 ¥ : is : Ve x \ BS : pee - % A Ly % z 1 pag ? 2 A ‘ ; F “ee Nad ri Fc 1 i “ee - at y gz / +4 Eye ¥ . : - on 7% n < Von - ee y 4 mk \ z ee - i Bre. } Shy , Pi af ~ a | foe \ . 7 Gn Journal and Proceedings of the Royal Society of New South Wales VOLUME LXXV PART Ill PERMIAN BLASTOIDS FROM NEW SOUTH WALES. By Ipa A. BROWN, D.8c., Department of Geology, The University of Sydney. (With Plate IV and two text-figures.) (Manuscript received, July 23, 1941. Read, August 6, 1941.) Abstract—The paper describes three species of blastoids (two regarded as new) from the Fenestella Beds of the Upper Marine Series (Permian) of the Hunter River District of New South Wales. At least two of these appear to be congeneric with forms from the Basleo Beds of the Permian of Timor, N.E.1. INTRODUCTION. Examples of recognisable Pelmatozoa are very rare in the Paleozoic rocks of New South Wales. No cystoids are recorded, few blastoids and relatively few crinoids. It is therefore interesting to find specimens of three blastoids, which are possibly congeneric with forms occurring in the Basleo Beds of the Permian of Timor, Netherlands East Indies. The paper deals with three species belonging to three genera, Family CODASTERIDZ Eth. and Carp. Notoblastus brevispinus gen. et sp. nov. Family PENTREMITID d’Orbigny. Calycoblastus casei Sp. Nov. Rhopaloblastus (7) belfordi (Crockford and Brown). Each species is represented by a single specimen. The first, Notoblastus brevispinus gen. et sp. nov., was collected by A. H. Voisey in February, 1941, in a rock specimen exposing only the basal plates, which, on development, yielded a complete specimen. The second, Calycoblastus casei sp. nov., was discovered by E. C. Case of Ann Arbor, in 1923, during a visit to this country, and it was mentioned by T. W. E. David‘) (p. 19), but was subsequently lost. A brief description of it has already been given (Crockford and Brown'")) based on a plaster cast and photographs of the original specimen. The latter has since been found in the Geological Museum, University of Sydney, and shows certain features not discernible in the cast or photographs, which permit of its more detailed descrip- tion and its identification with a genus from Timor. An isolated radial plate of the third species was described in the same paper (Crockford and Brown'?’), but its relation to another genus occurring in Timor, Rhopaloblastus, is suggested here. Since no specimens from the Basleo beds of Timor are available to me for examination, comparisons are based entirely on the descriptions and illustrations in papers of J. Wanner.‘!® 17.18) The first species is particularly interesting ‘ar - 3 18 PERMIAN BLASTOIDS FROM NEW SOUTH WALES. 97 morphologically in showing features that Wanner"® (p. 185) points out are particularly characteristic of the Permian blastoids of Timor, viz. : (1) The lengthening of the radials or interradials into arm- or wing-like projections. (2) The retreat of the ambulacra towards the peripheral parts of the “rays.” (3) The division of the posterior deltoid into a hypo- and epi-deltoid. GEOLOGICAL AGE. The specimens come from localities twenty miles apart, but all occur in the Fenestella Shales, a bed about 70 to 100 feet in thickness, in the Branxton stage of the Upper Marine Series, which was mapped by L. J. Jones (1932) and found to be consistently 1,500 to 1,600 feet above the Greta Coal Measures. The Upper Marine Series forms portion of the Permo-Carboniferous or Kamilaroi System (David and Sussmilch,‘* p. 483) of the Hunter River District, New South Wales, which is very fossiliferous on certain horizons. Few, if any, of the species, however, occur outside Eastern Australia, so that correlations are based on general considerations, occurrences of glacial beds, etc., rather than on specific identities in the faunas. The Series occurs between the Lower (or Greta) and the Upper Coal Measures, both of which carry a Glossopteris flora. The Upper Coal Measures have yielded a Labyrinthodont, Bothriceps major A. Smith Woodward,‘!*) regarded as Upper Permian by David (‘ p. 67), and the probable Upper Permian age of the Upper Coal Measures is also indicated by the fairly rich insect fauna described by Tillyard (in David,” 1932, p. 68). The age of the Basleo Beds of Timor has been discussed by several writers, including J. Wanner,"® J. Perrin Smith,“* H. A. Brouwer® and De Marez Oyens,'®) and there appears to be consensus of opinion, based chiefly on the occurrence of ammonites, that “the fauna of Basleo agrees fairly well with that of Sosio in Sicily and that of the Word Formation in Texas, in all three regions characterized by the occurrence of Waagenoceras’”’ (J. P. Smith), A. K. Miller?*) has reviewed the stratigraphical significance of all Permian genera of Ammonoids in the Sosio Beds, Sicily, and concludes: ‘‘ The Permian Sosio beds of Sicily represent a paleontological zone that is slightly but very distinctly younger than the cephalopod-bearing sandstone of the Artinsk group of the Ural Mountains’. He also correlates the Sosio beds with those of Basleo, Timor and the Word Formation of Texas, stating their age to be “ almost certainly Middle Permian ’’. In a later paper on “‘ Comparison of the Permian Ammonoid Zones of Russia with those of North America ”’, A. K. Miller“* places the Word Formation, Texas, with Waagenoceras, in the upper part of the Middle Permian. He regards the Artinskian as lower Middle Permian. In his classic paper “ The Type Permian: Its Classification and Correlation ’’, C. O. Dunbar“) places the Word Formation, Texas, on the basis of the Fusuline zones, in the upper part of the Parafusulina zone, and correlates it with the Kazanian Beds of the Permian of the U.S.S.R. Unfortunately no fusulinids and only a single specimen of an unidentified ammonoid (Etheridge,'®) p. 36) have been found in the Upper Marine Series in New South Wales. The occurrence of similar peculiar blastoids in New South Wales and in Timor suggests correlation of the beds in which they occur. Thus it is suggested that the Fenestella Beds in the Upper Marine Series are approximately equivalent to the Basleo Beds of Timor, and through them are to be correlated with the Sosio Beds of Sicily, the Word Formation of Texas and the Kazanian of the type Permian sequence. H—August 6, 1941. 98 IDA A. BROWN. DESCRIPTION OF SPECIES. Phylum ECHINODERMATA. Class BLASTOIDEA. Family CODASTERID& Eth. and Carp., 1886. Genus Notoblastus gen. nov. Genotype: Notoblastus brevispinus gen. et sp. nov. 14 miles south of Kitchener, near Cessnock, N.S.W. Diagnosis: Theca discoidal, pentagonal in outline. Basal cycle, almost flat, pentagonal in outline, consisting of three plates. Radials, five, sharply folded back on themselves at the equator; sinus short, on the upper surface only. Deltoids, five, on the upper surface only. Slightly domed. Posterior deltoid divided into an epi-deltoid and hypo-deltoid, the suture passing across the anal opening. Ambulacra on the upper side of the theca, sub-petaloid, and slightly elevated above the general surface, situated at some distance from the mouth. About 20 side-plates on each side of an ambulacrum. Hydrospire folds cross the radio-deltoid sutures, usually 12 to 14 on each half-suture but apparently none on the radial-hypo-deltoid sutures. Spiracles absent. Mouth central, small, pentagonal. Food grooves radiate to the ambulacra. Anal opening, elliptical and slightly elevated. Notoblastus brevispinus gen. et sp. nov. Plate IV, Figures 1-3, Text-figure 1 (a, b, c). Holotype: Australian Museum, F.39762. Locality: Quarry, 14 miles south of Kitchener and 44 miles south of Cessnock, New South Wales. Horizon : Fenestella Shales, Branxton Stage, Upper Marine Series, Permian. Only known Specimen is an almost complete theca, collected by A. H. Voisey, 1941. Description. The specimen is a cast in fine sandy shale and has probably been subjected to a certain amount of crushing. Theca very much flattened, pentagonal in outline, the angles being drawn out into short spines. Diameter of theca 30 mm., thickness now from 5 to 7 mm., probably originally more than this. Basal cycle consists of three plates, one small and two larger plates, pentagonal in outline, a ridge running from the centre to each point of the pentagon. Finely striated parallel to the outer margin. Basal plates 5 to 10mm. in length. No trace of any stalk. Radials, five in number, each about 17 mm. in width and 15 mm. in length. The body of each radial is about 10 mm. in length and the limbs 5 mm. The radials are almost doubled back on themselves at the equatorial margin of the theca, and are also drawn out into solid spines up to 3 mm. in length, at the ends of the radial sinuses. Radial sinus short and completely filled with plates of the ambulacra. Deltoids, five large plates, each quadrilateral and convex upwards. The posterior deltoid divided into an epi-deltoid and a hypo-deltoid by a suture which runs across the anal opening. Ambulacra, five, petaloid. They commence about one-third of the radial distance from the mouth, equal lengths being situated between the deltoids and in the radial plates. They do not extend on to the spines. Connected to the mouth by a food groove. The ambulacra stand up above the surface of the theca. Lancet plate not visible, completely covered by the side-plates, which are arranged alternately on either side of the central groove. There are about PERMIAN BLASTOIDS FROM NEW SOUTH WALES. 99 (b) one 10 20 30mm. Text-figure 1.—Noloblastus brevispinus gn. et spn. X 2. Diagrammatic sketch to illustrate structures. (a) Oral view, (b) aboral view, (c) view of posterior side. amb., ambulacrum (pseudambulacrum), with food groove ; s.p., side- plates; O, mouth aperture; A, deltoid; HA, epideltoid; HA, hypodeltoid; R, radial; h, hydrospire-folds; B, basal; As, anal opening. 100 IDA A. BROWN. 20 side-plates on each side of each ambulacrum (40 in all). Length of ambulacrum is 10mm. Length of the side plates: those nearest the mouth about 2-5 mm., those remote from the mouth less than 0:5 mm., inclined to the axis at angles of 50° and 70° respectively. No outer side-plates can be discerned in the specimen. The anal opening is oval in shape, 1-5 mm. by 3:0 mm., situated two-thirds of the radial distance from the mouth, lying between the epi-deltoid and hypo- deltoid. Mouth central, small. Hydrospire folds appear to be represented by a number (14 to 19) of narrow slits which cross the radio-deltoid sutures, and which resemble those in the pectini-rhombs of certain cystoids. Resemblances. Notoblastus brevispinus resembles the Indoblastus granulatus Wanner in the general arrangement of the plates, although it differs somewhat in shape, and in the occurrence of short, radial spines. From Péerotoblastus gracilus Wanner it differs in general shape, in the position of the ambulacra, the arrangement of the spiracles, and the division of the posterior deltoid into an epi-deltoid and a hypo-deltoid. It differs from Thaumatoblastus spp. Wanner in the length of the spines, the situation of the ambulacra, and the number, shape and arrangement of the side-plates. Thaumatoblastus is known only by small fragmentary remains and better material may show closer resemblance to the species under consideration. Family PENTREMITID d’Orbigny. Genus Calycoblastus Wanner. Wanner, J., 1924.—Palaontologie von Timor. XIV Lieferung, XXIII Die Permischen Echinodermen von Timor. II Teil, Stuttgart, 1924, pp. 35-40, Taf. CCI, (3), fig. i1-tb; Genotype: Calycoblastus tricavatus Wanner. Nordabhang des Somohole bei Soefa, Timor, East Indies. ‘Diagnose: Th knospenférmig, am Scheitel zusammengezogen, an der Basis triedrisch, trichterférmig. Querschnitt der Peripherie sub-pentagonal. RR lang und schmal, die Aste viel langer als der Kérper. DD klein, aber auf der Aussenseite der Th sichtbar. Ambulakra linear, im Sinus nur schwach eingesenkt. Lanzettstuck aussen ganz von den Seitenplattchen, innen von den Hydrospirenplatten bedeckt. Zahl der Seitenplattchen etwa 60. Spirakula 10, von Deltoid- und Seitenplattechen begrenzt ; das hintere Paar anscheinend mit der Analoffnung vereinigt. 5 Hydrospirentaschen auf jeder Seite des Ambulakrums.”’ Calycoblastus casei Sp. NOv. Plate IV, Figure 4, Text-figure 2 (a, )). Blastoid. T. W. E. David, 1923.—Pan-Pacific Science Congress, Australia, 1923. Guide-Book to the Excursion to the Hunter River District, footnote, p. 19. Blastoid. J.M. Crockford and I. A. Brown, 1940.—Proce. Linn. Soc. N. S. Wales, 1940, 65, p. 168, text-fig. 1, plate IV, figs. 4, 5. Holotype. Australian Museum, F.39408. Locality: Railway cutting, one mile west of Branxton Railway Station, N.S. Wales. Horizon: Fenestella Shales, Branxton Stage, Upper Marine Series, Permian. Only specimen known, a cast in fine ferruginous sandstone, collected 1923, by Dr. E. C. Case, in whose honour the species is named. PERMIAN BLASTOIDS FROM NEW SOUTH WALES. 101 Description. Theca imperfectly preserved, bud-shaped, about 55 mm. in height; maximum diameter at the base of the radial sinuses, 41 mm. by 26 mm.; equator about half-way between the base and the mouth. Cross- section pentagonal, two straight and three concave sides. Basal cycle, probably trigonal, the smaller basal (17 mm. long) and portion of one of the larger basals only visible. Funnel-shaped. Radials, five; each about three-fourths of the height of the theca, convex, 40 mm. in length; ratio of the body to the limbs varies from 20 : 20 to 20: 25. Interradial sutures straight. Sinus approximately half the length of the plate, with parallel sides, bordered on either side by a narrow triangular bevel, similar to that shown by Wanner for Calycoblastus tricavatus. In vertical section the sinus makes an angle of approximately 120° with the body of the radial. SA On a O 1O 20 3 40mrn. Text-figure 2. Calycoblastus casei sp.n. Diagrammatic sketch to illustrate structures. x1. (a) Side view, (b) oral view. amb., ambulacrum (pseudambulacrum) ; s.p., side-plates ; O, mouth aperture; /, deltoid; R, radial; h, hydrospire folds; S, spiracles ; B, basal. Deltoids, five, small, 6 to 7 mm. in length. Radio-deltoid suture convex upwards, so that the shape of the deltoid is a triangle with a concave base. The posterior deltoid, whose position is only partly preserved, probably contained the anus. Ambulacra, five, from 25 mm. to 30 mm. in length, and of a uniform width of 3 mm. to 4 mm., in grooves 1 mm. to 2 mm. in depth. No side-plates are preserved, but moulds of the side-plates occur at intervals, 20 in a length of 10 mm. on each side of the ambulacrum, indicating in all about 60 on each side of the ambulacrum. Impressions of the underlying lancet plate are exposed in some places, and at the lower ends of two of the ambulacra, impressions of the hydrospire-folds are visible, five on each side of the ambulacrum. _There are indications of 10 spiracles, situated in the inter-ambulacral regions. Mouth, represented by a protuberance or internal mould, 3 mm. by 2 mm., pentagonal in outline. 102 IDA A. BROWN. Resemblances. The specimen is very close to that of the genotype, Calyco- — blastus tricavatus Wanner, the chief. distinction apparently being the ratio of the parts of the radial plates. From the Carboniferous genus Tricoelocrinus Meek and Worthen, 1868, it differs in the shape of the deltoids, the proportions of the radials, the number of the hydrospire folds and the characters of the ambulacra. Genus Rhopaloblastus Wanner. Wanner, J., 1924.—Jaarb. Mijnw. Ned.-Oost-Ind. Verh. (1922) 1924, pp. 215-219. Taf. III, fig. 1-5. Genotype: hopaloblastus tumoricus Wanner. Basleo, Timor. ‘““ Diagnose: Th keulen- bis birnférmig, an der Basis verlangert, stielfo6rmig, vom Stielansatz bis zu den Radiallippen sich verbreiternd, am Scheitel breit, konvex, im Umriss finfseitig. Peripherie hoch tber dem Aequator, mit den Radiallippen zusammenfallend. Basalkranz hoch, trichterformig, normal zusam- mengesetzt. RR gross, kurzer als die BB. Ké6érper der RR mehr als doppelt solang als die Aeste am Radialsinus. DD klein, aber in der seitlichen Ansicht der Th deutlich sichtbar, im Umriss subtrigonal bis rhomboidisch. Ambulakra kurz, lanzettformig, nur wenig eingesenkt, fast den ganzen Sinus ausfillend. Lanzettstiick von den Seitenplattchen bedeckt. Spirakeln einfach, zuweilen mehr oder weniger vollstandig durch ein Medianseptum geteilt, proximal und seitlich von den Seitenplattchen begrenzt; hintere Spirakeln mit dem Anus zu einer gemeinsamen Oeffnung vereinigt. Hydrospiren auf jeder Seite des Ambulakrums anscheinend drei.” Dene oeate (?) belfordi (Crockford and Brown). Tricoelocrinus (?) belfordi J. M. Crockford and I. A. Brown, 1940. Proc. Linn. Soe. Vsw. 1940, 65, pp. 167-170, pl. IV, fig. 1, 2, (?) 3. Holotype: Australian Museum, F.39158. Locality: 100 yards west of Jump-Up Creek, Portion 14, Parish of Belford, 24 miles north of Belford Railway Station, New South Wales. Horizon: Fenestella Shales, Branxton Stage, Upper Marine Series, Permian. Description. There is nothing to add to the description previously given ; the specimen is a single radial plate with portion of the ambulacrum. Other Specimens are required to fix its generic affinities with certainty. Comparison with the described blastoids from the Permian of Timor suggests its relation with Rhopaloblastus timoricus Wanner, rather than with the Carboniferous genus T'ricoelocrinus Meek and Worthen, 1868. BIBLIOGRAPHY. @) Brouwer, H. A.: Feestbundel—-Dr. K. Martin, 1851-1931. Leedsche Geol. Mededeelingen, 1931, Deel V, pp. 558-561. (2) Crockford, J., and Brown, I. A.: A Permian Blastoid from Belford, N.S.W. Proc. Li Soc. N.S. W., 1940, 65, pp. 167-170, pl. iv. (3) David, T. W. E.: Pan-Pacific Science Congress, Australia, 1923. Guide-book to the Excursion to the Hunter River District, footnote, p. 19. (4) ________; Explanatory Notes to Accompany a New Geological Map of the Commonwealth of Australia, p. 67. Aust. Med. Pub. Coy., Sydney. 1932. (5) David, T. W. E., and Sussmilch, C. A.: Upper Paleozoic Glaciations of Australia. Bull. Geol. Soc. America, 1931, 42, p. 483. 6) de Marez Oyens, F. A. H. W.: Preliminary Note on the Occurrence of a New Ammonoid Fauna of Permian Age on the Island of Timor. Koninklijke Nederl. Akad. van Wetens., Proc., 1938, 41, No. 10, 1122. Journal Royal Society of N.S.W., Vol. LXXV, 1941, Plate IV PERMIAN BLASTOIDS FROM NEW SOUTH WALES. 103 (7) Dunbar, C. O.: The Type Permian: Its Classification and Correlation. Bull. Amer. Assoc. Petroleum Geol., 1940, 24, No. 2, pp. 237-281. (8) Etheridge, R., Junr.: Rec. Geol. Surv. N.S.W., 1894, 4, p. 3, pl. VII, figs. 9, 12, 14. (9) Etheridge, R., Junr., and Carpenter, P. H.: Catalogue of the Blastoidea in the Geological Department of the British Museum (Natural History). 20 plates. London, 1886. _ 40) Jones, L. J.: Coal Resources of the Southern Portion of the Maitland-Cessnock-Greta Coal District. Geol. Surv. N.S.W., Min. Res., 1939, No. 37, p. 91. 1) Meek, F. B., and Worthen, A. H.: Proc. Acad. Nat. Sci. Philadelphia, 1868, p. 356. 2) Miller, A. K.: Age of the Permian Limestones of Sicily. Amer. Jour. Sci., 1933, 26, pp. 409-427. 43) Miller, A. K.: Comparison of the Permian Ammonoid Zones of Russia with those of North America. Bull. Amer. Assoc. Petroleum Geol., 1938, 22, No. 8, p. 1016. Q4) Perrin Smith, J.: Permian Ammonoids of Timor. Jaarb. Mijn. Ned. Oost-Ind., 1926, Verhandelingen, 1-58. 45) Smith Woodward, A.: On a New Labyrinthodont from Oil Shale at Airly. Rec. Geol. Surv. N.S.W., 1909, 8, Part 4, pp. 317-319, pl. LI. @6) Wanner, J.: Die Permischen Blastoiden von Timor. Jaarboek van het Mijnwezen in Nederlandsch Oost-Indié (1922). Verhandelingen, 1924. (47) _______; Pie Permischen Echinodermen von Timor. II Teil. Paldontologie von Timor, XIV, Lieferung XXIII. Stuttgart, 1924. as)________; Neue Beitrage der Permischen Echinodermen von Timor. VI. Blastoidea. Wetensch. Mededeelingen, No. 16, Dienst. Mijn. Neder. Indié, 1931. DESCRIPTION OF PLATE LY. Figures 1-3.—WNotoblastus brevispinus gn. et spn. 2. Holotype. Near Kitchener, Cessnock _ District, N.S.W. Figure 1.—Theca from the oral side. Figure 2.—Theca from the aboral side. Figure 3.—Theca from the side. Figure 4.—Calycoblastus casei spn. 2 approx. Holotype. Near Branxton, N.S.W. View of portion of theca showing hydrospire folds at lower end of ambulacrum and radio- deltoid suture. (Photographs by H. G. Gooch.) BRYOZOA FROM THE SILURIAN AND DEVONIAN OF NEW SOUTH WALES. By JOAN CROCKFORD, B.Sc. (With Plate V and one text-figure.) (Manuscript received, July 2, 1941. Read, August 6, 1941.) CONTENTS. Page Summary .. ae a 4 Bs ie te us a sue AS .. 104 Introduction Be ye aN bike se 50 a8 aie es e sek) Description of Species... ss ee aus ke ae Be ae BY, .« 208 Acknowledgments Me - ae 15 at ae sie ee ees econ Mk ee Bibliography sic a fa oe 4 54 fh ah ie a visi, ae SUMMARY. Six new species and one new genus of Bryozoa (Trepostomata and Crypto- stomata) are described from the Upper Silurian Hume Series near Yass, and from the Devonian of Taemas (Murrumbidgee River) and Tamworth, New South Wales. INTRODUCTION. The specimens described were collected from the Upper Silurian near Yass, and from the Devonian near Taemas and Tamworth. The following species of Bryozoa are described : Order TREPOSTOMATA. Family HETEROTRYPIDA. Cyphotrypa (?) shearsbyi sp. nov. (? Middle Devonian, Taemas) .. p. 105 Order CRYPTOSTOMATA. Family PHYLLOPORINIDA. Pseudohornera (?) retiformis sp. nov. (Upper Silurian, Yass) we p. 106 Family FENESTRELLINID. Fenestrellina mouara sp. nov. (Middle Devonian, Tamworth) Ny p. 108 Semicoscinium vallatum sp. nov. (? Middle Devonian, Taemas) .. p. 109 Family ACANTHOCLADIIDA. Penniretepora lobata sp. nov. (Upper Silurian, Yass) ie a p. i298 Family ARTHROSTYLIDZ. Pesnastylus humet gen. et sp. nov. (Upper Silurian, Yass) ns p. 112 Of the genera recorded from the Upper Silurian Hume Series near Yass, Penniretepora d’Orbigny has not previously been recorded from below the base of the Devonian ; Pseudohornera Roemer, to which one species is provisionally referred, ranges from the Upper Ordovician to the Silurian; and species of BRYOZOA FROM THE SILURIAN AND DEVONIAN OF N.S.W. 105 Glauconome Goldfuss, to which Pesnastylus humei is most closely related, are typically Silurian. Fenestrellina d’Orbigny, which is recorded from the Moore Ck. Limestone near Tamworth, ranges from the Early Silurian to the Permian ; the age of the Moore Ck. Limestone (Middle Devonian) has been discussed by Benson. Semicoscinium Prout is known elsewhere from the Upper Silurian to the Devonian ; and Cyphotrypa Ulrich and Bassler ranges from the Ordovician to the Devonian, but Cyphotrypa (?) shearsbyi, which occurs at Taemas, is most closely related to a Middle Devonian form, C. (?) maculosa Duncan, from the Traverse Group of Michigan. Dr. Hill (p. 249) considers that a Lower Middle Devonian age is indicated by the coral fauna of the limestones at Taemas in which these last two genera occur. DESCRIPTION OF SPECIES. Phylum BRYOZOA Ebrenberg. Class GYMNOLAHZMATA Allman. Order TREPOSTOMATA Ulrich. Family HETEROTRYPIDZ Ulrich. Genus Cyphotrypa Ulrich and Bassler. Cyphotrypa Ulrich and Bassler, 1904. Smithsonian Miscellaneous Colln., Vols XLVEL, p: 29. “Massive Heterotrypide. Zocecial walls thin, amalgamated, the central portion light-coloured; tubes prismatic, with numerous. well-developed diaphragms ; mesopores wanting, acanthopores well-developed.’ (Original definition.) Genotype: Leptotrypa acervulosa Ulrich, 1895, Geol. and N.H. Survey of Minnesota, Vol. ITI, Pt. 1, p. 318, pl. XX VII, figs. 24, 25. Cyphotrypa (?) shearsbyi Sp. NOv. (Text-figure 1A-B.) Holotype: 1439, Sydney University Collection. Horizon and Locality: Basal Limestone Series, (?) Middle Devonian, Por. 229, Par. Waroo, near road about 200 yards north of Taemas Bridge, Murrum- bidgee River. Massie Cyphotrypa (?), with rather thick walls; diaphragms fairly abundant; acanthopores well developed. The zoaria are irregular in shape, about 3 cm. in their greatest diameter, and up to 2 cm. in height; they are composed of more than one layer of tubes, and individual layers may attain a length of over1 cm. The base of the zoarium is encrusting. The specimens could not be detached from the matrix, and the surface features are therefore not shown ; the presence of monticules is suggested, however, by areas composed of thicker walled tubes; these areas are up to 3 mm. in diameter, but may be much smaller; a few irregular, very thin-walled tubes sometimes occur in these monticules, but they have the appearance of abnormal zocecia rather than of mesopores ; these tubes may have broken down, leaving the centre of the monticule marked by sediment and brown flocculent material. The centres of the monticules are usually at least 4 mm. apart, but as the upper surface of the zoarium was irregular the distance may have been greater at the surface. The zoccia are sub-angular, usually from 0-2 to 0-3 mm. in diameter, but may be slightly larger at the monticules; smaller (young) zocecia are rather infrequently interpolated at the angles of the normal ones. The walls are usually from 0-05 to 0-08 mm. in width, but are slightly thicker i—August 6, 1941. 106 JOAN CROCKFORD. in the monticules, and thinner around the irregular zocecia. Over a large part of the sections the walls show a fairly broad median light band, bordered by slightly darker material; in some parts, however, the central light band is replaced by very finely granular dark material, or becomes indistinct. The acanthopores, which generally, but not always, occur at the angles of the tubes, are lamellar, and show a fine central lumen; they may slightly indent the tube walls. When the median light band of the walls is replaced by dark granules, these are interrupted by the acanthopores, which are surrounded by a light area. The lamelle of the acanthopores and walls are best shown in longitudinal sections. The zowcia over parts of the sections are lined by fine free granules ; the infilling of the tubes is usually clear calcite, but may be sediment. The walls are thickened for by far the greater part of their length ; for about 0:5 mm. near the base they are, however, thinner, and the tubes may be slightly bent horizontally. Thin, complete, horizontal or oblique diaphragms are developed at irregular intervals in the zowcia, and from 4 to 12 may occurin3 mm, There are no cystiphragms. Mesopores are not developed, the occasional smaller tubes shown being young zoccia. . Remarks: The central ight band of the walls resembles that shown in the Heterotrypide, but the dark granular band in the centre of the walls over part of the sections is unusual in this family ; Cumings and Galloway‘ (p. 359), however, have shown that a median dark band may be developed in the walls of some species of Heterotrypa. This species appears to be most closely related to species of Cyphotrypa (?) such as C. (?) maculosa Dunean, which it resembles in its rather thick walls. Order CRYPTOSTOMATA Vine. Family PHYLLOPORINIDA Ulrich. Genus Pseudohornera Roemer. Pseudohornera Roemer, 1876, Leth. Geognostica, 1, Leth. Pal., Vol. I, Atlas, Hxpl Pl Xt: Pseudohornera Roemer, Bassler, 1906, U.S. Geol. Surv., Bull. 292, p. 49. Pseudohornera Roemer, Bassler, 1911, U.S. Nat. Mus., Bull. 77, p. 172. Genotype: Retepora diffusa Hall, 1852, Pal. New York, II, p. 160, pl. XL co, Figs. la-f. ‘“Zoarium branching dichotomously at frequent intervals, on reverse longitudinally striated ; zocecia in several ranges, tubular, springing from a thin double plate, beneath which a number of vesicles (aborted zocecia?) are present; vestibules expanding from the orifices to the angular apertures.”’ (Nickles and Bassler, 1900, p. 37, as Drymotrypa Ulrich.) Pseudohornera (?) retiformis Sp. NOV. (Plate V, Figs. 4, 5, Text-figure 1D.) Holotype: F.28532, Australian Museum Collection. Horizon and Locality: % Lower Trilobite Horizon, Hume Series, near Bowning. Reticulate Pseudohornera (?), with usually three to four rows of zoecia on each — branch; acanthopores and mesopores absent; vesicles developed between the backs of the zoecia and the reverse surface. The holotype is a flat expansion, 3:5 cm. high by 5 cm. wide. The zoarium is reticulate, but there is no indication of the shape of the colony. The specimen is so weathered that no thin sections could be prepared, and the internal structure —— E. F, G. H, BRYOZOA FROM THE SILURIAN AND DEVONIAN OF N.S.W. NOG Text-figure 1. Cyphotrypa (?) shearsbyi ; vertical section. x10. Cyphotrypa (?) shearsbyi ; transverse section, X10; and x 20, showing the variation in the structure of the walls of the zocecia. Fenestrellina mouara ; reverse surface of the holotype. x 10. . Pseudohornera (?) retiformis ; cast of the celluliferous surface of the holotype, x 10, showing the shape of the zocecial apertures and of the casts of the zocecia, and the vesicles developed near the reverse surface. Semicoscinium vallatum ; celluliferous surface of a topotype (1441, Sydney University Collec- tion), x10, showing the expanded carina. Fenestrellina mouara ; celluliferous surface of the holotype, x 10. Pesnastylus humei ; sections across two midribs, and three lateral branches, x 10. I. Pesnastylus humei; sections parallel to the surface of the branches, showing zoccia of the lower row on the midrib and lateral branches, and apertures of the upper row, X 10. 108 JOAN CROCKFORD. is therefore known only from weathered surfaces. The branches are convex on both surfaces, and show usually four, or three, rows of zoccial apertures ; the lateral rows open on the sides of the branches, towards the fenestrules. The branches are from 0-85 to 1-2 mm. in width; the fenestrules, which are very irregularly placed and are irregular in shape, are from 0-5 to almost 3 mm. in width, and from less than 1 mm. to 7 mm.—usually from 3:5 to 6 mm.— in length. The zocwcial apertures are circular, from 0:16 to 0-23 mm. in diameter ; no peristomes are shown; the distance between the centres of suc- cessive apertures in the same row is from 0:5 to 0:83 mm. The cells are shown as casts, and are elongated and tubular, from about 1-0 to 1-65 mm. in length from their origin to the far side of the aperture ; since no sections could be made, the presence or absence of diaphragms could not be determined, but the complete infilling of the zoccia by sediment suggests that no complete diaphragms were developed. The interspaces between the apertures were thick and are invariably weathered away; no mesopores are shown, though the casts of the zoccia themselves are well preserved, so that if mesopores did occur it is probable that they were closed at the surface. No acanthopores are developed. The non- celluliferous reverse surface is not well shown ; it was not very thick, and seems to have been smooth and evenly rounded. Between the backs of the zowcia and the reverse surface small vesicles, often elongated, are developed. The basal plate has been weathered away. Remarks : The presence of vesicles between the backs of the zoccia and the reverse surface, and also the apparent absence of mesopores, separate this form from species of Phylloporina Ulrich, and suggest affinity with Pseudohornera Roemer, to which genus it is provisionally referred ; the form of the colony, reticulate in this species, instead of dichotomously dividing branches, and the circular apertures—the apertures in Pseudohornera are typically angular at the surface, becoming oval within a short distance on account of the thickening of the walls—separate this species, however, from all described species of Pseudohornera. Family FENESTRELLINIDZ Bassler (KENESTELLIDZ King). Genus Fenestrellina* d’Orbigny, 1849. Homonym: Fenestella Lonsdale, 1839, preoccupied for a pelecypod Fenestella Bolten, 1798. Zoarium flabellate or infundibuliform ; branches generally straight, some- times flexuous, connected at regular intervals by dissepiments; apertures in two rows, separated by a plain or tuberculated median keel. Genotype: Fenestella crassa McCoy, 1845, Synopsis of the Carboniferous Limestone Fossils of Ireland, p. 201, pl. 29, fig. 1. Fenestrellina mouara Sp. NOV. (Text-figure 1, C, F.) Holotype: Specimen 1437, Sydney University Collection. Horizon and Locality: Middle Devonian (Moore Ck. Limestone), Por. 41, Par. Woolamel, south of Moore (Mouara) Ck., near Tamworth. Fenestrellina with from four to twelve—usually about seven—zoecia to a fenestrule; fenestrules long and rectangular ; branches and dissepiments narrow. The form of the colony is not shown; the holotype is a fragment about 2 em. long and 5 em. wide; there are from rather less than 4, to 5, fenestrules * An application for suspension of the Rules of Zoological Nomenclature for the generic name Fenestella Lonsdale, 1839, has been submitted to the International Commission on Zoological Nomenclature (G. E. Condra and M. K. Elias, Journal of Paleontology, Vol. 15, No. 4 September, 1941), pp. 259-260). BRYOZOA FROM THE SILURIAN AND DEVONIAN OF N.S.W. 109 vertically, and from 10 to 11 branches horizontally, in 10 mm. The branches are straight and relatively narrow, from 0-3 to 0:35 mm. in width ; they bifurcate at infrequent intervals and increase to three rows of zoccia occurs immediately before branching. The celluliferous surface is poorly preserved, but shows a slight median carina; no nodes could be seen. The apertures are small and circular, about 0:11 mm. in diameter, and are placed on the flattened sides of the branches; they are separated by almost twice their own diameter, the distance between the centres of successive apertures being about 0-3 mm. ; the number of apertures to a fenestrule varies with the length of the fenestrule, and from four to twelve may occur; usually there are about seven. The fenestrules are sub-rectangular, from 1-1 to 3-55 mm. (usually about 2 mm.) in length, and from 0-47 to 0-85 mm. in width ; the dissepiments, which expand only slightly at their junction with the branches, are from 0-1 to 0:28 mm. in width. Both branches and dissepiments are evenly rounded on the reverse surface, which seems to have been coarsely granulose; they are of about the same thickness. The zocecia are rectangular in outline on the basal plate. Remarks: From Fenestrellina propinqua (de Koninck), a Lower Carbon- iferous (Burindi) species, this form is distinguished by the more regular shape, and less regular size, of its fenestrules, and by its much broader, thicker branches. Genus Semicoscinium Prout. Semicoscinium Prout, 1859, Trans. St. Louis Acad. Sci., Vol. I, p. 443. “ Zoarium funnel-shaped, celluliferous on the outer side; dissepiments wide, very short, the branches appearing to anastomose on the non-poriferous face, where the fenestrules are sub-rhomboidal or rounded; apertures in two rows, median keel very high and expanded at the summit.” (Nickles and Bassler, 1900, p. 38.) Genotype: Semicoscinium rhomboideum Prout, 1859, Trans. St. Louis Acad. aoe, Vol. I, No. 3, p. 443, pl. XVII, figs. 1, 1a-f. Semicoscinium vallatum Sp. NOV. (Plate V, Fig. 1; Text-figure 15.) Holotype: 1440, Sydney University Collection. Horizon and Locality: (?) Middle Devonian (Receptaculites Limestone), Por. 208, Par. Waroo. Infundibuliform Semicoscinium, with the celluliferous surface external ; two to three zoecia to a fenestrule ; carina high, expanded at the summit. The zoarium is infundibuliform, with the celluliferous surface external ; expansion of the zoarium commences about 5 mm. above the base of the colony ; near the base the outer surface is covered by a sheath, formed by the coalescence of the summits of the carine. There are about 20 branches horizontally, and 14 fenestrules. vertically, in 10 mm. The branches, which are from 0:29 to 0-35 mm. in width, show, where they are well preserved, a high median carina, flattened and expanded at the summit, so that the sides of the branches are partly concealed ; over the greater part of the branches, however, the upper part of the carina has been broken away, and it is shown only as a slight ridge along the centre of the branch. No nodes are shown. The zoccial apertures are placed on the slightly sloping sides of the branches, and are exserted but do not project into the fenestrules ; the apertures are circular, about 0:1 mm. in diameter, and are separated by rather more than their own diameter, the distance between the centres of successive apertures being from 0-23 to 0-29 mm. ; five apertures occur in the length of two fenestrules and two dissepiments, and there are about forty apertures in 10 mm. The fenestrules are oval, from 110 JOAN CROCKFORD. 0-27 to 0:34 mm. in length, and from 0-19 to 0:25 mm. in width; the dis- sepiments are from 0-29 to 0:4 mm. wide, and the length of one fenestrule and one dissepiment is from 0:62 to 0-72 mm. On the reverse surface both branches and dissepiments are rounded, and they are of about the same thickness. Increase to three rows of apertures occurs immediately before bifurcation. The zoaria have been replaced by silica, and were etched from limestone ; over parts of the surface granular silica has been deposited between the carinez, but this does not seem to be a replacement of vesicular tissue, such as that developed in the genotype and in Semicoscinium rhombicum Ulrich; vesicular tissue does not occur in all species of Semicoscinium (Ulrich and Bassler,@” 1913, p. 235 ;, Prantl,“9)p252). Remarks : This form is distinguished from described species of Semicoscintum by its small size. Family ACANTHOCLADIIDZ Zittel. Genus Penniretepora d’Orbigny. Penniretepora d’Orbigny, 1849, Revue et Magasin de Zoologie, 2e Ser., Tome 1, p. 501. [Non] Penniretepora d’Orbigny, 1850, Prodrome de Paléontologie Stratigraphique, Tome 1, p. 45. Penniretepora d’Orbigny, Bassler, 1934, Fossilium Catalogus, 1, pars 67, Bryozoa, pp. 20, 165. Homonym: Acanthopora Young and Young, 1875 (not d’Orbigny, 1849). Synonyms: Glauconome Auct. (not Goldfuss, 1826). Pinnatopora Vine, 1884. Pinnatopora Vine and Shrubsole, 1884. Original Definition: “ Deux rangées de cellules d’un seul coté d’un ensemble penniforme, composé d’une tige et de rameaux libres latéraux, non anastimosés.”’ Genotype: Retepora pluma Phillips, 1827, Geol. Yorkshire, pt. 2, p. 199, pl. 1, figs. 13-15. Penniretepora d’Orbigny, 1849, has priority over Pinnatopora Vine and Pinnatopora Vine and Shrubsole, 1884. Penniretepora d@Orbigny, 1850 (genotype Glauconome disticha Goldfuss, Lonsdale) is a synonym of Glauconome Goldfuss, 1826, as redefined by Lonsdale in 1839, but many species described as Glauconome should be referred to Penniretepora. Penniretepora has not previously been recorded from below the base of the Devonian—d’Orbigny in 1849 gave the range as Silurian to Permian, but was including Glauconome disticha in the genus. Penniretepora lobata Sp. NOV. (Plate V, fig. 3.) [?] ‘“‘ Pinnatopora’’ Shearsby, 1912, Rept. Austr. Assoc. Adv. Sci., Vol. XIII, p. 116. Holotype: F.30153, Australian Museum Collection. Horizon and Locality: Barrandella Shales (?), Hume Series, Derrengullen Ck., Por. 10, Par. Yass (holotype); Lower Trilobite Horizon, Hume Series, at the corner of the Bendenine and Boorowa Rds., Por. 12, Par. Derrengullen ; Barrandella Shales, Hatton’s Corner, Por. 7, Par. Hume. Penniretepora with a narrow midrib, from which thin, equidistant branches are given off; zoccia more closely spaced on the branches than on the midrib. The zoarium is pinnate; the midrib is thin, about 0:25 mm. in width, and is straight; lateral branches are given off from both sides of the midrib BRYOZOA FROM THE SILURIAN AND DEVONIAN OF N.S.W. 111 at intervals of from 0-85 to 1-0 mm., about 11 branches occurring on each side in 10 mm.; the branches on opposite sides of the midrib are sub-alternating. The branches are straight, and are from 0-19 to 0:25 mm. in width ; the longest branch shown reaches a length of 3 mm. and is incomplete. The angle of divergence between the branches and the midrib is about 55° to 60°. Both branches and midrib bear a slight median carina, on which small nodes may be developed; these are not well shown. The apertures are circular, about 0-13 mm. in diameter; they show slight peristomes, and are rather exserted. On the midrib there is one zocecial aperture at the end of each branch, and one between the branches, the distance between the centres of successive apertures being from 0:43 to 0-51 mm., about twenty-one apertures occurring in 10 mm. ; on the lateral branches the distance between the centres of successive apertures is from 0-3 to 0:41 mm., about twenty-seven occurring in 10 mm. On the reverse surface both branches and midrib are rounded, and they show very faint longitudinal striz ; the midrib (which is about 0-25 mm. thick) is much thicker than the branches. Internally the cells are triangular to sub-rhomboidal in outline, and their length equals the distance between their apertures. The inner layer of the reverse surface shows a number of strong longitudinal ridges and grooves. A specimen of this species from the Lower Trilobite Horizon at the corner of the Bendenine and Boorowa Rds. in Por. 12, Par. Derrengullen (1443, Sydney University Collection), shows a rather more complete zoarium, with a midrib 2 cm. long, and about 0-4 mm. wide near the base and 0-3 mm. wide at the top, from which a number of evenly spaced lateral branches are given off; two of these lateral branches, placed opposite one another, are themselves pinnate, giving off branches up to 2:2 mm. long, and placed the same distance apart as the branches on the midrib; the first of these tertiary branches arises at a distance of from 2-0 to 2:4 mm. from the centre of the midrib. The measurements of this specimen are the same as those of the holotype. hkemarks: From Pesnastylus humei sp. nov., this species is distinguished externally by possessing two, instead of four, rows of zowcia, by its much finer midrib and branches, and there is no anastomosis between the ends of the branches ; internally the shape of the zowcia is very different. Family ARTHROSTYLID Ulrich. Genus Pesnastylus gen. nov. Zoaria showing no articulation, pinnate, but with the lateral branches from adjacent midribs uniting; new midribs formed by the coalescence of two or more successive branches from adjacent midribs, never by bifurcation of a midrib ; stems celluliferous over about one-half of the circumference ; zoccia in four rows, two on each side of a median carina, on both midribs and branches ; zoecia sub-tubular ; hemisepta, mesopores, and acanthopores not developed, and diaphragms rarely developed; reverse surface smooth or with faint longitudinal stric. Genotype: Pesnastylus humei sp. nov. No articulation is shown in any of the specimens, and the base of the colony is not shown by any of the zoaria, so that it is possible that either no articulation is developed, as in Glauconome Goldfuss, or that articulation is restricted to the base of the colony, as in Nematopora Ulrich ; other genera of the Arthrostylide Show very much greater articulation, but very similar zocecial characters. From Glauconome Goldfuss, as redefined by Lonsdale (non Glauconome Auct.), this genus is distinguished by the coalescence of the ends of the lateral branches from adjacent midribs, and by the mode of formation of new midribs. 112 JOAN CROCKFORD. Pesnastylus humei Sp. Nov. (Plate V, Figs. 2, 6; Text-figure 1, G-I.) Cotypes: 1445, 1446, Sydney University Collection. Horizon and Locality: Barrandella Shales, outcrop in small creek west of Taemas Rd., Por. 16, Par. Boambolo (cotypes) ; and Lower Trilobite Horizon, anticline on Boorowa Rd., Por. 12, Par. Derrengullen, and at the corner of the Bendenine and Boorowa Rds., Por. 24, Par. Derrengullen. Zoarium pinnate, with the ends of the lateral branches from adjacent stems coalescing ; four rows of cells separated by a median carina on both branches and midribs ; reverse surface of midrib very thick, thinner on branches, smooth or with faint longitudinal strie. The base of the colony is not shown; incomplete specimens measure up to 4x7 cm. The zoarium is pinnate, with the ends of the lateral branches from adjacent stems coalescing, and consists of midribs from 0-7 to 1-3 mm. in width, and lateral branches from 0-4 to 0:65 mm. in width; the lateral branches are given off from the midribs at very variable angles, and may pass straight from one midrib to another, or may point upwards and join to form a new midrib. The distance between adjacent midribs is from 1-5 to 7 mm. The number of branches originating in 10 mm. on each side of a midrib is from 7 to 9; the branches on opposite sides of the midrib may be approximately level or may alternate. Both branches and midribs bear a strong, broad, flat-topped median carina, on either side of which are placed two rows of elliptical zocecial apertures ; on the midrib the apertures of adjacent rows may be placed level or may alternate, and on the branches they are usually alternating. On the midrib three to four apertures of the higher row (next to the carina) and usually one of the lower row occur between the origin of successive branches. The lateral rows of apertures on the branches are placed well down on the sides towards the reverse surface, and are shown only when more than half of the circumference is exposed ; on the midribs the apertures are restricted to the upper half, and the reverse surface is proportionately much thicker ; near the base of the colony extra deposits of calcium carbonate are extensively developed on both surfaces, and may obscure the apertures. The zoccial apertures are about the same size on both branches and midribs; they are from 0-24 to 0-3 mm. in length, and about 0-15 mm. in width, and the distance between the centres of successive apertures is from 0-36 to 0-43 mm. in the upper row of the midrib, and from 0-3 to 0-43 mm. on the branches; the apertures are on the whole rather more closely spaced on the branches; the spacing of the apertures of the lower row on the midrib depends on the development of the lateral branches. The cell mouths have been filled with sediment, but the greater part of the cells is filled with granular calcite, so that in weathered specimens the casts of the cell mouths are very prominent. The thickness of the midrib is usually between 0-8 and 1:35 mm., and the thickness of the lateral branches about 0-7 mm. The reverse surface is evenly rounded, and may either be smooth or show faint longitudinal strie. Internally the four rows of zoccia are arranged in two vertical series; the cells gradually move outwards from the centre as they approach their apertures, and are replaced near the centre by new zocecia. There is no sign of any mesial plate. The zoccia are elongate and tubular, with rather pointed extremities. Hemisepta are not developed, and diaphragms occur extremely rarely, but may be developed in any part of the zoccia. The length of a single zocecium from the tip to the far side of the aperture is from 0-85 to 1-0 mm. on the midrib, and very slightly less on the branches. The apertures are elliptical, but may appear circular where they are cut at a deeper level. The zowcial walls are unusually thick—about 0:02 mm. Neither mesopores, acanthopores, nor vesicular tissue are developed. The reverse surface shows internally a number of poorly Journal Royal Society of N.S.W., Vol. LXXV, 1941, Plate V \ ‘ a % A ‘ ~ 1 "i « a yi ras ” * i i é ‘ AY e ‘ oe < m / ; ‘ / > <4 a! i ) . ee id ‘ See t s BRYOZOA FROM THE SILURIAN AND DEVONIAN OF N.S.W. 113 defined longitudinal strie. The zocecia shown in Text-figure 1h and 7 are those of the lower row on the midrib, which are more widely spaced than usual. Remarks : This species resembles Glauconome disticha Goldfuss in its pinnate form, and in having the zocecia arranged in four rows, two on each side of a median carina, but differs in size, in its more regular branching, and in the coalescence of the ends of the lateral branches ; internally Glawconome disticha shows more numerous diaphragms. ACKNOWLEDGMENTS. I wish to thank Dr. I. A. Brown for her help in the preparation of this paper, and the Australian Museum for the loan of some of the specimens used in the descriptions. The photographs were taken by Mr. H. G. Gooch. This work has been carried out during the tenure of a Science Research Scholarship at the University of Sydney. BIBLIOGRAPHY. 1) Bassler, R. S.: The Bryozoan Fauna of the Rochester Shale. U.S. Geol. Surv. Bull, 292, 1906. (2) _________; The Early Palzozoic Bryozoa of the Baltic Provinces. U.S. Nat. Mus., Bull. 77, 1911. (3)________; Fossilium Catalogus, 1, Animalia; Pars. 67, 1934. Bryozoa. ‘4) Benson, W. N.: The Geology and Petrology of the Great Serpentine Belt of N.S.W., Pt. V, The Geology of the Tamworth District. Proc. Linn. Soc. N.S.W., 1915, 40, Pt. 3. (5) Cumings, E. R., and Galloway, J. J.: Studies of the Morphology and Histology of the Monti- culoporids or Trepostomata. Bull. Geol. Soc. America, 1915, 26, pp. 158, 349-374. ‘) Duncan, Helen: Trepostomatous Bryozoa from the Middle Devonian Traverse Group of Michigan. Mich. Univ. Mus. Pal. Conir., 1939, 5, No. 10, p. 171. (7) Goldfuss, A.: Petrefacta Germanize, Vol. 1. Dtisseldorf, 1827. (8) Hall, J.: Paleontology of New York, 1852, Vol. II, containing descriptions of the Organic Remains of the lower Middle Division of the New York System. Van Benthuysen, Albany, 1852. ) Hill, Dorothy : The Lower Middle Devonian Rugose Corals of the Murrumbidgee and Good- radigbee Rivers, N.S.W. Jour. Roy. Soc. N.S.W., 1941, 74, p. 247. 0) Koninek, L. G. de: Recherches sur les fossiles paléozoiques de la Nouvelle Galle de Sud. Mem. Soc. Roy. de Sciences de Liége, 2e Ser., 1877, 8. (41) _______; Descriptions of the Palzozoic Fossils of New South Wales. N.S.W. Geol. Surv., Mem. Pal. No. 6, 1898. 2) Lonsdale, W.: Jn Murchison, Silurian System. London, 1839. 3) McCoy, F.: Synopsis of the Carboniferous Limestone Fossils of Ireland, 1845. 44) Nickles, J. M., and Bassler, R. 8.: A Synopsis of American Fossil Bryozoa. U.S. Geol. Surv., Bull. 173, 1900. %5) q’Orbigny, A.: Descriptions de Quelques Genres Nouveaux de Mollusques Bryozoaires. Revue et Magasin de Zoologie, 1849, 2e Ser., Tome 1, p. 499. a6) ________: Prodrome de Paléontologie Stratigraphique, Tome 1. Paris, 1850. a7) Phillips, J.: The Geology of Yorkshire, 1827, Vol. 2. a8) Prantl, F.: Revise Ceskych Devonskych Fenestellid. Palewontographica Bohemic, 1932, 15. 9) Prout, H.: Fourth Series of Descriptions of Bryozoa from the Paleozoic Rocks of the Western States and Territories. Trans. St. Louis Acad. Sci., 1860, 1, p. 443. 49a) Shearsby, A. J.: The Geology of the Yass District. Rept. Aust. Ass. Adv. Sci., Vol. XIIT, 1912, p. 106. (20) Roemer, F. A.: Lethza Geonostica. I. Lethzea Paleozoica. Atlas, 1876. @1) Ulrich, E. O.: Paleozoic Bryozoa. Geol. Surv. Illinois, 1890, 8, Pt. 2, Sect. IV. (22) ______: Qn Lower Silurian Bryozoa of Minnesota. Geol. and N.H. Surv. of Minnesota, Es9p, 5, Pt. I. , and Bassler, R. S.: A Revision of the Paleozoic Bryozoa. Pt. II. On Genera and Species of Trepostomata. Smithsonian Miscellaneous Collections, 1904, 47, p. 165. : Systematic Paleontology of the Lower Devonian Deposits of Maryland, Bryozoa. Maryland Geological Survey Lower Devonian, 1913, and Devonian, Plates. J—August 6, 1941. (23) (24) 114 JOAN CROCKFORD. DESCRIPTION OF PLATE V. Figure 1.—Semicoscinium vallatum sp. nov. Celluliferous surface of the holotype. x10. Figure 2.—Pesnastylus humei sp.nov. Celluliferous surface of a cotype (1445, Sydney University Collection). Natural size. Figure 3.—Penmiretepora lobata sp.nov. Cast of the celluliferous surface of the holotype. x10. Figure 4.—Pseudohornera retiformis sp. nov. Holotype. Natural size. Figure 5.—Pseudohornera (?) retiformis sp.nov. Cast of the celluliferous surface of the holotype. x 10 Figure 6.—Pesnastylus humei sp. nov. Cast of the celluliferous surface of a topotype (1447, Sydney University Collection), showing the infilling of the mouths of the zoecia. x10. A NOTE ON DETERMINATIONS OF PHYSIOLOGICAL SPECIALISATION IN FLAX RUST. By W. L. WATERHOUSE, M.C., D.Sc.Agr., D.LC., and I. A. WATSON, B.Sc.Agr., Ph.D., The University of Sydney. (With Plate VI.) (Manuscript received, August 13, 1941. Read, September 3, 1941.) Flax rust, caused by Melampsora lini (Pers.) Lév., has long been known in Australia as a parasite attacking cultivated flax, Linwm usitatissimum L. and L. marginale Cunn., an indigenous “ wild flax ’’. McAlpine! records its occurrence as early aS 1885, and states that it is present wherever flax is cultivated. The rust does considerable damage to seed production under epidemic conditions, but much lighter infections cause serious injury when the crop is grown for fibre. It is for the latter purpose that the present extension of the crop is taking place. Numerous reports of rust damage in varieties which are otherwise suitable for fibre production indicate that a programme for breeding for rust resistance will have to be carried out. For this to be successful a knowledge of the physiological specialisation shown by the pathogen is essential. Rust fungi frequently show extreme specialisation. Thus in the wheat stem-rust fungus more than 200 physiological races have been determined. Studies of the flax rust have been made extensively in U.S.A. by Dr. H. H. Flor of North Dakota, who has recorded 24 races of the fungus. He has developed a series of differential hosts to sort out physiological races, and kindly made seed available for use in these studies. During the past year Mr. W. W. Poggen- dorff and other officers of the N.S. Wales Department of Agriculture, together with other workers, have forwarded samples of rusted flax which have been used in the determinations. Our thanks are tendered to them. The technique adopted by Flor? has been followed, excepting that no provision was made for a constant light day of 16 hours. Normal hours of daylight have been used. One of the rusted samples included in the tests was obtained by Dr. E. T. Edwards on L. marginale growing near Bourke. The others all came from cultivated varieties of flax growing in the following localities : N.S. Wales: Leeton (4 collections), Bourke and Macksville. Victoria: Jindwick. S. Australia: Mount Gambier (2 collections). Tasmania: Chudleigh. In addition to seed of the rust differentials Dr. Flor sent seed of “‘ Bison ”’, a variety he has found to be susceptible to all the races known to him. At the outset of our work, an attempt was made to use it for the purpose of multiplying the inoculum that was present on the specimens submitted. In no case was any infection obtained. Actually several early collections that were sent in were lost through this failure. As a result the variety ‘‘ Punjab ” is being used in 1 McAlpine, D.: The Rusts of Australia, 1906, 344 pp., 55 plates. Govt. Printer, Melbourne. * Flor, H. H.: Physiologic Specialization of Melampsora lini on Linum usitatissimum. Jour. Agr. Research, 1935, 51, 819-839, pla il 116 WATERHOUSE AND WATSON. place of “ Bison” to supply the mother culture from which the differential varieties are inoculated. It is well known that environmental conditions—and particularly variations in temperature—cause changes in the rust reactions exhibited by particular differential hosts. This becomes a very important consideration in the deter- mination of physiological races. Flor reports that certain of his differential varieties were very sensitive to such changes; one of them was “ Williston Brown ’’. The variety ““ Akmolinsk ”’ has shown a wide range of variation in our work; the reactions have varied between type “1” and type “3 with chlorosis’. In wheat stem-rust determinations this type of reaction would be styled “3°"”’, and would be indicative of host resistance. Flor? states that “attempts to differentiate too finely between degrees of resistance and suscept- ibility may lead to confusion and to a misunderstanding of results obtained at different localities or under variable conditions ’’. Keeping this in mind we eliminate minor differences shown in our determinations, and consider that all the collections studied may be regarded as falling within the one physiological race. The typical reactions are as follows: Differential ite C:l. Number. Reaction. Buda, ./: : ue igs 270-1 R Williston Golden me ie oe 25-1 R Akmolinsk A ae hs Di 515-1 SR J.W.S. nee ie aM a 708-1 I Abyssinian Be A Paes ab 701 I Kenya ie ee ae 709-1 it Williston Brown : i 803-1 R ““Very pale blue crimped of Hi 647-1 t Ottawa 770 B be fe 359 if Argentine a a se oh 462 I Bombay We : ote > 42 S The letters signify the plese reactions: I, immune; R, resistant; SR, semi-resistant ; and §S, susceptible. A comparison of these results with those recorded by Flor shows that this race is different from any listed by him. He corroborates this in personal correspondence about the results. Confirmatory evidence is available from two other sources. In the first place the variety “ Bison C.I. No. 389” has been immune in all our tests, although susceptible throughout the U.S.A. investiga- tions. Again, the variety “‘ Argentine C.I. No. 705-1 ”’ which was used in Flor’s earlier race determinations (loc. cit.) was supplied by him. In our tests it has been immune. He records reactions of 14 races on it. To only one, viz. race 10, was this variety immune. But the reactions of this race on other differentials of the group are quite different from those shown by our rust. Further work is in progress in which many other varieties of flax are being used. Endeavours are also being made to see whether any race separations can be made from such varied reactions as those shown on “ Akmolinsk’’. As further collections become available they also will be studied for specialisation. CONCLUSION. Determinations of 10 collections of rust from widely separated areas in Australia have shown that one physiological race is present. This is different from any of the races recorded to date. ACKNOWLEDGMENT. Grateful acknowledgment is made of financial assistance from the Common- wealth Research Grant. 3 Flor, H. H.: New Physiologic Races of Flax Rust, Jour. Agr. Research, 60, 575-591. Journal Royal Society of N.S.W., Vol. DXXV, 1941, Plate VI ‘ \ ue x sd ie 5 Sea) ‘ 1 . ‘ all . ql , f ¥ taeda is ’ r , "he e : 4 f ' ia rt F * . ; we 7 \ My * ' a i . i} 3 = * ~ P 2 * nee . é { ’ i) . * ' ( ae > e 7 . v * Fe 5 \ , " * ) 4 \— é it ‘ ‘ : * ’ ® ‘ we ) ay ‘ f ¢ e PHYSIOLOGICAL SPECIALISATION IN FLAX RUST. y 1B lar DESCRIPTION OF PLATE VI. Fig. 1.—Typical pot of flax seedlings at stage when infection notes are taken. Heavy attack of rust on leaf and stem is present. Five-eighths natural size. Fig. 2.—Typical rust reactions on pairs of leaves showing : (a) Strong resistance of ‘‘ Buda ”’ indicated by hypersensitive flecks. (6) Semi-resistance of “‘ Akmolinsk”’ in which scattered pustules occur in chlorotic and necrotic areas. (c) Susceptibility in “ Bombay ”’, showing large confluent pustules and no chlorosis. Magnified 3 times. THE THIAMIN (VITAMIN B,) CONTENT OF THE URINE OF TRICHOSURUS VULPECULA. By A. BOLLIGER, Ph.D., and C. R. AUSTIN, MSc., B.V.Se. (Manuscript received, August 19, 1941. Read, September 3, 1941.) In connection with physiological studies on Trichosurus vulpecula (Australian phalanger or possum) some evidence was forthcoming that the urine of this species contained comparatively large amounts of thiamin.” This apparent but not fully substantiated ‘* thiaminuria ’’ immediately gave rise to a number of questions, such as the source of the vitamin B, and whether or not it was manufactured in this animal’s body. ‘Therefore an investigation was undertaken to establish the amount of thiamin excreted in the urine of Trichosurus vulpecula. EXPERIMENTAL. A. The Collection of Urine. The animals were placed in metabolism cages and twenty-four hour specimens of urine were collected in the usual manner in bottles containing acid (1 c.c. 20% H,SO,). As previously reported, freshly voided specimens from these animals may readily be obtained at almost any time. They could be made to urinate by pressure on the bladder region, and in some cases they were found to micturate spontaneously on being picked up. However, no difference could be observed between the thiamin content of freshly voided specimens and of specimens collected in the metabolism cage. The animals kept in metabolism cages were given prepared diets consisting of lucerne, leaves from certain trees or other food materials. B. Analytical Methods. (a) Thiochrome Method. 'The principle of this method, originally described by Jansen, ‘*) les in the transformation of vitamin B, into its fluorescent derivative thiochrome by means of oxidation with alkaline ferricyanide. The fluorescent material is then extracted with butyl alcohol and the resulting solution com- pared with a similarly treated thiamin standard. Using the technique described by Wang and Harris,“ it was soon observed that the thiochrome method was not entirely satisfactory when applied to the analysis of the urine of the phalanger. For example, in spite of the fact that these urines required at least ten-fold dilution prior to assay on account of their high concentration of thiamin, interfering coloured and fluorescent substances often made comparison with the standard difficult. These substances frequently imparted to the butyl alcohol extract a greenish fluorescence in contrast to the blue fluorescence of the standard. For this reason the results could be expressed in increments of not less than 50 micrograms per 100 ml. Furthermore, it was found that certain substances with a blue fluorescence very similar to that of thiochrome were not extracted by butyl aleohol. The amount of unextracted blue fluorescence was frequently several times larger than that extracted by butyl alcohol (see Table IT) and the question arose as to whether all of the thiochrome had been extracted or whether a considerable THE THIAMIN (VITAMIN B,) CONTENT. J) part of it was unextractable from this specific medium. Finally, the Moreton Bay Fig leaves eaten by our phalangers produced a blue urinary fluorescence, which was as much as a thousand times stronger than that obtained by butyl - aleohol extraction after oxidation with alkaline ferricyanide. Thus a debatable point arose concerning the extent to which this non-extractable fluorescence influenced the fluorescence due to thiochrome. A further complication was introduced by the fact that the urine of Tricho- surus vulpecula seems to possess Oxidising properties which could apparently convert any thiamin present into thiochrome on the addition of sufficient alkali alone. Pre-treatment with potassium ferricyanide seemed unnecessary, but it was always added as a routine procedure. (b) Method of Melnick and Field. In these circumstances it was desirable to employ in addition to the thiochrome method another analytical procedure for the purpose of measuring the thiamin content of the urine of this marsupial. Accordingly, the highly specific method of Melnick and Field’ ® was adopted. The principle of this method consists in the coupling of thiamin with diazotised p-aminoaceto-phenone to give a purple-red compound, which is insoluble in water but soluble in certain organic solvents, such as xylene. The xylene solution is used for colorimetric assay. Prior to this reaction the vitamin is removed from the urine by adsorption on zeolite or by extraction with benzyl alcohol. The method was found to be quite suitable for determinations on the urine of Trichosurus vulpecula from which good recoveries of added vitamin could be made. FINDINGS. Some 25 urines obtained from four different animals were analysed by the method of Melnick and Field as well as by the thiochrome method. Seventeen of these urines were 24-hour specimens. The results from these analyses are listed in Table I. The former method gave values ranging from 255 to 1,630 micrograms per 100 ml., the average rate of excretion being 726 micrograms per 100 ml. In general the thiochrome method gave slightly lower results (varying from 350 to 1,300 micrograms per 100 ml.), particularly in urines with a high thiamin content. With this method the average excretion was at the rate of 650 micrograms per 100 ml. The average 24-hour output of thiamin as estimated on 17 urines by the method of Melnick and Field was found to be 515 micrograms (range 371 to 1,392 micrograms). With the thiochrome method the average excretion over 24 hours was 452 micrograms. As already pointed out, these animals when under investigation were kept on a definite diet, the nature of which is indicated in Table I. The diet consisted of leaves from either the Moreton Bay Fig (Ficus macrophylla), the Camphor Laurel (Cinnamomum camphora) or the Gum tree (Eucalyptus globulus), or of lucerne, or bran and pollard and bread. To our knowledge none of these foods is rich in vitamin B,, and none produced any definite influence on the excretion rate of thiamin. In every instance the urinary excretion of thiamin was large, whether measured by the coupling or by the thiochrome method. It has thus been shown that a phalanger of about 1 to 2 kg. body weight excretes in 24 hours several times the amount excreted by a fully grown man. (The human excretion is reported by Harris ef al.) to be of the order of 35-105 micro- grams daily.) Besides man the thiamin excretion of the rat and the dog have been studied.’®; 9) In both cases it was only a small fraction of that found in the phalanger. In considering the source of the excreted thiamin one is compelled to assume its synthesis in the animal body to a considerable extent at least. This 120 BOLLIGER AND AUSTIN. TABLE I. Method: Melnick and Method: Thiochrome.* Field. MRRAMRRLON NNN ET GON fDi Animal. Date. Diet. Buty] alc. Without Micrograms | Micrograms | Extraction. | Extraction. per per 24 hrs. | Micrograms | Micrograms 100 ml. Excretion. | per 100 ml. | per 100 ml. $57 10/5/41 Moreton Bay Fig. 800 300,000 Qi 23/5/41 no 56 ee 1,051 PrZ, 2/6/41 Bran and pollard. 400 $57 2/6/41 i Hp 700 Pr2 4/6/41 Moreton Bay Fig. 860 604 700 500,000 S57 4/6/41 be Any ese 560 371 600 400,000 Pr2 5/6/41 i Bae ee 1,500 1,295 1,300 S57 5/6/41 Be Bi re te 343 412 400 400,000 S57 6/6/41 i a ae 1,045 1,392 1,100 Pr2 7/6/41 5 ca ce 439 526 500 $57 7/6/41 Le See bles 255 375 500 Q1 19/6/41 Bran and pollard. 1,630 1,900 R1 5/7/41 Lucerne. 1,136 397 900 3,000 Q1 5/7/41 BS 1,164 686 800 4,000 Rl 6/7/41 ce 384 424 350 1,550 Rl 7/7/41 oe 604 531 400 1,800 Q1 7/7/41 As 443 753 450 1,800 Ql 8/7/41 a “32 7AM 600 2,000 RI 9/7/41 ae 588 588 550 1,550 QI 9/7/41 - 764 1,278 600 1,600 Rl 10/7/41 Camphor Laurel. 1,528 870 1,100 2,500 Ql 10/7/41 m * 1,238 1,000 Ql 12/7/41 ne 55 478 600 Q1 15/7/41 Eucalyptus. 1,366 546 900 2,500 Pooled urine, bread, bran and pollard. 350 * As indicated in the text the thiochrome method was carried out with and without the final butyl alcohol extraction. The last two columns in this table contain the results from these two variations. is borne out by the following example. Two animals were kept for five days on an average daily intake of 120 gms. of Moreton Bay Fig leaves which according to our analyses contained about 100 micrograms of thiamin per 100 gms. But over this period these animals had an average daily thiamin excretion of 714 micrograms. A similar picture was obtained when the phalangers were kept on other food, and, without going further into this aspect on this occasion, we would like to stress our conclusion that this marsupial must manufacture considerable amounts of thiamin. A few determinations of the fecal excretion of thiamin indicated that this is small, as in other mammals, and amounts to only about 10% of that of urine. SUMMARY. Urinary excretion of thiamin has been studied with the coupling method of Melnick and Field and the thiochrome method. For this particular case it would seem that the thiochrome method is of doubtful validity in view of the very considerable amount of fluorescence which is present in the urine as voided, or which appears on the addition of alkali. The nature of this fluorescence is as yet unknown, but we believe that it is mainly due to some substance other than thiochrome. With both methods the excretion was found to be large irrespective of the diet eaten by the animal, averaging about 500 micrograms per 24 hours. The amount of thiamin excreted relative to the amount of thiamin ingested with the food leads to the conclusion that the phalanger manufactures thiamin in its body. The Gordon, Craig Research Laboratory, Department of Surgery, and the Department of Veterinary Science, University of Sydney. THE THIAMIN (VITAMIN B,) CONTENT. 121 REFERENCES. @) Bolliger, A.: Austral. Journ. Sc., 1941. 2) Bolliger, A., and Carrodus, A.: Med. Journ. Austral., 1938, 1118. (3) Jansen, B. C. P.: Rec. Trav. Chim. Pays-Bas, 1936, 55, 1046. (4) Wang, Y. L., and Harris, L. J.: Biochem. Journ., 1939, 33, 1356. (5) Melnick, D., and Field, H.: Journ. Biol. Chem., 1939, 127, 505, 515, 531. (6) Melnick, D., and Field, H.: Journ. Biol. Chem,. 1939, 130, 97. (7) Harris, L. G., Leong, P. C., and Ungley, C. C.: Chem. Ind., 1938, 57, 85. 8) Light, R. S., Schultz, A. 8., Atkin, L., and Cracas, L. J.: Journ. Nutr., 1938, 16, 333. (9) Leong, P. C.: Biochem. Journ., 1937, 31. 367. K—September 3, 1941. THE CHEMISTRY OF BIVALENT AND TRIVALENT RHODIUM. PaRtT I. A QUALITATIVE STUDY OF THE EFFECT OF REDUCING AGENTS ON TRIVALENT RHODIUM SALTS; AND THE PROPERTIES OF SOME RHODOUS SALTS. By F. P. DWYER, M.Sc., and R. S. NYHOLM, B.Sc. (Manuscript received, August 19, 1941. Read, October 1, 1941.) Recently, attention was directed by Morgan and Burstall (“ Inorganic Chemistry—A Survey of Modern Developments ’’, London, W. Heffer & Sons, 1936, 230) to the surprisingly scant information available concerning bivalent rhodium compounds, of which six examples have been reported. The identity of three of these is extremely doubtful, and in the case of the latter three the rhodous compound appears to have been badly contaminated with the rhodic compound. The simple chloride RhCl, and the oxide RhO have been reported by J. J. Berzelius (Phil. Mag., 1829, (2), 5, 395 et al.) as arising from the action of chlorine on rhodium and the pyrolysis of the sesquioxide, respectively. More recently L. Wohler and W. Muller (Zeit. anorg. Chem., 1925, 149, 125) reported the preparation of these two compounds admixed with the monovalent compounds RhCl and Rh,O by the pyrolysis of the corresponding trivalent compounds at 965-970°. The reddish brown RhCl, was separated from the monovalent compound by levigation with carbon tetrachloride. The chloride or the oxide failed to dissolve in hydrochloric acid or water, and no other compounds could be prepared from either. According to J. J. Berzelius the chloride is greyish red, whilst the experience of the present authors is that it is almost black. Similarly, Berzelius (ibid.) reported the preparation of the sulphide as a steel-grey powder by either the pyrolysis of the sesquisulphide or the action of sulphur on rhodium. The compound was insoluble in all acids, whilst the experience of the present authors is that it is black, and soluble to a dark red solution in boiling concentrated hydrochloric acid. Seubert and Kobbé (Ber., 1890, 23, 2558) isolated a yellow compound to which the formula 2RhSO, . 3Na,SO, .44H,O was assigned. The existence of this compound as a rhodous salt was criticised by Reihlen and Huhn (Zeit. anorg. Chem., 1933, 214, 189), who showed that the substance was not oxidised by iodine, and was probably a basic rhodic sulphite associated with 2-4 molecules of sodium sulphite. Using various mixtures of sodium sulphite, sodium bi- sulphite, sodium sulphate, and bisulphate, these latter authors claimed to have isolated the following three compounds: WNa,(Rh(SO3)..SQ,) ; Na,(Rh,(SO3), .SO,); Na .(Rh(SO;),). The brownish yellow compounds were assigned the above formule by the method of ratios, were insoluble in water and organic solvents, but dissolved in dilute hydrochloric, sulphuric and oxalic acids to golden coloured solutions. At higher concentrations of sulphuric acid they dissolved to a redder colour, evolving sulphur dioxide and forming presumably sodium rhodous sulphate. During this research it was noted that rhodous chloride and sulphate were very dark red, and hence it would appear that Reihlen and Huhn in reality isolated sodium rhodic sulphites possibly containing traces only of the rhodous compounds. THE CHEMISTRY OF BIVALENT AND TRIVALENT RHODIUM. 123 EXPERIMENTAL. The rhodium trichloride solutions used were prepared by solution of the pure metal in potassium bisulphate, precipitation of the oxide and solution in hydrochloric acid. The solution was 1% concentration reckoned as rhodium metal, and was one normal with respect to hydro- chloric acid. The various reducing agents used were found to fall into the following five classes : Class (1). Those that carry the reduction completely to the metal without any indication of an intermediate rhodous stage, viz. chromous chloride in acid solution, alkaline solutions of formic acid, formaldehyde, hydrazine hydrate, and sodium hypophosphite, the metals copper, lead, antimony, bismuth and tin. At room temperature the metal was deposited slowly in brown colloidal form, but at boiling point as a black pulverulent precipitate. Mercury was without effect, as also was silver in the presence of chloride ion. In the presence of iodide ion at boiling point, silver gave a mixture of black rhodium triiodide and rhodium metal. Class (2). Those which under all conditions yield a mixture of rhodium metal and rhodous compounds, viz. sulphurous acid, formic acid, formaldehyde, and silver foil in the presence of bromide ion. No reaction was apparent at room temperature, but on boiling for some time the solution darkened considerably and simultaneously deposited a fine precipitate of rhodium metal. In weakly acid or neutral solution, under the conditions stated by Reihlen and Huhn, sodium sulphite gave a pale yellow precipitate presumably of basic sodium rhodic sulphite, since it was readily soluble in dilute hydrochloric acid to pale orange yellow solutions. On boiling for two to three hours the basic sulphite precipitate darkened slightly, and then dissolved in hydrochloric acid to a somewhat reddish solution. Under the latter conditions it would appear that slight reduction to the rhodous state occurred on the surface of the granules. Class (3). The reducing agents of this group may form some rhodium metal, but chiefly dark intensely red solutions of complex rhodous compounds, viz. hypophosphorous acid, sodium hydrosulphite, and sodium formaldehyde sulphoxylate (‘‘ Rongalite ’’). The reaction with hypophosphorous acid was autocatalytic. No reaction occurred at room temperature, but at the boiling point of the mixture, the solution commenced to darken after about 30 seconds, and then, almost instantly the solution became very darkred. With an amount of reducing agent corresponding to the theoretical equation H,PO,+ 4RhCl,; + 2H,0O>H,;P0,+4RhCl,+ 4HCl the reduction occupied 7-8 minutes at 102° C., but appreciable amounts of rhodium were deposited as metal. With double this amount of reducing agent the reaction was complete in 2-3 minutes at 100°C. An intensely dark red solution resulted, traces only of metal were deposited, and a gas identified as hydrogen was evolved. With an extremely large excess of reducing agent over the latter conditions, the reaction was complete almost instantly at 100°, large volumes of hydrogen gas were evolved, and the dark red solution deposited no rhodium metal even after 8 minutes at 102° C. Proof of the reduction of rhodium to the bivalent state in the above reactions has been afforded by the isolation of analytically pure specimens of tris-diphenylmethylarsine rhodous halides by treating rhodium trihalides with the arsine, the corresponding halogen acid, and hypophosphorous acid. These compounds will be described in a subsequent communication. Curiously enough, addition of the arsine and a halogen acid to solutions of rhodium trichloride previously reduced with hypophosphorous acid gave only very small amounts of tris-diphenyl- methylarsine rhodous halide. This suggested that the rhodium after reduction with hypo- phosphorous acid was bound in some form of a complex. This view was supported by the failure to prepare derivatives of bivalent rhodium by the addition of 8-hydroxy quinoline or ethylene- diamine bis-salicyaldehyde. Similarly, the simple sulphide RhS could not be prepared by passage of hydrogen sulphide except under such conditions of acidity that much rhodous phosphate or phosphite was co-precipitated. By using alkaline sodium hypophosphite and alkali rhodicyanide, Manchot and Schmid (Ber., 1931, 638, 1872) obtained a colourless solution with strong reducing properties, which were attributed to monovalent rhodium present as Na,Rh(CN)3. It was found that the reaction 124 DWYER AND NYHOLM. could be performed easily, but on acidification a very dark red solution resulted. Since this colour was found to be characteristic of bivalent rhodium compounds, it would appear that the substance prepared by Manchot and Schmid was probably Na,Rh(CN), containing bivalent rhodium and analogous to sodium cobaltocyanide. Some indications of monovalent rhodium were noted in the reductions performed with hypophosphorous acid. With an excess of the reducing agent, and heating to 100° unt! a violent evolution of hydrogen gas commenced, followed by rapid cooling in ice, a brownish yellow solution resulted which acted as an extremely powerful reducing agent. This solution probably contained monovalent rhodium and the evolution of hydrogen gas is due, it is suggested, to reaction between the mineral acid and the monovalent rhodium salt, which thereby passes to the bivalent state 2RhCl+ 2HCl—2RhCl,+ Hg. In hot hydrochloric acid, Asmanow (Z. anorg. Chem., 1927, 160, 209) has noted that solutions of chromous chloride are oxidised to chromic chloride with the evolution of hydrogen gas. Finally, it was noted that the reduction with hypophorous acid was catalysed by traces of copper of the order of 1%, but seemed to be inhibited by larger amounts of the order of 5% of the rhodium being used. The reduction was also inhibited by concentrated mineral acids. In hydrochloric acid solution from 1 N to 5N rhodium trichloride was reduced instantly at room temperature by sodium hydrosulphite to an intense red colour recalling the colour of concentrated ferric thiocyanate. Instantly at 100° and slowly at room temperature, the reduction proceeded to the metal. The reaction could be performed on sodium rhodite at 80° but the resultant precipitate which was dark brown, was only partly soluble in acid, and was contaminated with rhodium metal. The dark red solution appeared to contain a complex sodium rhodous sulphite, which could be precipitated with alcohol, but no simple derivatives such as the sulphide or the 8-hydroxyquinolate could be prepared from it. Sodium formaldehyde sulphoxylate even when present in large excess reduced rhodium trichloride at 40° C. to an intense ruby red coloured solution. Addition of alcohol precipitated a dark red powder, which was completely soluble in water, contained sodium, rhodium, formal- dehyde and sulphite, and was decomposed by iodine, or hydrogen peroxide. No simple rhodous salts could be prepared from this complex. Further investigation on the reducing agents in this group is proceeding. Class (4). Those that carry the reduction to the rhodous state only, but owing to the slow rate are impracticable except in inert atmospheres, viz. acid solutions of hydroxylamine chloride or sulphate, and the corresponding hydrazine salts. The reduction was found to occur only at boiling point, and was catalysed by a trace of cupric chloride, which was apparently reduced instantly to the cuprous state and then acted as the reducing agent for the rhodium. Curiously enough hydroxylamine hydrate failed to reduce sodium rhodite at 100°, the resulting yellow precipitate of rhodium sesquioxide containing no trace of either rhodium metal or rhodous oxide. Solutions of cuprous chloride are well known for the reduction of chloroplatinates to chloro- platinites. With rhodium trichloride the reduction to the rhodous state did not proceed beyond about 20%, and it is suggested that the reaction RhCl, + CuCl->RhCl, +CuCl, rapidly reaches an equilibrium—i.e. that the oxidation-reduction potential of the reaction Rh?+-+e—Rh?+ is of the same order as that of the reaction Cu?++e—>Cut (0:21 volts). This observation is supported by the fact that solutions of rhodous chloride prepared by another method only partly reduced cupric chloride solution, and by the failure of the arsine stabilised rhodous halides to yield more than a trace of cuprous chloride by reaction with alcoholic cupric chloride solution. The copper salt catalysed reaction with hydroxylamine hydrochloride apparently depended upon the continuous reduction of cupric ions preventing their accumulation in the solution. Class (5). Those that carry the reduction completely to the rhodous state without complex formation or the production of any rhodium metal, viz. stannous chloride and sodium stannite. According to J. J. Berzelius (loc. cit.), addition of stannous chloride to rhodium trichloride solution yielded a pale yellow precipitate easily soluble in excess acid to a yellow solution. N. W. Fischer THE CHEMISTRY OF BIVALENT AND TRIVALENT RHODIUM. 125 (Schweigger’s Journ., 1889, 53, 117, 173) claimed that a yellow or brown precipitate or a brown solution resulted depending on the acid concentration. More recently, W. Singleton (Ind. Chemist, 1927, 3, 121) advanced the reaction as a test for rhodium. At boiling point it was claimed that a brown colloidal solution resulted, and ultimately a fine crimson colour recalling Purple of Cassius. It has now been found that addition of weakly acid stannous chloride to almost neutral rhodium trichloride solution gave a fine yellow precipitate instantly at room temperature. At 100° for a few seconds, the precipitation was complete, and the residual solution was found to be free of rhodium and almost free of tin. The precipitate varied in colour from yellow to orange, and conformed to no fixed composition. The same types of precipitate could be prepared by the addition of stannous hydroxy-chloride to almost neutral rhodium trichloride. The substance was freely soluble in hydrochloric acid to orange yellow solutions, and consisted undoubtedly of mixtures of basic stannous and rhodic chloride. When the mixed basic salts were heated with water at 100° for fifteen minutes, the colour darkened considerably, and the precipitate then dissolved in hydrochloric acid to a dark red solution. Addition of sodium sulphate to this solution at boiling point precipitated some of the tin as stannic oxide, hence it is concluded that the dark precipitate consisted of a mixture of the basic salts of rhodous, rhodic, stannous and stannic chlorides. In hydrochloric acid solution above a concentration of 2 N mixtures of stannous and rhodic chloride gave no precipitate on boiling, but after a few minutes the colour darkened, changing at the end of four minutes to an intense red. No metal was deposited, and there was no evidence to suggest that any metal was in the colloidal form. By the addition of tertiary arsines to the red solution, it has been possible to prepare pure specimens of the compounds RhCl, . 3AsR,, and RhCl, . SnCl, . 3AsR3, which will be described in a subsequent communication. At room temperature sodium stannite was without effect on sodium rhodite but at 70-80° the colour changed to dark red and a dark red precipitate of indefinite composition consisting of rhodous hydroxide, stannic hydroxide and sodium stannate was deposited. At boiling point this precipitate changed in colour to almost black, due it is considered to the decomposition of the rhodous hydroxide to the hydrated oxide. Both the dark red and the black precipitate were soluble in hydrochloric acid to dark red solutions. Rh(OH),+RhO+H,0 All attempts to free the above preparations from tin salts have failed. Tests on samples of rhodous hydroxide and oxide after ten washings with hot caustic soda in an apparatus filled with nitrogen, showed them still to be contaminated with stannic tin. Since stannic sulphide normally does not precipitate in hydrochloric acid solution above 0:5 N, attempts were made to prepare pure rhodous sulphide by passage of hydrogen sulphide through solutions of rhodous hydroxide in 8N hydrochloric acid. Stannic sulphide, however, was co-precipitated. This behaviour recalls the co-precipitation of cadmium sulphide with mercuric sulphide in strongly acid solution, in which cadmium sulphide alone would fail to precipitate. (Feigl, Mikrochem., 1923, 1, 4.) The Properties of Some Rhodous Salts. Despite the unfortunate contamination with tin, it is considered valuable to indicate some of the properties of a few simple rhodous salts. The salts were prepared from rhodous hydroxide after ten washings with hot normal caustic soda, and contained approximately 10% tin as the stannic salt. Rhodous chloride was a black hygroscopic solid, and contained water of crystallisation. It was hydrolysed instantly by water, yielding an orange basic salt, but dissolved in hydrochloric acid to a dark red solution, which absorbed oxygen from the air with a progressive decrease in colour. Solutions of mercuric chloride were reduced slowly at room temperature to mercurous chloride, but instantly at boiling point to black mercury. Cupric chloride was only partly reduced at boiling point. Nitric acid oxidised rhodous chloride on warming, but hydrogen peroxide and potassium permanganate instantly at room temperature. On prolonged boiling in an inert atmosphere solutions of rhodous chloride underwent self oxidation and reduction with lightening 126 DWYER AND NYHOLM. of colour and the separation of metallic rhodium. Addition of sodium, potassium, ammonium or rubidium chlorides failed to precipitate a complex chloride. Rhodous bromide and iodide were soluble salts similar to the chloride although darker in colour. Rhodous iodide was extremely soluble in water to an intense purple solution, which rapidly oxidised in the air with the separation of the black insoluble rhodic iodide. Rhodous oxide and hydroxide were not so sensitive to oxidation as the chloride, but showed no amphoteric properties like the corresponding rhodic compounds. Rhodous sulphide was precipitated from solutions of the chloride by passage of hydrogen sulphide in acid concentrations up to 8N. The black flocculent precipitate was dark reddish brown by transmitted light, but settled to a fine black precipitate on heating for a few minutes at 100° C. It was insoluble in ammonium sulphide, but dissolved slowly in boiling concentrated hydrochloric acid to a dark red solution with the evolution of minute bubbles of hydrogen sulphide. The substance was easily soluble in dilute hydrochloric acid in the presence of a minute trace of nitric acid, but with higher concentrations of nitric acid the orange rhodic chloride was formed. Department of Chemistry, Sydney Technical College. THE CHEMISTRY OF BIVALENT AND TRIVALENT RHODIUM. Part Il. HEXACOVALENT COMPLEXES OF RHODOUS HALIDES WITH DIPHENYLMETHYLARSINE. By F. P. DWYER, MSc., and R. 8. NYHOLM, B.Sc. (Manuscript received, August 19, 1941. Read, September 3, 1941.) In the previous paper (Tus Journat, 1941, 122) evidence was adduced to show that trivalent rhodium salts were capable of reduction to the bivalent rhodous state by a variety of reducing agents, but owing to the difficulty of purification of the reduced products, no analytically pure compounds could be isolated. In accordance with the well accepted principle that unstable valency states might be stabilised by suitable coordinating groups, a great number of substances were tested including 8 hydroxyquinoline, thiourea, ethylene- thiourea, thioglycollic acid, dithiooxamide, and a number of tertiary arsines. Although evidence was obtained of complex formation in all cases, the latter series of substances proved the most suitable. These latter compounds have been studied extensively by Burrows and his co-workers (Tus Journar, 1940, 74,M 14), have been found to coordinate readily with a great variety of metallic salts, and further possess the excellent property of being mild reducing agents because of the tendency of trivalent arsenic to pass to the tetracovalent state. For instance, cupric chloride is reduced to cuprous chloride, which may be isolated as complex with the excess tertiary arsine (Burrows and Sandford, apid., 1935, 69, 182). When rhodium trichloride is heated with a tertiary arsine in alcoholic solution, the arsine coordinates fairly slowly and soluble rhodic coordinated compounds may be isolated in which the metal exhibits a coordination number of six. Even on continued boiling with alcohol these rhodic compounds, which will be described in detail in a subsequent paper, show no tendency to undergo reduction. However, they may be easily reduced with hypophosphorous acid in strongly acid solution and the insoluble rhodous complexes isolated in crystal- line form. Curiousiy enough, if a rhodic salt such as rhodic chloride is previously reduced with hypophosphorous acid and the arsine then added in the presence of a large excess of concentrated hydrochloric acid, there is no evidence of complex formation and the arsine may be recovered unchanged. This effect is due no doubt to the formation of a stable rhodous hypophosphite complex, which is unaffected by even concentrated hydrochloric acid. The arsine compounds described in this paper are coloured crystalline solids, with sharp melting points. The colour darkens progressively as the compounds pass irom chloride to iodide. They are insoluble in water, and ionising solvents such as alcohol, and yield no precipitate of the silver halide on treatment with Silver salts. This latter fact coupled with their relatively low melting points, and ready solubility in organic solvents such as chloroform or benzene, suggest that they are completely covalent. They possess the general formula Rh. X, .3((C,H;),Ch3;As) and are dimeric in boiling chloroform. In the pro- posed structure (I) the rhodous metal is given a coordination number of six, and the molecule is bridged by chlorine atoms in the well-known manner of 128 DWYER AND NYHOLM. aluminium chloride, and the compounds of cuprous and cupric chlorides, and _ palladous chloride with tertiary arsines and phosphines. x Askg te ge sana! dl SS ,€ EXPERIMENTAL. Tris-diphenylmethylarsine Rhodous Chloride. Rhodium trichloride 0-13 g. dissolved in water 20 mls., was treated with diphenyl methyl] arsine 0-9 g. dissolved in ethyl alcohol 120 mls., and concentrated hydrochloric acid 15 mls., and 30% hypophosphorous acid 1:5 mls. added. The mixture was refluxed until at the end of 40 minutes the bumping due to the precipitation of solid became very violent. After cooling, the brown crystalline precipitate was removed, washed with alcohol and water several times, and dried in the steam oven at 100°C. The compound may be crystallised from hot benzene. It crystallised in leaflets and rhombs, and by reason of the square twinning the crystals belong probably to the rhombic system. On heating the substance melted sharply at 171° to a black liquid which then evolved arsine and left a black or silvery residue of rhodium. The compound was insoluble in water and alcohol, very sparingly soluble in hot acetone, but easily soluble in warm benzene and chloroform to a red solution. In acetone or pyridine, the compound reduced silver nitrate to the metal, almost quantitatively, and mercuric chloride to mercurous chloride. In cold pyridine the reduction of silver nitrate was instantaneous (even in boiling acetone the arsine itself does not reduce silver nitrate). The compound was stable to boiling concentrated hydrochloric acid, and cold caustic alkali, but the latter reagent at 100° liberated the arsine and left a black tarry residue. The substance was analysed for rhodium by ignition, slowly at first to remove arsine, then at bright red heat in an oxidising atmosphere, and finally in a reducing atmosphere. This latter condition was easily realised by fitting the crucible with an oversize lid. The residue of metallic rhodium was always a bright silvery colour. The halogen was estimated by distillation of the compound with concentrated sulphuric acid, and absorption of the acid in standard silver nitrate solution. This method, which will be described later in detail, was checked by estimation of the halogen by the method of Burrows and Lench (THis JoURNAL, 1936, 70, 218). Found: Rh, 11-28%; Cl, 7-68%; mol. wt. (Chloroform, ebullioscopic), 2030, 1597. Calculated for [RhCl, . 3(C,H;)..CH,.As)],: Rh, 11-35%; Cl, 7-83; mol. wt., 1812. (After boiling with chloroform for some time a slight precipitate separated, due no doubt to oxidation. This probably accounts for the lower molecular weight in the second determination.) Tris-diphenylmethylarsine Rhodous Bromide. A solution of rhodium trichloride containing 0-216 g. of rhodium was treated with excess of sodium carbonate, and boiled for some time to precipitate the hydroxide completely. The yellow precipitate after washing was dissolved in 15 mls. of 10 N hydrobromic acid, and diphenylmethylarsine 1-52 g., alcohol 150 mls. and hypo- phosphorous acid (30%) 1:5 mls. added. After refluxing as before, the solution darkened at the end of three minutes, and the compound commenced to precipitate. The reaction was complete in sixteen minutes. The reddish brown leaflets melted at 180° C., and were insoluble in alcohol, very sparingly soluble in hot acetone, but easily soluble in hot chloroform to a red solution. As before, silver nitrate solution was reduced to metallic silver. Found: Rh, 10-27%; Br, 16-03%. Calculated for [RhBr, . 3(C,H;)..CH,.As)],: Rh, 10°34%; Br, 16-06%. Tris-diphenylmethylarsine Rhodous Iodide. Owing to the insolubility of rhodium triiodide in water, the method used for the preparation of the bromide was not available. A solution of rhodium trichloride containing 0-0864 g. of rhodium dissolved in 10 mls. of water was treated with 10 mls. of 64% hydriodic acid, previously just decolorised with hypophosphorous acid, and THE CHEMISTRY OF BIVALENT AND TRIVALENT RHODIUM. 129 immediately with 0-76 g. of diphenylmethyl] arsine dissolved in 100 mls. of ethyl alcohol. The resulting dark solution of tris-diphenylmethylarsine rhodic iodide was then reduced by refluxing with 1-5 mls. of 30% hypophosphorous acid. At the end of 30 minutes the dark brownish red precipitate was removed. The substance, like the chloride and the bromide, crystallised in leaflets, m.p. 168° C., and was insoluble in water and alcohol, but dissolved easily in chloroform to a dark red solution. A suspension in hot acetone rapidly reduced silver nitrate to the metal. Found: Rh, 9-34%. Calculated for [RhI, . 3(C,H;)..CH,.As)]o: Rh, 9-45%. SUMMARY. The preparation of three rhodous halides stabilised with diphenylmethyl- arsine is described. The compounds are shown to be dimeric and to act as powerful reducing agents. ACKNOWLEDGMENT. The authors are indebted to Mr. D. P. Mellor for making available samples of diphenylmethylarsine and other tertiary arsines. Department of Chemistry, Sydney Technical College. L—September 3, 1941. Amen oe 29 ch a PEC Say T ha : _ AUSTRALASIAN Company Viet Li OF New SOUTH WALES Pen AG Fe ee 1941 (INCORPORATED 1881) or os to 174: and pp. i to xxxv) ge a 3 : OF : VOL. LXXV_ and fades EDITED BY THE HONORARY SECRETARIES — } AUTHORS OF PAPERS ARE ALONE. RESPONSIBLE FOR THE aaa ig ete AND THE OPINIONS EXPRESSED 7 EET ran 3 6 154.3 : syDNEYE cca _ PUBLISHED BY THE SOCIETY, SCIENCE HOUSE GLOUCESTER AND ESSEX STREETS 1942 Fe %. : Part Vv By Toe Faeee M.A., D.Sc. issued Apa 2 22, 1942), ART. XVL —The Ghedtueny of Bivalent and ‘Trivalent Rhodhuen’ Pork u 1 _ Ce of Rhodic Halides with Tertiary Arsines. By F. P. oe M. Se., and LR. B.Se. (Issued Bnet. Paes Rare eaereee ae ag Arr. XVIL. The Triassic ‘Fishes OF alew: South Wales. ‘By cs T. Wade, - une April 22, sees. Rekaiee ae as A ete hed are 2 eae eee 4 - . ae ; ys By A. R. Penfold, FA. C. L, F. C. ae F. R. Moree: A: S. 7. Cn White, B.Se. Agr. (Issued ie pe sont Coveney : > to hee Magnetic Propet and the Cotton Effect. By D. is ‘Mello April me Beads ris ene ae i il ee ae eens Sek Arr. XX.—On the Proaveney of of the Primes. By: F. A. Behrend. _tTssued May iiss TITLE PAGE, CoNTENTS, Noricss, PUBLICATIONS. Orricers FoR 1941-42...) w. ABSTRACT OF PROCEEDINGS ...0 .. PROCEEDINGS OF THE SECTION OF GEOLOGY _ Sut ath ais % et ice comes: Ngee gl SAeaeS 2 ane ‘OF THE Bee « Inpustry > “Ixpex ‘TO Votume LXXV ar Yate Pies and Proceedings of the Royal Society of New South Wales VOLUME LXXV PART IV ey 0 1941, RADIAL HEAT FLOW IN CIRCULAR CYLINDERS WITH A GENERAL BOUNDARY CONDITION. II. By J. C. JAEGER, M.A., D.Sc. (Communicated by Professor H. S. Carslaw.) (Manuscript received, August 1, 1941. Read, October 1, 1941.) 1. In these Proceedings! a number of results were given on conduction of heat in regions bounded internally or externally by circular cylinders with boundary condition ov ov kya thom +k,v=k, © 0.6 0 © © 0 6 6. ne 0 0 0 0. @ «baa 16,0) wp folel\el eltelic lisiiaitariee (1) at a surface. The solutions were obtained by a formal method using the Laplace transformation and it was remarked that it could be verified by a procedure previously developed elsewhere? that they did in fact satisfy the differential equations and boundary and initial conditions of their problems. The verifica- tion procedure described in II is applicable to a wide range of one-variable problems in conduction of heat, and, since only some special problems of those in III were verified, it seems worth while indicating that the complete set of results obtained in I may be verified in this way. These include most of the results of III as special cases. In §§2, 3, 4 three results on the nature of the roots of certain equations involving Bessel functions, which were stated without proof in I and are of intrinsic interest, will be proved for a set of conditions including those of physical interest in I. 2. The Roots of the Equation.® (lz? —m) J (2) +-ned (2) =0 ......... J eee (2) where 1, m, 0 are real constants, are all real and simple (except possibly for z=0) provided 1220, M20, WO Las ie es ea ee (3) In (2) we may without loss of generality take />0 and if l=0 we take m > 0. This convention is implied, here and subsequently, in stating results such as (3), (6) and (8). If some of 1, m, n vanish the equation (2) reduces to a simpler form. If lm =0 the result is wellknown. Ifn=0 the equation becomes (lz*—m)J ,(z) =0, ' which if 1>0, m>0, may have double roots at +(m/l)}, if (m/l) is equal to a root of J,(z)=0. (i) A pure imaginary root z=vy of (2) is a real zero of (ly? pan) T (yg) ny y) oe ee on (4) Now /,(y) and J,(y) are both positive for real positive y, so the expression (4) is certainly always positive if y>0O and conditions (3) are satisfied. Thus (4) has no real positive zero, and since it is an even function it has no real negative 1 Journ. and Proc. Roy. Soc. N.S.W., 1940, 74, 342. This paper will be referred to as I. 2 Proc. Cambridge Phil. Soc., 1939, 35, 394. Proc. London Math. Soc., 1940, 46, 361. These papers will be referred to as II and ITI, respectively. 3This is I (13). WAR - 3 108 i + ae RADIAL HEAT FLOW IN CIRCULAR CYLINDERS. 131 zero. If the conditions (3) are not satisfied there may be no, one, or two real positive zeros of (4). (ii) The equation (2) has no complex roots if the conditions (3) are satisfied. For if & and 7 be conjugate complex roots of (2), we have (122 —m)dJ 9(&) —n&J" (6) =0 (In? —m)J (1) —n 4d" (4) =9. Thus U(r? —&?)J o(&)J o(9) +nET" 9(8)J o() — J" (n)F o(&)} =0. Therefore* ’ Un? —F?)J 9()J o(y) +-2(7? -f HI (&x)T o(nx)da =0. fy) If 1>0, n>0 this is impossible, so there can be no complex root. (iii) The equation (2) has no repeated roots, except possibly z=—0, if the conditions (3) are satisfied. For writing® | y = (le? —m)J o(2) +ned (2), we find yT (2) +2 (2) ef (2 +n) (2) 4nd (2). Thus if 240, 1>0, n>0, y and 2 cannot vanish simultaneously. 3. The expression® (eater PUN (zm CUN (Gi) a ctrehe ceo xa0es oh o's \eite) Be aliayloyinn'e (5) has no zeros for R(z)>0, provided PEO me Oe Ol Nise ey 6 aa ede heats (6) As in §2 we take />0, and if 1=0, m>0. If l=m=0 the result is well known. If n=0, 1>0, m>O there are zeros at +7(m/l)?. (i) The expression (5) has no zeros for real positive z if the conditions (6) are satisfied, since K,(z)>0, K,(z) >0, for real positive z. (ii) The expression (5) has no complex zero € For if 7 is the conjugate of €, using the argument of §2 (ii) with G. and M., p. 70 (30), we have oO (22 —7?)LK o(&)K o(7) —n(&? —¥?) i aK ((Ex)K o(nx)dx =0, and if 1>0, n<0 we have a contradiction. (1) The expression (5) has no pure imaginary ZeYO z=vy, for this implies (ly? —m)[J o(y) —1¥ o(y) ]—ny{d oly) —1¥'o(y)]=0. ae J ly) Y'oly) —Y o(y)F oly) =9, sve but this is equal to (2/zy) and so we have a contradiction. It follows that 4. The Zeros of? P (2) =[(l2* —m)J 9(az) +-ned ; (az) |[ (U2? —m') ¥ 9(bz) +-n'2 ¥ 4 (bz) | —[(UV22 —m')J 9(bz) +'2d (bz) |[ (le? —m) ¥ o(az) +-nzY,(az)] .... (7) are all real and simple (except possibly for z=0), provided Peel 0, 20 i Oy 0 ee aa a hie eee (8) ‘Using Gray and Mathews, Treatise on Bessel Functions, p. 69 (23). This work will be referred to as G. and M ‘I am indebted to a referee for this argument. . © This result is needed in I, §§5 and 6. ? This is I (30). 132 J. C. JAEGER. We suppose 6b >a in the discussion. The cases in which n or n’ vanish are discussed in (iv) below. (i) A pure imaginary zero z=-+1y of (7) is a real positive zero of [(ly? +m)L (ay) +-nyl, (ay) ][(U'y? +m')K (by) —n'yK (by) ] —EUy? +m')f (by) +n'yl, (by) (ly? +m) K (ay) —nyK,(ay)]=0 .. (9) which may be written (ly? +m) (Uy? +m’) [I (ay) K (by) —K o(ay)l (by) ] —nn'y? [T, (ay) (by) —K, (ay)1,(by)] : +ny (Uy? +-m'){ I, (ay)K (by) +K,(ay)l (by)] —n’'y (ly? +m) [1 (ay) K, (by) +1, (by) K p(ay)] ...-...-22-6ee (10) It is known that In(ay)Kn(by) —In(by)Kn(ay), n=0 and 1, have no real positive zeros. Taking b>a, it follows from the asymptotic expansions that they are negative for real positive y. Also I,(x), I(x), K(x), K,(#) are all positive for real positive 7. Thus if the conditions (8) are satisfied, all four terms of (10) are <0 for real positive y and thus there is no real positive zero of (9). (ii) Suppose « is a zero of (7), then U =[(la?—m) Y 9(aa) +na VY, (aa) ]J o(ar) —[ (la? —m) JS 9(aa) +nad (aa) |¥ (ar) ig @ non-zero solution of the differential equation _ mle =, +820 =O, @araed 1... eee (11) with boundary conditions dU 7 yp een — —— es SS oe (la? —m)U —n FE 0, Y= Also, for any 6, | V =[(UB? —m)¥ o(aB) +08 ¥4 (a8) lJ (Br) —[(L8* —m)J (a8) +B (a8) IY o(Br) satisfies 1 -d/ adv . - a” zr +-OV=0, 4rd... ae ee (13) with (iB? —m) V — —n =0, TOs chy isle, Sioa eee (14) From (11) and (13) it follows that b dU dV |b ee POV ar+|rV GU 4] =0, a a and hence, using ( ) and the notation (7), we have : (a2 — 2) ff pe a Lane SNA si ="7(6)[T] Suppose a 1s a complex zero of (7) and @ its conjugate. Then F(6)=0, and 1) becomes ° a” — 3%) a il Dips U2 — naa Gl te: a a r=b ™ r=4 Thus if 1>0, l’>0, n<0, n’>0 we have a contradiction, and no complex root is possible. (iii) To show that (7) has no repeated zeros, let « be a zero (real) of (7) and let 8 be real and tend to « Then as Ba, V-U and F()/(8 —«)>F"(«). RADIAL HEAT FLOW IN CIRCULAR CYLINDERS. 133 Thus (15) gives a a} * ode pO Shera pan | el is meat He Li Ly r=b If « is a repeated zero of (7), F’(a)=0. Thus if «540, and the conditions (8) are satisfied, we have a contradiction. | (iv) If n=0, l’>0, m’>0, n’>0 we have F(z) = (le —m)G (2), where G(z) =d (az) [(V'2? —m’) ¥ (bz) +n'2z¥ (bz) ] —Y ,(az) [(U'2? —m’) J 9(bz) + n'2d (62) J. The method of (ii) and (iii) may be used to show that the zeros of G(z) are all real and simple. If (m/l)? is equal to a zero of G(z), F(z) will have double zeros at -+(m/l)?. A similar result holds for the case n’=0, 1>0, m>0, n<-0. If n=n'=0, we have F(z) =(lz* —m) (V2? —m')C ,(az, bz) where C (az, bz) =d 9(az) ¥ 9(bz) — Y o(az)J 9(bz). The zeros of C,(az, bz) are known to be all real and simple. F(z) has a repeated zero if (m/l)? or (m’/l’)? coincides with one of them. 5. The method of solution used in I consisted of forming from the original differential equation and boundary conditions a subsidiary equation and boundary conditions, from the solution v(p) of which the solution v(t) of the original problem was derived formally by the use of the inversion theorem, namely a (Rigeacceae v(t) “al é DO D)VGK GG Bio 6 5 ele fayette ae eee (16) | ue and the solution was obtained in its final form from the line integral in (16) by using the contour of Fig. 1 or Fig. 2. To make the solutions rigorous we Fig. 1. Fig. 2. 134 J. C. JAEGER. verify (a) that v(t) given by (16) satisfies the conditions of the problem, and (b) that the integrals over the large circles of Figs. 1 and 2 tend to zero ag the radius tends to infinity. 6. The method of verifying that solutions obtained in the form (16) satisfy their differential equations and initial and boundary conditions consists of transforming the path L, (y—i0oo, y+70), of (16) into a path L’ which begins at infinity in the direction argA=—6, x >6>4n, keeps all singularities of the integrand to the left and ends in the direction argA=(. The verification is then performed on the integrals over ZL’. Most of the verification is performed by the use of Theorem 2 of II, which is restated here for convenience and to include two small extensions proved as in II. THEOREM 2. [If f(a, &) is an analytic function of on and to the right of the path L’, and if | | f0, &) |< OR* exp[—ER cos 30], when 4=Ret'O, rx >0,>050, R>R,, where C, k<1, Ro, and 0,>42 are constants, then . t dh At an (i) i “fA, I= | df, 8) S, | L L’ provided that either t>0, —>0, or t>0, &>0. i t dx (i) i} FQ, F ys * is uniformly convergent with respect to t in t>0 for fixed & >0, and with respect to Ein £50 for fixed t>0. Also the integral may be differentiated under the integral sign with respect to t in t>0 for fixed &>0, or in t>ty>0 for fixed €>0, and the resulting integral is uniformly convergent with respect to & in &>0, for fixed t>0. (iii) lim | he E)O—0, for fiwed &>0. ORK t+>o (iv) If, in addition, of/0& and of/0&? satisfy conditions of the type satisfied by f(A, ©) except that k need not be less than 1, then : Hi ia, )o NW may be differentiated twice under the integral sign with respect to &, in &>0, for fixed t>0. (v) If the range of & extends to infinity, lim Ul Pye, i a for fixed t>0. Proof of (v) is as for the special case in Paper II. In §§7, 8, 9 verifications of the solutions of §§2 and 5 of I and the source problem of I, §3 are given in detail. The results of I, §4 and the other source problems of I may be treated in the same way. RADIAL HEAT FLOW IN CIRCULAR CYLINDERS. 135 7. Verification that I (11) satisfies the conditions of I, §2. We write f(A)=(K,A+4K,)1 (ua) +khopl (ua) ........ eee eee ee eee (17) where p= /(A/x). From the asymptotic expansions of the Bessel functions it follows that yO Oeics isiale ole oielal alle wapeleld aleve se ds ie aa (18) | f(A) | >Coe exp[apt cos 40], if ele NENA alan Rey ou teia( (19) where® « is 3/4, 1/4, or —1/4 according as k,40; k,=0, k,40; or k,=k,=0; respectively. ene) TRE ON p9, O0, 0o To verify the boundary condition I (4) we take v in the form (22) and observe that by Theorem 2 (ii) we may differentiate under the integral sign with respect to r in 00, and with respect to ¢ in t>t,>0 for fixed r in O00. Thus kg OT Per er ——Wae 270 L’ mn th +k 3U ; ov Ov lim (k,= +k,—+k,v) = Ae WOE Once 8. Verification that I (36) satisfies the conditions of I, §5. Writing g(A) =(hyA +h) K (ua) —Khop Ky (pd) oo. cee cece ee eee (23) we find as in §7 that for A=xpe#, m>050, HK 9 ( Ele) |< op exp) —(7—a)o? cos 40], poy... 2.5. s's- (24) where a=—1, —4, or 0 according as k,=40; k,—0, k.40; or k,=k,=0, respectively. The derivatives satisfy similar conditions. Thus in all cases the conditions of Theorem 2 are satisfied and it follows that the path can be deformed into L’, that v satisfies the differential equation, and that lim v=—0. It is verified as in §7 that the boundary condition at t+o *C is used for any positive constant, 09, p,,. . . for fixed values of e, ete. 136 J. C. JAEGER. r=a is Satisfied. The remaining condition lim v=0 1—> CO follows from Theorem 2 (v). 9. Verification of the solution for an instantaneous cylindrical surface source - over r=r' in the solid cylinder 00,>050, ofr aerig) p,.... (29) | To(ur’ ){Zo(ur)g(A) — Ko(ur)fa)} | fa) with similar results for the derivatives. It follows from (29) and Theorem 2 that w satisfies I (19) and I (20). Also, it follows from (30) that the path of integration in (27) may be deformed into L’, and that the integral over L’ may be differentiated under the integral sign with respect to r in 7’ 0, and with respect to ¢ in ¢>t, >0 for fixed yin r0. Therefore | oy. (30) Ov Ov linn ( oe +k) =. as at or Since we have used the inversion theorem purely formally, and not estab- lished conditions for its validity, to complete the proof it is necessary to show that the application of the inversion theorem to I (21) gives I (18). We consider the region 00, 00, OO>0. | cosh (ua Fri) Pe exp[(n+4)z cos 40] ............ (31) where C is a constant independent of n. ey bas | cosh pa—jni) os cosh (n+ }) ret? — Fri =4) cosh [(2n+1)x cos 10}-+00s| (2n-+1) sin 0-5] = cosh [Qn +1) zt cos #0]{1+sin[(2n+1)x sin 40] sech[(2n-+1)z cos 40]} 2n +3/4 Oy tes Then 00>8. Also, when B>0>0, | sin[(2-+1)z sin 40] sech [(2n-+1)z cos $6] |< sech [(2n+1)z cos 48]0>0, cosh (ua—qni) >c exp [(n+4)x cos 40] Now let 8=2sin"} use The same argument gives, when A=x(n +3)? 68, >C exp [(n+4)z cos 40]...... (32) | cosh (va -7) 138 J. C. JAEGER. 12. The problem of I, §2. Here, using the notation (17) ee YH MT (urd ani ae Tinie: Now it follows from the asymptotic expansions of the Bessel functions that _2(kyA+ kz)et™ ie 2hopert™ = RW f(A) = ~ (2npa)t cosh La qn) “@nua)t cosh (wa a +similar terms 0( :) compared with the above. 2 Thus, if A=x(n-+4)? Sei6, x>0>0 | fo) > em exp[{(27+4)x cos 40), n>... 6s ee ee (34) hae the results (31) and (32) have been used and « is 3/2, 4 or —4 according aaae IN ear i: : Thus on A=x(n +4)? =e T(ur) | na ex if aL FO) be Py (n+3)n where « is —3/2, —3 or 4 according as k,40; k,=—0, k,40; or k,=k,=0. In all cases the conditions of II, Theorem 1, are satisfied and thus the integral over {— tends to zero as its radius tends to infinity if either 0O0 or 00. ee cos 10}, n>050, O0nNg 13. The source problem of I, §3. Here, in the notation (16), yO FETT our’ i Lolurdgr) —K o(uriflayyean An4% + — ico F(A) From the asymptotic expansions it follows that, for 2 A=x(n +4) 008, x>0>0 ,f Sra a, | Zour’) Lolurda(e) —Ko(ur fd} |< Cnx exp ((n +B)e 7% eos 48), rN where «=4, —4, —3/2 according as k,40; k,=0, k,=40; k,=k,=0. Thus, using (34), we have when 2 A=x(n +4500, r>00 T plan r’) o(ur’ XLo(ur) a K (ur) oye Des fin +H" cos cos 30+ Oifr ere. a, and similarly they are satisfied if 00>0 the conditions of II, Theorem 1, are satisfied. The University of Tasmania. THE CHEMISTRY OF BIVALENT AND TRIVALENT RHODIUM. PART III. COMPOUNDS OF RHODIC HALIDES WITH TERTIARY ARSINES. By F. P. DWYER, M.Sc., and R. 8S. NYHOLM, BSc. (Manuscript received, October 15, 1941. Read, November 5, 1941.) In a previous communication (Tus Journat, LX XV, p. 127), the preparation of a number of rhodous halides stabilised with diphenylmethylarsine was described. In all of these compounds the central metallic atom showed a coordination number of six achieved by bridging. Since it appeared probable that the compounds resulted by the reduction of the arsine coordinated rhodic halides, and not by reduction of the simple rhodic halides to the lower valency state followed by addition of the arsine, it was considered useful to investigate the coordination compounds with rhodic halides and various tertiary arsines, in order to determine the possibility of preparing rhodous compounds with the lower coordination number of four, as well as to contrast the stability and reactions of rhodium in both valency states. By working with diphenylmethylarsine, and dimethyl-p-tolylarsine it was found that compounds of only one type could be obtained, viz. RhX,. 3AsRz, where X=Cl, Br, or I. If the usual, well established, octahedral distribution of the bonds about hexacovalent rhodium : , is assumed, substances of this formula are capable of existence in two isomeric forms 9 » Two forms of many of the rhodic ASR, x Ask, x compounds were actually isolated, but ASR, x showed large differences in melting point “ and solubilities, and were obtained under A i widely different experimental conditions. Although not necessarily the case, isomeric forms of the type (A) and (B) might be expected to exhibit very similar properties and reactions. The lower melting compound form II was extremely soluble in organic solvents such as benzene and chloroform, and even on boiling with silver nitrate in acetone solution gave only a mere trace of the silver halide. (In this regard the iodides were anomalous.) The molecular weight was normal, and the lower melting form II must thus be considered the neutral complex (Rh. X, . 3AsR,)°. The higher melting form I of the same empirical formula was only sparingly soluble in organic solvents, but dissolved on long contact or on boiling. When the solvent was removed, however, it was found to have passed completely to the lower melting form II. Thus the molecular weight (cryoscopic) in benzene, was identical with that of the lower melting form in the same solvent, and this latter substance alone was found when the solvent was removed in a rapid stream of air at 6° C. The higher melting form I gave an appreciable precipitate with silver nitrate in alcohol or acetone solution. When tested for dimorphism by the method of Mellor (Tus Journat, 1937-38, 71, 536), it was found that the lower melting form II could be recrystallised from THE CHEMISTRY OF BIVALENT AND TRIVALENT RHODIUM. 141 aqueous alcohol containing halogen acid, provided that the operations were performed rapidly. With this particular solvent alone, the higher melting form I was also crystallisable. Thus the two forms are not different crystals of the same chemical entity. Further, the solution of form I is darker than that of form II. Finally, it was found that the higher melting form I tended to come down preferentially in solutions containing an excess of halogen acid, i.e. in which the rhodium was largely in the form of the complex ion (RhX,)’’’, and by refluxing the lower melting form IT in aqueous alcoholic solution with excess of the acid or potassium halide, the higher melting form I was deposited quantitatively, provided that the alcohol concentration was not too high. It is suggested, therefore, that the high melting form I is possibly the electrolytic complex dimeride (Rh(AsR,),) (RhX,)’’’.. With the exception of the above observations of the effect of halide ions in effecting the transformation of form IT to form I, the authors have not been able to find any crucial test for choosing between an isomerism based upon the two possible forms (A) and (B), or an interpretation based upon the complex dimeride shown above. In assessing the value of the effect noted with halide ions, it must also be pointed out that the actual form isolated (i.e. form I or form II) even in the presence of excess halide ion seems to depend on the relative solubilities of the two forms, since, whilst with diphenyl- methylarsine all six forms of rhodic chloride, bromide, iodide, with the more soluble dimethyl-p-tolylarsine the higher melting form I could be isolated in the ease of the iodide only. The compounds isolated, as might be anticipated, with increase in the molecular weight of the halogen increased in melting point, and darkened in colour, but also became more reactive towards silver nitrate. Thus form II of the chloride was almost without reaction towards this reagent, the bromide gave a just perceptible precipitate, but the iodide instantly precipitated the whole of the halogen as silver iodide. This reaction does not necessarily suggest that the bonding in the iodide is weaker than in the chloride, since the effect may well be due to the lower solubility of silver iodide. The rhodic compounds were found to differ considerably from the rhodous compounds, previously described, as regards solubility, but most notably in their failure to reduce silver nitrate to the metal even in boiling acetone or pyridine solution. EXPERIMENTAL. Compounds with Rhodic Chloride. (2) Diphenylmethylarsine.-—To 10 mls. of rhodium trichloride solution containing 0-096 g. of rhodium were added 0-7 g. diphenylmethylarsine dissolved in alcohol (80 mls.) and concentrated hydrochloric acid (10 mls.). The mixture was refluxed until a precipitate came down (about 10 mins.), and then heated for a further 5 minutes. The precipitated material was removed by filtration, washed many times with cold 60% alcohol, and dried at 100° C.: Form I. The filtrate after the removal of the form I was precipitated with water, and after washing, and drying at room temperature, was crystallised from benzene and petroleum ether: Form II. Form I.—This substance was obtained in orange rounded crystalline masses, m.p. 176-178° C. It was sparingly soluble in alcohol, acetone, benzene and chloroform, but dissolved by long contact or on boiling. The material recovered, after such dissolution, was found always to have undergone transformation to form II. The substance could be crystallised from alcohol con- taining a large excess of hydrochloric acid. On boiling with acetone and silver nitrate it gave a perceptible precipitate of silver chloride. 142 DWYER AND NYHOLM. Found: Rh, 11-32%; Cl, 11-20%; mol. wt., in benzene cryoscopic, 898, in acetone ebullioscopic, 796. (In both molecular weight determinations the recovered material was entirely in the form II.) Calculated for (Rh(AsRg).).(RhCl,): Rh, 11-23%; Cl, 11-31%; mol. wt., 1884. Form II.—This gave a lemon yellow microcrystalline powder, m.p. 122-124°C. It was extremely soluble in alcohol, acetone, benzene and chloroform. By boiling with alcohol con- taining a large excess of hydrochloric acid it was transformed into form I. No trace of silver chloride was precipitated by heating with acetone and silver nitrate. Found: Rh, 11-26%; Cl, 11-1%,; mol. wt. in benzene cryoscopic, 897. Calculated for (RhCl, . 3AsR3): Rh, 11-23%; Cl, 11-31%; mol. wt., 942. By varying the relative amounts of arsine and rhodium chloride over wide ranges no com- pounds other than the above could be isolated. Similarly, when either form I or II was refluxed with excess arsine or rhodium chloride in alcoholic solution they were recovered unchanged. (b) Dimethyl-p-tolylarsine.—Operating with this arsine under the conditions above a slight precipitate only was obtained. This was identical with the larger amount of material obtained by the addition of water, and appeared to be form II entirely. After crystallisation from benzene and petroleum ether, the yellow microcrystalline powder melted at 86—88° C., and was extremely soluble in alcohol, acetone and benzene. Found: Rh, 12-7%; calculated for (RhCl,.3AsR,): Rh, 12-9%. Repeated attempts to prepare the other form by boiling with aqueous alcohol and hydro- chloric acid failed to yield any trace. Compounds with Rhodic Bromide. (a) Diphenylmethylarsine.—Rhodic bromide treated in alcoholic solution with the arsine (3 mols) and hydrobromic acid was refluxed until about half of the rhodium was precipitated. After removal of the precipitate (form I), the filtrate was precipitated with water to give form II. Form I.—The bright red crystalline powder was very sparingly soluble in all solvents, and melted at 191°C. Treatment with silver nitrate and acetone precipitated about 20% of the halogen as silver bromide. Found: Rh, 9-72%; calculated for (Rh(AsR;),) (RhBr,): Rh, 9-57%. Form II.—After recrystallisation from benzene and petroleum ether the orange red micro- crystalline powder melted at 116°C. It was easily soluble in all organic solvents to deep red solutions. Found: Rh, 9:40%; calculated for (RhBr,.3AsR,): Rh, 9-57%. (b) Dimethyl-p-tolylarsine.-—Rhodic bromide treated with the arsine in the presence of hydro- bromic acid as above gave no precipitate even on prolonged boiling. The red solution after precipitation with water gave only form II, m.p. 109° C., extremely soluble in alcohol, acetone and benzene. Attempts to prepare form I by boiling with aqueous alcohol and hydrobromic acid were fruitless. Found: Rh, 10-98%; calculated for (RhBr,.3AsR,): Bh, 11-05%. Compounds with Rhodic lodide. (a) Diphenylmethylarsine—Owing to the insolubility of rhodic iodide in water or alcohol, the preparative methods used for the chloride and bromide compounds could not be used and the two forms were prepared by different methods. Form II.—Rhodium trichloride solution (10 mls.), containing 0-096 g. of rhodium, was treated with hydriodic acid solution 57% (20 mls.), alcohol (80 mls.), and diphenylmethylarsine (0-7 g.). The mixture was boiled until a faint precipitate commenced to form, filtered rapidly and cooled. The purplish red precipitate was washed several times with water, and finally with petroleum ether. The substance was extremely soluble in benzene and organic solvents, and was the covalent form: Treated with silver nitrate in acetone solution, the purplish red colour was instantly discharged and a precipitate of silver iodide thrown down. Found: Rh, 8-59%; calculated for (RhI, .3AsR,): Rh, 8-46%. THE CHEMISTRY OF BIVALENT AND TRIVALENT RHODIUM. 143 Form I.—Rhodium trichloride solution (10 mls.), containing 0-096 g. of rhodium was treated with alcohol (80 mls.) and the arsine (0-7 g.). The mixture was then warmed carefully until the arsine had dissolved completely, and potassium iodide (4 g.) dissolved in 10 mls. of hot water added. After refluxing for a few minutes, water was added until a precipitate commenced to form, and the refluxing continued, when a dense purplish red precipitate came down in large amount. The precipitate was washed with water and then with alcohol, in which it was com- pletely insoluble. The substance formed twinned plates and needles, m.p. 200°C. Treated with acetone and silver nitrate, it precipitated the whole of the halogen instantly. Found: Rh, 8-48%; calculated for (Rh(AsR;),(RhI,): Rh, 8-46%. (6b) Dimethyl-p-tolylarsine—Form I.—Prepared as above, this gave bright red plates and needles, m.p. 200° C. Found: Rh, 9-60%; calculated for (Rh(AsR,),)(RHI,): Rh, 9:75%. Form II.—Prepared in a similar manner to the compound with diphenylmethylarsine, this gave a purplish red microcrystalline powder from petroleum ether and benzene. It melted at 85-86° C., and was extremely soluble in organic solvents. Found: Rh, 9-74%; calculated for (RhI, .3AsR,): Rh, 9-75%. SUMMARY. The compounds of rhodic halides with tertiary arsines have been found to exist in two forms: one easily soluble in organic media, and the other probably a complex dimeride, only sparingly soluble in such media. In all cases the compounds were found to possess the general formula RbX, . 3AsKz, indicating a coordination number of six. They differ notably from the arsine coordination compounds with rhodous halides previously described in their failure to reduce silver nitrate to the metal. Department of Chemistry, Sydney Technical College. THE TRIASSIC FISHES OF NEW SOUTH WALES. By R. T. WADE, M.A., Ph.D. (With Plate VII and one Text-figure.) (Manuscript received, October 22, 1941. Read, November 5, 1941.) 99 (1) NoTE oN A “ FLYING FISH’’ FROM THE MIDDLE TRIASSIC OF BROOKVALE, N.S.W. Genus (?) Thoracopterus (Bronn, N. Jahrb, f. Min., 1858, p. 12.) Material.—T wo specimens, P.15793 in the British Museum, and U.8.G.D.151 in the Geological Museum, Sydney University. Description.—The specimen in Sydney shows a large part of a pectoral fin, which is 7-4 cm. long and includes not less than fifteen fin-rays. Distally these branch repeatedly, yielding six to eight fine rays each. In the other specimen the fin-rays are very long, rounded, divided into long segments, and branch distally. A few narrow, elongated, smooth scales are also preserved. Remarks.—Cephaloxenus, Dollopterus, Gigantopterus and Thoracopterus are Triassic fishes with such large pectoral fins that they have been thought to be “flying fishes’. From the scanty material here, it is, of course, impossible to determine the relationship of the specimens, and they are referred to Thora- copterus for convenience of record only. (2) CORUNEGENYS BOWRALENSIS, A NEW SEMIONOTID FISH FROM THE TRIASSIC OF BOWRAL, N.S.W. Sub-Class NEOPTERYGII. Order HOLOSTEI. Family Semionotide. Genus Corunegenys Nov. Diagnosis.—Small Semionotidse with fusiform bodies, deepened anterior to dorsal fin; dorsal margin descending rapidly from just behind back of head to snout. Eyes comparatively large, suspensorium not greatly inclined forwards : mouth of moderate size. Quadrate articulation well back; quadrate angle obtuse. Tabulars triangular, wide, bordering both parietals and supratemporals. Paired parietals small, nearly square. Supratemporals moderately wide, irregularly shaped. Frontals long, widest behind orbits. Nasals larger, longer than wide. Operculum large, deeper than long. Suboperculum much smaller than operculum. Interoperculum small, triangular, well below suboperculum. Median gular large. Maxilla small, tapering, slightly concave at oral margin. Mandible long, deep at coronoid area, tapering anteriorly. Hinder end of supra- orbital sensory canals in parietals. Post-temporals triangular. Supracleithra deep, triangular, slightly expanded at upper end. Cleithra of type normal to family. Dermal fin-rays few, well spaced, with long, tapering proximal shafts and distal division into small joints ; in caudal fin long proximal joints present only in middle rays; fulcra few; rays of paired fins slender. Journal Royal Society of N.S.W., Vol. LXXV, 1941, Plate VII —— e Bre as it ae i THE TRIASSIC FISHES OF NEW SOUTH WALES. 145 Tail abbreviate-heterocercal, not deeply cleft. Seales thick, smooth, rhombic, with entire margins; flank scales much deeper than long; ventral scales longer than deep. Genotype.—C. bowralensis. Remarks.—Among the Semionotide it is most like S. capensis in the structure of the head; but it cannot be assigned to that genus because of the absence of a circumorbital ring consisting of numerous bones, its more nearly vertical suspensorium, and its longer maxilla. Its name is derived from Gr. corune, a club and genus, jaw, in allusion to the club-like appearance of the tapering lower jaw and maxilla. Corunegenys bowralensis, Sp. Nov. Diagnosis.—As for genus, with the following additions: the dorsal fin, which arises slightly behind the middle point of the dorsal margin, comprises about thirteen rays; the anal fin, placed entirely behind the dorsal, includes about ten rays; the caudal fin has some twenty-three rays. The body is completely covered by about forty transverse rows of scales, abdominal rows including about fifteen scales in a row. The cranial roof is ornamented by a few indefinite longitudinal ruge. ~ Material.—The unique holotype, a nearly complete fish, F.18864, in the Australian Museum, Sydney. Measurements.—The length from tip of snout to base of tail is 66 mm. The trunk has a maximum depth of about 18 mm. The length of the head, including operculum, is approximately 16 mm. Thus the length of the fish is about three and three-quarters the maximum depth, but about four times the length of the head. The depth of the body diminishes rapidly behind the dorsal fin, where the dorsal margin slopes rapidly towards the tail. The fleshy upper lobe of the tail is produced to a length of 9 mm., and at its tip has tapered to the depth of one scale, most of the reduction taking place on the ventral margin. The principal flank scales are much deeper than long. Those along the lateral line are so greatly broken by crushing against vertebral arches that they cannot be satisfactorily measured, but three scales in the seventh transverse row behind the head and in successive rows below the lateral line have a combined depth of 64 mm., which is the total length of 54 of these scales. Head.—The head is only slightly longer than deep. The orbit, of moderate 81Ze, is well above the oral margin and about as far from the back of the operculum as from the snout. The mouth is small but larger than that of some Semionotide, and, since the quadrate articulation is below the middle of the orbit, the sus- pensorium, the operculum, and the lower end of the opercular series are not greatly inclined from the vertical, so that the interoperculum is largely below and not in front of the suboperculum. The position of the parasphenoid is marked by a prominent thick black ridge of the shape shown in the figure (Text-fig. 1). The impression of the well ossified palate is preserved, without sutures, but displaying its outer margins, which meet in the quadrate at a wide obtuse angle. Most of the snout is covered by large nasals, which are longer than wide. The long frontals are slightly excavated between the nasals, but widened behind them. Small, nearly square parietals and irregular supratemporals, both bounded behind by wide triangular tabulars, complete the cranial roof. In the circumorbital series only one bone can be distinguished and that doubtfully—a narrow deep bone just behind the orbit. The cheek plates are not preserved, having been broken, most probably against the palate. The preopercular canal is preserved, but because of the hinder end of the palate one cannot be certain of the anterior margin of the M—November 5, 1941. 146 R. T. WADE. preoperculum. The opercular apparatus is long; the operculum, the lower margin of which is nearly straight, is deeper than long and nearly half as deep - again as the suboperculum. The limits of the interoperculum are not clearly defined and the head is greatly damaged in the region of the branchiostegal rays. There is a well preserved median gular. The maxilla, placed far forwards from the preoperculum, is not quite clear posteriorly but is obviously deepest there, tapering forwards, with a slightly concave oral margin. The mandible, the upper portion of which is not clearly — defined, and none of whose components can be made out, is deepest at the coronoid region and tapers anteriorly. No teeth are preserved. The sensory canals are preserved as casts in the tabulars, preoperculum, and mandible. The supraorbital canal, too, is seen to pass from the nasals to the frontals (where it is concave downwards above the orbit) and to end back in the parietals. Fig. 1.—Corunegenys bowralensis. A. Sketch of head from No. F.18864. (For lettering see page 147.) B. Sketch of scales in seventh transverse row behind head and below lateral line. m.r.=—median fold. Shoulder Girdle.—Triangular post-temporals and deep triangular supra- cleithra with expanded heads connect to the head the short arcuate cleithra, the triangular anterior ends of which extend forwards beneath the branchiostegal rays and backs of the mandibule. The Trunk and Fins.—The trunk, which is of moderate depth in front of the dorsal fin, is reduced behind that fin by the rapid descent of the dorsal margin. The paired fins are very poorly preserved, and the few rays that remain are more delicate than those of the median fins, where the rays have long, tapering proximal shafts, succeeded by numerous short joints. There is no evidence of distal division of the rays. The long proximal shaft is found in only a few of the middle rays of the caudal fin, the remaining rays being closely articulated to the base. The dorsal fin, comprising thirteen well spaced rays, is almost completely in front of the anal, which is made up of ten similar rays. There are about 23 rays in the caudal fin, the upper fleshy lobe of which is greatly — produced. The Scales.—About forty transverse rows of smooth, thick, ganoine-covered scales invest the body from behind the head to the base of the caudal pedicle, THE TRIASSIC FISHES OF NEW SOUTH WALES. 147 and abdominally there seem to be sixteen scales in a row—the indefiniteness being due to uncertainty as to the ventral scales and the exact position of the ventral margin. The scales of the well preserved lateral line are crushed down upon the neural and hemal arches, which show dimly along the body. Some rows below the lateral line are about twice as deep as long, and, displaying their inner surfaces, show a short sharp on their upper margins, no socket, but articula- tion by means of a median ridge. Remarks.—Salient points in the structure are, the course of the supra- orbital sensory canal, the shape and size of the maxilla, the steep rise of the dorsal margin of the head, and the squamation. EXPLANATION OF PLATE. A. (2?) Thoracopterus sp. Pectoral fin, No. U.S.G.D. 151, Geological Museum, University of Sydney. x13. B. Corunegenys bowralensis sp. nov. The unique type, No. F.18864, Australian Museum, Sydney. xl. Text-fig. 1—Corunegenys bowralensis sp. nov. No. F.18864, Australian Museum, Sydney. A. Head. x3. Clei. =Cleithrum. Pas. = Parasphenoid. Fr.=Frontal. Pct.= Pectoral fin. Gu. =Gular. P.Op.C.=Preopercular canal. L.Op. =Interoperculum. P.T. =Post-temporal. L.L.C. =Lateral line canal. Qu.-Ptg. =Quadrato-pterygoid. Md. = Mandible. R.Br. =Branchiostegal rays. m.r.=Median fold. S.Cl. =Supra-cleithrum. Mx. = Mazxilla. S.0.C.=Supraorbital canal. Na. = Nasal. S.T.=Supratemporal. Op. =Operculum. Tab. =Tabular. Pa. = Parietal. B. Scales in seventh transverse row behind head and below the lateral line. 3. STUDIES ON THE CULTIVATION OF THE TUNG OIL TREE, ALEURITES FORDII. PART II. Stupy or A H®Avy YIELD OF FRUIT OBTAINED ON THE NORTH CoASTtT OF NEW SoutTH WALES.* By A. KR. PENFOLD, FAC, Mes F’. R. MORRISON, A.S.T.C., A.A.C.L., and S. SMITH-WHITE, B.Sc.Agr., Technological Museum, Sydney. (Manuscript received, October 18, 1941. Read, November 5, 1941.) CONTENTS. Page Introduction He af oF he us pee Ee a He: a so Ae Plantation at Coramba .. ee at aa ae Be ut e bil .. 149 Establishment of the Trees oP By: aa ie i ae ae re .. 149 General Yield ae ae a ave es ie a a es By oes Yield Studies is aa a ae A 2] ie an Ae a -. de Number of Fruits per Tree ae se is Bi a wid alt. ..) dee Fruit Analyses ae oe ake asd - a6 aie an A 3 és ~. De Variation in Husk, Seed-coat and Kernel ew ee it og es, os ee Variation in Oil Content .. oe Res ae: wis ae fe Nee .. ee Oil Analyses on sits it a ste ss Sup hs sie ius _. ie Acknowledgments vs he ie she se ae ae oe hi -. Leg References = ae as we sf a m2 ae ba ae s. 2S INTRODUCTION. The cultivation of the Tung Oil tree, Aleurites fordi, has been investigated by officers of the Sydney Technological Museum since 1923. The early results were obtained from a study of individual trees,‘) but by 1937 it became possible to study a commercial grove, one owned by Mr. A. H. Woolcott at Bargo, 62 miles south of Sydney. In pursuance of this study another commercial grove was selected, that of Mr. C. J. Frank at Coramba, 390 miles north of Sydney. This grove proved ideal in many ways. In the first place it is, as far as we can ascertain, the best yielding grove in Australia and, secondly, the trees are remarkably uniform in character. The returns have proved very profitable to this enthusiastic and painstaking grower. In view of the serious position confronting the tung oil industry generally through inability to obtain commercial supplies from China, the results obtained in the study of Mr. Frank’s grove are of considerable national importance. The commercial return from his two paddocks (A and B), of about two acres extent, for the present year is a record for Australia, and probably for the world. * Part I appeared Tu1s JourNAL, 1940, 74, 42. STUDIES ON THE CULTIVATION OF THE TUNG OIL TREE. 149 PLANTATION AT CORAMBA. This consists of approximately two acres of bearing trees, and in addition, about six acres of young trees. At the time the plantation was first visited, in October, 1940, the trees were in flower, and the uniformity of the flowering, the scarcity of the male-flowering type of tree, and the remarkable robustness and vigour of the trees were impressive. A good yield seemed to be indicated, and it was decided to keep the grove under close observation. A second visit was made in February, 1941, when the fruit crop was half grown. ‘The trees were so heavily laden that a high yield seemed certain, and in June-July of this year a special effort was made to record accurately the yield figures, and at the same time samples were taken for study in the laboratory. The plantation comprises two small paddocks of mature trees, details of which are given in Table I. Paddock A is situated on the west side of the railway, on a north-east slope. It is protected by a railway embankment on the east, and may gain some advantage in drainage from calf and pig pens adjacent. The soil is a clayey loam, possibly of basaltic origin. The surface soil, about 9 inches deep, is rich in humus; the subsoil is very deep. The actual area of this paddock is 80 ft. x 336 ft., or approximately five-eighths of an acre. Paddock B is situated on the east side of the railway. Its aspect and soil are similar to those of Paddock A, but it receives no special advantages. The area is approximately 11 acres. TaBLe. I. Details of Tung Plantation. Paddock A. | Paddock B. Area a i .. | = acre. | 14 acres. Aspect .. ae .. | North-east. North-east. Soil e nh .. | Clay loam. Clay loam. Source of seed .. =. |oy Whittell.” ‘“Whittell” and Queensland . Forests. Seed sown a .. | October, 1934. October, 1933, and October, 1934 Density of trees .. | 170 per acre. 180 per acre. THE ESTABLISHMENT OF THE TREES. Paddock B contains two plantings of trees. In 1933 seed was obtained from Queensland Forests Limited, and the seedlings planted out the following October, the planting being on the square system, 22 ft. apart, equivalent to 90 trees per acre. The following year, 1934, further seed was supplied by the “‘ Farmer and Settler ’’ Newspaper. This seed was apparently derived from stock known as Pennant Hills Trees.{4) The seedlings were planted in September, 1935. In Paddock B the original planting seemed so open that additional rows were interplanted, a new seedling being placed in the centre of each square, making a total planting of 180 trees per acre. In all, Paddock B contains 222 ay but over twenty of these, affected by poor drainage, yielded very little ruit. Paddock A consists entirely of trees from the Pennant Hills seed, sown in 1934 and planted out in October, 1935. The planting method adopted was to Stagger ’ the rows, to give a triangular system, planting distances of 16 ft. 150 PENFOLD, MORRISON AND SMITH-WHITE. between rows and 16 ft. between trees in the row, being equivalent to 170 trees — per acre. The land, which was first cropped in 1933 to pumpkins, after being given a dressing of lime, was planted with potatoes in 1934, and the seedlings of Tung were planted in the growing potato crop. The following year a crop of soya beans was raised between the rows, and intercropping has been practised until the growth of the trees has made this impossible. Sheep have been used for feeding off the haulms of soya beans and other intercrops and to keep down weeds. Young pigs have also had access to the paddock. Paddock B was first cropped with barley, then potatoes, and finally soya bean. The Tung seedlings were planted in the barley. In the present condition of the trees, intercropping or any cultivation between the rows is quite impossible. The weeds and undergrowth are kept down by sheep. Pruning or any inter- ference with the normal growth of the trees has been avoided. The climate at Coramba is well suited to tung, both in regard to the high rainfall experienced, and the rare occurrence of frosts after September. The average annual rainfall at Coramba over a three-year period (1938-1940 inclusive) was 49-89 inches, and the distribution is such that the greater part of this rainfall occurs during the growing season, October to April. During the seven-month period October, 1940-April, 1941, when the heavy crop was being carried, Coramba received 36-95 inches of rain. The close planting adopted by Frank appears to have several advantages over the wider spacings. Some of these advantages may be enumerated : (1) The heavy growth of leaf and other debris which covers the ground during the winter adds appreciably to the humus intake of the soil, and effectively prevents moisture loss. Tung appears to respond to a high humus and nitrogen content in the soil. (2) The trees provide their own protection from wind and weather damage. (3) Growth of the trees does not appear to be adversely affected in any way. GENERAL YIELD. The first fruit was obtained from the trees in 1937; they were then three years old, but this yield was very small. In 1938 an appreciable yield was obtained. The year 1939 was apparently a favourable season, for a good yield, double that of the previous year, was obtained. The yield was not so good in 1940. A late frost is said to have caused a big reduction in fruit setting, whilst the reduced yield may also have been a reaction to the high yield of the previous year. An exceptionally high yield of 12,291 lb. net of dry fruit was obtained during the present year (1941). On decortication, 6,145 lb. of seed was separated. The seed yielded on expression approximately 2,300 lb. of oil, or 18-0% of the whole fruit. YIELD STUDIES. When we visited Coramba at the end of June, 1941, for the purpose of recording the actual yield, the fruit had mostly fallen from the trees, although here and there occasional trees were still holding perhaps fifty per cent. of their crop. The hanging fruit, however, appeared mature, and was easily shaken down. Underneath, the ground was thickly covered with fallen leaf débris, amongst which the fruit was lying. Under such conditions the fruit would remain wet for a long time, and proper drying would require the collection and spreading of the fruit on open ground. aly =a STUDIES ON THE CULTIVATION OF THE TUNG OIL TREE. Tok Yields from Paddock A. Paddock A, which on casual inspection promised the higher yield, was selected for the most detailed study, but it is a matter for regret that time did not permit of equal attention being given to Paddock B. In the time at our disposal, it was quite impossible to collect all the fruit from Paddock A. Four ‘plots, each equivalent to ten trees or one-seventeenth of an acre, were marked out for the purpose of estimating the yields. These plots were marked out across the paddock, along the butt lines of two rows, with one included row, and comprised the fruit lying on the ground under five whole trees and ten half trees. Plot IV included the equivalent of eleven whole trees, but the yield from this plot has been reduced by the fraction 10/11 for the purpose of this analysis. The overlapping of adjacent trees made the collection of the fruit from individual trees quite impossible. The fruit from each plot was collected separately, weighed in the field, and spread in open grassland to dry. Corrected yield figures were obtained from a re-weighing when the fruit appeared thoroughly dry and ready for bagging. The results of these yield figures are given in Table II, together with figures for oil yield, which have been calculated from analyses of five samples from each plot. The mean yield per plot of 524 lb. of dry fruit and 113 lb. of oil is equivalent to yields of 3-98 tons and 1,960 lb. of fruit and oil respectively per acre. The moisture content of the fruit at time of collection and the consequent loss of weight on drying varied considerably between plots, depending on their positions. Plot 1, near the southern end of the paddock, was the most exposed, and had a lighter covering of leaf litter. The fruit was, in consequence, relatively dry when collected. TABLE II. Yield of Fruit from Plots. Mean Yield of Fruit. Oil Yields Oil Yields Weights Number of on Cal. from of 600 Fruits Plot. Air Dry Columns Fruits per tree Fruit. 3 and 4. as Cal. from As Per cent Lb. Collected. Columns Collected. Air Dry. 2 and 6. Al 692 531 20-86 110-9 37-25 1,113 +0-71 +1-11 A2 828 547 22-32 122-0 43-75 1,135 +0:21 42-21 A3 768 514 22-04 113-3 48-75 945 +0-62 +1-70 A4 804 503 21-45 108-0 49-60 972 +0-34 +2-94 Means 773 542 21-67 113-5? 44-84 1,041 +29-7 +9-7? +0-28 +1-10 Bl 467 373° 19-34 T2318 42-0 606-5 +1-66 42-74 * Means of analyses from five trees in each plot. * Equivalent to a yield of 3-98 tons of fruit, and 1,960 lb. of oil per acre. * Equivalent to a yield of 2-66 tons of fruit, and 1,250 lb. of oil per acre. 152 PENFOLD, MORRISON AND SMITH-WHITE. Number of Fruits per Tree.-—The impracticability of studying the yields from individual trees has already been pointed out. Since many yields given in the literature are calculated on the number of fruits per tree,‘?) an estimation of this figure was thought to be desirable. Whilst the fruit was being collected, counted lots of 600 fruits were weighed in the field, four replications of such counts being made for each plot. The number of fruits per tree in each plot was calculated from the mean weight of the fruit and the total weight of the half-dry fruit. Details are included in Table II. The average yield per tree exceeds 1,000 fruits. A yield approaching this figure has often been desired but has rarely been obtained, and this only on individual isolated trees (e.g. Grafton). Yields from Paddock B. In Paddock B a single plot of more or less equivalent size to those in Paddock A was marked out for the purpose of comparison. Owing to the different arrangement of the trees, the plot is not exactly equivalent, as it includes the fruit lying under five whole trees and twelve half trees, and equal to one-sixteenth of an acre. The ground was covered with less fruit débris and the fruit was more exposed and in a drier condition. The yield of 373 lb. of air-dried fruit from the plot is equivalent to 2-66 tons per acre. Details of the yield and number of fruits per tree are included in Table II. The yield from this plot is considerably lower than from those in Paddock A, but must still be regarded as very good. The yield from the whole of Paddock B would be lower than that indicated by the plot yield, because of the inclusion of the poor trees at the southern end, already mentioned. FrRuIT ANALYSES. Analyses of the proportion of husk, seed-coat, kernel, and oil in samples of fruit from a few individual trees at Bargo, reported previously indicated that considerable variation in these characteristics occurs. Similar results have been reported by authors in other parts of the world.“ Trees situated at Bargo were particularly favourable for this work by reason of their diverse origin. Further work on the trees at Bargo which had been anticipated had to be abandoned because of the severe drought conditions experienced in that district, and the almost complete failure of the Tung crop, and in fact, of all other crops. Until conditions in the district improve, the work at Bargo cannot be continued. The trees at Coramba offer a more limited scope in this study, the plantation being less extensive, the trees of less diverse origin and far more uniform in all characters. | Five samples of twenty fruits each were taken from each plot in Paddock A and from the one plot in Paddock B, for the purpose of these analyses and for work on the yield and quality of the oil. The fruits were taken from directly under the individual trees concerned, where possible mixture with fruit from adjacent trees was least likely. No attempt at selection of fruit was made. In addition, fruit from one tree selected on the basis of attractive fruit type was included. In this case, only well-developed, large fruits were collected. These fruits characteristically split readily on drying. At the time of collection, the fruit was still partially wet, and it was allowed to air-dry in the open for several weeks before analyses were commenced. The analyses were carried out over a period of two months, and considerable differences in the moisture content of the husk and seed were found. For the sake of uniformity, the results given have been calculated on moisture-free basis. The fruits generally are of good Aleurites fordii type, smooth or slightly furrowed between the sections, rarely rough and deeply furrowed. Fruits consist normally STUDIES ON THE CULTIVATION OF THE TUNG OIL TREE. 153 of five sections, occasionally of four, and rarely of six. In each section there is one kernel; very exceptionally twin kernels occur. The kernels were mostly sound and plump, but in some samples were soft and shrivelled, and occasional seeds were empty of kernel. Variation The general uniformity in the proportion of husk, seed-coat and kernel between the plots in Paddock A is remarkable, and in conformity with that of the trees and their fruit. In Table III detailed figures are given, and these show that on a moisture-free basis, the proportion of kernel varies from 39-6% to 41-7% between plots, and that these differences are scarcely, if at all, significant. In Paddock B, on the contrary, the proportion of kernel is appreciably low, and the husk is correspondingly thick. In the analysis of fruits, it has become obvious that the seed-coat does not vary to any marked extent, and that varia- tion is accounted for by changes in the proportion of outer husk to kernel. Comparison of these analyses with those previously reported from Bargo shows a much higher proportion of kernel in the Coramba fruit. Two samples of Bargo fruit analysed concurrently also show a high percentage of husk, which seems typical of the Bargo fruit. Analyses of a sample of fruit from the two historic trees at Grafton Experiment Farm,'?) which are now approximately twenty years old, give figures comparable with the Coramba results, and decidedly superior to the Bargo results. in Husk, Seed-Coat and Kernel. TaBLeE III. Means of Analyses of Fruit Samples. Composition of Fruit.+ Mean Oil in! Oil Yield? Plot.2 Weight Kernel in Whole Whole Husk Seed Coat | Kernel Per cent. Fruit Fruit.* Per cent. | Per cent. | Per cent. Per cent. Al se it ae 21-78 31-90 27-44 | 40-66 58-56 23°85 +0-27 +1-03 -+-0:55 +0-71 +0-38 A2 ay a ye 23-61 32-04 26-74 41-22 60-26 24-83 +0-95 +0-44 +0-62 +0-47 +0-50 A3 a a AS 24-64 32-68 25-58 41-74 59-80 24-95 +0-61 +1-29 +0-42 +1-05 +1-42 A4 i ne ne 22-81 33-7 26-63 39-62 59-78 23-68 +0-72 +0:67 | +0-42 +0-66 +0-46 Bl Bt i) “a 24-66 42-02 PARSE [4 34:86 62-60 21-81 +1-92 +1-57 +1-55 +1-10 +3-58 8-12 4 Re an 30°97 36-8 22-0 41-2 62-1 25-60 Grafton? ay ee 22-92 31-7 27-3 41-0 58-2 23-85 W1/4-114 ie 33-90 42-8 24-7 32-5 58°5 19-00 W1/6-114 He in 33:10 44-4 23-4 S22 60-2 19-40 | 1 Calculated on moisture-free basis. 2 A tree selected on basis of its large, attractive fruit. 3 Mixed fruit from two old Grafton trees. * Five-year-old trees at Bargo, derived from the Grafton parents. 154 PENFOLD, MORRISON AND SMITH-WHITE. The moisture content in the husk, seed-coat, and kernel shows a certain degree of variation. In the husk this averaged from 13:0% to 21-7%, and in the seed-coat from 10-:7% to 16:5%. The moisture content of the kernels showed a normal range from 2:6% to 8:2%, although two exceptional samples had moisture contents of 16-5°% and 30-2%. The reason for this high moisture content is not apparent, and does not seem entirely due to the state of dryness of the whole fruit. It may be due to premature falling of the fruit or some other cause. Slight but barely significant differences in proportion of kernels to husk are found between the samples from individual trees, the range being from 38-38% to 45-3% of kernel in Paddock A, and 31-4% to 38:2% in Paddock B. These results differ from results reported by many workers, who have found very considerable differences between individual trees. In view of the comparative uniformity in the husk-kernel ratio, and of the uniformity of the trees in other characters, e.g. vigour, habit of growth, absence of the undesirable ‘‘ male ”’ trees, uniform cluster-fruiting type, it must be presumed that the trees are of a relatively pure strain, compared with other plantations seen in New South Wales. The sample from tree marked 8-1 is worthy of mention. In spite of the definite selection of large, well-formed and well-developed fruit, it gives, weight for weight, no higher proportion of kernel than the other samples, which fre- quently included small and deformed fruits. The frequently reported correlation between high kernel proportions and large fruit size does not appear to be borne out by the figures obtained here. The mean weight of the fruit was from 20-2 to 31-1 gms., but the kernel content appears to have no relation to this mean weight. Variation in Oil Content. In Paddock A, the uniformity of the oil content of the kernels is notable, and contrary to the usual findings. Even the sample A 5-3, which had 16% moisture in the kernel, was little inferior to its adjacent trees. In Paddock Bb, a greater variation in oil content is shown, which might be expected, as trees include two origins. The oil content in the dried kernel varies from 57-1% to 61-6°% in Paddock A, and from 51:7% to 69-1% in Paddock B. Ort ANALYSES. The kernels separated from the various samples of fruit enumerated in Table III were examined for yield and quality of oil. The quantities available were not sufficient for mechanical extraction of the oil, and, consequently, the comminuted kernels were treated with ethyl ether in a Soxhlet extractor. What- ever slight differences might result from the two methods of treatment, the results of analyses are strictly comparable. Solvent extracted oils have, in our experience, given reasonably satisfactory results, although the Browne Heat Tests are invariably high. For purposes of comparison the results are set out in tabular form. (See Table IV.) No explanation can be offered at present for the variation in chemical composition of the individual oils, as revealed by the refractive indices and heat tests. At the same time, the specific gravities of the oils are quite normal. The chemical composition of these oils will be the subject of a separate investiga- tion. Meanwhile the following facts should be specially noted : (1) Although only one plot from Paddock B was examined, as against four plots from Paddock A, there is sufficient evidence to indicate that the oil from the drier Paddock B is of superior quality to that obtained from Paddock A, which is much wetter, and in which the soil appears richer in humus and nitrogen. STUDIES ON THE CULTIVATION OF THE TUNG OIL TREE. 155 TABLE IV. Physical Characters of Oils. 15-5° 25° Acid Browne’s Sample. dig. 5° | o Value. Heat Test. Remarks. | A 5-1 0-940 1-5100 0-53 193 mins. 5-2 0-939 1-5123 154 mins. 5-3 0-940 1-5110 15-2 Did not gel. Spongy kernels. 5-4 0-939 1-5136 14$ mins. 5-5 0-940 1-5013 0-73 174 mins. A 8-1 0-941 1-5169 13 mins. Crumbly “ gel ”’. 9-1 0-940 1-5148 142 mins. 9-2 0-939 15117 164 mins. 9-3 0-939 1-5120 0-54 16 mins. 9-4 0-939 1-5127 15 mins. 9-5 0-939 1-5117 16 mins. A 13-1 0-939 1-5126 eZ 143 mins. Kernels spongy. 13-2 0-942 1-5153 112 mins. Firm “ gel ’’. 13-3 0-939 P5125.) | 154 mins. | 13-4 0-941 1-5150 14 mins. 13-5 0-940 1-5147 0-45 14} mins. ae | el | Ee eS A 19-1 0-940 1-5142 14 mins. Firm “ gel ”’. 19-2 0-939 1-5120 1-04 16 mins. 19-3 0-939 1-5117 184 mins. 19-4 0-940 1-5143 0-45 134 mins. 19-5 0-939 1-5127 15 mins. 19-6 0-940 1-5110 0-57 174 mins. B 8-3 0-939 1-5118 0-68 164 mins. 8-4 0-942 1-5172 102 mins. Crumbly “ gel’. 8-5 0-941 1-5157 14} mins. Firm “ gel’’. 7-6 0-942 1-5167 12 mins. Crumbly “ gel’’. 9-6 0-942 1-5170 11 mins. Crumbly “ gel ”’. (2) The oil obtained from the mixed fruits from both paddocks by expression is of excellent quality, and meets the requirements of the Australian Standard Specification. (3) An average sample from the two paddocks taken from a total volume of 240 gallons, the product from 12,291 lb. of dried fruit collected from the two acres, gave the following results on examination : 15-5° din B 0-940 25 Dy ns a to) ae us 1-5164 Acid value .. ae a i ae 0-72 Saponification number... i .. 193°4 Iodine number (Wijs 2 hours) .. .. 164-4 Browne’s heat test ae we .. 12 minutes. ACKNOWLEDGMENTS. Our thanks are due to Mr. C. J. Frank for placing his grove at our disposal. 156 PENFOLD, MORRISON AND SMITH-WHITE. REFERENCES. {) Mowry, H.: Univ. Florida Agric. Exp. Station, Bulletin No. 247, 1932. 2) Penfold, A. R., and Morrison, F. R.: Syd. Tech. Mus. Bulletin No. 12, 1940. ‘3) Potter, G. F., Angelo, E., Painter, J. H., and Brown, R. T.: Proc. American Soc. of Horti- cultural Science, 1940, 37, 515. {4) Smith-White, S.: Jour. Proc. Roy. Soc. N.S.W., 1940, 74, 42. THE STEREOCHEMISTRY OF SOME METALLIC COMPLEXES, WITH SPECIAL REFERENCE TO THEIR MAGNETIC PROPERTIES AND THE COTTON EFFECT. By D. P. MELLOR, M.Sc. (Manuscript received, October 22, 1941. Read, November 5, 1941.) In recent investigations dealing with the stereochemistry of metal complexes Pfeiffer, Christelheit, Hesse, Pfitzner and Thielert (1938) and French and Corbett (1940) have used observations on rotatory dispersion as a basis for drawing conclusions concerning the orientation of valence bonds about metal atoms. As these are the first attempts, so far as the author is aware, to use rotatory dispersion measurements for this purpose, it is of some interest to check the findings based on rotatory dispersion studies against those based on other physical methods. Attention has already been drawn to the fact that some of the conclusions reached by Pfeiffer and his collaborators are not those one would have anticipated from the results of magnetic measurements made in this laboratory, on closely related compounds. (Mellor, 1941.) In certain favourable instances, bond type and orientation can be deter- mined from magnetic data. This can be done with greatest certainty in the case of the diamagnetic complexes of nickel, because for these, the results of magnetic studies have been verified by X-ray crystal analysis (Cox, Wardlaw and Webster, 1935; Elliott, 1938; Brasseur, 1938; Peyronel, 1941), synthesis of isomers (Tschugaeff, 1910; Sugden, 1932a) and studies of crystal optics (Mellor and Quodling, 1936). For this reason most attention has, in the present investigation, been paid to compounds of nickel; reference is however made to compounds of several other metals. The conclusions from magnetic measure- ments will be discussed first, and then, in some detail, the bearing of these conclusions on the optical data (dispersion and absorption). THE COMPOUNDS INVESTIGATED. The compounds on which susceptibility measurements have been made are listed in the first column of Table I. With ae one exception, their preparation has been Mek atl previously described by Pfeiffer et al. (1941), i) (al Lifschitz (1922) and others. The structures CH2—C—CH, proposed by these authors for the different | compounds (numbered as in Table I, except for XI) are shown as follows: compounds I, Mem ent cover cu) jak and Pil, Bio. Es TV and XT, Fie, 24 and 2B respectively; V, VI and VII, Fig. 3; IX and X, Fig. 4. = (XI) H Rig. 1. COOH Fig. 2a. Fig. 28. 158 D. P. MELLOR. TABLE I. Results of Susceptibility Measurements. Dia- Specific Molar magnetic Temper- Magnetic Number of Compound. Suscept- Suscept- Correction ature. Moment, Unpaired ibility ibility Applied. oK: ue Bohr Electron x X 108 XM x 10° x 108 agnetons. Spins. I. C,,H,,0,N.Ni Bis - salicylaldehyde - propylene-diimine- nickel ! as —0:1 Diamagnetic — _— ~0 0 II. C,,H,.0,N,Co | Bis - salicylaldehyde - propylenediimine- | cobalt ‘ ie 20 2,440 —174 293 2:48 1 HII. C,,H,,O,N.Cu Bis - salicylaldehyde- propylenediimine- copper a4 3:26 1,120 —174 295 1:76 | 1 IV. CyoH1,0,N.Ni Bis - salicylaldehyde - o-phenylenediimine - nickel ss ke —0:2 Diamagnetic — —_ ~0 0 V. Cy,.H;,0,Ni Bis - formylcamphor- nickel ye Apel 9-72 4,050 — 245 287 3°15 2, VI. Ci3H3,0,Co2H,0 | Bis - formylcamphor- cobalt dihydrate 23-8 10,785 — 266 286 5-05 3 VII. Cy,Hso0,Cu.C,H.0, | Bis - formylcamphor copper + dioxane of crystallisation 2742 1,283 — 304 288 1-89 1 VIII. Cs3H4,0 «Co | Tris-formyl camphor cobalt Be Ek 0-33 199 — 369 290 1:15 0 IX. C,,H;,0,N,Ni3H,0 Bis-formyl camphor- ethylenediimine- nickel trihydrate —0:4 Diamagnetic — — ~0 0 X. C.,H,0,N,Cu2H,0 | Bis - formylcamphor- ethylenediimine copper dihydrate BOV4// 1,574 — 294 288 2-08 1 CH H3 ‘ | H3C — C-CHs | S/ \ He te H3 | Fig. 3. Cc H3 CHs i] é | H;C- C-CHsl| ee | H;C-C-CHs| H,C —— CH—C-CH=N NECH-C —— CH —CH, | CH.—-C H> Fig. 4. Ale THE STEREOCHEMISTRY OF SOME METALLIC COMPLEXES. 159 The structures shown are in accord with the general theory concerning the formation of chelate compounds, confirmation of which has been obtained by various physical methods, including crystal structure analyses.? The main point at issue in the present work, however, relates to the character and orientation of the bonds by which the various organic groups are attached to the metal atoms. In order to arrive at a decision as to which of the various alternatives (as regards orientation and bond character) obtains in a given complex, the measured magnetic moment of the metal atom (see Table I) is compared with that predicted by Pauling and Huggins (1931) for the different bond types. A portion of the table of predicted moments, relevant to the present work, is reproduced in Table IT below. TABLE II. Electron Spins Predicted for Different Bond Types (Pauling and Huggins). For ionic or | Metal Atom. sp*® tetrahedral For square For octahedral bonds. dsp* bonds. dsp*® bonds. Nill a a a 2-83 0-00 — Cull af a - 1-73 1-73 -—— Coll me ot aif 3°88 1-73 a Coll... ie Ae 4-9 2-83 0-00 The sixth column of Table I shows the magnetic moments of the metal atoms as deduced from the data tabulated in the preceding columns of the table. These moments will form the basis of the discussion to follow. EXPERIMENTAL AND NOTES ON TABLE [. Preparation of Compounds.—The methods of preparation employed were substantially those used by earlier workers. In preparing (I), (II) and (III) optically inactive propylene- diamine was used. The formyl camphor used in the preparation of (V), (VI), (VII), (VIII), (IX) and (X) was prepared from synthetic camphor and was therefore optically inactive. In order to check its identification and purity, each compound was analysed for metal content. The results of the analyses which were kindly carried out for me by Dr. G. Burger of the Uni- versity of Adelaide are set out in Table III. Magnetic Measurements.—Magnetic susceptibility measurements were made by the Gouy method, a detailed account of which has been given by Sugden (19326). In calculating magnetic moments the substances were treated as “ magnetically dilute ”’ ; Curie’s Law was assumed to hold good in each case. Owing to the smallness of /\W for the diamagnetic compounds (I), (IV) and (IX), and the consequent uncertainty in %, calculations of molar susceptibilities and moments for these compounds have been omitted. Absorption Measurements.—These were made by means of a Hilger-Nutting spectrophoto- meter. Full details of the method used have been given by Twyman and Allsopp (1934). 1 Relatively few crystal analyses have been made on internal complexes, the type of compound with which this communication is mainly concerned. It is therefore of interest to note that confirmation (Peyronel, 1941) of the theory of internal complex formation has been obtained with the recent complete determination of the crystal structure of N-N! dipropyldithiocarbamate nickel. In this diamagnetic substance nickel is square coordinated. 160 D. P. MELLOR. TaBLe III. % Metal % Metal Substance. Found. Calculated. TCM GENT ten ee eee 17-4 17-3 STE GLH MOUNIGo hy ean ale 17-2 17-4 II. C,,H,,0,N,cuw. ee | My CH OLNLNT Oe 15-7 15-75 MET: On ROENT Oe hee 14-4 14-1 _VI. CypH90,Co2H,0 Eke nee 12-9 13-0 ; Vit Cot OlCne EE OL ane 12-5 12-5 VILL CygH4s0o Co ie Wee 9-75 9-88 IX. C,,H,,0,N,Ni3H,0 ce ea ee 11-9 11:9 X. C,,H,,0,N,Cu2H,0 eae 13-2 13-2 THE STRUCTURE OF METAL COMPLEXES As DETERMINED FROM MAGNETIC DATA. Nickel. The compounds of nickel fall into two classes, the first of which includes compounds (I), (IV) and (IX), which are diamagnetic. In these three com- pounds, the four bonds linking the nickel atom to the chelate molecule are both covalent and coplanar. This conclusion is consistent with the fact that all attempts to resolve compound (XI) (see Fig. 2B) which, except for the sub- stitution of a carboxyl group, is identical with (IV) (Fig. 24) have failed (Pfeiffer et al., 1938). If nickel is square coordinated in (XI) resolution into optical isomers is impossible. The magnetic data also make it clear why Pfeiffer and his collaborators failed to resolve bis-salicylaldehyde-propylenediimine-nickel (I) when prepared from bis-salicylaldehyde nickel and optically inactive propylenediamine. If the bonds about the nickel atom in bis-salicylaldehyde-propylenediimine-nickel were tetrahedrally oriented, the following isomeric forms would be theoretically possible : dD ID IL dL D and L refer to the configuration or the nickel atom, d and | to the con- figuration of the asymmetric carbon atom (asterisked in Fig. I). Repeated fractional crystallisation failed to bring to light any isomeric forms and Pfeiffer (1938) thus concluded that the nickel bonds were coplanar. The only paramagnetic nickel compound studied in the present work was bis-formyleamphor-nickel (V), the susceptibility of which indicates that the nickel atom contains two unpaired electrons. Although the prediction (Pauling, 1931) regarding the structure of paramagnetic nickel complexes has not yet been very satisfactorily verified by either chemical or physical methods,” it is concluded that, in bis-formyleamphor-nickel, the metal atom is tetra- hedrally coordinated. 2 The high electric dipole moment of paramagnetic [Ni(NO,),(Et;P).] (Jensen, 1936) can be accounted for by assuming that the complex possesses a tetrahedral configuration. THE STEREOCHEMISTRY OF SOME METALLIC COMPLEXES. 161 Cobalt. Bis-salicylaldehyde-propylenediimine-cobalt (II) has a moment of 2-4 Bohr magnetons which, when due allowance is made for orbital contribution, indicates that the cobalt atom contains one unpaired electron; this is the number of unpaired electrons predicted (Pauling, 1931) for square coordinated Cot. The planar structure of tetracovalent cobaltous complexes with one unpaired electron has not yet been verified by other physical methods or even by the synthesis of isomers, but the success, to date, of the stereochemical predictions based on magnetic data, for other metals, makes the planar structure of bis-salicylal- dehyde-propylenediimine-cobalt fairly certain. Bis-formyleamphor-cobalt® dihydrate (VII) is, by the magnetic criterion, an ionic complex, that is to say, the bonds linking cobalt to the surrounding oxygen atoms (octahedrally arranged) are predominantly ionic in character. The effect of this type of linking on certain optical properties of the compound will be discussed in a later section of the paper. Tris-formyleamphor-cobalt™ is weakly paramagnetic,® and in this respect it resembles tris-acetylacetone-cobalt!! (Takagi and Ishiwara, 1914). The paramagnetism of both these compounds is too small to be accounted for by unpaired electron spins in the cobaltic atom and is to be attributed to unquenched orbital moment. The cobalt atom in _ tris-formyleamphor-cobalt™ forms d*sp? bonds with the six surrounding oxygen atoms, as in potassium cobalt- ioxalate (Johnson, 1932). Copper. While magnetic data enable one to distinguish between cupric and cuprous copper, the latter of which is tetrahedrally coordinated, they do not permit one to draw any conclusions about the configuration of the cupric atom. There is, however, much evidence, chiefly from the X-ray analysis of crystals, to show that cupric copper forms square complexes. Square complexes have been found in the crystals of K,CuCl,2H,O (Chrobak, 1934), CuCl,2H,O (Harker, 1936), CuO (Tunnel, Posnjak and Ksanda, 1935), CuSO,5H.O (Beevers and Lipson, 1934), CuPy,Cl, (Cox, Sharatt, Wardlaw and Webster, 1936), and Cu(C,H,O,) (Cox and Webster, 1935). In the absence of factors known to change this form of bond orientation, Cu! will show uniform stereochemical behaviour, an assumption that can equally well be applied to other atoms such as Pt, Pd, Au, etc., for which square coordination has been firmly established. If a metal atom is to form square bonds, a d orbital must be available for bond formation. Although this is a necessary condition, it is not a sufficient one. The two disturbing factors at present known are steric effects of the kind observed in complexes formed with certain substituted pyrromethenes (Porter, 1938 ; Mellor and Lockwood, 1940), and also effects arising from pronounced electro- negativity differences* between the bonded atoms. Probably the more generally concerned factor is the electronegativity difference between the metal atom and the four surrounding non-metal atoms. Certain metal atoms, Ni! Co™ and Mn", for example, are more sensitive to electronegativity differences than others, in so far as the effect of such differences on the bond type is concerned. With the possible exception of its compound with phthalocyanin (Klemm and Senfr, 1939), no instance of a square Mn™ complex has yet been reported ; instances of square bonding are fairly common among the compounds of Ni and Co and quite common among those of Cu™. As already pointed out, Cul! forms square bonds in CuO, CuSO,5H,O and CuCl,2H,O; in the analogous compounds of Co™ and Ni™ no such bonds are found. It is only in the case of extreme 3 I am indebted to Mr. D. P. Craig for the preparation and measurement of this substance. : *The term electronegativity is here used in the sense defined by Pauling (1940). N—November 5, 1941. 162 D. P. MELLOR. electronegativity differences between the bonded atoms, as between Cu! and F, the most electronegative of all atoms, that square coordination of Cu™ fails to appear. Thus CuF, is an essentially ionic crystal with the fluorite structure. (Ebert, 1931.) Palladium is similar to copper in regard to its tendency to form square bonds, the only exception being PdF,, which has the rutile structure. (Ebert, 1931.) Since neither steric nor electronegativity factors are likely to affect the bond type in bis-salicylaldehyde-propylenediimine-copper (III) and bis-formylecamphor-ethylenediimine-copper (X) it is concluded that in each of these compounds the copper is square bonded. THE STRUCTURE OF METALLIC COMPLEXES IN RELATION TO THE COTTON EFFECT. It is in regard to the structure of the compounds containing optically active chelate groups that the conclusions based on magnetic data fail to accord with those based on rotatory dispersion measurements. The situation is briefly this. Pfeiffer and his collaborators (1938) infer that, because bis-salicylaldehyde- d-propylene-diimine-nickel shows the Cotton effect, the Ni atom is tetrahedrally coordinated. This latter inference is based on the assumption that for the Cotton effect to appear, a molecule like that of (I) must contain, in addition to the asymmetric carbon atom, a chromophoric metal atom—also with an asymmetric (tetrahedral) configuration. The inactive form of (I) which contains equal numbers of d and / asymmetric carbon atoms is diamagnetic. (See Table I.) This simply means that in the molecule of (I) the four bonds to the nickel atom are coplanar, irrespective of whether the molecule contains a d or | propylene- diamine residue. French and Corbett, making use of the same assumption, viz. that the existence of a tetrahedrally coordinated chromophoric metal is necessary for the production of the Cotton effect—have come to the conclusion that nickel is tetrahedrally coordinated in paramagnetic bis-d-formyleamphor nickel. In other words rotatory dispersion measurements have been used to show that both para and diamagnetic nickel complexes contain tetrahedrally coordinated nickel. Two important questions seem to be involved here: (1) There is first of all the question as to whether the metal complexes with anomalous rotatory dispersion really show the Cotton effect. (2) Assuming that the Cotton effect appears in diamagnetic nickel com- pounds, the question then arises as to whether there is not some way of accounting for its appearance which does not involve the assumption of a tetrahedrally coordinated nickel atom. In attempting to answer these questions it is necessary to consider briefly the nature of the Cotton effect itself. The Cotton Effect. Three phenomena are associated with the Cotton effect. A substance exhibiting it shows (a) anomalous rotatory dispersion ; (b) zero rotation in the neighbourhood of the maximum of an absorption band; (c) circular dichroism with the maximum ellipticity in the region of zero rotation (or maximum absorption). Measurements of circular dichroism afford the most certain means of detecting the Cotton effect (Bruhat 1930), but, in their absence, measurements of both absorption and rotatory dispersion may be used. With regard to the first question mentioned above it should be pointed out that, in general, anomalous rotatory dispersion is caused by the super- position of normal rotations of opposite sign and unequal dispersion. These rotations may have their origin either in the same molecule or in different molecules (Lowry, 1935). Anomalous rotatory dispersion is shown by a solution THE STEREOCHEMISTRY OF SOME METALLIC COMPLEXES. 163 made by mixing two colourless liquids with opposite rotatory power and unequal dispersion (Biot, 1836), but such a solution does not show the Cotton effect. For the Cotton effect to appear, the two rotations must have their origin in the same molecule; furthermore the rotatory dispersion must be anomalous in the region of an absorption band originating in the optically active molecules. A solution of sugar coloured with magenta, for example, does not show the Cotton effect (Cotton, 1895). The Cotton Effect in Diamagnetic Nickel Complexes. Pfeiffer and his collaborators relied on rotatory dispersion measure- ments alone to detect the Cotton effect. It is clear from what has been said above that their dispersion studies need supplementing with absorption measure- ments before the existence of the Cotton effect can be considered as established, Moreover, it is necessary to show that the bands in which the Cotton effect occurs are due to the presence of the metal atom in the molecule. The author has therefore ” studied the absorption of several of the metal com- plexes in the visible region by means of a _ Hilger- Nutting spectrophotometer. The absorption spectra for two nickel complexes, viz. (a) bis-formyleamphor- ethylenediimine-nickel (IX), (b) bis - salicylaldehyde - propylene-diimine-nickel (I) are shown in Figs. 5 and 6 respectively. Absorption measurements were made on optically inactive compounds, [] MOLECULAR ROTATION 4N313155305 NOILINUXI YVINIIION WAVE LENGTH in A but this introduces’ no Fig. V.—Ethylene-diimine-formyl-camphor-nickel difficulties since, as Brode i. VolUely dul He Urea eee ee and sorption eos Have shown Rotatory dispersion —-:—-:—-— (data from (1925), optical enantiomorphs are characterised by identical absorption spectra. From Fig. 5 it can be seen that the dispersion curve crosses the axis of zero rotation at a wave length very close to that of the maximum of the absorption band. The dispersion data for bis-salicylaldehyde-d-propylene- diimine-nickel (see Fig. 6)> were not continued sufficiently far towards the ultra-violet to allow the dispersion curve to cut the axis of zero rotation, but a rough extrapolation showed that it would most likely do so in the neighbourhood of 4,500 A., which represents a distance of 450 A. from the head of the absorption band at 4,050 A. Differences of this order, between band head and wave length for zero rotation have been observed by Mathieu (1936) in his study of the Cotton effect among cobaltic ammines. There are several important features to be noted in Figs. 5 and 6. In the former, the band with a maximum at 6,200 A. is definitely due to the presence Pfeiffer’s paper). __ °I am indebted to Dr. J. E. Mills for permission to publish the data relating to the ultra- violet region in this diagram. These data form part of a joint investigation of the absorption spectra of para- and diamagnetic nickel complexes, a short account of which is shortly to appear in J. Amer. Chem. Soc. 164 D. P. MELLOR. of nickel, since the colourless metal-free compound shows no absorption in this region. The Cotton effect for bis-formyleamphor-ethylenediimine-nickel (IX) — (Fig. 5) therefore, occurs in a band® which arises from the presence of the nickel atom in the molecule. This is an important point, since, as will be shown later, a metal complex may show the Cotton effect in a band not necessarily due to the presence of a metal atom. The effect of introducing a nickel atom into bis-salicylaldehyde propylene- diimine is clearly shown in Fig. 6, where the curve on the extreme right repre- sents the absorption of the metal-free compound, while the curve adjacent to it represents the absorption of the metal containing compound. The band with a maximum at 4,050 A. is clearly associated with the presence of the metal atom. In neither bis-salicylaldehyde-propylenediimine nor its nickel compound are there any bands in the visible region comparable in strength with those of the violet and ultra-violet. It will be noted that the strong band of bis-salicyl- aldehyde-ethylenediimine (I) with a maximum at 3,200 A. is shifted to the red (to 3,400 A.) in the metal compound. MOLECULAR ROTATION [iq 1N31314330> NONLONILXI UVINDIION "4600 WAVE LENGTH In A. Fig. VI.—Propylenediimine-bis-salicylaldehyde-nickel. 0- M in ethyl! alcohol. Absorption Rotatory dispersion —-:—-—-—- (Pfieffer). Propylenediimine-bis-salicylaldehyde absorption — — — — The combined dispersion and absorption measurements show that both compounds (I) and (IX) show the Cotton effect, notwithstanding the fact that, being diamagnetic, they both contain square coordinated nickel. Some explana- tion other than that which postulates the existence of tetrahedrally coordinated nickel must therefore be sought to account for the appearance of the effect. At the outset it must be stated that it always seemed inherently improbable that the mere presence of an asymmetric carbon atom in a compound like bis-salicylaldehyde-d-propylenediimine-nickel should cause the nickel to change from square to tetrahedral coordination as suggested by Pfeiffer et al. (1938). There is no difficulty in accounting for the optical behaviour of this and related compounds in another way. Some years ago Lowry and Walker (1933) put forward the view that ‘““chromophoric groups can exhibit ‘induced asymmetry ’ as a result of which 6 The band at 6,200 A. is not the only one which can be attributed to the nickel atom ; another and much stronger one occurs at 3,850 A. THE STEREOCHEMISTRY OF SOME METALLIC COMPLEXES. 165 they themselves become optically active when coupled sufficiently closely to an asymmetric complex.” This hypothesis was based upon the observation that ‘“‘the dispersion equations of camphor and its derivatives are haunted by a low frequency term the period of which is definitely characteristic of the ketonic group’’. In order to account for the occurrence of the Cotton effect among the planar (diamagnetic) complexes of nickel, it is suggested that the chromophoric nickel atom exhibits “induced asymmetry ’’ when linked to an asymmetric chelate group, in the same manner as the ketonic group in camphor derivatives. As will be indicated in a later section, it seems essential that nickel be bound to the asymmetric chelate group by covalent bonds, if the Cotton effect is to appear. A similar explanation can be given in regard to the appearance of the Cotton effect in the covalent complexes of Cu™ and Co", although it should be pointed out that evidence LIS aT evr ME EN ee ese a eos for the planar configura- tion in the complexes of these two metals, especially the latter, is not so complete as it is for nickel. From the argu- ments already outlined, however, there is strong indirect evidence for the planar distribution of bonds about copper (Cu!) and for this reason absorption measurements were extended to the com- pounds bis - formyl- camphor - ethylenediimine - copper (X) (Fig. 7) and bis - salicylaldehyde - pro - pylenediimine - copper me) 6 From Fig. 7 it 5 Ait Mints 9 can be seen that the former Fig. VII.—Ethylene-diimine-bis-formyl-camphor-copper. 0:00147 M in isobutyl alcohol. compound has an absorp- ne . . sorption tion band | the maxi Rotation —-:-—--—_:— (data from Pfeiffer’s paper). of which is in the close neighbourhood of the point where the dispersion curve cuts the axis of zero rotation. Owing to the slight solubility of (III), molecular extinction coefficients for this compound could not be satisfactorily determined. Measurements on supersaturated solutions, however, show that the substance possesses a band with a maximum at 5,650 A., whereas, from the rotary dispersion curve, a maximum would be expected in the neighbourhood of 5,700 A. It is clear, then, that these two copper compounds also show the Cotton effect notwith- standing the fact that there is a planar distribution of bonds about the copper atoms. MOLECULAR ROTATION [mJ £N 3193303 NOILINILXI YVINDIION 2 WAVE LENGTH In A The Cotton Effect In Paramagnetic Nickel Complexes. While most of the compounds described by Pfeiffer et al. (1938) showed anomalous rotatory dispersion in the visible spectrum, there were one or two notable exceptions, e.g. bis-formyleamphor-nickel (V). This compound shows no Cotton effect in the visible region of the spectrum (Pfeiffer et al., 1938). It is not surprising, therefore that the absorption of a dilute (0-006 M.) alcoholic solution showed no marked absorption bands in the region 7,000 A. to 4,300 A.— 166 D. P. MELLOR. at least, no bands with intensities comparable to those of bands due to the presence of the nickel atom in covalent complexes. In this respect nickel- formylcamphor solution resembles aqueous solutions of paramagnetic nickel compounds containing hydrated or ammoniated nickel ions which show only bands of very small molecular extinction (ec =10) (Ley, 1927, and Bjerrum, 1941). Bis-formyleamphor-nickel (V) has also been reexamined by French and Corbett (1940), who have extended both absorption and dispersion measurements well into the ultra-violet. These authors record a band maximum at 3,172 A. and also a rotatory dispersion curve which crosses the axis of zero rotation at about this point. On the basis of this observation French and Corbett conclude that in (V), nickel is tetrahedrally coordinated. While the compound shows the Cotton effect, it is by no means certain that the band in which the effect appears is one which can be attributed to the presence of the nickel atom. Thus formyleamphor itself has a band, the maximum of which is at about 2,630 A. and a second band with a maximum at less than 2,400 A. (Lowry and Southgate, 1910). In sodium formyleamphor the former of these bands appears to be shifted so that the maximum is at 3,000 A., while the position of the second band (in the sodium salt) cannot be fixed from the published data. The 3,172 A. band observed by French and Corbett for bis-formyleamphor-nickel may well be a band due to formyleamphor itself shifted from its position at 2,630 A. by the presence of the ionically bound nickel in much the same way as it is shifted to 3,000 A. by ionically bound sodium. In view of the uncertainty of the origin of the 3,172 A. band and also the fact that square (diamagnetic) complexes show the Cotton effect, it is clear that the optical studies of bis-formylcamphor- nickel (V) so far, reveal nothing about the orientation of bonds about the nickel atom in this compound. The Cotton Effect and Bond Type. There is some evidence that occurrence of anomalous rotatory dispersion among metallic complexes is related to the nature of the metal to non-metal bonds occurring therein. The nickel-oxygen bonds in bis-formyleamphor are predominantly ionic and, from certain regularities already noted in magnetic studies of nickel compounds, the same may be said of the nickel-oxygen bonds in bis-benzoyleamphor nickel which, like the formyl complex, shows normal rotatory dispersion in the visible region. In this connection it is interesting to note some observations made by Lifschitz (1923) on closely related cobalt compounds. Lifschitz states that bis-formyleamphor-cobalt (Cot) shows no Cotton effect. On the other hand the tris cobaltic compound does show the Cotton effect. Magnetic measurements indicate that in the cobaltous compound the Co-—O bonds are predominantly ionic (see Table I), while in the cobaltic compound the corresponding bonds are covalent. Other instances could be quoted to show that the Cotton effect is absent in ionic metal complexes.’ The whole question of the appearance or non-appearance of the Cotton effect is closely tied up with the differences between the absorption spectra of ionic and covalent? metal complexes. The two ionic complexes which fail to show anomalous rotatory dispersion in the visible region, viz. the nickel and cobaltous compounds of formyleamphor, also fail to show any absorption bands in that region—at least any bands of intensity comparable with that found at 6,200 A. in diamagnetic bis-formyleamphor-ethylenediimine-nickel (Fig. 5). The Usefulness of the Cotton Effect in Stereochemical Studies. It would be premature to generalise at this stage, but as far as the metal compounds studied in this paper are concerned, it appears that the manifestation 7 The terms ionic and-or covalent here refer to the metal—-non-metal bonds. Py THE STEREOCHEMISTRY OF SOME METALLIC COMPLEXES. 167 of the Cotton effect does not depend on the orientation of valence bonds about the chromophoric metal atom but on the character of these bonds, that is whether they are predominantly covalent or ionic. Bond character may determine bond orientation, as in the case of the nickel atom and in so far as this is true, the Cotton effect may be useful in determining structure. There are, however, indications that the determination of bond character may be achieved by a study of absorption spectra alone. Definite differences have already been noted in the absorption spectra of certain dia- and paramagnetic complexes of nickel® and in the limited field so far explored, bond type and orientation ean be determined without recourse to the more difficult measurements of rotatory dispersion. ACKNOWLEDGMENTS. The author is indebted to Mr. G. K. Hughes for specimens of formyl-camphor, ‘to Dr. R. Lemberg and the Council for National Health and Medical Research for the use of the Hilger-Nutting spectrophotometer, to Mr. J. McInnes for assistance in preparing the diagrams for this paper, and lastly to the Australian Commonwealth Government for a grant to purchase an electromagnet for the magnetic work. SUMMARY. Magnetic susceptibility measurements are used to determine the orientation and character of the bonds uniting metal atoms to various organic molecules. It is shown that the certain square coordinated complexes of nickel and copper exhibit the Cotton effect in bands due to the presence of the metal atom. The Cotton effect is attributed to the fact that the chromophoric metal atoms exhibit “induced asymmetry ’”’ when linked to asymmetric chelate groups. The possibility of using Cotton effect studies to determine the character and orienta- tion of chemical bonds is briefly discussed. REFERENCES. Biot, M.: C.R. Acad. Sc., Paris, 1836, 2, 543. Beevers, C. A., and Lipson, H.: Proc. Roy. Soc., 1934, (A), 146, 570. Bjerrum, J.: 1941 Dissertation, Copenhagen. Bose, D. M., and Datta, S.: Nature, 1931, 128, 725. Brasseur, H., and de Rassenfosse, A.: Bull. Soc. Min. France, 1938, LXI, 129. Brode, W. R., and Adams, R.: J. Amer. Chem. Soc., 1924, 46, 2032. Bruhat, M. G.: C.R. Acad. Sci., Paris, 1930, 47, 251. Chrobak, L.: Z. Krist., 1934, 88, 35. Cotton, A.: C.R. Acad. Sci., Paris, 1895, 120, 989, 1044. Cox, E. G., Sharatt, E., Wardlaw, W., and Webster, K. C.: J. Chem. Soc., 1936, 129. Cox, E. G., and Webster, K. C.: J. Chem. Soc., 1935, 731. Cox, E. G., Wardlaw, W., and Webster, K. C.: J. Chem. Soc., 1935, 1475. Kbert, F.: Z. anorg. allg. Chem., 1931, 193, 395. Elliott, N.: Dissertation, Calif. Inst. Technology, Pasadena, Calif., U.S.A., 1938. French, H. S., and Corbett, G.: J. Amer. Chem. Soc., 1940, 62, 3219. Harker, D.: Z. Krist., 1936, 93, 136. Jensen, K. A.: Z. anorg. allgm. Chem., 1936, 229, 265. Johnson, C. H.: Trans. Faraday Soc., 1932, 28, 845. Ley: Z. anorg. allgm. Chem., 1927, 164, 395. Lifschitz, J.: Z. Phys. Chem., 1923, 105, 27. Lowry, T. M., and Southgate, H. W.: J. Chem. Soc., 1910, 97, 905. Lowry, T. M., and Walker: Nature, 1933, 131, 566. Lowry, T. M.: Optical Rotatory Power, Longman, Green, London, 1935. Mathieu, J. P.: Bull. Soc. Chim. France, 1930, 47, 251. Mathieu, J. P.: Bull. Soc. Chim. France, 1936, Ser. 5, 3, 477. _ , *It is interesting to note that Raman spectra may also be used to discriminate between onic and covalent bonding in metal complexes. Of the two complexes, ionic [Co(NH,),]++ and covalent [Co(NH,),]+++ only the second gives Raman lines attributable to the Co—N bonds (Bose and Datta, 1931). 168 D. P. MELLOR. Mellor, D. P., and Quodling, F. M.: Tuis Journat, 1936, LXX, 205. Mellor, D. P., and Lockwood, W. H.: Nature, 1940, 145, 862; Tuts Journat, 1940, LXX, — Mellor, D. P.: Aust. J. Sc., 1941, 3, 99. - Pauling, L.: J. Amer. Chem. Soc., 1931, 53, 1367. Pauling, L., and Huggins, M.: Z. Krist., 1934, 87, 205. Pauling, L. : The Nature of the Chemical Bond, Cornell University Press, Ithaca, New York, 1940. Peyronel, G.: Z. Krist., 1941, 103, 157. Pfeiffer, P., Christelheit, W., Hesse, T., Pfitzner, H., and Thielert, H.: J. prakt. Chem., 1938, 150, 261. Porter, C. R.: J. Chem. Soc., 1938, 368. Sugden, S.: J. Chem. Soc., 1932, 246a. Sugden, S.: J. Chem. Soc., 1932, 161b. Takagi and Ishiwara : Se. Rep. Tohoku Imp. Univ., Ser. I, Maths. Phys. and Chem., 1914, 3, 127. Tschugaeff, L.: J. Russ. Phys. Chem. Soc., 1910, 42, 1466. Tunnell, G., Posnjak, E., and Ksanda, C. J.: Z. Krist., 1935, 90, 120. Twyman, F., and Allsopp, C. B.: The Practice of Absorption Spectrophotometry, Adam Hilger, London, 1934. Department of Chemistry University of Sydney. ON THE FREQUENCY OF THE PRIMES. By F. A. BEHREND. Communicated by PRorressor H. S. CarsLaw. (Manuscript received, November 4, 1941. Read, December 3, 1941.) k, m, n denote integers, p denotes primes. J. 8S. Broderick”) recently proved a theorem, equivalent to that of Chebyshev on the distribution of primes, by methods which involve only the elementary properties of the integers. Instead of the transcendental function log n he uses the numerical function (1) AMn)= 3 and proves that the number x(n) of primes a exceeding n satisfies the inequality, (2) sy < min <4 (n= 2) Simplifying Broderick’s proof I obtained ® the better estimate (3) =< m(nj <12 (n> 2)* Following up more rigorously the lines of my proof, I show in this paper that (4) 5 < n(n) <3 (n> 2) This estimate is easily deduced from the formula (6) (28) I 1, m>1).@ Proof: The left hand inequality holds forn=1andm>1. Using induction, A((w +1)m) = Mom gt a > Am) +A) L$ =D(m- +1) +2(m) — * By a slight alteration of the proof the sharper inequality 4< rou) <6 can be obtained. n O—December 3, 1941. 170 F. A. BEHREND. On the other hand, il 1 Nnm)=(1 tig tae ; | “(as it 1 = +.. +5 +a) ++ (a ta tt n+l By repeated application of (10), it follows that (11) k(A(n) —1) +11) AS nae) —Lt5+(5+ i}t flea =a +3] (12) can be sharpened to (12’) Sh+11); we have M2") =p (2k) + (2k-4) +... + (2) H1, hence, aS u(2n) is increasing with n, M2) < ky (2k) +1 (k= 0). On the other hand, as u(2m—1) >y(2n) (m1, n=), aL: »(2K) =p (2%) +(per SDE, ne +(ne =e ileal PO) "tip ea et SOR eee) (k>0); thus : Ge) kyu. (2*) 0). It is easily calculated that w(25) <2 and 1(20) >5, hence Dale op (2. Set i ae (14) wl2n) <2 5 (n>1), 2 (15) (27) ae (n> 10). It should also be noted that ee xe A) for m1 a depen n} a! nt btn cpt since (i) the primes with n 1). y (18) and (19) (20) gana (2n)" (en) +1 (n> (21) mt (2n)-T(n) << pan (n> Liyes 3. Lower bound for x(n). Let n=2m; then, by (12’’), (20) and (11), (22) 2my.(2?™) 2). ety as (24) (2m —1) 7 (22m) — By (23) and (24), (25) n(n) > (2a) ——— (n>2). 4. Upper bound for x(n) (26) 7(n)— <2u(2") Wi (n> 2). Proof : (i) 2 0) Ag alls ed 10 4. 10) eee Bue Xn) 328) ~ 3 7u(28) 413 mee. (vi) n=2m>128: Proof by induction: by (11), (21), (12”), (27) (zc(20) —m(0))(A(m) —1) 128 : nome) »(2m +1) n(Qm) (2m +1) (35) = (2m +1) Fa meee tS (0) Nie) ere erm it 2. (25) and (26) establish (5). 5. Proof of (4) By (i)-(v) (40) n(n _ ea ira Oe \A(256) _ 9 8u(256) +1 aes C Beg ho sorcn 2s aorecee 100 ony eo 5I21024, by (26), A) 2 ony lOO ele ? TS Ce aay yen 10 10 LOO. Be P EO e 3 7 Tulon(lonay a owmenasa 3 Thus, (40) holds for all n>2. On the other hand, a2) 81 Ghani na ieiet RD og MO a 200 , MV AS) ete ee 5 1e(5) 3 =) 5 acre & (0) (16) lee ve Fo A(m) Gy) MS 1732, by (25), 5 5. =+1 An) An) 2 82).2 TL ea Mec eh art alas Ree 32° 8 7 ee Hence a (41) n(n) Se (n> 2) (40) and (41) establish (4). REFERENCES. () Journal London Math. Soc., 1939, 14, 303-310. (2) Journal London Math. Soc., 1940, 15, 257-259. ABSTRACT OF PROCEEDINGS OF THE Royal Society of Nem South Wales April 2, 1941. The Annual Meeting, being the five hundred and eighty-fifth General Monthly Meeting of the Society, was held in the Hall of Science House, Gloucester and Essex Streets, Sydney, at 7.45 p.m. Professor A. P. Elkin, President, was in the chair. Eighty-five members were present. The minutes of the general monthly meeting of December 4, 1940, were read and confirmed. The following gentlemen were elected officers and members of the Council for the coming year : President : D. P. MELLOR, m.sc. Vice- Presidents : H. S. HALCRO WARDLAW, D.sc., F.A.€.1. | E. H. BOOTH, .c., pD.se., F.1nst.P. W. L. WATERHOUSE, m.c., D.Sc.Agr., | Pror. T. G. ROOM, m.a. D.1.C., F.L.S. Honorary Secretaries : Pror. A. P. ELKIN, .a., Ph.p. | C. ANDERSON, .a., D.sc. Honorary Treasurer : A. R. PENFOLD, F.A.c.1., F.c.s. Members of Council: Pror. V. A. BAILEY, M.A., D.Phil., F.Inst.P. Pror. C. E. FAWSITT, bD.sSe., Ph.p. A. BOLLIGER, pPh.p., 4.A.c.1. E. J. KENNY, M.Aust.1.M.M. G. H. BRIGGS, B.sc., Ph.p., F.Inst.P. W. H. MAZE, M.sc. IDA A. BROWN, p-.sc. G. D. OSBORNE, pD.sc., Ph.D. W. R. BROWNE, pD.sc. | A. CLUNIES ROSS, B.sc., F.c.a. (Aust.). XXli ABSTRACT OF PROCEEDINGS. The Annual Balance Sheet and Revenue Account were submitted to members by the Honorary Treasurer, and on the motion of Mr. M. B. Welch, seconded by Mr. R. H. Goddard, were adopted. THE ROYAL SOCIETY OF NEW SOUTH WALES. BALANCE SHEET AS AT 28th FEBRUARY, 1941. LIABILITIES. 1940. £ = Trust Funds— Clarke Memorial Fund— Balance as at 29th February, 1940 oo ESTES Add Interest for year ended 28th February, 1941 yA ne aa 68 £1,784 Less Expenses in connection with 1940 Lecture— Printing He £3 13 2 Advertising ae Je15 > 0 ——$_—_—_— + Walter Burfitt Prize Fund— Balance as at 29th February, 1940 .. 661 Add Interest for year ended 28th February, 1941 at ae ni 26 Liversidge Bequest— Balance as at 29th February, 1940 .. 703 Add Interest for year ended 28th February, 1941 ie ve a 28 £731 Less Expenses in connection with 1940 Lecture— Lecture Fee = | £4270. 0 Printing ne 213 8 Advertising O17. 6 45 3,081 10 Subscriptions Paid in Advance 11 1779 tae 688 7 3 686 1 4 156 Provision for Unexpired Proportion of Life Membership Subscriptions 26,686 Accumulated Fund £29,933 £ Ss. 3,154 7 15 15 124 0 27,204 17 £30,499 0 —) noon ABSTRACT OF PROCEEDINGS. XX ASSETS. 1940. 1941. £ Sen o@e ee eee | Cash at Bank and on Hand— The Union Bank of Australia Ltd. ee - 48 9 10 Commonwealth Savings Bank of Australia a 48 9 5 Petty Cash bss ie hs GE ae 315 7 214 ——_—_—_—— 100 14 10 Bonds and Inscribed Stock— Bonds (Face Value £1,600) .. ee ae hee HEGLI6730 Stock (Face Value £6,860) .. ae nie oh SG SZ7eble “3 7,839 ——————. 8, 438 16 3 Science House Management Committee— 14,590 Payments to date an ws as a a 14,650 0 0 Sundry Debtors— Subscriptions Unpaid os ae a a 197 12 10 — Less Reserve... u's as ong es sad 197 12 10 6,800 Library af ue as a Ae ee as 6,800 0 0 Furniture oe fe sup aie ay ee Bue 454 9 9 Less Depreciation written off vs da = 20 ll 5 411 433 18 4 Pictures oie ae ae es a Sis a 43 15 8 Less Depreciation written off She age sit Zao. 9 44 41] ll ll Microscopes .. we a6 ee a Se oe LOE Ss Less Depreciation written off ae avg of 019 6 19 18 9 2 Lantern Ds i. ae ake a oS ye 16 6 O Less Depreciation written off oe ne A 016 6 16 — 15 9 6 £29,933 £30,499 O O The above Balance Sheet has been prepared from the books of account, accounts and vouchers of The Royal Society of New South Wales, and is a correct statement of the position of the Society’s affairs on the 28th February, 1941, as disclosed thereby. We have obtained certificates showing that the whole of the Bonds and Inscribed Stock are held by the Society’s bankers for safe keeping. HORLEY & HORLEY, Prudential Building, Chartered Accountants (Aust.). 39 Martin Place, Sydney, 18th March, 1941. (Sgd.) M. B. WELCH. Hon. Treasurer. XX1V ABSTRACT OF PROCEEDINGS. REVENUE ACCOUNT FOR THE YEAR ENDED 28th FEBRUARY, 1941. Year ended 29th Feb., Year ended 1940. 28th February, 1941. £ (© pA ec (ane s. d. 4 To Advertising ake ots a6 aie a sf 3.6 9 30 ~,, Cleaning .. a Me ake bi ts Bs 32 2 6 26 ~=,, Depreciation f ia sige aan he 2411738 6 ,, Electric Light and Gas.. ba a ee ie 9 8.2 14 =~, Insurance ; ate af ok x he 14 6 1 da) ee ab rery: Maintenance .. oe ue Ev ue 39 12 6 56 ,, Miscellaneous Expenses a an Ty 54 11 10 259 «,, Office Salaries and Audit Fees | ee is de 283 19 6 29 ~=~«,, Office Sundries and Stationery ane ihe ake 16 6 7 119 © ,, Prnting a ite ie 115 4 7 273 ~=~«4, Printing anil Publishing Nournel a mm ms 362 4 6 6 ,, Repairs... eH aah te S 4. 13-2 49 ,, Stamps and Telegrams a es i sag 50 19 4 17 ~,, Telephone ae os Hee ate 7 ie 18 14 9 ,» Annual Dinner— 55 Expenses... ae aus ae £34 19 8 4] 14 Less Received os ae ait 29 8 0 —- —— 511 8 979 ——————— 1,035 13 1 », Balance, being Net Revenue for the Year, transferred 50 to Accumulated Fund me an me ie 443 7 4 £1,029 £1,479 O 5 Year ended | 29th Feb., Year ended 1940. 28th February, 1941. £ £ PA Ys PO s. d 476 By Members’ Subscriptions is a wt oh: 531 6 0 — ,, Government Subsidy .. is ae Ae ois 400 0 90 260 », science House Receipts ie ie We me: 275 0 O 16 Less Rent Paid 23 ae Rie ae a 41 16 2 —- 244 ———— 233 3 10 100 ,, Miscellaneous Receipts . . he oe ar a 98 9 3 297 », Interest Received “Me ave SH ae ihe 307 6 3 Less— Clarke Memorial Fund ne £68.12 7 Walter Burfitt Prize Fund .. 26 9 6 120 Liversidge Bequest oe wilt 28 2 10 ———_—_——— 123 4 11] —- 177 ————— 184 1 4 32 ,, Proportion of Life Members’ Subscriptions bis 32 0 8 £1,029 £1,479 O 5 ABSTRACT OF PROCEEDINGS. XXV ACCUMULATED FUND ACCOUNT FOR THE YEAR ENDED 28th FEBRUARY, 1941. 1941—February 28— Sa ese, To Arrears of Subscriptions, written off the Pe Poe ae ae 119 1 O Balance Carried Down .. a Ay ee Hie a ah ae 27,204 17 5 99 £27,323 18 5 1940—February 29— £ Sarde By Balance from last Account As uae a ne ae ae aCe 26,685 15 1 1941—February 28— By Amount transferred from Bad Debts Reserve Account .. ais fe 134 16 O .. science House Capital Account—Adjustment ane ste a a 60 0 0 ,». Net Revenue for the Year ae ave ie ae ns ae Ay 443 7 4 fZigowe wer oo 1941—February 28— By Balance Brought Down ke ae Be a 2h on ate £27,204 17 5 The Annual Report of the Council (1940-41) was read, and on the motion of Mr. A. R. Penfold, seconded by Mr. A. D. Ollé, was adopted. REPORT OF THE COUNCIL (RULE XXVI), 1940-1941. We regret to report the loss by death of eight members since April Ist, 1940: Mr. Frank Leverrier (1909), Mr. Henry H. Baker (1919), Mr. John Farrell (1910), Mr. John Patrick O’Neill (1932), Mr. Thomas Lindsay Willan (1921), Mr. Edmund Cooper Manfred (1880), Mr. James Nangle (1893), and Mr. George Henry Blakemore (1905). By resignation the Society has lost seven members: 8S. W. E. Parsons, Victor Marcus Coppleson, Frank Hambridge, Charles Vicars Potts, Elizabeth F. Lawrence, William Charles Wentworth, Percy Ash. Six members were written off the register of members. Sixty-two ordinary members were elected during the year. Annual Dinner.—In conformity with the precedent established during the World War of 1914-1918, it was resolved that the Annual Dinner should not be held durmg the present war. During the year beginning April Ist, there have been nine general meetings and ten Council meetings. The average attendance at general meetings was 53, and at Council meetings 14. Forty papers were read before the Society during 1940. The following short talks were given also: “Highlights of a Recent World Tour,’ by Mr. A. R. Penfold. ‘“ Submarine Canyons,’ by Dr. G. D. Osborne. “The Early History of Wireless,’ by Mr. G. G. Blake. Exhibits were shown by Professor A. P. Elkin and Mr. A. R. Penfold, whose “‘ glass textiles ” created great interest. Four Popular Science Lectures were given in the winter months, and all were very well attended both by members of the Society and the general public. July 18.—‘‘ An Inland People of New Guinea,’ by Phyllis M. Kaberry, M.A., Ph.D. August 15.—“‘ Insects and Disease in War-time, with Special Reference to Mosquito Biology,” by A. R. Woodhill, B.Sc.Agr. September 19—‘‘ Energy for Living,” by R. N. Robertson, B.Sc., Ph.D. October 17.—‘‘ Romances of Chemistry—Coal Stockings and Glass Ties,” by A. R. Penfold, FA.C.1., F.C.S. Symposium.—A very successful symposium on ‘“‘ Potassium ’ monthly meeting of August. The speakers were as follows : 2 was held during the general C. de Vahl Davis, B.Sc.Agr.: ‘“‘ The Commercial Potash Situation in Australia.” D. P. Mellor, M.Sc. : ‘‘ Some Aspects of the Chemistry of Potassium, with special reference to Potential Sources in Australia.”’ N. H. Parbery, D.Sec.: ‘‘ Potassium in Soil.” R. N. Robertson, B.Sc., Ph.D. (vice Professor E. Ashby): ‘‘ Potassium in Plants.” Mr. de Vahl Davis also showed a film entitled ‘‘ The Mining and Manufacture of Potash in Europe.” There was an attendance of 106 at the symposium, and the addresses delivered were later printed in pamphlet form for distribution to members and others who were interested. xvi ABSTRACT OF PROCEEDINGS. Clarke Memorial Lecture.—The Clarke Memorial Lecture was delivered on June 14th, by Mr. E. J. Kenny, and was entitled “‘ The Geologist and Sub-surface Water.” Liversidge Research Lecture.—The third Liversidge Research Lecture to be given under the auspices of the Royal Society was delivered on October 3lst, by Mr. G. J. Burrows, B.Sc., and was entitled *“‘ Organic Arsenicals in Peace and War.”’ Finance.—The finances of the Society as shown by the balance sheet are in a satisfactory condition. On the advice of the Finance Committee, an amount of £600 was invested in the Commonwealth War Loan during 1940. Government Grant.—The Government of New South Wales made a grant of £400 to the Royal Society of New South Wales for the year 1940. Science House.—The Royal Society has been represented on the Science House Management Committee by Mr. E. Cheel, who was appointed Secretary-Treasurer of the Committee, and by Mr. M. B. Welch, with Dr. C. Anderson and Dr. H. 8. H. Wardlaw as substitute representatives. The Society’s share of the profits on Science House has been of the same order as that of the past two or three years. Paper Rationing.—In response to representations made by its officers, the Royal Society was granted exemption from the proposed rationing of paper adopted as a war economy by the Department of Trade and Customs. The Department, in granting the exemption, asked that economy in paper should be observed, as far as was consistent with the publication of papers on research. Alteration of Rules.—An alteration was made to Rule VIII. Other alterations, concerning a proposed postal ballot, were referred to a committee. Members on Active Service.—It was resolved to remit for the duration of the war the sub- scriptions of any members of the Society on active service with His Majesty’s Forces. The LInbrary. Exchanges.—The number of societies and institutions with which publications are exchanged has declined considerably owing to the entry of more countries into the war, or their occupation by the enemy. The present number of exchange societies and institutions is 268. Since the war began, 97 exchanges in all have been removed from the exchange lists, including societies and institutions in Germany, Italy, France, Belgium, the Netherlands, Norway, and Rumania. Accessions.—Owing also to war conditions the number of accessions has decreased by about one-quarter since the war began, namely from 3,317 for the year ended March, 1939, to 2,348 for the year ending March, 1941. Borrowers and Readers.—The number of readers who visited the library during the year was thirty-three, and sixty-three periodicals were borrowed by members and accredited readers. Periodicals were sent out on loan to the following societies and institutions: The University of Sydney (Fisher Library, Geological Library and Botany School), the C.S.I.R. (Division of Plant Industry, Canberra, the McMaster Laboratory, Sydney, and the Food Preservation Laboratory, Homebush), the British Medical Association, Sydney, the Broken Hill Proprietary Ltd., Newcastle, the Standards Association, the Australian Institute for International Affairs, Sydney, the Uni- versity of Western Australia, the Royal Society of Tasmania, and the Irrigation Commission, Sydney. ; Bookbinding and Purchase of Periodicals ——A number of periodicals have been bound at a cost of £8 1ls. 6d. Periodicals have been purchased at a cost of £31 ls., the total amount for binding and purchase of books being £39 12s. 6d. Furniture and Fittings.—The portion of the library used as a reading room has been greatly improved in several ways. The floor has been covered with linoleum, and a carpet has been provided under the reading table. Comfortable chairs have been obtained, and a powerful new light for reading has been installed over the table. Shelving.—There is still considerable crowding on the shelves, and it is hoped to be able to dispose of a number of duplicates, which are now occupying valuable shelf space. A. P. ELKIN, President. The following donations were received: 798 parts of periodicals, and 32 whole volumes. The certificates of four candidates for admission as ordinary members of the Society were read for the first time. The President announced that the Clarke Memorial Lecture for 1941 would be given by Mr. C. A. Sussmilch, the title of the lecture being “‘ The Climate of Australia in Past Ages.” The President announced that the Clarke Memorial Medal for 1941 had been awarded to Professor F. Wood Jones, of the University of Manchester, England. ABSTRACT OF PROCEEDINGS. XxVli Format of the Journal and Proceedings.—It was announced that the Council was considering an alteration in the format of the Journal and Proceedings, to quarto size, in order to effect an economy in cost and in the amount of paper used, and also to bring the journal into line with other present-day journals. After discussion it was unanimously decided that the format be altered to quarto size. Election of Auditor —On the motion of Mr. A. R. Penfold, seconded by Mr. E. Cheel, Messrs. Horley & Horley were reappointed as the Society’s auditors for the year 1941-1942. The President, Professor A. P. Elkin, delivered his address, entitled *‘ Science, Society and ‘ Everyman ’.” Professor A. P. Elkin, the retiring President, then installed Mr. D. P. Mellor, M.Sc., as President for the year 1941-1942, and the latter expressed his thanks and his pleasure on taking office. On behalf of the members Dr. W. R. Browne expressed appreciation of the work of the retiring President, and of his interesting address. Professor Elkin briefly replied. Notice of Motion.—Mr. M. B. Welch moved “That the Council be requested to appoint a committee to consider revision of the Society’s Rules.” May 7, 1941. The five hundred and eighty-sixth General Monthly Meeting was held in the Hall of Science House, Gloucester Street, Sydney, at 7.45 p.m. Mr. D. P. Mellor, President, was in the chair. Thirty-one members and five visitors were present. The minutes of the preceding meeting were read and confirmed. The certificates of four candidates for admission as ordinary members of the Society were read for the second time. The following persons were duly elected ordinary members of the Society : Max Charles Cohen, Harold Theodore Clyde Howard, Dansie Thomas Sawkins, and Thomas Baikie Swanson. Popular Science Lectures.—It was announced that the following lectures had been arranged for 1941: June 19th.—*‘ Some Aspects of Hydatid Disease in Australia,’ by Professor H. Dew, M.B., B.S., F.R.C.S. July 17th.—‘‘ The Modern Aeroplane,” by Professor A. V. Stephens, M.A. August 21st.—‘‘ War and the Fisheries,’’ by H. Thompson, M.A., D.Sc. September i8th.—*‘ Weighing the Stars,” by R. van der R. Woolley, M.Sc., Ph.D. October 16th.—‘* The Cow, the Chemist and Ourselves—The Nutrition of Farm Animals in Plenty and in Drought,”’ by E. G. Hallsworth, B.Sc., Ph.D. (Leeds). It was announced that the Clarke Memorial Lecture would be given by Mr. Sussmilch on May 22nd. The following donations were received: 154 parts of periodicals, and 14 whole volumes. Revision of Rules.—It was announced that a committee had been appointed to continue with the revision of the rules. The following papers were read : “Progressive Rates of Tax in Australia,’ Professor H. 8. Carslaw. “ The Effect of the Synthetic Oestrogens, Stilboestrol and Hexoestrol on the Pouch and Scrotum of Trichosurus vulpecula,” by A. Bolliger, Ph.D., and A. J. Canny, M.B., Ch.M. “Magnetic Studies of Co-ordination Compounds. Part V. Binuclear Derivatives of Diphenyl Methyl Arsine,’’ by D. P. Mellor, M.Sc., and D. P. Craig. Lecturette.—A lecturette on “ Fiji and the Fijians ’’ was given by Dr. Arthur Capell, M.A. June 4, 1941. The five hundred and eighty-seventh General Monthly Meeting was held in the Hall of Science House, Gloucester Street, Sydney, at 7.45 p.m. Mr. R. W. Challinor, a past President, was in the chair. Thirty-two members and five visitors were present. The minutes of the preceding meeting were read and confirmed. The certificate of one candidate for admission as an ordinary member of the Society was read for the first time. The following donations were received : 186 parts of periodicals and 11 whole volumes. The following papers were read : “The Jurassic Fishes of N.S.W.,” by R. T. Wade, M.A., Ph.D. “ An Examination of the Essential Oils Distilled from the Tips and Normal Cut of Hucalyptus polybractea,” by Philip A. Berry, M.Sc., and Thomas B. Swanson, M.Sc. Films.—By courtesy of the Rural Bank of New South Wales, two films were shown : “The Menace of Soil Erosion.”’ “The Red Terror.”’ XXVill ABSTRACT OF PROCEEDINGS. July 2, 1941. ) The five hundred and eighty-eighth General Monthly Meeting was held in the Hall of Science House, Gloucester Street, Sydney, at 7.45 p.m. Mr. D. P. Mellor, President, was in the chair. Twenty-seven members and two visitors were present. The minutes of the preceding meeting were read and confirmed. The certificates of two candidates for admission as ordinary members of the Society were read for the first time. The certificate of one candidate for election as an ordinary member of the Society was read for the second time. The following person was duly elected as an ordinary member of the Society : Irvine Armstrong Watson. The following donations were received: 195 parts of periodicals, and 15 whole volumes. The following paper was presented by Professor T. G. Room, in the absence of the author : ‘Elementary Remarks on Goodness of Fit of Hypotheses and Pearson’s y? Test,’ by D. T. Sawkins, M.A. Lecturette.—A lecturette on the ‘‘ Mineral Resources of the Great Powers in Relation to the International Situation ’” was given by Dr. G. D. Osborne. Exhibit.—An exhibit of ‘‘ Some Recent Developments in Plastics ’? was shown by Mr. F. R. Morrison. August 6, 1941. The five hundred and eighty-ninth General Monthly Meeting, held in the Hall of Science House, Sydney, at 7.45 p.m. Mr. D. P. Mellor, President, was in the chair. Thirty-seven members and three visitors were present. The minutes of the preceding meeting were read and confirmed. The certificates of two candidates for admission as ordinary members of the Society were read for the second time. The following persons were duly elected as ordinary members of the Society: Samuel Raymond Brown and David Parker Craig. The following donations were received: 158 parts of periodicals and 10 whole volumes. The following papers were read : ‘* Permian Blastoids from New South Wales,” by Ida A. Brown, D.Sc. ‘* Bryozoa from the Silurian and Devonian of New South Wales,” by Miss Joan Crockford, B.Sc. Lecturettes.—The following lecturettes were given : “A Scale of Magnitudes,”’ by Dr. F. Lions. ““The Electron Microscope,” by Dr. R. E. B. Makinson. September 3, 1941. The five hundred and ninetieth General Monthly Meeting was held in the Hall of Science House, Gloucester Street, Sydney, at 7.45 p.m. Mr. D. P. Mellor, President, was in the chair. Twenty-nine members were present. The minutes of the preceding meeting were read and confirmed. The certificate of one candidate for admission as an ordinary member of the Society was read for the first time. The following donations were received : 196 parts of periodicals, and 13 whole volumes. The following papers were read : ‘* A Note on Determinations of Physiological Specialization in Flax Rust,” by W. L. Water- house, D.Sc.Agr., D.I.C., F.L.S., and I. A. Watson, Ph.D., B.Sc.Agr. ‘“‘“The Thiamine (Vitamin B,) Content of the Urine of Trichosurus vulpecula,” by A. Bolliger, Ph.D., and C. R. Austin, B.Sc. ‘The Chemistry of Bivalent and Trivalent Rhodium : Hexacovalent Complexes of Rhodous Halides with Diphenylmethylarsine,”’ by F. P. Dwyer, M.Sc., and R. 8. Nyholm, B.Se. Lecturette.—‘‘ Vitamin B,—its Discovery and Importance in Nutrition and Disease,” by Dr. A. Bolliger. October 1, 1941. The five hundred and ninety-first General Monthly Meeting was held in the Hall of Science House, Gloucester Street, Sydney, at 7.45 p.m. Mr. D. P. Mellor, President, was in the chair. Thirty-four members and one visitor were present. The minutes of the preceding meeting were read and confirmed. The certificate of one candidate for admission as an ordinary member of the Society was read for the second time, and the following was duly elected as an ordinary member: George Livingstone Melville. ABSTRACT OF PROCEEDINGS. XX1x The following donations were received : 130 parts of periodicals, and 3 whole volumes. The following papers were read by title : ‘‘ Radial Heat Flow in Circular Cylinders with a General Boundary Condition. Part IT,” by J. C. Jaeger. (Communicated by Professor H. 8. Carslaw.) ‘*The Chemistry of Bivalent and Trivalent Rhodium: A Qualitative Study of the Effect of Reducing Agents on Trivalent Rhodium Salts; and the Properties of Some Rhodous Salts,” by F. P. Dwyer, M.Sc., and R. S. Nyholm, B.Sc. Symposium.—A symposium on Light Metals was held. Aluminium, magnesium and other light metals are assuming ever-increasing importance in modern industry, particularly in aeroplane construction. It was decided, therefore, to devote the October general meeting to a Symposium on the Light Metals. The following were the subjects and speakers : 1. The Sources of the Light Metals, by Professor L. A. Cotton. 2. The Manufacture of and Demand for the Light Metals, by Dr. J. E. Mills. 3. Some Alloys of the Light Metals, by Miss V. Suvoroff, B.Sc. November 5, 1941. The five hundred and ninety-second General Monthly Meeting was held in the Hall of Science House, Gloucester Street, Sydney, at 7.45 p.m. Mr. D. P. Mellor, President, was in the chair. Thirty-three members and two visitors were present. The minutes of the preceding meeting were read and confirmed. The certificates of three candidates for admission as ordinary members of the Society were read for the first time. Guide to Authors.—The President drew attention to the *‘ Guide to Authors ’”’ which has recently been published by the Society. The following donations were received : 185 parts of periodicals and 2 whole volumes. The following papers were read : ‘*The Chemistry of Bivalent and Trivalent Rhodium : Compounds of Rhodic Halides with Tertiary Arsines,” by F. P. Dwyer, M.Sc., and R. 8. Nyholm, B.Sc. ‘“‘ Studies on the Cultivation of the Tung Oil Tree, Aleurites Fordiw. Part Il. Study of a Heavy Yield of Fruit Obtained on the North Coast of N.S.W.,” by A. R. Penfold, F.A.C.1., F.C.S., F. R. Morrison, A.A.C.I., F.C.8., and 8. Smith-White, B.Sc.Agr. ‘‘ The Stereochemistry of Some Metallic Complexes with Special Reference to their Magnetic Properties and the Cotton Effect,” by D. P. Mellor, M.Sc. ‘Triassic Fishes of N.S.W.,” by R. T. Wade, M.A., Ph.D. Exhibits —The following exhibits were shown : The Jelley-Leitz Refractometer, by Dr. G. D. Osborne. A Fluorescent Chromatographic Column, by Mr. A. J. Tow. December 3, 1941. The five hundred and ninety-third General Monthly Meeting of the Society was held in the Hall of Science House, Gloucester Street, Sydney, at 7.45 p.m. Mr. D. P. Mellor, President, was in the chair. Thirty-four members and two visitors were present. The minutes of the preceding meeting were read and confirmed. The certificate of one candidate for admission as an ordinary member of the Society was read for the first time. The certificates of three candidates for admission as ordinary members of the Society were read for the second time. The following persons were duly elected as ordinary members of the Society : Victor le Roy Alldis, Matthew John Morrissey, and Victoria Suvoroff. Walter Burfitt Prize—The President announced that the Walter Burfitt Prize for 1941 had been awarded to Dr. Frederick W. Whitehouse, Lecturer in Geology in the University of Queens- land, and at present a member of the A.I.F., for his work on the Geology of Queensland, in particular the Geology of Western Queensland and researches on the Cambrian trilobites. The following donations were received: 167 parts of periodicals, and 5 whole volumes. - The following paper was read by title: “On the Frequency of the Primes,” by Dr. F. A. Behrend. (Communicated by Professor H. 8. Carslaw.) Lecturette.—‘‘ The Sulphanilamide Drugs,” by Dr. F. Lions. ABSTRACT OF PROCEEDINGS OF THE SECTION OF GEOLOGY Chairman: Dr. W. R. Browne. Secretary: H. O. Fletcher. Eight meetings were held during the year, the average attendance being sixteen members and eight visitors. April 18th.—Exhibits: By Mr. J. A. Dulhunty: (a) Torbanites, consisting mainly of algal remains, from Rylstone, N.S.W.; (b) A specimen of Tasmanite made up of plant material = Cannel Coal; (c) Tasmanite, made up of spores; (d) New Zealand oil shale made up of macerated vascular plant material ; (e) A specimen of original torbanite, from Torbane Hill, Scotland ; (f) ‘‘ Oil-shale ” from Queensland—Cannel Coal of Jurassic age ; (g) “‘ Oil-shale,” vascular plant canneloid sapropel of Jurassic age from New South Wales; (h) “ Algal Cannel.’’ Algal and vascular plant sapropel. Capertee Valley, N.S.W. Mr. Lambeth recorded the discovery of a new horizon of torbanite 20-25 miles west of Mittagong. The outcrop is 1 mile 1 chain in length, and 14 inches thick. There are 30-40% volatile hydro- carbons. By Mr. T. Hodge-Smith : The Moorleah Aerolite, the first stony meteorite recorded from Tasmania. By Dr. Ida Brown: (a) Calyx of a crinoid, Tribrachiocrinus, with some of the arms attached to the dorsal cup, from the Upper Marine beds at Black Head, Gerrringong ; (6) A blastoid, Indoblastus ? sp. nov., from the Fenestella beds of the Permian ; (c) A brittle- star, Sturtzura? brisingoides (Gregory), from Silurian slates at Euchareena, N.S.W. By Miss Quodling : (a) A specimen of selenite showing dehydration ellipses, produced by placing a hot point on the surface of the crystal ; (b) A lead box for use in the cobalt nitrate staining process for distinguishing felspars ; (c) Microphotographs and slides showing staining of the felspars by the cobalt nitrate process. By Mr. Waterhouse: (a) A well crystallised specimen of manganhedenbergite, from the southern end of No. 10 level, Zinc Corporation Mine, Broken Hill; (6b) Arborescent native copper found in a cavity in gossan, Mt. Isa, Queensland. By Dr. W. R. Browne: Rock fragments of Devonian quartzite found in surface soil at Hay, N.S.W. Locally termed “cherts.”” By Mr. Fletcher: (a) A new gastropod from the Upper Marine beds at Rylstone ; (b) Three specimens of Martiniopsis subpentagonalis and M. inflata from the Lower Productus limestones of the Salt Range. By Dr. W. R. Browne : A series of slides illustrating features of physiographical interest in the New South Wales highlands. May 16th.—Address by Major C. T. Madigan, “‘ Sand Dunes and Ridges.” June 20th.—Address by Mr. E. C. Andrews, *‘ The Canyon of the Colorado.” July 18th.—Address by Mr. E. J. Kenny, “Some Ore-Deposits in N.S.W.” August 15th.—Address by Dr. W. G. Woolnough, “‘ The Tectonic Relations between Continental Australia and Alpine Foldings in the East Indies.” September 19th.—Exhibits: By Professor Cotton: (a) Recent conglomerate cemented round an old bayonet : (b) Native copper with gold in a quartz reef ; (c) Suite of fossils, Stutchburia, Astartila and Bellerophon from the Carboniferous, 70 feet below the surface, east of Breeza, N.S.W. By Mr. Whitworth: (a) Dumortierite, Pershing County, Nevada, U.S.A.; (6) Andalusite with crystallised pyrophyllite ; (c) Rich bauxite (60% Al,O,) from Trundle, N.S.W.; (d) Garnet, from schist, 30 miles west of Broken Hill, N.S.W.; (e) Tertiary leaf, Trunkey, N.S.W.; (f) Set of specimens of Archzeocyathine from Beltana, South Australia. By Dr. G. D. Osborne: The Dollar integrating micrometer for use in Rosiwal analysis. — By Miss Crockford : Short discourse on fossil Bryozoa. By Dr. Ida Brown: Martiniopsis subradiata partly silicified, showing spiral supports replaced by chalcedony, revealed by careful etching and drilling. By Mr. Fletcher: Tertiary fossil shells from Miocene limestone, Tobruk, Libya. By Professor W. R. Browne: (a) Slides showing unconformity between the Permian and Devonian, Glen Davis-Capertee Road; (b) Short account of coal seams in both the Upper Marine and Upper Coal Measures at Kanangra Walls, and of the fluvio- glacial conglomerates. October 17th.—Address by Mr. C. St. J. Mulholland, ‘‘ The Underground Water of the Sydney District.” December 5th.—Address by Dr. F. W. Whitehouse, “‘ Geological Aspects of the Artesian Basin, Queensland.”’ ABSTRACT OF PROCEEDINGS OF THE SECTION OF INDUSTRY Chairman: A. D. Ollé, F.C.S., A.A.C.I. Visits were made during the year to the following : 1941. May 13th.—Columbia Pencil and Crayon Co., McEvoy Street, Waterloo. June 10th.—Dental Hospital, Chalmers Street, Sydney. September 9th.—Stedman-Henderson’s Sweets Ltd., Waterloo. OBITUARY NOTICES. Henry HERBERT BAKER, who joined the Royal Society in 1919, was born in 1868. Mr. Baker was chairman of directors of the firm of W. Watson and Son, which he had established in Australia more than 50 years ago. He was well known to the members of the medical and dental professions, and was closely connected with the development of X-rays in Australia and with all aspects of optical science. He was keenly interested in the Astronomical Society and was a member of it and of the Millions Club. GEORGE HENRY BLAKEMORE, who died at the age of 73, was known in mining circles through- out Australia. At his death he was chairman of directors of Takuapa Valley Tin Dredging and Tartut Basin Tin Dredging Company. He was born at Copperfield, in North Queensland, his father having been also a prominent mining man. Mr. Blakemore began his career at Broken Hill as an assayer ; later he was manager of the Great Cobar Copper Mine, and then took charge of the old refinery at Lithgow. Some years later he began business as a private mining engineer. He leaves a widow and three sons. FRANK LEVERRIER, who became a member of the Royal Society in 1909, was born in Sydney in 1863, spent some of his early years in France, but returned to New South Wales, where he was educated at Fort Street Public School and the Sydney Grammar School. Proceeding to the University of Sydney, he graduated in Arts, in Law and in Science, and he chose to follow the legal profession. He was made a K.C. in 1911. In 1907 he was elected a Fellow of the Senate of the University ; was Challis Lecturer in Law; from 1914 to 1917 and again in 1921 Mr. Leverrier was Vice-Chancellor of the University of Sydney. EDMUND CooPER MANFRED, who had played a prominent part in the civic and business life of Goulburn for more than sixty years, died at Goulburn, aged 84 years. He was the father of M. E. Manfred, M.L.C., Assistant Minister. The only child of Mr. Edward Manfred, architect and surveyor, he was born at Kensington, London, on June 5, 1856. He qualified as an architect and began practice at Goulburn. He designed many of the town’s best known buildings, and served on almost every public body in Goulburn. He was an early member of the Royal Society of N.S.W. and the Royal Historical Society of N.S.W. and was a Mason. He is survived by six sons. JAMES NANGLE, who had been Government Astronomer for New South Wales for fifteen years, died on February 22, 1941, in his seventy-third year. He exerted an important influence in this State in the fields of architecture, education, and astronomy. He began practice as an architect late last century, several large buildings in Sydney being designed by him, and he specialised in school and church buildings. He was President of the Royal Australian Institute of Architects in the year 1936-37, and was elected a Fellow of the Royal Institute of British Architects in 1937. Several papers on the properties of Australian timbers and building stones were published by him in the Journal of the Royal Society of New South Wales, which he joined m 1893, and of which he was President in the year 1920-21. XXXil ABSTRACT OF PROCEEDINGS. While still in practice he undertook some teaching in architecture at Sydney Technical College, and this led to his important work in technical education. In 1913 he was appointed _ Superintendent of Technical Education. He reorganised the technical education courses, bringing the technical colleges into closer touch with industries and trades by setting up a series of advisory committees, on which the professions and trades as well as educational authorities were represented. Similar internal committees provided for coordination of effort by the adminis- trative and teaching staffs. He always stressed that a good system of technical education must be coordinated with the industries it was to serve. During his administration the attendance at technical colleges in New South Wales rose from four thousand to fourteen thousand. While he was Superintendent of Technical Education in New South Wales, he paid extended visits to Western Australia and Tasmania to advise the governments of those States on the organisation of their technical education systems. He retired in 1934. One important task undertaken by James Nangle was the supervision of the vocational training system for returned soldiers carried out by the Commonwealth Repatriation Department after the 1914-18 war. His services for this purpose were given by the Government of New South Wales to the Commonwealth Government, and altogether more than 20,000 returned soldiers who had been injured or whose training had been interrupted by active service were trained. He had to a marked degree the gift of the good administrator for obtaining cooperation and in making estimates of the absorptive capacities of the various trades and industries and in carrying out the training of the men he was very successful in getting support from the trade unions, technical colleges and universities. He was awarded the O.B.E. in 1920. His interest in astronomy began early. He joined the New South Wales Branch of the British Astronomical Association in 1905, and was its president on many occasions, his ability as a speaker being an asset to the meetings. In 1908 he was elected a Fellow of the Royal Astronomical Society. He maintained an observatory at his residence in Marrickville until he became Government Astronomer in 1926, when the Observatory had a difficult period through which his administration steered it. James Nangle had at all times been most approachable and helpful to newcomers to the science of astronomy, and many have had their interest awakened by his numerous popular lectures and writings. His friendliness and enthusiasm will be remembered by all who knew him. He is survived by his widow, daughter, and three sons. JOHN Patrick O’NEILL joined the Society in 1932. Mr. O’Neill had for some time been chief timber expert for the Department of Railways of New South Wales. THomas Linpsay WILLAN, who joined the Society in 1921, was born in Sydney in 1895. He was educated at the Sydney High School, whence he entered the University of Sydney. He gained first-class honours and the University Medal for Geology at the B.Sc. examination. He entered the Geological Survey of N.S.W., and in 1924 left it to go to the Federated Malay States, where he was engaged until 1933 in survey work. Later he went to Burma, where he remained until his death from malaria towards the end of 1940. INDEX A Page. Page Craig, D. P.—See Mellor, D. P... oi eT, Abstract of Proceedings .. bee oe eee! Crockford, Joan— Section of Geology .. as ab 6..< Bryozoa from the Silurian and Section of Industry .. 20:0.) Permian of New South Wales .. 104 Alteration of Rules Sox Annual Dinner... OY 4 Annual Report and Balance Sheat pee EGET Austin, C. R.—See Bolliger, A. -. 118 Determinations of eas Sch Authors, Notice to hye on mae Vv isation in Flax Rust pee Salis: Awards of— Devonian and Silurian of New South Clarke Memorial Medal XVili, xxvi _ Wales, Bryozoa from : .. 104 Liversidge Research Lectureship .. xx Diphenyl Methyl Arsine, Buinuclear Society’s Medal and oe Prize .. xix _ Copper Derivatives of -: -. 27 Walter Burfitt Prize _. XX Diphenylmethylarsine, Hexacovalent Complexes of Rhodous Halides with 127 Dwyer, F. P., and R. 8. Nyholm— B The Chemistry of Bivalent and Trivalent Rhodium. Part I. A Behrend, F. A.— Qualitative Study of the Effect of On the Frequency of the Primes .. 169 Reducing Agents on Trivalent Bequest, Form of = Rhodium Salts ; and the Properties q E ss of some Rhodous Salts : 122 Berry, P. A., and T. B. cea An Examination of the Essential Oils Distilled from the Tips and Normal Cut of Hucalyptus polybractea 65 Binuclear Copper Derivatives of Di- phenyl Methyl Arsine st 27 Blastoids, Permian, from New South Wales ne OO Bolliger, A., and ban Canny— The Effect of the Synthetic Cistrogens, Stilbcestrol and Hexcestrol on the Pouch and Scrotum of Trichosurus vulpecula : ee Bolliger, A., and C. BR. Austin— The Thiamin (Vitamin B,) Content of the Urine of Trichosurus vulpecula 118 Brown, Ida A.— Permian Blastoids from New South Wales . 96 Bryozoa from the Silurian. and Devonian of New South Wales Mt .. 104 Burfitt Prize Oe oad. Cc Canny, A. J.—See Bolliger, A.. iy ak Carslaw, H. S.— Progressive Rates of Tax in Australia 31 Clarke Memorial Fund . XVili Clarke Memorial Lecture ‘ a XVI, XXV1, SXVI; 47 . XVill, Xxvi Clarke Memorial Medal Climate of Australia in Past gi Rar: 3) Contents .. ; pep yeild Council, Report ofthe .. _ ei. 44 Q The Chemistry of Bivalent and Tri- valent Rhodium. Part II. Hexa- covalent Complexes of Rhodous Halides with Diphenylmethylarsine 127 The Chemistry of Bivalent and Tri- valent Rhodium. Part III. Com- pounds of Rhodic Halides with Tertiary Arsines ei .. 140 E Elkin, A. P.— Presidential Address, ‘* Science, Society and Everyman”... : as 4 Essential Oils of Hucalyptus BOL NaCe Ie 65 Eucalyptus polybractea, Essential Oils of 65 Exhibits— A Fluorescent Column The Jelley-Leitz Refractometer Chromatographic XX1X XXI1X Some Recent Developments of Plastics XXVIli F Films Shown XXVil Finance ‘ a am $e XXVI1 Fishes, The Jurassic, of New South Wales ‘ be > eevee a | Fishes, The Triassic, of New South Wales : 144 Flax Rust, Determinations of Physi ological Specialisation in s td XXXiV G Page. Goodness of Fit of pe ta and on Pearson’s y Test a neg auik 2103 Government Grant ae sees XXvl Guide to Authors a ait XX1x H Hexacovalent Complexes of Rhodous Halides with Diphenylmethylarsine 127 Hexeestrol, Effects of on Pouch and Scrotum of T'richosurus vulpecula.. 21 Jaeger, J. C.— Radial Heat Flow in Circular Cylinders with a General Boundary Condition 130 Journal and Piece eaneer Alteration of Format : XXvli Jurassic Fishes of Nexe South Ww Hina SRW ies L Lecturettes— Fiji and the Fijians o XXVii Mineral Resources of the Great Powers in Relation to the Inter- national Situation .. oe XXVill A Seale of Magnitudes aye XXVIli The Electron Microscope ae XXVIli Vitamin 3B,, its Discovery and Importance in Nutrition and Disease XXVIill The Sulphanilamide Drugs .. D-@-4D:¢ Etbrary, 3. a i oe: XXV1 List of Members oe Aenieb.2 Liversidge Research iene xX, XXXVI M Magnetic Studies of Coordination Com- pounds. Part V. Binuclear Copper Derivatives of ea aa Arsine. 27 Mellor, D. Pe aaa D. lee Greig Magnetic Genres of Coordination Compounds. Part V. Binuclear Copper Derivatives of Diphenyl Methyl Arsine ai ce ts ioe Mellor, D. P.— The Stereochemistry of some Metallic Complexes, with Special Reference to their Magnetic pee ee and the Cotton Effect .. 157 Members on Active Service, Reusion of Subscriptions by. . Ne XXVI1 Members, List of i 1x Morrison, F. R.—See Penola’ iN ea 148 INDEX. N Page. ~ Nyholm, R. S.—See Dwyer, F. P. 122, 127, 140 O Obituaries .. le ... XVil, oe Officers for 1941- 1942 an th «oD P Paper Rationing . sie “i Xxvi Pearson’s x Test . « 88 Penfold, A. R., F. ea Nora and Ss. Smith- White— Studies on the Cultivation of the Tung Oil Tree, Aleuwrites Fordiv. Part II. Study of a Heavy Yield of Fruit Obtained on the North Coast of New South Wales.. o» 288 Permian Blastoids from New South Wales an ar a .. 96 Physiological Specialisation in Flax Rust .. ° ihe :. ee Popular Science Lectures - EEXV, eu Presidential Address by A. P. Elkin, ‘* Science, Society, and Everyman” 4 Primes, On the Frequency of the » «ee Progressive Rates of Tax in Australia.. 31 Publications zt ihe - «|. R Radial Heat Flow in Circular Cylinders with a General Boundary Condition 130 Reducing Agents on Trivalent Rhodium Salts, Effects of ts . 122 Report of the Council, 1940- 1941 > Rhodium, The Chemistry of Bivalent and Trivalent 122, 127, 140 Rhodous Halides, Hexacovalent Com- plexes of, with aan. arsine { 127 Rhodous Salts, Propadiee of Sots 2 ie S Sawkins, D. T.— Remarks on Goodness of Fit of Hypotheses and on Pearson’sy Test 85 Science, Society, and Everyman— Presidential ee me ASR Elkin .. ais : : a Science House... xxvi Silurian and Devonian of New South Wales, Bryozoa from fs .. 104 Smith-White, S.—See Penfold, A. R... 148 Society’s Medal and Money Prize .. Stilbcestrol, Effect of, on Pouch and Scrotum of Trichosurus vulpecula.. 21 Sussmilch, C. A.— The Climate of Australia in Past Ages (Clarke Memorial Lecture) .. 47 INDEX. Page. Swanson, T. B.—See Berry, P. A. eGo Symposia— On Potassium XXV On Light Metals : XXIx Synthetic Gistrogens, Effect of, on the Pouch and Scrotum of Trichosurus vulpecula ae pee oe Stes aon 4% Tax in Australia, Progressive Rates of.. 31 Thiamin (Vitamin B,) Content of the Urine of Trichosurus vulpecula .. 118 Triassic Fishes of New South Wales.. 144 Trichosurus vulpecula, Effect of the Synthetic Cestrogens Stilbcestrol and Hexcestrol on the Pouch and Scrotum of .. ae sh, Slee 4 | XXX) Page. Trichosurus vulpecula, The Thiamin (Vitamin B,) Content of the Urine of ity uy a ee Ae tal ie: W Wade, R. T.— The Jurassic Fishes of New South Wales : 71 The Triassic TRESS. of New South Wales ; pelad Walter Burfitt eee eed wea to De XX1X F. W. NVehouse Waterhouse, W. L., and I. A. Watsone= A Note on Determinations of Physi- ological Specialisation in Flax Rust 115 Watson, I. A.—See Waterhouse, W. L. 115 AUSTRALASIAN MEDICAL PUBLISHING COMPANY LIMITED on o ae x ioe a » adit) LLNS ~ * Auten Sy rea on 7 re ¥ “ i : ~ ~s > rt ‘ 5 x Ee ae * ~ 4 - wy i 4 ; 5 Ge I, 3 . . = AUSTRALASIAN MEDICAL PUBLISHING 3 MER te aa ra nD me = a s oe ' : é iy me ais a Wy Kid x shee pig a2 ay - . } $i ig Mba ay Tk, eas Ra el, sep as Co JOURNAL AND PROCEEDINGS OF THE ROYAL SOCIETY OF NEW SOUTH WALES FOR 1942 (INCORPORATED 1881) VOLUME LXXVI Parts I-IV EDITED BY THE HONORARY SECRETARIES THE AUTHORS OF PAPERS ARE ALONE RESPONSIBLE FOR THE STATEMENTS MADE AND THE OPINIONS EXPRESSED THEREIN SYDNEY PUBLISHED BY THE SOCIETY, SCIENCE HOUSE GLOUCESTER AND ESSEX STREETS Issued as a complete volume, December 17, 1943 ial CONTENTS VOLUME LXXxXxVI Part I * Page, Art. I.—Presidential Address. By D. P. Mellor, M.Sc. (Issued September 21, 1942) .. 1 Art. IJ.—Methemoglobin Formation. By John Williamson Legge, B.Sc. (Issued September 21, 1942) Su ae aA ote ps bs ee ae of 47 Art. III.—A Note on the Essential Oil of Hucalyptus conglobata var. anceps. By P. A. Berry, M.Sc., and T. B. Swanson, M.Sc. (Issued August 12, 1942) .. aa ee 53 Art. [V.—Studies in Metamorphism and Assimilation in the Wellington District, N.S.W. II. The Dynamic and Contact Metamorphism of a Group of Ultrabasic Rocks. By Elizabeth M. Basnett, M.Sc. (Issued September 21, 1942) .. ot Se, 3 05 Art. V.—The Tertiary Land Surface in Southern New actin ey A. H. een: M.Sc. (Issued September 21, 1942) Be 82 Art. VI.—Spermatorrhea in Marsupials, with Special Reference to the Action of Sex Hormones on Spermatogenesis of Trichosurus vulpecula. By Adolph Bolliger, Ph.D. (Issued September 21, 1942) ee i a4 chs oe ns We he 1 80 Art. VII.—The Occurrence of Two Physiological Forms of Leptospermum citratum (Challinor, Cheel and Penfold) as Determined by Chemical Analysis of the Essential Oils. By A. R. Penfold, F.A.C.I., F.C.S., F. R. Morrison, A.A.C.I., F.C.S., and -§. Smith-White, B.Sc.Agr. (Issued September 21, 1942) see Suz 93 Part II + Art. VIII.—Clarke Memorial Lecture. The Heroic Period of Geological Work in Australia. By E. C. Andrews, B.A., F.G.S. (Issued November 6, 1942) im. 96 Art. IX.—The Chemistry of Bivalent and Trivalent Rhodium. Part IV. Polynuclear Complexes of Rhodium and Tin with Tertiary Arsines. By F. P. Dwyer, M.Sc., and R. 8S. Nyholm, B.Sc. (Issued November 6, 1942) oe af ae pee PA! Part III f Art. X.—The Chemistry of Bivalent and Trivalent Rhodium. Part V. Coordination Complexes of Rhodous Halides with Dialkyl Arsines. By F. P. Dwyer, M.Sc., and R. 8. Nyholm, M.Sc. (Issued December 21, 1942) .. we o aie a 1 Art. XI.—The Effect of Gonadotropin Obtained from Human Pregnancy Urine on the Pouch of Trichosurus vulpecula. By Adolph Bolliger, Ph.D. (Issued December 21, 1942) .. Re ne he Be vA ae Arr. XXXI.—The Imperfect Crystal. By J. 8. Sues Ph.D. (Second Liversidge Lecture.) (Issued September 1, 1943) 2 oa a ~. 48 TITLE Pacr, Contents, Noticks, PUBLICATIONS i OFFICERS ror 1942-43 vil List oF MremBers, AWARDS OF MEDALS, ETC. 1x ABSTRACT OF PROCEEDINGS xxl PROCEEDINGS OF THE SECTION OF GEOLOGY he mite te chs an XXXIV INDEX TO VOLUME LXXVI XXXV * Published December 17, 1943. a NOTICES. Vv NOTICE. Tue Royat Soctety of New South Wales originated in 1821 as the “ Philosophical Society of Australasia’; after an interval of inactivity, it was resuscitated in 1850, under the name of the ‘‘ Australian Philosophical Society ’’, by which title it was known until 1856, when the name was changed to the ‘* Philosophical Society of New South Wales ”’; in 1866, by the sanction of Her Most Gracious Majesty Queen Victoria, it assumed its present title, and was incorporated by Act of the Parliament of New South Wales in 1881. TO AUTHORS. Authors should submit their papers in typescript and in a condition ready for printing. All physico-chemical symbols and mathematical formule should be so clearly written that the compositor should find no difficulty in reading the manuscript. Sectional headings and tabular matter should not be underlined. Pen-illustrations accompanying papers should be made with black Indian ink upon smooth white Bristol board. Lettering and numbers should be such that, when the illustration or graph is reduced to 5 inches in width, the lettering will be quite legible. On graphs and text figures any lettering may be lightly inserted in pencil. Photo- micrographs should be rectangular rather than circular, to obviate too great a reduction. The size of a full page plate in the Journal is 5 x 7? inches, and the general reduction of illustrations to this limit should be considered by authors. When drawings, etc., are submitted in a state unsuitable for reproduction, the cost of the preparation of such drawings for the process-block maker must be borne by the author. The cost of colouring plates or maps must also be borne by the author. Further particulars regarding the preparation of manuscripts are contained in the “ Guide to Authors,’”’ which is obtainable on application to the Honorary Secretaries of the Society. FORM OF BEQUEST. I be yur ath the sum of £ to the Royat Society or NEw SoutH WALEs, Incorporated by Act of the Parliament of New South Wales in 1881, and I declare that the receipt of the Treasurer for the time being of the said Corporation shall be an effectual discharge for the said Bequest, which I direct to be paid within calendar months after my decease, without any reduction whatsoever, whether on account of Legacy Duty thereon or otherwise, out of such part of my estate as may be lawfully applied for that purpose. [Those persons who feel disposed to benefit the Royal Society of New South Wales by Legacies, are recommended to instruct their Solicitors to adopt the above Form of Bequest. | vi PUBLICATIONS. The following publications of the Society, if in print, can be obtained at the Society’s Rooms, Science House, Gloucester and Essex Streets, Sydney. Transactions of the Philosophical Society, N.S.W., 1862-5, pp. 374, out of print. Vols. Vol. I-xI Transactions of the Royal Society, N.S.W., 1867-1877 XI Journal and Proceedings XIII XIV XV XVI XVII XVIII XIX xx XXI XXII XXIII XXIV XXV XXVI XXVII XXVII XXIX XXX XXXI XXXII XXXII XXXIV XXXV XXXVI XXXVII XXXVITII XXXIX XI XLI XLII XLII XLIV XLV XLVI XLVII XLVIII XLIX LXI LXIi LXII LXIV LXV LXVI LXVII LXVIII LXIX LXX LXXI LXXII LXXITI LXXIV LXXV LXXVI 99 39 99 1878, 1879, 1880, 1881, 1882, 1883, 1884, 1885, 1886, 1887, 1888, 1889, 1890, 1891, 1892, 1893, 1894, 1895, 1896, 1897, 1898, 1899, 1900, 1901, 1902, 1903, 1904, 1905, 1906, 1907, 1908, 1909, 1910, 1911, 1912, 1913, 1914, 1915, 1916, 1917, 1918, 1919, 1920, 1921, 1922, 1923, 1924, 1925, 1926, 1927, 1928, 1929, 1930, 1931, 1932, 1933, 1934, 1935, 1936, 1937, 1938, 1939, 1940, 1941, 1942, pp. 324, price 10s. 6d. 255, 391, 440, 327, 324, 224, 240, 396, 296, 390, 534, 290, 348, 426, 530, 368, 600, 568, 626, 476, 400, 484, 581, 531, 663, 604, 274, 368, 377, 593, 466, 719, 611, 275, 318, 584, 587, 362, 786, 624, 414, 312, 418, 372, 421, 366, 468, 470, 492, 458, 263, 434, 366, 601, 511, 328, 288, 528, 708, 396, 344, 658, 224, 432, 99 99 99 price £1 1s. — ip Royal Society of New South Wales OFFICERS FOR 1942-1943 Patrons : His EXcELLENCY THE GOVERNOR-GENERAL OF THE COMMONWEALTH OF AUSTRALIA, THE LORD GOWRIE, v.c., P.c., G.c.M.G., C.B., D.S.O. His ExXcELLENCY THE GOVERNOR OF NEW SoutH WALES, THE LORD WAKEHURST, k.c.M.ca. President : Pror. H. PRIESTLEY, M.p., ch.m., B.Sc. Vice-Presidents : D. P. MELLOR, M.sc.* | A. BOLLIGER, Ph.p., A.a4.c.1. H. 8S. HALCRO WARDLAW, D.sc., F.A.C.1. IDA A. BROWN, D.sc.t E. J. KENNY, M.Aust.1.M.M. Honorary Secretaries : | C. ANDERSON, m.a., p.se.* D. P. MELLOR, m.sc.t Pror. A. P. ELKIN, M.a., Ph.p. Honorary Treasurer : A. CLUNIES ROSS, B.sc., F.c.a. (Aust.). Members of Council : G. H. BRIGGS, B.sc., Ph.D., F.Inst.P. J. E. MILLS, M.sc., Ph.p. IDA. A. BROWN, pD.sc.|| F. R. MORRISON, 4.4.c.1., F.c.s. J. A. DULHUNTY, B.sc. G. D. OSBORNE, D.sc., Ph.D. F, P. J. DWYER, M.sc. H. H. THORNE, M.a<., B.Sc., F.R.A.S. F. LIONS, B.sc., Ph.D., A.I.C. A. B. WALKOM, D.sc.t W. H. MAZBE, msc. * Resigned July 24, 1942. j Elected July 24, 1942. t Elected August 26, 1942. || Resigned August 26, 1942. “ateal al # LIST OF THE MEMBERS OF THE Royal Society of New South Wales as at March 1, 1943 P Members who have contributed papers which have been published in the Society’s Journal. The numerals indicate the number of such contributions. { Life Members. Elected. 1938 | P 2 |ftAlbert, Adrien, ph.p. Lond., B.sc. Syd., a.t.c. Gt. B., Commonwealth Research Fellow in Organic ‘Chemistry, University of Sydney ; p.r. “ Green- knowe,”’ Greenknowe-avenue, Potts Point. 1935 tAlbert, Michel Francois, ‘‘ Boomerang,’’ Billyard-avenue, Elizabeth Bay. 1898 tAlexander, Frank Lee, Surveyor, 67 Ocean-street, Woollahra. 1941 tAlldis, Victor le Roy, u.s., Registered Surveyor, Young, N.S.W. 1905 Pe. 3 Anderson, Charles, M.A., D.Sc. Hdin., C.M.z.S., 17 Towns-road, Vaucluse. (President, 1924.) 1909 Ee Andrews, Ernest C., B.A., Hon. Mem. Washington Academy of Sciences and of , Royal Society of New Zealand, No. 4, “ Kuring-gai,”’ 241 Old South Head- road, Bondi. (President, 1921.) 1930 | Aston, Ronald Leslie, B.sc., B.E. Syd., M.Sc., Ph.D. Cantab., A.M.1.E.Aust., Lecturer in Civil Engineering and Surveying in the University of Sydney ; p.-r. 24 Redmyre-road, Strathfield. 1919 P 1 Aurousseau, Marcel, B.sc., 16 Woodland-street, Balgowlah. 1935 ‘| Back, Catherine Dorothy Jean, M.sc., The Women’s College, Newtown. 1924 P| Bailey, Victor Albert, M.A., D.Phil., F.Inst.p., Professor of Experimental Physics in the University of Sydney. 1934 ol Baker, Stanley Charles, M.sc., F.Inst.P., Teacher of Physics, Newcastle Technical College, Islington ; p.r. 8 Hewison-street, Tighe’s Hill, N.S.W. 1937 Baldick, Kenric James, B.Sc., 19 Beaconsfield-parade, Lindfield. 1919 Bardsley, John Ralph, 76 Wright’s-road, Drummoyne. 1939 Prog Basnett, Elizabeth Marie, mM.sc., 36 Cambridge-street, Epping. 1933 Bedwell, Arthur Johnson, Eucalyptus Oil Merchant, “ Kama,” 10 Darling Point-road, Edgecliff. 1926 Bentivoglo, Sydney Ernest, B.Sc.Agr., 52 Crows Nest-road, Wollstonecraft. 1940 Betty, Robert Cecil, 67 Imperial-avenue, Bondi. 1937 P 6 Birch, Arthur John, M.sc., 15 Hilltop-road, Headington, Oxford, England. 1923 Birks, George Frederick, Wholesale Druggist, c/o Potter & Birks Ltd., 15 Grosvenor-street, Sydney; p.r. 42 Powell-street, Killara. 1916 Birrell, Septimus, 74 Edinburgh-road, Marrickville. 1920 Bishop, Eldred George, Manufacturing and General Engineer, 37-45 Myrtle- street, Chippendale ; p.r. 17 Thompson-street, Clifton Gardens. 1938 Black, Una Annie Frazer (Mrs.), B.sc., 16 Melrose, Billyard-avenue, Elizabeth Bay. 1939 Piti2 Blake, George Gascoigne, M.1.E.E., F.Inst.P., ‘‘ Holmleigh,’’ Cecil-avenue, ‘Pennant Hills. 1933- P21 ‘Bolliger, Adolph, Ph.p., Director of Research, Gordon Craig Urological Research Laboratory, Department of Surgery, University of Sydney. 1920 PQ Booth, Edgar Harold, M.c., D.sSc., F.Inst.p.. New England University College, Armidale. (President, 1935.) 1939 12 a Bosworth, Richard Charles Leslie, m.Sc., pD.sc. Adel., Ph.D. Camb., F.A.C.1., F.Inst.P., c/o C.S.R. Co., Pyrmont; p.r. 41 Spencer-road, Killara. 1922 Bradfield, John Job Crew, c.M.G., D.Sc. Eng., M.E., M.Inst.C.E., M.Inst.E.Aust., Barrack House, 16 Barrack-street, Sydney ; p.r. 23 Park-avenue, Gordon. 1938 | Breckenridge, Marion, B.Sc., Department of Geology, University of Sydney ; p.r..19 Handley-avenue, Thornleigh. *2 xX Elected. 2 1940 Brigden, Alan Charles, B.se., 22 Kelso-street, Enfield. Bs THE) ES Magellan! | Briggs, George Henry, D.Sc., Ph.D., F.Inst.P., Officer-in-Charge, Section of Physics, National Standards Laboratory of Australia, University Grounds, Sydney; p.r. 13 Findlay-avenue, Roseville. 1942 © Brown, Desmond J., B.Sc., 9 Agnes-street, Strathfield. 1935 P 3 | Brown, Ida Alison, D.se., Lecturer in Paleontology, University of Sydney. 1941 Brown, Samuel Raymond, 4.c.a. Aust., 87 Ashley-street, Chatswood. 1913 Pet Browne, William Rowan, D.sc., Reader in Geology in the University of Sydney. (President, 1932.) 1940 Buckley, Daphne M. (Mrs.), B.sc., 4 Sharland-avenue, Chatswood. 1940 Buckley, Lindsay Arthur, B.Sc., 4 Sharland-avenue, Chatswood. 1898 tBurfitt, W. Fitzmaurice, B.A., M.B., Ch.M., B.Sc. Syd., F.R.A.C.S., ‘‘ Radstoke,”’ Elizabeth Bay. 1926 Burkitt, Arthur Neville St. George, M.B., B.sc., Professor of Anatomy in the University of Sydney. 1919 P 23 Burrows, George Joseph, B.sc. 1940 Pot Cane, Reginald Frank, m.sc., A.A.C.L., National Oil Pty. Ltd., Glen Davis, N.S.W 1940 Callanan, Victor John, B.sc., 17 Wheatleigh-street, Naremburn. 1938 {Carey, Samuel Warren, D.sSc., Practising Petroleum Geologist, c/o Australasian Petroleum Co., Melbourne. 1903 PS Carslaw, Horatio Scott, Sc.D., LL.D., F.R.S.E., Emeritus Professor of Mathe- matics, University of Sydney, Fellow of Emmanuel College, Cambridge ; Burradoo, N.S.W. bo 1913 P 4 Challinor, Richard Westman, F.I.C., A.A.C.I., A.S.T.C., F.C.S. ; p.r: 54 Drumalbyn- road, Bellevue Hill. (President, 1933.) 1933 Chalmers, Robert Oliver, a.s.T.c., Assistant (Professional) in Mineralogy, Australian Museum, College-street, Sydney. 1940 Chambers, Maxwell Clark, B.sc., c/o J. and E. Atkinson Pty. Ltd., 469-75 Kent-street, Sydney. 1913 P 20 Cheel, Edwin, 40 Queen-street, Ashfield. (President, 1931.) 1935 iPaae Churchward, John Gordon, B.Sc.Agr., Ph.D., 1 Hunter-street, Woolwich. 1935 Clark, Sir Reginald Marcus, K.B.E., Central Square, Sydney. 1940 Clarke, Ronald Stuart, B.A., 28 Beecroft-road, Beecroft. 1938 Clune, Francis Patrick, Author and Accountant, 15 Prince’s-avenue, Vaucluse. 1941 Cohen, Max Charles, B.sc., No. 3, Explosives Factory, St Mary’s, N.S.W. 1940 Cohen, Samuel Bernard, M.sc., A.A.C.1., 24 Euroka-street, Northbridge. 1940 Py ol Colditz, Margaret Joyce, B.sc., 9 Beach-street, Kogarah. 1940 Cole, Edward Ritchie, B.sc., 14 Barwon-road, Lane Cove. 1940 iP SE Cole, Joyce Marie, B.sc., 14 Barwon-road, Lane Cove. 1940 Collett, Gordon, B.sc., 49 Liverpool-road, Summer Hill. 1920 Cooke, Frederick, c/o Meggitt’s Limited, Asbestos House, York and Barrack- streets, Sydney. 1913 Pd Coombs, F. A., F.c.s., Instructor of Leather Dressing and Tanning, Sydney Technical College; p.r. Bannerman-crescent, Rosebery. 1933 Corbett, Robert Lorimer, Managing Director of Robert Corbett & Co. Ltd., Manufacturing Chemists, Head Office, 379 Kent-street, Sydney. 1940 Cortis-Jones, Beverly, m.sc., 62 William-street, Roseville. 1919 Cotton, Frank Stanley, D.sc., Research Professor in Physiology in the University . of Sydney. 1909 Bry Cotton, Leo Arthur, M.a., D.sc., Professor of Geology in the University of Sydney. (President, 1929.) 1940 Cox, Morris Edward. 1941 Jet I Craig, David Parker, Research Scholar, 62 Springdale-road, Killara. 1921 P 1. |}Cresswick, John Arthur, A.A.C.1., F.c.s., Production Superintendent and Chief | Chemist, c/o The Metropolitan Meat Industry Commissioner, State Abattoir and Meat Works, Homebush Bay; p.r. 101 Villiers-street, Rockdale. 1940 Pye Crockford, Joan Marian, B.Sc., 219 Victoria-road, Gladesville. 1935 Pid Culey, Alma Gertrude, M.sc., 37 Neirbo-avenue, Hurstville. 1940 Dadour, Anthony, B.Sc., 25 Elizabeth-street, Waterloo. 1890 Dare, Henry Harvey, M.E., M.Inst.C.E., M.1.E.Aust., 14 Victoria-street, Roseville. 1919 Pii2 de Beuzeville, Wilfred Alex. Watt, 3.p., ‘‘ Mélamere,’”’ Welham-street, Beecroft. 1906 {Dixson, William, ‘‘ Merridong,’’ Gordon-road, Killara. 1913. A Beep 2 Doherty, William M., F.1.c., F.A.c.1., 30 Hampden-road, Pennant Hills. Elected. 1928 1937 aoa 1924 1934 P19 1923 P 21 1924 1934 pn? 1940 1937 1916 P.2 1908 1935 1921 1939 1909 Bes 1923 1940 1927 Pot 1940 1920 1940 1933 1879 1932 1905 1940 1940 1935 Pod 1939 iP 1926 1942 — 1940 1935 1936 1940 1938 1934 1892 RO xl Donegan, Henry Arthur James, A.S.1.C., A.A.C.1., Analyst, Department of Mines, Sydney ; p.r. 18 Hillview-street, Sans Souci. Dulhunty, John Allan, B.sc., Geology Department, University of Sydney. Dupain, George Zephirin, 4.A.c.1., F.c.s., Director Dupain Institute of Physical Education and Medical Gymnastics, Manning Building, 449 Pitt-street, Sydney; p.r. ““ Rose Bank,” 158 Parramatta-road, Ashfield. Dwyer, Francis P. J., m.sc., Lecturer in Chemistry, Technical College, Sydney. Earl, John Campbell, p.sc., Ph.p.,. Professor of Organic Chemistry in the University of Sydney. (President, 1938.) Eastaugh, Frederick Alldis, a.R.s.M., F.1.c., Professor in Engineering Tech- nology and Metallurgy in the University of Sydney. Elkin, Adolphus Peter, M.a., Ph.D., Professor of Anthropology in the University of Sydney. (President, 1940.) Emmerton, Henry James, B.sc., 41 Nelson-street, Gordon. English, James Roland, us. A.I.F. Enright, Walter John, B.A., Solicitor, High-street, West Maitland ; p.r. Regent- street, West Maitland. tHsdaile, Edward William, 42 Hunter-street, Sydney. Evans, Silvanus Gladstone, 4.1.4.4. Lond., A.R.A.1.A., 6 Major-street, Coogee. Farnsworth, Henry Gordon, Government Stores, Harrington-street, Sydney ; p.r. ‘‘ Rothsay,’’ 90 Alt-street, Ashfield. Faull, Norman Augustus, M.se., c/o National Standards Laboratory, University Grounds, City-road, Chippendale. Fawsitt, Charles Edward, D.sc., ph.p., Professor of Chemistry in the University of Sydney. (President, 1919.) Fiaschi, Piero, 0.B.E., v.D., M.D. Columbia Univ., p.p.s. New York, M.R.C.S. Eing., u.R.c.P. Lond., 178 Phillip-street, Sydney. Finch, Franklin Charles, B.sc., 1 Linden Court, Windsor, 8.1, Melbourne. Finnemore, Horace, B.Sc., F.I.c.. Reader in Pharmacy in the University of Sydney. Fisher, Robert, B.sc., 3 Sackville-street, Maroubra. Fisk, Sir Ernest Thomas, K.B., F.Inst.R.E., A.M.1I.E. Aust., Chairman of Directors, Amalgamated Wireless (Australasia) Ltd., Wireless House, 47 York-street, Sydney ; p.r. 16 Beaconsfield-parade, Lindfield. Flack, Arthur Charles Allenby, B.sc., Agricultural High School, Yanco, N.S.W. Fletcher, Harold Oswald, Assistant Paleontologist, Australian Museum, College-street, Sydney. {Foreman, Joseph, m.R.c.s. Eng., u.R.c.P. Hdin., ““ The Astor,’’ Macquarie-street, Sydney. Forman, Kenn. P., M.1.Refr.e., c/o Department of Aircraft Production, Box 20935, Melbourne, Vic. tFoy, Mark, c/o Geo. O. Bennett, 133 Pitt-street, Sydney. Franki, Robert James Anning, B.Sc., 891 New South Head-road, Rose Bay. Freney, Martin Raphael, B.sc., McMaster Laboratory, Sydney. Garretty, Michael Duhan, m.sc., Chief Geologist, North Broken Hill Ltd., Broken Hill, N.S.W. Gascoigne, Robert Mortimer, 5 Werona-avenue, Killara. Gibson, Alexander James, M.E., M.Inst.C.E., M.I.E.Aust., Consulting Engineer, 906 Culwulla Chambers, 67 Castlereagh-street, Sydney; p.r. ‘ Wirruna,”’ Belmore-avenue, Wollstonecraft. Gibson, Neville Allan, 3s.sc., Industrial Chemist, 217 Parramatta-road, Haberfield. Gillis, Richard Galvin, 1 Dundee, 35 Adams-street, South Yarra, S.E.1, Vic. Goddard, Roy Hamilton, F.c.a. Aust., Royal Exchange, Bridge-street, Sydney. Goulston, Edna Maude, B.sc., p.r. 83 Birriga-road, Bellevue Hill. Graves, John Nevil, B.sc., 96 Wentworth-street, Randwick. Griffiths, Edward L., B.Sc., A.A.C.I., A.I.c., Chief Chemist, Department of Agriculture ; p.r. 151 Wollongong-road, Arncliffe. Hall, Norman Frederick Blake, m.sc., Chemist, Council for Scientific and Industrial Research (Tobacco Section), Dept. of Organic Chemistry, University of Sydney; p.r. 154 Wharf-road, Longueville. tHalloran, Henry Ferdinand, L.s., A.M.1.E.Aust., F.S.I.Eng., M.T.P.1.Eng., 153 Elizabeth-street, Sydney; p.r. 23 March-street, Bellevue Hill. Xi Klected. 1940 Hanlon, Frederick Noel, B.sc., Geologist, Department of Mines, Sydney ; p-r. 4 Pearson-avenue, Gordon. 1905 P 6 |{Harker, George, D.Sc., F.A.C.1.; p.r. 89 Homebush-road, Strathfield. 1936 Harper, Arthur Frederick Alan, M.sc., A.Inst.p., National Standards Laboratory, University Grounds, City-road, Chippendale. 1937. Pies Harradence, Rita Harriet, D.Phil. (Oxon.), M.Sc. (Syd.), Research Scholar, c/o Dyson Perrins Laboratory, Oxford University, Oxford, England. 1934 Harrington, Herbert Richard, Teacher of Physics and Electrical Engineering, Technical College, Harris-street, Ultimo. 1923 Ps Harrison, Travis Henry John, D.sc.agr., D.1.c. London, Commonwealth Fruit Officer, Australia House, Strand, London, England; p.r. 41 Queen’s Gardens, Ealing, W.5, London. 1929 Hawley, J. William, J.p., Financial Agent, 4 Castlereagh-street, Sydney ; p-r. 12 King’s-road, Vaucluse. 1934 Hayes, William Lyall, a.s.v.c., a.A.c.1., Works Chemist, c/o Messrs. Wm. Cooper & Nephews (Aust.) Ltd., Phillip-street, Concord; p.r. 101 Essex-street, Epping. 1919 Henriques, Frederick Lester, 208 Clarence-street, Sydney. 1940 Heselton, Thomas William, B.sc., c/o Munition Laboratories, Maribyrnong, Victoria. 1938 Pp 4 Hill, Dorothy, M.sc. Q’ld., Ph.D. Cantab., Geological Research Fellow, University of Queensland, Brisbane. 1918 Hindmarsh, Percival, M.A., B.Sc.Agr., Principal, Hurlstone Agricultural High School, Glenfield. 1936 Hirst, Edward Eugene, A.M.1.E., Vice-Chairman and Joint Managing Director, British General Electric Co. Ltd.; p.r. ‘‘ Springmead,’’ Ingleburn. 1928 Hirst, George Walter Cansdell, B.sc., A.M.1.E. (Aust.), A.M.Inst.T.; p.r. “St. Cloud,’’ Beaconsfield-road, Chatswood. 1916 Hoggan, Henry James, a.M.1.M.E. Lond., A.M.1.E. Aust., Consulting and Designing Engineer, “‘ Lincluden,”’ 81 Frederick-street, Rockdale. 1941 Howard, Harold Theodore Clyde, B.sc., Principal, Wollongong Technical High School, Wollongong. 1935 Howarth, Mark, F.R.A.s., Grange Mount Observatory, Bull-street, Mayfield, Newcastle, N.S.W. 1936 Howie, Sir Archibald, k.B., M.uL.c., 7 Wynyard-street, Sydney. 1938 P 4 Hughes, Gordon Kingsley, B.sc., Lecturer in Chemistry, University of Sydney. 1923 P 3 |tHynes, Harold John, D.sc., B.sc.agr., Biologist, Department of Agriculture, Box 36a, G.P.O., Sydney ; p.r. “ Belbooree,”” 10 Wandella-avenue, Rose- ville. 1942 12 ut Jaeger, John Conrad, M.A., D.Sc., c/o Radiophysics Laboratory, The University, Sydney. 1940 Johns, Thomas Harley, 130 Smith-street, Summer Hill. 1909 121s Johnston, Thomas Harvey, M.A., D.Sc., C.M.Z.S., Professor of Zoology in the University of Adelaide. (Cor. Mem., 1912.) 1935 P 6 Joplin, Germaine Anne, B.Sc., Ph.D., Geological Department, University of Sydney; p.r. 18 Wentworth-street, Eastwood. 1930 Judd, William Perey, 123 Wollongong-road, Arncliffe. 1911 Julius, Sir George A., Kt., B.Sc., B.E., M.I.Mech.E., M.I.E.Aust., Culwulla Chambers, Castlereagh-street, Sydney. 1935 Kelly, Caroline Tennant (Mrs.), “‘ Eight Bells,’ Castle Hill. 1935 Kelly, Francis Angelo Timothy, “ Eight Bells,’ Castle Hill. 1940 Kennard, William Walter, 9 Bona Vista-avenue, Maroubra. 1924 Pert Kenny, Edward Joseph, Geological Surveyor, Department of Mines, Sydney ; pr. 17 Alma-street, Ashfield. 1934 Kerslake, Richmond, 4.S.T.c., A.A.C.1., Industrial Chemist, c/o Australian Paper Mfrs. Ltd., Macauley-street, Matraville; p.r. 55 Harold-street, Matraville. 1940 King, Leonard Esmond, 161 Nelson Bay-road, Bronte. 1920 Kirchner, William John, B.Sc., A.A.C.1., Manufacturing Chemist, c/o Messrs. Burroughs Wellcome & Co. (Australia) Ltd., Victoria-street, Waterloo ; p.r. 18 Lyne-road, Cheltenham. 1939 Lambeth, Arthur James, B.Sc., 44 Meek-street, Kingsford. 1936 Leach, Stephen Laurence, B.A., B.Sc., A.A.C.I., P.O. Box. No. 21, Concord. 1924 Leech, Professor Thomas David James, B.Sc., B.E. Syd., Professor of Engin- eering, Auckland University College, Auckland, N.Z. Elected. 1934 1936 1920 1940 1929 1942 1940 1940 1906 1927 1940 1942 1939 1940 1940 1940 1906 1891 1932 1927 1940 1924 1935 1941 1912 1929 1940 1928 1940 1940 1940 1941 1922 1934 1915 1940 1923 1930 1932 1935 1938 ry 3 P 55 lea Po 1 ip? Pt iP 2 Peck P 18 m1 P27. eg 2 Po x6 ica xl Leech, William Dale, Californian Institute of Technology, Pasadena, California, U.S.A. Lemberg, Max Rudolf, b.Phil., Biochemist, Royal North Shore Hospital ; p.r. 12 de Villiers-avenue, Chatswood. Le Souef, Albert Sherbourne, 3 Silex-road, Mosman. Lincoln, Gordon James, B.Sc., 15 Turner-avenue, Haberfield. tLions, Francis, B.Sc., Ph.D., A.1.c., Department of Chemistry, University of Sydney; p.r. 31 Chesterfield-road, Epping. Lippmann, Arthur S., M.p., 175 Macquarie-street, Sydney. Lipson, Menzie, B.sc., Chemist, C.S.I.R., Central Wool Committee Testing House, 17 Randle-street, Sydney; p.r. 5 Phillip Court, Latimer-road, Rose Bay. Lockwood, William Hutton, B.sc., Institute of Anatomy, Canberra, A.C.T. tLoney, Charles Augustus Luxton, M.Am.soc.Refr.z., National Mutual Building, 350 George-street, Sydney. Love, William Henry, B.Sc., Ph.p., Lecturer in Physics, University of Sydney. Luciano, Albert Anthony, 16 Arthur-street, Bellevue Hill. Lyons, Raymond Norman Matthew, m.sc., Biochemical Research Worker, 8 Boronia-avenue, Wollstonecraft. Maccoll, Allan, M.sc., 76 Springdale-road, Killara. Maccoll, Mrs. Margaret Elphinstone, B.A., B.Ec., 76 Springdale-road, Killara. McGrath, Brian James, 40 Mooramie-avenue, Kensington. McGregor, Gordon Howard, 4 Maple-avenue, Pennant Hills. tMcIntosh, Arthur Marshall, ‘“* Moy Lodge,” Hill-street, Roseville. tMcKay, R. T., M.1nst.c.z., Eldon Chambers, 92 Pitt-street, Sydney. McKie, Rev. Ernest Norman, B.a. Syd., St. Columba’s Manse, Guyra. McMaster, Sir Frederick Duncan, kt., ‘‘ Dalkeith,’’ Cassilis, N.S.W. Malone, Edward E., No. 4, Astral, 10 Albert-street, Randwick. Mance, Frederick Stapleton, *‘ Binbah,’’ Lucretia-avenue, Longueville. Maze, Wilson Harold, mM.sc., Lecturer in Geography, University of Sydney. Melville, George Livingstone, Managing Director, Federal Machine Co. Ltd., Loftus-street, Arncliffe. Meldrum, Henry John, B.A., B.Sc., Lecturer, The Teachers’ College, University Grounds, Newtown ; p.r. 98 Sydney-road, Manly. Mellor, David Paver, M.sc., Lecturer, Chemistry Department, University of Sydney ; p.r. 137 Middle Harbour-road, Lindfield. (President, 1941-42.) Mercer, Edgar Howard, McMaster Laboratory, Parramatta-road, Glebe. Micheli, Louis Ivan Allan, M.sc., Ph.p., Research Chemist, c/o Colonial Sugar Refining Co., Pyrmont. Millership, William, m.sc., Chief Chemist, Davis Gelatine (Aust.) Pty. Ltd., 15 Shaw-avenue, Earlwood. Mills, James Edward, M.sc., Ph.D., 16 Smith-road, Artarmon. Morris, Benjamin Sydney, B.sc., 22 Kelso-street, Enfield. Morrissey, Matthew John, B.a., A.s.T.c., Auburn-street, Parramatta. Morrison, Frank Richard, A.A.c.1., F.c.s., Assistant Chemist, Technological Museum, Sydney. Mort, Francis George Arnot, Manufacturing Chemist, 16 Grafton-street, Woollahra. Murphy, Robert Kenneth, pr.Ing., Chem.Eng., A.S.T.C., M.I.Chem.E., A.A.C.I., Lecturer in Charge of Chemistry and Head of Science Department, Sydney Technical College. Murray, Alban James Moore, B.sc., 54 Sydney-road, Willoughby. Murray, Jack Keith, QX34748, B.A., B.Sc.Agr., N.E. Reinf. Training Centre, Warwick, Queensland, and Professor of Agriculture in the University of Queensland. Naylor, George Francis King, M.A., M.Sc., Dip.Ed., A.A.I.I.F., Squadron Leader, R.A.A.F., Headquarters, Melbourne; p.r. ‘‘ Kingsleigh,’? Ingleburn, N.S.W. Newman, Ivor Vickery, M.Sc., Ph.D., F.R.M.S., F.L.S., Department of Biology, Victoria University College, Wellington, N.Z. Nicol, Phyllis Mary, m.sc., Sub-Principal, The Women’s College, Newtown. Noble, Norman Scott, D.Sc.agr., M.Sc., D.1.c., Secretary, Linnean Society of N.S.W., Science House, Gloucester-street, Sydney. X1v Elected. 1920 1940 1940 1935 1903 1921 P 4 ‘tNoble, Robert Jackson, M.sc., B.Sc.Agr., Ph.D., Under Secretary, Department of Agriculture, Box 364A, G.P.O., Sydney; p.r. 324A Middle Harbour-road, Lindfield. (President, 1934.) Norrie, Jack Campbell, B.sc., 28 Ray-road, Epping. Po .6 Nyholm, Ronald Sydney, M.sc., 77 Bland-street, Ashfield. O’Connell, Rev. Daniel J. K., .3., M.Sc., F.R.A.S., Riverview College Observatory, Sydney tOld, Taine. **“ Waverton,” Bay-road, North Sydney. P 5 Osborne, George Davenport, D.sc. Syd., Ph.D. Camb., Lecturer and Demonstrator in Geology in the University of Sydney. P 74 Penfold, Arthur Ramon, F.A.c.1., F.c.s., Curator and Economic Chemist, Technological Museum, Harris-street, Ultimo; p.r. 67 Park-avenue, Roseville. (President, 1935.) Penman, Arthur Percy, B.E. Syd., Mining Engineer, 10 Water-street, Wahroonga. Pettingell, William Walter, B.sc., 28 Conder-street, Burwood. Phillips, Marie Elizabeth, B.sc., 4 Morella-road, Clifton Gardens. Phillips, Orwell, 55 Darling Point-road, Edgecliffe. Poate, Hugh Raymond Guy, m.B., ch.m. Syd., F.R.c.S. Hng., L.R.c.P. Lond., F.R.A.C.S., Surgeon, 225 Macquarie-street, Sydney ; p.r. 38 Victoria-road, Bellevue Hill. tPope, Roland James, B.A. Syd., M.D., Ch.M., F.R.C.S. Hdin., 185 Macquarie- street, Sydney. Pov Powell, Charles Wilfrid Roberts, F.1.c., A.A.c.1., Company Executive, c/o Colonial Sugar Refining Co., O’Connell-street, Sydney ; p.r. “* Wansfell,”’ Kirkoswald-avenue, Mosman. Powell, John, Director, Foster Clark (Aust.) Ltd., 17 Thurlow-street, Redfern ; p.r. “‘ Elgarth,’’ Ranger’s-road, Cremorne. Powell, John Wallis, A.s.T.c., A.A.c.1., Managing Director, Foster Clark (Aust.) Ltd., 17 Thurlow-street, Redfern. Price, William Lindsay, B.E., B.Sc., Teacher of Physics, Sydney Technical College; p.r. 8 Wattle-street, Kullara. Priestley, Henry, M.D., Ch.M., B.Sc., Professor of Biochemistry, Faculty of Medicine, the University of Sydney. (President, 1942-43.) tPurser, Cecil, B.A., M.B%, Ch.m. Syd., ‘‘ Ascot,’ Grosvenor-road, Wahroonga. P 3. |{Quodling, Florrie Mabel, B.sc., Demonstrator in Geology, University of Sydney. | 128%) Raggatt, Harold George, D.sc., Director, Mineral Resources Survey, Depart- ment of Supply, Canberra, A.C.T. Ralph, Colin Sydney, B.sc., 24 Canberra-street, Epping. P 3 Ranclaud, Archibald Boscawen Boyd, B.sc., B.E., Lecturer in Physics, Teachers’ College, The University, Sydney. Randall, Harry, Buena Vista-avenue, Denistone. Peat Rayner, Jack Maxwell, B.sc., F.mst.p., Chief Geophysicist, Mineral Resources Survey, Department of Supply and Shipping, Census Building, Canberra, — AKC: Reid, Cicero Augustus, 19 Newton-road, Strathfield. Richardson, Henry Elmar, Chemist, Chase-road, Turramurra. P 6 Ritchie, Ernest, B.Sc., 6 Military-road, North Bondi. Roberts, Richard George Crafter, Electrical Engineer, c/o C. W. Stirling & Co., Asbestos House, York and Barrack-streets, Sydney. Robertson, Rutherford Ness, B.se. Syd., ph.p. Cantab., Flat 4, 43 Johnston- street, Annandale. Robinson, Albert Jordan, Managing Director, 8. T. Leigh & Co. Ltd., Raleigh Park, Kensington. | Pee? Room, Thomas G., M.A., F.B.S., Professor of Mathematics in the University of Sydney. Rosenbaum, Sidney, 44 Gilderthorp-avenue, Randwick. Elected. 1928 1940 1929 1940 1935 1941 1920 1940 1933 1936 1938 1936 1917 1900 1933 1940 1922 1919 1921 1916 1914 1900 1942 1909 1916 1940 1918 1901 1919 1920 1941 1941 1915 1939 1919 Pp 1 iP legal Pi) Py] P 16 P 2 Pe 3 XV Ross, Allan Clunies, B.Sc., F.c.A. Awust., Chartered Accountant Aust., 544 Pitt-street, Sydney ; p.r. The Grove, Woollahra. (Member from 1915 to 1924.) Ross, Jean Elizabeth, B.sc., Dip.Ed., 5 Stanton-road, Haberfield. Royle, Norman Dawson, M.D., Ch.M., 185 Macquarie-street, Sydney. Sarroff, Carlyle Joseph. Savage, Clarence Golding, Director of Fruit Culture, Department of Agriculture, Sydney. Beis: manele Thomas, M.A. Syd., B.A. Camb., Reader in Statistics, The University, Sydney ; p.r. 60 Boundary-street, Roseville. Scammell, Rupert Boswood, B.sce. Syd., A.A.C.1., F.C.S., c/o F. H. Faulding & Co. Ltd., 98 Castlereagh-street, Redfern ; p.r. 10 Buena Vista-avenue, Clifton Gardens. Scott, Reginald Henry, B.sc., 154 Highfield-road, Camberwell, Vic. Selby, Esmond Jacob, Dip.com., Sales Manager, Box 175 D, G.P.O., Sydney. Sellenger, Brother Albertus, Marist Brothers’ College, Randwick, N.S.W. Sheahan, Thomas Henry Kennedy, B.sc., Chemist, 2 Edward-street, Gordon. Sherrard, Kathleen Margaret Maria (Mrs.), m.sc. Melb., 43 Robertson-road, Centennial Park. Sibley, Samuel Edward, Mount-street, Coogee. tSimpson, R. C., Lecturer in Electrical Engineering, Technical College, Sydney. Slade, George Hermon, B.sc., Director, W. Hermon Slade & Co. Ltd., Manu- facturing Chemists, 23 Rosebery-avenue, Rosebery; p.r. “ Raiatea,’’ Oyama-avenue, Manly. Smith, Eric Brian Jeffcoat, 1 Rocklands-road, Wollstonecraft. Smith, Thomas Hodge, Australian Museum, College-street, Sydney. Southee, Ethelbert Ambrook, 0.B.E., M.A., B.Sc., B.Sc.Agr., Principal, Hawkes- bury Agricultural College, Richmond, N.S.W. Spencer-Watts, Arthur, “‘ Araboonoo,”’ Glebe-street, Randwick. Stephen, Alfred Ernest, F.c.s., c/o Box 1158 HH, G.P.O., Sydney. Stephens, Frederick G. N., F.R.C.S., M.B., Ch.M., 135 Macquarie-street, Sydney ; p.r. Captain Piper’s-road and New South Head-road, Vaucluse. tStewart, J. Douglas, B.v.sc., F.R.C.v.s., Emeritus Professor of Veterinary Science in the University of Sydney; p.r. “ Berelle,’’ Homebush-road, Strathfield. (President, 1927.) Still, Jack Leslie, B.sc., Ph.D., Department of Biochemistry, The University, Sydney. Stokes, Edward Sutherland, m.B., chm. Syd., D.p.H. Irel., Medical Officer, Metropolitan Board of Water Supply and Sewerage, 341 Pitt-street, Sydney ; pr. 15 Highfield-road, Lindfield. Stone, Walter George, F.S.T.C., A.A.c.1., Senior Analyst, Department of Mines, Sydney; p.r. 14 Rivers-street, Bellevue Hill. Stroud, Richard Harris, B.sc., ‘‘ Dalveen,’’ corner Chalmers and Barker-roads, Strathfield. tSullivan, Herbert Jay, Director in Charge of Research and Technical Depart- ment, c/o Lewis Berger & Sons (Australia) Ltd., Rhodes; Box 23, P.O., Burwood; p.r. “ Stonycroft,’”’ 10 Redmyre-road, Strathfield. tSussmilch, C. A., F.G.s., F.S.T.c., Consulting Geologist, 11 Appian Way, Burwood. (President, 1922.) tSutherland, George Fife, a.n.c.sc. Lond., Assistant Professor of Mechanical Engineering in the University of Sydney. Sutton, Harvey, 0.B.E., M.D., D.P.H. Melb., B.sc. Oxon., Professor of Preventive Medicine and Director, School of Public Health and Tropical Medicine, University of Sydney ; p.r. “‘ Lynton,’ 27 Kent-road, Rose Bay. Suvoroff, Victoria, B.Sc., Chief Chemist and Metallurgist, c/o G. E. Crane & Sons, Pty., Burwood-road, Concord. Swanson, Thomas Baikie, m.sc. Adel., Lecturer in Chemistry, New England University College, Armidale. 7 Taylor, Brigadier Harold B., M.c., D.Sc., F.1.C., F.A.C.I., Second Government Analyst, Department of Public Health, 93 Macquarie-street, Sydney ; p-r. 44 Kenneth-street, Longueville. Thomas, Mrs. A. V. M., 12 Clifton-avenue, Burwood. Thorne, Harold Henry, M.A. Cantab., B.sc. Syd., F.R.A.S., Lecturer in Mathe- matics in the University of Sydney ; p.r. 55 Railway-crescent, Beecroft. xvi Elected. 1935 1923 1940 1932 1940 1921 1935 1933 1903 1919 1913 1921 1924 1919 1919 1941 1911 1936 1920 1921 1909 1940 1928 1942 1940 1940 1936 1906 1916 1921 { | Pl PZ | Tommerup, Eric Christian, M.sc., A.A.c.1., P.O. Box 97, Atherton, North Queensland. Toppin, Richmond Douglas, A.I.C., 51 Crystal-street, Petersham. Tow, Aubrey James, m.sc., No. 5, “‘ Werrington,” Micentoe -avenue, Rose Bay. Trikojus, Victor Martin, B.Sc., D.Phil., Professor of Biochemistry, The University, Melbourne. ‘Vernon, James, Ph.D., A.A.C.I., Chief Chemist, Colonial Sugar Refining Co., 1 O’Connell- street, Sydney. Vicars, Robert, Marrickville Woollen Mills, Marrickville. Vickery, Joyce Winifred, M.sc., Botanic Gardens, Sydney; p.r. 17 The Promenade, Cheltenham. Voisey, Alan Heywood, m.sc., Lecturer in Geology and Geography, New England University College, Armidale. tVonwiller, Oscar U., B.Sc., F.Inst.p., Professor of Physics in the University of — Sydney. (President, 1930.) Walkom, Arthur Bache, D.sc., Director, Australian Museum, Sydney ; p.r. 45 Nelson-road, Killara. (Member from 1910-1913.) Wardlaw, Hy. Sloane Halcro, D.se. Syd., F.A.c.1., Lecturer and Demonstrator in Biochemistry in the University of Sydney. (President, 1939.) tWaterhouse, Gustavus Athol, D.Sc., B.E., F.R.E.S., F.R.Z.S., 39 Stanhope-road, Killara. Waterhouse, Leslie Vickery, B.z. Syd., Mining Engineer, Shell House, Car- rington-street, Box 58 CC, G.P.O., Sydney; p.r. 4 Bertha-road, Neutral Bay. Waterhouse, Lionel Lawry, s.r. Syd., Lecturer and Demonstrator in Geology in the University of Sydney. Waterhouse, Walter L., M.c., D.Sc.Agr., D.I.C., F.L.S., Reader in Agriculture, University of Sydney; p.r. “‘ Hazelmere,’’ Chelmsford-avenue, Lindfield. (President, 1937.) Watson, Irvine Armstrong, Ph.D., B.Sc.Agr., Assistant Lecturer, Faculty of Agriculture, University of Sydney. Watt, Robert Dickie, M.a., B.Sc., Professor of Agriculture in the University of Sydney ; p.r. 64 Wentworth-road, Vaucluse. (President, 1925.) Wearne, Harold Wallis, 22 Yarabah-avenue, Gordon. Wellish, Edward Montague, m.a., Associate-Professor of Applied Mathematics in the University of Sydney ; p.r. 15 Belgium-avenue, Roseville. Wenholz, Harold, B.sc.agr., Director of Plant Breeding, Department of Agri- culture, Sydney. tWhite, Charles Josiah, B.Sc., Lecturer in Chemistry, Teachers’ College, Uni- versity Grounds, Newtown. White, Douglas Elwood, M.sc., D.Phil., Chemistry Department, The University, Melbourne. Wiesener, Frederick Abbey, M.B., Ch.M., D.o.M.s., Ophthalmic Surgeon, 143 Macquarie-street, Sydney; p.r. Jersey-road, Strathfield. Williams, Gordon Roy, B.sc., 45 Conder-street, Burwood. Willison, Alan Maynard, m.sc., 3 Stanley-street, Randwick. Wogan, Samuel James, 34 Neich-parade, Burwood. Wood, Harley Weston, M.Sc., A.Inst.P., F.R.A.S., Assistant Astronomer, Sydney Observatory ; p.r. 4 Ormond-street, Ashfield. tWoolnough, Walter George, D.sc., F.c.s., No. 4, “‘ Aylesbury,” 1524 Ernest- street, North Sydney. (President, 1926.) Wright, George, Company Director, c/o Hector Allen, Son & Morrison, 16 Barrack-street, Sydney; p.r. ‘“‘ Wanawong,”’ Castle Hill, N.S.W. Yates, Guy Carrington, Seedsman, c/o Arthur Yates & Co. Ltd., 184 Sussex- street, Sydney; p.r. Boomerang-street, Turramurra. pie: ‘ Xvil HoNORARY MEMBERS. Limited to Twenty. Elected. 1939 Chapman, Frederick, A.L.S., F.R.S.N.Z., F.G.S., “‘ Hellas,’ 50 Stawell-street, Kew, E.4, Victoria. 1914 Hill, James P., p.sc., F.R.S., Professor of Zoology, University College, Gower- ‘ street, London, W.C.1, England. 1931 Lyle, Sir Thomas Ranken, K.B., C.B.E., M.A., D.Sc., F.R.S., “‘ Lisbuoy,”’ Irving- road, Toorak, Melbourne, Victoria. 1915 Maitland, Andrew Gibb, F.a.s., ‘‘ Bon Accord,’ 28 Melville-terrace, South Perth, W.A. 1912 Martin, Sir Charles J., C.M.G., D.Sc., F.R.S., Roebuck House, Old Chesterton, Cambridge, England. 1922 Wilson, James T., M.B., ch.m. Hdin., F.R.S., Professor of Anatomy in the Uni- versity of Cambridge; p.r. 24 Millington-road, Cambridge, England. OBITUARY, 1942-1943. Elected. 1894 James Adam Dick. 1913 John Clifford Firth. 1880 Gerald Harnett Halligan. 1896 Kelso King. 1913 Archibald Durrant Ollé. 1920 Marcus Baldwin Welch. 1915 Joseph J. Thompson (Honorary Member). THE REV. W. B. CLARKE MEMORIAL FUND. The Rev. W. B. Clarke Memorial Fund was inaugurated at a meeting of the Royal Society of N.S.W. in August, 1878, soon after the death of Mr. Clarke, who for nearly forty years rendered distinguished service to his adopted country, Australia, and to science in general. It was resolved to give an opportunity to the general public to express their appreciation of the character and services of the Rev. W. B. Clarke “ as a learned colonist, a faithful minister of religion, and an eminent scientific man.’’ It was proposed that the memorial should take the form of lectures. on Geology (to be known as the Clarke Memorial Lectures), which were to be free to the public, and of a medal to be given from time to time for distinguished work in the Natural Sciences done in or on the Australian Commonwealth and its territories ; the person to whom the award is made may be resident in the Australian Commonwealth or its territories, or elsewhere. The Clarke Memorial Medal was established first, and later, as funds permitted, the Clarke Memorial Lectures have been given at intervals. CLARKE MEMORIAL LECTURES. Delivered. 1906. ‘“‘ The Volcanoes of Victoria,’ and “The Origin of Dolomite ’”’ (two lectures). By Professor E. W. Skeats, D.Sc., F.G.S. 1907. ‘“‘ Geography of Australia in the Permo-Carboniferous Period” (two lectures). By Professor T. W. E. David, B.A., F.R.S. ‘** The Geological Relations of Oceania.”” By W. G. Woolnough, D.Sc. ‘* Problems of the Artesian Water Supply of Australia.” By E. F. Pittman, A:R.S.M. ‘“'The Permo-Carboniferous Flora and Fauna and their Relations.”” By W. 8S. Dun. 1918. ‘‘ Brain Growth, Education, and Social Inefficiency.” By Professor R. J. A. Berry, M.D. H R28.E: 1919. ‘‘ Geology at the Western Front,” By Professor T. W. E. David, C.M.G., D.S8.O., F.R.S. 1936. ‘The Aeroplane in the Service of Geology.” By W. G. Woolnough, D.Sc. (THIS JOURN., 1936, 70, 39.) 1937. ‘‘ Some Problems of the Great Barrier Reef.’’ By Professor H.C. Richards, D.Sc. (THs JOURN., 1937, 71, 68.) 1938. ‘‘The Simpson Desert and its Borders.” By C. T. Madigan, M.A., B.Sc., B.E., D.Sc. (Oxon.). (THis Journ., 1938, 71, 503.) 1939. ‘‘ Pioneers of British Geology.’ By Sir John 8S. Flett, K.B.E., D.Sc., LL.D., F.R.S. (THis JouRN., 1939, 73, 41.) 1940. ‘The Geologist and Sub-surface Water.” By E. J. Kenny, M.Aust.I.M.M. (THIs | JOURN., 1940, 74, 283.) 1941. ‘‘ The Climate of Australia in Past Ages.”’ By C. A. Sussmilch, F.G.S. (THis Journ., 1941, 75, 47.) 1942. ‘‘ The Heroic Period of Geological Work in Australia.”’ By E. C. Andrews, B.Sc. AWARDS OF THE CLARKE MEDAL. Established in memory of The Revd. WILLIAM BRANWHITE CLARKE, M.a., F.R.S., F.G.S., etc. Vice-President from 1866 to 1878. The prefix * indicates the decease of the recipient. Awarded. 1878 *Professor Sir Richard Owen, K.Cc.B., F.R.S. 1879 *George Bentham, C.M.G., F.R.S. 1880 *Professor Thos. Huxley, F.R.s. 1881 *Professor F. M‘Coy, F.R.S., F.G.S. 1882 *Professor James Dwight Dana, LL.D. 1883. *Baron Ferdinand von Mueller, K.C.M.G., M.D., Ph.D., F.R.S., F.L.S. 1884 *Alfred R. C. Selwyn, Lu.D., F.R.S., F.G.S. 1885 *Sir Joseph Dalton Hooker, 0.M., G.C.S.1., C.B., M.D., D.C.L., LL.D., F.R.S. 1886 *Professor L. G. De Koninck, M.D. 1887 *Sir James Hector, K.C.M.G., M.D., F.R.S. nee xix Awarded. ‘1888 *Rev. Julian E. Tenison-Woods, F.G.S., F.L.S. 1889 *Robert Lewis John Ellery, F.R.S., F.R.A.S. 1890 *George Bennett, M.D., F.R.C.s. Eng., F.L.S., F.Z.S. 1891 *Captain Frederick Wollaston Hutton, F.R.S., F.G.s. 1892 *Sir William Turner Thiselton Dyer, K.C.M.G., C.I.E., M.A., LL.D., S¢.D., F.R.S., F.L.S. 1893 *Professor Ralph Tate, F.L.s., F.G.S. 1895 *Robert Logan Jack, LL.D., F.G.S., F.R.G.S. 1895 *Robert Etheridge, Jnr. 1896 *The Hon. Augustus Charles Gregory, C.M.G., F.R.G.S. 1900 *Sir John Murray, K.C.B., LL.D., Sc.D., F.R.S. 1901 *Edward John Eyre. 1902 *F. Manson Bailey, C.M.G., F.L.S. 1903 *Alfred William Howitt, D.Sc., F.G.S. 1907 *Professor Walter Howchin, F.c.s., University of Adelaide. 1909 *Dr. Walter E. Roth, B.a. 1912 *W. H. Twelvetrees, F.G.s. 1914 Sir A. Smith Woodward, LL.D., F.R.s., Keeper of Geology, British Museum (Natural History), London. 1915 *Professor W. A. Haswell, M.A., D.Sc., F.R.S. 1917 *Professor Sir Edgeworth David, K.B.E., C.M.G., D.S.0., M.A., SC.D., D.Sc., F.R.S., F.G.S. 1918 *Leonard Rodway, c.M.c., Honorary Government Botanist, Hobart, Tasmania. 1920 *Joseph Edmund Carne, F.G.S. 1921 *Joseph James Fletcher, M.a., B.Sc. 1922 *Richard Thomas Baker, The Crescent, Cheltenham. 1923 *Sir W. Baldwin Spencer, K.C.M.G., M.A., D.Sc., F.R.S. 1924 *Joseph Henry Maiden, 1.S.0., F.R.S., F.L.S., J.P. 1925 *Charles Hedley, F.L.s. 1927 Andrew Gibb Maitland, F.c.s., ‘‘ Bon Accord,’’ 28 Melville Terrace, South Perth, W.A. 1928 Ernest C. Andrews, B.A., F.G.S., 32 Benelong Crescent, Bellevue Hill. 1929 Professor Ernest Willington Skeats, D.Sc., A.R.C.S., F.G.S., University of Melbourne, Carlton, Victoria. 1930 =L. Keith Ward, B.a., B.E., D.Sc., Government Geologist, Geological Survey Office, Adelaide. 1931 *Robin John Tillyard, M.A., D.Sc., Sc.D., F.R.S., F.L.S., F.E.S., Canberra, F.C.T. 1932 Frederick Chapman, A.L.S., F.R.S.N.Z., F.G.S., Melbourne. 1933. Walter George Woolnough, D.sSc., F.c.s., Department of the Interior, Canberra, F.C.T. 1934 *Edward Sydney Simpson, D.sc., B.E., F.A.C.I., Carlingford, Mill Point, South Perth, W.A. 1935 George William Card, a.R.s.M., 16 Ramsay-street, Collaroy, N.S.W. 1936 Sir Douglas Mawson, kKt., 0.B.E., F.R.S., D.Sc., B.E., University of Adelaide. 1937. J. T. Jutson, B.sc., 1u.B., 9 Ivanhoe-parade, Ivanhoe, Victoria. 1938 Professor H. C. Richards, p.sc., The University of Queensland, Brisbane. 1939 C. A. Sussmilch, F.G.s., F.S.T.c., 11 Appian Way, Burwood, N.S.W. 1941 Professor Frederic Wood Jones, M.B., B.S., D.Sc., F.R.S., Anatomy Department, University of Manchester, England. 1942 William Rowan Browne, D.sc., Reader in Geology, The University of Sydney, N.S.W. AWARDS OF THE SOCIETY’S MEDAL AND MONEY PRIZE. Money Prize of £25. Awarded. 1882 John Fraser, B.a., West Maitland, for paper entitled ‘‘ The Aborigines of New South Wales.”’ 1882 Andrew Ross, M.p., Molong, for paper entitled “‘ Influence of the Australian climate and pastures upon the growth of wool.” The Society’s Bronze Medal and £25. Awarded. 1884 W. E. Abbott, Wingen, for paper entitled ‘‘ Water supply in the Interior of New South Wales.” 1886 8S. H. Cox, F.e.s., F.c.s., Sydney, for paper entitled ‘‘ The Tin deposits of New South Wales.” 1887 Jonathan Seaver, F.c.s., Sydney, for paper entitled ‘‘ Origin and mode of occurrence of gold-bearmg veins and of the associated Minerals.” 1888 Rev. J. E. Tenison-Woods, F.G.S., F.L.S., Sydney, for paper entitled ‘‘ The Anatomy and Life-history of Mollusca peculiar to Australia.”’ 1889 Thomas Whitelegge, F.z.m.s., Sydney, for paper entitled ‘‘ List of the Marine and Fresh- water Invertebrate Fauna of Port Jackson and Neighbourhood.” xX Awarded. 1889 Rev. John Mathew, m.a., Coburg, Victoria, for paper entitled ‘‘ The Australian Aborigines.” 1891 Rev. J. Milne Curran, F.c.s., Sydney, for paper entitled “‘ The Microscopic Structure of Australian Rocks.’’ ; 1892 Alexander G. Hamilton, Public School, Mount Kembla, for paper entitled “‘ The effect which settlement in Australia has produced upon Indigenous Vegetation.” 1894 J. V. De Coque, Sydney, for paper entitled the ‘‘ Timbers of New South Wales.” 1894 R. H. Mathews, L.s., Parramatta, for paper entitled “‘ The Aboriginal Rock Carvings and _ Paintings in New South Wales.”’ 1895 C. J. Martin, D.Sc., M.B., F.R.S., Sydney, for paper entitled ‘‘ The physiological action of the venom of the Australian black snake (Pseudechis porphyriacus).”’ 1896 Rev. J. Milne Curran, Sydney, for paper entitled ‘“‘ The occurrence of Precious Stones in New South Wales, with a description of the Deposits in which they are found.” AWARDS OF THE WALTER BURFITT PRIZE. Bronze Medal and Money Prize of £50. Established as the result of a generous gift to the Society by Dr. W. F. Burritt, B.A., M.B., Ch.M., B.Sc., of Sydney. Awarded at intervals of three years to the worker in pure and applied science, resident in Australia or New Zealand, whose papers and other contributions published — during the past three years are deemed of the highest scientific merit, account being taken only of investigations described for the first time, and carried out by the author mainly in these Dominions. Peet ee ee eee Ae ee eee ee ee Cee ea) en eee ee SY Br Awarded. 1929 Norman Dawson Royle, M.D., ch.m., 185 Macquarie Street, Sydney. 1932 Charles Halliby Kellaway, M.c., M.D., M.S., F.R.c.P., The Walter and Eliza Hall Institute of Research in Pathology and Medicine, Melbourne. 1935 Victor Albert Bailey, M.a., D.Phil., Associate-Professor of Physics, University of Sydney. _ 1938 Frank Macfarlane Burnet, m.p. (Melb.), ph.p. (Lond.), The Walter and Eliza Hall Institute _ of Research in Pathology and Medicine, Melbourne. 1941 Frederick William Whitehouse, D.sc., Ph.D., University of Queensland, Brisbane. Pe a Oe hey eee Se Vial PS lass ak AWARDS OF LIVERSIDGE RESEARCH LECTURESHIP. This Lectureship was established in accordance with the terms of a bequest to the Society ey by the late Professor Archibald Liversidge. Awarded at intervals of two years, for the purpose _ of encouragement of research in Chemistry. (THis JouRNAL, Vol. LXII, pp. x-xim, 1928.) Awarded. =a x 1931 Harry Hey, c/o The Electrolytic Zinc Company of Australasia, Ltd., Collins Street, — Melbourne. 1933. W. J. Young, D.sc., M.sc., University of Melbourne. 1940 G. J. Burrows, B.Sc., University of Sydney. 1942 J. S. Anderson, B.Sc., Ph.D. (Lond.), A.R.C.S., D.I.c., University of Melbourne. OF NEW SOUTH WALES ee ee «(INCORPORATED 1881) 23 Deeeay PA corey ; a _- PART I (pp. 1 to 95) . See VOL. mu =e "Containing, Papers read in “April ent Maa ee ‘EDITED BY THE HONORARY SECRETARIES | oat ! UTHORS, OF PAPERS ARE ALONE RESPONSIBLE FOR THE Se, oie ae a : | PUBLISHED BY THE SOCIETY, SCIENCE HOUSE = GLOUCESTER AND ESSEX STREETS ere 82 ey ; ; > art * me b Arr. I,—Presidential Address. By D. P. Mellor, Mise. s ee ta —Methemoglobin Foner By J ohn ‘Williamson “tae. 2 September 21, 1942) . oe satiate rie Te ; s. * Arr. III.—A Note on the Essential Oil of Eucal, yptus sonnet var. anceps. Berry, M. Sc., and aia B. Satin, M. eee eee meus eke * Y Art, IV. —Studies in Metemorphicn and sdcreloelans in the Wellington D IT. The Dynamic and Contact Metamorphism of a Group of Ultra a 31 Elizabeth M. Basnett, M.Sc. (Issued nepioner 21, 1942) ae Art, V.—The Tertiary Land Surface in pouphers Now Bngland. By A a (Issued beinaeanty 21, 1942) ae ag ey wy Ea Son Seas ART. VI. RAL Se in A aientpintee with Special Reforanne’ ‘to iis Hormones on Spermatogenesis of PBs vulpecula. ~ BY. AC Boll (Issued cee tae 2b 1942) i alae eter = 3S \, , : Oils. pas on R. Pantcld: F.AC.L, FAC. 8. Wom. ‘Morrison, ALAC 8. Bait: sate ‘&B. Se. je. Agr: oes eects 21, age oh PRESIDENTIAL ADDRESS By D. P. MELLOR, MSc. Delivered to the Royal Society of New South Wales, April 1, 1942. 2 Part I. THE PAST YEAR. As the present world conflict grows more widespread, it is inevitable that there will be an increasing diversion of science from its normal peace-time activities and a consequent diminution in the output of fundamental research work. We must accept this as a condition of the survival of science as we know it, and it is in this light that we must view the falling off in the number of papers received for reading and publication from 40 in 1940 to 20 in 1941. A part of the fall may be due to a normal fluctuation, the remainder reflects the prevailing conditions. The number of our exchanges is also falling steadily, having dropped from 268 to 239 during the past year and from 361 since May, 1939. We will be fortunate indeed if our difficulties in the coming months are no more than these. _ .In thus commencing the survey of the past year I have drawn the worst side of the picture first. Actually most activities of the Society have followed - their usual courses. The membership stands at the satisfactory total of 298, gains during the year roughly counterbalancing losses. Several years ago (1935) women were admitted to the Society for the first time. As a logical sequence to this I am pleased to be able to report the first election of a woman member, Dr. Ida Brown, to the Council. To another of our Council members, Professor T. G. Room, has fallen the signal distinction of election to the F.R.S., and we offer him our heartiest congratulations. In addition to the twenty papers accepted for reading and publication during the year, the following short addresses were given : “Fiji and the Fijians’’, by Arthur Capell, M.A., Ph.D. *‘ Mineral Resources of the Great Powers in Relation to the International Situation’, by G. D. Osborne, D.Sc. “A Seale of Magnitudes’’’, by F. Lions, Ph.D. “The Electron Microscope’’, by R. E. B. Makinson, Ph.D. “Vitamin B,—its Discovery and Importance in Nutrition and Disease- prevention’, by A. Bolliger, Ph.D. “The Sulphanilamide Drugs ’”’, by F. Lions, Ph.D. The following exhibits were shown at meetings : “Some Recent Developments in Plastics ’’, by F. R. Morrison, A.A.C.I. “A Fluorescent Chromatographic Column ’”’, by A. J. Tow, B.Sc. “The Jelley-Leitz Refractometer’”’, by G. D. Osborne, D.Sc. By courtesy of the Rural Bank of N.S.W., films were shown and a com- mentary provided, on “‘ The Menace of Soil Erosion’ and “‘ The Red Terror ”’ (bush fires). Popular lectures dealing with a wide variety of topics were delivered during the months of June to October (inclusive) and were well attended. They were: 19th June.—‘‘ Some Aspects of Hydatid Disease in Australia ’’, by Professor H. Dew, M.B., B.S., F.R.C.S. 17th July.—*‘ The Modern Aeroplane ”’, by Professor A. V. Stephens, M.A. A—April 1, 1942. 2 D. P. MELLOR. 21st August.—‘‘ War and the Fisheries’, by H. Thompson, M.A., D.Sc. 18th September.—* Weighing the Stars’’, by R. van der R. Woolley, — M.Se., Ph.D. 16th October.—*‘ The Cow, the Chemist and Ourselves—The Nutrition of Farm Animals in Plenty and in Drought’’, by E. G. Hallsworth, B.Se., Ph.D. The Society is indebted to the lecturers who kindly gave their services on the above occasions. Owing to uncertainty about conditions which may prevail in the coming winter months, the Council has decided to abandon the ordinary form of popular lecture, for the time being at least, and to use the present as an opportunity for trying out a new experiment. Arrangements are in hand for a series of popular broadcast talks to be delivered over the national stations, under the Society’s auspices. In the absence of facilities for experiment and illustration there is no doubt that broadcasting will prove a more difficult medium for a popular lecture, if it is to deal with more than the magic and gadgetry of science. It may be that the limitations of the medium and of the time available for each talk do not permit one to go any deeper than this. Experience alone will prove whether or not it will be wise to incorporate broadcast talks by experts in their particular fields as a permanent part of our popular science programme. One symposium was held during the year, the subject chosen for discussion being “‘ Light Metals’. The following were the speakers and subjects : ““Sources of Light Metals ’’, Professor L. A. Cotton. ‘““Manufacture of and Demand for Light Metals ’’, Dr. J. E. Mills. ‘“Some Alloys of the Light Metals ’’, Miss V. Suvoroff, B.Sc. Like the symposia held in previous years, this one proved most valuable and interesting. So far, practically all our symposia have been devoted to the various elements, sulphur, phosphorus, potassium, etc. It would seem worth while now to strike out into new fields, even if it is difficult to find a subject which provides a suitable common meeting ground for different specialists. The tenth Clarke Memorial Lecture was delivered on 22nd May, 1941, by Mr. C. A. Sussmilch, and was entitled ‘“ The Climate of Australia in Past Ages’’. The Clarke Memorial Medal for 1941 was awarded to Professor Wood Jones, F.R.S., formerly of the Universities of Adelaide and Melbourne, and later Professor of Anatomy in the University of Manchester. The medal was presented to Professor Wood Jones at the Anniversary Meeting of the Royal Society (London), held on 1st December, 1941. The Walter Burfitt Prize was awarded to Frederick W. Whitehouse, D.Sc., Ph.D., Lecturer in Geology in the University of Queensland. It is perhaps a little disappointing to have to report that the revision of Rules was not completed before the end of the year. What started as the revision of a few Rules finished up as the revision of Rules from beginning to end. The magnitude of the task and wisdom of hastening slowly were largely responsible for the prolongation of this work. I should here like to place on record my appreciation of the untiring efforts of all those who served on this and other committees throughout the year. On my own and your behalf I sincerely thank members of the Council for their help and loyal cooperation. I would especially mention the two Honorary Secretaries, Professor A. P. Elkin and Dr. C. Anderson, upon whom so many of the burdens of the Society fall. Our thanks are also due to the chairmen and honorary secretaries of Sections; to the Librarian, Mr. W. H. Maze, and his assistant, Dr. A. Bolliger, who with the help of Dr. Anderson did yeoman ~ service in restoring order to the Society’s vast collection of old volumes of the Journal. PRESIDENTIAL ADDRESS. 3 THE JOURNAL. It is widely recognised that one of the most important functions of our Society is the publication of the Journal, and in this connection I have to record several events of interest. Perhaps the most noteworthy is the enlargement of theformat. Ishould explain that this was done not to improve the appearance of the Journal—from an esthetic point of view the old size probably had more to recommend it—but for reasons of economy and efficiency. A very thorough analysis of the costs of publishing scientific periodicals has been carried out under the auspices of the National Research Council (U.S.A.).1 From this it was clear that economies could be effected in the publication of our Journal. It was shown, for example, that as the number of words per page increases, so the cost per word per 1,000 copies of a journal (the basis for comparison) diminishes. An upper limit is set to the number of words per page and page size, by considera- tions of handling and shelving bound volumes, and there is no danger that any enthusiast will so extend the enlarging process as one day to startle members with a volume of newspaper size. For a time the Journal may appear painfully slim, but I hope that, as better times return, it will assume its usual substantial appearance. During the year a small pamphlet entitled ‘“‘ Guide to Authors ’’ was com- piled by a committee and published for the mutual assistance of editors and authors. It is hoped that it will prove helpful in regard to such matters as standard nomenclature, symbols and abbreviations for titles of journals, etc.? The maintenance of the quality of papers for a journal is, to some extent, dependent on refereeing. Several changes, designed to assist referees in their task, have recently been introduced. Among these is the issue of a special printed form which sets out clearly the course of action open to a referee and, when signed, serves as a kind of standardised certificate in regard to the character of the paper with which it is duly filed. SCIENTIFIC PERIODICALS. During the year several questions relating to periodicals have come up for discussion both by the Council and Library Committee. Among the results of these discussions was the passing of a resolution by the Council to the effect that our library be essentially one for scientific periodicals. The question of a central library for Science House was again canvassed, but I regret to say that there is no immediate. prospect of any move in this direction. However, the enquiry was not altogether barren of results, as it stimulated further investigation into the overlapping between our own library and that of the Linnean Society. The overlapping here is considerable but there is every prospect of a reduction where duplication is proved unnecessary. It is recognised that some duplication may be desirable and that each case must be considered on its merits. I should like to see steps to eliminate unnecessary duplication and to effect closer coordination taken further and extended to cover all the important periodical libraries in Sydney. An example, chosen at random, will serve to show the kind of thing- that may happen in the absence of some coordination. The Royal Society purchases a journal known as the ‘‘ Observatory ”’, for which there is, I understand, little demand by our members. The same journal is taken by the Government Observatory and the Public Library, both copies being readily available to bona fide enquirers. Other instances of this kind of duplication could be found, and it is clear that the Society would be assisting the cause of science here by dropping unnecessary duplication so that it might fill some important gaps in the supply of scientific periodicals. I believe that 1J. R. Schramm, 1939. Proc. Amer. Phil. Soc., 80, 1. * See also ‘“ Abbreviations for Titles of Scientific Periodicals’, 1941, Aus. J. Sci., 4, 71. 4 D. P. MELLOR. by steps of this kind we might greatly improve the usefulness of, and demand for, the facilities of our library. Many of us are aware of important journals that are not available in Australia and equally well aware that funds are not likely to be forthcoming for their purchase in the near future. By proper coordination and without putting undue strain upon the present satisfactory inter-library borrowing system, I feel sure that the situation could be improved with little or no further financial expenditure. I may be a little over-optimistic about the prospects in this direction, but at least the experiment would be worth trying. The Society might well take the initiative in forming a repre- sentative committee of members of scientific societies and professional librarians to look into the whole question of coordination of scientific periodical collections in Sydney. A CENTRAL REGISTER OF SCIENTIFIC AND TRAINED PERSONNEL. If we are to make wise and efficient use of our national resources, an indis- pensable prerequisite would seem to be that we at least know what they are and where they are. Yet, in regard to one important field of our human resources, namely that covering scientific and trained personnel, we, in this country, have done next to nothing to answer either of these questions. In this we lag far behind England and U.S.A., where it is widely recognised that a complete central register of scientific personnel is a sine qua non for the efficient use of brain power in time of national emergency. At the present moment the Common- wealth Government is engaged in making a national register of all its citizens between 16 and 60, but in regard to scientists it does not go nearly far enough. The scope of the information required can be seen from a glance at the American questionnaires.* It is too late for any survey to be of use in the crises expected in the coming months, but in the long distance struggle ahead there can be no doubt of its usefulness. Experience in England and U.S.A. has already proved the registers of great national value, and there is every evidence that this will be true in times of peace no less than war. It is the latter that concerns us most closely now. ‘“‘ A chemist whose work has been done in some specialised and relatively obscure field may suddenly become the one man in the country able to devise a means of protection against some new chemical weapon. A specialist in an obscure dialect of a foreign language may possess a skill which will have a far-reaching significance in an emergency.” Our chances of locating such individuals with speed and certainty when required are considerably greater if a properly devised national register is available. A country without a register may be likened to a library whose books are neither systematically arranged nor catalogued, and just as a catalogue does not in itself guarantee that a library will be well used, so it is with a national register of scientific and trained personnel. There is no sense in making a national register if it is not going to be widely and wisely used by the civil services, the fighting services and private institutions of all kinds. It is true that some sectional registers of chemists, engineers, etc., have already been compiled, but there is evidence that the registers have not been as widely used as they might and also evidence of a general lack of centralisation. — The English register was compiled under the auspices of the Royal Society of London. The job is much too big for the limited resources of such a society as our own, or even of the Australian National Research Council, which is attempting to do something about the matter. The administration of such a scheme would seem more properly to belong to the sphere of the Federal Government as it is in U.S.A. The most this Society can do is to lend the * For information on the national roster of scientific personnel in U.S.A., see Carmichael, L., 1940, Science, 92, 135; 1941, 93, 217; 1942, 95, 86. PRESIDENTIAL ADDRESS. 5 weight of its authority to advocating such a scheme, and in the event of it coming into being to proffer the advice of its specialists in regard to the details of the register. THE AWARD OF MEDALS. | Last year your President (Professor A. P. Elkin) suggested the revival of the practice of awarding the Society’s medal together with substantial prize money for meritorious work without limitation of the field of research. While nothing has yet been done to implement this suggestion, it has not been lost sight of. Experience of the past year confirms that of previous years that there is need for the revival of the practice of awarding the Society’s own medal to supplement the awards which are now made on the basis of certain bene- factions. This presupposes, of course, that there is general agreement on the practice of making awards of medals at all. To satisfy my own doubts on this matter I turned to the records relating to the awards of medals by the Royal Society of London, and there I came across what to my mind is an excellent statement of the arguments for and against honorary rewards. In concluding this part of my address, I will take the liberty of quoting it to you at some length, in the hope that when the question comes up for consideration it may prove useful as a basis for discussion. “It is said that they must either confirm or contradict the judgment which has been either already pronounced, or which Posterity will most certainly hereafter pronounce, upon the merits, pretensions and influence of the discoveries or series of investigations which such medals are designed to commemorate; that in the first case they can confer no additional honour upon their author, whose rank has already been ascertained and fixed by the sentence of a higher tribunal, while, in the second, they can only tend to compromise the character of the scientific body by whose advice they are conferred. It is true that I would not claim infallibility for the united judgment of any association, or body of men, however eminent their scientific rank may be: but it is the peculiar privilege of the great masters of science (and more particularly so when acting or speaking as a body), to be able to anticipate, though not without the possibility of error, the decision of Posterity, and thus to offer to the ardent cultivator of science that highest reward of his labours, as an immediate and well assured possession, which he might otherwise be allowed silently and doubtingly to hope for, but never be permitted to see realised; and though some powerful minds might be content to trust the complete development of their fame to the fullness of time, and might pursue their silent labours under the influence of no other motives but such as are furnished by their love of truth, the gratification derived from the discovery of the beautiful relations of abstract science, or from the contemplation of the agency of a Divine Mind in the harmonies and constitution of the physical world, yet it is our duty and business to deal with men as we find them constituted, and to stimulate their exertions by presenting to their view honourable distinctions attainable by honourable means; to assure them that the results of their labours will neither pass unnoticed nor unrewarded; and that there exists a tribunal to which they may appeal, or before which they can appear, whose decision is always for honour, never for con- demnation . . .”—H.R.H. Duke of Sussex, K.G., F.R.S., J.P. of R.S., vol. XLVII, 106. OBITUARY. __ I regret to record the deaths during the past year of the following members : Richard Thomas Baker, Edward George Noble and Carl Gustav Sundstrém. RICHARD THOMAS BAKER died at his residence, Cheltenham, N.S.W., on the 14th July, 1941, at the age of 87. Mr. Baker was born at Woolwich, Kent, — England, on the 1st December, 1854. He came to Australia in September, 1879. In June, 1880, he joined the staff at Newington College, Sydney, as Senior Housemaster and Science and Art Master, a position he subsequently resigned upon his appointment in June, 1888, to the scientific staff of the Sydney Technological Museum. Mr. Baker became Curator and Economic Botanist in 1901 in succession to J. H. Maiden, and continued in that position until his retirement in 1920. Mr. Baker became a member of this Society in 1894 and contributed twenty- eight papers to the Journal and Proceedings. Altogether he published over 100 original papers in the Journal and Proceedings of this Society as well as in the Journal and Proceedings of the Linnean Society of New South Wales. Mr. Baker’s name will always be remembered for his collaboration with the late H. G. Smith in a celebrated series of investigations into the economics of the eucalypts. The results were published in 1902 in a volume entitled ‘‘ A Research on the Eucalypts and Their Essential Oils’’. This was revised and republished as a second edition in 1920 upon the retirement of the authors from the Public Service of New South Wales. The outstanding feature of their work was a classification of the eucalypts based on the chemical characters of the essential oils derived from each species. The use of this method as an aid to the morphological classification has given valuable results and contributed greatly to our knowledge of the Australian flora. In addition, Mr. Baker was the author of a number of monographs on other groups of Australian forest plants and their economic products. He was joint author with Mr. H. G. Smith in a publication issued in 1910 entitled “‘ A Research on the Pines of Australia’, which was a further example of the successful collaboration between botanist and chemist. A number of other useful technical books were published by Mr. Baker during his career: ‘ Building and Orna- mental Stones of Australia ’’, ‘“ Cabinet Timbers of Australia ’’, “‘ The Australian Flora in Applied Art ’’ and ‘“‘ Hardwoods of Australia ’’, which latter he claimed as his magnum opus. He was the protagonist for the adoption of the waratah as our national emblem in place of the wattle. Mr. Baker occupied the position of Lecturer in Forestry to the University of Sydney from 1913 to 1924. He was a Fellow of the Linnean Society of London and served on the Council of the New South Wales Society during the period 1897 to 1922. | Mr. Baker was the recipient of several honours from scientific societies for his researches in pure and applied science. In 1921 he was awarded the Mueller Medal by the Australian Association for the Advancement of Science, and in 1922 he received the Clarke Memorial Medal of the Royal Society of New South Wales. He was an honorary member of the Pharmaceutical Societies of Great Britain and New South Wales and the College of Pharmacy, Philadelphia, United States of America. EDWARD GEORGE NOBLE, who died on 4th May, 1941, aged 76, was a life member of the Royal Society, which he had joined in 1891. He was a licensed surveyor and civil engineer. After some years in the Public Works Department, he was appointed as Assistant Engineer to Mr. Milner at Newcastle to carry out the sewerage works. At the outbreak of the last war of 1914-18, while travelling to Rabaul, the Matunga, on which he was a passenger, was seized by the raider Wolf, and Mr. Noble became a prisoner in Germany for the duration of the war. In later years he was employed at St. Andrew’s Cathedral on survey work. 6 D. P. MELLOR. PRESIDENTIAL ADDRESS. 7 Mr. Noble, who was the brother of the Rev. H. J. Noble and of M. A. Noble, the noted cricketer, left a widow and four daughters. CARL GUSTAF SUNDSTROM was elected to the Society in 1918. He was born at Norrké6ping, Sweden, in 1882, and died on the 5th July, 1941. He left Sweden at an early age and after several trips around the world settled in Australia where later, in 1913, he founded the Federal Match Co. at Alexandria, Sydney. From very small beginnings the factory now occupies five acres and is looked upon as a model industrial establishment in many respects. Mr. Sundstrém took a very active interest in the technical branch of the factory, and was a keen student of chemistry, being for many years a member of the Sydney Technical College Chemical Society. He was very energetic in the discharge of his duties and was noted for his administrative ability. His activities outside of the scientific world were numerous, and his boundless generosity made him extremely popular in these spheres. Part Il. THE STEREOCHEMISTRY OF SQUARE COMPLEXES. In the design of molecules Nature uses relatively few fundamental units of pattern or configurations, and it is naturally important to know what these are and under what circumstances any particular configuration is likely to be found. We shall here be concerned with the narrow field of stereochemistry which deals with the orientation in space of the four valence bonds of quadri- covalent elements. The tetrahedral disposition of four valence bonds about the carbon atom was the first configuration to be discovered, and so widespread did its occurrence eventually prove to be, not only among the compounds of carbon, where it was universal, but also among some forty other elements, that attention to this type of structure for long overshadowed that given to an alternative arrangement of four bonds in space, namely the square arrangement. Indeed, the tetrahedral arrangement proved to be so dominant a feature of molecular architecture that the very existence of the square pattern was, and for that matter, in some quarters, still is, a matter of controversy. Nevertheless the evidence on this question has grown steadily over the last few years and the time is opportune for some attempt to evaluate the significance of the square configuration for the stereochemistry of the metals. In attempting to do this, two main questions will be considered : firstly, how strong is the evidence for the square disposition of valence bonds, and secondly, with what elements and under what circumstances does it occur? In tracing the developments leading to the proof of square coordination, attention will be centred on the compounds of platinous platinum (Pt™), because it is with these that the most abundant and satisfactory evidence has been obtained. Notwithstanding this, there has been a good deal of controversy about the structure of platinum compounds. Some idea of the controversial nature of this field may be gathered from a few excerpts, chosen at random, from the recent literature: “‘ Platinum salts combine with an enormous number of inorganic and organic groups or molecules and many of these salts have been known for a hundred years, yet the constitution of the isomeric diammines of the type [PtA,X,] is still a subject of controversy.” (F. H. Burstall, 1938, Annual Reports of the Progress of Chemistry, p. 167.) “It is still an open question whether the experimental work (relating to planar and tetrahedral structures) has been correctly interpreted or not or whether some elements can assume more than one structure.” (J. R. Bailar, 1936, Chemical Reviews, 19, 67.) “In any event, the problem presented by these salts (certain allegedly optically active platinous salts) does not seem to be finally cleared up.” (O. K. Rice, 1940, Electronic Structure and Chemical Binding. McGraw Hill, London and New York, p. 303.) 8 D. P. MELLOR. Although in a certain sense no scientific problem is ever cleared up, I believe that the main outlines of the stereochemistry of bivalent platinum are well established, and that the above quotations, even after due allowance is made for their isolation from their context, scarcely do gue to all the experimental work which has been done in this field. The stereochemistry of carbon was developed by means of investigations essentially chemical in nature and the results of subsequently developed physical methods were often regarded as merely confirming already well established findings. In the study of platinum compounds however, physical methods have played a much more important role, partly because of their more recent development, but mainly because of certain limitations of the chemical method. Thus the burden of final proof of structure has had to be borne by a number of entirely independent chemical and physical methods of attack and it is to these we shall now turn. THE DISCOVERY OF THE SQUARE CONFIGURATION. It is not surprising that the square configuration was first discovered among the compounds of Pt", because, as we now know, no other element forms so many compounds which exhibit isomerism on account of this stereochemical characteristic. The two substances primarily concerned with the development of our knowledge in this field, namely « and 8 dichlorodiammine platinum, [Pt(NH,;),Cl,], were discovered nearly a century ago, the former by Peyrone (1845) and the latter by Reiset (1844).} The methods used in their preparation involve two similar processes ; the « compound is made by replacing two chlorine atoms of the [PtCl,]= ion with ammonia molecules, the 6B by replacing two ammonia molecules of the [Pt(NH,),]+*+ ion with chlorine atoms. The latter operation is effected either by heating solid [Pt(NH;),]Cl, under carefully controlled conditions or by treating the aqueous solution with concentrated hydrochloric acid: the former by treating K,PtCl, with aqueous ammonia . There is little doubt that each of the ale hei: proceeds stepwise : cetcl,}-- Bs ppeqH,)oL,-_ “Ps (Pt(NH,),Clel° (Pt(NH,),]++ OC : [Pt(NH,),C1]+_O (Pt(NH,),CleI° The intermediate compounds have been isolated and each step has been carried out separately. The problem of explaining the existence of the « and 8 compounds resolves itself, as a first step, into deciding whether they are (a) isomers (structural or geometrical), or (b) polymers, or (c) dimorphs. These alternatives, though not explicitly formulated by the earlier workers, can as a result of their work be narrowed down. The last was eliminated first. Cleve (1872), a very active early worker in this field, clearly established the different chemical behaviour of the « and 6 forms of [Pt(NH,),Cl,]. By treating each form with a series of reagents, including the appropriate silver salts, he prepared and described new (isomeric) compounds such as the « and 6 forms of 1 Since their discovery considerable confusion has arisen in regard to their names. They were first known as the chlorides of Peyrone and Reiset respectively and later as plato semi- diammine and platosammine chloride. In 1893 Werner introduced the terms « and 8; finally, Drew and his collaborators, for no very good reason, reversed the usage of « and 8. In this address Werner’s nomenclature will be retained. PRESIDENTIAL ADDRESS. 9 [Pt(NHs).Brz], [Pt(NH;)2I2], [Pt(NH3)o(CN )2], [Pt(N H3)2(NOs)2] and [Pt(NH3)(NOp)2]. Although this and later work leaves no doubt that the « and £ forms are not just simply different crystalline modifications of the same substance, it is interesting to note recent confirmation along physical lines. Dimorphous molecular crystals contain the same molecules packed in different ways, so that when each structure is broken down by solution in any given solvent, the resulting solutions should be identical, a point which can, for example, be tested by an examination of absorption spectra (Mellor and Morris, 1938). Small, but definite differences have been noted in the absorption spectra of the aqueous solutions of the « and 8 [Pt(NH,),Cl,] (Babayeva, 1938). There is little doubt that, had chemical and physical tests along these lines been carefully applied, many of the issues created by the announcement of an alleged third (y) form of [Pt(NH,),Cl,] (Drew, Pinkard, Wardlaw and Cox, 1932a) would have been avoided. If we make the assumption that the coordination number of Pt" is four,? and experience has shown this to be practically universal, the number of polymers of empirical composition [Pt(NH3),Cl.]x is, for x >I, limited to the following : 1. [Pt(NH,),] [PtCl,] (Magnus, 1828). 2. fPt(NH,),Cl] [Pt(NH,)Cl,] (Peyrone, 1844, 1846). 3. [Pt(NH,),] [Pt(NH,)Cl,], (Cossa, 1890). 4, [Pt(NH,);Cl], [PtCl,] (Cleve, 1872). The « and 6 diammines are distinct from all of these. Anticipating the discussion in a subsequent section, one may add that, with one rather puzzling exception, molecular weight measurements on « and 6 forms of compounds of the type [PtA,X,] (where A=NH,, Py, EtNH.,, etc., and X=Cl, Br, CNS, OH, ete.) show that both forms are monomeric. With the elimination of the possibilities (0) and (c)—polymerism and dimorphism respectively—the problem now resolves itself into deciding whether the « and 6 diammines are structural or geometrical isomers. One of the first attempts to understand their constitution was made by Cleve (1872), who proposed structures which, in the light of the then prevailing theories of valency, seemed plausible enough. They were: NH—-C1 NH— NH-Cl f 3 We 3} 5) Pt ee Cl 3 Cl A (3 Fig. 2. 2 Unless this limitation is specified it would be necessary to consider a structure like NH3 NH3 NH3 G2 ci | Ucn, ep ap Gs GD Pt ea @& @® @® cl~ | Sc1“ yp Sci | NH3 NH3 NH3 Bipael: There is, however, no evidence for this structure among any platinous compounds of empirical composition Pt(NH,) Clg. B—April 1, 1942. 10 D. P. MELLOR. . These formulations which were also supported by Blomstrand, Jorgensen and others, implied, of course, that the substances were structural isomers. With present-day knowledge of atomic structure, which enables an upper limit — to be placed on the number of covalent bonds that can be formed by first row elements of the periodic table, these structures can be ruled out immediately, since they both involve five covalent bonds to nitrogen. Ag will appear in the sequel, there are many other reasons for rejecting them. Nevertheless some attempt was made to revive them a few years ago (Drew et al., 1932a) and they are occasionally still seriously discussed in the literature. The revival was the result of an attempt to explain certain reactions of the two compounds but, without going into detail here, it can be stated that all these reactions can equally well be explained on an alternative view of their constitution. While Cleve’s formulations of the two compounds are no longer tenable, they served the very useful purpose in focusing attention on the problem of their constitution. Some fifteen years after Cleve’s work, Jorgensen (1886) set out to determine experimentally whether the assignment of the structures to the « and 6 forms as above had been correctly made or not, and in so doing he laid the experimental foundation upon which one of the most important advances in our knowledge of the structure of platinous compounds was made. This was Werner’s introduction of the hypothesis of square coordination. Rejecting all previous explanations in terms of structural isomerism, Werner (1893) applied to the problem those principles which he had so successfully used to account for the constitution of the cobaltic ammines. Realising that, unlike cobaltic ammines, which were universally characterised by a coordination number of six, the compounds of platinous platinum were always four co- ordinated,* he put forward the idea that the « and 6 diammines were geometrical isomers (cis and trans) owing their existence to a planar distribution of the four bonds about the platinum atom as in Fig. 3. ae pat i. Dain Vane > : H., Cle een NH. “ (eis) — p(trans ) Fig. 3. With regular tetrahedral bonds from platinum, two isomeric diammines are not possible. Although it would seem that Werner never at any time explicitly stated that the coplanar bonds were directed towards the corners of a square, it is clear from the diagrams of his classical 1893 paper that he considered them to be so directed. He never stressed the size of the bond angles in the plane, presumably because it was not essential in explaining the geometrical isomerism. Actually the term square coordination was first used by Pauling (1932) in connection with his quantum mechanical treatment of the directed valence bond. 3 Some probable exceptions to this statement will be referred to later. PRESIDENTIAL ADDRESS. 11 Strictly speaking any one of a number of structures would equally well account for the geometrical isomerism of the « and 6 dichlorodiammines. The four bonds from platinum might be directed towards : (1) The corners of a square or rectangle (Fig. 4 (b) and (e)). (2) The corners of a pyramid (on a square or rectangular base). Fig. 4 (d) shows the first case only. (3) The corners of a tetragonal or rhombic bisphenoid. (Fig. 4 (a) shows the tetragonal bisphenoid.) (a) (6) (ce). 4". (d) Fig. 4. Each one of these alternatives has been introduced from time to time, to explain the results of some chemical investigation. Thus the third was discussed by Rosenheim and Gerb (1933) in explaining the existence of certain Supposedly optically active platinous and palladous complexes. Under the name “ paired coordination ’’ it was also used by Drew, Pinkard, Wardlaw and Cox (19326) to account for the isomerism of certain tetrammines. The pyramidal structure (2) was suggested by Dwyer and Mellor (1934) as a means of reconciling results of experiments on mirror image and geometrical isomerism. It does not seem to have been realised before, that the results of purely chemical methods of investigation do not permit a final decision between alternatives (1), (2) and (3), and that herein lies the origin of much of the con- troversy mm this field. To decide between any of these alternatives one must have accurate information about the sizes of the platinum bond angles. Up to the present, chemical methods of investigation (study of composition, isomerism and chemical reactions, etc.) do not enable one to measure the size of these angles. This would seem an inherent limitation of the chemical method of studying molecular structure unless it is able to call on help in the shape of accurately known atomic dimensions derived from physical measurements. This limitation applies, of course, to the classical stereochemistry of carbon, but fortunately for the development of organic chemistry it has not been of great significance. For optical activity to appear in the molecule CR,R,R,R,y, all that is required is that the bonds have a general tetrahedral orientation ; there is no need for the bond R,-C-R, to be 109° 28’—it might be 150° or more. It was left to investigators using the techniques of electron diffraction and crystal analysis, etc., to show that the carbon bonds are actually directed to the corners of a regular tetrahedron. There may be very rare exceptions to the above statement of the limitations of the chemical method but none has come to light in the chemistry. of platinous compounds. In view of the impasse which thus confronts the chemical method, it would perhaps be more logical now to pass on to the physical methods of studying the problem. This course will not be followed—partly for historical reasons and partly, since the issue has been raised, to show that there is no chemical evidence that permits an unequivocal choice between the above alternatives. The verdict reached in the final summing-up of the physical evidence is that Pt™ forms square bonds, a verdict with which the chemical evidence is entirely consistent. In other words, all cases of isomerism in the sections to follow 12 D. P. MELLOR. undoubtedly originate from square bonding, and while this is assumed, through- out it will be seen that any one or other of the three alternatives might equally well have applied. GEOMETRICAL ISOMERISM. THE DETERMINATION OF THE CONFIGURATION OF THE DIAMMINES. Having decided that the « and 6 diammines were geometrical isomers, Werner went a step further and by very ingenious reasoning determined which of the two forms was cis and which trans. The reactions concerned (Jorgensen, 1886) may be summarised under two headings : 1. Addition Reactions. When treated with two molecules of pyridine, « dichlorodiammineplatinum forms « diamminedipyridineplatinous chloride. This latter compound can also be prepared by treating « dichlorodipyridineplatinum with two molecules of ammonia : eee Cl 5) + oe eee ee C15 |', ee (1) A [Pt(Py), Cl] + te ane, of Similar reactions are observed with 8 dichlorodiammineplatinum : [Pt (NH, iB Gu a4 + 2Py a eas: [Pt(Py), Cl] + 2NH, ‘erica a ] Cig’ eee (2) \ 2. Hlimination Reactions.* By heating the solids alone or by warming aqueous solutions with concen- trated hydrochloric acid, the « and @ tetrammines revert to the dichloro- diammines. Thus a dipyridinediammineplatinous chloride, when heated, reverts to $ dichloropyridineammineplatinum : [Pt(NH,).(Py), |Cl,—— ate (Py)Cl,]+-NH,+Py ........ (3) 4 On the other hand, 8 dipyridinediammineplatinous chloride gives rise to a mixture of 8 dichlorodiammine and 6 dichlorodipyridineplatinum pierre ks C1, ] [Pt(NH3)5(Py)o) Cig: (2 ~2NH \ /? 4 These reactions might also be called substitution reactions if we regard them from the point of view of the complex ion only. The names have been used in reference to the molecules as a whole. sy ao PRESIDENTIAL ADDRESS. 1g} The last reaction has been queried by Reihlen and Nestlé (1926), but the experimental work of Jorgensen (1886) and Drew et al. (19326) shows that the reaction which takes place is the one formulated. The products were separated by fractional crystallisation and identified by preparing distinctive derivatives. All other addition and elimination reactions have been checked by Drew et al., who used them, not to confirm Werner’s hypothesis, but as a basis for the hypothesis of paired coordination links. Suffice it to say that the experimental foundation upon which Werner built his “‘ configuration determination ’’ has stood the test of time. Whereas Jorgensen was forced to introduce several arbitrary assumptions to account for the above reactions in terms of structural isomerism, Werner was able to account for them in a perfectly straightforward manner with the help of only one further assumption, viz. “‘ trans elimination’. Werner pictured reactions (1) to (4) as proceeding in the following manner (Fig. 5) : Py pl x Ve avers) QNEs Py Cl on Se aN he A (trans) Pt 5 Fig. 5. In attributing the cis structure to the « compound and the trans structure to the 6 as above, Werner’s final conclusions have been anticipated. His argument in support of this assignment is based on the assumption that, in the 14 D. P. MELLOR. course of the elimination reactions, pairs of groups in trans positions only are removed. The results of trans elimination are made clear in the following diagrams where the dotted lines enclose the eliminated trans pairs (Fig. 6). Fig. 6. An examination of the structure of « (cis) dipyridinediammine platinous chloride will show that elimination of pairs of cis groups should result in the formation of a mixture of three compounds, viz. [Pt(NH,),Cl,], [Pt(Py),Cl] and [Pt(Py)(NH,)Cl,], whereas actually only one, the last, is obtained. On the other hand, cis elimination from the 6 (trans) dipyridinediammine complex should result in the formation of only one compound, viz. [Pt(Py)(NH;)Cl,]; actually two are found: [Pt(Py),Cl,] and [Pt(NH,),Cl,]. If we accept the hypothesis of trans elimination, all the reactions find consistent interpretation in terms of a cis structure for « and a trans structure for 8B [Pt(NH,),Cl,]. Such then is the experimental foundation upon which Werner, duly acknow- ledging his debt to Jorgensen, built the planar hypothesis. Yet nearly forty years later when reviewing this question, Angell, Drew and Wardlaw (1930) remarked : ‘‘ Werner, ignoring the relevant chemical evidence of his predecessors, (sic.) attributed the isomerism to the presence of cis and trans planar types in which platinum exhibited four coordination.”’ Perhaps the chief weakness in the interpretation of the elimination reactions is that at one stage (elimination from the « (cis) [Pt(Py)s(NH:;),|Cl,) it depends on a negative result—failure to find more than one compound. It is a striking tribute to Werner’s remarkable insight into the structure of coordination com- pounds that all subsequent determinations of the configuration of « and B dichlorodiammine platinum have proved the correctness of his assignment of PRESIDENTIAL ADDRESS. 15 cis and trans structures, and at the same time justified his hypothesis of trans elimination—at least for these reactions. FURTHER CHEMICAL EVIDENCE CONFIRMING WERNER’S ALLOCATION OF CONFIGURATIONS. With the exception of results from dipole moment studies and from one or two incomplete X-ray crystal analyses, confirmation of Werner’s work has been obtained along chemical lines. | In the course of extensive investigations of “‘ ammoniacal platinum bases ”’ Cleve (1872) reported a very interesting difference in the behaviour of « and 6 [Pt(NH,).(NO 3),] towards oxalic acid solution: the « form was converted to a compound with the empirical composition [Pt(NH,;),.C,0,]; the @ to a com- pound [Pt(NH3).(C,0,H),]. Some sixty years later Grtinberg (1931) confirmed these observations and first suggested their interpretation. In doing so he made use of a method developed by Werner in his study of cis-trans configurations among the octahedral complexes of Com. Thus Grtinberg proceeded on the assumption that the C,0,= group acted as a bidentate chelate only when it replaced two NO, groups in cis positions ; when it replaced NO, groups in trans positions the oxalic acid molecule occupied one coordination position. It is clearly sterically impossible for the C,0,= group to span trans positions if square bonding is to be maintained.® Since the oxalate group enters the « [Pt(NH;).(NO,),] as a bidentate chelate, this form obviously has the cis configuration. Now [Pt(NH,),NO,] RAs cl pHs 0o-C# se Ve HC] | aN VA Ae NH 0.CO0.Co,0H Cl NH3 HOO C.C.0 0 NHs Fig. 7A. > The existence of the so-called trans PtPy,SO, would seem to be an exception to this state- ment. The compound is, however, a dihydrate and is probably [PtPy,(H.O),]SO,. 16 D. P. MELLOR. is prepared by treating corresponding («) chloro compound with silver nitrate, and if it be assumed that the substitution of NO, for Cl occurs without change of configuration, then «[Pt(NH,),Cl,] must also be a cis form, in agreement with Werner’s contention. That no change of configuration does occur is shown by the behaviour of the oxalate compounds towards hydrochloric acid: the oxalate compound made from cis [Pt(NH5),(NO;),] regenerates cis [Pt(NH,),Cl,] while the second oxalate compound regenerates the trans dichloro compound. These reactions may be represented schematically (Fig. 7A). A very similar cycle of reactions has been carried out with « (cis) [PtPy,Cl, ] (Drew, Pinkard, Wardlaw and Cox, 1932a) (Fig. 7B). [Pt Pyo( 0H)g] Holo, pred CSAC A [Pepyecisicay Jel Tae 1:-79 > —0:-137 fie (Pipe NELChI ine ? 1-624 1-732 | >1-79 > —0-166 Ri ECCL@ sa 1,05) 0) 0) imenecunicl <1-627 Me 1-717 | >—0-090 NH, [PtCl,C,H,]H,0* .. | Monoclinic. <1-623 ay 1-702 | >? 0-079 Na,[Pt(CN oH O87...) Drchnuic: -— a — High and negative. Sr[Pt(CN),]5H,0,” .. | Monoclinic. 1-547 1-613 1-637 — 0-090 K,[Pt(COS),J8 ve .. | Monoclinic. — — — Extremely high. 1 Mellor and Quodling, 1935. THis JOURNAL, 69, 167. 2 Winchell. ‘‘ The Optic and Microscopic Character of Artificial Minerals ’’, No. 4, p. 15. Univ. Wisconsin Studies in Science, 1475. 3 Gaubert, 1917. Bull. Soc. Fr. Min., 40, 177. 4Winchell. Jbid., p. 20. 5 Gelman, 1939. C.R. Acad. Sc. U.R.S.S., 22, 107. 6 Jorgensen, 1900. Z. anorg. Chem., 24, 153. ? Brasseur and de Rassenfosse. Mem. Acad. Roy. Belg., 16, 1. 8 Cox, Wardlaw and Webster, 1935. J. Chem. Soc., 1475. ® Brasseur and de Rassenfosse. Jbid., 1941 [2], 4, 397. is conceivable that a very low double refraction could be produced. Thus, while high double refraction undoubtedly indicates the presence of highly anisotropic units in a structure, low double refraction does not necessarily mean that such units are absent. In this connection another situation which may arise must be kept in mind. Double refraction is subject to dispersion, that is, it varies with wave length and one may just happen to choose, for making a measurement, a wave length where the double refraction is low or at a minimum. This point is well brought out in Brasseur and Rassenfosse’s recent (1937 and 1941) extensive studies of the crystal optics of a whole series of complex cyanides of the types Ba[Me(CN),]4H,O, CaMe(CN),5H,O, Sr[Me(CN),]4H,O and Na,[Me(CN),]3H,O where Me=Pt, Pd and Ni. Without exception, these substances show high double refraction, and for all except three, BaPt(CN),4H.O, Mg[Pt(CN),]7H,O and Ca[Pt(CN),]5H,O, the sign of the double refraction is negative. A complete crystal structure analysis of BaNi(CN),4H,O reveals a structure which accords with high negative double refraction. The positive sign of the isomorphous platinum compound is an extremely puzzling anomaly for which no explanation has yet been given. There is little doubt about the observations on the positive sign since the same results have been reported by several workers. It would seem that Bragg’s theory of the origin of double PRESIDENTIAL ADDRESS. 31 refraction of planar complexes needs further refinement if it is to take account of these platinum compounds. Magnetic Anisotropy. Practically nothing has been done on the diamagnetic properties of platinous compounds, but it can reasonably be expected that like CaCO,, NaNO,, etc., they will show pronounced anisotropy. Some very early observations on Ca[Pt(CN),]5H,O were made by Grailich (1858), who reported that the direction of greatest diamagnetic susceptibility is parallel to the “‘c ”’ axis of the (ortho- rhombic) crystal. This would place the plane of the [Pt(CN),] group approxi- mately perpendicular to the “‘c”’ axis, whereas the optical properties suggest a different orientation. The crystal optics of the isomorphous nickel compound, Ba[Ni(CN), ]4H,O, place the plane of the [Ni(CN),] group approximately parallel to the “ c ’’ axis in qualitative agreement with the observations on the diamagnetic anisotropy of the platinum compound. Further work, possibly along the lines of that of Born (1923) and Hylleraas (1927) on quartz and calomel, is needed to clear up the anomalous behaviour of these platinum compounds. SoME REACTIONS OF SQUARE COMPLEXES. Trans Elimination. In the light of the crystal structure determinations of K,PtCl, and [Pt(NH,),]|C],H,O it is of interest to note at this stage certain features of the reactions involved in the formation of the isomeric diammines. The most important of these is the process of trans elimination discovered by Werner. So far little has been done towards providing a satisfactory understanding of this phenomenon, and all that will be attempted here will be to formulate some of the problems that arise. At the outset it is obvious that trans elimination cannot be a perfectly general reaction, because although it provides an explana- tion of some of the transformations, cis elimination must be invoked to explain others. | Let us consider first the reaction responsible for the discovery of trans elimination 2HCl [Pt(N Hs) 4]** _, [Pt(NHs),Cl, | trans If we regard the elimination of the two molecules of ammonia as occurring simultaneously, we might suppose that as the two trans molecules depart two chlorine atoms enter the trans octahedral positions to form a new trans square complex, as shown in the accompanying diagram. Cl Fig. 19. 32 D. P. MELLOR. But matters are not so simple as this. As already pointed out, the two reactions below proceed stepwise : (Pt(wH,),J++_S petaw,),c1y+_ [POON HL) NH NH, [PtCl,]}- tc PCN Chin _, [Pt(NH,),Cle] (og If the complexes were tetrahedral it would be impossible to account for the two different end products of these reactions. Let us imagine we have a square complex A Alig ey, ae — into which another X is to be substituted for one of the A’s. In what circum- stances does the first X group direct the second one entering, to the cis position as in [PtNH,Cl,]- or to the trans position as in [Pt(NH3),Cl]+? At first sight it might seem as though X groups are trans directing when present in cationic complexes. Pinkard, Saenger and Wardlaw (1933) have studied very thoroughly the elimination reactions occurring with tetrammines containing ammonia, pyridine and hydroxylamine, and in every instance the reaction indicates trans elimination. (See Fig. 20.) It will be seen that no other X group than Cl was investigated, and as far as the author is aware no systematic work has been done on this point. In this connection the behaviour of certain nitro palladium compounds is worthy of note. From the evidence available (Mann et al., 1935b) it would seem that NO,- group is cis directed when it enters the complex [Pd(NH,),NO,]* and trans directed when it enters the complex [Pd(NH,)(NO,),]-, which is just the opposite of the behaviour of chlorine in the above platinum complexes. Two examples will suffice to show that the charge on the complex as a whole is not the factor determining directive influences. When [Pt(NH,).dipy ]Cl, is treated with hydrochloric acid, the cis ammonia molecules are eliminated. This is perhaps hardly a fair test case because if ammonia molecules are to be eliminated there is no choice, but cis elimination. A more convincing case is the one discovered by Jensen (1935a) who, in the course of his dipole moment investigations, found that when an aqueous solution of K,PtCl, is treated with four molecules of triethylphosphine, a colourless solution of [PtP(C,H;), ,]Cl is formed. This solution on standing deposits cis [Pt(P(C,H;)3),Cl,] (u=10-7 D) and the only way this latter substance can be formed is by cis elimination from [PtP(C,H,)s 4]Cl,. Cis Elimination. The reaction between ammonia and the [PtCl,]= ion seems typical of many amines. Cis elimination from this ion is known to occur with ethylamine, pyridine, hydroxylamine, aniline, etc., but again the reaction is not a perfectly general one. Some very interesting work in this field has been published by Tscherniaev and his school (Tscherniaev and Gelman, 1936; Gelman and Bauman, 1938). One of their most important findings is that order of substitu- tion plays an important part in some complexes. Thus it was found that when ethylene is passed through OCossa’s_ potassium salt, K[Pt(NH;)Cl,], cis [Pt(NH;)(C,H,)Cl,] is formed. On reversing the order of introduction of the PRESIDENTIAL ADDRESS. 33 [aH Py Py of a HCl NS va a t > a NHz + NH50H Nu T 2NH20H Pt NHj0H + NHs Cl NH50!} NH20H NHoOH NHoOH Cl NH50H Cl ~ Va HCl yi Pt SSS vy Pt NH20H Py [oi P cl NH=0 Fig. 20. groups, i.e. by treating Zeise’s salt, K[PtC,H,Cl,], with ammonia trans [Pt(NH;)(C,H,)Cl,] is formed. Similar behaviour was observed on substituting carbon monoxide for ethylene but the effects of ordered substitution are confined to unsaturated substances like ethylene and carbon monoxide. It does not, for example, make any difference whether K[PtPyCl,] is treated with ammonia or K{[Pt(NH,)Cl,] with pyridine, cis [PtPy(NH,)Cl,] is the result. These instances are sufficient to show that the directive influences in substitution in Square complexes present an interesting problem for the theoretical chemist. THE UNIVERSALITY OF THE SQUARE STRUCTURE AMONG PLATINOUS COMPOUNDS. It now remains to consider whether the square structure is universal among Pt® compounds and as characteristic of that atom as the tetrahedral structure is of carbon. The cases put to the test in physical investigation are necessarily few in number. As there is now no doubt about the origin of the geometrical isomerism, a better idea of the extent of the occurrence of the square structure can be gained from a brief survey of isomeric forms. Final warrant for extra- polating to cover all platinous compounds will be found in the quantum theory of the directed valence bond. D—April 1, 1942. 34 D. P. MELLOR. Varieties of Isomeric Square Complexes. It is a simple matter to draw up a scheme showing the types of isomeric complexes which are possible on the assumption that Pt! is square coordinated, and it is interesting to see how far these possibilities have been realised in practice. At the same time the scheme will give some idea of the complexity introduced into the chemistry of Pt® by its habit of forming square bonds. All finite mononuclear complexes of quadricovalent Pt must fall into one or other of these classes : (a) [PtA,]** (b) [PtA,X ]* (c) [PtA,X,]° (d) [PtAX,]- (e) [PtX,4}- In the scheme adopted the following symbols have been used : (1) A, B, ©, etec., to represent neutral molecules, e.g. NH;, C;H;N, NH,OH, N.H,, MeNH,, EtNH,, AsCl,, P(CH3)3,, Et.S, ete. (2) A~~B to represent an unsymmetrical bidentate chelate group attached by two coordinate links, e.g. isobutylenediamine. (3) A~~Z to represent an unsymmetrical chelate group attached by a coordi- nation link and one primary link, e.g. glycine. (4) X, Y¥, Z... ete., to represent a negatively charged atom or group such as Cl-, CN-, NO,-, OH-, ete. Class A. Non-Electrolyte or Uncharged Complexes. A DT i A D.C by A vy A Bae Pt Pt Pt Pt xX A A x x B xX x +, a Ay 2 As, & A 50) AA: OE ea Bic A Yoo. Bi Pt Pt Pt Pt Pt x A X ¥ xX ii xX B Y xX ESE Se a, ee As, Ax, 8) PNG Re WA Pa ae un A ain seein Al eae Pt Pt Pt Pt A Y ‘Yt A DS ali A Ze I nd he Ajo 11 | Ajay 18 Haamples. Ayo : cis and trans [Pt(NH;),Cl, A3s,4 : cis and trans [Pt(NH;)(Py)Cl,] (Jorgensen, 1866). As,g : cis and trans [Pt(NH,).(NO,)OH ]. 5 [Pt(C,H;).S(C,H;),Sel, Cl] (Petren, 1898). Aiov1, : No examples known. Ayes ig: [Pt(NH,.CH,.COOQO),] (Grunberg and Ptizyn, 1933). Numerous examples of classes A,, , and B,, , have been described throughout the literature. On a rough estimate there must be several hundred examples of isomeric forms of all kinds. The most comprehensive lists are to be found in ‘‘ A Comprehensive Treatise on Inorganic and Theoretical Chemistry ’’, Vol. 16, 1937, J. W. Mellor, Longman and Green, London, and in ‘“ Handbuch der anorganische Chemie’, Bd. 5, Teil 3, Gmelin and Kraut, Heidelberg. All Ip] PRESIDENTIAL ADDRESS. 35 allegedly isomeric forms in excess of those required by the hypothesis of square coordination have been shown to be either impure or forms or dimorphs. (Jensen, 19350.) Class B. Divalent Cationic Complexes. A A]tt+ A Bl++ A C]++ A Alt+ Pt Pt Pt Pt B B B A B A B C +, —/ I EY B,, 2 Bs, 4 eee fA. Oy TA By A BI+ A > B]t+ Pt Pt Pt Pt Pt Se ann 6 ieee De he A scale Be aA Bs, 6) 7 Bg, ona TA: ie B aan A wae BB rletcy A Lae: Beige: A aa B +--+ Pt Pt Pt Pt Gaye | D Dia C D D C Le TT Bio, 11 By, 13 B,,. : cis and trans [Pt(NH,),Py).]** (Jorgensen, 1866). Bs, 5 : cis and trans [Pt(NH, . C(CH;), . CH,NH,),]t* (Drew and Head, 1934). Bio 2 «cis and trans [Pt(NH,. CH, . CH, . C,H; . NH,)(C,.H,.N .CH,NH,) }* + (Reihlen, Seipel and Weinbrenner, 1935). Bie: cis and trans [Pt(NH.)(C,H, . NH,)(NH, . C(CH,), . CH,NH,)|*~ (Drew and Head, 1934). Class C, Monovalent Cationic Complexes. A Alt A Bit A iis B Cit C Byt Pt Pt Pt Pt Pt B X xX A C X A x A X ee on C,, 2 Cs, 4) 5 0 ies wi lg A eae Mesa ct Ne AD oe Pb Rt Pt Pt C xX xX C B © © B sO ———_ ———(Y Ce, 7 Cg 9 Hzamples. Ci, : cis and trans [Pt(NH,).(NH,OH)NO,]+ (Tscherniaev, 1926, 1928). Cs, 4,5: three isomers of [Pt(NH,;)(Py)(NH,OH)NO,]* (Tscherniaev, 1926, 1928). No examples of the other classes are known. A classification along the same lines could be drawn up for anionic classes of the types: PtX,Y,-, PtX,YZ-....PtAXYZ-, PtAX,Y-, etc., but as only 14 Groups other than uni and bidentate have been omitted from this scheme. 36 D. P. MELLOR. one case of isomerism appears to have been recorded among these compounds, and as the classification would simply repeat much of that already given, the scheme will not be pursued further. The discovery of two forms (Riabtchikov, 1940) of Fig. 21A. would seem to make it worth while reinvestigating substances like K,Pt(NO,),I., (Nilson, 1886) and K,Pt(NO,),C,0, (Vezes, 1903). The scarcity of isomeric forms may well be due to the fact that it is more difficult to make the appropriate substitutions in anionic complexes. No attempt has been made to draw up a scheme for isomeric polynuclear compounds, mainly because no single example of isomerism has yet been found even among those of the simplest type like Ie An ve ao Pt (Anderson, 1934), Jensen (1935) and others). More complex cl Jon A polynuclear forms with correspondingly increased possibilities of isomerism are conceivable, but there is practically no evidence for them to date. In this regard certain cyano compounds would probably repay investigation. For example the composition of one of them described long ago by Cleve (1872), namely [PtNH,(CN).|x, suggests that it may have the structure N I | NH, C | | N=C—Pt—N =C-—Pt—NH, | | C N II il N C | | NH,—Pt—C =N-—Pt—C=N | NH, | N Fig. 21B. THEORETICAL EVIDENCE. By the application of general quantum mechanical principles to the problem of the orientation of chemical bonds Pauling (1931) has, on the basis of a single PRESIDENTIAL ADDRESS. ot postulate,!> derived a large number of results of great stereochemical interest. It is perhaps no serious test of the theory of the directed bond that it predicts the square bonding of Pt", although the general evidence for this latter was not so strong at that time (1931). Nor should it be implied that support for the quantum mechanical theory of the directed bond comes only from the experi- mental results dealing with quadricovalent elements. It is, however, necessary to restrict the discussion here to the deductions of the theory relating to such elements. The relevant rules are these : (1) Square bonds will be formed whenever dsp? orbitals are involved in bond formation. (2) Tetrahedral bonds will be formed whenever sp? orbitals are involved in bond formation. Any atom whose structure is such as will permit the use of dsp? orbitals, that is any atom with a vacant d orbital just within its valence shell, will form square, rather than tetrahedral bonds, because by so doing a more stable structure will result. The electronic structure of Pt™ fulfils just these conditions. From the numerous examples of planar structure already dealt with, and from the above rule, it is a fair inference to conclude that square bonding is as universal among platinous compounds as tetrahedral bonding is among carbon compounds. Non-Planar Structures. Such an inference does, however, require several qualifications. Firstly the above bonding rules refer only to electron pair or covalent bonds. If the difference between the electronegativities of the atoms is sufficiently large they may be held together by predominantly ionic tetrahedral bonds which do not involve pairing of electrons as in covalent bond formation. The mere fact of an atom forming square bonds shows that the bonds are covalent, since the configuration of minimum potential energy for four ionic bonds is the tetrahedral one. As will be discussed more fully in the sequel, the magnetic criterion may be used to distinguish between the two bond types. If Pt formed ionic bonds, i.e. if platinum existed as the Ptt+ ion in any of its com- pounds, these should be paramagnetic with susceptibilities corresponding to the presence of two unpaired electron spins. As a matter of actual experience all platinous compounds examined to date have proved to be diamagnetic, from which we can infer that platinum does not exist in the ionic condition in any of these compounds. About the only likely compounds in which Ptt+ might be found are those with fluorine, the most electronegative of all elements, but very little is known of such compounds. The few referred to in the literature (Mellor, J. W., 1937) are by no means well defined, and in no case has any magnetic work been done on them. Nevertheless this possible exception to the general rule must be borne in mind. Secondly the bonding rules refer only to compounds in which Pt" has a coordination number four. While this number seems almost universal, there are one or two rare but well authenticated cases where it rises to six. So far the proofs are chemical, and some useful work remains to be done in checking the chemical findings by crystal structure analyses or by some other means. There are at least two compounds in which the chemical evidence for a coordina- 15 “ Of two orbitals in an atom the one which can overlap more with an orbital of another atom will form the stronger bond with that atom and moreover, the bond formed by a given orbital will tend to be in that direction in which the orbital is concentrated ”’ (Pauling, 1939). Another way of putting this is to say that “‘ the bond energy is lowest and the bond conse- quently most stable, if there is as much overlapping as possible between the wave function or orbital of a given electron and that of the electron with which it is paired and as little as possible between it and those of all other electrons on other atoms ”’ (Rice, 1940). 38 _ D. P. MELLOR. tion number six is strong: the platinous bis «#y-triaminopropane complex (Mann and Pope, 1926a ; Mann, 1929) and cis and trans bisacetonitrile tetram- mine platinous chloride (Tschugaeff, 1915). There may be other instances, but they are rare and certainly do not include substances like [Pt(NH;), Cl, to which Hantzsch and Rosenblatt (1930) have attributed an octahedral structure. Crystal structure evidence on this last substance is quite definitely against octahedral coordination. Finally, it must be emphasised that the quantum mechanical rules relating to the directed chemical bond refer only to bonds free to arrange and that where this condition obtains the bond angles found are very close to those required by theory. Thus electron diffraction studies show that in methylene chloride, chloroform, propane, isobutane and other such molecules the angles between single bonds to carbon are from 109° to 112°, close to the tetrahedral value of 109° 28’. Yet there is not the slightest doubt that in cyclopropane the angles between single bonds to carbon are 60°. Permanent bond angle distortions inherent in the configuration adopted by a molecule are by no means rare (Mellor, 1940) and must be allowed for in discussing the stereochemistry of platinum. Crystal structure analyses reveal bond angles of 90° in K,PtCl,, Pt(NH,),Cl,, etc., but there may well arise instances where, under duress, as it were, such large bond angle distortions may be produced as to alter completely the symmetry of a complex. Two examples of what may be called “ forced configurations ’’ will be considered here. The first is the compound 66’8” triaminotriethylamine platinous chloride described by Mann and Pope (1926)). If platinum is regarded as having a coordination number four, then it is sterically impossible for it to be square coordinated here. (See Fig. 22.) @ NH, TaN Gas Platinum might conceivably be octahedrally coordinated in this compound but without a crystal analysis it is difficult to eliminate this possibility with any degree of certainty. The same objection does not apply to compounds con- taining bis - 3: 3’:5:5’ - tetramethyl - 4:4’ - dicarbethoxydipyrromethene (Fig. 23A). PRESIDENTIAL ADDRESS. 39 CH ie H is aos ae a Fig. 23A. Porter has shown that if this substituted pyrromethene, with methyl groups in the « positions, functions as a bidentate chelate group, and the evidence is that with many metals it does, then any attempt on the part of the chelate to assume a planar configuration is prevented by steric hindrance. The « methyl groups (asterisked in Fig. 234) must clash. The clashing is more serious than might be gathered from Fig. 234. In redrawing it with the appropriate dimen- sions (Fig. 23B) the extent of the overlapping of the methyl groups is indicated by horizontal shading. It should be pointed out that, owing to resonance in the pyrrole ring, the « methyl groups and the ring would normally be coplanar. 40 D. P. MELLOR. Under stress the methyl groups might be bent to some small extent out of the plane of the pyrrole ring, but because of the large van der Waal’s radius of the methyl group, 2 A.U., no amount of distortion of the C-CH, could accommodate chelating dipyrromethene groups in square coordinated positions. By assuming that the methyl groups remain in the plane of the pyrrole rings, and that all the distortion occurs in the Me-N bonds, a rough calculation shows that the distortion amounts to about 40° (Mellor and Craig, 1940a). Although quite a number of metal derivatives of this di-pyrromethene have been described, curiously enough the platinum derivative does not appear among them. However the palladium compound has been prepared (Porter, 1938 ; Mellor and Lockwood, 1940), and there is little doubt that platinum can also form a compound. INCIDENCE OF THE SQUARE CONFIGURATION AMONG OTHER METALLIC COMPLEXES. The metals for which square coordination is theoretically possible are those whose electronic structures permit the use of dsp? orbitals in bond formation, that is to say, those which have a vacant d orbital within the valence shell. The elements which fulfil this condition are confined to the three transition series of the periodic table. Table 4, drawn up primarily (Pauling and Huggins, 1934) to show the magnetic moments predicted for the transition elements in different stereochemical configurations, will be used as a basis for discussion. TABLE 4. Predicted Magnetic Moments of Complexes Containing Transition Elements. No. of |For ionic | | electrons; or sp? For 4 For 6 The Iron The Palladium | The Platinum in d shell) (tetra- dsp? d?sp$ | Group. Group. | Group. (3d, 4d | hedral) | (square) | (octahedral) | | or 5d). | bonds. | bonds. bonds. | | | 1 | KiCalScWITilV | RbiSrITYWQrIVNbVMoVI | CsIBal_HfIVTaVWVI On, | 0-60 0-00 0:00 2 | vIV NbIVMoV wv ee a= 1:73 3 | VIICrIV MoIVRuVI | WIVOsvI 2 | 9-83 | (a3 |) Sores 4 | VUCriuniv Moll 3 3-88 | 3-88 3-88 5 | CriMnitrelv | MolRulv | OsIV 4 4-9 4-9 2-83 6 | MnllFellICoIV Rulll | OstIlIrIV | 5 5-91 3°88 17/83 7 | FellColll RullRhUIPdIv TrllIPtiv 6 4-90 2°83 0-00 8 | ColINiIN Rbl | ; 7 3-88 | 1-73 9 | Nill | RhIPdIAgIl | PtlTAulll 8 2-83 0-00 10 | Cull | Agi 9 1-73 11 | CulZWGelv AgiCdUIniW | AULHgITUINPpIVBV 10 0-00 | | This table is taken (modified) from the paper by L. Pauling and M. L. Huggins, Zeit. fiir Krist., 87, 1934, 214. It should be explained that the magnetic dipole moment of an atom arises from the existence in it of unpaired electron spins : the magnitude of the moment, in Bohr magnetons, the units employed in the table, is given by the ° / we . . e * . expression 4 = Vn(n+2), where n is the number of unpaired spins. For diamagnetic substances n=0. Several interesting features of Table 4 call for comment. In the first place it will be seen that the magnetic distinction between ionic, tetrahedral, and Square coordination can be made only with elements in horizontal rows 6, 7, 8 and 9. Secondly, although square coordination is theoretically possible with any element of the three transition series it has actually been found with very few (shown in heavy type), and these are confined to the relatively small portion PRESIDENTIAL ADDRESS. 4] of the table marked off with a heavy line. It is significant that the square structure is most common among elements with 0 or 1 unpaired electrons (Pt®, Pdu, Aut, Nit, Cot, Cut, Ag"), very rare or doubtful among those with 2 or 3 (Fett, Mn"), and as far as is known non-existent among those with the maximum number possible, four. The numbers of unpaired electrons just quoted refer of course to the different atoms in the square coordinated condition. The same tendency to assume configurations with small numbers of unpaired electrons is to be seen among the diamagnetic complexes of Cot!, Ptvl® Pdi’, and Ir”, which are invariably octahedral. These observations may be summarised in a general rule which states that, when a metal atom of the transition series forms a covalent complex, it tends to assume that configuration (tetrahedral, square, octahedral, etc.) which involves the least possible number of unpaired electrons. The usefulness of a theory is determined largely by the extent to which its predictions check satisfactorily with experiment. In this respect the quantum theory of the directed valence bond has fared well. For example, it predicted (Pauling, 1931)" that the diamagnetic complexes of Ni# and Aul™ would have the square structure ; in both instances crystal analyses and other investigations have amply borne this out. ‘Where definite evidence for square coordination has been found for any element it may be assumed that it will be found in this condition generally, unless (1) the element is octahedrally coordinated, (2) steric effects cause bond angle distortion, (3) marked electronegativity differences produce predominantly ionic (tetrahedral) binding. It is true that some elements, notably Fe™ and Mn, are so very sensitive to this last factor that they are seldom square coordinated. On the other hand the above provisos rarely have to be invoked for Pt®, Pd, Cum and Aut, SQUARE COMPLEX FORMATION WITH METALS OTHER THAN PLATINUM. Palladium. This element resembles platinum very closely except in one respect. Neither the geometrical nor the optical isomers of Pd! retain their configurations with the same tenacity as those of Pt. Geometrical isomerism is confined, so far as the observations go, to neutral complexes. In summarising the evidence for this and the metals to follow, the nature of the investigation will first be indicated and then the compound in which the square structure has been found. Crystal Structure—K,PdCl, (Dickinson, 1922; Theilacker, 1937), PdO (Lunde, 1927), [Pd(NH3),|Cl, (Dickinson, 1934), K,[/Pd(COS),] (Cox, Wardlaw and Webster, 1935d), (Me,S)PdCl, (Cox, Saenger and Wardlaw, 1934), PdS (Gaskell, 1937), PdCl, (Wells, 1938), (Me,As),Pd,Br, (Mann and Wells, 1938), [(NH,;),PdC,0,] (Mann, Crowfoot, Gattiker and Wooster, 19350). Geometrical Isomerism.—Cis and trans forms of benzylmethylglyoxime palladium (Dwyer and Mellor, 1935), cis and trans bis-glycine-palladium (Pinkard, Sharratt and Wardlaw and Cox, 1934), cis and trans dichlorodiammine palladium (Grunberg and Schulman, 1933), cis and trans [(NH;),Pd(NO,),] (Mann et al., 1935b). : 16 If the results of the incomplete X-ray study (Cox and Webster, 1935a) of Pt(CH;),Cl are correct, this compound should have a magnetic moment of 4:9 Bohr magnetons, which, in view of the data so far available for platinum compounds, is very unlikely. Platinum is most likely octahedrally coordinated in this compound as in Pt(CH,), (Pauling, 1940). 17 At the time this prediction was made the observation that bis methylgloxime nickel exists in two forms (Tschugaeff, 1910) which might reasonably be cis-trans planar isomerides appears to have been overlooked. In any case, magnetic susceptibilities of nickel glyoxime complexes ae not investigated until 1932 (Sugden), when further instances of isomerism were brought to light. 42 D. P. MELLOR. Optical Isomerism.—Isobutylenediaminestilbenediamine palladous salts (Lidstone and Mills, 1939). Dipole Moments.—PdCl,(AsR 3). (Mann and Purdie, 1935a), PdCl,(Et,Sb), (Jensen, 1956a). Crystal Optics.—K,PdCl, (Mellor and Quodling, 1935), BaPd(CN),4H,O, etc. (Brasseur and de Rassenfosse, 1937). Magnetic Susceptibilities—K,PdCl,, etc. (Janes, 1935). Nickel. This is the first element so far considered for which there is evidence of both the square and tetrahedral configuration, although it must be admitted that the evidence for the latter is as yet rather meagre. Except in one instance, geometrical isomerism is confined to internal complexes and is not specially common even here. From some preliminary work on the factors which determine whether nickel shall be square or tetrahedrally coordinated it would seem that electronegative differences between nickel and the atoms linked to it play a major role (Mellor and Craig, 1940). There is also evidence that extensive deflection of bond directions, which, in the absence of steric influences would be expected to assume the square orientation, results in a marked change bond character (Mellor and Lockwood, 1940). Paramagnetic and diamagnetic nickel compounds lend themselves to studies on correlations between bond character and absorption spectra and one or two interesting results in this connection have already been reported (Mills and Mellor, 1942). A notable characteristic of diamagnetic nickel compounds is their marked resistance to assuming sixfold coordination. Paramagnetic nickel complexes with a coordination number four, on the other hand, quite readily take up two additional groups to assume the octahedral configuration (Dwyer and Mellor, 1941). It is very interesting to note a similar kind of behaviour in ionic Fe! com- plexes with coordination number four (ferrohemoglobin, etc.), where the change to a diamagnetic octahedral covalent Fe" complex can be readily brought about. The metals which easily form square bonds could not well play the same role as Fe™ in the blood pigments. Crystal Structure.-—K,[Ni(COS),] (Cox, Wardlaw and Webster, 1935d; Elliott, 1938), Ba[Ni(CN),]4H,O (Brasseur and de _ Rassenfosse, 1938), Na,[Ni(CN),]3H,O (Brasseur and de Rassenfosse, 1941), bis N-N’-dipropyl- dithiocarbamate-nickel (Peyronel, 1941). Geometrical Isomerism.—Bis-methylglyoxime nickel (Tschugaeff, 1910), bis benzylmethylglyoxime (Sugden, 1932), bis thiosemicarbazide nickelous sulphate (Jensen, 1936b). Dipole Moments.—[NiBr,(Et,;P),] (u=0) and related compounds (Jensen, 1936a), nickel glyoximes (Cavell and Sugden, 1935). Crystal Optics.—K,[Ni(CN),] (Mellor and Quodling, 1936), Ba[Ni(CN),, etc. (Brasseur and de Rassenfosse, 1937). Magnetic Susceptibilities—Nickel ethyldithiocarbonate, etc. (Cambi and Szego, 1931), a wide range of nickel complexes (Mellor and Craig, 1940), bis- phenylethylenediamine nickel chloride, etc. (Lifschitz, Bos and Dijkema, 1939). All the compounds mentioned in the above summary are diamagnetic. Evidence relating to tetrahedral paramagnetic nickel compounds has been discussed in this Journal (Mellor, 1941). Gold (Autit), In the trivalent condition gold undoubtedly forms square bonds, but it is extremely doubtful whether it does so in the monovalent condition. Further PRESIDENTIAL ADDRESS. 43 work substantiating the claims of Dothie, Llewellyn, Wardlaw, and Welch (1939) is needed before it can be accepted that Au! can be grouped with Au, It is noteworthy that no geometrically isomeric auric compounds have been observed in spite of the definite searches made for them. Crystal Structure —K[AuBr, ]2H,O (Cox and Webster, 1936c), [(AIK),AuBr, ], etc. (Burawoy, Gibson, Hampson and Powell, 1937), [Pr,AuCN ], (Powell and Phillips, 1938), Cs,Au,Cl, (Elliott and Pauling, 1938), [N(C,H;),]AuCl, (Huggins, unpublished data). Crystal Optics.—[N(C,H;),|AuCl,, K[AuBr,]2H,O (Mellor e¢ al., 1936). Silver (Aglt), The only instance so far described is argentic picolinate. An incomplete X-ray analysis of this substance made by Cox, Wardlaw, and Webster (19360) shows the presence of square complexes. Copper (Cult), An outstanding characteristic of copper is that it is much less sensitive to electronegative differences (from a stereochemical viewpoint) than its close neighbours like Nit, Cot. Several hydrated salts of copper are known, from crystal analyses, to form square complexes, e.g. CuCl,2H,O, K,CuCl,2H.O and CuSO,5H,O. No diamagnetic hydrated nickel chloride or sulphate has been reported. It is very doubtful whether any tetrahedral cupric complexes have yet been found. Arguing by analogy Mills and Gotts (1926) concluded that cupribenzoyl- pyruvic acid had a tetrahedral structure. It is practically certain that the analogy does not hold. Large numbers of internal copper complexes containing unsymmetrical chelate groups have been described throughout the literature, and it is extra- ordinary that so few geometrical isomers have been discovered. One can only conclude that cis isomers must be so unstable as to be incapable of existing for any length of time. Crystal Structure-—CuCl,2H,O (Harker, 1936), K,CuCl,2H,O (Chrobak, 1934), copper diketones (Cox and Webster, 19356), CuSO,5H,O (Beevers and Lipson, 1934), CuO (Tunnel, Posnjak and Ksanda, 1935), CuPy,Cl, (Cox, Sharatt, Wardlaw and Webster, 1936a). Geometrical Isomerism.—[Cu,Cl,(Ph,Me),As),] (Mellor, Burrows and Morris, 1938a), cupric polymethylene bis-imino-acid complexes (Schlesinger, 1925), cupric picolinate (Cox, Wardlaw and Webster, 19365). Cobalt (Col). The only evidence to date comes from magnetic susceptibility measure- ments which show that certain internal complexes have a moment corresponding to the existence of one unpaired electron, the number to be expected for a square structure. Magnetic data show that « and ® CoPy,Cl, are not square forms. Magnetic Susceptibilities.—Bis-benzildioxime cobalt (Cambi and Malatesta, 1939), many other internal complexes (Mellor and Craig, 1940b), CoPy,Cl, (Barkworth and Sugden, 1937; Mellor and Coryell, 19380). Rhodium (Rh1), All attempts to prepare square rhodous complexes with one unpaired electron spin have so far resulted in failure.!§ 18 Unpublished experiments with F. P. Dwyer. 44 D. P. MELLOR. Iron (Fell) and Manganese (Mnt), Many compounds have been examined’? in the hope of finding evidence for the square configuration, but without success. Such compounds appear to be very rare and the only ones reported to date are ferrous and manganous phthalocyanine (Senff and Klemm, 1939). Several years ago, Cox, Shorter, Wardlaw, and Way (1937), on the basis of a determination of unit cell dimensions, reported that manganous dipyridine chloride [MnPy,Cl,] had the trans square structure. This was subsequently shown to conflict with the magnetic data, which indicated that manganese in this compound was definitely in the ionic condition (Mellor and Coryell, 19386). An alternative octahedral structure was suggested as a way of explaining the small cell dimensions. The structure attributed to the [Mn(H,O),]+*+ ion in K,Mn(SO,),.4H,O (Anspach, 1939) is almost certainly incorrect. Iridium (Ir!). As already pointed out, the higher valence states of iridium, platinum, etce., are invariably octahedrally coordinated. It is only in its lowest valency state, in a compound like IrCl for example, that iridium is likely to have the square structure. So far no results have been reported for compounds of this metal. Before concluding this brief survey, some reference must be made to a number of claims regarding the square configuration for metals not listed in Table 4 as capable of forming dsp? bonds. The evidence for square TE and Aut rests mainly on a small unit of dimension for certain of their compounds (Cox, Shorter and Wardlaw, 1938; Dothie et al., 1939) and cannot be regarded as satisfactory. With regard to earlier claims relating to the structure of Cd™ (Brasseur and de Rassenfosse, 1936), Pb"! and Sn® (Cox, Shorter and Wardlaw, 19370), all that need be stated here is that subsequent investigation has shown that octahedral coordination prevails (Brasseur and de Rassenfosse, 1939 ; MacGillavray, De Wilde and Bijvoet, 1938) in these compounds. SUMMARY. Traditional chemical methods of unravelling questions of molecular structure fail to provide a unique solution to the problem of the structure of bivalent platinum compounds. The various alternative interpretations of the phenomena of geometrical and mirror image isomerism can be narrowed down by spectro- scopic and dipole moment measurements but the final solution is provided by the results of crystal structure analysis. The great mass of data on platinum together with that just listed for other metals leaves no reasonable doubt that certain elements can form square bonds. With the reservation that it applies only to bonds free to arrange, the theory of the directed valence bond makes it clear just what metal atoms are likely to form square bonds and at the same time it provides certain criteria for deciding whether any given atom has adopted that configuration. While the purely stereochemical problem of the existence of square complexes can be considered as settled, much remains to be done on problems relating to their general chemical behaviour. REFERENCES. Anderson, J. S., 1934. J. Chem. Soc., 971. Angell, F. G., Drew, H. D. K., and Wardlaw, W., 1930. J. Chem. Soc., 349. Anspach, H., 1939. Z. Krist., 101, 39. Babayeva, A. A., 1938. C.R. Acad. Sc. U.R.S.S., 20, 365. Bannister, F. H., and Hey, M. H., 1932. Min. Mag., 23, 188. Barkworth, E. D. P., and Sugden, S., 1937. Nature, 139, 374. Beevers, C. A., and Lipson, H., 1934. Proc. Roy. Soc. A., 146, 570. 19 Unpublished work with D. P. Craig. PRESIDENTIAL ADDRESS. 45 Born, M., 1923. Atomtheorie des Festen Zustandes. Teubner, Leipzig. Bragg, W. L., 1924. Proc. Roy. Soc. A., 105, 370. Brasseur, H., and de Rassenfosse, A., 1936. Z. Krist., 95, 474. Brasseur, H., and de Rassenfosse, A., 1937. Mem. Acad. roy. Belg., 16, 1. Brasseur, H., and de Rassenfosse, A., 1938. Bull. Soc. Fr. Min., 61, 129. Brasseur, H., and de Rassenfosse, A., 1939. Z. Krist., 101, 389. Brasseur, H., and de Rassenfosse, A., 1941. Mem. Acad. roy. Belg., [2], 4, 397. Burawoy, A., Gibson, C. S., Hampson, G. C., and Powell, H. M., 1937. J. Chem. Soc., 1690. Cambi, L., and Malatesta, L., 1939. Gazz. Chim. Ital., 69, 547. Cambi, L., and Szego, L., 1931. Ber. disch. Gess. Chem., 64, 2591. Cavell, H. J., and Sugden, S., 1935. J. Chem. Soc., 621. Chrobak, L., 1934. Z. Krist., 88, 35. Cleve, P. T., 1872. Kong. Svenska Vetens Akad. Handl., 9, 1. Cossa, A., 1890. Ber. disch. Chem. Gess., 23, 2504. Cox, HE. G., 1932: J. Chem. Soc., 1912. Cox, E. G., and Preston, G. H., 1933. J. Chem. Soc., 1089. Cox, E. G., Saenger, H., and Wardlaw, W., 1934a. J. Chem. Soc., 182. Cox, E. G., and Webster, K. C., 1935a. Z. Krist., 90, 561. Cox, E. G., and Webster, K. C., 19356. J. Chem. Soc., 731. Cox, E. G., Pinkard, F. W., Wardlaw, W., and Webster, K. C., 1935c. J. Chem. Soc., 459. Cox, E. G., Wardlaw, W., and Webster, K. C., 1935d. J. Chem. Soc., 1475. Cox, E. G., Sharrat, E., Wardlaw, W., and Webster, K. C., 1936a. J. Chem. Soc., 129. Cox, E. G., Wardlaw, W., and Webster, K. C., 1936b. J. Chem. Soc., 775. Cox, E. G., and Webster, K. C., 1936c. J. Chem. Soc., 1635. Cox, E. G., Shorter, A. J., Wardlaw, W., and Way, W. J. R., 19387a. J. Chem. Soc., 1556. Cox, E. G., Shorter, A. J., and Wardlaw, W., 19376. Nature, 139, 71. Cox, E. G., Shorter, A. J., and Wardlaw, W., 1938. J. Chem. Soc., 1886. Dickinson, R. G., 1922. J. Amer. Chem. Soc., 44, 2404. Dickinson, B. N., 1934. Z. Krist., 88, 281. Dothie, H. J., Llewellyn, F. J.,. Wardlaw, W., and Welch, A. J. E., 1939. J. Chem. Soc., 426. Drew, HD. K., 1932. J. Chem. Soc., 2328. Drew, H. D. K., Pinkard, F. W., Wardlaw, W., and Cox, E. G., 1932a. J. Chem. Soc., 988. Drew, H. D. K., Pinkard, F. W., Wardlaw, W., and Cox, E. G., 1932b. J. Chem. Soc., 1004. Drew, H. D. K., and Head, F. S. H., 1934. J. Chem. Soc., 221. Dwyer, F. P., and Mellor, D. P., 1934. J. Amer. Chem. Soc., 56, 1551. Dwyer, F. P., and Mellor, D. P., 1935. J. Amer. Chem. Soc., 63, 1392. Dwyer, F. P., and Mellor, D. P., 1941. J. Amer. Chem. Soc., 63, 81. Elliott, N., and Pauling, L., 1938. J. Amer. Chem. Soc., 60, 1846. Elliott, N., 1938. Dissertation. Calif. Inst. Technology, Pasadena. Fritzmann, E., 1912. Z. anorg. Chem., 73, 239. Gaskell, T. F., 1937. Z. Krist., 96, 203. Gelman, A. D., and Bauman, M., 1938. C.R. Acad. Sc. U.R.S.S., 18, 645. Grailich, J., 1858. S.B. Akad. Wiss, Wien, 32, 50. Grunberg, A. A., 1926. Z. anorg. Chem., 157, 299. Grunberg, A. A., 1931. Helv. Chim. Act., 14, 455. Grunberg, A. A., and Ptizyn, B. W., 1933a. J. prakt. Chem., 136, 1438. Grunberg, A. A., and Schulman, V. M., 1933b. C.R. Acad. Sc., U.R.S.S., 218. Hantzsch, A., and Rosenblatt, F., 1930. Z. anorg. Chem., 187, 24. Hantzsch, A., 1926. Ber. ditsch. Gess. Chem., 59, 2761. Harker, D., 1936. Z. Krist., 93, 136. Helmholtz, L., 1936. J. Chem. Phys., 4, 316. Hibben, J. H., 1939. The Raman Effect, Reinhold, New York. Hylleraas, E., 1927. Z. Krist., 65, 469. Janes, R. B., 1935. J. Amer. Chem., 57, 471. Jensen, K. A., 1935a. Z. anorg. Chem., 225, 97. Jensen, K. A., 1935b. Z. anorg. Chem., 225, 115. Jensen, K. A., 1936a. Z. anorg. Chem., 229, 225. Jensen, K. A., 1936b. Z. anorg. Chem., 229, 265. Jensen, K. A., 1938. Z. anorg. Chem., 241, 115. Jorgensen, S. M., 1886. J. prakt. Chem., 33, 489. King, H. J. S., 1938. J. Chem. Soc., 1938. Kurnakow, J., 1894. J. prakt. Chem., 50, 483. Lidstone, A. G., and Mills, W. H., 1939. J. Chem. Soc., 1754. Lifschitz, I., Bos, J. G., and Dijkema, K. M., 1939. Z. anorg. Chem., 242, 97. Lunde, G., 1927. Z. anorg. Chem., 163, 345. Magnus, G., 1828. Poggendorff’s Ann., 14, 239. MacGillavry, C. H., de Wilde, J. H., and Bijvoets, J., 1938. Z. Krist., 100, 212. Mann, F. G., and Pope, W. J., 1926a. J. Chem. Soc., 482. Mann, F. G., and Pope, W. J., 1926b. J. Chem. Soc.. 2675. 46 D. P. MELLOR. Mann, F. G., 1929. J. Chem. Soc., 651. Mann, F. G., and Purdie, D., 1935a. J. Chem. Soc., 1549. Mann, F. G., Crowfoot, D., Gattiker, D., and Wooster, N., 1935b. J. Chem. Soc., 1642. Mann, F. G., and Wells, A. F., 1938. J. Chem. Soc., 702. Mathieu, J. Pi 1939. J. Chim. Phys., 36, 271, 308. Mellor, D. P., land Quodling, F. M., 1935. Tis Journat, 69, 167. Mellor, D. pe and Quodling, F. M., 1936. Tis JournaL, 70, 205. Mellor, D. P., and Morris, B. S., 1938. TuHIs JOURNAL, 71, 536. Mellor, D. P., Burrows, G. J., and Morris, B. S., 1938a. Nature, 141, 414. Mellor, D. P., 1940. Tuts JouRNAL, 74, 129. Mellor, D. P., and Lockwood, W. H., 1940. Tuis Journat, 74, 141. Mellor, D. P., and Craig, D. P., 1940a. Tuts JourNat, 74, 495. Mellor, D. P., and Craig, D. P., 1940b. Tris Journat, 74, 475. Mellor, D. P., and Coryell, C. Ds 1938b. J. Amer. Chem. Soc., 60, 1786. Mellor, J. W., 1937. A Comprehensive Treatise on Inorganic and Theoretical Chemistry, Vol. 16. Longman, London. Mills, J. E., and Mellor, D. P., 1942. J. Amer. Chem. Soc., 64, 181. Mills, W. H., and Quibell, T. H. H., 1935. J. Chem. Soc., 839. Mills, W. H., and Gotts, R. A., 1926. J. Chem. Soc., 3121. Moore, W. J., and Pauling, L., 1941. J. Amer. Chem. Soc., 63, 1392. Morgan, G. T., and Burstall, F. H., 1934. J. Chem. Soc., 965. Nilson, J., 1886. J. prakt. Chem., 21, 179. Ostromisslensky, I., and Bergmann, A., 1910. Ber. dtsch. Chem. Gess., 43, 2768. Pauling, L., 1931. J. Amer. Chem. Soc., 53, 1367; 1932. Ibid., 45, 994. Pauling, L., and Huggins, M., 1934. Z. Krist., 87, 214. Pauling, L., 1939. The Nature of the Chemical Bond. Cornell Univ. Press, New York, Ist ed., 81. Pauling, L., 1940. The Nature of the Chemical Bond. Cornell Univ. Press, New York, 2nd ed., 102. Peyrone, M., 1844. Ann. Chim. Phys., 12, 93. Peyrone, M., 1846. Ann. Chim. Phys., 16, 462. Peyrone, M., 1845. C.R. Acad. Sci. Paris, 18, 1103. Peyronel, G., 1941. Z. Krist., 103, 57. Petren, I., 1898. Dissertation Lund. 1910, Z. anorg. Chem., 20, 62. Pinkard, F. W., Saenger, H., and Wardlaw, W., 1933. J. Chem. Soc., 1056. Pinkard, F. W., Sharrat, E., Wardlaw, W., and Cox, E. G., 1934. J. Chem. Soc., 1012. Porter, C. R., 1938. J. Chem. Soc., 368. Powell, H., and Phillips, R. F., 1938. Br. Assn. Adv. Sce., 50. Reihlen, H., and Nestle, K., 1926. Liebig’s Ann., 447, 211. Reihlen, H., and Huhn, W., 1931. Letbig’s Ann., 489, 42. Reihlen, H., Seipel, G., and Weinbrenner, E., 1935. Leibig’s Ann., 520, 256. ° Reiset, J., 1844. C.R. Acad. Sc. Paris, 18, 1103. Riabtchikov, D. I., 1940. C.R. Acad. Sci. U.R.S.S., 3, 236. Rice, O. K., 1940. Electronic Structure and Chemical Binding. McGraw Hill, London and New York. Robertson, J. M., and Woodward, I., 1940. J. Chem. Soc., 36. Rosenheim, A., and Gerb, L., 1933. Z. anorg. Chem., 210, 289. Senff, H., and Klemm, W., 1939. J. prakt. Chem., 154, 73. Schlesinger, N., 1925. Ber. dtsch. Gess. Chem., 58, 1877. Sugden, S., 1932. J. Chem. Soc., 246. Theilacker, W., 1937. Z. anorg. Chem., 234, 161. . Tscherniaev, I., 1926. Ann. Inst. Platine, 4, 243. Tscherniaev, I., 1928. Ann. Inst. Platine, 6, 55. Tscherniaev, I., and Gelman, A. D., 1936. C.R. Acad. Sci. U.R.S.S., 18, 181. Tschugaeff, L., 1910. J. Russ. Phys. Chem. Soc., 42, 1472. Tschugaeff, L., 1915. C.R. Acad. Sc. Paris, 161, 563. Tunnel, G., Posnjak, E., and Ksanda, C. J., 1935. Z. Krist., 90, 120. Vezes, 1903. Bl., 29, 83. Wells, A. F., 1936. Z. Krist., 95, 74. Wells, A. F., 1938. Z. Krist., 100, 189. Werner, A., 1893. Z. anorg. Chem., 3, 267. Wooster, W. A., 1938. Crystal Physics, Camb. Univ. Press, Cambridge, p. 177. METHAMOGLOBIN FORMATION. By JOHN WILLIAMSON LEGGE,* B.Sc., Institute of Medical Research, Royal North Shore Hospital, Sydney. Communicated by M. R. LemBere, D.Phil. Manuscript received, January 16, 1942. Read, April 1, 1942, INTRODUCTION. The slow autoxidation of oxyhemoglobin to methemoglobin has been known since Hoppe-Seyler discovered the latter compound in 1864. Neill (1925) and Neill and Hastings (1925) drew attention to the réle that the partial pressure of oxygen played in the reaction. They observed that the autoxidation of oxyhemoglobin reached a maximum rate at 20 mm. oxygen pressure. At this pressure they assumed the hemoglobin to be half saturated. The reaction was formulated as an oxidation of reduced hemoglobin by oxygen. Brooks (1932, 1935) examined the effect on the reaction of variables such as pH, oxygen pressure, ionic strength, specific salt effects, as well as the method of preparation of the sample of hemoglobin used. Other variables remaining constant, he showed that the reaction was of the first order with respect to the unchanged hemoglobin. When the partial pressure of oxygen was varied the reaction velocity reached a maximum at 19-7 mm. To explain this effect of the partial pressure of oxygen on the rate of reaction he assumed that there were two competing reactions between oxygen and reduced hemoglobin, i.e. the addition of oxygen to form oxyhzemoglobin (oxygenation—no change of valence), and the oxidation of the ferrous iron in hemoglobin to the ferric iron in methemoglobin. At high oxygen pressures the reduced hemoglobin was removed as oxyhemoglobin, and hence the second reaction proceeded at a slower rate. On this hypothesis he derived an empirical equation which described fairly well the dependence of the rate of reaction on the oxygen pressure. He concluded that the partially oxygenated intermediates expected on Adair’s hypothesis played no réle in the reaction. In this paper it is proposed to show that a re-examination of Brooks’ experimental results, in the light of the structural interpretation of hemoglobin proposed by Pauling (1935), can lead to a new hypothesis for the dependence of the rate of methemoglobin formation on the partial pressure of oxygen, in which partly oxygenated intermediates play a réle. Reasons for preferring this mechanism to that suggested by Brooks are given below. THE STRUCTURE OF HMOGLOBIN. Following on the demonstration that a molecule of hemoglobin of molecular weight 68,000 contained four prosthetic groups, each able to combine with oxygen, Adair (1925) put forward his intermediate compound hypothesis. In this he suggested that unoxygenated hemoglobin could combine successively with four oxygen molecules, leading to partly oxygenated intermediates Hb,O,, Hb,O, and Hb,O,, as well as fully oxygenated Hb,O,;. He found that the equilibrium between hemoglobin and oxygen could be described by an equation * Working under a grant from the National Health and Medical Research Council. 48 JOHN WILLIAMSON LEGGE. with four equilibrium constants corresponding to the four oxygenated intermediates. On the basis of further assumptions as to the nature of the hemoglobin molecule, Pauling subsequently derived an equation for the equilibrium between oxygen and hemoglobin which contained only two constants. He assumed that interaction occurred between adjacent HbO, groups in such a way that the free energy of addition of oxygen to hem, RTInK, is diminished by RTIna where such interaction occurs. If the hems are arranged on the surface of the hemoglobin molecule with the iron atoms at the corners of a square (square configuration) and interaction between adjacent hem groups could occur, equation I could be derived for the equilibrium ; if the hems are arranged at the corners of a tetrahedron, each hem equidistant from the other three, equation II holds, — Kp (204-1) p44 302K ep? ot Kp IT C4K p+ (40-42) K2p?+4e2K 2p? + oth 4p! Oo pee Me och poe IT TAK p 160K p? + 4o3Kp3 -a°K4*p! where y equals the oxygen saturation of hemoglobin, p the oxygen pressure in mm. mercury, A the equilibrium constant, and « the interaction constant (K and « as defined above). Pauling (1935) and Coryell et al. (1939), as well as Altschul and Hogness (1940) prefer the square configuration. Optical studies by Perutz (1939), evidence from diffusion and viscometric studies (Neurath 1938), and from the asymmetry constant from sedimentation data (Svedberg 1938), all point to an ellipsoidal molecule. Pederson and Anderson (cited by Svedberg 1938) report that on dilution hemoglobin dissociates reversibly into two equal parts, while Steinhardt (1938) has observed such a dissociation in solutions of amides. Altschul and Hogness suggest that an explanation of the salt effect on the oxygen equilibrium may be due to such dissociation. If all the hems are assumed equivalent to one another, it is difficult to see how an ellipsoidal molecule can have the four hems arranged tetrahedrally and yet dissociate into two parts of equal molecular size. Nor could the hems be arranged in one plane, as demon- strated by Perutz, and still be equivalent. Hence a square configuration is more probable. At a given oxygen pressure p, the relative concentrations of the various intermediates for the square configuration Hb,, Hb,O,, Hb,O,, Hb,O,, Hb,O, are aS 1:4Kp: (4a+2)Kp?: 402K ?p3: ath 4p4. Having solved the equation for K and « from various experimental values for y and 7p, it is possible to calculate the concentrations of the intermediates at various pressures. This solution is simplified by a method used by Altschul and Hogness. Since in equations I and II K and p~ occur to the same power while « does not, a plot of y against log Kp, where various values of « are taken, will give a family of curves, the Slopes of which vary with « A plot of y against log p for the experimental figures gives a curve which can be fitted to the nearest member of the family. This gives the nearest value for «, while the difference between log p (experi- mental) and log Kp (calculated) gives the value for K. Brooks’ experimental results for the equilibrium are expressed in this way in Figure 1; the best agreement with equation I is found when «=3 and K=0-0174. Where a similar procedure is carried out with equation II (tetrahedral configuration), the experimental results can be expressed by this equation when «=2 and K =0-0186. The values for « and K which fit the experimental results having been determined, it is possible to calculate the fraction of hemoglobin which is present in each of the intermediates at a given oxygen pressure. This has been done in Table I for the square configuration at the oxygen pressures at which Brooks measured the rate of methemoglobin formation. METHAMOGLOBIN FORMATION. 49 log Km Figure 1. Ordinate the oxygen saturation of hemoglobin, abscissa log Kp. Solid lines represent theoretical plots for equation I when «=2, 2-5 and 3. Points superimposed on curve «=3 are the results of Brooks, plotting y against log p. TABLE [. BO.intmn| 4-5 | 6-0x,| 13-7 | 16-0 | 25:8 | 33-3 | 63-1 | 92-9 | 192 | 182 | -082 | 0-041 | 0-005 | Hb, .. | 0-705 | 0-618 | 0-286 | 0-224 | 0 0-001 | 0-000 | 0-000 Hb,O, .. | 0-221 | 0-258 | 0-273 | 0-250 | 0-148 | 0-096 ; 0-024 | 0-009 | 0-004 | 0-002 Hb,O, .. | 0-060 | 0-094 | 0-227 | 0-243 | 0-232 | 0-195 | 0-090 | 0-049 | 0-031 | 0:021 Hib,O, .. | 0-012 | 0-024 | 0-139 | 0-174 | 0-268 | 0-290 | 0-254 | 0-203 | 0-167 | 0-141 bios 7.2.1 /0°002 | 0-006 | 0-075 |, 0-109 |)0-270 | 0-378 | 0-627 | 0-738 | 0-797 | 0-836 It can be seen that the fraction of intermediate Hb,O, increases to a maximum at about 13-7 mm. oxygen pressure, while intermediate Hb,O, increases to a maximum at about 20 mm. oxygen pressure, approximately the pressure at which the rate of formation of methemoglobin reaches its maximum. A similar calculation for the fraction of hemoglobin present in each of the intermediates when the tetrahedral configuration is assumed leads to the same result, that Hb,O, is the intermediate the concentration of which is maximal at the same pressure at which the rate of methemoglobin formation is greatest. THE REACTION MECHANISM. Brooks had formulated the reaction as one between reduced hemoglobin and oxygen, competing with the oxygenation of hemoglobin to oxyhemoglobin. It is hard to imagine how the iron atom in hemoglobin ean react in two different H—April 1, 1942. 50 JOHN WILLIAMSON LEGGE. ways towards oxygen, since in each case the point of attack must be on the sixth co-ordination valency of the iron. This makes it likely that the first addition compound of oxygen and hemoglobin is the same for both reactions. Furthermore the first order rate constant does not favour the bi-molecular reaction which Brooks assumes unless the rate determining step depends on the breakdown of a particular intermediate. Brooks had taken the intermediates into account only as reactants with oxygen. While at a constant pressure, k, the rate constant, is defined by the equation dx ap le —2), when the pressure is varied he defined the rate constant k by the equation k=K, (intermediate) . p. The concentration of the intermediate (intermediate) can be written as f(p), and K, is a constant. From this equation follows (intermediate) = k Kp ct As p increased k/p diminished. Hence for K, to remain constant the concentration of the intermediate must diminish as p increases. Calculating the concentrations of the intermediates from Adair’s equation Brooks found that the only intermediate which fulfilled this condition was Hb,. But the substitution of the values for the fraction of Hb,, calculated in this way, did not lead to a constant value for K,. Hence, Brooks concluded, the intermediates cannot be shown to play a role. A simpler assumption for the mechanism of the methemoglobin formation is that the rate depends on the concentration of a particular intermediate, which breaks down spontaneously into methemoglobin. This would explain the order of the reaction without the difficulties inherent in Brooks’ hypothesis, the dependence of the rate constant on the pressure being due to the variation of the concentration of the intermediate with pressure. If this is the case k—(Gntermediate). Ko. 2)... ss.» «10 eee IV where K, is a constant, and the concentration of the intermediate (intermediate) may be written as f(p). It should be noted that Brooks’ formulation of the rdle of the intermediates as k=(Hb,) . K,. p can be written as k=(Hb,0O,) . K’,, since (Hb,O,) = K (Hb,)(p) where K is the equilibrium constant and K’,;=K,/K. The procedure which Brooks carried out to show that Hb, was not a reactant according to his hypothesis also excluded the possibility that Hb,O, is an intermediate on the hypothesis put forward as equation IV. Table II shows the values of K, calculated from equation IV from the experimental values of k found by Brooks, and the values for the concentration of Hb,O, from Table I. This is the only intermediate which gives any sort of constancy for the values of K,, as might be expected since the other inter- mediates have their maximum concentrations at pressures other than the maximum pressure for the rate of methemoglobin formation. The above calculation has been derived from the square configuration of the hems. If the tetrahedral configuration is used as the theoretical basis, the same intermediate, Hb,O,, is implicated as the one whose concentration most closely parallels the change of the rate constant with pressure. No distinction can be made between the cis and trans forms of Hb,O,, since their concentrations are proportional to one another at any pressure. METHAMOGLOBIN FORMATION. 51 TABLE II. a a) pO, in mm. kx10? (Hb,O,) | K,x10? (Hb,0O,) , K,x10? | ie 4°5 9-9 0-060 165 0-065 152 DeZ 6-0 12:6 0-094 134 0:099 127 2-24 13-7 15:9 0-227 70 0: 232 69 1:79 16-0 17°6 0-243 ie 0-249 roll 1-94 25°8 Weve. 0-232 76 0: 239 74 1-94 Bare 14-5 0-195 74 0-200 74 Levi 63:1 10°3 0-090 114 0-089 114 2-01 k rate constant for methemoglobin formation (Brooks). (Hb,O,) fraction of hemoglobin as Hb,O, (a) from Table I, (b) taken from Brooks’ table of intermediate concentrations. K, constant according to equation IV, (a) using (Hb,O,) from Table I, (6) using (Hb,0,) from Brooks’ table. k” constant from Brooks empirical equation. As comparison, in Table II is given the constant k” derived from Brooks’ experimental equation for the rate of methemoglobin formation dA, bp — =k" .m.(a—a). Tans where k” is a constant (1:95), m equals the fraction of hemoglobin as Hb,, (a —x) per cent. hemoglobin unoxidised at time f, and b is a constant (0-0118). DISCUSSION. The conclusion that Hb,O, is the intermediate which breaks down spon- taneously into methemoglobin suggests that the reaction may perhaps be formulated as follows, assuming that water is co-ordinated to a hem group when oxygen is not. [Hb ,(O2).(H.O).]+ H*—[Hb* ,(OH),]+0,+H,0 [Hb* ,(OH),]+-OH’—+[Hb,(OH),) The light thrown on the mechanism of the reaction by Pauling’s theory is, conversely, an additional indication of the validity of the assumption of inter- action between the hems. The spontaneous formation of methemoglobin can be added to the reactions of hemoglobin which show hem interaction. Coryell (1939) has shown that in the redox system hemoglobin-methemoglobin inter- action occurs. In the reaction between ascorbic acid and oxyhemoglobin Lemberg et al. (1941) have shown that at low oxygen pressures the breakdown of oxyhexmo- globin proceeds faster than at atmospheric pressure. Here a coupled oxidation takes place where the porphyrin ring is oxidised to form choleglobin. It has not yet been possible to carry out for the latter reaction the necessary experiments which would show which intermediate, if any, is most important here. In the latter paper it is also shown that H,O, forms more choleglobin when it reacts with reduced hemoglobin than when it reacts with oxyhemoglobin. This result may throw light on the mechanism of the coupled oxidation. A hemoglobin H,O, compound, formed in the coupled oxidation in which H,O, is attached to only two of the available hems, may undergo oxidation of the porphyrin nucleus more readily than one in which there are also O, molecules attached to a molecule of hemoglobin. 52 JOHN WILLIAMSON LEGGE. It seems likely, then, that the formation of both methemoglobin and choleglobin can be added to the list of hemoglobin systems (Coryell 1939) which can be best interpreted in terms of hem-hem interactions. SUMMARY. The hypothesis put forward by Brooks to explain the dependence of the rate of methemoglobin formation on oxygen pressure is rejected. A recalcula- tion of his experimental results in the light of Pauling’s theory of the equilibrium of oxyhemoglobin suggests that Hb,O, breaks down spontaneously to methemo- globin. This reaction is of the first order at constant pressure. When the pressure is varied the rate depends on the concentration of Hb,O,. ACKNOWLEDGMENTS. The author wishes to thank Dr. R. Lemberg for his help and encouragement, and Professor V. A. Bailey and Mr. Alan Maccoll, of the University of Sydney, for their help in the mathematical aspects of the problem. REFERENCES. Adair, G. S., 1925. Proc. Roy. Soc. (London), A, 109, 292. Altschul, A. M., and Hogness, T. R., 1939. J. biol. Chem., 129, 315. Bernal, J. D., Fankuchen, I., Perutz, M., 1938. Nature, 141, 523. Brooks, J., 1932. Proc. Roy. Soc. (London), B, 109, 35. Brooks, J., 1935. Proc. Roy. Soc. (London), B, 118, 560. Coryell, C. D., Pauling, L., and Dodson, R. W., 1939. J. phys. Chem., 43, 825. Coryell, C. D., 1989. J. Phys. Chem., 43, 841. Lemberg, R., Legge, J. W., and Lockwood, W. H., 1941. Brochem. J., 35, 339. Neill, J. M., 1925. J. Hup. Med., 41, 561. Neill, J. M., and Hastings, A. D., 1925. J. biol. Chem., 63, 479. Neurath, H., 1938. Symposia on Quantitative Biology, 6, 196. Pauling, L., 1935. Proc. Nat. Acad. Sc. Washington, 21, 186. Perutz, F. M., 1939. Nature, 143, 731. Steinhardt, J., 1938. J. biol. Chem., 123, 543. Svedberg, T., 1938. Proc. Roy. Soc. (London), B, 127, 1. ERRATUM. Page 53, in Table I, column 3, for ‘‘ 24/11/27” read “‘ 24/11/37.” A NOTE ON THE ESSENTIAL OIL OF EUCALYPTUS CONGLOBATA VAR. ANCEPS. By P. A. BERRY, MSc., and T. B. SWANSON, MSc. Manuscript received, February 9, 1942. Read, April 1, 1942. In connection with another investigation, a quantity of eucalyptus oil was distilled from a species of eucalypts which has now been identified as EH. con- globata var. anceps. A quantity of growing tips from this species was collected by H. J. Wiadrowski at MacGillivray, Kangaroo Island, in November, 1937, and distilled in the experimental still at American River. This species is common to the better class of soils and is associated with HF. cneorifolia. The leaf was collected from country which had been burnt about four years earlier. A search through the literature has failed to reveal a prior publication of the constituents of this oil. Two distillations were made, using 100 lb. leaves and growing tips for each run. Ten gallons water was used in the still for each distillation, 6 gallons of aqueous distillate collected during a 5 hours distilling period. (See Table I.) TABLE I. Distillation of Leaves. Distilled Distilled 23/11/37. 24/11/27. Yield of crude oil .. ae oe ae oe a 0:69% 0-74% ty 15-5/15-5° ae “ee fe a: ae 0-908 0-907 [x99 an i< ie a: A ae ae oe +13-37 +14:-11 Mister value... es aye 4 4-9 2:8 Total alcohols calculated as GO Aek © i oa by 6-1% 6-7% Total aldehydes and ketones as C,,H,,0 ot Bi 1-5% 1:5% Cineol (by ortho-cresol method) .. or 580% OH 2G Terpenes, etc., by difference (principally ‘d- -O- -pinene) oe 34°-4% 34:-6% The two distillations yielded oils of closely uniform composition. The oils were free from appreciable quantities of phellandrene (negative result with nitrosite test). The crude oils were mixed for further work. 300 ml. of oil was shaken with resorcin solution 50% to remove cineol. In all 2,500 ml. resorcin solution was used (1,400 ml., 700 ml. and four successive portions of 100 ml.). Crude cineol recovered by steam distillation of the resorcin solution 178 ml. The oil remaining after this treatment was steam distilled, 35 ml. distillate, had the following constants. Density 15-5/15-5, 0-864, [«]*°+42-9, contained cineol 10-2%. 54 BERRY AND SWANSON. Examination for Presence of Cymene. 25 ml. was oxidised at room temperature with potassium permanganate solution (20 g. in 500 ml. water) to which solid potassium permanganate was added until oxidation was complete. In all 193 g. KMnO, was used. On steam distillation only 0-2 ml. oil was obtained, indicating the absence of appreciable amounts of cymene. Examination for Terpenes. 7:7 ml. (of 35 ml. separated above) was distilled rapidly at atmospheric pressure. Distillation commenced at 130° C. and the temperature rose quickly to 158° C. and then slowly to 163° C. TABLE II. Distillation of Terpene Fraction. Density Fraction. Temperature. Time. Yield. [x2 16-5/15-5° l 158-163° C. 3 min. 5:8 ml. +44°-3 0-864 2 163-168° C. Dee 1-3 mil. —— — The fractions smelt strongly of pinene and the presence of d-a«-pinene was suspected from the physical constants. Since the yield of nitrosochloride diminishes with increased optical rotation, the preparation of the nitrosochloride was not attempted, and oxidation with potassium permanganate at ice temper- ature was carried out (Gildemeister and Hoffmann, Vol. I, 2nd edition, p. 299). Three g. of fraction 1 was oxidised with 7 g. KMnQ,, dissolved in 90 ml. water, the mixture being kept cold in a bath of ice and water. After oxidation was complete, the mixture was filtered, washed with ether and the aqueous filtrate evaporated and acidified with sulphuric acid, the precipitated acid extracted with petroleum ether and the solvent evaporated. A thick viscous mass resulted, which did not crystallise on standing; [«]*) (e=5-842 in alcohol) =+13:1. This would appear to be impure pinonic acid. Semi- carbazone was prepared from the crude material and recrystallised from alcohol. Melting point, 203-204° C. (melting point of semicarbazone of d-pinonie acid, 204° C.) thus confirmed the presence of d-«-pinene in the oil. The terpene fraction (see constants of steam distillation above) appears to consist principally of d-a-pinene. | SUMMARY. The oil from the growing tips of this species consists principally of cineol (58%) and pinene, with a small proportion of alcohols, aldehydes and ketones. We are indebted to the Commonwealth Government for a grant from the Federal Research Grant and also to Miss C. M. Eardley, M.Sc., of the Botanical Department of the Adelaide University, for the identification of the species. Johnson Chemical Laboratories, The University of Adelaide, and New England University College, Armidale, N.S.W. STUDIES IN METAMORPHISM AND ASSIMILATION IN THE WELLINGTON DISTRICT, N.S.W. Il. THE DYNAMIC AND CONTACT METAMORPHISM OF A GROUP OF ULTRABASIC ROCKS.* By ELizABETH M. BASNETT, M.Sc.T With one map and ten text-figures. Manuscript received, March 18, 1942. Read, April 1, 1942 I. INTRODUCTION AND PREVIOUS RECORDS. The ultrabasic lamprophyres crop out in at least twelve sills to the east of Wellington, in the parishes of Wuuluman, Nanima and Bodangora. Although individual sills are generally narrow and of no great length (see Fig. 1), the eroup extends for about twelve miles in a north-south direction. These rocks were first recorded by Matheson (1930) as lamprophyre, from the Wuuluman Road crossing on Poggy Creek. He believed that the outcrop was of limited extent and that the rock represented a “ basic differentiation product of the granite magma’”’. Later Jones (1935) reported that the same outcrop was a small amphibolite intrusion, probably of late Silurian age. To the south of the Wuuluman Road the lamprophyres have suffered intense dynamic metamorphism along a fault zone. This alteration is accom- panied by migration of material. Although some directional structures are visible even north of the Mudgee Road, the northern part of the area suffered relatively little shearing. Furthermore the lamprophyres in part of the area were contact-altered by the Wuuluman granite (see Fig. 1). On Poggy Creek there is a small intrusion of hornblende porphyrite most likely connected with the granite, but it has not affected the surrounding lamprophyre. II. NATURE OF THE INTRUSION AND FIELD OCCURRENCE. The lamprophyres have been injected as a series of parallel sills. In the south, along Poggy Creek, they occur between the Sedimentary and Volcanic Stages of the Silurian Series, and have been folded into a northward plunging anticline, with the lavas and breccias exposed along the southern part of the crest. Along the eastern and western boundaries of the intrusion, between the edge of the granite and the Wuuluman Road, the overlying shales contain a narrow bed of banded calcareous tuff. South of the road this continues along the whole of the eastern boundary of the lamprophyre, but on the western side grades into fairly coarse non-calcareous tuff (Fig. 1). North of the Wuuluman Road, on the western edge of the granite, the sills are injected into the Sedi- mentary Stage above the calcareous tuff. The sills range from a few feet to almost three-quarters of a mile in width on Poggy Creek, where folding has occurred. Occasionally, narrow veins and stringers less than an inch wide penetrate the shales. Many sills occur in the sediments west of the granite, but are visible only in creeks and gullies. Two * Part I appeared THis JOURNAL, 1939, 73, 161. tf The greater part of this work was carried out at the University of Sydney during the tenure of a Commonwealth Research Scholarship. 56 ELIZABETH M. BASNETT. well defined sills, approximately 18 feet wide, run parallel to the granite boundary for about one and a half miles (Locality (I) on Fig.1). In Por. 14, Par. Bodangora there are three narrow sills and a small dyke (Locality (2) on Fig. 1), and in Por. 179, Par. Bodangora there are two sills, one about ten feet wide, the other smaller (Locality (3) on Fig. 1). In all these cases the outcrops are shown as single sills on the map. ToWellingto LEGEND Alluvium SILURIAN VA Sedimentary Stage Igneous Stage INTRUSIONS P. hwuGluman Fault f} H eee Lamprophyre Granite Fig. 1. III. PETROGRAPHY. (I) The Original Lamprophyre. Although the nature of the original rock is generally masked as a result of dynamic or contact metamorphism, some idea of the original mineralogical STUDIES IN ASSIMILATION. 57 constitution can be gained. There are three main types which have been classified according to their phenocrysts, namely : (1) Augite lamprophyre (Fig. 24). (2) Augite-Plagioclase-Lamprophyre (Fig. 2B). (3) Hornblende lamprophyre. The nomenclature is discussed on page 72. The first occurs throughout the area, the second in Por. 31, Par. Bodangora, and the hornblende lamprophyre in Mitchell’s Creek a little above the Mudgee Road crossing. For the sake of brevity they will be described together. Fig. 2. The original lamprophyre. A. Augite lamprophyre. The large zoned augite phenocryst shows a corroded central portion. The inclusion is a pseudomorph after olivine. Towards the top of the diagram a pyroxene phenocryst has been almost entirely replaced by chlorite and epidote. The groundmass consists of augite, fibrous hornblende, plagioclase, a little chlorite, and epidote. x16. B. Augite-Plagioclase Lamprophyre. The large plagioclase phenocrysts consist of acid plagio- clase and granules of epidote. The pyroxene phenocrysts have been replaced by fibrous amphibole, with some biotite. Epidote forms fairly large crystals and grains. The ground- mass consists of hornblende, biotite, some plagioclase and epidote. x16. The pyroxene phenocrysts vary greatly in size and abundance in the different sills, but in individual sills are fairly constant ; in some of the augite- lamprophyres they occur in two generations. The larger ones range in size from 2 mm. to 3 mm. in some sills, and up to 20 mm. in others; those of the second generation are less than 2 mm. Glomeroporphyritic development is rare. Zoning is well shown in the larger phenocrysts (Fig. 24), although variable even within the one rock section. The central zones are lighter in colour and only noticeable under crossed nicols, while the outer zone varies greatly in width and may have a larger extinction angle. Corrosion of the central zone is marked F—April 1, 1942. 58 ELIZABETH M. BASNETT. (Fig. 2A), often reducing crystals to irregular grains with pseudo-inclusions of groundmass. The outer zone has generally preserved the shape of the grains, but occasionally produces crystal faces. At times this zone has been moulded on to the plagioclase of the groundmass, giving a sub-ophitic fabric, and in finer grained rocks the two may be intergrown. The colour ranges from colourless to pale greenish grey, yellow-green or light yellow-brown. The yellow-green variety is pleochroic, X=pale yellow, Y=deeper yellow, Z=pale green (XY>X). The colourless and blue- green varieties are optically negative, with positive elongation, ZAc=14° to 24°, «=1-622, y=1-648. They therefore belong to the tremolite-actinolite series, the larger extinction angle being indicative of high magnesia (Larsen and Berman, 1934). In the yellow green variety present in the epidote amphibolite Z/Ac may be as large as 30°, and «=1-628, y=1-656. The negative sign and large extinction angle suggest that it is probably closer to pargasite. Occasionally crystals up to 2 mm. long have a brown pleochroic core in which there is much magnetite. This possibly indicates an original hornblende. Chlorite is often developed. In the pleonaste amphibolite it may form large round patches (0-5 mm. to 2 mm. in diameter) (Fig. 7B). It is colourless to faintly green, is optically positive and 8=1-585. In other cases it is green and shows ultra blue and leather brown interference colours. Both belong to the pennine group. Grains of diopside up to 0:25 mm. in diameter are developed as a result of contact metamorphism (see Fig. 7c). They are colourless, optically positive, Z /Ac=39° and 2V is large.. It comprises as much as 50 per cent. of the ground- mass but is rare in the replaced phenocrysts except along fractures. Magnetite is fairly abundant, especially in the spinel amphibolite. Sphene may be present, also fractured crystals of apatite showing a purplish-grey central zone. (b) Felspathic Types. These are much less common in the contact zone than are the non-felspathic amphibolites. They crop out chiefly along the southern boundary of the granite, but in Por. 14, Par. Bodangora almost on the contact, there is a narrow sill about one foot wide. As in the previous types blastoporphyritic fabric and relict structures are common (Fig. 8B), while the Bodangora specimen is blastophitic (see Fig. 8A). There is only a local development of a true granoblastic fabric. Amphibolisation of the phenocrysts is similar to that already described for the non-felspathic varieties. Hornblende may also develop as grains and stout crystals up to 0-25 mm. in length round the edge of the phenocrysts (Fig. 84), while some are completely replaced in this way. The type from Bodangora originally had a fairly coarse-grained groundmass with plagioclase crystals up to 2 mm. long. The felspar is often clouded, or contains minute needles of hornblende (see Fig. 8A). Occasionally a grano- blastic fabric has been produced. In the southern area the groundmass is entirely recrystallised, but still shows directional structures (Fig. 8B). Along the southern boundary of the granite there are a few vugh-like areas produced either by deuteric alteration or by dynamic metamorphism. These now consist of an outer ring of magnetite grains or blue green hornblende followed by plagioclase and quartz with pleochroic epidote in the centre (Fig. 8B). Biotite may also be developed. The amphibole is yellow green, strongly pleochroic,, X=yellow green, Y=dark yellow green, Z=dark bluish green (ZS Y>X), Z/Ac=27°, optically positive with positive elongation, «—1-641, y=1-662. It therefore has a composition near pargasite and is a more aluminous variety than that found in the majority of the non-felspathic amphibolites. The recrystallised plagioclase is only occasionally twinned, is optically negative, with extinction | 010=21°; hence it is andesine (Ab,,Angg). Plagio- clase which has not been recrystallised is slightly more basic and generally shows undulose extinction. STUDIES IN ASSIMILATION. Fig. 8. Felspathic amphibolites produced by contact metamorphism. A. Augite phenocrysts have been almost entirely replaced by amphi- bole. Small crystals of hornblende are developing around and through the replaced phenocrysts. In the top right quadrant the phenocryst shows blastophytic relations to the surrounding felspar. Original felspar laths are still visible, but contain many small rods and needles of hornblende. To the left of the figure a granoblastic fabric is locally developed. x16. This rock shows remnants of a schistose structure produced during dynamic metamorphism, but a granoblastic fabric is beginning to develop. The phenocrysts are replaced by amphibole. In the top right-hand corner is a vugh which is now replaced by plagioclase and epidote with an outer zone of amphibole. x16. Hybridised aplite vein. Note irregular and indefinite boundaries to the vein. Diopside is developing around the edges and through a mass of hornblende which has been practically surrounded by aplite. x 16. 71 72 ELIZABETH M. BASNETT. Magnetite occurs as small crystals, which may reach 1 mm. in length. Granular sphene is sometimes developed. Epidote and clinozoisite granules are formed in the groundmass. At Poggy Crossing the felspathic type is banded with a rock containing very little felspar. It has been strongly sheared and consists chiefly of a more blue green amphibole associated with brown biotite. Epidote and some biotite occur in patches throughout the rock and also in the replaced phenocrysts. It seems that these bands have suffered considerably from the earlier dynamic metamorphism but were not greatly altered by the later contact metamorphism. In the contact altered hornblende lamprophyre the amphibole has been partially replaced by brown pleochroic biotite, epidote, and carbonates. Where a blue green amphibole is produced in association with the biotite the replaced phenocrysts were probably augite. Small felspar phenocrysts are still visible, but show undulose extinction, clouding or contain needles of amphibole, flakes of biotite and grains of epidote. The groundmass consists of plagioclase, needles and rod-shaped crystals of amphibole, flakes of biotite, and granular epidote. Veins of epidote and carbonates are common. (iv) Hybridised Aplite Veins. In the region between the Wuuluman Road and the southern boundary of the granite, the contact-altered lamprophyres have been intruded by large numbers of aplite dykes which do not appear to have been hybridised. However, these have given rise to small veins, often less than 2 mm. across, which penetrate the lamprophyre and show marked signs of hybridisation. The constituent minerals of the aplite are quartz, microcline, plagioclase (Ab,;An,;), and small quantities of biotite and magnetite ; sphene and apatite are rare. Quartz and microcline are extremely abundant. At times they are intergrown, the latter forming plates up to 4 mm. across. The constituent minerals of the veins are microcline, plagioclase, diopside, hornblende, and small quantities of quartz; apatite and sphene are fairly abundant; biotite is not developed. The fabric is allotriomorphic granular to slightly monzonitic. Solid material, chiefly hornblende with some felspar, is incorporated in the veins and together with diopside, produced 2m situ, may occur between lath-shaped crystals of felspar developed from the hybrid magma (Fig. 8c). In other veins the felspar, diopside, and hornblende form granular masses. Where potash felspar is more abundant than plagioclase, the veins are narrow and ferromagnesian minerals are rare. In some parts of the veins sericite is developed in great quantities, often entirely replacing the felspar. Diopside forms allotriomorphic to subidiomorphic grains, and tends to be more abundant towards the edges of the veins (Fig. 8c). It also develops in the hornblende of the surrounding lamprophyre. In these cases the boundaries of the veins are very indefinite (Fig. 8c). Where they traverse amphibolised phenocrysts, diopside is formed along the broken edges, and may extend right across the fracture. Occasionally the phenocrysts are almost entirely replaced. The diopside is pale green with a slight bluish tinge, non-pleochroic, optically positive, and Z Ac=43°. . These veins occur in an area which has been impregnated by copper-bearing solutions. Some of the ferromagnesian minerals both of the lamprophyres and. the veins have been attacked and partially replaced by copper carbonates. IV. NOMENCLATURE. As all these rocks have been metamorphosed to some extent, the naming ot the original rocks is difficult. They were first called lamprophyres by Matheson (1930), and in hand specimen this name is very suitable. In this paper the name STUDIES IN ASSIMILATION. 73 is still used, but it is prefixed by the names of the dominant phenocrysts (see p. 57). The augite-plagioclase lamprophyres could possibly be called porphyrites, and in one locality an augite lamprophyre which has an ophitic fabric might be termed a porphyritic dolerite, except that the felspar is rather tabular. Chemical analyses have been made of three contact altered augite lampro- phyres (Table I, columns I, II, III). They all contain high lime and magnesia, with low alumina and alkalies, indicating an ultrabasic composition. The norm shows a considerable percentage of olivine, and pseudomorphs after olivine are present in some rocks. These analyses do not compare closely with those of any lamprophyres, most of which have higher alkalies and lower magnesia and lime. They agree best with an olivine gabbro from the Ural Mts. (Table I, column IV), and a dolerite from Rhonegebirge (Table I, column V). They compare mineralogically with the original descriptions of augitites as defined by Doelter, but these are volcanic types with a glassy groundmass. No augitite listed by Iddings agrees closely with those of the Wellington rocks. So the most suitable name for these rocks still seems to be lamprophyre. TaBLe I. ie oe III. IV. V. Si0, 45°49 47-52 49-24 47-68 49-92 Al,O; 10:49 12-50 13°85 11-43 13-39 Fe,0, 6:44 1-08 4:88 0-16 8-07 FeO 4-36 6-26 6-55 8-90 4-82 MgO 18:48 16:50 8-34 14:81 6:13 CaO 10:72 13-07 10-94 12-48 10-68 Na,O 0-89 0-46 2-55 1-01 2-83 K,O 1-25 0-92 132 0-52 1-11 H,O+ 1-55 0-85 0-72 222 0-94 H,O — 0-11 — 0-16 — — TiO, 0-36 0-67 0-62 0-59 1-80 P.O; 0-24 tr 0-31 0-00 1-06 MnO 0-15 0:14 0:17 0:07 — Total: .. He ith 100:53 99-97 99-65 99-87 100-75 Sp. Gr. ibe ae 3-10 3°13 3°09 ‘I. Spinel Amphibolite. Por. 14, Par. Bodangora. Anal. E. M. Basnett. II. Epidote Amphibolite. Por. 83, Par. Bodangora. Anal. M. J. Colditz. III. Felspar-bearing Amphibolite. Wuuluman Road Crossing on Poggy Creek. Anal. E. M. Basnett. IV. Olivine Gabbro. Ural Mts. Anal. Pisani. A Lacroix. N. Arch. Mus., 1911, 3, p. 114. V. Dolerite, Rhonegebirge. Anal. P. Schmidt, Neues Jahr., 1905, II, p. 213. V. PETROGENESIS. (i) Physical Conditions of the Invading Magma. The lamprophyres contain large numbers of pyroxene phenocrysts which in some sills form more than fifty per cent. of the rock. The nature of these phenocrysts (see p. 57) suggests that during the early stage of their formation the crystals grew slowly in a constantly changing environment, and towards the G—April 1, 1942. 74 ELIZABETH M. BASNETT. end of crystallisation they became unstable and hence were strongly resorbed. The deposition of the outer zone without later resorption indicates fairly stable conditions in the final stage of their formation. This may be explained if the phenocrysts of the first generation were well crystallised before the injection of the magma. The change in physical and chemical conditions caused by injection into the upper crust must have resulted in strong resorption. After emplace- ment the establishment of stable conditions once more would enable further deposition to take place around the corroded phenocrysts. A large proportion of the sills have a fine grained groundmass, suggesting rather rapid cooling. This would not allow large zoned augite phenocrysts to develop im situ. Also, there are no signs of chilled margins, and phenocrysts at the edges are as large as these: throughout the mass, while tiny veins 4 inch wide contain phenocrysts up to } inch across (Fig. 9). Hence it is concluded that, at the time of injection, the 1 magma was crowded with phenocrysts formed in the intratelluric reservoir. Fig. 9. A diagram of a small vein intruding sandy shales. Note size and abundance of phenocrysts, and their presence at the edge of the vein, the lack of chilled margins, and the presence of narrow stringers through the intruded shale. N.S. That such a magma could be injected over so wide an area and even in veins only half an inch in width must mean, either that it was extremely fluid and cooled rapidly after injection, or that it was injected into very soft sediments. The lamprophyres intrude sediments overlying the Silurian andesites, and are believed to be consanguineous with the lavas. This suggests that when injection occurred the sediments were soft or only partially consolidated, and that the weight of overlying strata could not have been great. The presence of water in the sediments may also have helped to keep the magma fluid during its injection. (ii) Dynamic Metamorphism. (a) Structural Changes. The dynamic alteration of the lamprophyres resulted from local faulting, probably at no great depth in the earth’s crust. The introduction of solutions along the fractures made possible the mineralogical changes already described. These two factors are together responsible for the structural changes. In the rare cases where the original phenocrysts show shattering there has been little mineralogical adjustment. Generally, however, they have yielded by the development of new minerals, with the result that a blastoporphyritic fabric exists in rocks now entirely reconstituted mineralogically. As a result of the replacement of the phenocrysts (see petrography) under pressure they 75 STUDIES IN ASSIMILATION. ‘POAOUIAL [4S [VleyeW pesBoloy “oPIJOUIEIY puB opWOsIUY (¢€) ‘oyopide pue o4yjour -013 ‘outuued ‘az11081yuUeO1I0,q (Z) ‘eqyopide puv outuued ‘oz1[ourery, (T) : Aq pooe,dor ‘[BLI9}PVUL JO [BAOULOI SUISBOIOUI UFLM AZISOYSTYOS POULIOF IOIIVS OY} SSO10B SOSSVUL OIL] JO uoTzeULIOJ 04a AQ pomoyjoy ‘oyjpourery euy Aq poorldoy ‘o[8} pus opLIOSIQUB ‘oZI[OWTOLY, (g) “OFITOULOI4 pue opwo0sy4uBol1ey ‘ouruueg (Z) ‘sysey_qorAyd ‘ezITOUIOIy pue ouTUUE (T) -10d opjoursr3 Aq sydiouropnesd : Aq yuoutsoe[dor oyoTyo jo yuourcoRjder yenpeity | [el1e}VUL JO [PAOUIOI SUISBOIOUT YIM ‘OAISSVUL PUB yoeduUIOD ZUTULODEG yoor ey. ‘orqey o1taAydaodo4se[q pue Se 0 le lel O+N=0 a theoretical value of 10,737 cals./grm. for the gross heat of combustion is obtained. ia OD ‘The Heat Necessary to Decompose a Known Mass of Shale. The theoretical heat for the low temperature carbonisation of shale may be divided into the following sections : 1. The warming of the shale and contained moisture from room temperature to 100° C. The heat of vapourisation of the water. The heating of the shale from 100° C. to the point of decomposition. The heat to decompose the shale. The heat to volatilise the products of pyrolysis. wo bo aage Various values have been found for these operations, varying from 190 cals./grm. for Estonian shales to 480 cals./grm. for American shales. ‘* Heat of Reaction ’’ of the Shale. By “heat of reaction ’’ it must be understood that this term is not used in its common sense, but is meant to convey “ the heat necessary to convert a given mass of shale into oil, gas and coke under standard conditions ’’. The “‘ heat of reaction ’’ of the shale may be obtained by one of three methods : 1. Direct determination of the heat necessary for the pyrolysis, calculated from the application of the Stefan-Boltzmann Law, allowing for radiation and conduction and convection losses. However, owing to the great complexity of the equations involved, and the many assumptions that have to be made, this method of determining the heat necessary for the decomposition is not satis- factory in the present case. 2. By the use of Hess’s Law it follows that, if we determine the heat for the complete oxidation of one gram of shale and subtract from that the heat evolved when the total products of pyrolysis are oxidised completely, the differences should be the amount of heat necessary to cause the above pyrolysis. It is realised that the heats involved on both sides of this equation are comparatively large and are quite large in relation to the difference between them (the quantity which we wish to determine), and consequently some errors may be introduced but this method, although approximate, gave the most reliable results. 3. Measurement of the heat necessary to cause shale pyrolysis by calori- metric methods. A quantity of heat shghtly in excess of that needed for the pyrolysis is added to the shale under consideration, and that measured by Suitable means. Gray King Assay of the Shale to Determine the Heat Balance. Two Gray King assays were carried out on a type sample of shale. The normal condensing system was replaced by a freezing mixture of solid CO,, in which a U-tube was immersed. Every precaution was observed to see that the weight balance was as accurate as experimental details allowed. The Runs (5 and 6) were carried out under strictly controlled conditions, and the results are set out in Table 9. ; 200 R. F. CANE. ~ is} Ss min y als ear fo 9 he n S ™. Temperature Flow mil per Ss G Or Production ° S eS eS ee minures Fig. 4.—Gray King Assay of Shale. TABLE 9. Run No. .. ae oe 5 6 Weight of shale .. ake 10-314 grms. “11-131 germs: Weight of coke .. oe 4-261 ,, 4-766, Weight of oil 4 Bes 5-510 ,, Dap ere Volume of gas— At 25° C. and 712 m.m. 557ml. 550 ml. AGES ER ae 478 ,, 472: .,, | Weight of gas... ae 0-547 grms. 0-552 grms. Shale (per cent.) .. us 100 100 Coke (per cent.) .. ae 41-31 42-82 Oil (per cent.) .. if 53-42 52-26 Gas (per cent.) .. eS 5-30 4-96 ‘ 100-03 100-04 Analysis of the gas and coke produced during Run 6 showed the di Pant : given in Table 10. f TABLE 10. ~ Composition of Gas... Composition of Coke. % Run 5. Run 6. Acid gases . 0-13 Volatile matter =A :. (8:14) 10-58 Oxygen ~ O- 17 Fixed carbon .. = 5. 29°95 - 27-42 Olefines . 0°36 Ash oe Br Bice .. 61°91 62-30 Ethylene . 0-18 Carbon monoxide . 0-18 Hydrogen . 0°45 Methane ae 2-70 Ethane and higher paraffins eee) Nitrogen . 0-68 4-95 100-0 100-0 THERMOCHEMICAL PROPERTIES OF TORBANITE. 201 Heat Balance on Run 6. Heat of Reactants : Heat of combustion of the shale = 7211-8 cals./grm. (observed). Heat of Products: Coke— Volatile matter. . ee 10-58 4-53 406-6 cals. Fixed carbon .. a 27-12 11-61 1123-6 . Ash a eve a 62-30 26-68 100-0 42-82 1530-2 cals. Oil— Mean of three determinations sie 52-26% 5661 cals. Gas— From gas analysis and calculation sip 472 ml. 4-95% 44-6 cals. | Heat Balance. Shale .. a ih .. Oil + Gas + Coke. LOOP. o ae .. 52°26 + 4-96 + 42-82 (weight balance) Weal ae ae a aS .. 5682 + 45 + 1530 + R R = 45 calories/grm. of shale. = 86 cals./grm. of oil produced. From the above results, which must be regarded as approximate only on account of the experimental errors involved, it may be seen that there is only a small quantity of heat transfer in the conversion of the shale into oil. The comparatively large amount of heat which is found to be necessary in the commercial retorting of shale is accounted for by heat losses and the low thermal conductivity of the shale. The determination of thermal conductivity of shale is a matter of some difficulty in the present case as, owing to the low value of this characteristic, one face of the shale has to be maintained at a relatively high temperature, and this will always cause some decomposition. The thermal conductivity of American oil shale has been determined by McKee and Lyder (1922), for which they report a value of 0-00086 c.g.s. units. Winkler has recorded a result of 0-0005 as the thermal conductivity of Estonian oil shale, but he does not state whether it is air-dried or moisture free. As an interesting comparison, the following equations have been proposed by the International Conference in Pittsburgh in 1931 for the thermal conductivity of coals. For a coking coal: Thermal conductivity = 0-003 + 0-0016 x 10-*t + 0:0016 x 6 x 10> ®?. For a middle gravity coal: Thermal conductivity = 0-003 + 0-0013 x 10-%t + 0:0015 x 10-?. Cp. U.S. Bureau of Mines value = 0-0038 ¢.g.s. units [Gavin and Sharp (1920) ]. SUMMARY. Several salient features of torbanite pyrolysis have been investigated, and it has been shown that the oil is produced by the decomposition of a semi- solid intermediate phase, and there is no direct conversion of the original organic matter into crude oil and gas. The nature of this reaction is by no means regular—the two controlling factors in the nature of the oil produced are time and temperature. Values have been found for the following properties of the crude oil obtained from Glen Davis torbanite, viz., thermal expansion, viscosity, specific heat and heat of combustion, and in most cases ; 202 R. F. CANE. values have been determined also for the torbanite or oil shale as it is generally known. ACKNOWLEDGMENT. The writer acknowledges with thanks the permission granted by National Oil Pty. Ltd. for the publication of this paper. REFERENCES. Constan and Kolbe, 1908-1909. Jour. fur. Gasbeleucht. Dulhunty, J. A., 1941. The Physical Effects of Heat on the Torbanites of New South Wales. Proc. Linn. Soc., 66, 335. Gavin, M. J., and Sharp, L. H., 1920. Some Physical and Chemical Data on Oil Shales. Ouzl and Gas Jour., 19, 86. Hollings and Cobb, 1915. J. Chem. Soc., 107, 1106. Kraussold, H., 1932. The Specific Heat of Mineral Oil. Petroleum. Luts, K., 1935. Der Estlandische Brennschiefer.—Kukersite. Tartu, 2, 69. McKee, R. M., 1925. Oil Shale. A.C.S. Monograph. New York, 4, 78. McKee, R. H., and Lyder, E. E., 1922. The Thermal Decomposition of Oil Shales. Petroleum Times, Nos. 160, 163, 164. Methods of Analysis of Coal, 1927. Dept. Sc. Ind. Res., Fuel Research Publication 7. von Strache, 1922. The Heat Necessary for the Dry Distillation of Shale. Brennstoff Chemie, Sudo. MOVING SOURCES OF HEAT AND THE TEMPERATURE AT SLIDING CONTACTS. By J. C. JAEGER. Manuscript received, August 19, 1942. Read, October 7, 1942. & 1. INTRODUCTION. Problems involving moving sources of heat arise frequently in practice, notably in the calculation of temperatures at sliding or cutting contacts, but despite their importance they have not been studied systematically. One reason for this is the uncertainty of the nature of the contact, and another the very wide range possible in the numerical parameters ; these facts practically limit mathematical discussion to numerical calculations for a particular model of a particular system, and make general discussion difficult. In this paper an attempt is made, in connection with the problem of plane sliding, to set out fully the assumptions made and the numerical consequences of the mathematical theory in a form in which it is hoped they can easily be used by experimenters to discuss particular models of sliding surfaces. In §§2-9 the theory of uniform plane sources of heat cf various shapes moving with constant velocity in the surface of a semi-infinite medium with no loss of heat from the surface is discussed. In §§4, 5 the temperatures attained in the plane of the source when the motion has gone on infinitely long are given, and in §6 the way in which these temperatures build up is considered. The temperatures within the medium are calculated in §7. The maximum and average steady temperatures over the area of the source are collected in §9. In these sections the strength of the source is taken to be constant over its area ; a brief discussion of variable strength is given in §12. One case in which the strength and velocity of the moving source vary with the time, namely the temperature flash occurring with a simple type of relaxation oscillation, is considered in §13. All these solutions are exact; in $10 the problem of one substance sliding on another is considered approximately by a method due to Blok (1937).* Some numerical calculations for this problem are given in $11. 2. Notation and fundamental solutions. The notation of Carslaw’s “ Conduction of Heat” [Ed. 2 (1921)] will be used throughout, namely, v for temperature, K for conductivity, ¢ for specific heat, op for density, x= /oc. When numerical values are used they are always in ¢.g.8. units. The temperature at the point (7, y, z) at time ¢ in an infinite solid, initially at zero temperature, due to a quantity of heat Y instantaneously liberated at the point (x’, y’, 2) at zero time ist x (ee ae Pe acta C =a 8. (axt)? ? vara Ayt This we shall call the temperature due to an “ instantaneous point source ”’. * In this important paper the sliding of a square source is considered with its application to the problem of the surface temperature of sliding metals. The discussion, however, is very condensed, the mathematical problems are not considered in detail, and there are few numerical results. The point of view also is different ; the average temperatures, which are made funda- mental here, are not discussed. + Carslaw, loc. cit., p. 150. His solution is for a quantity of heat Qoc liberated at the point. 204 J. C. JAEGER. If we replace Y in (1) by Ydy’, and integrate with respect to y’ from — oo to oo, we obtain the solution for an “ instantaneous line source ’’ parallel to the y-axis and through the point (x, 0,2’). Here Q heat units are instantaneously liberated . per unit length of this line at zero time in the infinite solid. The temperature at the point (#, y, z) at time ¢t due to this is [Carslaw, loc. cit., §72] q) (% —a")*? +-(2—2")? ake tut | The solutions for moving sources below are obtained by integration of these fundamental solutions. 3. Problems on moving plane sources. The ultimate object of this paper is the calculation of the temperature in a semi-infinite solid, <0, on which another body slides. We shall always take the plane of sliding as the plane z=—0, and the sliding to be with constant* velocity V along the axis of x We shall usually assume that heat is liberated at a constant rate of qg, per unit time, per unit area, over the instantaneous surface of contact, and that there is no loss of heat from the remainder of the surface. If the sliding body were a non-conductor, the whole of the heat would be taken up by the solid <0, and the problem would be that of a uniform source of heat moving in the surface z=—0 of this region with no loss of heat from the surface. This idealised problem can be solved exactly and the sclution is given in §§4-9; the case in which the sliding body is of finite conductivity is then discussed approximately in §§10, 11. The shape of the surface of contact is usually not known, but it may approximate either to a long narrow band, as in the case of cutting tools, or to a closed region of approximately constant diameter, as in the ordinary case of the sliding of one body on another. Accordingly we consider pte mathematically most tractablet cases of these types, namely (i) The band source of lengtht 2l in which heat is fiberaned uniformly at the rate q per unit area per unit time over an infinite strip parallel to the y-axis and of length 2/ along the a-axis. The source moves with velocity V in the x-direction. 7 (ii) The rectangular source of sides 21 parallel to the x-axis and 2b parallel to the y-axis in which heat is liberated uniformly at the rate of,q per unit time per unit area over the rectangle. The centre of the rectangle moves with velocity V along the a-axis. Numerical results will mostly be given for the square source in which b=l, but it is of some advantage to have the more general theory. The temperatures due to the band and square sources are calculated in §$4, 5; other shapes are considered in §9. 4. The steady temperature due to a band source of width 21 moving with velocity V in the plane z~=0 of the semi-infinite solid z<0 with no loss of heat yee the plane z=0. The- band source is to be parallel to the y-axis and of length 2/ parallel to the x-axis ; heat is liberated at the rate q per unit time, per unit area, over the area of the source. The result will be twice that for the same source moving * There is no difficulty in considering variable velocity. Systems in which V and q vary with the time are frequently specified by the physical problem ; one such case is discussed in §13. It is possible also that q varies over the surface of contact, though it would be capes to find the law of variation ; some cases of this type are considered in §12. t In these cases the integrations in x and y can be performed independently. t We shall always call the dimension of a source in the direction of motion its length, and that perpendicular to the direction of motion its width. MOVING SOURCES OF HEAT. 205 in the same way in infinite medium, since in the latter case there is no flow of heat over the plane ¢=0 and half the heat liberated will go into the region 240) We suppose that the motion has gone on infinitely long, so that steady conditions have been attained, and that at the instant considered, zero time, the centre of the band is at the origin. We calculate the temperature at this time at the point (#,0,z). At time ¢ earlier, the centre of the band was at (— Vt) and by (2) the temperature at zero time at the point (#,0,z) due to a line source of 2qdx'dt heat units per unit length, parallel to the y-axis and through the point (x —Vt,0,0) is qdx' dt (w—av’ + Vt)? +2? 2rKt ed Axt | To find the temperature at zero time for the band of length 21 which has been moving for infinite time, we integrate (3) with respect to x’ from —l to l, and with respect to ¢ from 0 to oo, and obtain i oo) can | a; dt e (c—av'+ Vt)? +2? al dx { ; ©XP Ea is te (4) —l e/0 peed Be" \ 9 Ue ee ss eV (e@— x") [2% Ke Jal vy tat hae ako) —l where K(x) is the modified Bessel function of the second kind* of order zero. Introducing the dimensionless quantities Va Vy Vz VI Tepe Y¥=5 Aas) L=> silecesren eivelie Msi ket sl's: ire. 6 (6; 6/846 (6) (5) becomes X+D ne 20% —wuU ; 2\h ray: Ce P(A Ee os sce noe 8 (7) X—L For the present only the temperature in the plane of the source, z=0, will be discussed, other values of 2 are considered in §7. Putting Z=—0 in (7) it is seen that the temperatures in the plane of the source are given by TH V Fy (CNN OG 0) ed A @. Co 0) tak ae er mare ee Dears rarer en (8) x where Tt I(x) =|. ZEUN GS ROHN GL) aa Cosas ron Che ok UMC Ra Dt (9) 0 x so that 1 -=—-| CUI SUNG Sauer, eet seit ae (10) 0 * Cf. Gray and Mathews, Treatise on Bessel Functions (Hd. 2, 1922), p. 21 (definition), p. 313 (tabulation). The integral required in (4) above is p. 51 (31). t|ul|=u if u>0. =—u if u<0. Q—October 7, 1942. 206 J. C. JAEGER. TABLE 1. x I(x) x I(a) £ I(2) £ I(a) z I(2) ~20 | —10-277 —2-0 —2-750 —1-0 —1-781 0 0 1-0 0-932 —15 —8-789 —1-9 —2-665 —0-9 —1-664 0-1 0-328 1-1 0-945 —10 —7-024 24-8 —2-578 || —0-8 —1-541 0-2 0-505 1-2 0-956 —9 —6-623 || —1-7 —2-489 —0-7 —1-412 0-3 0-626 1-3 0-965 ay —6-199 1-6 —2-+397 —0°6 —1-275 0-4 0-713 1-4 0-972 a7 —5-748 21 45 —2-302 —0°5 —1-128 0-5 0-778 1-5 0-977 6 —5-265 —1-4 —2-205 —0-4 —0-969 0-6 0-827 1-6 0-981 —5 —4-741 —1-3 —2-105 —0-3 —0-794 0-7 0-864 1-8 0-987 ey —4-164 —1-2 —2-001 —0-2 —0-595 0:8 0-892 2-0 0-991 28 —3-513 Tal ~1-893 —0-1 —0°357 0-9 0-914 © 1-0 For small x I (2) = —2°303:@ log, |#|+1-116@ 2 29. eee (11) If x is large and negative, say «< —10, we have approximately a) —4/(27|x]) +1 $003 a vets bee sites le eee (12) In Table 1 a short table of values of I(x) is given ; (11) and (12) will be seen to give adequate approximations in the relevant regions. In Fig. 1 the values of (xKV/2qx)v, which give the temperature variation in the plane of the moving source, are plotted, for various values of L, in terms of the ratio Ch oil, MOVING SOURCES OF HEAT. 207 These vary from the symmetrical form for very small L, given, for small X, by ee = —2-303(X +L)log,)|X +L| +2-303(X —L)log,)|X —LD|+2-232 D0 .......... (33) to the form for large L, given, approximately, by THK V Acca ay —_X)yt tie oe v={2r(L—X)} ied OE C8 Oh (14) =(2n)K(L—X)t—(|X+L))3, X<—L this has a maximum at the rear end of the source, X = —L. For intermediate values of Z the curves show @ maximum at some point between the centre and the rear of the source, which moves progressively towards the rear as ZL increases. 5. The steady temperature for a rectangular source of sides 21 and 2b, parallel to the x and y axes respectively, whose centre moves with velocity V along the x-axis in the plane z2=0 of semi-infinite solid z<0 with no loss of heat from the plane Via Ms Here, by the method of §4, using (1) in place of (2), we obtain for the temperature at the point (%,y,z), when the centre of the source is at the origin, Says Y+B ae | Da exp in Cs Ze aa : a/ epensezae, where the notation (6) has been used, and bV /2x =B. In the plane <=0 there is now a temperature variation in y aS well as in x; the temperature is greatest at points on the res Here, putting Y=Z=0 in (15), we have TH V me ny) 24 €2)3 : GA UE rn) WN eG ba ne ye 16 Ong a, i if (7 “(n? +02)8 repay U6 (16) A +L oo = eK o(|q|)an — "dy eee 4 XxX —L X —L B Ree Pie eae e (17) For large B the result (17) tends to that for the band source, (7), and for moderate values the difference is small. For small values of Z, X and B we may replace the exponentials in (16) by unity and obtain approximately THY oy Se ie oe i A) Be a 0—=(X +L) loge YALL POOL: amare iaT B+ [(L—X)?+B?}2 L—X +[(L—X)?+B?} amex) jenn UE pig, 2 208 J. C. JAEGER. for the most important case —L1 the behaviour of band and square sources is so similar, it fellows that when discussing more complicated problems such as those of §§7, 12, 13 it is sufficient, if Z is not too small, to treat those for the band source, for which calculations are usually much easier, and the results for the square source may be expected not to be very different. MOVING SOURCES OF HEAT. 209 6. The case in which motion of the source has taken place for a finite time T. We consider a rectangular source with sides 2/ parallel to the x-axis and 2b parallel to the y-axis. Its centre moves with velocity V along the v-axis in the plane z=0 in semi-infinite medium z<0 with no loss of heat from the plane z=0. Suppose that at time 7 the centre of the source has just reached the origin. It follows from (1) that the temperature at time 7 at the point (x,y,z) is sin ( (P—13? [- Je exp tera’ +Vr otters) Ay (T —t) V2T /2x ee aa du, -Z?/2u (ie ae Ae ie 2K V (21) wa (2u)8 (2u)3 . 5 | X+0+4u X—L+u x je f pane e rf “Bak (19) where, as before, Va Veen Ve oe EV ‘C= oy! Loy? ay L=>z) Bas @ (ell¥e. eile tei fe-) epey eweh eve. 6) 0101 ¢,, © (20) and 2 tf 2 SY Gi CCAD Mee ed SP Sg spain ened so (21) VAL: Oo so that erf oo=1. | Letting B=oo in (19) we find for the band source V2T /2x mere fa \ 2 D2 ne XG ae X—L+4u) du age #(5) é ge lo wan tak (22) 0 and if 7’ =—oo in this we obtain an alternative form of (7). For points on the x-axis, we put Y=Z=0 in (19). This gives VAD PV, fs if T\F du( ,A+L+4 X—L+u) B 2x °=1(5) aI rf ~ (Quyt —erf (uk j erf (Quy 0 ARCA Ne Ace st erat a (23) and if 7’=oco in this we obtain an alternative form of (17) which is sometimes convenient. We may also obtain from (19) a convenient form for the average temperature over the area of the source wine | 2 4s DOME Pee a Renee rc AT | (24) 210 J. C. JAEGER. It is given by V2T /2x TH V 1 /x\? at $ Y 2 Bi Vav za(5) utdu®(B(2/u)*) Oo 20+ [20 —u| oe jt x} 0( all mal 20 (1/2) i 3. ple (25) x where O(a#) = erf « dx 0 oe pes == /OTr 2-5 HN THO eee ne cee Ale (26) Letting B-—>oo in (25) we obtain the corresponding result for a band source V2T /2x THK V ae (4, (2L+u [2D —u| Tea Irony apy thaiia evel Sova yt. 2/3 sae Ty 1® (ar) +°( oan) 200 haw 0 As an illustration of the way in which the temperatures build up to the final values given in §§4, 5 the temperatures at the centre, XY =Y =Z=0, of a square source, B=L, calculated from (19) are shown in Fig. 3. (xk Vv/2qx) is plotted against V?7'/2x for the values 0-2, 0-5, 1, 2,5 of LZ. In Fig. 4 the time T’ to reach half the final value is shown, V?7'"/2x being plotted against L. 7. Penetration perpendicular to the plane of the source. The most important quantities for practical applications are the temperatures in the plane of the source, z=0, but the temperatures for other values of 2 are easily obtained from (7) or (22) for the band source, and from (15) or (19) for the square source. Only those for the band source will be dis- cussed here since they are easier to calculate and contain all the essential features ; the temperatures for the square source are of course lower. In Fig. 5 curves of (xKV/2qx)v plotted against §=X/L=a/1 are given for a band source of length Z =1 for the values 0, 0-2,0-5,1,2,40fZ. The maxima ef the curves are seen to move steadily to the left as Z increases ; ; this effect is caused by diffusion of heat from the surface inwards after the source has passed. To show how the temperature varies with Z for different values of the length of the source, (rH V/2qx)v at the rear end of the source, X =—JZ, is plotted against Z in Fig. 6 for the values 0:2, 0-5,1, 2,4 of. As a numerical example we consider the case discussed in §11, Table III, 1=0-001 cm., V =700 cm./sec., %=0-173, so that L=2. Here it follows from Fig. 6 that the temperature in the medium below the rear end of the source has fallen to 1/10 of its surface value when Z=3, i.e. at a depth of 0-0015 cm. Thus in most cases the penetration into the medium is extremely shallow, and from this several results of practical importance follow : (i) the thermal stresses due to these fluctuating temperatures will be very superficial, (ii) a change in thermal properties of a thin layer on the surface may make a large change in the surface temperature.* If the con- * This remark applies in moving sources and not to the stationary sources of §8 for which the penetration, given by (28), is deeper. 211 MOVING SOURCES OF HEAT. S°l ¥e/ 1A Fig. 4. J. C. JAEGER. Fig. 5. £ [A | o42 /4/\ Hs 212 Fig. 6. MOVING SOURCES OF HEAT. 21a ductivity of the surface layer is raised, for example by applying a thin coating of a good conductor, the surface temperature will be lowered; while if the conductivity of the surface layer is lowered, the surface temperature will be raised. At the same time it should be remarked that, although the penetration is small, it is fairly large on a molecular scale, and thus estimates of surface temperature based on the heating of monolayers will not be satisfactory. 8. Stationary sources. The temperature at time ¢, at the point (#,y,z), in the semi-infinite solid z<0 with no flow of heat over the surface z=0, due to heat supplied at the rate q per unit time per unit area over the square —l5, the maximum temperature is (using (14)) 4qxL? 2q/2xl\} KVxt =a =r o 6 © © 6 'e 8 0 © © © © © @ a © © © @ © ee © ‘© & 6 (e\ B a) wie) en etal = in (33) and the average temperature over the area of the source is L -06 4 Se TON (34) 3K Vxt KOON Vi (ii) If Z is small, say 2<0-1, the maximum temperature is (using (13)) 0 (—2-303L log, D416) oo. (35) and the average temperature is ait {—2-3081 log, 20-+1-616D} ....2).. 3 ee (36) For the square source we have from the results of §5: (i) If L is large, the maximum and average temperatures are nearly the same as those for a band source, namely, (33) and (34). (ii) If Z is small, the maximum temperature is, from (18) 8qul | ete ql KY loge (1+ +/2) =1-122 5 (37) and the average temperature over the area of the source is 8xqL(, = 2-1) gl TRV) lee GVA Lo 946 Fe cence ene. (38) For intermediate values, i.e. 0-1<2<5, where the above formule do not hold, the maximum temperatures must be obtained from curves such as those of Figs. 1 and 2 and the average temperatures are most easily calculated from (25) and (27). These results are given in Fig. 7 where (rxK V/2xq) times the maximum and average temperatures for band and square sources are plotted against LZ. Curves I and IT are the maximum temperatures for the band and Square sources respectively, while curves III and IV are average temperatures for band and square sources. It can now be seen that the temperatures (and in particular the average temperatures of Fig. 7) for the square source may be used for any not too irregular Shape of source. Several cases may arise: (i) If L>2 the difference between the band and square source solutions is small, it follows that for lengths of this order elongation of the source perpendicular to the direction of motion does not affect the result. (ii) For very small Z the results for the band and square sources do differ, the former behaving like Z log Z and the latter like Z. (iii) For very small Z the results for the moving source tend to those for a stationary source of the same size and strength, this was pointed out by Blok (loc. cit.) ; for example, (37) and (38) for the moving square source with small L are identical with (29) and (30) for the stationary square source. This result enables us to compare the results for shapes other than rectangular; for example, (29) for the maximum temperature in a square source of side 21, and (31) for a cireular source of diameter 21 differ by 12%, so that such a change of shape of the source which does not affect the length in the direction of motion may be expected not to affect the temperature materially. (iv) There remains the possibility of a source elongated in the direction of motion; an increase of LZ for constant B will give a large increase of temperature which may be calculated from the rectangular source formule, but the question of the greatest practical interest MOVING SOURCES OF HEAT. 215 |_L -ap2 ann BS | a A | A a AWAY te N ies | Sa ipa Jat ee NON lene SHERRI A See AH IN} I BNE. HALEN BMBSEAGAa ERESSh SERRE easeo UR BERR BE SS BASSAS BREESE ER USL eaeee HEBER RaAaMNe BESRASRER IGS EERE RR SARS NISC INEINIEN ISIS E Ieee Slee alee SSE ee Tal a ALA HBR RREEE Bae IaA BRU Sa. SREeEs GEBeReSS LINAS eel eles re SRESaIRE CERNSS TP SNIE Neg YEA (SRNR BB | @ Fig. 7. in this and the other cases is the way in which the average temperature over the area of the source varies when the shape of the source varies but its area remains constant. This is most easily studied by considering rectangular sources with constant LB: in Table II average temperatures are given for the case DB=1. TABLE 2. 1 Bp B. (wEKV /2xq)vav- 5 0-2 1-243 2 0-5 1-792 il ih 1-879 0:5 2 1-580 0-2 5 0-994 It is seen that increasing the width B of the source at the expense of the length Z lowers the average temperatures, which for large widths tend to those for a band source. Increasing the length at the expense of the width also lowers the average temperature, but to a rather less degree. The most interesting point which emerges from Table IT is that for the wide range of shapes considered there, the average temperatures differ by a factor of less than two. Finally it may be remarked that the curves of Fig. 7 show the relative orders of magnitude of the average and maximum temperatures ; thus if the average temperature is known (e.g. experimentally) the maximum temperature can be inferred. 216 J. C. JAEGER. 10. Application to the surface temperature of sliding solids. The practical problem arising in connection with the generation of heat by friction is the following : one substance, which we shall call the slider, of thermal properties K,, x, slides with velocity V over the surface of a second substance, KK, %, which is at rest. a A —~ V V Ye \\ “ Fig. 8. We shall discuss two types of slider, represented by Fig. 8, (a) and (bd). In the former a protuberance of the semi-infinite substance 2 slides on the semi-infinite substance 1; this is the case normally encountered, the latter case of a long thin slider has been discussed by Bowden and Ridler (loc. cit.), who have used it to discuss their experimental results. We may reasonably assume that heat is generated at a uniform rate per unit time per unit area over the common surface, and that there is no loss of heat from the portions of the surfaces not in contact, so that the model of the preceding sections in which a source moves in the surface of a semi-infinite medium provides a first approximation. If the substance 2 were a perfect insulator the moving source theory of §§3-7 would be exactly applicable in the , medium 1; likewise if the substance 1 were a perfect insulator the stationary. source theory of §8 would be exactly applicable in the medium 2. The practical case in which both bodies have finite conductivity is much more difficult, the slider is heated by the source and cooied by the oncoming cooler portions of substance 1, while the substance 1 is heated both by the source and by conduction from the slider. An exact discussion seems to be out of the question* at present so we use the following approximate method. We assume that when a steady statet has been attained a fraction « of the heat g per unit time per unit area generated over the area of contact passes to the substance 1 and the remaining fraction (1 —«) to the substance 2. « then will be calculated by the requirement that the average temperature over the area of contact calculated by §9 for a moving source «gq in substance 1 equals the average temperature calculated for substance 2 by §8 with a stationary source (1—«)g. Any method of this sort * It is possible to give an exact treatment of particular models, but these are very cumber- some and add nothing to the general conclusions. + Due to Blok, loc. cit. He uses it first for a stationary source at a junction of two media of different conductivities and then applies it to the problem of a moving slider, using a different criterion to that developed here. It should be remarked that even for a stationary source the method is only strictly accurate after infinite time when steady state conditions have been attained : for finite time the heat will divide between the two media in a different ratio, for example an instantaneous infinite plane source at the junction divides in the ratio K,x,3/K,%,?. in place of K,/Kg. { This assumes that motion has gone on for a time of the order of those in §6, Fig. 4. MOVING SOURCES OF HEAT. 2A will necessarily be approximate since the two temperature distributions over the area of contact calculated in this way will be different, thus any reasonable criterion for calculating « may be used; that of equating average temperatures used here has been chosen because the average temperature is the quantity experimentally observed, and also because it is easily calculated and the single quantity best representative of the temperature distribution. « of course will depend both on the velocity, the area of contact, and the thermal constants of the two substances. Bowden and Ridler, loc. cit., consider the slider only and take « to be a constant, so their discussion is not satisfactory. We now calculate the average surface temperatures on the above assumptions. Case (1). A semi-infinite slider K,, x, with a square contact of sides 21 moving with velocity V on a semi-infinite medium K,, x, [ef. Fig. 8 (a)]. We suppose a fraction « of the heat q generated per unit time per unit area to go to the medium and (1—«) to the slider. If L=Vl/2x, is small, equating the average temperatures over the area of contact given by (38) and (30) we have eee yee (Mea Ky 2 K. Thus «= DEAE OMIM Nie ina a tiveWsas ih oc Wb det aed aT ilo eds 5, 39 ‘aati GAGs ee and the average temperature is 0-946 FTE OA oc a (40) For the case in which LF is large, comparing (34) and (30) we have 3 ae 1 0647 (5 _9-g4g 4b 2H)ee Ae Ns KG te K, (lV )t Thus aa ES D3 00o8 11 6 ee (41) and the average temperature over the area of contact is , R 4 pe eC kr a (42) 1:125 K,x,?+K,(lV)t If V is large enough for the first term of the denominators of (41) and (42) to be neglected, we have «=1 and (42) reduces to (34); no heat is taken by the slider and the surface temperature is that due to a source gq moving in the medium 1 with no loss of heat over the plane z—0. For intermediate values of Z the average temperatures for the substance 1 must be obtained from Fig. 7, curve IV. If y=(rK,V/2aqx,)vay is the ordinate of this curve for abscissa Z we find, equating this value to that obtained from (30) «1-486 1K,V 1-486 LK, V +x,Koy and the average temperature is od 0-946 lxy¢q 1-486 1K,V +,Koy Case (w%). A long square slider of side -2/, with thermal constants K,, x, and emissivity o from its sides, slides with velocity V on a semi-infinite medium K,, %, [cf. Fig. 8 (b)]. Tf, as before, we suppose a fraction « of the heat generated to go to the medium 1, comparing average surface temperatures (38) and (32) gives, for the case of LZ small, 218 J. ©. JAEGER. K, Thus *K, +1-338(1K,o) aa ei aN ree univ Johan ah Ca od CUM toa ASR tieay se s cl Sits oper |i ta ca See (45) and the mean temperature over the area of contact is 0-946 ql K, +1-338(lK,c)t a 6 © 2 © #6 «© ee © 6 oe eas) 6) 6 "ee Ke (46) If L is large, using (34) and (32), we find a 47 “i Wand pode Ke) oe |» lenny! kaaana de taegogane (47) and for the average temperature 1-064 q(x,l)? Q(%yl) (48) K,V#+1-504(x,K.c)? eeeeceee ev eseeseee Here, as in Case (i), if V is large, «1 and the average temperature to (34). For intermediate values of ZL we use (32) and the results of Fig. 7. 11. Numerical calculations of particular cases. Any attempt to calculate temperatures on the above basis requires a knowledge of g, and this requires a knowledge of the size and number of the points of contact. For this reason we consider only the case of a single contact which we shall take to be a square of side 2/7. Then if the load on the slider > is W gm., the coefficient of friction yu, and J the mechanical equivalent of heat We consider first the model of Fig. 8 (a), §10, Case (i); inserting (49) in the results (40) and (42) we find for the average temperature over the area of contact, if L=lV/2x, is small, 0-236 uWgV | ii aR meee ay eG oe hae eee and if LZ is large the result is 0:266 x 3uWgV lJ (1-125 K,x,?+ K,(lV)) If the area of contact remains fixed the temperatures attained are thus proportional to the velocity when ZL is small, and to the square root of the velocity for large Z. For intermediate values of Z a transition curve given by (44) and (49) is obtained. This is best illustated by a numerical example involving this range. We consider mild steel sliding on mild steel with K, —H,—0-144, % =%, =0-173, W =400, p=0-23, 1=10-%. The results are shown in Table IIT, where the values of L, « defined as in $10, and the average temperature Vay are given for various values of V. TABLE 3. V. L. | a. Vay- bo S i) SOoOOCOCOFNNR Or ~J ie 2) oooocoooco or QO iJ) i=) fo) MOVING SOURCES OF HEAT. 219 It will be seen that « tends to 4 for small values of V, and increases steadily as V increases. Also the curve of vay against V shows a slight curvature over all but the early part of its length, say for V> 200, ie., L>0-5. The experi- mental curves of temperature against velocity in B.R. are linear for temperatures not too close to the melting point, this indicates that small values of LZ must be in question, say 2<0-5. For example the curves, B.R. Fig. 6 (a), for constantan on mild steel are linear up to V =1,000, and the criterion Z <0-5 implies for this case 1<1-7x10-4 cm. The temperature calculated from (44) and (49) for constantan on mild steel with V=1,000, /=1-7 x10-4, is 3,140° C. as against 940° C. experimentally. Thus the criterion [<0-5 is perhaps too restrictive ; if we take 1=4-5 x10~-4, which gives theoretically 940° C. at V =1,000, the curve of temperature against velocity has a slight curvature, for example its value at V=500 is 560° C. as against 470° C. experimentally. It appears that fairly good agreement between theory and experiment can be obtained in this rather extreme case provided J is taken to be small ; in most cases | will be small and V moderate, so that LZ will be small, the temperature curves will be linear, and (50) may be regarded as the most suitable simple formula for comparison with experiment. We now consider the model of Fig. 8 (6) and §10, Case (ii); this has the considerable disadvantage that 4/? enters both as the area of the slider and the area of contact ; in practice, even with a narrow slider, the area of contact will be much less than the area of the slider and the problem will approximate to that of Fig. 8 (a). It seems worth while discussing the model briefly on account of its use in B.R. Introducing (49) in (46) and (48), the average temperature over the area of contact for small Z is found to be 0-236 uwWgV lJ (K, +1:338(LK,c)3) and for large L 0-266 wWgVx,?t WIS RKeV A SOMGaRea\e | (52) and (53) are free from the objectionable features* of the formula [B.R. (5), 718 replaced by 4 to correspond to a square slider, and « by 1 —a« to correspond with the present notation ] (l—a)uWgV RBaKEIR ses eens which, if « is taken to be constant as in B.R., makes the temperature tend to infinity as o—0, or as K,—0. In Table IV calculated average temperatures for several values of / are given for the case considered in B.R. [Table I, p. 643] of a constantan slider, K,=0-055, c=0-00095, sliding on a mild steel surface, K,=0-144, x,=0-173, with V=100, W=100, »=0-23. The three columns give the result calculated from (54) with «4, that calculated as in §10, Case (ii), and that calculated as in §10, Case (i), for constantan on mild steel. It will be seen that (54) with «=4 indicates results which are far too high, since the value of « in all cases is in fact almost 1. The conclusion seems to be that, though high temperatures can be obtained theoretically, they require much smaller areas of contact than those indicated in B.R., Table I. * The formula (54) has been criticised by Morgan, Muskat and Reed (1941), on the ground that it makes the temperature tend to infinity asJ]+0. This, however, is simply a consequence of the assumption (49) that a finite quantity of heat nWgV/J per unit time is liberated at the source ; if the area of the source tends to zero we have a point source of finite strength which gives infinite temperature at the point. 220 J. C. JAEGER. TABLE 4. l (54) Case (li). Case (i). cm. ie Oh, Gs AcE 0:05 59 0-4 0:3 0:0158 332 1:9 1-7 0-005 1,860 9-8 8-1 0:001 20,770 75:0 57:0 0: 0005 59,000 164-0 120-0 0:0001 880-0 640-0 Finally the way in which, other things being equal, the average temperatures vary with the conductivities of the two substances may be considered. It has been remarked above that (50) is the simplest formula likely to give reasonable agreement with experimental results. This gives a temperature proportional to iL Ky +Ky while (54) gives a temperature variation with K,~*, and rather better agreement with experiment.* The way in which the temperatures vary can be seen from 1 ae! Table V, which shows ——— and KK, for various combinations. K,+K, TABLE 5. 1 Substance 2. Substance 1. ik. KG. | eee K,73. Copper... .. | Mild steel 0-918 0-144 0-94 1-04 Mild steel .. .. | Mild steel 0-144 0-144 3°47 2-63 Lead sive .. | Mild steel 0-0827 0-144 4-4] 3:48 Bismuth .. .. | Mild steel 0-0194 0-144 6-12 7°18 Copper ne .. | Copper 0-918 0-918 0-54 1-04 Glass si .. | Copper 0-0017 0-918 1-09 24-0 Silk. . si .. | Copper 0-0001 0-918 1-09 100-0 Silk. . ts .. | Glass 0-0001 0-0017 550-0 100-0 It is seen that for ordinary values of the conductivity, with the 1/(,-+4,) law a fairly large variation in average temperature can be obtained by varying the conductivity of one of the substances, but extremely high values of the temperature cannot be obtained unless both substances are of very low conductivity. 12. Sources whose strengths vary over their area. In all the preceding sections the strength of the source has been assumed to be constant over its area. If the strength of the source varies over its area the problem may be treated in the same way ; since there is no clear indication from physical considerations of the law of variation we confine ourselves to showing that for the simplest problem of this type, namely a band source of length 21 moving with velocity V in the «#-direction in the plane z=0 of semi-infinite solid z<0 with no loss of heat from the plane ¢=0, the * The comparisons with experiment are not very satisfactory since for fixed V and W it may be expected that and / will also depend on the sliding substances. ———— MOVING SOURCES OF HEAT. 221 temperature distributions for various simple laws of variation which give the same total heat emission per unit time per unit length of the band are not very different. If the strength of the source is qf(#’) we obtain as in $4 in place of (5) for the temperature in the plane z—0 a/ 0 Pion sont \ils Vig—ax’ eee ; pat | Vee reg, PPR" puna —-| X +L end UK Vee 55 saan e- "Kh (|u|) f r ee Me Rageh ake Beets “(5)) X—L In Fig. 9, curves (i) . . . (iv) show (xKVv/2xq) plotted against §=«/l for the following cases : | (i) f(#’)=1, the constant source previously discussed. (ii) f(a’) =q(a’ +1)/1, a linear law with a maximum at the front of the band and zero at the rear. (iii) f(v’) =q(l—a’)/l, a linear law with zero at the front of the band and a maximum at the rear. (iv) f(#’) =3q(7? —x?)/(21?), a parabolic law. R—October 7, 1942. 227, 5. CO FARCE: The curves, though differing in shape, do not differ much in maximum or average temperatures, so it appears that the previous results for constant sources should give results of the right order of magnitude for any not too extreme law of variation. 13. A ease tn which the velocity of the source 1s not constant. There is no difficulty in treating cases in which the position of the centre of the source is a given function f(t) of the time; the strength of the source (taken to be uniform over its area) may either be constant, another arbitrary function of the time, or, as in the most important practical case, proportional to the velocity, say Qf’(t) per unit time per unit area. Any case can be treated by the appropriate integration of (1) or (2). As an example we determine the temperature at the centre of a band source which executes a simple type of relaxation oscillation. It has been suggested by Morgan, Muskat and Reed (loc. eit.), and others, that the stick-slip behaviour observed by Bowden and Leben may be due to relaxation oscillations in which the kinetic friction is less than the static friction. The simplest possible problem of this type, neglecting damping and assuming constant coefficients of friction, is the folowing : a mass m is held by force P against a plane which moves with velocity V, the coefficient of static friction is uw’ and the coefficient of kinetic friction is py, u’>pu. Motion of the mass m parallel to the plane is resisted by a spring of stiffness mn?*. We suppose the mass to be moving with the plane ; this will continue until its displacement is UP Co eaaeny 8 mn- when it will commence to slip backwards. Taking this time as the origin of time the new motion is given by m(d?x/dt?) = —mn*7 +P with initial velocity V and initial displacement w’P/mi?*. The displacement in this motion is bP (ue Vt: = , te H) cos nt-+— sin nt minr= mn H and the velocity Is P (u’—p)P. V cos nt— ued Es sin 2. mir This motion continues until the relative velocity is zero, when shding ceases; this happens at time eas ee =e f=" Stent EE (57) a n mnV and the process repeats. As a numerical example, let uw’ =0-5, u=0-45, /’-=400 em., V =0-006 em./sec., m==0°5 gm., ==2,0007, so that #,=—0-0099 cm., 7,=—0-0079 cm., T,=0-33 sec., 7 =7/n=-0- 0005 secs) mearky. | hat) ete t : MOVING SOURCES OF HEAT. 223 Then in the slip region the displacement is approximately 0-009 -+0-001 cos 2,000nt, 0 ae a, ’ - ‘ i Cees 4 ae rear aL ‘ ee Sipe . 0 ‘ » Pe a a # bP ealal é 4 ue * . 1 ¢ . ot g 3 ae Ae 5 AUSTRALASIAN MEDICAL PUBLISHING Company, Limi 2 bt 4 rf Po eM Ok NEY oh ee See ee ae TED iS Attn i ods shah OR ‘ ‘ i i > P f ‘4 R - La } PBe : > ) 1942, (INCORPORATED 1881) OL. ‘LXXVI- THE HONORARY SECRETARIES @ 2 2 || E Bhan — MADE AND THE OPINIONS: EXPRESSED THEREIN ie Part, Ve, ¢ Arr. XIX.—A Revision of Certain Species of Leptospermes. ‘By Bawin c el. Seaver August: 2, 1943). he, Art. XX.—Physiography of the Wellington District, N.S.W. By Marga BSc. (Issued August 2, 1943) Ciel Re EF V4 see ee ‘ Art. XXI.—Upper Ordovician Graptolite Horizons in. the Yass-Jerrawa Di tri - By Kathleen Sherrard, M.Sc. — (Issued August 2, 1943) wie e ART. XXIT. —Permian Bryozoa of Eastern Australia. Part II. _ Baie Crockford, M.Sc. (Issued August 2, 1943) ea ee te peck ART. XXIII. —The Ketan of Solvents on Torbanite and the Matus of eee By J. A. Dulhunty, B.Sc. (Issued August 2, 1943) — sa somes oe Art. XXIV.—The Chemistry of Bivalent and Trivalent Rhodium. ‘Part VI = yric Complexes of Rhodous Halides. ay BoP: Dee, M. se and R. S. Ny. .10lm, (Issued August 2, 1943) a Sa ae ea : : a oe ne eer Art. XXV.—A Note on the Magnetic Behaviour of Potassium Cyanonicketite, ie. : Mellor, M. Se., and D. P. eee M.Sc. a ques 28, eS é Production cee a Pouch-like Structure in ihe Male of Trichioce ‘eulpecul Adolph Bolliger, Ph.D. (Issued August 2, 1943) oh ae uy cae e Monee Art. XXVII.-—Co-ordination Compounds Derived from Nicotinylacetone. : Lions, B.Sc.. Ph.D. » Benjamin S. aos M. Sc., and Ernest tone M. Se. September 1, 1943) PA ae aS ae ae ee a ArT. XXVIII.—Progressive Rates of Tax i in 1 Australia. 11. ae H S. os September 1, 1943) .. er ey oa Pe a Pe Ant. XXIX.—Galileo and Newton : Their Times and Ours. oo 50: [ (Issued September I, 1943)... Bakes fie 2 PEN ene ss eee Hee ae ae Art. XXX.—Chemistry of the arth. ¢ By i , Anderson, Ph. D. | (First Lecture.) (Issued September i 1943) re Gee Be ee es Arr. XXXI.—The Imperfect Crystal. By J. S. Anderson, Ph. D. Lecture.) (Issued September J, a) a ae TITLE PaGR, ConTENTs, Notices, PunLications . — Pee oe OFFICERS FoR 1942-438... ee ‘ “ atayee . % 7 s HS Y vwv vvv = S/L VRIAN —————_—_, Tuff ~SILN. RECENT ag Alluvium DEVAN ae re ia: UL} ee tuff s (Silurian and Middle Devonian sediments have been grouped together and Tertiary intrusions omitted.) Generalised geological map of the Wellington district. Pig. 2. T—December 2, 1942. 238 MARGARET J. COLDITZ. 2. GENERAL GEOLOGY AND STRUCTURE. The greater part of the area mapped (Fig. 2) consists of limestones, shales, tuffs and volcanic rocks of Silurian age, overlain by Lower and Middle Devonian limestones and shales, and Upper Devonian sandstones, shales and conglomerates. These Middle Paleozoic rocks have been folded into a series of plunging anti- clines and synclines which have a north-south trend and are intruded by the Yeoval and Wuuluman granites in the south-west and north-east respectively. Sills of augite-lamprophyre (Basnett, 1942) occur in Silurian slates to the west and north-west of Wuuluman. The repetition of the volcanic and sedimentary stages by folding has pro- duced more or less parallel bands of rock which differ in their resistance to erosion and so have formed alternating ridges and valleys whose direction conforms with the strike of the rocks. The syneclinal formation of the Upper Devonian sediments of the Catombal Range and the folded Silurian strata of the Wuuluman Range have shown the greatest resistance and now form sub- meridional ranges nearly 2,000 ft. in height and 1,000 ft. above the present river levels (Pls. XIII, Fig. 2; XIV, Fig. 2). In the vicinity of Wellington TS. and of Mumbil, the voleanic rocks reach almost to this height. The north-western boundary of the area is delimited by Jurassic sandstones and shales which extend to the north-east and to the west and have a gentle dip to the north-west. Small plugs and dykes, probably of Tertiary age, are numerous, and patches of Tertiary basalt and of alluvium occur at different levels, overlying both Paleozoic and Jurassic strata. 3. TERTIARY BASALT. Scattered outcrops of basalt, probably of Tertiarv age, occur throughout the district and are sometimes underlain by alluvial deposits. These few remnants of a once extensive basaltic sheet have preserved small portions of the pre-basaltic topography and from them the contour of the old land surface can be partly reconstructed. The most elevated outcrop of basalt is that which caps Mt. Bodangora (Lincoln T.8.), a prominent landmark 2,500 ft. above sea level lying 13 miles north-east of Wellington. The base of the basalt is at 2,240 ft. approximately and below it lie 25 ft. of current-bedded sandstones and grits which are probably Jurassic but may be a later, pre-basaltic deposit. These sediments were deposited on an old surface of weathered granite which is 200 ft. above the highest parts of the present granitic surface. (Figs. 3,7; Pl. XIV, Fig. 1.) CATOMBAL RANGE quarie R lithe f Soil -covered Areo Ae a, HORIZONTALS © SCAUEIn Poceeate co ees) at artery a On O TT / Z fiesoneenia ge EE ee ee eer el a MLE VERTICAL SCALE WELLINGTON Bell River Mac Fig. 3. Generalised section from the Little River through Wellington to Mt. Bodangora. x= On the southern flank of the mountain a small conical hill is capped with basalt at 2,000 ft. As this basalt resembles the higher one petrologically, it is either a continuation of this flow at a lower level, or more probably, a plug filling the vent through which the basalt was extruded. Thin cappings of basalt cover old alluvial deposits in the vicinity of and south-east from Newrea (Fig. 6). They form flat-topped hills along the eastern PHYSIOGRAPHY OF THE WELLINGTON DISTRICT, N.S.W. 239 margin of the present river valley, the base of the basalt being about 400 ft. above river-level and 1,480 ft. above sea-level (Pl. XIII, Fig. 3) and continue southwards towards Molong, where the outcrops are more continuous and appear to link up with basalts in the Orange district. Similar occurrences are to be found along the valley of the Macquarie River between Lewis Ponds Creek and the Cudgegong River (Fig. 4). -Coorangooree ES ; 2090 Ft nN STUART TOWN Muckerwa. (reck Mocg varie River 1000 Fig. 4. Section from the Bell to the Macquarie River through Stuart Town showing basaltic terraces in the river valleys. (Drawn from information supplied by F. W. Booker, M.Sc.) Small residuals occur three miles south of Ponto at about 1,200 ft. above sea-level and other cappings are to be found one and a quarter miles west of Maryvale (1,250 ft.), at Nobby, five miles north-east of Wellington at 1,860 ft., and two miles to the south-west of Nobby at 1,600 ft. The last two basalts are similar petrographically but not in field occurrence ; the latter is thin and lies on the shoulder of a hill which rises 150 ft. above it whilst Nobby is an isolated hill capped with 75 ft. of basalt (Fig. 3). Basalt cappings occur at intervals along the Jurassic escarpment, as at Purseglove T.8., Geurie Bald Hill and Geurie Hill. At the first of these, 70 ft. of basalt overlies Jurassic sandstone at 1,500 ft. above sea-level, whilst Geurie Hill is at 1,250 ft. and 450 ft. above the Macquarie River, the total thickness of basalt being 225 ft. At Geurie Bald Hill (1,443 ft.) the base of the basalt lies. above 1,200 ft. but is obscured by talus. Back from the margin of the Jurassic the outcrops of basalt become more continuous and are found at Wongarbon at 1,200 ft. and at Eulomogo at 1,100 ft. (Fig. 1). 4, ALLUVIAL DEPOSITS. The alluvial deposits range in age from Tertiary to Recent; some of the oldest underlie the basalt at Newrea and are 350 ft. above the alluvial flats (of the Bell River); they are as much as 60 ft. in thickness and consist of gold- bearing sands and gravels (Fig.6; Pl. XIII, Fig.3). Similar deposits occur along the valley of the Bell River towards Molong and also in the Macquarie River valley (Fig. 4). At Muckerwa Creek they consist of sand and quartz-gravels, some of which have become cemented with iron oxide (Jaquet, 1894). : About two miles west of Ponto in Por. 101, Par. Terrabella, quartz-gravels cap low hills on the eastern margin of the Little River alluvium. They have a cement of iron oxide and are between 150 and 200 ft. above the Macquarie River. Similar iron-cemented deposits occur between this locality and Dubbo and it is likely that they have been formed by the outpouring of basalt—now eroded away—over the gravels. Younger alluvials than these are to be found on the north-eastern boundary of the town of Wellington on a terrace 1,000 ft. above sea-level and 50 ft. above the river, where they are quarried for use as road metal (Fig. 5; Pl. XITI, Fig..1).. Similar gravel-covered terraces occur on the Yeoval Rd., about two 240 MARGARET J. COLDITZ. — miles from Wellington and also about four miles (direct) south-east from Ponto. Scattered gravels lie above the caves and on the lower terrace at Newrea (Fig. 6). All these deposits consist of pebbles which are usually not more than one inch in diameter and are chiefly quartz admixed and interbedded with coarse sand. uu cv) = Se x a Ss 3 SS S = Bell River about 1 mile Fig. 5. Generalised section across’ the Fig. 6. Section across the valley of the Bell Macquarie River near Wellington, looking River a few miles above Newrea, looking downstream. The configuration of the buried upstream. channel is hypothetical. Thick deposits of bones and red earth occur in the Wellington Caves six miles south of the town in the valley of the Bell River. These are thickest in the topmost caverns and their mode of origin is uncertain, though there can be no doubt that they are younger than the caves which they fill. Thompson (1882) described the caves and suggested that they were filled from above. This infiling was probably caused by floods as well as by birds and other animals which frequented them. Gravels which must be younger than those on the Wellington terrace and yet older than those of the present-day lie buried 100 ft. below the Macquarie River at Wellington, where they are being dredged for gold (Jones, 1935) (Fig. 5). They occur in an ancient channel of the Macquarie, of which there is evidence in other parts of the river course. Upstream near Stuart Town, Harper (1909) records an old channel 30 ft. below the present river bed, whilst downstream at Dubbo, gravels have been found 75 ft. below the river flats (Lloyd, 1934). At the Jawbone lead, east of Maryvale, auriferous gravels which were deposited by a tributary of the Macquarie River were worked to a depth of 60 ft. from the surface (Jones, 1935). | These buried river-deposits are not limited to the Macquarie as they have been recorded from the Lachlan River basin by E. C. Andrews (1910) thus: ‘* Around Parkes old watercourses are found from 50 to 100 ft. below the present surface of the alluvium ; near Tichborne the old channels lie from 100 to 150 ft. below the present surface of the black-soil plain ; the famous South lead of Forbes has its channels as far below the surface as 210 ft.”’ The most recent of the alluvial deposits are those which form the present flood-plains and river-channels ; the former are fairly extensive and consist of grey loam whilst in the bed of the river coarse water-worn gravels occur. 5. TOPOGRAPHY. The town of Wellington (1,000 ft.) is situated in the valley of the Bell River at its junction with the Macquarie and is built on a terrace which forms a barrier as much as 100 ft. in height between the two rivers (Pl. XIII, Fig. 1). | The Bell River flats, which are two miles in width, are bounded on the west by the Catombal Range and extend southwards for about five miles (Pl. XIII, Fig. 2), whilst the alluvium of the Macquarie River continues north- wards from the town towards Maryvale. The Catombal Range trends in a north- PHYSIOGRAPHY OF THE WELLINGTON. DISTRICT,N.S.W. 241 north-westerly direction to the Macquarie River, north of which a ridge continues for about two: miles and passes imperceptibly into the remnants of a former erosion-surface 1,250 ft. in height. Towards its northern limit the range, which is strongly dissected by insequent streams draining to the two main rivers, consists of a series of peaks, the chief of which, Mt. Arthur, has an altitude of 1,875 ft. and is 880 ft. above Wellington railway station. . The topography of the whole of the south-eastern part of the area has been strongly influenced by the strike of the Paleozoic rocks (Figs. 2, 7). Valleys carved from shale and limestone alternate with ranges of hills which consist either of Silurian volcanic rocks or of resistant sediments. The relief of the country varies from 300 to nearly 1,000 ft., increasing eastwards from the Bell River (Fig. 4). Catombal Ka. Wuuluman Ra, [WELLINGTON Yeoval MtBoclangore: Sunfop Maryvale. / ~ a yy ~ 2 a 7 , LB ALN v Fd M 4, SO, 4 A NY -—— 24 miles 5 =-,. approx. Fig. 7. Block diagram of the Wellington District. (See Fig. 2.) The area between Yeoval and Bodangora is much more mature than this, and although the original trend of the hills has been retained in places the slopes are gradual and relief is usually between 50 and 100 ft. (Pl. XIV, Fig. 2). Outcrops are rare as the underlying rock has been covered with a thick mantle of reddish- brown soil probably derived in part from preceding surfaces of erosion. This soil is very suitable for wheat growing and resembles the ‘* thick waste sheet of exceedingly gentle slope, often extending from the alluvium proper up to the very summits of the low hills which rise from the plains ”’ of the Forbes-Parkes district (Andrews, 1910). Along the courses of the Macquarie River and its tributaries alluvial flats have been formed varying in width according to the nature of the underlying rocks. . . The Jurassic sandstones crop out as a low escarpment which rises above the Palwxozoic basement. The base of the scarp rises to the north-east and falls to the west; at Purseglove T.S. it is 1,500 ft. above sea-level, at Geurie 1,000 ft. 242 - MARGARET J. COLDITZ. (150 ft. above the river), while at Geurie Hill it is almost at river-level. The Jurassic rocks form an undulating surface which extends towards Dubbo from Geurie, and also to the north ; near Geurie it is about 1,300 ft. but this elevation increases northwards and decreases to the west. North-east of Wellington the Wuuluman granite forms an elevated area of small extent which rises at the margins to 2,000 ft. and slopes from 1,800 ft. in the south-east to 1,300 ft. near Bodangora, where Mitchell’s Creek flows from it towards the Talbragar River. On its north-eastern edge (2,000 ft.) Mt. Bodangora rises to a height of 500 ft. (Figs. 1, 2,7; Pl XIV, Fig. 1). 6. DRAINAGE SYSTEM. (1) General. The Macquarie, known above Bathurst as the Fish River, rises to the south of Oberon, where the plateau is about 4,000 ft. above sea-level, and flows north- wards towards Tarana, where it emerges from a deep “‘ gorge ”’ on to the so-called Bathurst Plains, across which it takes a west-north-west course to Bathurst. This broad valley has been carved from granite and at Bathurst the river (2,150 ft.) is about 1,000 ft. below the level of the Orange Plateau. A few miles to the west it enters another “ gorge ”’ through which it flows in a north-north- westerly direction to its junction with the Cudgegong River (Fig. 1), whence its general direction changes to the north-west as it flows through Wellington towards Dubbo. In this part of its tract the steep-walled valley gradually gives place to one of more gentle configuration and alluvial flats become more extensive. Between Geurie and Dubbo entrenchment within the Jurassic surface is evident, though to a depth no greater than 400 ft. The gradients for these portions of the river’s course are as follows : Oberon- Tarana, 27 ft. to 1 mile; Tarana-Bathurst, 11 ft. to 1 mile; between the Turon and Cudgegong Rivers, 9! ft. to 1 mile (Harper, 1909) ; between the Cudgegong and Little Rivers, nearly 3 ft. to 1 mile. Feet 4,000 | -~~ OBE RON 7: O'CONNELL Bs Ss ww vu c ce 2 = u a i —e BATHURST Muackerwa Ch. =S— 3,000 7 C udgegong R 2,000 > es / ——}- WELLINGTON 1,000 S.L. Miles O 25 50 100 150 200 250 Fig. 8. Thalweg of the Macquarie River between Oberon and Wellington. The broken line indicates the probable height of the Miocene peneplain before erosion, in the vicinity of the river course. Below Dubbo the Macquarie soon reaches the Western Plains, and of this part of its course H. G. McKinney (1885) writes as follows: ‘‘ As the river reaches the plains and passes in a tortuous course towards the Darling, the rate of fall diminishes (2 ft. 6 in. per mile from Dubbo downwards) and the channel decreases in size till it reaches the Macquarie Marshes, where it divides into a number of creeks ; with a low discharge in the upper parts of the river the water disappears before it reaches the Marshes. In ordinary floods the diminished — section of the channel obstructs the passage of the flood-water and forces a portion of it over the left or lower bank ; the remainder of the flood-water passes on to the Marshes, where it spreads out in a thin sheet over immense reed beds PHYSIOGRAPHY OF THE WELLINGTON DISTRICT, N.S.W. 243 and is there retained till it disappears by evaporation and absorption. In extraordinary floods only, does the Macquarie water reach the Darling ; on such occasions the floods escape over the left bank of the Macquarie in many places, the first being at Narromine, and flow in a series of creeks to the Bogan and thence to the Darling.” Between Wuuluman Creek and the Little River the Macquarie flows in a north-westerly direction and is fed by several tributaries, the Bell and Little Rivers being the only ones of importance (Fig. 2). Creeks which flow eastwards from the eastern margin of the Wuuluman granite reach the main stream by way of the Cudgegong River, and Mitchell’s Creek, which rises in the granite, flows north-west to the Talbragar, which joins the Macquarie four miles below Dubbo. The direction of flow of the Macquarie River in the Wellington area, as well as the structure of its valley, indicate that it is an entrenched consequent stream fed by tributaries of a subsequent character, these in turn having smaller insequent tributaries. In the less mature parts of the district the nature of the rocks and their structures have had an important bearing upon the direction of flow of both consequent and subsequent streams and upon the relative maturity of their valleys. Owing to the extent of its catchment it is only during exceptionally dry summers that the Macquarie River ceases to flow at Wellington. The Bell, which has a more restricted drainage area (Fig. 1), is normally a small stream which may cease flowing for part of the summer, but waterholes remain and wells along its banks also yield a permanent supply of water. Other watercourses, with the exception of Curra Creek, contain water only after heavy rain, as it is transported rapidly to the main stream. (2) Valley Form and its Relation to Geological Structure. (a) The Macquarie River. Below Wuuluman Creek the Macquarie River has the characteristics of a superimposed consequent stream as it meanders obliquely across the strike of the country towards its junction with the Little River (Fig. 2). The form of these meanders appears to have been influenced to some extent by the nature of the rocks and probably by jointing, as the river has repeatedly carved its way first along, and then across, the strike of the beds, so that in its north-westerly journey it proceeds in short distances to the west and longer distances to the north. Below its junction with the Little River, where it flows through the more homogeneous Jurassic rocks, the course of the flood-plain is more direct and the river meanders through it in a northerly direction to Dubbo. In the eastern parts of the area where the river cuts its way through hardened slates and porphyry the valley-floor is narrow and the walls rise steeply from it to a height of 500 ft., but north-west of Wellington the flood-plain widens considerably along the strike of easily eroded sediments. The western wall of the valley is steep where the river course impinges on the Upper Devonian rocks of the Catombal Range, and when it cuts across the strike of these rocks the valley narrows suddenly. Once this barrier is passed, however, the flood-plain becomes extensive and the valley walls are low and gently sloping. The accumulation of alluvium along the strike of the beds is probably due, not only to less resistance to erosion in this direction, but also to the fact that the hard rock downstream forms a barrier to the flood-waters, which deposit their silt behind it. The same effect is produced in the lower reaches of the Bell and Little Rivers and in less important tributaries by the flooded Macquarie which backs up the flood-waters of its confluents and so causes them to drop their burden of silt. Throughout its course the river flows between banks of alluvium usually between 30 and 50 ft. in height and rock barriers occur at intervals along a bed of 244 MARGARET J. COLDITZ. sand and gravel. Terraces are developed in the banks and flood plain and small anabranches are common. (b) The Tributaries of the Macquarie. hike that of the parent stream the tributary valleys vary according to the nature of the rocks in which they are cut. Many of them trend in a northerly or southerly direction and are separated by strike-ridges (Fig. 7). Where they join the Macquarie the alluvium is usually deep and extensive and the angle of confluence may be very acute ; this is particularly the case with the Bell River where a long narrowing tongue of alluvium extends between the two rivers approaching their junction. The gradual slope of this tongue from 100 ft. above the river (Pl. XIII, Fig. 1) suggests that there has been a'westerly migration of the junction from a position east of Wellington and two miles above its present locality. Matheson (1931) was also of this opinion. The same process has probably occurred with the Little River, which may have originally flowed into the Macquarie on the eastern boundary of its present alluvium (Fig. 2). The Bell River, which has its source near Orange (Fig. 2), has a course much more accordant with the structure than has the Macquarie in the area studied (Fig. 2). From above Newrea it flows in a mature valley along a line of faulting towards the Catombal Range, against which it turns to the north, leaving the Upper Devonian on the west and carving its valley in the Middle Devonian and Silurian limestones. Its alluvial banks are from 15 to 20 ft. high, and terraces and anabranches occur on the flats. Chief of the tributaries of the Bell is Curra Creek, which rises near Catombal T.S. and flows northwards along the strike of the Middle Devonian sediments on the western side of the Catombal Range (Pl. XIV, Fig. 2). Its valley here is wide and mature but at the Arthurville Road crossing, it bends suddenly to the © south-east, then to the north and finally flows to the north-east through the range in a narrow, flat-floored but steep-walled valley till it reaches the alluvial flats of the Bell. The peculiar course of this stream may be due to the capture of a north- flowing tributary by a stream which had cut.back through the Catombal Range, the new creek subsequently becoming entrenched. This suggestion is borne out by the fact that water-worn gravels occur a few miles to the north of Suntop at a height of 1,300 ft. above sea-level and 220 ft. above the level of Curra Creek at the Arthurville Road crossing. Mitchell’s Creek meanders across the Wuuluman granite through banks of coarse sand studded with pink felspar crystals from the weathering of the porphyritic granite. Further downstream it flows through Silurian lavas and tuffs for more than ten miles before reaching the Jurassic sandstones. The voleanic rocks offer more resistance to erosion than does the granite and crop out along the banks and bed of the stream. The nature of its valley within the Jurassic has not been observed. The northerly direction of flow of this stream suggests that its source may have lain somewhere near the southern limit of the old Jurassic cover. The sediments probably existed here as a thin mantle on the granite, at least until the outpouring of the Mt. Bodangora basalt, after which further erosion removed both basalt and Jurassic rocks, leaving the creek to become superimposed, in its upper reaches, on the underlying Paleozoic rocks. One of the naost interesting of the minor tributaries of the Macquarie River is Poggy Creek, which rises in the south of the Wuuluman granite and flows throughout its course in an alluvial channel between 15 and 20 feet deep. For two miles south of the granite it has carved a broad valley in the augite lampro- phyre, an easily weathered rock, but where the volcanic series comes to the surface the creek is forced to flow through a gorge to the alluvium of the main PHYSIOGRAPHY OF THE WELLINGTON DISTRICT, N.S.W. 245 river (Fig. 2). Upstream from the gorge the wide flood-plain has well developed terraces probably due to the damming effect of the gorge. A small intermittent creek with a narrow channel joins the Macquarie River in the flats about two miles north of Wellington. Its junction with the main stream has been effected through a resistant barrier of volcanic rock, in contrast to the upper part of its tract, which lies in a zone where easily eroded shale and limestone have been further weakened by intense folding and faulting. The resistant band has probably played some part in the damming back of the stream and the deposition of the wide sheet of alluvium which covers the gravels at Jawbone. The latter however indicate the presence of a more vigorous tributary 60 ft. below the present surface at a time when the Macquarie flowed through its déeper, more youthful valley. The streams, both large and small, are entrenched in alluvium, but whereas the former have banks which are terraced and often slope gently, the small channels are usually narrow with almost vertical banks carved from soil or alluvium. The floors of these channels are often formed of soil with occasional boulders and many have undoubtedly been formed by the effect of heavy storms on ploughed fields and cleared land. Increased run-off due to clearing must also have caused entrenchment of existing small watercourses. . 7. EROSION SURFACES. Within the Wellington district there are remnants of what appear to be five surfaces of erosion, of which the three most recent are represented by valley-in- valley structures. Most of the levels can be seen to the east and south of Newrea, some ten miles to the south of Wellington, where remnants of the old valleys of the Bell River and its tributaries have been preserved. In the areas of more mature dissection the different erosion surfaces are sometimes difficult to define as they grade into one another. In the Parkes-Forbes district which les 60 miles to the south-west of Wellington and is in the Lachlan River drainage basin, Andrews (1910) has recorded ‘‘ remnants of at least four of these old valley floors which are distinctly enclosed by the high and widely separated quartzitic and granitic walls of the main valley ’’. Though these have not been described in sufficient detail to permit of correlation with the Wellington levels, their existence suggests the probability of such a correlation with this and also with other districts. A section across the Macquarie River east of Orange shows definite valley-in-valley structures which have been compared with the Wellington surfaces (Fig. 9). Milker's Flat T.S. 2500 Macquarie River 2000 PORIEONTIAU (OCA UE NT) truce ARUP O ORNS IS TE Miles Fig. 9.. Section across the Macquarie River Valley, 15 miles east of Orange, looking downstream. r (Drawn from Orange Military Survey Map.) 246 MARGARET J. COLDITZ. The localities in which the various erosion surfaces have been best preserved are set out in Table 1 in order of decreasing age. The numbers have been referred to in the text and in some of the sections. TABLE 1. Remnants of Erosion Surfaces. Surfaces. Deposits. Altitude. Reet a) — Feet. (1) Mt. Bodangora (Lincoln T.8.).. é .. | 260 Basalt, 25 Gravels 2,500 (2) N. and E. margins of Wuuluman granite ve | = 2,000 Wuuluman Range .. Sc ote — —_ (3) Terrace above Bell R., E. “of Newrea .. | 20 Basalt, 60 Gravels 1,500 Upper terrace at Wellington xe Hed ae | — 1,150 One mile W. of Maryvale. . | 15 Basalt 1,235 Three miles S. Ponto (Por. 130, ‘Par. Ponto) . Basalt 1,200 Geurie Hill . | 225 Basalt, Gravels 1,250 Two miles W. Ponto (Por. 101, Par. Terrabella) | Ferruginous Gravels 1,050 Two miles N. of Suntop .. ; . Sal Gravels 1,300 Nobby ame 75 Basalt 1,875 Two ne S. W. Nobby (Por. 92, Par. Nanima) _ | Basalt 1,600 Ponto-Walmer es — 1,300 (4) Lower terrace above Bell Be Newrea a. vr Gravels 1,250 Apsley ; s8 an lua as a —— 1,100 Wellington terrace se Gravels 1,050 (5) Buried Macquarie valley at Wellington. . ae Gravels ? 850 ee (1) At Mt. Bodangora sandstone and grit underlie a thick terraced deposit of basalt and represent what must once have been a continuous surface, but is now an isolated remnant standing 500 ft. above the surrounding country and 2,500 ft. above sea-level (Pl. XIV, Fig. 1). This surface is correlated with residuals rising above the Hargreaves-Hill End-Blue Mountain peneplain surface, i.e. with Mts. ‘Hay, Tomah and King George and others. (2) In the vicinity of Mt. Bodangora, particularly along the north- cee and eastern margins of the Wuuluman. granite, an old surface 2,000 ft. above sea-level is represented by hills of this elevation (Pl. XIV, Fig. 1). Further to the south the Wuuluman Range rises almost to this height, which is also approached by the higher points of the area, e.g. Mumbil T.S. (1,910 ft.), Mt. Arthur (1,875 ft.). This surface is believed to be an extension of the plateau which is so much in evidence in the Central Highlands, extending from Hargreaves to Orange and eastwards to the Blue Mountains (Fig. 1). Harper (1909) referred to this surface in its extension from the divide at Sunny Corner to Wellington as the ~ Macquarie River Peneplain. (3) Remnants of a wide valley floor about 500 ft. lower than surface (2) have been preserved along the Macquarie and Bell Rivers by patches of basalt which overlie alluvial material (Fig. 4). Alluvial cappings are to be seen at their best at Newrea and upstream along the Bell, where the base of the basalt is about 1,480 ft. or 400 ft. above river level (Pl. XIII, Fig. 3). Basalt-covered alluvial deposits occur along the Macquarie River between Muckerwa Creek and Lewis Ponds Creeks at heights comparable with those at Newrea. Along the Bell River the cappings extend southwards towards Molong where the outcrops of basalt are more continuous and the depth of its dissection is much less. The basalt here appears to have filled a broad valley separated from the drainage of the Macquarie on the east and the Lachlan on the west by low PHYSIOGRAPHY OF THE WELLINGTON DISTRICT, N.S.W. 247 divides which now rise above the level of the valley basalts and are not themselves basalt-covered (verbal communication from D. Moye, B.Se.). The broad valley extends southwards to Orange and merges gradually into the Orange Plateau. | At Wellington the public hospital and town reservoir are situated at 1,150 ft. on an old terrace (Pl. XIII, Fig. 1) between 200 and 250 ft. above the river (Fig. 5); the absence of gravels and basalt prevents a definite correlation, but it is comparable in elevation with other terraces included as remnants of this surface (Fig. 5). Basalt cappings occur west of Maryvale, south of Ponto and at Geurie Hill. South of Geurie Hill and on the southern bank of the Macquarie River iron- cemented gravels occur 150 to 200 ft. above the river. It is thought that these were deposited by the river when surface (3) was in existence, and if this be so the gravel terraces between this locality and Dubbo must be a continuation of the old river bed. Large water-worn pebbles of Upper Devonian quartzite have been, found about two miles north of Suntop. They are 1,300 ft. above sea-level and more than 200 ft. above the height of Curra Creek at the Arthurville Road crossing. Basalt occurs at Nobby, five miles north-east of Wellington at a little less than 1,800 ft. above sea-level, and another small patch is found two miles to the south-west at 1,600 ft. The latter is 300 ft. above the floor of a small valley and the country rises to nearly 1,800 ft. both to the north and south (Fig. 3). The Nobby flow may represent the higher part of the surface on which the basalt was poured out, and the lower level the old valley floor. Between Yeoval and the Catombal Range surface (3) is probably represented by hills which rise above a lower undulating surface and are 1,300 to 1,400 ft. in the Suntop-Walmer area, rising fairly rapidly to the south. In the Geurie- Maryvale-Bodangora area, conditions are similar to those at Suntop and the different surfaces are usually obscure. The basalt-covered valley floor which lies 500 ft. below the plateau level and 400 ft. above the river is comparable with the valley floor represented by basalt- covered alluvials at Bald Hills and Stewart’s Mount, near Bathurst. Here, the gravels are between 700 and 400 ft. below the plateau and 300 to 600 ft. above the river. From Cargo, in the Lachlan River drainage basin, Andrews (1915) has described alluvial wash on hills 500 to 600 ft. below Orange and in places this wash is covered with basalt ; this also probably represents a stream course which existed during the formation of surface (3) at Wellington. (4) At Newrea a terrace lower than the basaltic one and 150 to 200 ft. above the river has been much dissected but can be traced quite easily in places (Fig.6; Pl. XITI, Fig. 3) and is sometimes capped with water-worn gravels. It can be followed along the valley of the Bell to Wellington and includes the Wellington Caves limestone belt ; at Apsley it is at 1,100 ft. and from there it can be followed down to the higher parts of the ridge on which the town of Wellington is situated. This ridge is capped with gravels and its greatest altitude is 1,050 ft. (Fig. 6; Pl. XIII, Fig. 1). (5) The lowest valley floor of the Macquarie River is hidden beneath a deposit of alluvium which is 100 ft. thick at Wellington, 30 ft. at Stuart-Town and at least 75 ft. at Dubbo. There is therefore no visible record of the form of this valley except in those parts of it which are as yet unburied. These, taken in conjunction with the width of the present flood-plains, indicate that it was wide in some places and steep-sided and narrow in others, according to the nature of the underlying rock. 248 MARGARET J. COLDITZ. 8. AGE OF EROSION SURFACES. The allocation of ages to the erosion surfaces which have been described is a matter of some difficulty owing to the lack of fossil evidence. The scheme which has been adopted, admittedly conjectural, is set out in Table 2. TABLE 2. Physiographic History. Age. Events. Type Locality. Correlation. (1) Peneplain formed by streams flowing | Mt. Bodangora, | Mts. Hay, ? Eocene. to the north-west. 2,250 ft. at base Tomah, etc. Uplift (250 ft.). of basalt. (Blue Mts.). Extrusion of basalt. | (2) Development of extensive peneplain | Margins of Wuulu- | Hargreaves- Oligo- with residuals. man granite, Hill End, Miocene. Uplift (500 ft.)—in one or more stages. 2,000 ft. Blue Mt. | Plateaux. (3) Erosion of wide river valleys. Upper terrace, | Cargo, Bald Extrusion of valley basalts. Newrea, 1,500 ft. Hills and Pliocene. Uphft (250 ft.). Mt. Stewart (Bathurst). (4) Erosion of mature valleys. Lower terrace, | Parkes. Uplift (200 ft.). | Newrea, 1,250 ft. | - (5) Excavation of new river channels; | Channel 100 ft. | Parkes. Pleistocene- filling of caves with bones and earth. | below Macquarie Recent.- | Silting up of river channel to depth of | River (800 ft. 100 ft. a.s.l.). Present flood plain. A Miocene age is suggested for surface (2) on the basis of its correlation with the Hargreaves-Hill End Plateau and thence with the Blue Mountain Plateau. The latter is considered to be Miocene by physiographic writers such as KE. C. Andrews (1910a) and C. A. Sussmilech (1937). Surface (1), lying above the Miocene surface, is comparable with the residuals on the Blue Mountain Plateau, which are commonly believed to have been formed probably in Eocene time, partly covered with basalt, and uplifted possibly at the close of Eocene. Taking the Oligocene and Miocene periods for the development of the peneplain of the Central Tablelands, the formation of valleys in this surface has been put into the Pliocene, though it may have commenced in the latter part of the Miocene. The basalt which lies in the wide valley of surface (3) covers leaf beds at Forest Reefs near Orange and a lower Pliocene age was suggested for these by Andrews (1914) on rather indefinite fossil evidence. The erosion of the valleys of surface (4) has been assigned to the later Pliocene since it pre-dated the formation of the Wellington Caves and the deposits within them which probably range from Pleistocene to Recent (Anderson, 1933). Andrews (1933) suggested that broad mature valleys were developed in the warped, basalt-filled valleys of eastern Australia before the Kosciusko movement, and this conclusion seems to agree with the late Pliocene age assigned to surface (4 ) at Wellington. PHYSIOGRAPHY OF THE WELLINGTON DISTRICT, N.S.W. 249 Deep leads similar to those of surface (5) have been described from Parkes by Andrews (1910b) who places them in the Pleistocene together with the Diprotodon-bearing black soil plains of the district. 9. INTERPRETATION AND HISTORY. It is not known. whether the Macquarie River existed on the oldest of the Tertiary land surfaces at Wellington, but it is quite probable that it flowed in a north to north-westerly direction across surface (1) to an inland lake during (?) Eocene time. Jensen (1907) believes that this and other north-westerly flowing rivers were formed as consequent streams on the uplifted Mesozoic surface. | The (?) Eocene plain was partly covered with basalt and was raised 200 ft. at the close of Eocene. During the long period of quiescence which followed during Oligocene and Miocene a new peneplain was formed with a few scattered remnants of the old surface rising above it. The Macquarie River certainly existed at this time and flowed in much the same direction as it does today. Between Bathurst and the Cudgegong River it followed the strike of the Paleozoic rocks, after which it changed direction and flowed as a consequent stream across the Wellington district. The river was fed by subsequent tributaries which flowed from north and south towards the parent stream and the whole system was in a State of extreme old age by the time the Miocene peneplanation was completed. The peneplain produced was so extensive that great stretches of it are still preserved in the highlands of eastern Australia. Further uplifts and periods of stillstand at the close of Miocene and during Pliocene resulted in the successive entrenchment and widening of the streams, leaving a system of terrace levels to mark the positions of preceding valley floors. The highest of these: terraces at Newrea indicates that the peneplain was raised about 500 ft. at the close of the Miocene, following which valleys at least as much as five miles wide were eroded and to the east of Newrea the divide between the Bell and Macquarie was lowered to little more than 200 ft. The Catombal Range formed a ridge about 500 ft. high which was somewhat dissected in the north, while the country about Wellington T.S. was undulating with valleys 100 to 200 ft. deep, its general level being about 300 ft. below the plateau, which still existed to the east. West of the Catombal Range and in the Geurie- Bodangora area, wide, undulating and soil-covered expanses sloped gently towards the river, broken here and there by a low ridge or an isolated peak. A further uplift of over 250 ft. in Middle Pliocene time was accompanied by an outpouring of basalt on the plateau, so extensive that it flowed down the valleys of the Bell and reached the Macquarie River by way of Lewis Ponds Creek. The flows reached at least to Newrea and to Stuart Town and at the same time extrusions probably occurred in the north-east of the region. Tributaries of the Lachlan River were also filled with basalt (Andrews, 1915) and the leaf beds at Forest Reefs were covered (Andrews, 1914). In late Phocene the rivers became entrenched, first of all into the basalt, most of which was removed in the process, and then into the old valley floor. Again there was a sufficient period of rest for the formation of mature valleys, not quite so wide as the previous ones. To the east of Wellington the meridional valleys were deepened, the strike ridges became more prominent and to the west and north a lower undulating surface was developed. At this time the topmost caverns of the Wellington Caves, destined to be filled with bones and earth, began to form. The uplift which closed the Pliocene, and the subsequent entrenchment of the streams, left the upper caves (surface (4)) above river level but within easy reach of floods ; they probably had many openings to the surface, facilitating the entrance of materials and also-of animals, while the lowest channel was being 250 MARGARET J. COLDITZ. excavated during the Pleistocene. Since the old river courses have been filled by alluvial deposits, the configuration of their lower portions is unknown. The silting up of the Macquarie River was probably due to the same causes as resulted in the silting up of the Lachlan. Andrews (1915) suggests that this was caused ‘*‘ by a warping movement or one of irregular subsidence, by the decrease of stream action attendant on a decreasing rainfall, or again by the mature dissection of the hinterland ’’. The movements of uplift which raised the Miocene peneplain to 3,000 ft. at Hargreaves caused an elevation to 2,000 ft. at Wellington and to less than 1,500 ft. at Dubbo (Fig. 8). This slope was produced by a series of differential uplifts which attained their maxima in the south-east and decreased rapidly to the north-west of Wellington. The total effect of the movement is comparable to the eastern monoclinal fold of the Blue Mountains except that in the west the slope is much more gentle and the uplift was more gradual. The effect of the differential uplift on the Macquarie River has been pro- found. Each successive movement has caused rejuvenation, and upstream from the Cudgegong junction, uplift has been much greater than in the lower Macquarie, with the result that the river gradient changes fairly abruptly near Wellington (Fig. 8). Here also the river valley becomes mature and there is evidence of silting up of a deeper channel. Another important fact is that the terraces appear to converge downstream. It is impossible to give an accurate estimate of the amount of each move- ment in this region, which is not far from the western hinge of uplift, but sufficient information is available to show that total uplift was distributed throughout the Tertiary period and that there was no culmination of movement at the close of the Tertiary as there was further to the east (Andrews, 1910a). The history of both the Wellington and Cargo districts may well be summarised in the words of E. C. Andrews after he had examined the Cargo Gold Field, west of Orange, in 1915: ‘ The elevation of the region proceeded intermittently, while the intervening periods of stable equilibrium and stream erosion were of great duration. This appears to have been the work of the earlier Tertiary and the great lesson of the Tertiary movements in this district is the slow and intermittent nature of the uplifts which culminated in the formation of the high plateaux, only after long, intervening periods of erosion.”’ 10. SUMMARY. In the Wellington district, N.S.W., where Silurian and Devonian rocks are folded meridionally, part of the Macquarie River drainage system, during Tertiary and post-Tertiary times, produced two peneplains ; into the younger of these it was entrenched by separate movements of uplift giving rise to valley- in-valley formations. The structure of the rocks has determined the direction of flow of the subsequent tributaries and strike ridges have been developed. The Macquarie itself is a consequent river which originally flowed across the epi-Cretaceous land surface. | The history of previous land surfaces has been determined from the remnants of alluvial deposits and basalt flows. It is summarised in Table 2. 11. REFERENCES. Anderson, C., 1933. The Fossil Mammals of Australia. Proc. Linn. Soc. N.S.W., 58, 1x. Andrews, E. C., 1910a. The Geographical Unity of Eastern Australia in Late and Post-Tertiary Time. J. Roy. Soc. N.S.W., 44, 420. Andrews, E. C., 1910b. The Forbes-Parkes Gold Field. Geol. Surv. N.S.W. Min. Res. 13. Andrews, E. C., 1914. The Tertiary and Post-Tertiary History of New South Wales. B.A.A.S. N.S.W. Hdbk., 1914, p. 518. Andrews, E. C., 1915. The Cargo Gold Field: Geol. Surv. N.S.W., Min. Res. 19. Andrews, E. C., 1933. Origin of Modern Mountain Ranges. J. Roy. Soc. N.S.W., 67, 251.. Journal Royal Society of N.S.W., Vol. LDXXVI, 1942, Plate XIII Fig. 2. Journal Royal Society of N.S.W., Vol. LXXVI, 1942, Plate XIV tijyy Uy ay oil Saray ne ‘ PHYSIOGRAPHY OF THE WELLINGTON DISTRICT, N.S.W. 251 Harper, L. F., 1909. Notes on the Physiography and Geology of the North-Eastern Watershed of the Macquarie River. Geol. Surv. N.S.W., Rec. VIII, Pt. I, p. 321. Jaquet, J. B., 1894. Report upon Auriferous Drifts on the Macquarie River. Dept. Mines and Agriculture, N.S.W. Ann. Rept., p. 1438. Jensen, H. I., 1907. The Geology of the Warrumbungle Mountains. Proc. Linn. Soc. N.S.W., 32, 557. Jones, L. J., 1935. Geological Survey of Wellington Gold Field. Progress Report. Dept. Mines N.S.W., Ann. Rept., p. 76. Lloyd, A. C., 1934. Geological Survey of the Dubbo District, with Special Reference to the Occurrence of Sub-Surface Water. Geol. Surv. N.S.W. Ann. Rept., 1934, 84. Matheson, A. J., 1931. The Geology of the Wellington District, with Special Reference to the Origin of the Upper Devonian Series. J, Roy. Soc. N.S.W., 64, 171. McKinney, H. G., 1885. Ist Rept. Roy. Comm. Cons. Water, p. 61. (Parl. Paper N.S.W.) Sussmilch, C. A., 1937. The Geological History of the Cainozoic Era in New South Wales. Proc. Linn. Soc. N.S.W., 62, viii. Thompson, A. M., 1882. Exploration of the Caves and Rivers of New South Wales. (Parl. Paper), pp. 11, 12, 13. Whitehouse, F. W., 1940. Studies in the Late Geological History of Queensland. Univ. Qd. Papers, Dept. Geol., n.s., 2, 1. DESCRIPTION OF PLATES. PLATE XIII. (1) A view of Wellington from the Yeoval Road (S.W. of the town). The town is built on a terrace (surface 4) on which gravel deposits occur at an altitude of 1,000 ft. Between this terrace and the hills behind it the Macquarie flows towards its junction with the Bell River, which meanders from right to left across the cultivated alluvial flats in the foreground. Pebbles from a gravel deposit similar to that at Wellington are visible in the immediate foreground. Wellington T.S. (1,793 ft.) is situated in the central distance. (2) Looking S.S.W. up the valley of the Bell River from Wellington Common. In the background, on the Catombal Range, the boundary between cleared and uncleared land shows approxi- mately the junction between Middle Devonian limestone and Upper Devonian sediments. Wellington Caves are situated in the low country shown about one inch from the left of the photograph. (3) Looking to the N.W. across the Bell River valley, three miles east of Newrea, to a flat-topped ~ hill on which basalt overlies alluvial deposits at an altitude of 1,480 ft. and 400 ft. above the river (surface 3). A lower terrace at about 1,250 ft. (surface 4) is shown by the long spur stretching towards the left from the basalt capping and also by shorter spurs in front of it. The river flows from east to west and an old position of the river bed is visible in the left foreground. PLATE XIV. (1) Mt. Bodangora (2,500 ft.), from the south-eastern margin of the Wuuluman granite. The land slopes from 1,700 ft. in the foreground to 2,000 ft. above sea-level, the latter height extending on either side of the mountain (surface 2). The flat, terraced capping of basalt overlies about 20 ft. of fine grit which forms an escarpment at 2,220 ft. (surface 1). (2) A south-easterly view of the Catombal Range from a few miles east of Gunner’s Dam. The valley in the middle distance is that of the upper part of Curra Creek. This valley is lower than the undulating surface in the foreground which extends to the west, north and south of this locality (surface 3 ?). UPPER ORDOVICIAN GRAPTOLITE HORIZONS IN THE YASS-JERRAWA DISTRICT, N.S.W. By KATHLEEN SHERRARD, M.Sc. (With two text-figures and table.) Manuscript received, October 30, 1942. Read, December 2, 1942. Graptolites have been found in slate in a large number of localities to the east of Yass. The slate is of Upper Ordovician age and belongs to what has been called the Mundoonen Series (Sherrard, 1939). The graptolite-bearing localities are distributed about two centres, the first and larger being on both sides of the Yass River, between 12 and 16 miles upstream from Yass, and the second being about 14 miles west of Jerrawa railway station (see maps, Figs. 1 and 2). Through comparison of graptolites from all localities, it is possible to distinguish two different horizons in the graptolite-bearing beds. Some of the beds can be correlated with the lowest horizon among the Upper Ordovician beds in Victoria, which is designated Gisbornian, while others contain graptolites characteristic of the middle or Hastonian horizon (Harris and Thomas, 1938). The Bolindian or highest horizon has not been found. I am indebted to Mr. R. A. Keble, F.G.S., of the National Museum, Mel- bourne; to Dr. D. E. Thomas, D.Sc., of the Geological Survey of Victoria ; and to Dr. W. J. Harris, B.A., D.Sc., of Victoria, for their kindness in examining many of these graptolites and for the helpful advice they have given me. In no case, however, are they to be held responsible for any of the views expressed here. My thanks are also due to Dr. Ida Brown, of the Sydney University, for advice about the manuscript. TABLE OF GRAPTOLITES AND LOCALITIES. Graptolites found at each of the localities are shown in the accompanying table. All specimens are in the author’s collection. Localities corresponding to the numbers in the table are as follows: Locality 1.—Por. 24, Par. Morumbateman, on Yass-Gundaroo roadside, 100 yards west of 12th mile-post; in greyish shale, rarely blue-black on fresh surfaces, cross-jointed and iron stained. Locality 2.—Por. 1, Par. Mundoonen, 200 yards north of Morumbateman Creek road junction with Yass-Gundaroo road ; in fissile blue slate. Locality 3.—Por. 152, Par. Manton; on top of river cliff about centre of portion, 50 yards north of Yass River; in bluish grey silicified slate. Locality 4.—Por. 61, Par. Manton, eastern half ; on bank rising from alluvial flood plain, in grey-blue slates with the close, fissile cleavage of roofing slates. Locality 5.—Reserve No. 43134, Par. of Morumbateman, at waterfall, about half a mile north-west of junction between this reserve and Pors. 150 and 94, Par. of Morumbateman, in blue shale. Locality 6.—Por. 31, Par. Morumbateman, near north-west corner, 50 yards south of Yass River; in silicified and shattered slate. 253 02) Zz ie) N Lae] = o) se co S ke = e) H Ay < e- ido) Z < = oO ‘onl > co) =) pe io) ec = = =) "EG pue ‘Sp ‘ZF ‘OS ‘Ge ‘ZS ‘OZ ‘6 ‘ST ‘ZT ‘8 ‘9 SalgRoo'T 4v and0O sqUaWISeI] oBT[OIUVIS OVVUIULIOJpUT x x x x x x | x x x x x x | x x x x x x x x x x | x x x x x | x x x x x = x x x x | x x x x x x x x x x x x x x x x x x x | x x x x x x Xx x x 5a Po x x x x x|x|x|x x x | x x x x x x x x x x x x x x x x x x x Xe x x x x x x x x x x x x x x x | x x x x | x GG | [S| 0G | [Iv] OF | 68 | 48] 9E | SE] FE] EF | GE} TE | 62) 8S} 42 | 9S| FS) ES} TS ).21T | 9L| PL} SL} TL] OL] 6 4 g mm ~ LcianLanal F & al an G “USUT DNDLIAL-S8D { AY} UL saYyVyVI0] Snorwma Ww Bursinaz0 sazyjordvsy Buinoys 31qQv,L 4 Byes nn se ‘yopul ‘ds -7 ae (ieadens snsnjat (1G) “T “JO x _CUSIN) wsauyioy (1) “T “JO oe i (UOSTOYDIN ) Ussouysy (Gnitndinine tan) snido.borvsn'T : (S1oyANAIV)) stusos. snadvibodhsp 2 uosulydoH, wsyoury snidvibosso7 4) QO PUB prIeIIEYS sisuassvh snidvibovyoy ‘gopul ‘ds snjdvbo]avqd ee ee 3 Yqaom eT snqwanoxaiod pP (iabiiovenaee) ‘ad “M pue “W SNMII “IVA (SIF) SNyNIsSNiyawe? "JO (YM) °C (t9SUISTH) sngnasnijasay ‘jo (snjidnsboj}dfiyy) a “M pues snyowednnd “eA “MAeT snynouns (CO) ‘ad a es “MdeT snqnouni "JO (O) °C S33 “MdvT snqmoUnd) CO) ‘ad of ee . “MaeT snqobjna | “IVA “Waar snqnin9q99 "JO (0) °C “MAVT 8n20L09109 “JO (OO) ‘TC “Mav SnaysDy “IBA "MdvT snyo.i09}09 CO) ‘ad : YyIOM dey snyp.L09]09 (snjdns60y140) ie ad ‘gapul ‘ds ‘9 “*(sroygndieg) snwuiuiw ‘Jo *O poOOM PU SaT[W Stdaug “JO “OY "* poom pus SIIW staalq °O “MaBT snzyopnvsd *jO °O Yyyomdey snqpnns *p “Madey snsafyngn, “jo °O YQIOMAVT snuafyngn? °O SLLIVE, pue sIqQoy sess *O T?H $2U10919 SNIADLBOIDWY OD TH “S “L Suny ‘d UWOMAVT an2 022 “JO -G UWoMdeyT on2 002 “G : WeH snqwoinf “jo "qd UH snqwoung SNIADLBOV DAIL ‘* ‘qopul ‘ds °q 18H “SL snufp “Jo “Gd IPH “S \L snuify * YUWOMAeT snaonpva "MadVT snpvwund “jo yuNomdeyT snpwund ZYULIH) waumwunyosof “Jo eH sunzxas “jo : UOSULYAOF, S1410UW “jo --yqomde'y SNpiwbit “IVA T[VH snqooar.warp °C sLoygniieg suvfhaja snjdv.16071000q aqgqqqaags : ‘yapul ‘ds ‘7 Gree) emer U—December Pp ee Aqyeoo'7, 254 : KATHLEEN SHERRARD. Locality 7.—Por. 126, Par. Morumbateman, on timbered ridge, about half a mile west-south-west of north-east corner post of portion in silicified slate, almost chert. Locality 8.—Por. 126, Par. Morumbateman, on timbered ridge half a mile south of locality 7, in chert. Locality 9.—Por. 126, Par. Morumbateman, on timbered ridge, a quarter of a mile west of north-west corner post of Por. 93 in compressed and weathered slate. SSAA ] « _ RAILWAy oa {JERRAWA x Ck Ou wy ell & Diy, NS EES I N cD as | z a] N a =: x7 ES eee = 5 VA | wn ity 2, Vy x Ae) Q Ne 22 © 4 IS A ile ( 7 @ a aay Vv SD xy» VEp Se HATTONS Cin Mag, CORNER fr Us eee a A ER LEE: SS | Se es \ S x : INS x \ PLAN SHOWING RELATIVE N YS POSITIONS OF MAPS Lan II \ KMS SCALE 2 2 Miles x Bigw 1: Locality plan showing relative positions of Maps I and II. Locality 10.—Reserve 43134, Par. Morumbateman, in dry creek bed, nearly a mile west of north-east corner of reserve ; in silicified grey slate. Locality 11.—Por. 81, Par. Mundoonen, west fence near north-west corner on south slope above creek, in blue fissile slate, rather weathered. Locality 12.—Por. 158, Par. Mundoonen, in panhandle of portion beside north-west corner of Por. 81, Par. Mundoonen ; in grey mudstone. Locality 13.—Por. 81, Par. Mundoonen, south-west quadrant in bluish-grey Shale, good cleavage. Locality 14.—Por. 110, Par. Mundoonen, 150 yards west of south-west corner post of Por. 81, in silicified slate overlying chert. Locality 16.—Por. 80, Par. Mundoonen, top of ridge above Corrigan’s Creek, on north boundary of portion ; blue-grey slate, silicified and weathered. Locality 17.—Por. 80, Par. Mundoonen, 100 yards north of Corrigan’s Creek, nearly 200 feet lower in elevation than locality 16. UPPER ORDOVICIAN GRAPTOLITE HORIZONS. 255 MAP L PARISH OF MALOY TRIG. U NDOONEN are y PARISH OF TOUAL : ae Spo soy} LEGEND eS = Fone, | GTA aes UPPER ORDOVICIAN Or Sandstone, Slate, etc. ERRAWA NY Eastonian MANTON MUNDOONEN SERIES| Gisbornian State Scale Sa aa a Or nage nian, tt GRAPTOLITE LOCALITIES Li7 e OF PARISH BOUNDARIES PORTION NUMBERS 19S c | Fig. 2. Map I. Geological sketch-map of the Yass River District. Map II. Geological sketch-map of the Jerrawa District. 256 KATHLEEN SHERRARD. Locality 18.—Por. 111, Par. Mundoonen. Locality 19.—Por. 111, Par. Mundoonen. Locality 20.—Por. 213, Par. Mundoonen, just south of Por. 111. Locality 21.—Por. 213, Par. Mundoonen, 200 yards south-east of south-east corner post of Por. 111; in highly silicified slate. Locality 22.—Por. 1, Par. Mundoonen, 100 yards south of Por. 213 and 300 yards east of road. Locality 23.—Por. 28, Par. Morumbateman, 300 yards south of road and 100 yards west of river, in creek ; poorly preserved in shale. Locality 24.—Por. ce Par. Mundoonen, across Yass River from Por. dl, Par. Morumbateman, and close to ford across river on Morumbateman Creek road ; in dense blue-black shale, fossils preserved in silvery chitin, very small forms, few more than one centimetre in length. Locality 25.—Pors. 32 and 133, Par. Morumbateman, eastern margin. Locality 26.—Pors. 69 and south-east 31, Par. Morumbateman, in blue slate. Locality 27,—Por. 132, Par. Morumbateman, south-east of north-west corner post, in compressed blue slate. Locality 25.—Por. 150, Par. Morumbateman, along north fence, 600 yards east of road, on top of ridge, in blue-grey slate. Locality 29.—Por. 213, Par. Mundoonen, on ridge, about 600 yards south of Corrigan’s Creek and two- thirds of a mile east of Yass-Gundaroo road, in blue silicified slate. Locality 30.—Boundary of Pors. 1 and 213, Par. Mundoonen, about half a mile west of east fence of Por. 213. Locality 31.—Por. 1, Par. Mundoonen, on ridge on diagonal fence through portion about 500 yards west of east fence of portion, in blue slate. Locality 32.—Por. 1, Par. Mundoonen, 400 yards east-south-east of ridge end where is Locality 31, and: 150 feet lower in elevation than 31, in blue-black Shales. Locality 33.—Por. 1, Par. Mundoonen, in small quarry, 150 yards north of Yass-Gundaroo road, slightly east of 15th mile post in blue-grey slate. Locality 34.—Boundary between Pors. 1 and 8, Par. Mundoonen, about 150 yards north of Yass-Gundaroo road, near small waterfall, in dense blue-black shaly slate, all fossils small, seldom 2 cms. in length. Locality 35.—Boundary between Pors. 8 and 31, Par. Mundoonen, 250 yards north of Yass-Gundaroo road, in weathered grey-blue slates. Locality 36.—Por. 79, Par. Morumbateman, north-east corner, 100 yards south of river, poorly preserved in siliceous slate. Locality 3 7, —Por. 79, Par. Morumbateman, in gorge, about centre of portion, 300 yards south of river, in siliceous slate, poorly preserved. Locality 39.—Por. 142, Par. Morumbateman, at south-east corner of Por. 141, poorly preserved in silicified Slate. Locality y 40.—Por. 142, Par. Morumbateman, 150 yards east of Por. 131, boundary, in slightly silicified blue slate. Locality 41.—Por. 131, Par. Morumbateman, on bridle track to Toual, 300 yards west of fence of Por. 141, preserved in highly silicified slate. Locality 42.—Por. 221, Par. Mundoonen, on ridge west of road to Jerrawa about half a mile north of Yass-Gundaroo road, in highly compressed slate, much weathered. | Locality 43.—Corner Pors. 131, 142 and 149, Par. Morumbateman. Locality 50.—Boundary of Por. 200, Par. Manton, and Por. 72, Par. Jerrawa, on ridge, 500 yards west of west road from Jerrawa railway station to Hume Highway, in greyish-blue slate. Locality 51.—Por. 72, Par. Jerrawa, near south-east corner of Por. 139. UPPER ORDOVICIAN GRAPTOLITE HORIZONS. 257 Locality 52.—Por. 72, Par. Jerrawa, on top of ridge, about 400 yards east of junction between Pors. 189 and 203, poorly preserved in blue-grey slate. Locality 53.—Por. 239, Par. Jerrawa. in low railway cutting, immediately east of road crossing to Needles Trig. station. HORIZONS IN THE UPPER ORDOVICIAN. The table shows that the graptolite bearing localities fall into two distinct horizons. The beds at localities 17, 24 and 34 characterised by such forms as Lasiograptus harknessi (Nich.), Cryptograptus tricornis Carr., and Climacograptus bicornis Hall can be correlated with the Gisbornian (perhaps high in that horizon) of the Upper Ordovician as defined by Harris and Thomas (1938) for rocks in Victoria. The Gisbornian includes the zones of Nemagraptus gracilis and Climacograptus peltifer. The graptolites of the beds at these localities are all small, none larger than 2 ems. in length. They are fairly well preserved as silvery, chitinous films on dense blue-black slates. The localities where they occur are all on or about river level, that is about 1,800 to 1,850 feet above sea-level, and their exposure is due to the erosive action of the Yass River and its tributaries, which have worked down through the centre of the anticline into which the Mundoonen series is folded (Sherrard, 1939). Localities 4, 23 and 36, for instance, are also near the level of the Yass River, but they occur at some distance from the central fold axis of the anticline, and are hence in higher beds and forms characteristic of the Gisbornian do not occur in these latter localities. The rocks at localities 1, 3, 4, 13, 23, 28, 31, 32, 37 and 50 characterised by such forms as Dicellograptus elegans Carr., D. affinus T. 8. Hall, Dicranograptus hians T.8.H., Climacograptus caudatus Lapw., C. tubuliferus Lapw., C. bicornis Hall, with long, drooping spines, Diplograptus calcaratus Lapw. and its varieties, D. truncatus Lapw. and its varieties, Leptograptus flaccidus (Hall) can be correlated with the Eastonian of Victoria, which includes the zones of Climacograptus wilson and Dicranograptus hans (Harris and Thomas, 1938). The graptolites in the beds with Eastonian affinities are large. At locality 13, Diplograpti up to 10 cms. long have been found, and at locality 16, a virgella of great length attached to the same genus. At locality 50, a Diplograptus of the calcaratus type 7 mm. wide was obtained, though distortion by compression may have taken place. Climacograptus tubuliferus with spines was obtained in locality 28. Dvicellograpti with stipes 12 cms. long were found at locality 13. The best preserved forms occur at localities 4, 13, 31 and 32. Most of the localities in this horizon occur at about 2,000 feet above sea-level, that is, nearly 200 feet above the beds whose fossil contents have enabled their correlation with the Gisbornian. Beds at localities 2, 40 and 41 contain forms characteristic of both Eastonian and Gisbornian and may be near the junction of the two horizons. The upturned edges of the beds which occur at locality 2, outcrop on a steeply sloping hillside, and may pass from one horizon up to the other. Localities 40 and 41 occur in an area which has been intersected by quartz veins and may have been faulted. Localities 5, 7, 8, 9 and 10 yielded but few forms, none well preserved. They occur in rugged, broken, heavily timbered country, and such as they are, are consistent with an Eastonian age. All the forms found in the localities in the Jerrawa area, localities 50 to 53, can be referred to the Eastonian. REFERENCES. Elles, G. L., 1925. Geol. Mag., 62, 337. Elles, G. L., and Wood, E. M. R., 1903-08. Mon. Pal. Soc., 57-62. Harris, W. J., and Thomas, D. E., 1938. Min. Geol. J. Dept. Mines Vict., 1, 62. Sherrard, K., 1939. Proc. Linn. Soc. N.S.W., 64, 577. Sherrard, K., and Keble, R. A., 1937. Proc. Linn. Soc. N.S.W., 62, 303. PERMIAN BRYOZOA OF EASTERN AUSTRALIA. PART III. BATOSTOMELLIDH AND FENESTRELLINIDA FROM QUEENSLAND, NEW SoutH WALES, AND TASMANIA. By JOAN M. CROCKFORD, M.Sc. (With Plate XV and two text-figures.) Manuscript received, November 16, 1942. Read, December 2, 1942. SUMMARY. Fourteen species of Bryozoa belonging to the Batostomellide and Fenestrellinide are recorded or described from localities in the Permian of Queensland, New South Wales, and Tasmania; of these species six are described as new. INTRODUCTION. The species of Bryozoa described occur in the Upper Marine Series of the Hunter River District and the South Coast of New South Wales, the Lower Marine Series of the Hunter River District, and the Permian of central Queens- land and Tasmania. . The following species are described : Order TREPOSTOMATA. Family Batostomellide. Page Dyscritella restis sp. nov. oh cfs we te a ae .. 259 Dyscritella porosa sp. nov. ae x6 ue fi +P re .. 259 Stenopora gracilis (Dana), 1849 om af rf ie a 265 Stenopora nigris sp. nov. ans “f si aE ft NE .. 263 Stenopora frondescens sp. nov. .. ae iy + Fn a3 .. 264 Stenopora grantonensis sp. nov. ie ue ts at Le .» 265 Order CRYPTOSTOMATA. Family Fenestrellinide. Page Fenestrellina dispersa sp. nov. .. Be Ae Be: Lae pe .. 265 Seven species are recorded from additional localities; one of these (Fenestrellina horologia (Bretnall)) has not previously been known to occur in eastern Australia. : Thin sections of specimens of some of the species described were lent for comparison by the Australian Museum; an impression of the surface of the lectotype of Stenopora gracilis (Dana), used for comparison with material from the type locality, was sent by Dr. R. S. Bassler; records of the occurrence of three species in the Permian of Queensland are made with the permission of Shell (Queensland) Development Pty. Ltd. ; specimens from the Upper Marine Series near Cessnock were collected by Mr. A. H. Voisey. My thanks are due to Dr. Ida Brown for the help she has given me during the preparation of this paper, and for a number of the specimens described, which she: collected in Tasmania. PERMIAN BRYOZOA OF EASTERN AUSTRALIA. 259 This work was commenced during the tenure of a Science Research Scholar- ship at the University of Sydney. Catalogue numbers of specimens, except where it is otherwise stated, refer to specimens in the museum of the Department of Geology, University of Sydney. DESCRIPTION OF SPECIES. Genus Dyscritella Girty, 1911. Dyscritella Girty, 1911, 193; Dyscritella Girty, Lee, 1912, 151; Bassler, 1941, 178. Genotype: Dyscritella robusta Girty, 1911. Zoarium ramose or incrusting, usually with smooth macule ; zoecia tubular, without diaphragms ; zoecial walls thin in the axial and evenly thickened in the mature regions ; apertures oval or rounded ; mesopores numerous, usually aggregated at intervals to form macule ; acanthopores abundant, frequently in two series. Dyscritella restis Sp. Nov. Plate XV, fig. 9; Text-fig. 2A, B. Holotype: 2448. Occurrence: Allandale Stage, Lower Marine Series, above Eurydesma conglomerate, railway cutting east of Allandale Station ; and Por. 34, Par. Middlehope, near Eelah Rd. crossing of North Coast Railway. Ramose Dyscritella, with large, not numerous acanthopores, and mesopores about equalin number to the apertures. The zoarium is ramose with cylindrical branches from about 1-2 to 1-8 mm. in diameter—the branches of most specimens from the type locality are flattened and appear to be of greater width ; smooth macule about 1 mm. in diameter and composed of aggregations of mesopores are rarely developed. The apertures are elliptical, and arranged in irregular diagonal rows; they are 0-24 to 0-41 mm. long, and 0-14 to 0:21 mm. wide; about 10 occur in 10 mm. longitudinally. The rims of the apertures may be slightly raised, so that the interspaces between them may be rounded or slightly concave. The acanthopores are in two series ; there are usually five or six large acanthopores around each aperture, but from four to eight may occur, and a few very small acanthopores also occur. Mesopores are about equal in number to the apertures ; they are rounded or oval, 0-03 to 0-2 mm. long, and 0-03 to 0-1 mm. wide. The radius of the mature zone is 0-3 to 0-35 mm.; the bend of the zowcia from the axial to the mature zone is at an angle of 15° to 35°. The zoecial walls are very thin in the axial region, but they are evenly thickened in the mature region to a width of up to 0-13 mm. between adjacent, and 0:25 mm. between consecutive, zocwcia. No diaphragms are developed in either zoccia or mesopores. Dyscritella porosa Sp. Nov. Plate XV, fig. 8; Text-fig. 3A-C. Holotype: 3402. Occurrence: Allandale Stage, Lower Marine Series ; Jackson’s Hill, Por. 132, Par. Pokolbin. Ramose Dyscritella, with abundant acanthopores and mesopores. The zoarium is ramose, consisting of cylindrical branches, usually between 1-5 and 1:75 mm. wide, but which broaden considerably before bifurcation, which occurs at intervals of about 7 mm.; the angle between the branches after bifurcation is about 50°. The apertures are elliptical, 0:29 to 0-38 mm. long and about 0-2 mm. wide; they are irregularly arranged, and are almost com- pletely separated by numerous small, angular mesopores, up to about 0-17 mm. 260 ' JOAN M. CROCKFORD. yw Fig. Fig. Fig. Fig. ~& U0 0 (A. Vertical section. B. Tangential section. C. Transverse section.) 1.—Stenopora grantonensis sp. nov. A’, vertical section, with the axial region crossed by an arcuate zone of thickening, here composed of two distinct rows of monile. (Specimen 2446.) x10. 2.—Dyscritella restis sp. nov. (Specimen 3400a, 6.) (The width of the zoarium has been increased by compression of the specimens.) X10. 3.—Dyscritella porosa sp. nov. B. Tangential section, showing the mesopores near the base of the mature zone. B’. Surface of the zoarium, showing mesopores (B’, holotype; A, B. Specimen 3403a, b). x10. 4.—Stenopora frondescens sp. nov. (Holotype.) x10. PERMIAN BRYOZOA OF EASTERN AUSTRALIA. 261 in length ; about 10 apertures occur in 10 mm. longitudinally. Acanthopores are fairly numerous ; aS many as eleven, but generally less than six, surround each aperture; they are rather blunt, and project only slightly above the surface. Neither monticules nor macule were seen. ‘The zoccia are very thin-walled in the axial zone but the walls in the mature zone are evenly thickened to a width of 0-1 to 0:15 mm. ; the bend of the zowcia from the axial to the mature zone is not very sharp. The radius of the mature zone is 0:24 to 0:35 mm. No diaphragms are shown in either zoccia or mesopores. Genus Stenopora Lonsdale, 1844. Stenopora Lonsdale, 1844, 178; Stenopora Lonsdale, Lonsdale, 1845, 262 ; Nicholson and Etheridge, 1886, 173; Etheridge, 1892, 32; Duncan, 1939, 242 ; Bassler, 1941, 173; Lee, 1912 [pars], 148; [non] Stenopora Lonsdale, Ulrich, 1890, 375, 436; Bassler, 1929, 54, 58. Genotype: Stenopora tasmaniensis Lonsdale, 1844. Synonym: Ulrichotrypa Bassler, 1929. Zoarium massive, ramose, incrusting, laminar, or frondescent ; zoccia tubular, thin-walled in the axial region, but with the walls in the mature region irregularly thickened (moniliform) ; diaphragms absent or extremely rare; acanthopores well developed, generally large and very numerous, and commonly occurring im two series ; mesopores not tabulated, generally fewer in number than the zoecia ; monti- cules or less often macule characteristically developed, except in some fine ramose species. Lonsdale described (1844) and figured (1845) the genotype of Stenopora from the Permian of southern Tasmania; Bassler (1941) has considered that Ulrichotrypa Bassler, 1929, is synonymous with Stenopora, and this course is followed here. Stenopora gracilis (Dana), 1849. Plate XV, figs. 1, 2; Text-fig. 5A-C. Cheetetes gracilis Dana, 1849, 712, t. 11, figs. 10, 10a-c ; [?] Stenopora tasmaniensis Lonsdale, Etheridge, 1892 [pars], 60; [non] Stenopora tasmaniensis Lonsdale, 1844, 178. Lectotype (here chosen): Specimen figured by Dana (1849, t. 10, figs. 10, 10a-c), which is with Dana’s collection of fossils from Australia in the Smithsonian Institution, United States National Museum ; erroneously stated by Etheridge (1892, 2) to have been destroyed by fire. Plastotype: Specimen 2417, Sydney University Collection. Occurrences: The lectotype is from either the Westley Park Tuffs, Crinoidal Stage, Upper Marine Series, at Black Head, near Gerringong, N.S.W., or the Crinoidal Stage, Upper Marine Series, at Flagstaff Point, Wollongong, "N.S.W. (Dana, 1849); Stenopora gracilis occurs also in the Westley Park Tuffs on the rock platform below Gerringong Trig. Station. Fine, ramose Stenopora, with a very narrow mature zone with two rows of monile, and a broad axial zone crossed by remote arcuate rows of monile ; mesopores not numerous ; acanthopores well developed; diaphragms extremely rare; small macule irregularly developed. The zoarium is ramose, attached to the substratum by a flattened circular base, about 13 mm. in diameter, from which a single cylindrical branch arises ; . this bifurcates about 7 mm. above the base, and gives rise to a large ramose colony. The branches are cylindrical, 3-25 to 4-0 mm. in diameter, increasing 262 JOAN M. CROCKFORD. <0 0S Oo" x oy i Seah Yaa [e) Sa a ae . Fj s o (A. Vertical section. B. Tangenital section. C. Transverse section.) Fig. 5.—Stenopora gracilis (Dana). (Specimens 3406-3408.) x10. Fig. 6.—Stenopora nigris sp. nov. (Holotype.) x10. (Camera lucida diagrams.) pis pears PERMIAN BRYOZOA OF EASTERN AUSTRALIA. 263 considerably in size immediately before branching, which occurs at very irregular intervals. The apertures are oval, 0-24 to 0:33 mm. long and 0-17 to 0-21 mm. wide; they are of normal size and shape near the base of the colony. The interspaces between the apertures are ridged or flat, with a single or double row of acanthopores, up to about 16 surrounding each aperture. Mesopores are far less abundant than the apertures ; their openings are up to 0-14 mm. in length, but are generally very small; they are aggregated at irregular and rather infrequent intervals to form the macule. The apertures are irregularly arranged ; about 11 occur in 5 mm. longitudinally, and from 35 to 40 occur around the circumference of a transverse section. The mature zone comprises only about one-quarter of the radius, its width being 0:33 to 0-46 mm.; the bend of the zowcia from the axial to the mature region is at an angle of about 40°, and the tubes meet the surface at almost a right angle. The zoccia are thin-walled in the axial zone; they are oval in the mature zone, where the walls are thickened to a width of up to 0-27 mm. between two apertures longitudinally, or 0-16 mm. transversely. The walls are not strongly moniliform ; two rows of thickening generally occur in the mature zone, but these often appear confluent; the outer row of monile is from half to three-quarters of the width of the mature zone. In addition remote arcuate rows of monile cross the axial zone at intervals of 5 to 15 mm. or more ; each consists of a single row of thickening up to 0:15 mm. in length. The acanthopores are in two series; about eight large acanthopores, originating near the base of the mature zone, surround each aperture ; the small acanthopores originate close to the surface—these are not usually shown in sections. Diaphragms are extremely rare; when developed they are thin, complete, and slightly curved backwards. Remarks: Dana (1849) described this species from material collected at ‘‘ Wollongong Point and Black Head, [llawarra’”’ in 1839; his specimens are in the United States National Museum collections, but a gutta percha impression of the specimen which he figured has been compared with the specimens from Black Head and Wollongong, from which this revision has been made. Etheridge (1892, 60, 64) considered Stenopora gracilis possibly a synonym of Stenopora tasmaniensis Lonsdale, which is, however, a much larger form—Lonsdale gives the size of the branches as half an inch in diameter. Stenopora nigris Sp. Nov. Plate XV, fig. 7; Text-fig. 6A-C. Stenopora tasmaniensis Lonsdale, Etheridge, 1892 [pars], 91, pl. VII, fig. 9; [non] Stenopora tasmaniensis Lonsdale, 1844, 178. Holotype: 2444. Occurrence: Westley Park Tuffs, Crinoidal Stage, Upper Marine Series, at Black Head, near Gerringong. Ramose Stenopora, with smooth cylindrical branches 6 to 7 mm. in diameter ; very narrow mature zone with two rows of monile, and broad axial zone crossed by remote arcuate rows of monile ; mesopores few ; acanthopores small, fairly abundant ; diaphragms extremely rare. The zoarium is ramose, with a flattened oval base about 20 mm. long and 12 mm. wide, which gives rise to a single thick branch; this bifurcates about 1 cm. above the base, and the two thick branches formed by this bifurcation rapidly divide and give rise to a large ramose colony. The branches are cylindrical, 5-8 to 6-8 mm. in diameter ; no monticules or macule are developed. The apertures are oval, 0-4 to 0-53 mm. long and 0:19 to 0:24 mm. wide, and the interspaces between them are flat or slightly rounded, with a single row of small acanthopores. The apertures are not regularly arranged, but about 9 264 JOAN M. CROCKFORD. occur in 5 mm. longitudinally, and from 54 to 64 are cut around the circumference of a transverse section. Small oval or rounded mesopores, up to 0:18 mm. long, occur rather infrequently. The mature region is very narrow, comprising about one-fifth of the radius, being 0-43 to 0-7 mm. wide. The zoccia bend from the axial to the mature zone at an angle of 25° to 45°, and the tubes meet the surface obliquely. The zocecia are very thin-walled in the axial zone ; the walls in the mature zone are moniliform—there are usually two distinct rows of thickening, but these occasionally appear confluent ; at intervals of about 4 mm. or more arcuate axial rows of thickening are gradually given off from these peripheral rows. The length of individual monile in the mature zone is 0-22 to 0-38 mm.—the two rows are of sub-equal length—and their width up to 0-2 mm., though they are more often about 0-1 mm. in width. Each arcuate row of thickening is composed of a single row of smaller monilze about 0-2 mm. long and 0:05 mm. wide. Thin complete diaphragms occur extremely infrequently in the axial region (the “ tabulum ”’ in a slide of this form figured by Etheridge (1892, pl. VII, fig. 9) is one of the monile cut obliquely). Small acanthopores originate close to the surface in the mature zone, up to about twelve surrounding each aperture. Remarks: A section of a specimen of this form was figured by Etheridge (1892, pl. VII, fig. 9) as Stenopora tasmaniensis Lonsdale, which is a larger form, the diameter of the branches being, according to Lonsdale’s original description, about twice the diameter of the branches of this species ; differences are shown also in the arrangement of the acanthopores and in the monile of the mature zone. No species which could be identified with Stenopora tasmaniensis appears to occur in New South Wales. Stenopora frondescens Sp. Nov. Plate XV, fig. 10; Text-fig. 4A, B. Holotype: 3401. Occurrence: Westley Park Tuffs, Crinoidal Stage, Upper Marine Series, at Black Head, near Gerringong. Frondescent Stenopora, with a very narrow mature zone with two or three rows of monile, and a broad axial zone crossed by arcuate rows of monile ; acantho- pores abundant ; mesopores numerous ; diaphragms extremely rare. The zoarium is composed of anastomosing frondescent branches which may cover an area of more than 30 cm.; individual branches are from 9 to 14 mm. in thickness. On the surface of these branches there are regularly placed monticules 2 to 3 mm. in diameter, raised about 1 mm. above the surface ; the distance between the centres of adjacent monticules is 5 to 7mm. The zoecia in the monticules are thicker-walled than those on other parts of the surface, and mesopores are more numerous than usual. The apertures are oval, the longer axes parallel to the direction of growth; their length is 0-35 to 0-6 mm., and their width 0-32 to 0-46 mm. ; 7 to 8:5 apertures occur in 5 mm. parallel to, and about 14 at right angles to, the direction of growth; smaller mesopores are frequently developed at the angles of the zowcia. Over a part of the surface the apertures are closed by a thin complete calcareous plate. The interspaces between adjacent apertures are broad and fairly flat, with numerous acanthopores. In the central portion of the branch the tubes are normally thin-walled, but well-marked arcuate rows of thickening, spaced about 9 to 13 mm. apart and each consisting of a single row of monile, 0-24 to 0:36 mm. in length, and about 0-08 mm. wide, cross this central part ; between each of these stronger rows of thickening one or two very poorly developed rows may occur. Complete diaphragms are very infrequently developed. The zowcia curve gradually from the axial to the mature zone, which is about 0-4 mm. in width, and shows either two or three well-developed rows of thickening ; from this outer zone of PERMIAN BRYOZOA OF EASTERN AUSTRALIA. 265 monile the strong arcuate rows of thickening which cross the axial zone are eradually given off. The zoccia are thin-walled in the axial zone ; the thickness of the walls at the level of the monile in the mature zone is up to 0:22 mm. Round or oval untabulated mesopores from 0-05 to 0-2 mm. in diameter are rather frequently developed in the mature zone. There is no mesial lamina. Acanthopores are very well developed, and may project 0-1 mm. above the surface ; they occur in a single row in the walls between adjacent apertures, but are more crowded at the angles of the zocecia, especially where mesopores are developed ; sixteen to twenty acanthopores surround each aperture ; they are generally large, but a few smaller ones occur. Remarks: The form of the zoarium, narrow mature zone, and abundant acanthopores, distinguish this form from described species of Stenopora; it differs from species of Amphiporella Girty in lacking macule and in having complete diaphragms, and from species of Stenocladia Girty in wall structure and in the absence of a mesial lamina. Stenopora grantonensis Sp. NOV. Plate XV, figs. 3, 6; Text-fig. 1A-C. Holotype: 2446. Occurrence: Berriedale Limestone, Granton Stage, at Granton Quarry, near Hobart, Tasmania. Very fine, ramose Stenopora, with a broad mature zone generally without well-marked monile, and a relatively narrow axial zone crossed by arcuate zones of thickening ; mesopores rare; acanthopores very numerous. The zoarium is ramose, with cylindrical branches 1-6 to 2 mm. in diameter, which bifurcate at intervals of 7 mm. or more; the angle between the branches after bifurcation is 65° to 85°. Neither monticules nor macule are developed. The zoccia are not very regularly arranged, though they may form rough longitudinal or diagonal rows ; from about 9 to 10 apertures occur longitudinally inlOmm. The apertures are elliptical, 0:35 to 0-4 mm. long and 0-17 to 0:22 mm. wide ; the interspaces between adjacent apertures are broad and slightly rounded, with generally two or more rows of fine acanthopores. Small, sub-circular mesopores, up to 0:17 mm. long, are rather infrequently developed. The mature zone is 0-33 to 0-5 mm. in radius ; the bend from the axial to the mature zone is gradual, at an angle of about 45°; the thickness of the zoccial walls in the mature zone is up to 0-22 mm., and is typically greater between consecutive than between laterally adjacent apertures. Generally the tubes are angular and very thin-walled in the axial zone, and oval with evenly thickened to slightly moniliform walls in the mature zone, but arcuate thickened zones cross the axial zone at relatively distant intervals; they are developed usually within 3 mm. before bifurcation of a branch, and at intervals throughout the length of the zoarium ; each is less than 0:2 mm. in length, and typically they are composed of a Single row of monile, though a second row may occur. Very rarely thin, complete diaphragms are developed in the zoccia in the axial zone; the meso- pores are untabulated. Acanthopores are small and very numerous; about 18 surround each aperture ; they are of two sizes, of which the smaller are more numerous ; the small acanthopores originate much closer to the surface than the larger ones. About ten apertures occur around the circumference of a transverse ~ section. Genus Fenestrellina d’Orbigny, 1849 (Fenestella Lonsdale, 1839). Fenestrellina dispersa Sp. NOV. Plate XV, figs. 4, 5. Holotype: 3404. Occurrences: Ulladulla Mudstones, Upper Marine Series, at Warden Head, Ulladulla (holotype) ; Allandale Stage, Lower Marine Series, 266 JOAN M. CROCKFORD. at Jackson’s Hill, Por. 132, Par. Pokolbin, and railway cutting east of Allandale Station ; Fenestella Shales, Branxton Stage, Upper Marine Series, at Branxton railway cutting, Por. 126, Par. Mulbring, Por. 15, Par. Belford, and Kitchener’s Hill, near Cessnock; Branxton Stage (above Fenestella Shales), in Wattle Ponds Creek, Por. 41, Par. Darlington ; Muree Stage, Upper Marine Series, at Abbey Green, Por. 44, Par. Wittingham ; Permian at Marlborough ; 1,000 feet above sea level, Huon Rd., Mt. Wellington; Grange Quarry, near Hobart, Tasmania ; and Consuelo Creek (two miles above Cattle Creek) (Reid, 1930, 157, loc. 6), Springsure District, Queensland. Fine Fenestrellina with three zoecia to a fenestrule and with a slight carina and small, regularly-spaced nodes ; colony infundibuliform with the celluliferous surface external. The colony is infundibuliform with the celluliferous surface external ; there are 17 to 23 branches horizontally, and generally between 12 and 16 fenestrules vertically, in 10 mm. The branches are straight, bifurcating at very distant intervals ; increase to three rows of zoccia occurs immediately before bifurca- tion ; they show a slight median carina, on which there is a single row of small nodes placed from 0:24 to 0-4 mm. apart. The apertures are circular, about 0-12 mm. in diameter; the distance between the centres of successive apertures is 0-24 to 0:33 mm.; about 34-5 apertures occur in 10 mm., and three in the length of each fenestrule ; very thin peristomes surround the apertures, which do not project into the fenestrules. The fenestrules are sub-rectangular in shape, 0:46 to 0-71 mm. long and 0-13 to 0-33 mm. wide; the dissepiments are rounded on both surfaces and are 0-13 to 0:24 mm. wide. The branches are 0-24 to 0-33 mm. wide ; they are thicker than the dissepiments, and are rounded on the reverse surface, which is finely granular and is ornamented by small to fairly large tubercles. Remarks : This form is possibly the most widespread and abundant species of Fenestrellina in the Permian of eastern Australia; it is a smaller species than Fenestrellina fossula (Lonsdale), with which it is commonly associated, and differs in the characters of the reverse surface. Ff. texana (Girty), 1908, from the Delaware Mountain formation, Southern Delaware Mountains, Texas, is a larger species, and has a very high carina with more closely and regularly spaced nodes. The following species are recorded from additional localities : Fenestrellina fossula (Lonsdale), 1844: Dilly (Reid’s Locality, 1930, 157) and Consuelo Creek (two miles above Cattle Creek) (Reid, 1930, 157, Loc. 6), Springsure District, Queensland. Fenestrellina horologia (Bretnall), 1926: Consuelo Creek (two miles above Cattle Creek) (Reid, 1930, 157, Loc. 6), Springsure District. Fenestrellina granulifera Crockford, 1941): Huon Rd., Mt. Wellington, Tasmania, 1,000 feet above sea level. Fenestrellina altacarinata Crockford, 1941b: Fenestella Shales, Par. Coongevoi, just south of Por. 26, Par. Aellalong. Polypora montuosa (Laseron), 1918: Fenestella Shales, Kitchener’s Hill, near Cessnock (Por. 50, Par. Quarrybylong). Polypora virga lLaseron, 1918: Fenestella Shales, Par. Coongevoi, just south of Por. 26, Par. Aellalong. Protoretepora ampla (Lonsdale), 1844 (s. str.): A specimen from the -Upper Marine Series in conglomerate on west side of Mudgee railway cutting, 1In the original description of this species, the distance between the nodes was given as ‘0-37 mm.’’; this should have been corrected to “‘ 0:5 to 0:65 mm.”’ © Journal Royal Society of N.S.W., Vol. LXXVI, 1942, Plate XV Pai . 3 PERMIAN BRYOZOA OF EASTERN AUSTRALIA. 267 13 miles north of Rylstone (F.39640, Australian Museum Collection) is conspecific with specimens from Bundanoon tentatively referred to Protoretepora ampla (Lonsdale) (Crockford, 1941a, 406, pl. XIX, fig. 4). BIBLIOGRAPHY. Bassler, R. S., 1929. The Permian Bryozoa of Timor. Paladontologie von Timor, XVI Lief., XXVIII Teil, 37. E. Schweizerbart’sche Verlagsbuchhandlung, Stuttgart. Bassler, R. S., 1941. Generic Descriptions of Upper Paleozoic Bryozoa. Jour. Washington Acad. Sci., 31, (5), 173. Bretnall, R. W., 1926. Palzeontological Contributions to the Geology of Western Australia, VII, (XIII). Descriptions of some Western Australian Fossil Polyzoa. Bull. geol. Surv. W.A., 88. Crockford, Joan, 194la. Permian Bryozoa of Eastern Australia. Part I. A Revision of Some Previously-named Species of Fenestrellinide (Fenestellide). Jour. Roy. Soc. N.S.W., 74 (for 1940), (IV), 397. Crockford, Joan, 19416. Jbid. Part II. New Species from the Upper Marine Series of New South Wales. Jour. Roy. Soc. N.S.W., 74 (for 1940), (IV), 502. Dana, J. D., 1849. Fossils of New South Wales. In Wilkes’ U.S. Exploring Expedition, X, Geology, Appendix and Atlas. Philadelphia. Duncan, Helen, 1939. Trepostomatous Bryozoa from the Traverse Group of Michigan. Michigan Unw. Mus. Pal., Contr., 5, (10), 171. Etheridge, R., Jnr., 1892. A Monograph of the Carboniferous and Permo-Carboniferous In- vertebrata of New South Wales. Part I. Coelenterata. Mem. geol. Surv. N.S.W.., Pat.; 5,’ (2). Girty, G. H., 1908. Guadalupian Fauna. Prof. Paper U.S. geol. Surv., 58. Girty, G. H., 1911. New Genera and Species from the Fayetteville Shale of Arkansas. Ann. New York Acad. Sci., 20 (for 1910), 189. Lee, G. W., 1912. The British Carboniferous Trepostomata. Mem. geol. Surv. Great Britain, Pal., 1, (3), 135. Lonsdale, W., 1844. Description of Six Species of Corals, from the Palzeozoic Formation of Van Diemen’s Land. Jn Darwin, Geol. Obs. on Vole. Is., Appendix, 161. Smith, Elder and Co., London. Lonsdale, W., 1845. Polyparia. Jn Strzelecki, Phys. Descr. N.S.W. and Van Diemen’s Land, VI, Zoology, Paleozoic Fauna, 262. Longman, Brewn, Green and Longmans, London. Nicholson, H. A., and Etheridge, R., Jnr., 1886. On the Tasmanian and Australian Species of the Genus Stenopora. Ann. Mag. Nat. Hist., Ser. V, 17, 173. Orbigny, A. d’, 1849. Descriptions de Quelques Genres Nouveaux de Mollusques Bryozoaires. Rev. Mag. Zool., 2e Ser., Tome I, 499. Reid, J. H., 1930. Geology of the Springsure District. Queensland Government Mining Jour., 31 (April), 149. Ulrich, E. O., 1890. Paleozoic Bryozoa. Geol. Surv. Illinois, 8, (2), sect. IV. EXPLANATION OF PLATE. Figs. 1, 2.—Stenopora gracilis (Dana). 1. (Specimen 410), natural size. 2. Surface of branch (Specimen 3405). x10. Figs. 3, 6.—Stenopora grantonensis sp. nov. 3. Surface of holotype. x10. 6. Natural size. Figs. 4, 5.—Fenestrellina dispersa sp. nov. 4. Obverse surface of holotype. 10. 5. Reverse surface of holotype. x 10. Fig. 7.—Stenopora nigris sp. nov. Part of holotype. Natural size. Fig. 8.—Dyscritella porosa sp. nov. Part of holotype. x10. Fig. 9.—Dyscritella restis sp. nov. Part of holotype. x 10. Fig. 10.—Stenopora frondescens sp. nov. Part of holotype. x 4. Photographs by H. G. Gooch. THE ACTION OF SOLVENTS ON TORBANITE AND THE NATURE OF EXTRACTED PRODUCTS. By J. A. DULHUNTY, B.Sc. Manuscript received, November 18, 1942. Read, December 2, 1942. SUMMARY. The paper deals with the action of solvents on torbanite, the general principles of extraction and the nature of the extracted products. It is shown that, in general, aromatic compounds are more efficient solvents than those of aliphatic nature. Evidence bearing on the mechanism of solvent action is discussed, and the conclusion is drawn that thermal extraction depends on the preliminary absorption of the solvent by the organic matter at an early stage in the depolymerisation, followed by solution in the absorbed solvent at a later stage. Some important treatment principles are suggested, and the results of a preliminary examination of the products of benzene extraction are recorded. INTRODUCTION. Preliminary work on the extraction of oil from torbanite by solvents (Dulhunty, 1942) has shown that the organic matter normally insoluble in common organic solvents, may be rendered almost completely soluble by heating at temperatures considerably below those which cause thermal decomposition into gas, oil vapour and carbon. This change to the soluble form, occurring between 340° and 400°C., has been described as a form of depolymerisation (Dulhunty, 1942, and Cane, 1942). It precedes later thermal decomposition and evolution of oil vapours which take place above 400° C. when torbanite is heated comparatively rapidly, as in the usual retorting process. It has been shown also that the rate of depolymerisation and conversion to the soluble form are functions of both time and temperature. As much as 90% of the organic matter has been extracted in the form of oil by prebeating and extraction with benzene under pressure. SOLVENT ACTION. Relative Solvent Properties of Some Different Organic Substances. Results recorded previously by the author (Dulhunty, 1942) were based on benzene extraction of preheated torbanite. Subsequent work on the relative solvent properties of various compounds has shown that only some of the common organic solvents are suitable for complete extraction of the soluble products. The following qualitative experiments were carried out with the object of comparing the relative efficiency of different solvents for use in low temperature extraction of preheated torbanite, as well as extraction of unheated torbanite at the temperature necessary to render the organic matter soluble. EXPERIMENTAL. Preliminary tests were made to determine the ability of different solvents to redissolve the products extracted with benzene. It was found that chloroform, pyridine, quinoline, tetralin, carbon tetrachloride, coal tar naphtha, toluene and torbanite crude oil distillate (B.P. 150-230° C.), all readily dissolve the extracted products at room temperature, and solutions of LT THE ACTION OF SOLVENTS ON TORBANITE. 269 high concentration were built up without the precipitation of any of the solute. Naphthalene, which was tested at temperatures slightly above its melting point, completely dissolved the extract. Ethyl ether, ethyl alcohol and light petroleum (B.P. 40-60° C.) would dissolve only a portion of the extract, even in the case of hot solutions of low concentration. Petroleum kerosene dissolved the extract completely at temperatures above 200° C., but small quantities were precipitated on cooling, especially from concentrated solutions. A series of experiments was carried out to test the ability of different solvents to extract the soluble products from preheated torbanite. Finely powdered torbanite, preheated at 380° C. for 4 hr., was extracted with each of the solvents mentioned in the above experiment, at their respective boiling points under atmospheric pressure, for a period of 24 hr. After cooling, the solid residues were separated from the extract solutions by filtration, and were washed with cold solvent until the washings were no darker in colour than the fresh solvent. They were then washed with fresh hot solvent—any further removal of material being indicated by the depth of colour of the washings—and were finally washed with cold benzene. In all cases black extract solutions were produced. The residues from the extractions with chloroform, carbon tetra- chloride, tetralin, toluene, torbanite crude oil distillate, and coal tar naphtha, did not appreciably colour the washings from the hot fresh solvents and cold benzene. The residues from the pyridine and quinoline extractions, after being washed with cold solvent, coloured the washing from the hot solvents, but did not yield any further solute when washed with cold benzene. In the case of extractions with ethyl alcohol, ethyl ether, light petroleum and petroleum kerosene, the washings from the hot fresh solvents were slightly coloured and those from cold benzene considerably coloured. A further series of experiments was carried out to determine the suitability of selected solvents for the extraction of torbanite at temperatures above 350°C. (these temperatures being necessary to render the organic matter soluble) with the object of eliminating preheating by dissolving the soluble products as they are formed. The pressure vessel used in this work has been described (Dulhunty, 1942). The critical temperature regions of the solvents were tested by heating them in the pressure vessel to a temperature of 410° C., and plotting the pressure-temperature relations. Those which gave curves showing sudden increases in pressure below, or approaching, 400° C., were discarded as they could not be kept in the liquid phase at the extraction temperature. The solvents were also examined for decomposition, or polymerisa- tion, resulting from the high temperature. Those selected for high temperature extraction were coal tar naphtha (B.P. 150—220° C.), petroleum kerosene (B.P. 190—210° C.), and torbanite crude oil distillate (B.P. 230—260°C.). Tetralin and quinoline should be suitable, but sufficient quantities were not available for testing when these experiments were made. The extractions were carried out by mixing 1 lb. of powdered torbanite with 1 Ib. of solvent, and heating at a temperature of 390° C. for a period of 4hr. After cooling the volume of residual gas was measured, and the extract solution separated from the solid residue by filtration. The residues were first washed with the fresh solvents, then with benzene and finally extracted with benzene under pressure at 200°C. The residues from the extractions with coal tar naphtha, and torbanite crude oil distillate, did not yield any further solute when washed with benzene and subjected to pressure-benzene extraction. The residue from the petroleum kerosene extraction yielded a considerable quantity of solute to the benzene washing, and a small quantity to the pressure-benzene extraction. CONCLUSIONS. The preliminary tests on the solubility of the benzene extract in different solvents show that aromatic compounds are more effective solvents than those of aliphatic nature. Ethyl alcohol, ethyl ether and light petroleum are entirely unsuitable as they dissolve only a portion of the extract. Petroleum kerosene is somewhat more efficient owing to the high temperature at which-it may be used but some of the extract is precipitated on cooling. Torbanite crude oil distillate possesses good solvent properties which are probably due to the presence of considerable quantities of cyclic compounds. V—December 2, 1942. 270 J. A. DULHUNTY. The extractions of preheated torbanite at atmospheric pressure, and at the boiling points of the different solvents, indicate that ethyl alcohol, ethyl ether, light petroleum and petroleum kerosene are capable of dissolving only a portion of the soluble product, and they precipitate some of their solute on, cooling. Pyridine and quinoline appear to extract all the soluble product, but precipitate some constituents on cooling. The aromatic solvents and torbanite crude oil distillate, completely extract the soluble products, and are capable of holding all the extracted material in solution when cold. The low boiling aromatic solvents can be separated from the extracted products by fractional distillation, but those of high boiling point (150° C. and over) cannot be recovered successfully in this way. The results of the pressure extractions at 390° C., using torbanite which had not been preheated, indicate that coal tar naphtha and torbanite crude oil distillate are capable of complete extraction, and of holding all the extract in solution when cold.. Petroleum kerosene is somewhat less efficient in its solvent properties, leaving a small residue of unextracted product as well as precipitating a considerable quantity of its solute when cold. Coal tar naphtha, which underwent some decomposition and polymerisation at the high temperature of the extraction, is an efficient solvent, but cannot be separated from the extracted products by distillation. Petroleum kerosene and torbanite crude oil distillate both underwent a considerable amount of cracking with the production of gas, Spirit and carbon. In the case of torbanite crude oil distillate, however, the heavy portion of the solvent oil was replaced by oils extracted from the torbanite, giving a final oil stock similar in volume and composition to the original solvent oil. This result suggests the possibility of eliminating the preheating process by using torbanite oil as the solvent at temperatures between 350° and 400° C., in such a way that the cracking of the oil, which inevitably occurs in the presence of torbanite at these temperatures, could be controlled to give an efficient pro- duction of spirit; the solvent oil stock being simultaneously replaced by oils extracted from the torbanite. Further work along these lines is being carried out at present. MECHANISM OF SOLVENT ACTION. Experimental work on solvent extraction of torbanite has produced evidence which suggests that the physical action of solvents is not a simple surface solution effect. This evidence is as follows: (i) Tests were carried out to determine the effect of the particle size of torbanite powder on solvent extraction. Unexpected results were obtained : torbanite powdered to a maximum particle size of 0-2 mm., and the same material in a granular condition in which the fragments averaged 5 mm. in diameter, yielded exactly the same quantity of solute and required the same length of time for complete extraction. A one-inch cube of torbanite was preheated at 375° C. for 1 hr., which produced a “‘ rubbery ”’ condition ; but the block was tough and could not be broken by hand. It was then heated in torbanite crude oil at 200° C. for 1 hr., after which it appeared swollen and could be crushed readily in the hand. When granular torbanite, which has been preheated so as to render a portion of the organic matter soluble, is extracted with a solvent such as benzene or torbanite oil, the particles swell considerably, in some cases to almost twice their original size. (ii) When unheated torbanite, either powdered or granular, is mixed with torbanite oil and heated at a temperature below 250° C. (too low to cause depolymerisation of the organic matter) there is no difficulty in subsequently filtering the solid material from the oil. If it is heated with the oil at a temper- ature above 300° C., which is sufficient to cause depolymerisation and conversion to the soluble form, for a length of time to render only a portion of the organic , 4 | 2 ~~, THE ACTION OF SOLVENTS ON TORBANITE. Del matter soluble, it is impossible to separate the oil from the solid material by filtration, even using strong suction. If, however, the heating is continued until complete, or almost complete, conversion to the soluble state is effected, the extremely fine-grained, solid residue can be separated by filtration with ease and rapidity. (iii) It has been shown by pressure-benzene extraction (Dulhunty, 1942) that less than 1% of the organic matter can be extracted from torbanite by heating it with a solvent at 270° C. for 8 hr. Later work has shown, however, that this treatment causes swelling and softening of the powder, and it is difficult to separate it from the solvent by filtration after heating. The foregoing evidence is interpreted as follows: Torbanite undergoes no change at all when heated at temperatures below 250° C.; between 250° and 300° C. depolymerisation of the organic matter commences, and some solvent is absorbed by the torbanite particles, which become soft and swollen, although no appreciable quantity of soluble product is formed ; with continued heating between 300° and 350° C., depolymerisation continues and a considerable quantity of soluble product is formed, and more solvent is absorbed with further swelling and softening of the particles, accompanied by a partial breakdown in the physical structure of the torbanite which forms an intimate mixture with the solvent and produces a jelly-like mass which cannot be filtered. Continued heating between 350° and 400° C. causes the organic matter to dissolve in the solvent it has absorbed, producing a complete breakdown in the physical structure of the torbanite and the formation of a true solution of the organic matter in the solvent oil, accompanied by the separation of free carbon and inorganic matter which can be removed readily by filtration. CONCLUSIONS CONCERNING TREATMENT PRINCIPLES. Some important conclusions concerning treatment principles can be drawn from the foregoing results and discussion. (a) It is evident that the production of oil from torbanite by solvent extraction may be accomplished in at least two different ways: (i) by preheating the torbanite at temperatures between 350° and 400° C. for a sufficient length of time to render the organic matter soluble, and then extracting the soluble products with a suitable low-boiling solvent such as benzene, followed by the separation of the solvent from the solute by distillation. In this method the product of extraction is the depolymerised organic matter which has not under- gone cracking into light oils and spirit. It is a heavy oil which would require further treatment, such as cracking or hydrogenation, for the production of light fuel oil or motor spirit. (ii) By extracting the torbanite with its own oily extract at temperatures between 350° and 400° C. and under pressures between 150 and 300 lb./sq. in. In this method the preheating and extraction occur simultaneously, and at the same time the solvent oil stock is cracked, with the production of gas and carbon, into lighter oils and spirit, and is replaced by the extracted oils. The products of the extraction are gas, spirit, carbon and solvent oil, which is a mixture of hydrocarbons at all stages of cracking from the depoly- merised organic matter to light oils. The cracking which occurs during the extraction can be controlled to give optimum yields of motor spirit, or light fuel oil, aS required. In both the above methods, the yields of final products are much higher than those obtained by first retorting torbanite and then cracking the crude oil, as the inefficient cracking associated with the retorting process is Substantially eliminated. (6) The absorption of the solvent by partially depolymerised torbanite, and the difficulty in separating such material from an extract solution, mean that residues containing unextracted oils, due to insufficient preheating in (a) (i) above, cannot be returned for further preheating and extraction unless 272 J. A. DULHUNTY. a method of washing and decantation is adopted, such as that used by the author (Dulhunty, 1942) in experimental work. (c) Success in separating the solid residues from the extract solution, by any type of filtration, depends on the complete extraction of the torbanite. (dq) The fact that solvent extraction depends on the preliminary absorption of the solvent, rather than a simple surface solution effect, means that it is not necessary to reduce the torbanite to a fine powder for solvent extraction. (e¢) The solution of the organic matter is accomplished by the solvent which the torbanite absorbs, thus comparatively small quantities of solvent are required, good results being obtained by using quantities varying from 1:1 to 2:1 by weight of solvent and torbanite respectively. It also follows that stirring is not essential. (f) The difficulties involved in preheating dry, powdered or granular torbanite, evenly throughout its bulk, make it desirable to adopt a method in which preheating and extraction are effected simultaneously in the presence of a solvent oil. PRELIMINARY EXAMINATION OF EXTRACTED PRODUCTS. The material examined was the product obtained by preheating torbanite at temperatures between 360° and 380° C. for periods varying from 2 to 6 hr., followed by pressure-benzene extraction at 260°C., and the separation of the solute from the benezene by fractionation. (See (a) (4) under Treatment Principles.) Particular care was taken to ensure that the final product was free from benzene. (a) Physical Properties. Just fluid at room temperatures ; flowing freely above 40°C, Colour: Black; completely opaque. Odour: Faint aromatic odour, quite distinct from that of crude oil produced by retorting torbanite, and faintly resembling the odour of heavy residues from the distillation of coal tar. Specific gravity: 0:92 at 20°C. Refractive index: 1:55 at 20°C. (b) Distillation at Atmospheric Pressure. A small quantity of distillate was obtained amounting to about 16% by volume of the original product, and boiling from 150° to 275°C. Distillate below 275° C. was pale yellow to light red in colour, comparatively colour-stable, and possessed the odour of the original product. Cracking commenced when the vapour temperature reached 275° C., and the distillate obtained was light red in colour but darkened to dark red soon after distillation and eventually became black. This distillate con- tained a “light end ’’, and possessed the odour of retort crude oil. (c) Distillation under Reduced Pressure. Distillate amounting to 30% by volume of the original product was obtained, boiling from 60° to 250° C. under 15 mm. of mercury. Cracking commenced when the vapour temperature reached 250°C. Distillate from 60° to 170° C. was pale yellow to light red, and colour-stable, and paraffin wax separated on standing, but the oils did not possess the properties of lubricants. Residue above 250° C. was solid at room temperatures, but soft and greasy, melting at 60° to 80° C. (d) Fractional Solution. The product was extracted with light petroleum (B.P. 40°-60° C.) at 50°C. The soluble fraction was separated from the light petroleum and distilled under reduced pressure. The fraction insoluble in light petroleum, was extracted with ethyl alcohol at 60°C. The fraction THE ACTION OF SOLVENTS ON TORBANITE. 273 insoluble in alcohol, was boiled with 20% sodium hydroxide for 3 hr., filtered, and the filtrate acidified with hydrochloric acid. The results were as follows : (i) Fraction soluble in light petroleum : 87° by weight, 88-5°% by volume, black oil, fluid at room temperatures, specific gravity 0-914, refractive index 1-5211, odour of original product, distillation under reduced pressure, see Table I. (ii) Fraction insoluble in light petroleum: 13% by weight, 11-5% by volume, black solid, brittle at room temperatures, softening point about 100° C., odourless, refractive index 1-6452, specific gravity 1-04. (iii) Fraction insoluble in lght petroleum but soluble in ethyl alcohol : about 2°5% by weight, black semi-solid, tarry material. (iv) Fraction insoluble in light petroleum and ethyl alcohol: Black solid, brittle at room temperatures, softening point about 100° C., odourless, refractive index 1-6498, specific gravity 1-05. The treatment with sodium hydroxide had no effect, the alkaline solution was not coloured, and the filtrate gave no precipitate when acidified. CONCLUSIONS. The results of distillation under atmospheric and reduced pressures suggest that the product consists largely of very heavy paraffin compounds, including waxes and, possibly, substances of even higher molecular weight from which the waxes were derived. The lighter fractions obtained by distillation under reduced pressure possess a pale yellow colour, which does not become darker on standing. This would suggest the absence of those compounds which cause the rapid darkening in colour of all distillates from retort crude oil. The lght- petroleum-insoluble fraction evidently represents the source from which the soluble oils were derived, as further heat treatment renders it soluble. Work being carried out shows that there is no accumulation of residue, insoluble in light petroleum, when successive extractions of torbanite are made with pre- viously extracted oils at temperatures between 350° and 400°C. From this it would seem that the difference between the fractions, soluble and insoluble in light petroleum, depends on the degree of depolymerisation rather than any fundamental difference in chemical nature. Only 2:5% of the light-petroleum- soluble fraction is soluble in ethyl alcohol, indicating the absence of soluble resinous material in any appreciable quantity. The fact that this fraction is not attacked by hot alkali seems to suggest the absence of soluble ulmins and tar acids. TaBLE I. Vacuum Distillation of Light-petroleum-soluble Fraction of Product from Pressure-benzene Extraction of Preheated Torbanite. (Pressure of distillation, 18 mm. of mercury.) Calculated Per Cent. by Boiling Range : Boiling Range : Volume of Specific Refractive Reduced Pressure. Atm. Pressure. Original Gravity. Index. oc. ac: Product. 85-120 150-210 8-67 0-7909 1-45 120-140 210-245 3-55 0: 8347 1-46 140-180 245-290 5:92 0-8478 1-47 180-220 290-335 6-70 0: 8672 1-48 220-250 335-370 6-31 0- 8865 1-49 Residue Se ne -—- 60-95 0-972] 1-54 Original product... = — 0-9264 1-53 Light - petroleum - soluble fraction .. — 88-5 0-9148 1-52 Light - petroleum - insoluble fraction —- 11-5 1-04 1-64 274 J. A. DULHUNTY. The results of the distillation of the light-petroleum-soluble fraction under reduced pressure are summarised in Table I. The very heavy nature of the oil is emphasised by the fact that only 39°, by volume, boils below a temperature equivalent to about 370°C. at atmospheric pressure. The specific gravities and refractive indices. of the various fractions increase with the boiling ranges, and the values found for the residue from the distillation, are considerably higher than those of the heaviest fraction distilled, indicating the presence of very heavy hydrocarbons, possessing high refractive indices and Specific gravities. ACKNOWLEDGMENTS. In conclusion the author wishes to acknowledge valuable discussion with - Messrs. L. J. Rogers and E. J. Kenny, and members of the staff of National Oil Pty. Ltd. and the departments of Chemistry and Engineering Technology of the University of Sydney. Valuable technical assistance was also given by Messrs. A. J. Tow and [. S. Haviland, University of Sydney, in connection with the examination of extracted products and other chemical work. REFERENCES. Cane, R. F., 1942. Proc. Roy. Soc. N.S.W., 76, 190. Dulhunty, J. A., 1942. Proc. Linn. Soc. N.S.W., 67, 239. THE CHEMISTRY OF BIVALENT AND TRIVALENT RHODIUM. PART VI. PYRIDINE COMPLEXES OF RHODOUS HALIDES. By F. P. DWYER, MSc., and R. S. NYHOLM, MSc. Manuscript received, November 10, 1942. Read, December 2, 1942. In previous communications (Dwyer and Nyholm, 1941, 1942), a number of arsine coordinated rhodous halides, prepared by the reduction of the corres- ponding rhodic compounds with hypophosphorous acid, were described. This method has now been applied to the preparation of a number of pyridine co- ordinated complexes. Reduction in the presence of excess of pyridine gave the hexakis compounds, which by subsequent treatment with acids yielded other derivatives, but all with the common coordination number of six. By reason of the ease of oxidation of the iodides, and unsuitable solubility relation- ships in the chloride series, it has been possible to work out the whole series, with one exception, with the bromides only. However, there is little doubt that under suitable experimental conditions the various reactions involved are general for the whole halogen group. The hexakis pyridine bromo compound (II) was easily formed by the reduction of the rhodic compound (I) formed in situ, by hypophosphorous acid at 100° C., and obtained in pale yellow crystals by cooling in carbon dioxide to 0°C. Treatment with ice cold hydrobromic acid gave the pale yellow crystalline pentakis compound (III). One halogen atom in this compound was ionised in aqueous solution, and treatment with potassium iodide at room temperature gave the bromo-iodide (IV), which could be reconverted to the bromide (III) by treatment with excess of potassium bromide. By heating in aqueous solution with potassium iodide, the second bromine atom in (IV) could be replaced to yield iodo-pentapyridine rhodous iodide. The pentakis compound (III) when refluxed with hydrobromic acid in the presence of a trace of hypophosphorous acid gave the highly insoluble pale buff tetrakis compound (V) which was stable towards boiling aqueous hydrobromic acid, but transformed into the darker tris-pyridine dimeride (VI) by treatment with alcoholic hydrobromic acid. Compound (VI) is the pyridine analogue of the tris-arsine complexes previously described. Long boiling with alcoholic hydrobromic acid gradually dissolved (VI) yielding a red solution from which a small amount of red-brown crystals of the two pyridinium salts (VIT) and (VIII) was deposited, leaving a reddish solution containing (probably) the very soluble pyridinium salt (IX). An excellent yield of a mixture of the two pyridinium salts (VII), (VIII) was obtained by treatment of any of the previous compounds with alcoholic hydrobromic acid containing pyridinium bromide. By prolonged boiling, the Compound (VII) in the mixture was gradually transformed into (VIII). Although the pyridinium salt (VII) was not obtained pure in the bromide series, pure specimens of both (VII) and (VIII) were obtained in the chloride series. 7 The easily water-soluble compound (IX) which was not isolated owing to its high solubility is put forward as the logical end of the series, since it is incon- ceivable that the halogen bridged dimeric structures which have been maintained 276 DWYER AND NYHOLM. so consistently from compound (VI) onwards should suddenly revert to the normal monomeric octahedral type. It is significant that the transformation from the monomeric tetrakis compound (V) to the bridged type of structure still occurs when (V) is treated with pyridinium hydrobromide and hydrobromic acid, when the monomeric structure might well be maintained by the formation of compounds such as PyH(RhBr,.3Py). It is proposed to attempt the preparation of compounds of type (IX) shortly. In the chloride series the reaction could not be stopped at stages corres- ponding to compounds (V), or (VI), presumably owing to higher solubilities than with the corresponding bromides, and even the chloro compound of type (IV) was difficult to obtain pure. The iodide series gave the only analytically pure specimen of the hexakis compound of type (IL), which could be washed free of impurity with aqueous pyridine by reason of its relatively low solubility. The compound lost one molecule of pyridine if it was washed with water, and was highly sensitive to oxidation—as might be expected from its two ionisable iodine atoms. Similarly the preparation of the pentakis iodo compound of type (II) was easily achieved, but all attempts at the preparation of other compounds failed owing to self oxidation and the liberation of hydrogen from hot acid solutions. In the presence of hypophosphorous acid designed to prevent this oxidation, the evolution of hydrogen became even more violent, and the same purplish-brown compound was obtained. In a series of experiments using the bromo-iodo compound (IV), which in the presence of potassium iodide in hot solution is transformed into di-iodo compound, it was found that the characteristic darkening and the deposition of the purplish brown compound did not occur until hypophosphorous acid was added. This suggested that the reaction involved the reduction to monovalent rhodium—possibly RhPy,I—and this compound was then instantly decomposed with the evolution of hydrogen. It is curious that this reaction occurs only with the iodide, and this suggests that the intermediate of a mono- valent compound is feasible since the reduction potential is generally lowest with the iodide. The compounds obtained were usually variable in com- position, but two compounds gave analyses consistent with a formula Rh,Py,I,, which is possibly a compound of bivalent and trivalent rhodium. All of the compound prepared reduced alcoholic silver nitrate to the metal, but curiously enough the reduction was slow and very incomplete in aqueous solution. The colour of the compounds darkened progressively as the coordinated pyridine was removed—thus the hexakis compounds were yellow, and the pyridinium salts were red or reddish brown. EXPERIMENTAL. Hexakis-pyridine rhodous bromide (II). Rhodium trichloride solution (20 mls.), containing 0-176 g. of rhodium, was treated with potassium bromide (10 g.) and pyridine (10 mls.). The mixture was heated to boiling to form the coordinated rhodic compound, and then treated whilst hot with hypophosphorous acid (3 mls. of 30%) solution. It was boiled for a further one minute, when the colour diminished somewhat, and then rapidly cooled in ice to 0° C. in the presence of carbon dioxide, when glistening yellow rhombs of the required compound came down. It was difficult to purify owing to its solubility in water, and even after washing with aqueous pyridine gave unsatisfactory analyses due to the presence of potassium bromide. This substance could be detected by dissolving in alcohol in which the impurities were insoluble. The compound in aqueous solution instantly precipitated the whole of its bromine, and further evidence of its ionisation was given by its precipitation due to the common ion effect by the addition of bromides. The alcoholic solution of the compound reduced hot alcoholic silver nitrate to the metal. Bromo-pentakis-pyridine rhodous bromide (III). The hexakis compound prepared as before was cooled in ice and treated with constant boiling hydrobromic acid (15 mls.), when golden yellow flat plates of the pentakis compound were precipitated. The precipitate was washed with ice THE CHEMISTRY OF BIVALENT AND TRIVALENT RHODIUM. 2G cold 1 N. hydrobromic acid in which it is nearly insoluble, and then rapidly with ice water in which it is easily soluble. An aqueous alcoholic solution instantly precipitated part of the bromine in the cold, and the remainder on heating, followed by reduction of the silver nitrate to the metal. The compound was easily soluble in alcohol and acetone, but insoluble in benzene. In the air it darkened due to oxidation, but the rhodic compound formed was easily removed by washing with water containing a trace of hydrobromic acid. In the preparation of this compound and of the previous one, if the boiling with hypophosphorous acid is prolonged, small yields only are obtained, and some metallic rhodium is produced. This suggests that the reduction possibly proceeds to the monovalent stage, and this view is supported by the evolution of hydrogen when such highly reduced solutions are acidified. Found: Rh, 15-6%; Br, 24:2%. Calculated for (Rh(C;H,N);Br)Br: Bh, 15-63%; Br, 24-31%. Bromo-pentakis-pyridine rhodous iodide (IV). Bromo-pentakis-pyridine rhodous bromide (0:5 g.) was dissolved in warm water, which had been previously freed from dissolved air and saturated with carbon dioxide. The clear yellow aqueous solution was filtered from traces of impurity, a few drops of hypophosphorous acid added, heated to 80°C. for a few minutes and then cooled to room temperature. Potassium iodide (1 g.) was then added and gave a voluminous pale yellow precipitate of the required compound. The precipitate was washed once with water, then several times with very dilute hydriodic acid, and finally once with ice water in which it is quite soluble. It was dried over concentrated sulphuric acid. The compound was precipitated from its aqueous solution by the addition of potassium iodide. In the cold alcoholic silver nitrate precipitated immediately all of the iodine as silver iodide, and on heating the bromine as silver bromide, and finally was reduced to metallic silver. Found: Rh, 14:9%; calculated for (Rh(C;H;N);Br)I: Rh, 14-62%. Dibromo-tetrakis-pyridine rhodium (V). Bromo-pentakis-pyridine rhodous bromide (0-4 g.) was refluxed with 2 N. hydrobromic acid (30 mls.) in the presence of a few drops of hypophos- phorous acid. The substance was gradually dissolved to a yellow solution, and then replaced by a voluminous pale buff precipitate. The refluxing was continued for a further five to ten minutes to increase the particle size, and after filtermg was washed many times with warm water. It was insoluble in water and benzene, but slightly soluble in alcohol or acetone. The alcoholic solution gave no reaction with cold alcoholic silver nitrate, but precipitated a mixture of silver bromide and metallic silver on boiling. The substance, which crystallised in minute needles, was stable in air, and not affected by long boiling with aqueous hydrobromic acid. Found: Kh, 17-8%; Br, 27-35%. Calculated for (Rh(C;H,;N),Br,): Rh, 17:78%; Br, 27-64%. Dibromo-hexakis-pyridine ww. dibromodirhodium (VI). Finely powdered dibromo-tetrakis- pyridine rhodium (0:8 g.) was refluxed with constant boiling hydrobromic acid (12 mls.), water (12 mls.), alcohol (20 mls.) and 30% hypophosphorous acid (7 drops). The substance gradually darkened in colour, commencing to dissolve after about five minutes. After approximately 50% had dissolved, the substance was filtered whilst hot, and the reddish filtrate reserved. The precipitate was well washed with hot 50% alcohol, and dried over sulphuric acid. The substance was insoluble in water, and sparingly soluble in hot alcohol, acetone, or chloroform. The substance was also more stable to heat than any of the compounds previously described. Found: Rh, 20:2%; Br, 31-5%. Calculated for (Rh(C;H,;N),Br,).: Rh, 20-18%; Br, 31-37%. Bis-pyridinium-tetrabromo-tetrakis-pyridine . dibromodirhodium (VII) and Tetrakis-pyridinium- hexabromo-bis-pyridine dibromodirhodium (VIII). The bright red filtrate from the preparation above on cooling deposited reddish buff twinned needles and plates. After filtering from the still reddish mother liquor, and well washed with water, it was dried over sulphuric acid. The filtrate from which no further crystalline material could be obtained, is considered to contain the last substance in the degradation series, since the crystalline material by refluxing with alcoholic hydrobromic acid can be transformed into the same reddish water-soluble compound, which is considered to be hexakis-pyridinium-octabromo dibromodirhodium (IX). 278 DWYER AND NYHOLM. The crystalline material gave the following analyses for different preparations: Rh, 15-62%, 16-02%, 15-83%, 15:70%, 16-11%; Br, 44-06%, 41:0%, 41-6%, 41-56%, 39-36%. Calculated for (C;H,;N.H).(Rh,Br,(C;H;N),): Rh, 17-68%; Br, 41-4%. Calculated for (C;H;N.H),(Rh,Br,(C;H;N),): Rh, 15-56%; Br, 48-34%. Attempts to separate the mixtures by extraction with solvents were fruitless owing to their sparing solubility ; but ultimately the tetrakis pyridinium compound was isolated by prolonged treatment with boiling hydrobromic acid in aqueous alcoholic solution. The best yields of the pyridinium salts were obtained by the following procedure: tetrakis pyridine dibromo rhodium (V) (0:8 g.) was refluxed with constant boiling hydrobromic acid (14 mls.), water (14 mls.), hypo- phosphorous acid (5 drops) and a mixture of pyridine (6 mls.) and hydrobromic acid (12 mls.). The boiling was continued until the tris pyridine compound which is the first decomposition product had just dissolved. The heavy beautifully crystalline red pyridinium salts were well washed with water, and dried at 100°C. By further action with squeous alcoholic hydrobromic iz, By Yr 2 Br Br Br 2 7a r Reflux (HR). HBr H Y 2, 2| Py Py @ Py Vi Sr Br (HPy) Die pio Thies val lux HBr (HA) sae Vil = acid, the bis pyridinium salt was gradually transformed into the tetrakis compound, which also decomposed slowly to the compound (IX), which contains no coordinated pyridine. Found for purified product: Rh, 15-6%, 15-62%; Br, 49-77%, 47-4%. The pyridinium salts were somewhat soluble in alcohol in the absence of pyridinium bromide or bromides. They were soluble in aqueous sodium hydroxide to orange solutions, which had a powerful odour of pyridine and were reprecipitated by acids. With silver nitrate they gave a voluminous precipitate of silver bromide and metallic silver on heating. Heaxakis-pyridine rhodous chloride. This was prepared in a manner similar to the bromide, save that potassium chloride was substituted for the potassium bromide. On cooling in ice and salt glistening pale yellow crystals of the compound came down, together with some potassium chloride. The substance was exceedingly soluble in water except in the presence of metallic chlorides, and thus a sample suitable for analysis could not be obtained. The substance darkened in the air owing to oxidation, instantly precipitated all of its chlorine by the addition of alcoholic silver nitrate which was reduced to the metal on heating. The substance was very soluble in alcohol and acetone. Chloro-pentakis-pyridine rhodous chloride. The hexakis compound prepared as above was cooled in ice and treated with ice cold 5 N. hydrochloric acid (30 mls.), when very pale yellow THE CHEMISTRY OF BIVALENT AND TRIVALENT RHODIUM. 279 flat plates were precipitated. The precipitate was washed with ice cold dilute hydrochloric acid, and finally with a small amount of water. As before, the compound was extremely soluble in water except in the presence of chloride ions, and analytically pure specimens were difficult to obtain. The substance was easily soluble in alcohol or acetone, and with alcoholic silver nitrate precipitated part of its chlorine in the cold, and the rest on heating. Finally, metallic silver was deposited. Treatment of the aqueous solutions with potassium iodide or bromide gave pre- cipitates of probably chloro-pentakispyridine rhodous iodide and bromide. Found: Rh, 18:3%; Cl, 13:2%. Calculated for (Rh(C;H,N);Cl)Cl: Rh, 18-08% ; Cl, 12-48%. Bis-pyridinium tetrachloro tetrakis-pyridine wu dichlorodirhodium. This substance, which is the chlorine analogue of (VII), was prepared by refluxing the pentakis compound (0:8 g.) with 1 N. hydrochloric acid (30 mls.) and a few drops of hypophosphorous acid in an atmosphere of carbon dioxide. The yellow solution after a short time deposited a mass of fine pinkish buff needles which were washed with dilute hydrochloric acid in which they were completely insoluble. The substance was also insoluble in benzene and chloroform and very slightly soluble in hot alcohol. With alcoholic silver nitrate on heating, a precipitate of silver chloride was obtained followed by metallic silver. In the preparation of this compound, which involves the removal of three pyridine molecules from the pentakis compound, despite a great many attempts it has not been possible to stop the reaction at the stages represented by the tetrakis or tris pyridine com- pounds. If the reaction were stopped when only part of the pyridinium salt was precipitated, and the filtrate cooled, it always contained unchanged pentakis compound. Found: Rh, 23-04%; Cl, 23-:8%. Calculated for (C;H;N.H),(Rh,CI,(C;H;N),: Rh, 23-029, ; Cl, 23-8%. Tetrakis-pyridinium hexachloro bis-pyridine w dichlorodirhodium. This substance, the chlorine analogue of (VIII), was obtained from the filtrate of the previous preparation or by carrying on the reaction with hydrochloric acid until the bis-pyridinium salt had almost dissolved. On cooling the red solution, it deposited bright reddish orange needles, which were washed with dilute hydrochloric acid, and finally to prevent loss of chlorine, with 0:1 N. hydrochloric acid. The substance was slightly soluble in alcohol and acetone, and reduced alcoholic silver nitrate to the metal. By treatment of the compound for an hour with hydrochloric acid, it gave a water- soluble compound, which is probably the chlorine analogue of compound (IX). Found: Rh, 21:6%; Cl, 29:7%. Calculated for (C;H;N.H),(Rh,Cl,(C;H;N).): Rh, 21-23%; Cl, 29-34%. | Hexakis-pyridine rhodous iodide. Rhodium trichloride solution (10 mls.), containing 0-09 g. rhodium, was treated with potassium iodide (5 g.) and water (10 mls.). The mixture was heated to form the deeply coloured potassium iodorhodite, and then treated with pyridine (15 mls.), followed by 30% hypophosphorous acid (2 mls.). The mixture was refluxed in an atmosphere of carbon dioxide until it became pale yellow in colour, and a slight precipitate of rhodium metal had come down. The solution was then filtered in an atmosphere of carbon dioxide, and cooled in the same atmosphere to 0°C. The glistening pale yellow rhombs belonging probably to the rhombic system, were filtered in an’ atmosphere of carbon dioxide and washed with oxygen- free 30% aqueous pyridine solution. The substance was finally dried over sulphuric acid in an inert atmosphere. The compound lost pyridine immediately by washing with water, and was transformed into the more insoluble pentakis compound. It rapidly oxidised in the presence of oxygen to the dark purple rhodic compound, which however was easily soluble in aqueous pyridine. The pure hexakis compound was readily obtained by dissolving the pentakis compound (see later) in pyridine in the presence of hypophosphorous acid and cooling in ice in the presence of carbon dioxide. The substance was easily soluble in alcohol or acetone, and precipitated the whole of its iodine by treatment with silver nitrate, which was reduced to the metal on heating. Found: Rh, 12:6%; I, 31-2%. Calculated for (Rh(C;H;N),)I,: Rh, 12-39% ; I, 30-56%. LIodo-pentakis-pyridine rhodous iodide. This substance was prepared as for the hexakis compound above, except that the filtrate, after cooling in ice, was treated with cold freshly reduced constant boiling hydriodic acid (15 mls.), the solution warmed to 30° C. and then cooled again in 280 DWYER AND NYHOLM. ice. The pale yellow microcrystalline precipitate was filtered in an inert atmosphere, and washed several times with oxygen-free ice cold water. The substance was easily soluble in hot water, and crystallised out again on cooling. It was also readily soluble in alcohol, in which alcoholic silver nitrate precipitated part of the iodine at room temperature, and the remainder, with reduction to metallic silver, on heating. The substance readily oxidised in the air, becoming brown. Found: Rh, 13:9%; I, 33-6%. Calculated for (Rh(C;H,N),I)I: Rh, 13-69%; I, 33-78%. The effect of hot acids or hypophosphorous acid on todo-pentakis-pyridine rhodous iodide. In attempts to prepare other pyridine coordinated compounds with rhodous iodide, the usual procedure of boiling with decolourised hydriodic acid was carried out. This resulted, however, in the evolution of large volumes of hydrogen gas, and the formation of black insoluble precipitates of variable composition. Substitution of a mixture of hydrochloric acid and potassium iodide for hydriodic acid, and the use of sulphurous acid in lieu of hypophosphorous acid to keep the substance reduced, also gave no satisfactory results. Finally, bromo pentakis rhodous bromide was dissolved in water, which had been boiled free of oxygen, treated with potassium iodide and a little hydrochloric acid, and heated to boiling. Apart from the production of iodo pentakis rhodous iodide, which came down on cooling, no reaction occurred. Addition of hypophos- phorous acid, however, instantly caused the formation of a deep purplish precipitate, and the evolution of hydrogen gas. Continued boiling then dissolved the purple precipitate, and from the pale yellow solution no compound could be isolated. The purplish precipitate was variable in composition, insoluble in alcohol, but reduced alcoholic silver nitrate to the metal. Asa result of the analyses, a possible formula Rh,(C;H;N),I, is suggested. Found: Rh, 16:6%, 17:7%; I, 50:84%, 53:8%. Calculated for Rh,(C,;H;N),;I,;: Rh, 16:65%; I, 51-39%. SUMMARY. The reduction of hexakis pyridine rhodic halides by hypophosphorous acid in the presence of excess pyridine has been found to yield the corresponding hexakis pyridine rhodous halides as yellow crystalline solids. By treatment with acids the pyridine molecules can be successively removed to yield other pyridine coordinated compounds. Practically the whole series, from the hexakis compound to the pyridinium salts, have been obtained with rhodous bromide, but owing to unsuitable solubility relationships, or extreme ease of oxidation, various compounds in the series with rhodous chloride and iodide are missing. Department of Chemistry, Sydney Technical College. A NOTE ON THE MAGNETIC BEHAVIOUR OF POTASSIUM CYANONICKELITE. By D. P. MELLOR, MSc., and D. P. CRAIG, M.Sc. Manuscript received, November 18, 1942. Read, December 2, 1942. Monovalent nickel (Ni!) is isoelectronic with bivalent copper and should therefore exhibit, in its compounds, a paramagnetic susceptibility consistent with the existence of one unpaired electron spin. Some time ago Szeg6é and Ostinelli (1930) reported that potassium cyanonickelite is diamagnetic, a finding which is contrary to the above prediction. Because of this deviation from predicted behaviour and because of the meagre experimental detail given by Szeg6 and Ostinelli, it was thought worth while to reinvestigate the compound. An added reason is to be found in the recent work of Eastes and Burgess (1942) who, for the first time, isolated pure specimens of solid potassium cyanonickelite and definitely established its composition as K,NiCN, (and not K,NiCN,). Some difficulty is experienced in working with the cyanonickelite owing to the extraordinary ease with which it undergoes oxidation. It was found most convenient in the present work, to deal with aqueous solutions. EXPERIMENTAL. A solution of potassium cyanonickelate was made up to contain 0-02346 g. Ni/ml; 25 ml. of this solution were reduced with sodium amalgam containing | g. of sodium. The whole was vigorously shaken during the reaction and when reduction had ceased a 10 ml. sample was with- drawn for analysis ; a second sample was immediately used for a determination of its susceptibility by the Gouy method. It is important to note that reduction was never, at any time, complete. Method of Analysis. A 10 ml. sample of the reduced solution was poured into 25 ml. of ammoniacal silver nitrate solution and the resulting black precipitate of silver washed with ammonia, sodium thiosulphate and water; it was then dried and weighed. The corresponding weight of Ni was used to calculate the percentage conversion of Ni" to Nil. Results. From the tube constant and other data it was calculated that, in the most favour- able instance (case B in table below), a change in Aw of the order of +10 mgm. would have been observed had K,NiCN, become paramagnetic with Ni! possessing one unpaired electron spin. No such change in Aw was observed ; oxidation and reduction produced very little change in the susceptibility of the various solutions as shown in the accompanying table. Analysis of Results. Susceptibility of Solution. the Solution. A. Containing 0-0116 g. Nil/ml. representing 49-5% conversion of Nill to Nil... £% oie < a nah i an —0-66 x 10-® B. Containing 0-0170 g. Nil/ml. representing 72% conversion. . the —0-65 x 10-6 C. Containing 0-:0119 g. Nil/ml. representing 51% conversion. . as —0Q-66 x 10-6 D. Blank solution... 5 - ae un a Ss —0-68 x 10-6 E Me@cidised solution (C, above) .. 0: .. ee —0-65 x 10-8 282 MELLOR AND CRAIG. The blank solution referred to contained K,Ni(CN), (0-02346 g. Ni/ml) and NaOH, the latter at the same concentration as in A, B and C. The oxidised solution was obtained by bubbling air through a reduced solution until all the typical deep red colour had disappeared. DISCUSSION. From the above it may be inferred that K,NiCN, is diamagnetic with a susceptibility not very different from that of K,NiCN,. The finding of Szeg6 et al. (1930) is thus confirmed. The observed diamagnetism may mean either (1) that there is no unpaired electron spin to be observed, or (2) that the unpaired electron spin exists but is quenched because of some inter- or intra-atomic interaction. As there are no theoretical grounds for believing that the second suggestion is correct, the first is adopted. It can be reconciled with the prediction made earlier, by postulating a structure involving a metal-metal bond: — r CN ON 4 ++++ [a CN—Ni—-Ni—-CN ral Hs CN CN 4 In the formation of the metal-metal bond the odd electron on each metal atom is paired up. Precisely the same kind of bond is formed in mercurous chloride (Hg,Cl,); but for formation of the Hg-Hg bond, mercurous chloride would be paramagnetic. Further instances of metal-metal bonds could be cited but one other must suffice. Recent electron diffraction studies (Davidson et al., 1940) have revealed the presence of a metal-metal bond in aluminium trimethyl Al,(CH;),. There would seem to be no inherent reason, then, why such a bond should not occur in the cyanonickelite ion. This explanation of the diamagnetism of the ion has the additional advantage of giving Nit a coordination number of four which is the number one would anticipate from a comparison with isoelectronic Cul. From the same comparison it is highly probable that the complex ion [ Ni,CN,]--—~ has a planar structure with Ni! forming dsp? bonds. REFERENCES. Eastes, J. W., and Burgess, W., 1942. J. Amer. Chem. Soc., 64, 1187. Davidson, N. R., Hugill, J. A. C., Skinner, H. A., and Sutton, L. E., 1940. Trans. Far. Soc., 36, 1212. Szego, L., and Ostinelli, P., 1930. Gazz. Chim. Ital., 60, 946. FUNCTIONAL RELATIONS BETWEEN SCROTUM AND POUCH AND THE EXPERIMENTAL PRODUCTION OF A POUCH-LIKE STRUCTURE IN THE MALE OF TRICHOSURUS VULPECULA. By ADOLPH BOLLIGER, Ph.D. (From the Gordon Craig Research Laboratory, Department of Surgery, University of Sydney.) (With Plates XVI-XVIII.) Manuscript received, November 18, 1942. Read, December 2, 1942. INTRODUCTION. Edward McCrady, Jr. (1939), in his book on the embryology of the opossum (Didelphys virginiana Kerr) states that the perfect parallelism between the development of the scrotal anlagen and the lips of the pouch makes it impossible for him to avoid the conclusion that the lips of the pouch represent the labia majora, the homologues of the scrotum in higher mammals. To this statement, however, he adds that this homology has never been suggested before, though a number of investigators have studied the development of the pouch and the descent of the testes, which suggests that there must be some obvious and fundamental objection to it, though McCrady confesses that he has been unable to think of any such objection. On the other hand, Abbie (1941) in his recent paper on ‘ Marsupials and the Evolution of Mammals ”’ states that essentially the pouch is formed by an insinking of the mammagenous skin of the ventral abdominal wall through a gap in the underlying cutaneous musculature. The sole peculiarity in connection with the pouch according to this author is the hiatus in the musculature which permits insinking of the mammagenous zone and the reader is left with the impression that the homologous organ in the male would be the mammary glands or nipples if any were present. Studies in this laboratory on the response of the scrotum and the pouch of the diprotodont marsupial Trichosurus vulpecula, the common Australian phalanger or possum, have furnished a number of functional results which have a direct bearing on this subject. Some of these findings have already been published in connection with other problems, but many more recent experi- mental observations necessitate a summary ob the situation which will be given under the following headings : | (1) Anatomical considerations. (2) Materials. (3) Response of scrotum and pouch to testosterone propionate, an androgen. (4) Response of scrotum and pouch to progesterone. (5) Response of scrotum and pouch to gonadotropin obtained from pregnancy urine. (6) Response of scrotum and pouch to estrogens. (7) Eversion of pouch in untreated females. 284 ADOLPH BOLLIGER. (1) ANATOMICAL CONSIDERATIONS. This paper deals with reactions of a skin area located on the lower abdomen of Trichosurus vulpecula, in which in later life scrotum and pouch are formed and which will be referred to as the scroto-marsupial area. In contrast to the abdominal region in general this area is characterised by the presence of only little skin muscle as shown by histological examination and electrical stimulation experiments. In the fully developed animal this area is further characterised by the sparseness of hair growth as compared with the rest of the abdomen. A few days after birth paired lateral swellings or ridges arise in this area. They are the first indication of the future pouch and scrotum. In the ease of a male these swellings soon begin to fuse at the caudal end and a hemispherical extrusion is formed which is the beginning of a definite scrotum. As the scrotum increases in size the lateral swellings fuse completely to form ultimately the large sac and neck of this organ. In the case of a female the lateral swellings fuse only inferiorly, and not an extrusion as in the case of the male, but an invagination of skin takes place beneath the point of fusion. This invagination or infolding takes place also laterally along the ridges. Fusion except at the caudal end does not occur, but in order to form a practically closed pouch the original swellings which now represent the lips of the pouch approximate along the mid-line. In T7'richosurus vulpecula as weli as in other marsupials the skin musculature, as pointed out before, extends into the lips of the pouch, where its fibres are present in such increased numbers as to justify their separate name “ sphincter marsupii ”’, as distinct from the panniculus carnosus in general. The skin lining the pouch itself contains only few muscle fibres, as does the scrotal sac. From the anatomical development it would follow that the scrotum is an extrusion of the ‘‘ sexual ’”’ skin constituting the scroto-marsupial area and that the pouch is an invagination of it. In the male this extrusion of skin, the scrotum, houses the testes ; in the female the mammary glands become situated in the posterior wall of this invagination which is commonly referred to as the pouch. This arrangement again becomes evident if we consider the cremaster muscles in the two sexes. In the male they pass right into the interior of the scrotum, while in the female they do not penetrate the pouch wall. (2) MATERIALS. In a previous communication (Bolliger, 1940) it has been mentioned how to capture possums and how to keep them in captivity. The technique of measuring the capacity of the pouch in the female has also been reported (Bolliger, 1942). The sex hormones used in this investigation were all administered sub- cutaneously or intramuscularly. They were obtained in the form of the following commercial preparations: Perandren (Ciba), a solution of testosterone pro- pionate in sesame oil; Lutocyclin (Ciba), an oily solution of progesterone ; Gonan (B.D.H.), the dry gonadotropic substance obtained from human pregnancy urine which was dissolved in water prior to injections ; Stilbcestrol (B.D.H.), — an oily solution of diethylstilbcestrol ; Ovocyclin (Ciba), an oily solution of cestradioldipropionate. (3) RESPONSE OF SCROTUM AND POUCH TO TESTOSTERONE PROPIONATE, AN ANDROGEN. As pointed out in a previous communication (Bolliger and Carrodus, 1940c), in sexually immature animals these organs showed a pronounced response to the administration of testosterone propionate. For example, in a male pouch young FUNCTIONAL RELATIONS BETWEEN SCROTUM AND POUCH. 285 of about 35} months of age as well as in a male of about 10 months of age, the scrotum became markedly elongated as compared with untreated males. In females of about similar age the pouch also developed precociously. It rapidly increased in size and the lips became thickened. But in spite of sustained injections the increase in size of pouch as well as scrotum was only temporary and was followed by a marked decrease in size which amounted almost to atrophy. In general these experiments indicated that pouch and scrotum responded in a similar manner towards the administration of testosterone propionate. (4) RESPONSE OF SCROTUM AND POUCH TO PROGESTERONE. Progesterone, the action of which is mainly concerned with the change of the uterine endometrium during the menstrual cycle and pregnancy has also a definite influence on the pouch as shown on a previous occasion (Bolliger and Carrodus, 19400). The administration of progesterone to young or fully grown females brought on a relaxation of the pouch after a preliminary enlargement and the lips “became separated. The injection of progesterone into fully grown males gave no definite results but in adolescent animals a broadening and relaxation of the neck of the scrotum was noticed. This broadening made it possible to push the fully developed testes readily out of the scrotum, while in the untreated animal of similar age it was impossible for them to leave the scrotum on account of the presence of a far too narrow scrotal neck (Bolliger and Carrodus, 1939a). These experiments seem to indicate that progesterone possesses a relaxing and broadening property which makes itself manifest on the tissues of the pouch as well as on those of the serotum. (5) RESPONSE OF SCROTUM AND POUCH TO GONADOTROPIN OBTAINED FROM HUMAN PREGNANCY URINE. Recently it has been shown (Bolliger, 1942) that gonadotropin obtained from pregnancy urine brings on an enlargement of the pouch after a preliminary short-lived contraction. With large doses the enlargement may be as much as 20 times measured on the capacity of the organ. In previously unpublished experiments it was noted that in the fully grown male an elongation of the neck of the scrotum took place after the administration of chorionic gonadotropin. But the results were not spectacular, amounting to a maximum elongation of about 1 cm. In the young animal of about es 6 months of age after the administration of gonadotropin “the scrotum was found to be as much as four times the size of that of untreated males. It was further observed that such an enlargement was independent of the presence of the testes and epididymes because after their removal the empty scrotal sac became even more markedly enlarged following further injections of gonadotropin. Comparing the experimental results obtained from the administration of gonadotropin one may again state that both scrotum and pouch responded similarly, there being a large expansion in each case. (6) RESPONSE OF SCROTUM AND POUCH TO CESTROGENS. The response of the scroto-marsupial area to cestrogens can be divided into three phases : (a) Swelling. b) Contraction. (c) Formation of a pouch-like structure in males. W—December 2, 1942. 286 ADOLPH BOLLIGER. (a) Swelling. Twenty-four hours after the injection of about 0-3 mg. or more of cestrogen (stilbcestrol, cestradioldipropionate, etc.) into adolescent or fully grown males, a swelling of the scrotum was noticed. The fairly thin scrotal skin as seen in the untreated animal became thickened, giving it a felt-like texture. Particularly in adolescent animals or after repeated injections this swelling was sometimes so marked as to alter the typical heart-shaped outline of the scrotum into that of — a round or a plum-shaped body. A swelling of the abdominal skin surrounding the scrotal stalk was also noticed. Then within a week or two after the last injection the swelling subsided and provided a sufficiently large amount of cestrogen had been administered the phase of contraction became very noticeable. In the female a similar swelling of the skin of the pouch and of the tissue surrounding it was noted after the administration of cestrogen. Externally this was first observed in the lips of the pouch, which became thickened (Bolliger and Carrodus, 1940a). As far as the interior of the pouch was concerned the swelling was short- lived only, i.e. one or several days, and it passed almost imperceptibly into a contraction of this organ. There is little to hinder this as in contrast to the scrotum the pouch is essentially an empty structure. Otherwise the swelling as observed in the scroto-marsupial area after the administration of oestrogen was similar in nature in males and females. In both sexes after it had subsided it could be reproduced again by a subsequent injection of cestrogen. This was also the case when a high degree of contraction was already present. (b) Contraction. In the female one of the first external signs indicating that the process of contraction had begun was a puckering of the swollen lips. In addition, the interior of the pouch itself contracted markedly. For example, a pouch which in its pre-experimental and resting stage had a capacity of about 5 ml. of water, showed two weeks after the injection of 2-5 megs. of an estrogen, such as cestradi- oldipropionate, no capacity due to the rigid apposition of its anterior and posterior walls and its depth was only about 0-3-0-4 cm. in contrast to the pre-experi- mental depth of 3-4 cm. This was accompanied by a thickening of the skin musculature situated in and near the lips of the pouch (Bolliger and Carrodus, 1940). This contraction, however, was not permanent and within a few weeks the pouch began to expand again (Bolliger and Carrodus, 1940a). In the male the first sign of contraction was a shortening of the scrotal neck. This was followed by a diminution in size of the testes together with a somewhat corresponding amount of scrotal contraction. The next step in the process was that of the ascent of the testes, which ultimately led to an emptying of the scrotum. The scrotal sac now not only collapsed, but actually disappeared to a large extent. For example, in a fully grown animal in which testicular ascent had taken place only a small area or a small heap of wrinkled skin remained where previously a large pendulous scrotum was present (Bolliger and Carrodus, 1939; Bolliger and Ganny, 1941). —-— In the work published so far, testicular ascent and complete scrotal collapse was only accomplished in immature males, while in fully grown animals where this process required more intensive treatment only partial ascent was obtained. This was mostly due to the fact that frequent injections were repeated at weekly intervals till the animal became moribund. However, in recent experiments it has been found that complete ascent could also be readily obtained in sexually mature males when the injections were stopped before a lethal dose had been administered. Complete testicular ascent and scrotal collapse were observed in two sexually mature males about five to six weeks after the last injection of cestrogen. Approximately after another month the scrotum began to reform js FUNCTIONAL RELATIONS BETWEEN SCROTUM AND POUCH. 287 and the testes to descend as described previously in the case of younger animals (Bolliger and Canny, 1941). Again a marked similarity in response by scrotum and pouch towards westrogens could be observed during the stage of contraction and restoration. The next chapter, however, deals with an effect which necessarily is confined to males only. (c) Formation of a Pouch-like Structure in Males. On both sides of the collapsed scrotum a semilunar fold appeared which suggested the formation of a rudimentary pouch. However, the nature of these folds was not quite clear because usually they became very prominent only when the animal wilfully contracted the lower region of the abdomen, which took place, for example, on stroking the scrotal region. Furthermore, these folds disappeared a few weeks after the injection of cestrogen was stopped when the serotum began to reform. In order to obtain a more definite and if possible a permanent formation of the semilunar folds, testicular ascent and scrotal collapse were produced several times in succession in the same immature animal. ee eI I<} shes eben CO-ORDINATION COMPOUNDS DERIVED FROM NICOTINYLACETONE. 295 Nicotinylacetone was found to react readily with metal hydroxides, such as those of copper, zine, nickel and cobalt, to give co-ordination compounds of the type VI—insoluble substances which char without melting when heated. On the other hand, ferric hydroxide was readily dissolved by excess nicotinylacetone to give a deep red complex, VII, containing three nicotinylacetone residues to each iron atom, not melting below 300°, and readily soluble in water, alcohol, benzene and acetone. CH emer Soh Gg, PN |S eege im 6) ye Hl | N NS Oo Me / —OdO pak a Ya N H é ee ae CH Fe N Va : ee \ lest € C—CH vege | | 3 C es Neti GH 3 See es Me Cu,Zn,Ni,Co, Me Cu, Zn, Ni, Co ; Xp ClsSO, fete. vill id Is These same complexes (VI) could also be obtained in other ways—e.g. (a) by the action of sodio-nicotinylacetone solutions on solutions of the appropriate metal salts; or (b) by the action of sodium hydroxide on the appropriate metallic salt complexes VIII described below. It is important to note that the pyridine nuclei of the nicotinylacetone residues in these complexes VI are not concerned in the co-ordination process, and, consequently, retain their basic properties. The complexes VI can, therefore, be combined with acids to give salts of the type VIII. They can also react with methyliodide to give metho salts of the type IX. CHL r fi tee CH; O ne ae 1G CHE 1 O | N Me=Cu,Zn,Be Te The salts VIII are also conveniently prepared by the direct union of nicotinyl- acetone with the appropriate metallic salts ; whilst the metho salts, LX, can also be obtained from metallic hydroxides and the methiodide of nicotinylacetone (X), a crystalline substance readily prepared from the diketone by heating with excess methyliodide in a closed tube at 100°. This methiodide (X) could be converted in absolute alcoholic solution by sodium ethoxide to the pale brown, extremely water-soluble betaine XI. The salts of type VIII were found to be soluble usually in water or hydroxylic solvents, and behaved as typical electrolytes containing a complex cation. 296 LIONS, MORRIS AND RITCHIE. Silver chloride and barium sulphate could be quantitatively precipitated by addition of silver nitrate or barium chloride solutions to the aqueous solutions of the respective chlorides or sulphates (VIII). CH CH c~ “c—cH; e~ | ~c—cn, Lobe = Le) O fe) ° fe) N N'+ oe | CH; CHy x Xt Nicotinylacetone reacted apparently normally with chromic chloride in acetone solution to give the complex XII; but with ferric chloride a substance was obtained whose structure is, apparently, not so simple. Analysis showed it to possess the formula C,,H,.0,N,FeCl,—indicating the combination of one ferric chloride molecule with two nicotinylacetone molecules. Such a substance should have molecular weight 488-5. However, cryoscopic determinations with water as solvent showed the molecular weight to be of the order of 128—130— about one-quarter of the expected value. These results suggest a dissociation of the complex in aqueous solution into fourions. Measurements of conductivity also supported this view. On the other hand, the behaviour of dilute aqueous solutions of the complex with silver nitrate leads to the conclusion that at least two of the chlorine atoms are covalently held in the molecule, only a slight precipitation of silver chloride occurring. The precipitation was increased on heating, but the chlorine could not be completely precipitated until after the addition of nitric acid. A formula such as XITI would express this non-ionic Gee CH a“ | ie eae | i “Ech re) fo) H fe) re) ees paae Cl ie ss Cl; SS re i fe) ii fo) O LO ES | pe ecw : Nee : x XIV state of two-thirds of the chlorine present in the complex, but fails to account for the dissociation of the complex in dilute solution into four ions. A formula such a8 XIV, in which the iron is considered to be 4-covalent, would account for the dissociation of the complex into four ions, but would not account for the CO-ORDINATION COMPOUNDS DERIVED FROM NICOTINYLACETONE. 297 non-ionic behaviour of the chlorine ; and, further, would not account adequately for the ready formation of the complex from ferric nicotinylacetone (VII) by action of hydrochloric acid. In attempts to prepare salts of the type VIII in which the acid radical was optically active, cupric «-bromo camphor-z-sulphonate, and the corresponding zine salt were prepared and combined in correct proportions with nicotinylacetone but only gummy materials, which could not be crystallised, were obtained. Resolution experiments with them could not, therefore, be attempted. Morgan and Main Smith (1926) established that the condensation product of ethylene diamine with acetyl acetone (ethylene diamine bis acetylacetone (XV)) could function as a quadridentate group, the violet copper salt of which (XVI) had been described by Combes (1889). It seemed, therefore, to be of interest cH, CHz-CH, CH, CH, ets CH, ial NO / Cx==N N==C =N N==6 Ve \ V, \ N CH Vi < ie ae \:—oF HO—C yi (eo) 210) Le \ Cre Ch CH3 CH, xv xv to study the behaviour of the condensation product of ethylene diamine and nicotinylacetone with suitable metallic hydroxides and metallic salts. Since nicotinylacetone is an unsymmetrical diketone it might be expected that con- densation of ethylene diamine with nicotinylacetone would lead to the three ethylene diamine bis nicotinylacetones (XVII), (XVIII) and (XIX). However, N aN Seen CH, CH=CH, CH, CN ees sel eee Va VA a oN \ CH CH GH CH UY a ee C—OH HO—C—> N N N AVL XVUT N N= ami e. (C5) N==G < \ CH We \ Yee On Tad \ Ch; CH3 xIK experiment shows that ethylene diamine condenses readily with nicotinylacetone to give one substance only in practically quantitative yield, and there can be little doubt from the work of Kuick and Adkins (loc. cit.) that this has the formula XVII. This substance behaves as a quadridentate group, co-ordinating through two primary valencies and two secondary valencies. It reacts with metallic acetates, such as copper acetate, nickel acetate and zine acetate to form metallic complexes of the type XX. Of these, the nickel and copper complexes each contain one molecule of water, behave as non-electrolytes, are 298 LIONS, MORRIS AND RITCHIE. soluble in organic solvents, and have definite melting points. The nickel complex may even be boiled out of contact with air, only slight decomposition occurring. The complexes are stable to ethylene diamine and may be recrystallised unchanged from solutions in ethylene diamine monohydrate. Morgan and Main Smith postulated a coordination valency of five for copper in the green monohydrate corresponding to the violet anhydrous copper compound XVI, but in view of the similarity between the abovementioned copper and nickel complexes, and the fact that a coordination valency of five is very unlikely for nickel it seems more reasonable to assume that in them both nickel and copper exhibit coordination valencies of four, and that the molecule of water is necessary for the building of the crystal lattice or is held by hydrogen bonds to one or other of the two oxygen atoms of the complex. The zinc complex is anhydrous, and in it zine appears to have its normal covalency of four. CH, (CHE —CH cy "9 CH, CH=CH) lige a a ; Me : = N= C'==N N= '¢ i. ue Nea ay) x 2 aN ye Cc— a re oe é oes N ian XX Xx Me =Cu, Ni, Zn. Me =Cu,Ni, 2n. X= cl,etc. The complexes XX each contain two pyridine nuclei, the nitrogen atoms of which take no part in the formation of the central co-ordination complex. They are therefore capable of union with acids to form salts of the type XXI. These salts may also be directly obtained from ethylene—diamine bis-nicotinylacetone itself and metallic salts such as the chlorides of copper, nickel, zine, cobalt, etc., and come down in anhydrous condition by precipitation from alcoholic solution. They are all soluble to some extent in hydroxylic solvents, but. insoluble in anhydrous organic solvents. EXPERIMENTAL. Nicotinylacetone (I) was prepared by a method substantially similar to that developed by Kuick and Adkins (loc. cit.). It readily formed a yellow picrate, which was obtained in yellow needles melting at 155°. Found : C, 45-8, H, 3-3%;- caleulated for C,,H,,O,N,, ©, 46:9, Ho 3-19F Nicotinylacetone Methiodide (X). Nicotinylacetone (16 g.) and methyl iodide (30 g. ; excess) v were heated together in a closed tube at 100° for 30 minutes. The first-formed homogeneous — yellow solution soon deposited a mass of yellow crystals. Recrystallised from alcohol or water the substance was obtained in yellow prisms melting at 184°. * td Found : C, 39-0, H, 4:0, I, 41:6%; calculated for C,,H,,O,NI, C, 39:4, H, 3-9, I, 41-6%2 4 This metho salt is very soluble in water, and soluble in alcohol, but is insoluble in anhydrous — organic solvents. When its solution in absolute alcohol was treated with the theoretical amount _ of sodium ethoxide in dry alcoholic solution a light yellow precipitate, which soon turned brown, _ was formed. When collected, washed with absolute alcohol and dried in vacuo a brown powder, — 2 extremely soluble in water and aqueous alcohol, but insoluble in absolute alcohol was obtained- It was difficult to obtain it free from traces of sodium iodide, but analysis indicated strongly that it was the betaine IX. Found: C, 66-4, H, 6-2%; calculated for C,,H,,0,N, C, 67-9, H, 6-8%: ne a ae ee a a CO-ORDINATION COMPOUNDS DERIVED FROM NICOTINYLACETONE. 299 Ethylenediamine bis-Nicotinylacetone (XVII). (8: 8’-Ethylenediamino bis (propenyl-3- pyridyl ketone). Nicotinylacetone (16:3 g.; 2 mols.) was mixed with ethylenediamine mono- hydrate (3:9 g.; 1 mol.) in a large test-tube, and the mixture gently warmed. Water was separated in the moderately vigorous reaction which set in. The mixture was finally heated at 100° for an hour. After cooling the crystalline yellow mass was recrystallised from benzene and. thus obtained in yellow prisms melting at 170°. The yield was almost theoretical. The substance was readily soluble in water, alcohol, benzene and chloroform. Hound": ©, 68-0, H, 6-3, N, 15-89%; calculated for C,,H..O.N,, C, 68-6, H, 6-3, N, 16-0%. The methods employed for preparation of the metallic complexes VI and the salts VIII were quite similar in experimental details, which are described in full for the preparation of the copper and zinc derivatives, whilst only a brief description of the complexes containing nickel and cobalt is given. Cupric Nicotinylacetonate (VI; Me=Cu). (a) The well washed cupric hydroxide from copper sulphate (2-4 g.) and potassium hydroxide solution (40 ml. of 0-5 N) was suspended in an alcoholic solution of nicotinylacetone (3 g.) and digested for several days. The gelatinous hydroxide was gradually converted into an insoluble green powder which was well washed with water and alcohol, and dried in vacuo over sulphuric acid. (6) A purer sample was prepared by mixing an aqueous solution of copper sulphate (2-4 g.) and an aqueous alcoholic solution containing nicotinylacetone (3 g.) and potassium hydroxide solution (40 ml. of 0-5.N). The precipitated metallic complex formed green micro crystals insoluble in water or organic solvents, readily decomposed by excess of mineral acids, and charring above 320° without melting. ounde: ~ ©u, 16-4, ©) 55-7, H, 4:2%; calculated for C,,H,,O{N.Cu, Cu, 16-4, C, 55-8, EA Oe. Treatment of this complex (1 g.) with sulphuric acid (0-25 g.) led to formation of the complex bis nicotinyl acetone cupric sulphate (Cu, 13-39%) described below ; whilst treatment of it (1 g.) with hydrochloric acid (0-18 g.) led to formation of the complex bis nicotinyl acetone cupric chloride (Cu, 14:1%, m.p. 189°) described below. Bis Nicotinyl Acetone Cupric Chloride (VIII ; Me=Cu, X=Cl). To a solution of nicotinyl acetone (1-6 g.; 2 mols.) in a little alcohol was added an alcoholic solution of cupric chloride (0-85 g.; 1 mol.). A green powder was obtained, practically insoluble in most of the solvents tried, but slightly soluble in dioxane. Recrystallised from this latter solvent it was obtained as a fine green crystalline powder melting at 190°. Hound : (Cu, 13-7,-C, 46-6, H, 3-9%; calculated for C,,H,,0,N,CuCl,, Cu, 13-8, C, 46-9, Hea 9%. Bis Nicotinyl Acetone Cupric Sulphate (VIII; Me=Cu, —X, =SO,). A concentrated solution of cupric sulphate (2-4 g.; 1 mol.) in hot water was added to a solution of nicotinyl- acetone (3 g.; 2 mols.) in alcohol. A thick green precipitate was formed. It was collected and dried. It appeared to be insoluble in alcohol and organic solvents but was moderately soluble in water. Recrystallised from this solvent it was obtained in fine green needles which charred at about 280°. Hound: Cu, 13-0, C, 44:0, H, 3-7, SO,, 194% ; calculated for C,,H,,0,N.CuSO,, Cu, 13-1, C, 44-4, H, 3-7, SO,, 19-8%. Addition of a solution of sodium hydroxide (0:08 g.; 2 mols.) to an aqueous solution of this complex sulphate led to formation of a green precipitate of the cupric nicotinyl acetonate (found : C, 55:4, H, 4-:2%) described above. Cupric bis Nicotinyl Acetone « Bromocamphor- t-Sulphonate. An alcoholic solution of nicotinyl acetone (3:6 g.; 2 mols.) was added to a moderately concentrated aqueous solution of cupric a«-bromocamphor-7t-sulphonate (9 g.; 1 mol.). The resulting green solution was then evaporated to dryness in vacuo, leaving a green gum which, on prolonged drying, was converted into a green glass. This was found to be soluble in alcohol, acetone, chloroform and water, but was insoluble in benzine and ether. All attempts to crystallise the substance failed. Analysis of portion of the glass gave Cu, 6-:03% ; the calculated value for anhydrous C,,H,,0,,Br.N.S,Cu is Cu, 6:3%. 300 LIONS, MORRIS AND RITCHIE. Zine Nicotinyl Acetonate (VI; Me=Zn). (a) Well-washed zine hydroxide (from zinc nitrate (3 g.) and 0-5 N potassium hydroxide solution (40 ml.) was digested for some days with an alcoholic solution of nicotinylacetone (3 g.) in alcohol. The gelatinous hydroxide was slowly converted to a yellow, micro-crystalline powder (containing 17-3% of zinc): (6) A solution of zine nitrate (3 g.) in aqueous alcohol was added to an aqueous alcoholic solution containing nicotinyl acetone (3 g.) and 0-5 N alkali solution (40 ml.). The yellow powder which precipitated was washed and dried. (c) Addition of the correct quantity of sodium hydroxide solution to an aqueous solution of bis nicotinyl acetone zinc chloride (described below) gave a yellow precipitate of zinc nicotinyl acetonate. This zinc complex is a yellow insoluble powder which chars without melting above 300°. Found: Zn, 16-6, C, 55-2, H, 4:2%; calculated for C,,H,,O,N.Zn, Zn, 16-8, C, 55-5, Ea Oe This complex (0:4 g.; 1 mol.) dissolved readily in dilute hydrochloric acid (0-073 g. HCl; 2 mols.) to a yellow solution, which, on evaporation, yielded yellow crystals melting at 140° of bis nicotinyl acetone zine chloride (described below). Bis Nicotinyl Acetone Zinc Chloride (VIII ; Me=Zn, X=Cl). Alcoholic solutions of zine chloride (1-4 g.) and nicotinylacetone (3 g.) were mixed, and then reduced to small bulk, when yellow needles separated. After recrystallisation from alcohol they melted at 140°. They were slightly soluble in water. Found: Zn, 13-9, C, 46-3, H, 3-9, Cl, 15-19%; calculated for C,,H,,O, N,ZnOl,, Zn, 14-1, C, 46:7, H, 3-9, Cl, 15-3%. Treatment of an aqueous solution of this salt (0-5 g.) with a solution of sodium hydroxide (0-08 g.) gave a yellow insoluble precipitate of the zinc nicotinyl acetonate (Zn, 16-6%) described above. Bis Nicotinyl Acetone Zinc Sulphate (VIII ; Me=Zn, X,=SO,). This substance was obtained as a yellow insoluble powder, infusible below 300° by mixing solutions of zine sulphate (1-4 g.) and nicotinylacetone (3 g.). Found: Zn, 13-1, C, 44:0, H, 3-7%; calculated for C,,H,,0,N,ZnS, Zn, 13-4, C, 44-3, BEST Zinc bis-Nicotinylacetonate-x«-Bromocamphor-t-Sulphonate. Alcoholic solutions of zine x-bromocamphor-t-sulphonate (30 g. ; 1 mol.) and nicotinylacetone (11-8 g. ; 2 mols.) were mixed, | and the solution then cautiously evaporated in vacuo. A clear yellow glass was left. It was found to be extremely soluble in water and in alcohol but insoluble in organic solvents. Additions of dry ether to its alcoholic solution effected its precipitation as a slightly gummy mass, which was dried in vacuo to a yellow powder. Found: Zn, 6:44%; calculated for C,,H,,0,.Br.N,S,Zn, Zn, 6-47%. Many attempts were made to recrystallise this substance but all resulted only in the formation of yellow gums. Nickel bis Nicotenylacetonate (VI; Me=Nz). Prepared by the usual methods this substance formed a green micro-crystalline insoluble powder which charred above 300° without melting. Found: Ni, 15-6, C, 55-9,.H, 4:1%; caleulated for C,,H,,O,N,Ni: Nietb-4) °C) bones EE 4-207. Bis-Nicotinylacetone Nickel Chloride (VIII ; Me=Ni, X =Cl). Prepared by mixing alcoholic solutions of nickel chloride (2-4 g.) and nicotinylacetone (3-2 g.) and then recrystallisation from aqueous alcohol, this substance was obtained in fine green needles slightly soluble in alcohol and water, but insoluble in solvents such as benzene. Above 300° it chars without melting. Found: Ni, 13-1, C, 45:9, H, 3-9%; calculated for C,,H,,0,N,NiCl,: Ni, 12-9, C, 47-3; Ha OOF: Bis-Nicotinylacetone Nickel Sulphate (VIII ; Me=Ni, X,=SO,). This substance, prepared in the usual way, was a greenish yellow powder, which charred on heating without melting. It was very insoluble in all the usual solvents. Found : Ni, 11-9, C, 45:6, H, 3:8% ; calculated for C,,H,,0,N, . NiSO,: Ni, 12-2, C, 44-9, H51378%: 3 CO-ORDINATION COMPOUNDS DERIVED FROM NICOTINYLACETONE. 301 Cobaltous bis Nicotinylacetonate (VI; Me=Ce). Prepared by the usual methods, this substance formed a yellow powder, insoluble in water and organic solvents, and charring when heated. Found: Co, 15-3, C, 54-9, H, 4-2%; calculated for C,,H,,0,N.Co: Co, 15-4, C, 56-4, H, 4-2%. Bis-Nicotinylacetone Cobaltous Chloride (IX ; Me=Co, X=Cl). This substance was obtained crystalline as a brown solid after recrystallisation from alcohol. It is readily soluble in alcohol and in water. Found: Co, 12-6, C, 46:6, H, 4:0%; calculated for C,,H,,0,N,.Cl,Co: Co, 12-9, C, 47-3, H, 4:0%. Bis-Nicotinylacetone Silver Nitrate. Hot aqueous alcoholic solutions of silver nitrate (3-4 g. ; 1 mol.) and nicotinylacetone (6-5 g.; 2 mols.) were mixed. On cooling, white acicular crystals separated. They were collected, washed, and dried. They then melted at 121°, and were found to be soluble in alcohol, chloroform acetone, ethylacetate, but only slightly soluble in water and insoluble in benzene and toluene. Addition of a chloride to an aqueous alcoholic solution of the complex led to an immediate precipitation of silver chloride. Found: Ag, 22-5, C, 45:4, H, 3-8%; calculated for C,,H,,0;N,Ag: Ag, 22:4, C, 44-2, ior OG. Addition of potassium hydroxide (1 mol.) in aqueous solution to this complex (1 mol.) gave a black tarry precipitate containing metallic silver—formed probably owing to the formation and subsequent decomposition of silver nicotinylacetonate—a behaviour similar to that of silver acetylacetonate (cf. Morgan and Moss, 1914). Ferric Nicotinylacetonate (VII). Freshly precipitated ferric hydroxide from ferric alum (5 g.; 1 mol.) was well washed with water and alcohol, and then dissolved in an alcoholic solution of nicotinylacetone (4-5 g.; 3 mols.). The deep red solution so formed was evaporated to dryness and the red solid residue well washed with ether, then dried. The substance was eventually obtained in red scales not fusible below 300°, and extremely soluble in water, acetone, alcohol and benzene. Found’: We, 10-6, C, 59-3, H, 4-4%; calculated for C,,H,,O0,N,Fe: Fe, 10-5, ©, 59-8, H, 4:4%. ; Bis Nicotinylacetone Ferric Chloride. A solution of nicotinylacetone (4:99%,; 3 mols.) in aqueous alcohol was added to a solution of anhydrous ferric chloride (1-6 g. ; 1 mol.) in aqueous alcohol (25 ml.). The solution was then evaporated to about 50 ml. on the water-bath and allowed to cool. The small dark red crystals which separated were collected. ‘They were found to be very soluble in water but insoluble in absolute alcohol and anhydrous solvents. They did not melt below 300°. Bound: Be, 11-1, C, 43-3, H, 3-8, Cl, 21-4% ; calculated. for C,,H,,0,N,Cl,Fe: Fe, 11:4, C, 4f-2, H, 3-7, Cl, 21-8%. Excess caustic soda solution precipitates ferric hydroxide from aqueous solutions of this complex, but silver nitrate solution in the cold gives only a small precipitate of silver chloride. The complex can also be obtained from ferric nicotinylacetonate by treating it (1-1 g.; 1 mol.) with N/2 hydrochloric acid (12 ml.; 3 mols.). Tris-Nicotinylacetone Chromic Chloride (XII). Anhydrous chromic chloride (1:6 g.; 1 mol.) was dissolved in acetone by refluxing in presence of a small amount of metallic chromium. An acetone solution of nicotinylacetone (3-2 g.) was then added, and the resulting green solution evaporated to small bulk when fine green needles separated. After recrystallisation from alcohol, these melted at 105° to a green liquid. Wound: Cr, 7-4, C, 45:2, H, 4-7%:; calculated for C,,H,,0,N,Cl,Cr. 4H,0: Cr, 7-24, C, 45-1, H, 4-8%. Cupric bis Nicotinylacetonate Methiodide (IX ; Me=Cu). (a) Well washed cupric hydroxide from cupric nitrate (1-5 g.) was digested on a water-bath with an aqueous alcoholic solution of nicotinylacetone methiodide (3 g.; 2 mols.). It gradually dissolved, forming a green solution from which the complex crystallised on cooling. X—December 2, 1942. 302 LIONS, MORRIS AND RITCHIE. (6) Cupric bis nicotinylacetonate was heated in a sealed tube at 100° with an excess of methyl iodide. After removal of the excess the product was recrystallised from aqueous alcohol. It forms fine yellowish green needles, soluble in water and alcohol, but insoluble in organic solvents. When heated, it darkens above 100° and melts at 188°. Found: Cu, 8-7, C, 32-5, H, 4-:1%; calculated for C,,H,.O,N,I,Cu.4H,O: Cu, 8-6, C, 32:4, H, 4:0%. Zinc bis Nicotinylacetonate Methiodide (IX; Me=Zn). Prepared by methods exactly similar to those described for the copper salt, this derivative was obtained in short yellow needles, melting at 146°, when recrystallised from aqueous alcohol. Found: Zn, 8-4, C, 30-6, H, 3-9, I, 32-6%; calculated for C,,H,.O,N,I,Zn . 6H,O : Zn, 8-4, C, 30-7, H, 4-4, I, 32-6%. Beryllium bis Nicotinylacetonate Methiodide (IX ; Me=Be). An aqueous solution of beryllium sulphate (1-4 g.; 1 mol.) was treated with 0-5 N sodium hydroxide solution (30 ml.) and the white flocculent precipitate collected, thoroughly washed, and then dissolved in an alcoholic solution of nicotinylacetone methiodide (4:5 g.; 2 mols.) to a yellow solution. Concentration of this to about 30 ml. and cooling led to a crystallisation of fine yellow needles of the complex. After recrystallisation from aqueous alcohol these melted at 214°. They were soluble in water and alcohol, but insoluble in other organic solvents. Found: Be, 1-37, C, 39:0, H, 3-6, I, 41:5%; calculated for C,,H,.0,N,Bel,: Be, 1-46, C7 3895, Hel od 7 Olena, Cupric Ethylenediamine bis-Nicotinylacetonate (XX ; Me=Cuw).