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JOURNAL AND PROCEEDINGS
OF THE
ROYAL SOCIETY
OF NEW SOUTH WALES
FOR
1949 (INCORPORATED 1881)
VOLUME LXXXilll
Parts I-IV
EDITED BY
W. B. SMITH-WHITE, M.A., B.Sc.
Honorary Editorial Secretary
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 6, 1950
' r i) i eal
4 vat i
“
ale ny
Rios
fs . R ( oar ; ‘ ‘ fh y q 0 Tals) } At ) Kari if U,, p ' i fee ‘ :
* 5 . y v i of n! te i " be : : ~ H \ } or ul ; * \ ‘a Ps i i i" to + { : ® ' My \ - 7 i t- y y j if i Lids 1 ‘ i f f! 7 ! i N ‘ A * i rt ty) yi ¥ } ae r har why , i ; , y 1 ; ) : : : I i ; “ i Pe Nei sn j , ; ' WD pec ree Rea + ae ae ; fis vp Poy g f ys een} } a Fae ao (ey ies len ks Sey one aa ei a Woke fe oer a ait, Sere eget eee ie niet ar sees tee ie AeA eee yd i ae a aes ds ie ith vi es ra Aco Snare ne y , : ' ye te, A ; F: i ‘ rf Ai ‘ ;
on baa fi" i i y Thin | 4 iy wale a i} ~ . tT 5 J j ‘ , i p tightens * H if \ eT) i ; ; i ih Key “ih i ta] ev : i ; f ‘\ f f is Hl i i , 5 i | { 4 i y i i 1
CONTENTS VOLUME LXXXIII
Part I*
TITLE PAGE
OFFICERS FOR 1949-50
NorTIcEs
List OF MEMBERS»
AWARDS, ETC. :
REPORT OF THE Councrn
BALANCE SHEET
OpiTuaRY NOTICES :
Art. I.—A Contribution to the Stratieeaphy: ana Phesioeranhy of tite Gloneatat District, N.S.W. By P. B. Andrews. (Issued July 19, 1950) :
Art. IJ.—The Effect of Diffusional Processes on the Rate of Comocign: By R. C. ib Bosworth. (Issued July 19, 1950) ae es ;
Art. III.—The Influence of Forced Convection on the pineaes of Goreouion: By R. C. ibs Bosworth. (Issued July 19, 1950) ‘
Art. IV.—The Influence of Natural Convection on a Process of Gonahan: By R. C. ity Bosworth. (Issued July 19, 1950)
Art. V.—The Formation of Mobile and Immobile ila at Oxygen on Tungsten. By R. C. L. Bosworth. (Issued July 19, 1950)
Art. VI.—A Note on the Sens Phenomenon. By R. C. i. BeewoLEe (ssved J uly 19, 1950)
ArT. VII.—A Note. on the Besonial Oil of Backhose anisata cvaclrory ana the Gtcueones of Anethole. By H. H. G. McKern. (Issued July 19, 1950) :
Art. VIII.—Nitrogen in Oil Shale and Shale Oil. Part VIII. The Detection of Tar Bases. By Geo. E. Mapstone. (Issued July 19, 1950)
Art, [X.—Nitrogen in Oil Shale and Shale Oil. Part IX. Density- ‘eeaperaturs Relation: ships in Shale Tar Bases. By Geo. E. Mapstone. (Issued July 19, 1950)
ArT. X.—Occultations Observed at Sydney eoeey uae 1948. ae Wie Eb. Robertson. (Issued July 19, 1950) :
Art. XI.—Processes in Dielectrics Containing ree Changes By B. Broyer or F. Gutman. (Issued July 19, 1950)
Art. XIT.—The Effect of pH upon the Ultra- Violet Ideorstien Species of Pyridine Type Compounds. By L. E. Lyons. (Issued July 19, 1950) ans
Part II}
Art. XIII.—Nitrogen in Oil Shale and Shale Oil. Part X. Nitriles in Shale Oil. By Geo. E. Mapstone : an
Art. XIV.—Synthetic Sex Heeiones Part II. The Bale antl mice lone of p-Methylmercaptopropiophenone and the Preparation of Dithiodienestrol aes Ester. By G. K. Hughes and E. O. P. Thompson
ArT. XV.—Clarke Memorial Lecture. Metallogenetic Epochs anal Ore Rogions in ie Commonwealth of Australia. By W. R. Browne :
Art. XVI.—Nitrogen in Oil Shale and Shale Oil. Part XI. Nitriles i Grieled Shale Gasoline. By Geo. EH. Mapstone .. : ae ae ae whe
Art. XVII.—The Cyclization of Anils of 8- eto: Wdoldes: ae G. E. Calf and E. Ritchie
Art. XVIII.—Some Reactions of an Angular aero wee By K. H. B. Green and EK. Ritchie
Art. XIX.—Anodic and Gapnadic Balanzation of Copper in nestle INGal By R. C. L. Bosworth e ne sat
ArT. XX.—The ence of eet Part IIT. The Ronee Potentials of the Ruthenium II Complexes with Substituted Derivatives of 2: a and o-Phenanthroline. By F. P. Dwyer
Art. XXI.—The Chemistry of Ruthenium. Part Ly ‘The Boronia! of Fie Qe ica
Trivalent Ruthenium Couple in eee ae and hata: Acids. By J. R. Backhouse and F. P. Dwyer : ‘ se sy
* Published August 4, 1950. + Published September 6, 1950.
138
} ; ' Pichi Ad aa ba U L Ay em td uf)
i CONTENTS
Part III*
Art. XXII.—The Chemistry of Ruthenium. Part V.—The Potential of the Bivalent/ Trivalent Ruthenium Sue in ee ee Acid. my J. R. Backhouse and F. P. Dwyer :
ART. Sanh Risies Problem. By Harley Wood
ART. XXIV.—A New Method of Measurement of the Surface Tension of Viscous ss by P. R. Johnson and R. C. L. Bosworth a 4 ne
Art. XXV.—The Chemistry of Ruthenium. Part VI. The Existence of the Tris-o- Phenanthroline Ruthenium III Ions in can gee eh Forms. By F. P. Dwyer and EK. C. Gyarfas ; bd 8 : bs uae 2% Ay fi
Art. XXVI.—The Chemistry of Ruthenium. Part VII. The Oxidation of D and L Tris 2: 2’Dipyridyl Ruthenium II Iodide. By F. P. Dwyer and E. C. Gyarfas..
ArT. XX VII.—Complex Compounds of Aurous Halides and Aurous Cyanide with ain methyl and Dimethylphenyl Arsine. By F. P. Dwyer and D. M. Stewart
Art. XXVIII.—Kepler’s Problem—The Parabolic Case. By Harley Wood
Art. XXIX.—Rank Variation in Vitrain and Relations to the sii Nature of its Carbonised Products. By Nora Hinder ..
ART. XXX.—The Australian Social Services Contribution and Income Tax Gi 1949. By H. Mulhall ,
ArT. XXXI.—Studies in the peel ee of Platinum Sees Part I. The Tetrammine Platinum (II) Fluorides. By R. A. Plowman ane des iD,
Part IV} ArT. XX XII.—Involutions of a Conic and Orthogonal Matrices. By F. Chong
ArT. XX XIII.—Nature and Occurrence of Peat at Hazelbrook, New South Wales. By J. A. Dulhunty .. q ;
ArT. XXXIV.—The Resolution of the Tris o-Phenanthroline Nickel II Ion. By F. P. Dwyer and (Miss) E. C. Gyarfas .. a te ‘2 me i as
ART. XXXV.—A Note on the Reaction between Chromium II Salts and o-Phenanthroline. By F. P. Dwyer and H. Woolridge ‘ :
ArT. XXXVI.—Determination of the eeu ee Points of f Aqueous Nitric Acid. mr L. M. Simmons and M. J. Canny ~e w+
Art. XX XVII.—Reduction by Dissolving Metals. Part VIII. Some Effects of Structure on the Course of Reductive Fission. By A. J. Birch , , ss ;
ArT. XXXVITI.—Pebbles from the Upper Hunter River Tele N.S.W. bah D. Carroll, R. Brewer and J. E. Harley a
Art. XXXIX.—The Resolution of the Tris o-Phenanthroline Ferrous Ion and the Oxidation of the Enantiomorphous Forms. By F. P. Dwyer and (Miss) E. C. Gyarfas
Art. XL.—A Note on Some 4-Methoxybenzeneazo Derivatives of Resorcinol. a Pe Gore and G. K. Hughes a ay ah : : :
ArT. XLI.—Studies in the Pere eee ae of Thioanisole. Pe G. K. aeere and E. O. P.
Thompson ArT. XLIIT.—Action of Photochemical Produced Radicals on Actylone By L. E. Lyons , SA ae a
Art. XLIII.—A Further Contribution to the ce cey of the Goulburn District, N.S.W. By G. F. K. Naylor.. ;
Art. XLIV.—The Kuttung Vulcanicity of the Hunter-Karuah District, with - Special Reference to the Occurrence of Ignimbrites. By G. D. Osborne
INDEX TO VOLUME LXXXIII
* Published September 26, 1950. + Published December 6, 1950.
164
170
174
177 181
195
210
216
220
228
232
235
238
245
251
263
266
269
275
279
288
2 | Xxx
¥ sik Nae
OCEEDINGS
3) ;
OF NEW SOUTH WALES
PART I (pp. i-xxvii, 1-79) | ; eS pea OF
. Oe VOL. LXXXIII Containing List of Members, Report of Gonna’
Balance Sheet, Obituary Notices and Papers read in April and May, 1949,
EDITED BY
W. B. SMITH-WHITE, M.A., B.Sc.
oat Honorary Editorial Secretary.
THE AUTHORS OF PAPERS ARE ALONE RESPONSIBLE FOR THE STATEMENTS MADE AND THE OPINIONS EXPRESSED THEREIN
i " SYDNEY |
ay ae _ PUBLISHED BY THE SOCIETY, SCIENCE HOUSE ,
eS _ GLOUCESTER AND ESSEX STREETS r 1950
CONTENTS
VOLUME LXXXIII ee
Part I } Page TitLe PAGE a me ae ye ae 2: ny 6 “i BR sia? Sate 1 OFFICERS FOR 1949-50... ae ape vg eT ss me. ee = be ili Novices x as By xe ny Ae ats ce iN td ae ee iv List oF MEMBERS ay “a ae Ms as ae oe we is a Vv AWARDS, Etc. at a 2 ie me age :* pt i. ps ate tS REPORT OF THE COUNCIL a aap at Ne ee ae ‘a ae ie Soe BALANCE SHEET .. we A Me aor es ip) oy i ae ua SRD OxsiTtuaRY NOTICES as ae av ne ie 43 a nh nis hii hy. %. 4g Arr. I.—A Contribution to the Stratigraphy and Physiography of the Gloucester District, N.S.W. By P. B. Andrews. (Issued July 19, 1950) , 1 Art. II.—The Effect of Diffusional Processes on the Rate of Corrosion. By R. C. L. Bosworth. (Issued July 19, 1950) my a Ae ay ts “Se i 8 Art. I11.—The Influence of Forced Convection on the Process of Corrosion. By R. C. L. : Bosworth. (Issued July 19, 1950) nt a a, at the yi al 17
Art. 1V.—The Influence of Natural Convection on the Process of Corrosion. By R. C. L. Bosworth. (Issued July 19, 1950) oe 2h ay ue ig se CO. a aay
Art. V.—The Formation of Mobile and Immobile Films of ayees on Tae By R. C. L. Bosworth. (Issued July 19, 1950) .. i : EN a 31
ArT. VI.—A Note on the coe Phenomenon. pe R. C. L. Bosworth. (Issued July 19, LODO). A : Ae oie ie as aa ae
Arr. VII.—A Note on the Essential Oil of Backhousia anisata Vickery and the Occurrence of Anethole. By H. H. G. McKern. (Issued July 19, 1950) oh - .. 44.
Art. VIII.—Nitrogen in Oil Shale and Shale Oil. Part VIII. The Detection of Tar . ‘Bases. By Geo. E. Mapstone. (Issued July 19, 1950) i sy Co a ae
ArT. 1X.—Nitrogen in Oil Shale and Shale Oil. Part IX. Density-Temperature Relation- ships in Shale Tar Bases. By Geo. E. Mapstone. (Issued July 19,1950) .. 5 ae
ArT. X.—Occultations Observed at Sydney pi se sd ere 1948. By W. H. Robertson, (Issued July 19, 1950) dis Es ap 64 ©
Art. XI,—Processes. in Dielectrics Containing Free mae ee B. Breyer and F. Gutman. Uesied July 19, 1950) it iy : =a ue oe OG
Art. XII.~—The Effect of pH upon the Ultra-Violet Absorption ean of esis”: Type Compounds. By L. E. Lyons. (Issued July 19, 1950) : 75
JOURNAL AND PROCEEDINGS a
OYAL SOCIETY @
OF NEW SOUTH WALES i FOR _
1949 a
(INCORPORATED 1881) : :
VOLUME LXXxXilll *
EDITED BY a
W. B. SMITH-WHITE, M.A., B.Sc. "
Honorary Editorial Secretary ‘
Py
THE AUTHORS OF PAPERS ARE ALONE RESPONSIBLE FOR THE q STATEMENTS MADE AND THE OPINIONS EXPRESSED THEREIN lat, ii ae ah ae
SYDNEY :
PUBLISHED BY THE SOCIETY, SCIENCE HOUSE ‘
GLOUCESTER AND ESSEX STREETS
Royal Society of New South Wales
OFFICERS FOR 1948-1949
Patrons His EXceELLENCY THE GOVERNOR-GENERAL OF THE COMMONWEALTH OF AUSTRALIA THE Rr. Hon. W. J. McKELL, P.c.
His EXcELLENCY THE GOVERNOR OF NEw SoutH WALES, LIEUTENANT-GENERAL JOHN NORTHCOTT, c.3., M.v.o.
President: HARLEY WOOD, M.sc., F.R.A.S.
Vice-Presidents :
R. L. ASTON, B.sc., B.E. (Syd.), M.Sc., | D. P. MELLOR, D.sc., F.A.¢.1. Ph.D. (Camb.), A.M.1.E. (Aust.). | F. R. MORRISON, 4.a.C.1., F.C.S.
H. O. FLETCHER.
Honorary Secretaries :
R. C. L. BOSWORTH, m.sc., D.Sc. (Adel.), W. B. SMITH-WHITE, m.a. (Cantab.), Ph.D. (Camb.), F.A.C.1., F.Inst.P. B.Sc. (Syd.).
Honorary Treasurer : A. BOLLIGER, Ph.p., F.A.c.1.
Members of Council:
IDA A. BROWN, D.S8c. C. St. J. MULHOLLAND, B.sc.
R. O. CHALMERS, A:S.T.C. D. J. K. OPCONNELL, 8.J., M.sSc., D.Ph., F. P. J. DWYER, D.sc. F.R.A.S.
F. N. HANLON, B.sc. O. U. VONWILLER, B.sc., F.1nst.P.
R. J. W. LE FEVRE, D.Sc., Ph.D., F.R.1.C. N. R. WYNDHAM, m™.p., mM.s. (Syd.), C. J. MAGEE, D.sc.agr. (Syd.), M.Sc. (Wzs.), F.R.C.S. (Hng.), F.R.A.C.S.
WAR 1 6 195%
lv NOTICES.
NOTICE.
Tur 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.
Particulars regarding the preparation of manuscripts of papers for publication in the Society’s Journal are to be found in the “ Guide to Authors,’ which is obtainable on appli- cation to the Honorary Secretaries of the Society.
FORM OF BEQUEST.
I bequeath the sum of £ to the Royat Socrety or New SoutH WaAzgs, Incorporated by Act of the Parliament of New South Wales in 1881, and I deelare 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. |
The volumes of the Journal and Proceedings may be obtained at the Society’s Rooms, Science House, Gloucester Street, Sydney.
Volumes XI to LIII (that is to 1919) at 12/6 each - LIV ,, LXVIII (1920 to 1934) ,, 25/- ,, ‘5 LXX>,5') LXXXITE (1986 to 1948)- ., “25/a.0.2;5 as LXXXIII onwards » 30/- ie
Volumes I to X (to 1876) and Volume LXIX (1935) are out of print. Reprints of papers are available.
LIST OF THE MEMBERS
OF THE
Ruyal Socivty of New South Wales
as at April 1, 1949
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.
1944 1938
1935 1898 1941 1948 1948 1930
1919 1945
1935 1924
1934
1937 1946
1919 1947
1933 1926 1940 1937 1916 1920 1939 1948 1946 1933 1920 1939
1948
Pee
Pu Peay
Adamson, Colin Lachlan, Chemist, 36 McLaren-street, North Sydney. tAlbert, Adrien, D.sc., Ph.D. Lond., B.Sc. Syd., A.R.1.C. Gt. B., Professor of Medical Chemistry, The Australian National University, 183 Euston-road, London N.W.1. tAlbert, Michael Francois, ** Boomerang,’ Billyard-avenue, Elizabeth Bay. tAlexander, Frank Lee, Surveyor, 5 Bennett-street, Neutral Bay. tAlldis, Victor le Roy, 1.s., Registered Surveyor, Box 57, Orange, N.S.W.
Anderson, Geoffrey William, B.sc., 37 Elizabeth-street, Allawah.
Andrews, Paul Burke, Department of Geology, University of Sydney; p.r. 5 Conway-avenue, Rose Bay.
Aston, Ronald Leslie, B.sc., B.E. Syd., M.Sc., Ph.D. Camb., A.M.1.E. Aust., Lecturer in Civil Engineering and Surveying in the University of Sydney; p.r. 24 Redmyre-road, Strathfield. (President, 1948.)
Aurousseau, Marcel, B.sc., 16 Woodland-street, Balgowlah.
Ayscough, Frederick William, B.sc., 118 Oxford-street, Woollahra.
Back, Catherine Dorothy Jean, m.sc., The Women’s College, Newtown.
Bailey, Victor Albert, M.A., D.Phil., F.Inst.P., Professor of Experimental Physics in the University of Sydney.
Baker, Stanley Charles, M.sc., A.1Inst.P., Head Teacher of Physics, Newcastle Technical College, Tighe’s Hill; p.r. 8 Hewison-street, Tighe’s Hill, N.S.W.
Baldick, Kenric James, B.Sc., 19 Beaconsfield-parade, Lindfield.
Barclay, Gordon Alfred, Chemistry Department, Sydney Technical College, Harris Street, Ultimo, N.S.W.; p.r. 78 Alt Street, Ashfield.
Bardsley, John Ralph, 76 Wright’s-road, Drummoyne.
Beckmann, Peter, a.s.T.c., Lecturer in Chemistry, Technical College, Wol- longong.
Bedwell, Arthur Johnson, Eucalyptus Oil Merchant, ‘“‘ Kama,” 10 Darling Point-road, Edgecliff.
Bentivoglio, Sydney Ernest, B.sc.agr., 42 Telegraph-road, Pymble.
Betty, Robert Cecil, 67 Imperial-avenue, Bondi.
Birch, Arthur John, M.sc., D.Phil. (Oxon.), 6 Beechcroft-road, Oxford, England.
Birrell, Septimus, 74 Edinburgh-road, Marrickville.
Bishop, Eldred George, Manufacturing and General Engineer, 37-45 Myrtle- street, Chippendale; p.r. 264 Wolseley-road, Mosman.
Blake, George Gascoigne, M.I.E.E., F.Inst.P., ‘‘ Holmleigh,’’ Cecil-avenue, Pennant Hills.
Blanks, Fred Roy., B.sc. (Hons.), Industrial Chemist, 12 Culworth-avenue, Killara.
Blaschke, Ernst Herbert, 6 Illistron Flats, 63 Carrabella-street, Kirribilli.
Bolliger, Adolph, Ph.p., F.a.c.1., Director of Research, Gordon Craig Urological Research Laboratory, Department of Surgery, University of Sydney. (President, 1945.)
Booth, Edgar Harold, M.c., pD.sSc., F.Inst.P., ‘‘ Hills and Dales,’’ Mittagong. (President, 1935.)
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. Ltd., Pyrmont; p.r. 41 Spencer-road, Killara.
| Boyd, Eric Harold, B.A., B.Sc., Dip.Ed., F.P.S., The King’s School, Parramatta.
Boyd, Joan, B.sc. Hons. Lond., pip.zd. Lond., The King’s School, Parramatta.
Breckenridge, Marion, B.Sc. , Department of Geology, The University of Sydney ; ; p.r. 19 Handley-avenue, Thornleigh.
Breyer, Bruno, M.D., Ph.D., M.A., F.A.C.I., Lecturer in Agricultural Chemistry, Faculty of Agriculture, University of Sydney, Sydney.
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.
Brown, Desmond J., M.sc. (Syd.), Ph.D. (Lond.), D.1.c., Department of Medical anaes Australian National University, 183 Euston-road, London, N.W.1
Browne, Ida Alison, D.sc.,Senior Lecturer in Palzontology, University of Sydney.
Brown, Norma Dorothy (Mrs.), B.Sc., Biochemist, 2 Macauley-street, Leich- hardt.
Brown, Samuel Raymond, 4.c.A. Aust., 87 Ashley-street, Chatswood.
P22 |{Browne, William Rowan, D.se., Reader in Geology,University of Sydney.
rg Fg
m= bo
(President, 1932.)
Buchanan, Gregory Stewart, B.Sc. (Hons.), Lecturer in Physical Chemistry, Sydney Technical College; p.r. 52 Mary-street, Beecroft.
Buckley, Lindsay Arthur, B.sc., 29 Abingdon-road, Roseville.
Bullen, Keith Edward, m.a., B.sc. N.Z., M.A. Melb., Ph.D., Sc.D. Camb., F.B.S., Professor of Applied Mathematics, University of Sydney, Sydney, N. 8. W.
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.
tCarey, Samuel Warren, D.Sc., Professor of Geology, University of Tasmania, Tasmania.
Carroll, Dorothy, B.A., B.Sc., Ph.D., D.I.c., Secretary, Linnean Society of New South Wales, Science House, 157 Gloucester-street, Sydney.
tCarslaw, 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.
Carter, Harold Burnell, s.v.sc., Research Officer, C.S.I.R., McMaster Laboratory, University Grounds, Sydney.
Cavill, George William Kenneth, m.sc., c/o Department of Organic Chemistry, The University, Liverpool, Great Britain.
tChallinor, Richard Westman, F.R.1.C., A.A.C.I., A.S.T.C., F.0.S.; p.r. 54 Drum- albyn-road, Bellevue Hill. (President, 1933.)
Chalmers, Robert Oliver, a.s.t.c., Australian Museum, College Street, Sydney.
Chambers, Maxwell Clark, B.sc., c/o Coty (England) Ltd., 35-41 Hutchinson- street, Moore Park; p.r. 58 Spencer-road, Killara.
tCheel, Edwin, 40 Queen-street, Ashfield. (President, 1931.)
Churchward, John Gordon, B.Sc.Agr., Ph.D., 1 Hunter-street, Woolwich.
Clark, Sir Reginald Marcus, K.B.z., Central Square, Sydney.
Clune, Francis Patrick, Author and Accountant, 15 Prince’s-avenue, Vaucluse.
Cohen, Max Charles, B.Sc., 80 ‘‘ St. James,” Stanley-street, Sydney.
Cohen, Samuel Bernard, M.Sc., A.A.C.1., 8 Roseville-avenue, Roseville.
Cole, Edward Ritchie, B.sc., 7 Wolsten-avenue, Turramurra.
Cole, Joyce Marie, B.sc., 7 Wolsten-avenue, Turramurra.
Cole, Leslie Arthur, Company Executive, 21 Carlisle-street, Rose Bay |
Collett, Gordon, B.sc., 20 Duchess-avenue, Fivedock.
Cook, Cyril Lloyd, M.sc., 176 Ben Boyd-road, Neutral Bay.
Cook, Rodney Thomas, A.s.T.c., 10 Riverview-road, Fairfield.
Cooke, Frederick, c/o Meggitt’s Limited, Asbestos House, York and Barrack- streets, Sydney.
Coombes, Arthur Roylance, A.s.T.c. (Chem.), 14 Georges River-road, Croydon.
{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.
Cornforth, Rita Harriet, D.Phil. (Oxon.), M.sc. (Syd.), c/o Dyson Perrin’s Laboratory, South Parks-road, Oxford, England.
Cortis-Jones, Beverly, M.sc., 62 William-street, Roseville.
Cotton, Frank Stanley, D.sc., Research Professor in Physiology in the University of Sydney.
Elected. 1909
1941 1921
1935 1948
1940 1890 1919 1906 1913 1928
1947 1948
1943 1937 1948 1924
1934
1945 1934
1940 1937 1916
1944 1908 1935
1944 1909 1940 1940 1933 1879 1932 1905 1940 1943 1940
1944 1945
1948
rg —
P 40
{Cotton, Leo Arthur, M.A., D.Sc., 113 Queen’s Parade East, Newport Beach. (President, 1929.)
Craig, David Parker, Lecturer in Inorganic Chemistry, University of Sydney; p.r. 62 Springdale Rd., Killara.
t{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.
Culey, Alma Gertrude, m.sc., 37 Neirbo-avenue, Hurstville.
Cymerman, John, Ph.D., D.I.C., A.R.C.S., B.Sc., A.R.I.C., Lecturer in Organic Chemistry, University of Sydney.
Dadour, Anthony, B.sc., 25 Elizabeth-street, Waterloo.
t{Dare, Henry Harvey, M.E., M.Inst.c.E., M.I.E.Aust., 14 Victoria-street, Roseville.
de Beuzeville, Wilfred Alex. Watt, 3.p., ‘‘ Mélamere,’’ Welham-street, Beecroft.
{Dixson, Sir William, “‘ Merridong,’’ Gordon-road, Killara.
{Doherty, William M., F.R.1.C., F.A.C.1., 36 George-street, Marrickville.
Donegan, Henry Arthur James, A.S.T.c., A.A.c.1., Analyst, Department of Mines, Sydney ; p.r. 18 Hillview-street, Sans Souci.
Downes, Alan Marchant, B.sc. (Hons.), Grandview-avenue, Croydon, Victoria.
Doyle, Shirley Kathleen, B.sc., Microbiologist to H. Jones & Co.; p.r. 74 Duntroon-avenue, Roseville.
Dudgeon, William, Manager, Commonwealth Drug Co., 50-54 Kippax-street, Sydney.
Dulhunty, John Allan, p.sc., Geology Department, University of Sydney; p-r. 40 Manning-road, Double Bay. (President, 1947.)
Dunlop, Bruce Thomas, B.sc., Schoolteacher, 77 Stanhope-road, Killara.
Dupain, George Zephirin, a.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., p.sc., Lecturer in Chemistry, University of Sydney, Sydney.
Eade, Ronald Arthur, B.Ssc., 21 Steward-street, Leichhardt.
Elkin, Adolphus Peter, M.A., Ph.D., Professor of Anthropology in the University of Sydney. (President, 1940.)
Emmerton, Henry James, B.Sc., 1 Rosedale-road, Gordon.
English, James Roland, L.s., Sydney.
Enright, Walter John, B.4., Solicitor, High-street, West Maitland ; p.r. Regent- street, West Maitland.
Erhart, John Charles, Chemical Engineer, c/o “‘Ciba” Coy., Basle, Switzerland.
tEsdaile, Edward William, 42 Hunter-street, Sydney.
Evans, Silvanus Gladstone, 4.1.4.4. Lond., A.R.A.1.A., 6 Major-street, Coogee.
Fairweather, Alwynne Drysdale (Mrs.), B.sc., 338 Chapple-street, Broken Hill.
{Fawsitt, Charles Edward, p.sc., ph.p., F.A.C.1., Emeritus Professor of Chemistry, 144 Darling Point-road, Edgecliff. (President, 1919.)
Finch, Franklin Charles, B.sc., Kirby-street, Rydalmere, N.S.W.
Fisher, Robert, B.sc., 3 Sackville-street, Maroubra.
Fletcher, Harold Oswald, 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.z., 35 Riversdale-road, Hawthorn, Victoria.
tFoy, Mark, c/o Geo. O. Bennett, 133 Pitt-street, Sydney.
Franki, Robert James Anning, B.Sc., 891 New South Head-road, Rose Bay.
Frederick, Robert Desider Louis, B.E., 162 Buckley-street, Essendon, W.5, Victoria.
Freney, Martin Raphael, B.sc., Central Wool Testing House, 17 Randle-street, Sydney.
Friend, James Alan, 16 Kelburn-road, Roseville.
Furst, Hellmut Friedrich, B.p.s. (Syd.), D.M.p. (Hamburg), Dental Surgeon, 158 Bellevue-road, Bellevue Hill.
Gardiner, Edward Carson, Electrical Engineer in Charge of Construction at the Captain Cook Graving Dock, for the Department of Works and Housing p.r. 39 Spencer-street, Rose Bay.
Elected.
P 14
Garretty, Michael Duhan, p.sc., 477 St. Kilda-road, Melbourne, 8.C.2, Victoria.
Gascoigne, Robert Mortimer, Chemistry Department, University of Liverpool, England.
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, M.sc., A.R.1.c., Industrial Chemist, 217 Parramatta-road, Haberfield.
Gill, Naida Sugden (Miss), B.sc., 45 Neville-street, Marrickville.
tGill, Stuart Frederic, School Teacher, 45 Neville-street, Marrickville.
Gillis, Richard Galvin, Senior Lecturer, Organic Chemistry, Melbourne Technical College; p.r. 4 Tennyson-avenue, Caulfield, S.E.7, Victoria.
Glasson, Kenneth Roderick, B.sc., Geologist, Lake George Mines Ltd., Captain’s Flat, N.S.W.
Goddard, Roy Hamilton, F.c.a. Aust., Royal Exchange, Bridge-street, Sydney.
Goldsworthy, Neil Ernest, M.B., ch.m. Syd., Ph.D., D.T.M. & H. Camb., D.T.M. & H. Eing., D.P.H. Camb., 65 Roseville-avenue, Roseville.
Goulston, Edna Maude, B.sc., 83 Birriga-road, Bellevue Hill.
Gray, Charles Alexander Menzies, B.Sc., B.E., 75 Woniora-road, Hurstville.
Griffiths, Edward L., B.Sc., A.A.C.I., A.R.I.C., Chief Chemist, Department of Agriculture; p.r. 151 Wollongong-road, Arncliffe.
Gutmann, Felix, Ph.D., F.Inst.P., M.I.R.E., Commonwealth Research Fellow, Faculty of Agriculture, University of Sydney, Sydney.
Gyarfas, Eleonora Clara, M.sc. Budapest, Research Assistant, University of Sydney; p.r. 53 Simpson-street, Bondi.
Hall, Lennard Robert, B.sc., Geological Survey, Department of Mines, Bridge- street, Sydney.
Hall, Leslie Lionel, Works Chemist, 494 Kent-street, Sydney.
Hall, Norman Frederick Blake, M.sc., Chemist, 154 Wharf-road, Longueville.
{Halloran, Henry Ferdinand, L.s., A.M.I.E.Aust., F.S.I.Eng., M.T.P.I.Eng., 153 Elizabeth-street, Sydney ; p.r. 23 March-street, Bellevue Hill.
Hanlon, Frederick Noel, B.sc., Geologist, Department of Mines, Sydney.
tHarker, George, D.Sc., F.A.C.I.; p.r. 89 Homebush-road, Strathfield.
Harper, Arthur Frederick Alan, M.sc., A.Inst.P., National Standards Laboratory, University Grounds, City-road, Chippendale.
Harrington, Herbert Richard, Teacher of Physics and Electrical Engineering, Technical College, Harris-street, Ultimo.
Harris, Clive Melville, Laboratory Assistant, Museum of Technology and Applied Science; p.r. 12 Livingstone-road, Lidcombe.
Harrison, Ernest John Jasper, B.sc., Geologist, N.S.W. Geological Survey, Department of Mines, Sydney.
Hayes, William Lyall, a.s.T.c., A.A.c.1., Works Chemist, c.o. Wm. Cooper & Nephews (Aust.) Ltd., Phillip-street, Concord; p.r. 34 Nicholson-street, Chatswood.
Henriques, Frederick Lester, 208 Clarence-street, Sydney.
Higgs, Alan Charles, Manager, Asbestos Products Pty. Ltd.; p.r. 10 Cremorne- road, Cremorne.
Hill, Dorothy, m.sce. Q’ld., Ph.p. Cantab., Geological Research Fellow, University of Queensland, Brisbane.
Hinder, Nora (Miss), B.sc. Syd., 22 Chester-street, Epping.
Hirst, Edward Eugene, a.M.1.z., 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. (Awst.), ‘‘ St. Cloud,” Beaconsfield- road, Chatswood.
Hogarth, Julius William, 8 Jeanneret-avenue, Hunter’s Hill.
Hoggan, Henry James, A.M.1.M.E. Lond., A.M.I.E. Aust., Consulting and Designing Engineer, 81 Frederick-street. Rockdale.
Howard, Harold Theodore Clyde, B.sc., Principal, Technical College, Granville.
Howarth, Mark, F.R.A.s., Grange Mount Observatory, Bull-street, Mayfield, Newcastle, N.S.W.
Hughes, Gordon Kingsley, B.sc., Department of Chemistry, University of Sydney, Sydney.
Humpoletz, Justin Ernst, B.sc. Syd., 21 Belgium-avenue, Roseville.
tHynes, Harold John, p.sc., B.Sc.agr., Biologist, Department of Agriculture, Box 36a, G.P.O., Sydney ; p.r. “‘ Belbooree,”’ 10 Wandella-avenue, Rose- ville.
Elected. 1943
1942 1946 1909 1935 1948 1930
1935 1940 1924 1934
1948 1943
1920
1948 1948
1939 1936
1946 1947
1936
1920 1929
1942 1947
1940 1906 1947 1943 1945 1948
1942
1939 1943 1940
1940 1948
Pik P 15 P 6 Py 1
P 56
1x
Iredale, Thomas, D.Sc., F.R.1.c., Chemistry Department, University of Sydney, p.-r. 96 Roseville-avenue, Roseville.
Jaeger, John Conrad, M.a., D.Sc., University of Tasmania, Hobart, Tasmania.
Johnson, Guy Frederick, 644 Botany-road, Alexandria.
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.
Jopling, Alan Victor, B.sc., B.E., 28 Cliff-street, Manly.
Judd, William Percy, 123 Wollongong-road, Arncliffe.
Kelly, Caroline Tennant (Mrs.), Dip.anth., “‘ Eight Bells,’ Cast e 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.s.T.c., A.A.C.I., Industrial Chemist, 29 Nundah-street, Lane Cove.
Kimble, Frank Oswald, Engineer, 16 Evelyn-avenue, Concord.
Kimble, Jean Annie, B.Sc., Research Chemist, 383 Marrickville-road, Marrick- ville.
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.
Knight, Oscar Le Maistre, B.E. Syd., A.M.I.C.E., A.M.I.E.Anst., Engineer, 10 Mildura-street, Killara.
Koch, Leo E., Ph.p., D.Sc. (Cologne), Department of Geology, The University of Sydney.
Lambeth, Arthur James, B.Sc., ‘“‘ Naranje,’” Sweethaven-road, Wetherill Park, N.S.W.
Leach, Stephen Laurence, B.A., B.Sc., A.A.C.I., British Australian Lead Manu- facturers Pty. Ltd., Box 21, P.O., Concord.
Lederer, Michael, 67 Edgecliff-road, Bondi Junction.
Le Fevre, Raymond James Wood, D.Sc., Ph.D., F.R.I.C., Professor of Chemistry, Chemistry Department, University of Sydney, Sydney.
Lemberg, Max Rudolph, pD.phil., Institute of Medical Research, Royal North Shore Hospital, St. Leonards.
Le Souef, Albert Sherbourne, 3 Silex-road, Mosman.
tLions, Francis, B.Sc., Ph.D., A.R.I.C., Reader, Department of Chemistry, Uni- versity of Sydney. (President, 1946-47.)
Lippmann, Arthur S., m.p., 175 Macquarie-street, Sydney.
Lloyd, James Charles, B.sc. Syd., N.S.W. Geological Survey, 41 Goulburn-street, Liverpool.
Lockwood, William Hutton, B.sc., F. & A. Inspectorate, 64 H.Q., C.C.G., Minden, Germany.
tLoney, Charles Augustus Luxton, M.Am.soc.Refr.E., National Mutual Building, 350 George-street, Sydney.
Lowenbein, Gladys Olive (Mrs.), B.sc. Melb., F.R.1.c. Gt. B., A.A.c.1., Director of Research, Australian Leather Research Association ; p.r. ‘* Cahors,”’ No. 75, 117 Macleay-street, Potts Point.
{Luber, Daphne (Mrs.), B.sc., 98 Lang-road, Centennial Park.
Luber, Leonard, Pharmacist, 80 Queen-street, Woollahra.
Lyons, Lawrence Ernest, B.a., M.Sc., Lecturer in Chemistry, The University of Sydney ; p.r. 13 Albert-road, Strathfield.
Lyons, Raymond Norman Matthew, m.sc., Biochemical Research Worker, 84 Marine-parade, Maroubra.
Maccoll, Allan, m.sc., Department of Chemistry, University College, Gower- street, London, W.C.1.
McCoy, William Kevin, Analytical Chemist, c/o Mr. A. J. McCoy, 39 Malvern- avenue, Merrylands.
McGrath, Brian James, 40 Mooramie-avenue, Kensington.
McGregor, Gordon Howard, 4 Maple-avenue, Pennant Hills.
McInnes, Gordon Elliott, Department of Geology, The University of Sydney ; p.r. 46 Laycock-street, Bexley.
B32 heap PG
P 28
tMcIntosh, Arthur Marshall, ““ Moy Lodge,” Hill-street, Roseville.
tMcKay, R. T., M.inst.c.z., Eldon Chambers, 92 Pitt-street, Sydney.
McKenzie, Hugh Albert, B.sc., c/o Frick Chemical Laboratory, Princeton University, Princeton, New Jersey, U.S.A.
McKern, Howard Hamlet Gordon, A.s.T.C., A.A.C.1., Assistant Chemist, Museum of Technology and Applied Science, Harris-street, Ultimo; p.r. Flat 2, 42a, Waimea-street, Burwood.
McMahon, Patrick Reginald, m.agr.sc. N.Z., Ph.D. Deeds, A.R.1.C., A.N.Z.I.C., Lecturer-in-charge, Sheep and Wool Department, Sydney Technical College, East Sydney.
McMaster, Sir Frederick Duncan, xt., ‘“‘ Dalkeith,” Cassilis, N.S.W.
McNamara, Barbara Joyce (Mrs.), M.B., B.S., Yeoval, 7.W.
McPherson, John Charters, 14 Sarnar-road, Greenwich.
McRoberts, Helen May, B.sc., New England University College, Armidale.
Magee, Charles Joseph, D.sc.agr. Syd., M.Sc. Wis., Chief Biologist, Department of Agriculture; p.r. 4 Alexander-parade, Roseville.
Maley, Leo Edmund, M.Sc., B.Sc. (Hons.), A.A.C.I., A.M.A.I.M.M., 116 Maitland road, Mayfield.
Malone, Edward E., 33 Windsor-road, St. Mary’s.
Mapstone, George E., M.Sc., A.A.C.I., M.Inst.Pet., Chief Chemist of National Oil Pty. Ltd., Glen Davis; p.r. 2 Anderson Square, Glen Davis, N.S.W.
Martin, Cyril Maxwell, Chemist, 22 Wattle-street, Haberfield.
May, Albert, Ph.p., M.A., 94 Birriga-road, Bellevue Hill.
Maze, Wilson Harold, m.sc., Deputy Registrar, University of Sydney, Sydney.
tMeldrum, Henry John, B.a., B.sc., Lecturer, The Teachers’ College, University Grounds, Newtown; p.r. 98 Sydney-road, Manly.
Mellor, David Paver, D.Sc., F.A.c.I., Reader, Department of Chemistry, Uni- versity of Sydney; p.r. 137 Middle Harbour-road, Lindfield. (President, 1941-42.)
Melville, George Livingstone, Managing Director, Federal Machine Co. Ltd., Loftus-street, Arncliffe.
Micheli, Louis Ivan Allan, m.sc., Ph.p., Research Chemist, ‘‘ Walla Walla,”’ Hull-road, Beecroft.
Millership, William, m.sc., Chief Chemist, Davis Gelatine (Aust.) Pty. Ltd. 15 Shaw-avenue, Earlwood.
| Morrissey, Matthew John, B.A., A.S.T.c., Auburn-street, Parramatta.
Morrison, Frank Richard, 4.A.C.1., F.c.S., Deputy Director, Museum of Tech- nology and Applied Science, Harris-street, Ultimo.
Mort, Francis George Arnot, A.A.C.I., Chemist, 16 Grafton-street, Woollahra.
Mosher, Kenneth George, B.Sc., Geologist, Geological Survey, Department ef Mines, Bridge-street, Sydney.
Moye, Daniel George, B.sc., Geologist, Warragamba Dam.
Mulholland, Charles St. John, B.sc., Geologist, Department of Mines, Sydney.
Mulley, Joan W., Technical Officer, C.S.I.R.; p.r. 4 Billyard-avenue, Elizabeth Bay.
Murphy, Robert Kenneth, Dr.Ing., Chem., A.S.T.C., M.I.Chem.E., F.A.C.I., Principal, Sydney Technical College, Sydney.
Murray, Colonel Jack Keith, B.A., B.Sc.agr., Administrator, Territory of Papua- New Guinea, Government House, Port Moresby.
Naylor, Betty Yvonne, B.sc., 6 Niblick-avenue, Roseville.
Naylor, George Francis King, M.A., M.Sc., Dip.Ed., A.A.1.1.P., Lecturer in Philosophy and Psychology, University of Queensland, Brisbane, Qld.
Neuhaus, John William George, 190 Old Prospect-road, Wentworthville.
Newman, Ivor Vickery, M.Sc., Ph.D., F.R.M.S., F.L.S., Professor of Botany, The University of Ceylon, ‘Colombo, Ceylon.
Nicol, Alexander Campbell, a.s.T.c., A.A.C.1., Chief Chemist, Crown Crystal Glass Co.; p.r. No. 2 Flat, corner Hendy- avenue and Rainbow-streets, Coogee.
Nicol, Phyllis Mary, m.sc., Sub-Principal, The Women’s College, Newtown.
Noakes, Lyndon Charles, Geologist, c/o Mineral Resources Survey, Canberra, A.C.T.
Noble, Norman Scott, D.sc.agr., M.Sc., D.1.c., c/o C.S.I.R., 314 Albert-street, East Melbourne, Vic.
tNoble, Robert Jackson, M.sc., B.Sc.Agr., Ph.D., Under Secretary, Department of Agriculture, Box 364, G.P.O., Sydney ; p.r. 324 Middle Harbour-road, Lindfield. (President, 1934.)
Elected.
1947 1948 1940
1935 1947 1921
1920 1948 1938 1935 1946 1943
1919
1896 1946 1921 1938 1945 1927 1918
1945 1893
1935
1922
1940 1919 1936 1947 1947
1931 1935 1947 1946 1947 1947 1939
1939
P 25
rg kg we
P 16 P 3
xi
Nordon, Peter, A.S.T.c., A.A.C.I., Chemical Engineer, 1 Edgecliff-road, Bondi Junction.
Northcott, Jean, B.Sc. (Hons.), Chemistry Department, The University of Sydney; p.r. 38 Canberra-street, Lane Cove.
Nyholm, Ronald Sydney, m.sc., Chemistry Department, University College, Gower-street, London, W.C.1, England.
O’Connell, Rev. Daniel J. K., s.J., M.Sc., D.Ph., F.R.A.S., Riverview College Observatory, Sydney.
Old, Adrian Noel, B.sc.agr., Chemist, Department of Agriculture ; p.r. 4 Spring- field-avenue, Pott’s Point.
Osborne, George Davenport, p.sc. Syd., Ph.p. Camb., Senior Lecturer in Geology in the University of Sydney. (President, 1944.)
Penfold, Arthur Ramon, F.a.c.1., F.c.S., Director, Museum of Technology and Applied Science, Harris-street, Ultimo. (President, 1931.)
Perry, Hubert Roy, B.sc., 74 Woodbine-street, Bowral.
Phillips, Marie Elizabeth, B.sc., 4 Morella-road, Clifton Gardens.
Phillips, Orwell, 55 Darling Point-road, Edgecliff.
Pinwell, Norman, B.A. (Q’land), The Scots College, Bellevue Hill.
Plowman, Ronald Arthur, A.s.T.C., A.A.c.I., Analytical Chemist, 78 Alt-street, Ashfield.
Poate, Hugh Raymond Guy, M.B., ch.m. Syd., F.R.c.S. 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.
Potter, Bryce Harrison, B.sc. (Hons.) (Syd.), 13 Fuller’s-road, Chatswood.
Powell, Charles Wilfrid Roberts, F.R.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 Wallis, A.s.T.c., A.A.C.1., Managing Director, Foster Clark (Aust.) Ltd., 17 Thurlow-street, Redfern.
Prescott, Alwyn Walker, B.eng., Lecturer in Mechanical and Electrical Engineering in the University of Sydney ; p.r. Harris-road, Normanhurst.
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. (President, 1942-43.)
Proud, John Seymour, Mining Engineer, 4 View-street, Chatswood.
tPurser, Cecil, B.A., M.B., chm. Syd., “‘ Ascot,’ Grosvenor-road, Wahroonga.
tQuodling, Florrie Mabel, B.sc., Lecturer in Geology, University of Sydney
Raggatt, Harold George, D.sc., Director, Mineral Resources Survey, Depait- ment of Supply, Canberra, A.C.T.
Ralph, Colin Sydney, B.sc., 24 Canberra-street, Epping.
Ranclaud, Archibald Boscawen Boyd, B.sc., B.E., 57 William-street, Sydney.
Randall, Harry, Buena Vista-avenue, Denistone.
Ray, Nancy Evelyn (Mrs.), Plastics Manufacturer, 14 Hedger-avenue, Ashfield.
Ray, Reginald John, Plastics Manufacturer and Research Chemist, 14 Hedger- avenue, Ashfield.
Rayner, Jack Maxwell, B.sc., F.Inst.P., Chief Geophysicist, Bureau of Mineral Resources, Geology and Geophysics, 485 Bourke-street, Melbourne, Vic.
Reid, Cicero Augustus, 19 Newton-road, Strathfield.
Reuter, Fritz Henry, ph.p. (Berlin, 1930), F.4.c.1., 94 Onslow-street, Rose Bay.
Rhodes-Smith, Cecil, 261 George-street, Sydney.
Ritchie, Arthur Sinclair, a.s.t.c., Lecturer in Mineralogy and Geology, New- castle Technical College; p.r. 188 St. James-road, New Lambton, N.S.W.
Ritchie, Bruce, B.Sc. (Hons.), c/o Pyco Products Pty. Ltd., 576 Parramatta- road, Petersham.
Ritchie, Ernest, m.sc., Senior Lecturer, Chemistry Department, University of Sydney, Sydney.
Robbins, Elizabeth Marie (Mrs.), M.sc., 344 Railway-parade, Guildford.
xii Elected. 1933
1940
1935 1940 1948 1940
1948 1945
1945 1945
1941 1920
1948 1946 1940 1933 1936
1948 1938 1936 1948 1945 1945
1948 1943 1933
1940 1947
1919 1921
1916 1914
1948 1900
1942 1916 1918
P
rg rd
P
P
2
bo
1
Roberts, Richard George Crafter, Electrical Engineer, c/o C. W. Stirling & Co., Asbestos House, York and Barrack-streets, Sydney.
Robertson, Rutherford Ness, B.sc. Syd., Ph.D. Cantab., Senior Plant Physiologist, C.S.I.R., Division of Food Preservation, Private Bag, P.O., Homebush ; p.r. Flat 4, 43 Johnston-street, Annandale.
Room, Thomas G., M.A., F.R.S., Professor of Mathematics in the University of Sydney.
Rosenbaum, Sidney, 44 Gilderthorp-avenue, Randwick.
Rosenthal-Schneider, Ilse, Ph.pD., 48 Cambridge-avenue, Vaucluse.
Ross, Jean Elizabeth, B.sc., Dip.Ed., 5 Stanton-road, Haberfield.
Ross, Leonard Paul, B.sc., 137 Burwood-road, Enfield.
Rountree, Phyllis Margaret, m.sc. Melb., pip.Bact. Lond., Royal Prince Alfred Hospital, Sydney.
Sambell, Pauline Mary, B.a. (Zoology), Assistant Research Officer, McMaster Laboratory ; p.r. 83 Woniora-road, Hurstville.
Sampson, Aileen (Mrs.), Sc.Dip. (A.S.T.c., 1944), 9 Knox-avenue, Epping.
Sawkins, Dansie Thomas, m.a. Syd., B.A. Camb., 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.
Schafer, Harry Neil Scott, B.sc., 18 Bartlett-street, Summer Hill.
Scott, Beryl (Miss), B.sc., Geology Department, University of Tasmania.
Scott, Reginald Henry, B.sc., 3 Walbundry-avenue, East Kew, Victoria.
Selby, Esmond Jacob, Dip.com., Sales Manager, Box 175 D, G.P.O., Sydney.
Sellenger, Brother Albertus, St. Ildephonsus College, New Norcia, W.A.
Sharp, Kenneth Raeburn, Geology Department, The University of Sydney ; p.r. Kitchener-road, St. Ives.
Sheahan, Thomas Henry Kennedy, B.sc., Chemist, c/o Shell Co. of Aust., North Terrace, Adelaide.
Sherrard, Kathleen Margaret Maria (Mrs.), M.sc. Melb., 43 Robertson-road, Centennial Park.
Sherwood, Ian Russell, D.Sc., F.A.c.I., Research Bacteriologist, Research Laboratory, Colonial Sugar Refining Co. Ltd., John-street, Pyrmont. Shulman, Albert, B.Sc., Industrial Chemist, Flat 2, Linden Court, Linden-
avenue, Woollahra.
Simmons, Lewis Michael, B.sc. (Hons.) Lond., ph.p. Lond., F.A.C.1., Head of Science Department, Scots College; p.r. The Scots College, Victoria-road, Bellevue Hill.
Simonett, David Stanley, B.sc., Geography Department, The University of Sydney; p.r. 14 Selwyn-street, Artarmon.
Simpson, John Kenneth Moore, Industrial Chemist, ‘‘ Browie,’” Old Castle Hill-road, Castle Hill.
Slade, George Hermon, B.Sc., Director, W. Hermon Slade & Co. Pty. Ltd., Manufacturing Chemists, Mandemar-avenue, Homebush; p.r. “ Raiatea,”’ Oyama-avenue, Manly.
Smith, Eric Brian Jeffcoat, New College, Oxford, England.
Smith-White, William Broderick, m.a. Cantab., B.sc. Syd., Department of Mathematics, University of Sydney; p.r. 7 Henson-street, Summer Hill.
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.
Stevens, Neville Cecil, B.sc., Geology Department, The University of Sydney ; p.r. 12 Salisbury-street, Hurstville. 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.
Stone, Walter George, F.S.T.c., F.A.C.1., Chief Analyst, Department of Mines, Sydney; p.r. 79 Ocean-street, Woollahra.
{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.
xiii
Elected.
1919 {Sutherland, George Fife, a.r.c.sc. Lond., Assistant Professor of Mechanical Engineering in the University of Sydney.
1920 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.
1941 PP 2 Swanson, Thomas Baikie, m.sc. Adel., c/o Technical Service Department, Icianz, Box 1911, G.P.O., Melbourne, Victoria.
1948 Swinbourne, Ellice Simmons, Organic Chemist, 183 Sydney-road, Balgowlah.
1915 12a} Taylor, Brigadier Harold B., M.c., D.Sc., F.R.I.C., F.A.C.I., Government Analyst, Department of Public Health, 93 Macquarie-street, Sydney; p.r. 44 Kenneth-street, Longueville.
1944 Thomas, Andrew David, Squadron Leader, R.A.A.F., M.sc., A.Inst.P.. 17 Millicent-avenue, Toorak, Melbourne, E.2., Vic.
1946 Thomas, Ifor Morris, M.sc., Department of Zoology, University of Adelaide, Adelaide, S.A.
1919 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.
1935 Tommerup, Eric Christian, M.Sc., A.A.C.I., Queensland Agricultural College, Lawes, via Brisbane, Queensland.
1923 Toppin, Richmond Douglas, a.R.1.c., 51 Crystal-street, Petersham.
1940 Tow, Aubrey James, m.sc., No. 5, “* Werrington,’’ Manion-avenue, Rose Bay.
1943 Turner, Ivan Stewart, M.A., M.Sc., Ph.D., Lecturer in Mathematics, University of Sydney; p.r. 120 Awaba-street, Mosman.
1921 Vicars, Robert, Marrickville Woollen Mills, Marrickville.
1935 Vickery, Joyce Winifred, M.sc., Botanic Gardens, Sydney; p.r. 17 The
Promenade, Cheltenham.
1933 P 5 | Voisey, Alan Heywood, p.sc., Lecturer in Geology and Geography, New England University College, Armidale.
1903 P10 |{Vonwiller, Oscar U., B.Sc., F.Inst.p., Emeritus Professor of Physics in the University of Sydney ; p.r. “‘ Eightbells,’’ Old Castle Hill-road, Castle Hill. (President, 1930.)
1948 Walker, Donald Francis, Surveyor, 13 Beauchamp-avenue, Chatswood.
1943 Walker, James Foote, Company Secretary, 11 Brucedale-avenue, Epping.
1919 ie Walkom, Arthur Bache, D.sc., Director, Australian Museum, Sydney; p.r. 45 Nelson-road, Killara. (Member from 1910-1913. President, 1943-44.)
1913 P 5 |{Wardlaw, Hy. Sloane Halcro, D.sc. Syd., F.A.c.1., Lecturer and Demonstrator in Biochemistry in the University of Sydney. (President, 1939.)
1944 Warner, Harry, A.S.T.c., Chemist, 6 Knibbs-street, Turner, Canberra, A.C.T.
1921 {Waterhouse, Gustavus Athol, D.sc., B.E., F.R.E.S., F.R.Z.S., c/o Mrs. Millett, Tlloura-avenue, Wahroonga.
1919 Poul Waterhouse, Lionel Lawry, B.z. Syd., Reader in Geology in the University of Sydney.
1919 Pane Waterhouse, Walter L., M.c., D.Sc.Agr., D.1.C., F.L.S., Research Professor of Agriculture, University of Sydney ; p.r. ‘“* Hazelmere,”’ Chelmsford-avenue, Lindfield. (President, 1937.)
1944 Watkins, William Hamilton, 8B.sc., Industrial Chemist, 57 Bellevue-street, North Sydney.
1911 P 1 |{Watt, Robert Dickie, M.a., B.sc., Professor of Agriculture in the University of Sydney; p.r. 64 Wentworth-road, Vaucluse. (President, 1925.)
1947 Webb, Gordon Keyes, A.F.1.A., A.C.1.8., Accountant, c/o Max Wurcker (1930) Pty. Ltd., 99 York-street, Sydney. :
1921 Wenholz, Harold, B.Sc.agr., Director of Plant Breeding, Department of Agri- culture, Sydney.
1947 Werner, Ronald Louis, Industrial Chemist, 25 Dine-street, Randwick.
1946 Weston, Margaret Crowley, B.A., 41 Bulkara-road, Bellevue Hill.
1909 P 3 |{White, Charles Josiah, B.sc., Lecturer in Chemistry, Teachers’ College, Uni- versity Grounds, Newtown.
1943 Whiteman, Reginald John Nelson, M.B., Ch.M., F.R.A.C.S., 143 Macquarie-street, Sydney. 1928 Wiesener, Frederick Abbey, M.B., Ch.M., D.O.M.S., Ophthalmic Surgeon, Bram
Hall, Jersey-road, Strathfield. 1942 Williams, Gordon Roy, B.sc., 45 Conder-street, Burwood.
XIv Elected. 1945 1943 1940 1936 1906 1916
1946
1948
Elected. 1949
1949 1914 1946 1915 1912 1948 1948 1946
Pog
Willis, Jack Lehane, B.sc., Flat 5, ‘‘ Narooma’’, Hampden-street, North Sydney.
Winch, Leonard, B.sc., 60 Baldwin-avenue, Asquith.
Wogan, Samuel James, Range-road, Sarina, North Queensland.
Wood, Harley Weston, M.Sc., A.Inst.P., F.R.A.S.. Government Astronomer, Sydney Observatory, Sydney.
P12 |{Woolnough, Walter George, D.sc., F.G.S., c/o Mr. W. L. Woolnough, ‘“‘ Calla-
bonna ’’, 8 Park-avenue, Gordon.
Wright, George, Company Director, c/o Hector Allen, Son & Morrison, 7 Wynyard-street, Sydney.
Wyndham, Norman Richard, m.p., m.s. (Syd.), F.R.c.s. (Hng.), ¥F.R.A.C.S., Surgeon, 225 Macquarie-street, Sydney.
Zingel, Judith, B.sc., Geology Department, The University of Sydney; p.r. 89 Sydney-road, Manly.
Honorary MEMBERS.
Limited to Twenty.
| Burnet, Frank Macfarlane, M.D., Ph.D., F.R.S., Director of the Walter and Eliza
Hall Research Institute, Melbourne.
Florey, Sir Howard, M.B., B.S., B.Sc., M.A., Ph.D., F.R.S.,; Professor of Pathology, Oxford University, England.
Hill, James P., D.sc., F.R.S., Professor of Zoology, University College, Gower- street, London, W.C.1, England.
Jones, Sir Harold Spencer, M.A., D.Sc., F.R.S., Astronomer Royal, Royal Observatory, Greenwich, London, 8.E.10.
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, Engiand.
Oliphant, Marcus L., B.Sc., Ph.D., F.R.S., Professor of Physics, The University, Edgbaston, Birmingham 15, England.
Robinson, Sir Robert, M.A., D.Sc., F.C.S., F.I.C., F.R.S., Professor of Chemistry, Oxford University, England.
Wood-Jones, F., D.Sc., M.B., B.S., F.R.C.S., L.R.C.P. (Lond.), F.R.S., F.Z.S., Professor of Anatomy, University of Manchester, England.
OBITUARY, 1948-49.
1909 Ernest Clayton Andrews. 1923 George Frederick Birks. 1932 Ernest Norman McKie. 1920 Edward Montague Wellish.
THE REV. W. B. CLARKE MEMORIAL FUND.
The Rev. W. B. Clarke Memoriai 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., 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. (Tus JouRN., 1936, 70, 39.) 937. ‘‘ 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 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. (Tus 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 Australa.’’ By E. C. Andrews, B.Sc. 1943. ‘‘ Australia’s Mineral Industry in the Present War.” By H. G. Raggatt, D.Sc. 1944, ‘‘ An Australian Geologist Looks at the Pacific.” By W. H. Bryan, M.C., D.Sc. 1945. ‘‘Some Aspects of the Tectonics of Australia.”’ By Professor E. 8. Hills, D.Sc., Ph.D. 1946. ‘‘ The Pulse of the Pacific.”” By Professor L. A. Cotton, M.A., D.Sc. 1947. ‘‘ The Teachers of Geology in Australian Universities.”” By Professor H. S. Summers, DSe. 1948. ‘‘ The Sedimentary Succession of the Bibliando Dome: Record of a Prolonger Proterozoic Ice Age.” By Sir Douglas Mawson, O.B.E., F.R.S., D.Sc., B.E.
AWARDS OF THE CLARKE MEDAL.
Established in memory of The Revd. WILLIAM BRANWHITE CLARKE, .a., F.R.S., F.G.8S.. 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.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, LL.D., F.R.S., F.G.S.
xvi
Awarded.
1885 *Sir Joseph Dalton Hooker, 0.M., G.C.S.I., 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.
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.pD., 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.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, 1.8.0., F.R.S., F.L.S., J.P.
1925 *Charles Hedley, F.L.s.
1927 Andrew Gibb Maitland, r.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.sSc., 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, 4.R.s.M., 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., Lu.B., 9 Ivanhoe-parade, Ivanhoe, Victoria.
1938 *Professor H. C. Richards, pD.sc., The University of Queensland, Brisbane.
1939 *C. 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.
1942 William Rowan Browne, D.sc., Reader in Geology, The University of Sydney, N.S.W.
19438 Walter Lawry Waterhouse, M.C., D.Sc.Agric., D.I.C., F.L.S., Reader in Agriculture, University of Sydney.
1944 Professor Wilfred Eade Agar, 0.B.E., M.A. D.Sc, F.R.S., University of Melbourne, Carlton, Victoria.
1945 Professor William Noel Benson, B.A., D.Sc., F.G.S., F.R.G.S., F.R.S.N.Z., F.G.S.Am., University of Otago, Dunedin, N.Z.
1946 Black, J. M., a.t.s. (honoris causa), Adelaide, S.A.
1947 *Hubert Lyman Clark, A.B. D.Sc., Ph.p., Hancock Foundation, v.s.c., Los Angeles, California.
1948 Walkom, Arthur Bache, D.sc., Director, Australian Museum, Sydney.
AWARDS OF THE JAMES COOK MEDAL. Bronze Medal.
Awarded annually for outstanding contributions to science and human welfare in and for the Southern Hemisphere.
1947 1948
Smuts, Field-Marshal The Rt. Hon. J. C., P.c., C.H., K.C., D.T.D., LL.D., F.R.S., Chancellor, University of Capetown, South Africa.
Houssay, Bernado A., Professor of Physiology, Instituto de Biologia y Medicina Ex- perimental, Buenos Aires, Argentina.
xvi 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.
1884 W. E. Abbott, Wingen, for paper entitled ‘‘ Water supply in the Interior of New South Wales.”
1886 S. H. Cox, F.a.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, F.R.M.s., Sydney, for paper entitled “‘ List of the Marine and Fresh- water Invertebrate Fauna of Port Jackson and Neighbourhood.”
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.”
1943 Edwin Cheel, Sydney, in recognition of his contributions in the field of botanical research and to the advancement of science in general.
1948 Waterhouse, Walter L., M.s., D.Sc.Agr., D.I.C., F.L.S., Sydney, in recognition of his valuable contributions in the field of agricultural research.
AWARDS OF THE WALTER BURFITT PRIZE. Bronze Medal and Money Prize of £75.
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, which was augmented later by a gift from Mrs. W. F. Burrirr. 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 six 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.
1944 Hereward Leighton Kesteven, D.sc., M.D., c/o Allied Works Council, Melbourne.
1947 John Conrad Jaeger, M.A., D.Sc., University of Tasmania, Hobart.
XVili
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.se., 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.1.c., University of Melbourne.
1944 F. P. Bowden, ph.pD., Sc.D., University of Cambridge, Cambridge, England.
1946 Briggs, L. H., p.phil. (Oxon.), D.sc. (N.Z.), F.N.Z.1.C., F.R.S.N.Z., Auckland University College, Auckland, N.Z.
1948 Ian Lauder, M.Sc., Ph.D., University of Queensland, Brisbane.
Royal Society of New South Wales
REPORT OF THE COUNCIL FOR THE YEAR ENDING 3lst MARCH, 1949.
PRESENTED AT THE ANNUAL GENERAL MEETING OF THE SOCIETY, 6TH APRIL, 1949 (RULE XXXVI).
The membership of the Society at the end of the period under review stood at 354. Thirty- eight new members were elected during the year, the Council having made a special effort towards increased enrolment; however, twelve members were lost by resignation and four, who were in arrears with subscriptions, were removed from the register. Four members have been lost to the Society by death since Ist April, 1948:
Ernest Clayton Andrews (1909). George Frederick Birks (1923). Ernest Norman McKie (1932). Edward Montague Wellish (1920). Professor Marcus L. Oliphant, B.Se., Ph.D., F.R.S., and Professor Sir Robert Robinson,
M.A., D.Sc., F.C.S., F.I.C., F.R.S., were elected to honorary membership of the Society at the annual meeting on 7th April, 1948.
During the year nine general monthly meetings were held, at which the average attendance was 49. Thirty-nine papers were accepted for reading and publication by the Society, an increase of four from the previous year.
“™ At the annual and general monthly meeting of 7th April, 1948, the Acting President, Dr. F. Lions, welcomed Professor Griffith Taylor, of the University of Toronto, Canada, formerly of Sydney University. Professor Taylor gave an address describing the application of geography, geology and physiography to national planning.
The Council decided to devote portion of the time of general meetings to “‘ Notes, Exhibits and Questions’’. This seems to have met with success, and the following questions have been answered :
4th August :
‘‘ There is evidence that ice ages have occurred simultaneously in both hemispheres of the world—what is the evidence of this?’’ Answered by Dr. G. D. Osborne.
‘* What is a Transcendental Number?” Answered by Mr. W. B. Smith-White. ‘* What are Cosmic Rays?” Answered by Dr. R. E. B. Makinson.
6th October : ‘‘ Why are there black and white races?’ Answered by Professor A. P. Elkin. ‘“* Why does the moon always turn the same face towards the earth ?”’ Answered by Mr. Harley Wood. Ist December :
‘What is the principle of the electron microscope ?’”’ Answered by Mr. R. L. Werner. ‘‘ What was the cause of the change of longitude of Sydney Observatory amounting to some 166 yards in about the year 1932, as indicated by certain one-inch military maps ? ”’ Answered by Mr. Harley Wood. Exhibits discussed were : 5th May : ‘* Bouncing Putty’, by Dr. D. P. Mellor.
3rd June:
‘** Enlarged photographs of the Second Positive Spectrum of Nitrogen, showing some features of interest ’’, by Professor O. U. Vonwiller and Miss D. P. Tarrant.
BB
xx REPORT OF COUNCIL.
A symposium on the “ Education of a Scientist ”’ was held at the general monthly meeting on lst September, the following addresses being given :
‘“ Science in Secondary Education ’’, by Mr. J. B. Thornton.
“The Teaching of Science in the Universities’, by Professor N. A. Burges.
‘* The Scientist and Scientific Method ”’, by Professor K. E. Bullen.
The topic stimulated a deal of discussion, which was continued by other speakers at the next general meeting. :
Addresses commemorating great scientists and important scientific events were given at the general monthly meeting on 3rd November :
‘‘ Simon Stevin ”’ (Stevinus), by Mr. H. H. Thorne.
‘* Berzelius’’, by Mr. J. B. Thornton.
‘“‘ Important Events in the History of Public Health’, by Professor Harvey Sutton.
In continuance of its programme of popular education as to atomic energy, the Society made arrangements with the University Extension Board for the delivery of a series of lectures on atomic physics during July :
‘‘The Atom and Radioactivity ’’, by Dr. D. P. Mellor.
‘* Artificial Transformations and Nuclear Fission ’’, by Dr. R. E. B. Makinson.
‘Atomic Physics and Human Welfare’’, by Dr. F. Lions.
‘“* International Control of Atomic Energy ”’, by Dr. G. H. Briggs.
Four Popular Science Lectures were delivered during the year, and much appreciated by members of the Society and the public:
20th May: “ The Struggle between Fungi and Roots”’, by Professor N. A. Burges.
17th June: ‘‘ Plant Growth Regulators or Hormones ’’, by Dr. C. J. Magee.
16th September : “ The Making of an Australian—A Study in Migration ”, by Mrs. C. Kelly. 21st October: ‘‘ Weights and Measures ’’, by Mr. N. A. Esserman.
A visit to the National Standards and Radiophysics Laboratories on 30th July was arranged through the courtesy of the C.8S.I.R. The opportunity to see the work in progress in these laboratories was appreciated by members.
The Annual Dinner of the Society was held at the Sydney University Union on 31st March, 1949. There were present 98 members and friends.
The Section of Geology, whose chairman was Mr. C. St. J. Mulholland and honorary secretary Mr. R. O. Chalmers, held six meetings during the year, at which the average attendance was fourteen members and six visitors. The activities were :
16th April: Address by Mr. F. N. Hanlon.
21st May: Notes and Exhibits by Miss F. Quodling and Messrs. N. C. Stevens, C. St. J. Mulholland, H. O. Fletcher and R. O. Chalmers. ;
23rd July : Exhibit by Mrs. K. Sherrard and an address by Dr. L. E. Koch. 27th August: Address by Dr. J. A. Dulhunty.
17th September : Address by Dr. G. D. Osborne and Mr. P. B. Andrews. 19th November: Address by Dr. L. E. Koch.
The Council of the Society held ten ordinary meetings and one special meeting during the year, at which the average attendance was 13. The special meeting of the Council was held to discuss the ‘‘ Freedom of Science ’’. It was resolved that at the time no action beyond remaining vigilant appeared desirable, but a motion defining the Council’s attitude was recorded in the minute book.
The Council has decided that in future the Annual Report, Financial Statement and List of Members will be published in Part I of the Journal, and that the abstract of proceedings of meetings will be omitted. This will effect more prompt publication of the reports and eliminate some duplication.
Professor O. U. Vonwiller and the Rev. D. J. K. O’Connell were given leave for periods of travel abroad. Among other activities, they represented Australian Science at the Zurich meeting of the International Astronomical Union. Professor Vonwiller represented the Society at the celebration in Sweden of the one hundredth anniversary of the death of Jacob Berzelius. Mr. W. B. Smith-White was elected to the office of Honorary Editorial Secretary rendered vacant by the resignation of Professor Vonwiller.
REPORT OF COUNCIL. Xx]
' The President, Dr. R. L. Aston, has represented the Royal Societies of Australia on the National Co-operating Body in Natural Sciences of UNESCO. At the A.N.Z.A.A.S. Conference, January, 1949, at Hobart, the Society was represented by Drs. R. L. Aston, A. Bolliger and C. J. Magee. At the Seventh Pacific Science Congress, which was held in New Zealand, February, 1949, the Society was represented by Dr. Dorothy Carroll.
Dr. A. B. Walkom was one of Australia’s representatives at the General Assembly of UNESCO at Beirut, and was president of the Hobart meeting of the Australian and New Zealand Association for the Advancement of Science in January, 1949.
Professor K. E. Bullen has been elected as a Fellow of the Royal Society.
On Science House Management Committee the Society was represented by Messrs. H. O. Fletcher and F. R. Morrison, with substitute representatives Dr. R. L. Aston and Mr. H. H. Thorne.
Science House Extension Committee has been working on the proposals for the eventual extension of Science House to York Street North, the representatives of the Royal Society of New South Wales being Drs. A. Bolliger and R. L. Aston.
The Clarke Memorial Lecture for 1948 was delivered by Sir Douglas Mawson, O.B.E., D.Sc., F.R.S., on 15th July, the title being ‘‘ The Sedimentary Succession of the Bibliando Dome : Record of a Prolonged Proterozoic Ice Age”’.
The Liversidge Research Lecture for 1948 was delivered by Professor Ian Lauder, M.S8c., Ph.D., on 19th August, on ‘‘ Some Recent Work on the Separation and Use of Stable Isotopes ”’.
The Clarke Memorial Medal for 1948 was awarded to Dr. Arthur B. Walkom, Director, Australian Museum, Sydney, in recognition of his contributions to natural science, and particularly for researches in paleobotany.
The Clarke Memorial Medal for 1949 was awarded to the Rev. H. Montague Rupp for his work on Australian orchids.
The Royal Society’s Medal was awarded to Professor W. L. Waterhouse, M.C., D.Sc.Agr., D.I.C., F.L.S., in recognition of his valuable researches in the field of agriculture.
The James Cook Medal was awarded to Professor Bernado A. Houssay, of the Instituto d Biologia y Medicina Experimental, Buenos Aires, Argentina, for his distinguished work for science and human welfare in the southern hemisphere, particularly through his contributions to endocrine research.
The Edgeworth David Medal, which is for Australian research workers under thirty-five years of age, was awarded for the first time. It was decided to make a joint award to Mr. R. G. Giovanelli, M.Sc., for his work in astrophysics, and Mr. E. Ritchie, M.Sc., for his work in organic chemistry.
The initiation of the James Cook Medal, in 1948, and the Edgeworth David Medal completes the scheme of the Society’s awards which has been envisaged in recent years.
During the year several scientists from overseas visited the Society’s rooms and were enter- tained by the President. Among these were :
Sir Harold Hartley, now Chairman of the British Overseas Airways Corporation (23rd November, 1948).
Sir Henry Tizard, who visited Australia at the invitation of the Commonwealth Government to advise on defence research (8th December, 1948).
Dr. Wang Ghing-Hsi, senior member of the Natural Sciences Department, UNESCO Secretariat, Paris (28th February, 1949).
Drs. A. Sison, P. Valenzuela and J. M. Feliciano, who were members of a party of Philipino scientists returning from the Seventh Pacific Science Congress in New Zealand (14th February, 1949).
Dr. 8S. Krishna, Lt.-Col. M. L. Ahuja, Dr. B. P. Pal and Mr. V. P. Sondhi, who were members of an Indian scientific delegation visiting Australia at the invitation of the Common- wealth Government (28th March, 1949),
The financial position of the Society, as disclosed by the annual audit, reveals the difficulties which in these years beset institutions whose income tends to remain steady but whose expenditure continues to increase obstinately despite efforts at economy which, if the tendency continues, may eventually affect the efficiency of the Society’s work. The most serious example of rising costs for us is in the cost of printing the Journal and Proceedings, which in 1947 was increased from £13 to £16 per forme of 16 pages ; we are now faced with an increase to £32.
The Royal Society’s share of the profits of Science House for the year was £390 18s. 6d. The grant from the Government of New South Wales of £400 has been received. The continued interest of the Government in the work of our Society is much appreciated.
The Library. The amount of £58 6s. 3d. has been spent on the purchase of periodicals, and £121 11s. 3d. on binding, the increased expenditure on binding being due to shortage of book- binding materials in 1947-1948.
xxii REPORT OF COUNCIL.
Exchange of publications is maintained with 406 societies and institutions, an increase of 19 over the previous year.
The number of accessions entered in the catalogue during the year ended 28th February, 1949, was 2,501 parts of periodicals.
The Society sold its set of the Journal of the Royal Asiatic Society of Great Britain and Ireland to the Library, the Parliament of the Commonwealth, for the sum of £222 12s. 6d. Also, incom- plets sets of medical journals were sold to Stechert-Hafner, Inc., of New York, and realized the sum of £202 5s. 11d.
Among the institutions which made use of our library through the inter-library borrowing scheme were: The University of Sydney, Department of Health, University of Queensland, Commonwealth Observatory, C.S.I.R. Food Preservation, Linnean Society of N.S.W., Forestry Commission, C.S8.I.R. Plant Industry, National Standards Laboratories, M.W.S. and D. Board, McMaster Laboratory, Taubman’s Paints, Ellotts and Australian Drug Co. Ltd., A.W.A. Ltd., C.S.I.R. Industrial Chemistry, Department of Agriculture, Defence Research Laboratories, Water Conservation and Irrigation Commission, Australian Paper Mills, Sydney Technical College, the University of Melbourne, Colonial Sugar Refining Co. Ltd., C.S.I.R. Aeronautics, Standards Association of Australia, C.S.I.R. Coal Survey, Sydney Grammar School, the Australian Museum, Institute of Engineers, James Hardie & Co.
R. L. ASTON, President.
1948, £ 189
25 102
200
7,173
25,877 (902)
£33,566
396 29 9
£33,566
THE ROYAL SOCIETY OF NEW SOUTH WALES. BALANCE SHEET AS AT 28th FEBRUARY, 1949.
LIABILITIES. 1949. ao s. d. £, Ss: ed. Accrued Expenses 141 5 9 Subscriptions Paid in indvanee : seal 26 5 O Life Members’ Subscriptions—Amount — ‘carried forward 90 0 O James Cook and Edgeworth David Medals— Amount carried forward — Trust and Monograph Capital Funds (detailed below)— Clarke Memorial 1,960 4 7 Walter Burfitt Prize 1,055 17 5 Liversidge Bequest : : 707 10 3 Monograph Capital Fund | .. 3,520 18 4 — 7,244 10 7 ACCUMULATED FUNDS ae 26,081 18 2 Contingent Liability—In connection with tenancies of the Australian National Research Council and the Pharmaceutical Society of N.S.W.— Maximum Liability £901 16s. 8d. £33,583 19 6 ASSETS. 1949. a8 s. d. £ s. d. Cash at Bank and in Hand ae if ee 439 14 3 Investments—Commonwealth Bonds and Inscribed Stock, ete.—at Face Value— Held for— Clarke Memorial Fund 1,800 0 O Walter Burfitt Prize Fund 1,000 0 O Liversidge Bequest .. 700 0 0 Monograph Capital Fund Als ae te 3,000" O70 General Purposes... ane a os .. 4,660 0 0O — 11,160 0 0O Prepayment a 24 2 9 Debtors for Subscriptions aa 85 5 0 Deduct Reserve for Bad Debts 85 5 0 Science House—One-third Capital Cost 14,745 18 6 Library—At Valuation 6,800 0 0O Furniture—At Cost—less Depreciation 379 0 O Pictures—At Cost—less Depreciation 27 4 O Lantern—At Cost—less Depreciation 8 0 0 £33,583 19 6
XX1V BALANCE SHEET
TRUST AND MONOGRAPH CAPITAL FUNDS.
Clarke Memorial. Seu ae Capital at 29th February, 1948 .. 1,800 0 0 Revenue— Balance at 29th February, 1948 128 3 8 Interest for twelve months .. 64 13 11 T92 ta Deduct Expenditure A 32 13 0 Balance at 28th February, 1949 .. £160 4 7
Walter Burfitt Prize.
Cty Scns
1,000 0 0
of 5a LO 34 15 0
1382 2 10
16°55
£55 17 5
ACCUMULATED FUNDS.
Balance at 29th February, 1948
Add—
Surplus for twelve months shown by Income and Ex-
penditure Account)
Less—
Amount written off re James Cook and Edgeworth David Medals
Bad Debts written off
ee
Decrease in Reserve for Bad
(as
Debts
£227 10 32° 7
4 12
oom
we
700 25 25
ol 43
£7
2
26,1
Liversidge
59.17 6
36 18 5
55 0 3
£26,081 18 2
Monograph
Capital Fund. £ s
3,000 0
421 13 99 ~5
520 18
£520 18
d. 0
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, 1949, as disclosed thereby.
We have satisfied
ourselves that the Society’s Commonwealth Bonds and Inscribed Stock are properly held and
registered.
Prudential Building, 39 Martin Place, Sydney, 24th March, 1949.
HORLEY & HORLEY, Chartered Accountants (Aust.).
116
99
99
29
BALANCE SHEET.
INCOME AND EXPENDITURE ACCOUNT. 1st March, 1948, to 28th February, 1949.
To Printing and Binding Journal—Vol. 81
Salaries . Library—Purchases and Binding Printing—General .. Miscellaneous :
Postage and Telegrams
Rent—Science House Management Committee
Cleaning Depreciation Telephone Insurance Audit. . Electricity Repairs Reprints— Expenditure Less Received
Annual Dinner— Expenditure Less Received
Conversazione
Surplus for Twelve Months
By Membership Subscriptions
99
Government Subsidy ‘
Science House—Share of Surplus
Interest on General Investments
Proceeds Sale of Old Library Books Other Receipts :
Proportion of Life Members’ Subscriptions
Deficit for Twelve Months
£153 18 97 9
£88 13 49 16
XxXV 1948-9
Lio Sa hGs Soy eSeos 639 13 4 467 15 1 Nod8 00 o 103 9 2 96 ll 5 74 0 10 54 18 5 37020 Vint Koay ( Die Od. Papas EES Bat) 18 18 O S-l8 2 119 6 56 9 2 SOorLiaeeO
————— 1,800 8 0
227 10 6
£2,027 18 6
1948-9.
£, os. d.
586 8 6
400 0 O
390 18 6
155 12 1
477 18 7
5 010
12 0. 0
£2,027 18 6
Obituary,
ERNEST CLAYTON ANDREWS died July Ist, 1948. He was born in 1870 and had occupied a distinguished position in Australian Science for many years. He became a member of the Royal Society of New South Wales in 1909 and was a member of its Council from 1917 to 1932 except in 1919 and in 1927, during the latter of which he was invited to the United States of America to deliver the Silliman Lectures at Yale University. He was president of the Society in 1921 and was awarded the Clarke Memorial Medal in 1928 and the Clarke Memorial Lectureship in 1942.
Andrews was a graduate of the School of Geology of Sydney University, under Professor David, and joined the Geological Survey of New South Wales in 1899, becoming Government Geologist in 1920. His many published papers, twelve of them in the Journal and Proceedings of the Society, show a grasp of a wide variety of geological subjects, but reveal his special insight into the principles governing the evolution of physiographic features and their relation to geological structure. His work in this field in New South Wales may be said to have laid the foundation for all later researches of similar character. In the sphere of economic geology he was equally a master, and his rare geological acumen is displayed in the monumental work on the Broken ‘Hill lode. His studies of the distribution and evolution of floras in Australia and the Pacific Islands form a contribution of high and lasting merit.
Besides his work for our Society, Andrews interested himself widely in the administration of Australian Science. Among the organisations in which he was prominent were the Linnean Society of New South Wales, of which he was president in 1937; the Australian and New Zealand Association for the Advancement of Science, Honorary General Secretary 1922 to 1926 and President in 1930; the Australian National Research Council; and the Australian Institution of Mining and Metallurgy, President 1929. On a number of occasions he represented Australian Science at important international congresses.
Andrews received many honours besides those already mentioned, among which were honorary membership of the Washington Academy of Sciences and the Geological Society of America; honorary fellowship of the Royal Society of New Zealand ; the Mueller Medal of the Australian and New Zealand Association for the Advancement of Science (1946); the Lyell Medal of the Geological Society of London (1931); and the David Syme Prize and Medal of the University of Melbourne. Through it all he remained a deeply serious and generous worker among his fellow scientists, among whom he was as much esteemed for his personal qualities as he was respected for his scientific attainments.
GEORGE FREDERICK BrrKs died May 4th, 1948. He was 82 years of age and had been a member of the Society since 1923. He was a member of the party which went to Paraguay under the leadership of William Lane to found a socialist colony. After he returned to Australia he entered upon a business career, later becoming a director of several undertakings and chairman of directors of Potter and Birks, Pty., Ltd., a firm of manufacturing chemists which was founded by him. He was much interested in the Rotary movement and was a World Vice-President of the Rotary International. He was also a devoted worker for crippled children, and the Activity School at the Royal Alexandra Hospital for Children is named after him.
Ernest NorMAN MCKIE died May 19th, 1948. He was born at Guyra, New South Wales, in 1882, and spent most of his life around the New England district.
He at first intended to take up a business career and worked with the Commercial Banking Company of Sydney. Later he resigned to enter St. Andrew’s College, Sydney University, from which he graduated as Bachelor of Arts in 1906. He completed the theological course in 1908 and took his first church appointment at Manilla, whence he moved to Bendemeer in 1909 and Guyra in 1912. He served as Moderator of the General Assembly of the Presbyterian Church in 1938.
Mr. McKie was an amateur botanist of distinction and had a detailed knowledge of the eucalypts and native grasses of the New England district. His knowledge and help were always available to research workers visiting the district, Beside his interest in botany he took an active part in movements to improve the standard of agriculture in his district, being the first secretary of the local branch of the New South Wales Agricultural Bureau, and for many years associated himself with the fostering of modern trends in agricultural work.
He was a member of the Australian Institute of Agricultural Science, the Linnean Society of New South Wales, to the Journal of which he contributed, and since 1932 of the Royal Society of New South Wales.
Epwarp MontTaGuE WELLISH, M.A., Emeritus Professor of Mathematics of University of Sydney, died after a short illness at his home in Roseville in July, 1948.
OBITUARY XxXvVli
He entered the University in 1900 from Fort Street School after a brilliant pass at the Senior Examination in December, 1899, being equal with another student for the John West and Grahame Medals for general proficiency. He attended the evening classes, his guide in mathematics being the late Assistant Professor A. Newham. He graduated with first-class honours and the University Medal in Mathematics. He and Professor C. E. Weatherburn were awarded the University Medal for Mathematics for the M.A. degree in the year 1906.
In 1907 he was awarded the first Graduate Barker Scholarship and entered Emmanue College, Cambridge, in October of that year. He commenced research in the Cavendish Laboratory under Sir J. J. Thomson. His research was on the theory of ionisation of gases, his chief papers during this period being ‘‘ The Laws of Mobility and Diffusion of Ions formed in ‘Gaseous Media’”’, Proceedings of the Cambridge Philosophical Society, November, 1908; and “The Mobilities of the Ions Produced by Réntgen Rays in Gases and Vapours”’, T’ransactions of the Royal Society of London, January, 1909 ; and ‘“‘ The Passage of Electricity through Gaseous Mixtures ”’, Proceedings of the Royal Society of London, June, 1909.
Emmanuel College awarded him a special scholarship and a little later the excellency of his work was emphasised by the award of the Clerk Maxwell Studentship. After graduating B.A. (Research) at Cambridge, Professor Wellish accepted the post of Assistant Professor at Yale University, U.S.A. In 1913 he published in the Philosophical Magazine ‘“‘ Experiments on Columnar [onisation ’’ and in the American Journal of Science he published two papers, ‘‘ The Mobilities of Ions in Air ”’ and ‘‘ The Motion of Ions and Electrons through Gases ”’.
He returned to Sydney in 1916 and was appointed to a lectureship in the Department of Mathematics and in 1926 he was given the status of Associate Professor of Applied Mathematics. His time for research in Physics was naturally restricted, his next papers appearing in 1924 and 1931, when he published ‘‘ Photo-electrons and Negative Ions ’”’ in the Proceedings of the Royal Society of London.
During the nine years when Professors Carslaw and Room were absent from the Department of Mathematics, Professor Wellish was in charge. He retired in 1946, but to the regret of all his friends his health improved only slightly.
Professor Wellish was outstanding in his research, his lecture work and his administrative work. He rendered signal service on the Board of Secondary School Studies. As chief examiner in Mathematics for the Leaving Certificate Examination, he was always sympathetic to school teachers and their problems. His colleagues will always remember his consideration and kindness.
ate oe ey re id ph late ii a | 7 | La ER | : | Capt ¢ Lea | | : | | | in 2 % Awa {iy ; , | h a 1 ; ae } ; by 9 wa a at an ae ry a. Reames iy ‘| \ J ) | | i. ry | Aelia lu i pa
A CONTRIBUTION TO THE STRATIGRAPHY AND PHYSIOGRAPHY OF THE GLOUCESTER DISTRICT, N.S.W.
By P. B. ANDREWS, B.Sc., Teaching Fellow in Geology, University of Sydney.
With one text-figure.
Manuscript received, January 7, 1949. Read April 6, 1949.
I. INTRODUCTION.
In a recent paper (Osborne and Andrews, 1948) the geological structure of the northern end of the Stroud-Gloucester Trough was discussed. <A full account of previous investigations and a geological map of the area were included in that work. The present paper deals with some aspects of the stratigraphy and physiography of the same area. The major contributions to these subjects have been those of Sussmilch (1921) and Voisey (1940), who have discussed the stratigraphy of part of the area in considerable detail. Carey and Browne (1938) and Voisey (1945) have also discussed the Carboniferous succession at Gloucester and have correlated it with those of other areas. The following notes are intended primarily to extend the work of these investigators, particularly to the areas immediately to the south and east which have an important bearing on the final elucidation of the geology of this interesting district.
II. STRATIGRAPHY. (a) Carboniferous.
Sussmilch (1921) described a section across the Carboniferous strata on the west side of the Gloucester Trough in the neighbourhood of Barrington village and divided the sequence into the marine Burindi Series and the overlying terrestrial Kuttung Series. Carey and Browne (1938) further subdivided the Burindi Series into lower and upper sections, the Upper Burindi Series being the marine equivalent of the terrestrial Lower Kuttung Series of the Hunter River type area. Voisey (1940) described further sections from the same locality.
The recognition of a large fault separating the Devonian and Lower Burindi strata on the western side of the Trough (Osborne and Andrews, 1948) has confirmed the fact that the base of the Burindi Series is not exposed in these sections. The conglomerates outcropping on the Giro and Copeland Roads which are mentioned by Sussmilch and Voisey appear, however, to be close to the base of the series. A greater development of these conglomerates occurs
Cc
2 P. B. ANDREWS.
on the western side of the Barrington River on the ‘‘ Manchester ’”’ Road, and here the following section was measured in descending order :
Feet
Conglomerate and tuff .. ae ae ¥. 2) 2G . ait a ob ne ae al a Be vias LS Mudstones .. ae oe i, a ae x 10 Tuff and tuffaceous conglomerate ey ae a 35 Tuffaceous conglomerate and mudstones Re saan 6) |) AN Gd ess a 3 ii a 7 - ee 15 Coarse conglomerate Oe: oF ot ae ae 60 AUbhiG as Be oe Be ay a - 2a) 30 Tuffaceous conglomerate a is me : 70 Tuffs and mudstones a” Ne Lh bx bd 85 (MUTE a cf tp * “ ay a 50 Conglomerate ap ons ad af oes a 15 Tuffs and mudstones a o so Se 5a 85 Conglomerate nek ss oh oe: ae Re 25 Tuffs and mudstones st Be ay me ay 80 Total Se By he ee .. 1,065
The lowest beds in this sequence are separated by the Manchester Fault from Devonian rocks which outcrop on the flank of Mechanic’s Mountain a short distance to the east. Figure 1 shows a columnar section of the Carbon- iferous strata in this neighbourhood and includes a revised estimate of the upper part of the Carboniferous sequence for the western side of the Stroud-Gloucester Trough.
The series which is shown in Figure 1, and which represents essentially the sections measured by previous workers, can be traced from the Bowman Road Fault, about 24 miles west of Gloucester, westwards to Barrington village, and thence southward to the Rawdon Vale Road in the vicinity of Cut Hill, where the beds appear to be cut off by an East-West fault.
Work in the area between the Rawdon Vale Road and Spring Creek on the western side of the Trough, and also on the eastern side between the Gloucester- Taree road and Ward’s River, has shown, however, that this type section is not developed in any other part of the Gloucester-Stratford district, and none of the datum beds which have been referred to have been located elsewhere in the area.
Owing to the extensive faulting which has taken place, it was found impossible to measure a complete section of the Carboniferous Series on the eastern side of the Trough. Strata of Lower Burindi age outcrop in the country immediately to the south of the Gloucester-Krambach road from a point near the junction of the Mograni Creek road, east at least as far as Gangat, being cut off by faults from Devonian strata to the north and Upper Kuttung and Upper Burindi rocks to the south. These beds consist of mudstones and tuffs dipping steeply to the north. In Brushy Cutting near Gangat a thick series of greenish- grey friable mudstones with subordinate thin bands of tuff is exposed along the road. These beds closely resemble those of the Lower Burindi Series on the west side of the Trough. No fossils have been found in them.
An approximate section of the Upper Burindi and Upper Kuttung rocks on the eastern side of the Trough was measured from Mograni Creek School in a westerly direction. This revealed a total thickness of about 7,400 feet for the Upper Burindi Series, consisting essentially of felspathic and pebbly tuffs and mudstones. These beds are very similar to those of the Upper Burindi Series
STRATIGRAPHY AND PHYSIOGRAPHY OF THE GLOUCESTER DISTRICT.
on the western side of the Trough, but no fossils were found in them. Over much of this area the beds are dipping vertically, and it is probable that some strike faulting has occurred, thus accounting for the very great thickness measured for the series.
About halfway up in this section is a flow, about 20 feet thick, of green dacitic pitchstone which was traced along its strike for about 14 miles but lenses out. Under the microscope the groundmass of this rock is seen to be partly glassy, but is crowded with microlites. A few corroded phenocrysts of quartz are scattered through the rock, and clusters of oligoclase phenocrysts are also present. This may possibly be cor- related with a very similar flow which outcrops for a short distance on the ridge to the south of the Rawdon Vale road, where it crosses Cut Hill, where it immediately underlies the topmost flow of quartz-kerato- phyre in the Upper Burindi sequence.
The top of the first main ridge in the Mograni section is composed of a coarse tuffaceous conglomerate which was con- sidered to be the basal bed of the Upper Kuttung Series, the overlying beds con- sisting almost entirely of pebbly tuffs and conglomerates in which some obscure plant remains were found. Farther to the south Upper Burindi strata outcrop along the Waukivory Road, and here consist of mud- stones and light-coloured coarse felspathic tuffs. Marine fossils were found in Portion 211, A. A. Coy’s Grant, close to the road, in a locality mentioned by Voisey (1940). These were not sufficiently well preserved for identification, but included pelecypods and a small gastropod. On the ridge between this point and Phillip’s Creek a bed of coarse tuff was found which contains crinoid stems, but most of the considerable thickness of pebbly tufis and mudstones are apparently unfossiliferous. The presence of the East Stratford Fault, which separates these beds from the Upper Kuttung Series, prevents the determination of the exact position in the sequence of the fossiliferous horizons.
The rugged country at the head of Dog Trap Creek and Ward’s River consists of a great thickness of apparently unfossil- iferous tuffs and tuffaceous conglomerates , with subordinate mudstones. The ridge on ‘which is situated Craven Trigonometrical Station is formed of one of the beds of coarse tuffaceous conglomerate. These sedi-
Volcanic Series (Rhyolites, breccias, etc.) Tuffs, mudstones and
Conglomerates
Tuffs and
Mudstanes
TRE RW Ee AEE) Cusertz-keratophyre Dacitic Pitchstone
= a Tuff
Pebbly Tuffs
Productus barringtonensis bed
Tuffs
AW) Quartz-keratophyre
Coarse tuffs Quartz-keratophyre
Tuffs
and Mudstones Quartz-keratophyre Tuffs
and Mudstones
LOWER
1000
Fig.l. Generalised Section of Carboniferous Strata on western side of Stroud-Gloucester Trough.
4 P. B. ANDREWS.
ments are again very similar to those of the Upper Burindi Series on the western side and are provisionally correlated with them. In this neighbourhood the strata dip to the east at angles of about 70 degrees and are cut off on the west by the East Stratford Fault.
The steep ridges on the western side of the Stroud-Gloucester Trough, south of the Rawdon Vale road, also consist almost entirely of pebbly tuffs. However, a flow of rhyolite forms the highest part of the ridge between Cut Hill Creek and the upper Avon River. South of the Avon River the crest of the Faulkland Range is formed of another thin flow of acid lava, in this case a light grey, wholly glassy rock with numerous veinlets of quartz. Here, however, the associated sediments, which include dark-coloured cherts and a few thin beds of carbonaceous shale, appear to belong to the Upper Kuttung Series. Pebbly tuffs and mudstones which outcrop on the western flank of the Faulklands Range are believed to be of Upper Burindi age, but no detailed work was carried out in this locality.
Carey and Browne (1938) suggested that the type section of the Upper Burindi Series on the western side of the Gloucester Buckets Range was a predominantly terrestrial sequence with thin marine intercalations. Voisey (1945) considers that the whole of the Upper Burindi Series is marine. A careful study of these beds has shown that fragments of marine fossils are widely distributed through the series, but it is possible that there are some terrestrial sediments interbedded in an essentially marine sequence. It must be emphasized that the whole facies is indicative of shore-line conditions.
The almost complete absence of marine fossils from the corresponding beds on the eastern side of the Trough may indicate that this particular area was one of predominantly terrestrial deposition, the same types of tuffs and pebbly beds being present as in the marine series on the western side. It is also significant that no marine fossils have been found in similar beds on the western side farther south than the Rawdon Vale road.
Thus it is probable that much of the strata indicated on the previously published map (Osborne and Andrews, 1948) as belonging to the Upper Burindi Series is, in fact, of terrestrial origin. As the distinction is purely one of facies and not of age it has been considered advantageous to classify all these rocks under a single head.
The most notable feature of the Upper Kuttung Series in the Gloucester- Stratford district is the great development of volcanic rocks. These have been discussed by Sussmilch (1921) under the name of the ‘‘ Gloucester Rhyolites ’’, but Voisey (1945) has pointed out that the greater part of the voleanic series consists of fragmental material. This is particularly the case on the eastern side of the Stroud-Gloucester Trough where these strata attain their greatest development. The total thickness of the volcanic series in the neighbourhood of Mograni Mountain is about 3,000 feet. No attempt has been made to map individual flows, of which there are a large number, but many different varieties have been collected. A great deal of brecciated material is present, the fragments consisting largely of banded rhyolites and tuffs of several kinds. Many of the lavas exhibit large vughs and veins filled with chalcedony, and it is interesting to note that this is also the case at Pokolbin, where lavas occur which are almost identical chemically with some of those of the Gloucester Buckets Range. The lavas range in composition from rhyolites to andesites, blue dacites showing strong flow structure being particularly well developed in the vicinity of Oaky Creek Falls.
The Upper Kuttung Series to the west of Stratford and Craven consists almost entirely of tuffs and tuffaceous conglomerates, and the typical volcanic sequence is not developed, although it still appears in the ranges on the east
STRATIGRAPHY AND PHYSIOGRAPHY OF THE GLOUCESTER DISTRICT. 5
side of the valley. At the head of the Upper Avon road, pink and purplish volcanic breccias outcrop, but these are of an entirely different type from the brecciated lavas of Mograni Mountain.
(b) Permian.
Rocks of Permian age occupy the central part of the Stroud-Gloucester Trough and consist of conglomerates, grits, sandstones, shales and coal seams. These beds have been assumed to belong to the Upper Coal Measures (Sussmilch, 1921; Voisey, 1940) but no direct correlation. can be made as they are isolated from the main coal basin of the Hunter River Valley and a correlation based purely on lithological similarities cannot therefore be accepted.
Owing to the presence of much minor folding and variations in dip, and to the paucity of good outcrops, the thickness of the Coal Measures cannot be accurately measured, but in the neighbourhood of Gloucester there is a total thickness of at least 1,900 feet. No clearly defined junction between these beds and the underlying Upper Kuttung Series has yet been found, owing to the characteristic talus slopes which everywhere mark the boundary of the volcanic series, but in a track cutting close to the Barrington River near Kiaora Crossing, and in the railway cutting immediately north of the bridge over the Avon River, the two series appear to be separated by an erosional disconformity, the Permian rocks occupying hollows in the surface of the Upper Kuttung lavas. The basal bed of the Permian sequence wherever studied is a coarse conglomerate containing pebbles of rhyolite and tuff which gives further evidence of a probable erosional break between the two series.
The best exposures of the Coal Measures are to be seen in the railway cuttings between Spring Creek and Craven, in the southern part of the area under discussion. A large number of outcrops of coal seams appear in these cuttings, but most of the seams are very thin. These beds show many minor folds and faults (Osborne and Andrews, 1948). In the bed of Coal Creek about one-quarter mile south of Craven Railway Station a section was measured totalling 146 feet of sediments, of which 24 feet is coal, but this is distributed between thirteen distinct seams.
To the east of Craven, along the Glen road and south at least as far as Stoney Creek, is a faulted outlier of Coal Measures consisting essentially of sandstone and conglomerate. A 14-foot seam of coal is exposed in the bed of Stoney Creek a Short distance above its confluence with Ward’s River.
Ill. PHYSIOGRAPHY.
Sussmilch (1921) briefly discussed the major physiographic features of the Gloucester district and mentioned the contrast between the relatively flat and low-lying valley of the Gloucester, Avon and Ward’s Rivers, excavated in soft Permian strata, and the steep country on either side occupied by Carboniferous rocks.
Extensive alluviation of the lower reaches of the Gloucester and Avon Rivers at the northern end of the valley has taken place, and this is probably partly due to the blocking of the Gloucester River immediately above its junction with the Barrington River by a hard bar of Carboniferous lavas which is an extension of the Mograni Range. This would have formed a local base-level for the river. This is confirmed by the presence of a river terrace which is revealed in a road cutting where the river passes on the north side of the town of Gloucester and which is about 40 feet above the present river level.
In the main valley, the divide between the Avon River system flowing northward and the Ward’s River system flowing to the south is very low and
6 P. B. ANDREWS.
irregular. Ward’s River flows out of the ranges on the eastern side in a narrow valley at an average elevation about 100 feet lower than the land immediately to the north, and its tributaries, cutting back in this direction, threaten to capture the headwaters of Swamp Creek which now flows over an almost level plain before joining the Avon River. In a similar way Spring Creek, which flows into Ward’s River from the west, threatens to capture the heads of some of the small creeks which flow northward to the Avon River on the western side of the North Coast Railway. If these changes were to take place the whole drainage pattern of the Avon River would be reversed.
Sussmilch noted that the main stream channels appear to antedate the present topography, and it may be noted that this also applies to many of the smaller streams, which have cut across hard and weak structures alike. On the eastern side of the main valley Ward’s River, Waukivory Creek, Dog Trap Creek and Mograni Creek all rise in the country to the east of the Mograni Range and have cut steep gorges through it as they flow westward, cutting at right angles across the general trend of the country to do so. Waukivory Creek flows in a relatively mature valley on the eastern side before plunging into a narrow gorge through the range, which rises to a height of over 1,000 feet on either side.
In the same way the Gloucester River and Gap Creek have cut through the Gloucester Buckets Range on the western side. The case of Gap Creek is particularly noteworthy, as it rises in low hills within a mile of the Barrington River, but flows eastward by way of a deep and narrow gorge through the Gloucester Buckets into the Gloucester River.
The course of the Barrington River is of great interest. Between Berrico and Faulklands are a series of entrenched meanders, but at the latter locality the river turns sharply and flows northward, approximately parallel to the strike of the Carboniferous strata. Where the strike of these rocks swings round to the east in the vicinity of Barrington village the river continues northward for another mile and then turns sharply to the east. Farther downstream the river flows approximately parallel to the strike of the Devonian strata on the northern bank, but here its course is determined primarily by the presence of the Barrington River Fault. The reasons for the two abrupt changes of course are difficult to visualize, but that at Faulklands may have been caused by piracy of the head of the old river by a young stream cutting back along the strike from the north, the old river having previously flowed to the east, as is still the case with the Gloucester River.
IV. CONCLUSION.
The above notes are intended primarily to extend the work of previous investigators and to present some aspects of the stratigraphy and physiography of the Gloucester-Stratford district which have not previously been discussed. It is emphasized that the important Carboniferous sequence of the western side of the Stroud-Gloucester Trough, which has been the subject of much discussion is developed only within a comparatively limited area, and in particular is not found on the eastern side of the Trough in the neighbourhood of Gloucester.
V. ACKNOWLEDGEMENTS.
I wish to thank Dr. G. D. Osborne of Sydney University for his help during the field work and in the preparation of the paper, and Mr. and Mrs. J. BR. Ross of Gloucester for their hospitality.
VI. REFERENCES. | Browne, W. R., and Walkom, A. B., 1911. The Geology of the Eruptive and Associated Rocks of Pokolbin, N.S.W. THis JouRNAL, 45, 379. Carey, S. W., and Browne, W. R., 1938. Review of the Carboniferous Stratigraphy, Tectonics and Paleogeography of N.S.W. and Queensland. Tuis JouRNAL, 71, 591.
STRATIGRAPHY AND PHYSIOGRAPHY OF THE GLOUCESTER DISTRICT. 7
Osborne, G. D., 1922. Geology and Petrography of the Clarencetown-Paterson District. Part I. Proc. Linn. Soc. 46, 161. —— 1938. On Some Major Geological Faults North of Raymond Terrace and their Relation to the Structure of the Stroud-Gloucester Trough. Tuis JOURNAL, 71, 385. Sussmilch, C. A., 1921. The Geology of the Gloucester District of New South Wales. Tuis JOURNAL, 55, 234. Voisey, A. H., 1940. The Upper Paleozoic Rocks in the Country between the Manning and Karuah Rivers, New South Wales. Proc. Linn. Soc. N.S.W., 65, 192. ——___—_——— 1945. Correlation of Some Carboniferous Sections in New South Wales. Proc. Innn. Soc. N.S.W., 70, 34. Osborne, G. D., and Andrews, P. B., 1948. Structural Data for the Northern End of the Stroud- Gloucester Trough. THIs JOURNAL, 82, 202.
THE EFFECT OF DIFFUSIONAL PROCESSES ON THE RATE OF CORROSION.
By R. C. L. BOSWORTH, Ph.D., D.Sc., F.Inst.P.
Manuscript received, December 6, 1948. Read, April 6, 1949.
LIMITATIONS OF CORROSION TESTS.
Reviews of corrosion test procedure by White (1934), McKay and La Que (1937), La Que and Knapp (1945) and by others have stressed the necessity for a very close standardization of conditions. If measurements of the rate of loss of mass from a metal test piece in a given corrodant liquid are to be any guide to the behaviour of metal members under large-scale conditions, very close attention must be paid to a number of details, such as the depth of immersion, the methods of suspension or support and the conditions of aeration and circula- tion of the fluid ; as well as to such more obvious factors as the temperature and pH of the corrodant liquid and the presence or absence of other metals forming electro-chemical couples with the test specimen. White, indeed, has emphasized the difficulty in getting reproducible results even with different specimens of the same dimensions, and La Que and Knapp have stressed the necessity for a detailed evaluation of the proposed conditions of application in order that these may be duplicated as closely as possible in the laboratory tests.
The overall reaction of a metal dissolving in an electrolyte to give either a soluble or insoluble ionic product has long been recognized as a complicated one. Many successive physical and chemical operations are involved. Much attention has recently been given to some of these operations, especially those of a more chemical nature, such as interphase ionic transfer, anodic and cathodic polarization, and the effect thereon of inhibitors and accelerators. On the other hand the effect of the transport processes which bring the active depolarizing agent up to the seat of attack and remove therefrom the products of reaction has not received such close attention. It is clear, for example, that in the corrosion of copper by acetic acid in which the reaction is maintained by cathodic depolarization produced by dissolved oxygen, the maintenance of the chemical attack is dependent on the continuity of the supply of oxygen to the cathodic areas ; and it is conceivable that, under certain conditions, the rate of diffusion of oxygen might become a rate determining factor.
The conception of a set of physical transport phenomena entering into the final determination of the rate of chemical attack by a corrodant liquid is one which has been paralleled in recent years in other fields of applied chemistry. Thus Damkéhler (1936), Edgeworth Johnstone (1939), Laupichler (1938), Hurt (1945) and Bosworth (1947) have all discussed the effect of such factors as the flow of heat and flow of reactants and resultants on the course of chemical reactions in small and large scale reactors. Further, Agar and Hoar (1948) have discussed the effect of a change of scale on an electrochemical system and have concluded that the rate controlling step for a large scale system is not necessarily the same as for a small scale system under otherwise identical chemical and physical conditions.
EFFECT OF DIFFUSIONAL PROCESSES ON RATE OF CORROSION. 9
VARIABLES OF THE TRANSPORT PROCESS.
It appears desirable, therefore, to examine the process of corrosion with a view to enumerating and, if possible, devising methods of measuring the factors which are concerned in the transport of matter to and from the corroding surface. In this object there is one obvious mode of attack. Recently a number of authors (Sutton, 1934 ; Powell and Griffiths, 1939 ; Pasquill, 1943 ; and Boelter, Gordon and Griffin, 1946) have traced a degree of parallelism between heat loss and loss of matter by evaporation from geometrically similar bodies. Since it is not unreasonable to expect that matter loss from corroding bodies might also behave similarly, and further since the laws of conduction and convection of heat are particularly well known, the first object of this paper and of the two succeeding papers will be an attempt to trace a degree of parallelism between heat loss and matter loss by corrosion from geometrically similar bodies. This paper will be specifically concerned with transport under stagnant fluid conditions, analogous to the transport of heat in a fluid by thermal conductivity alone.
The corrosion rate g, in mass flow per unit area per unit time, and the corrosion cell e.m.f. H are, clearly, two of the properties with which we will be concerned. The quantity His the driving force which produces a flow of matter gq. While much has been discovered from purely electrochemical measurements concerning the mechanism whereby HL produces the matter flow q, we are not here immediately concerned with this subject. We are, however, concerned with the property which might be defined as the overall chemical resistance (or impedance) of the system—that is to say the factor which determines the magnitude of the driving force required to produce a given flow rate. Since various successive reactions are involved in the corrosion process, this overall resistance can presumably be spht into a number of series (or parallel) com- ponents, one corresponding to each step in the corrosion process ; in much the same way as the flow of heat in a multi-component system can be represented by a number of series (or parallel) thermal resistances. Among the factors contributing components to the overall chemical resistance are the transport processes leading to the removal of the anodic and cathodic products of corrosion from the immediate vicinity of the interface under attack. Removal may be effected by diffusion, turbulent diffusion, or by the convection currents set up either as a result of density changes produced by the solution of heavy metal ions, or from temperature changes. Since the mechanism of removal of the products of reaction controls the degree of polarization, it also controls the magnitude of the electric current across the metal-electrolyte interface and thus the rate of corrosion. The transport processes involved in the removal of matter from the vicinity of the interface bear a formal similarity to those exhibited by the heat loss from a hot body immersed in a fluid. Heat may be carried from such a body by molecular conduction, turbulent conduction, by forced convection if the fluid is stirred, or by natural convection.
Examples of corrosion in which an insoluble phase resulting from chemical reaction consequent to corrosion builds up a barrier to the diffusion process, or those in which the corrosion reaction is maintained by the presence of a bimetallic system providing a permanent cell e.m.f. obviously involve a transport mechanism which is more complicated than that involved in the flow of heat. However, when uniform, or general corrosion alone occurs, it would appear that the transport processes have features in common, and it is this suggested similarity which will be discussed below.
EXPERIMENTAL.
The subjects of experimentation were selected so as to avoid the more complicated types of corrosive attack. The subjects consisted of copper,
D
10 R. C. L. BOSWORTH.
certain copper alloys and steels in acetic acid-acetic anhydride mixtures. Com- mercial acetic acid has a high electrical resistivity of the order 1:5 x10-§ ohm-cems., and accordingly bimetallic corrosion is not serious. The acetates are soluble, and thus complications due to the formation of barriers are avoided. Further, experience has shown that these systems do not show the phenomenon of dezincification in which one component of an alloy selectively dissolves. The only type of corrosion is a general attack all over the surface exposed to the acid. Accordingly these systems are particularly suitable for the examination of the influence of convection on the process of corrosion.
The equipment used consisted of a cylindrical body C of the metal under test, 3 cms. in diameter and 1-8 cms. long. One flat face of this body contained a cylindrical hole 1-0 cm. in diameter and 0-8 cm. deep coaxial with the body as a whole. Into this hole there fitted snugly a second cylinder, B, of the same metal, the two top faces being coplanar. These two faces were polished together. Cylinder B was removed and weighed and then placed back in position. The air was pressed out through a hole at the back of C, and this hole was finally closed by means of a screw also of the same metal. A thin film of an acid-proof grease used for lubrication prevented the corrodant from coming into contact with any portion of B other than the front face. This equipment thus permitted a study of the attack on a definite area of a single metal face surrounded on all sides by a surface of the same metal, which thus acted as a guard ring and, by eliminating irregularities in the field of the corrodant at the edges, reduced the geometrical pattern of the flow of matter to and from the face under attack to one in a single dimension.
After subjection to the corrosive conditions for a measured time, cylinder B
was removed, the acid-proof grease was dissolved in a volatile solvent and the cylinder dried and weighed.
Fig. 1.
THE EFFECT OF ORIENTATION.
The equipment as described above was first used in a study of the effect of orientation on the rate of corrosion. An iron (mild steel) surface was immersed 4 ems. in a 60/40 acetic acid-acetic anhydride mixture and the rate of corrosion measured at different orientations as the face was turned in a vertical plane through 2x. The results are shown in the form of a vector diagram in Figure 1. In this diagram the 7 co-ordinate measures the rate of corrosion and the 0 co-ordinate the azimuth.
EFFECT OF DIFFUSIONAL PROCESSES ON RATE OF CORROSION. chal!
It will be seen from the figure that the rate of loss of matter is a minimum when the corroding surface is facing upwards and a maximum when facing downwards. Evans and Mears (1934) have already remarked on the flow of heavy metal salt solution under gravity away from all surfaces except those facing vertically upwards. This flow constitutes a convection current opposite in direction, but essentially similar in nature, to the convection currents surrounding a hot body in a fluid. Thus it is seen from Figure 1 that the corrosion rate is 4 maximum when the convection current is most intense and @ minimum when there is no convection and when the loss of matter takes place entirely by a ‘“‘ conductive ”’ mechanism.
In taking measurements of the corrosion rate with all transport processes restricted to those of the ‘“‘ conductive ”’ type, it is of importance to be able to estimate the error involved in any slight departure of the surface from the horizontal position—say by an angle 0. Since the top of Figure 1 is flat, it follows that the error is of the order q/cos 0 or q(1 +67), where q is the measured rate. Errors of magnitude sensible in comparison with the random errors usual even in the best corrosion measurements are thus not incurred unless 9 is greater than 0-2 radian or 12°, which quantity is thus a measure of the tolerance allowed on the orientation.
EFFECT OF VARYING THE DEPTH OF IMMERSION.
The property of thermal conductivity plays a large part in all successful attempts at the co-ordination of experimental determinations on the rate of conductive and convective transfer of heat. If a similar co-ordination of the effects of convection on the corrosive transfer of matter is to be attempted, it is
B
important to find that property concerned with the transport processes involved in corrosion which plays the same part as thermal conductivity does to heat flow in fluids. Such a property could be measured by an adaption of the guard- ring method of measuring thermal conductivity. If we set up the equipment, described in the section above, horizontally at a distance z below a free surface, we will effectively be concerned with one-dimensional diffusion through a distance z, the depolarizing agent (atmospheric oxygen) having to travel that distance through a stagnant layer of the corrodant liquid.
In Figure 2, let A represent the free surface of the corrodant and B and C respectively the surface under attack and the guard-ring both at a distance 2 from the free surface and parallel to it. We are concerned with a flow of matter
12 R. C. L. BOSWORTH.
from B to the liquid ; the flow, on account of the influence of the guard-ring, being normal to the surface. This flow, the magnitude q of which may be measured by weighing the central cylinder before and after a measured time interval, is stoichiometrically connected with all chemical steps in the corrosion reaction. One of these steps is the ‘‘ conductive ”’ flow of the depolarizing agent through a distance z. The magnitude of q therefore might be expected to vary with z in the same way as the flow of heat from a geometrically similar hot plate separated from another plate, at a temperature difference 0 from the former, by a convectionless thermal conductor of conductivity kg. In such a thermal system the heat flow qo per unit area per unit time is related to 0 by an equation :
uae i= Q° If dqg is the heat flow change associated with a change dz in the thickness of the thermal conductor, we have A nae ke =~ ee ceca wie tne pee ae 1 9 aja) a
In the mass flow system involved in the corrosion process we may readily measure the change in the rate of corrosion (dq), in units of mass crossing unit area in unit time, produced by a change dz in the length of the path through which the depolarizing agent is conducted. In this system now we may define a corresponding conductivity term ke by means of an expression analogous to equation (1), viz.
I dz = = 7 ailvty pleut. @ ae! (eo: @ ap esse fe o& Te ce. We) oie tenis nen ele. ere 2 where by H is to be understood the overall driving force for the corrosion reaction, or the corrosion cell e.m.f.
If for a given system k, is a constant, or if in other words the system follows a law analogous to Fourier’s law, then we expect to get a straight line when the depth z is plotted against the reciprocal of the rate of corrosion (1/q). Experi- mental data obtained on the guard-ring equipment are represented in Figures 3 and 4, where 1000/q is plotted against 2 for the different systems studied. The experiments were conducted in a thermostat at two different temperatures, namely 20°C. and 70°C. The 1/q versus z lines are straight, but do not pass through the origin. Each system may thus be described by two constants ; the intercepts 1/q, on the 1/¢ axes which incidentally are always positive, and
dz the slopes (zara) , which we shall denote hereunder by the symbol j7. We
see, therefore, that the process of transport of matter involved in a corrosion reaction taking place under ‘‘ conductive ”’ conditions involves two properties of the system, 7 and q. The significance of these properties will be discussed below, but first it is desirable to consider the units in which these quantities are to be measured and the magnitude of these properties for typical systems.
UNITS.
Many problems connected with the transport of matter and of heat which are too complicated for a complete mathematical treatment have been successfully treated by the use of dimensionless quantities. In order to combine the quantities connected with the transport phenomena concerned with corrosion, it is first necessary to use a consistent set of units throughout. The various phenomena involved can be reduced to four fundamental dimensions. Now q the rate of corrosion is, in the technical literature, commonly measured in units
EFFECT OF DIFFUSIONAL PROCESSES ON RATE OF CORROSION. LS
of milligrammes decimetres~? days—1, while H, the corrosion cell e.m.f., is com- monly measured in volts. We shall accordingly take for our four fundamental units the quantities, decimetres, milligrammes, days and volts. Thus the quantity j above is to be measured in milligrammes decimetres-! days-}, while k, is to be measured in milligrammes decimetres~! days—! volts—1.
The units in which the other properties of importance are to be measured will be given later. For convenience this system of units will be referred to as the d.m.d.v. system.
RESULTS.
The experimental results calculated from the lines shown in Figures 3 and 4 are tabulated in Table 1. For each system and temperature studied the two properties j and q, are recorded, each of course, in d.m.d.v. units.
TABLE 1. Reciprocal
| Slope j Intercept q
Metal. Corrodant. |Temperature.| Milligrammes | Milligrammes
| ie dim. dayiet.. |) dima day. 4. Copper. | Acetic anhydride .. | 202 at 9-6 | 51 _ 60/40 acetic acid/acetic anhydride a | 10-5 | 125 Glacial acetic acid ee | 13-8 150 5s 50% aqueous acetic acid aa 3 | 6-0 | 97 - 50/50 acetic acid/benzene ed 195 | 405 5 60/40 acetic acid/acetic anhydride USS OF 0h 190 2000 a Glacial acetic acid cs | 710 | 2000 Brass. Acetic anhydride .. 20° C. 1-6 | 71 e 60/40 acetic acid/acetic anhydride | os 6-2 | 66 b 50% aqueous acetic acid. ie | oe 70 Phosphor | 60/40 acetic acid/acetic anhydride 202 Cx ‘182 | 135 bronze. Glacial acetic acid | As | 20-0 | 130 oS 50% aqueous acetic acid he ‘5 | 16-0 100 Be Glacial acetic acid sins ay On Ce P| 660 | 1050 Mild steel. | 60/40 acetic acid/acetic meee | 20cC, «| 52-0 1000 3 Glacial acetic acid | : | 62-0 950
DISCUSSION.
The lines represented on Figures 3 and 4 relating the variation of the rate of corrosion with the depth can be put in the form
Gy Gory J A similar expression would have been given for the heat loss across a thermal conductor of various thickness from a hot body, which however is not bare but thermally lagged so that the rate of heat loss can never exceed a certain figure. The property 7 is related to the correction conductivity ke by the expression
j=Ek, Shisteolncmell eitomed ieveticitelies (op ss side fey ot ocbho!).6y foype (4)
and is more convenient than ke because the quantity H is not directly concerned in corrosion measurements. The quantity 7 is a measure of the conductivity of the corrodant for the depolarizing agent and is thus a measure of a sensitivity of
14 R. C. L. BOSWORTH.
the reaction concerned to control through limiting the supply of depolarizing agent. <A reaction giving a small 7 such as brass in acetic anhydride is strongly dependant on the supply of atmospheric oxygen.
The quantity gq, is a measure of the rate of corrosion when the depolarizing agent is made instantly available at the surface and is thus a quantity of more direct chemical significance than measures of g under any standard conditions of
100
LECEVO O ACETIC ANAVORIDE © 6040 47 At/0/ atl, LDRIDE @Q SOL 4QUEOUS ACETIC JACIO
BEASS /M. (a ae
{| A ACETIC =ANAYORIOE 1) 6040 ACETIC C10) HH YORIOE © GLACIAL ACETIC A A SOL 4006005 AEETIC ACID
75
7, —
- 505 AQUEDWS/ACETIC ACID « 60/40 ACETIE AWO/APHYDRIDOE -t- GLACIAL ACAIIC ACO
LY BEONZEIA COPPER JA a
! '
|
AL AT KEOE
O-2 0-3 O-4. DEPTA OE, (2S)
Fig. 3.
immersion or aeration. The ratio H/q, is a measure of the resistive force opposing the corrosion process when the effect of all physical factors limiting the supply of the depolarizing agent to the surface have been eliminated. If we denote this resistance by 1, Viz.
et Oy PUNT AC Ie DO NIERY ON) oy (5)
We then have, for the net driving force available for maintaining the transport of depolarizing agent to the surface under attack when the specimen is corroding at a rate q,
E—gqr or E(1—q/q) volts.
EFFECT OF DIFFUSIONAL PROCESSES ON RATE OF CORROSION. 15
This is the factor with which we will be concerned in treating the more com- plicated phenomena concerned with transport processes involving forced and natural convection.
SUMMARY.
The influence of the processes involving the transport of matter on the rate of corrosion has been studied by means of a circular dise protected by a guard-ring. This device reduced the geometrical nature of the flow of matter to one in a single dimension. The variation of the corrosion rate of such a surface was
JO
LEGEND. COPPER IN GLACIAL ACETIC ACID AT 7O°C.
+ COPPER I 60/40 ACID/ANWYORIDE WT .7O°C.
X COPPER I $050 BENZENE / ACETIC AC1O 47 2O° C.
arias —e—' DYVOSPHOR BRONZE S14 GLACIAL 4 ACETIC ACIO AT 7O°C.
O MLD STEEL I GLACIAL ACETIC ALD AT 20°C,
© 0 STEEL WY 60f4O ACIOY” 4MHYORIDE AT 20°C.
x + | moe © 0:3 0-4
DELI GOS)
Fig. 4.
studied as a function of the orientation of the surface and shown to be @ minimum when it faced upwards. It was concluded that convective transfer was absent under these conditions. The corrosion rate, from a horizontal surface facing upwards and protected by an electro-chemical guard-ring, was then studied as a function of the depth of immersion.
The systems studied included copper, copper alloys and steel in acetic acid, acetic anhydride mixtures. Experimental results plotted in the form : reciprocal
16 R. C. L. BOSWORTH.
of the corrosion rate (1/q) versus the depth (z) of immersion give straight lines with positive intercepts on the 1/q axis. These intercepts have been interpreted as a measure of the rate of corrosion under such conditions that the depolarizing agent (atmospheric oxygen) is made freely available at the surface. The slopes have been interpreted as a measure of the ‘‘ conductivity ”’ of the corrodant for the depolarizing agent, a factor which, it is suggested, would be of primary importance in the interpretation of the effect of convection of the rate of corrosion.
ACKNOWLEDGEMENTS.
The author is indebted to the Management of the Colonial Sugar Refining Company of Sydney, Australia, for permission to publish this work.
REFERENCES.
Agar, J. N., and Hoar, T. P., 1948. Trans. Farad. Soc.
Boelter, L. M. K., Gordon, H. 8., and Griffen, J. R., 1946. Ind. Eng. Chem., 28, 596-600. Bosworth, R. C. L., 1947. Tuis Journat, 81, 15-23; Trans. Farad. Soc. 43, 399-406. Damkohler, G., 1936. | Zeits. Electrochem., 42, 846-862.
Edgeworth Johnstone, R., 1939. Trans. Inst. Chem. Engrs. (London), 17, 129-136.
Evans, U. R., and Mears, R. B., 1934. Proc. Roy. Soc. A 146, 153-165.
Hurt, D. M., 1943. Ind. Eng. Chem., 35, 522-528.
La Que, F. L., and Knapp, B. B., 1945. ‘* Corrosion and Material Protection,” 2 No. 1, 17-23. Laupichler, F. G., 1938. Ind. Eng. Chem., 30, 578-586.
McKay, R. J., and La Que, F. L., 1937. A.S.T.M. Symposium on Corrosion Testing Procedure, 87 Pasquill, F., 1943. Proc. Roy. Soc., A 182, 75-95.
Powell, R. W., and Griffiths, E., 1939. Trans. Inst. Chem. Engrs. (London), 36, 125-1438. Sutton, W. G. L., 1934. Proc. Roy. Soc., A 146, 701-722.
White, A. S., 1934. Industrial Chemist, 10, 98-101.
The Research Department, C.S.R. Co., John Street, Pyrmont, N.S.W., Australia.
THE INFLUENCE OF FORCED CONVECTION ON THE PROCESS OF CORROSION.
By R. C. L. BOSworRTH, Ph.D., D.Sc., F.Inst.P.
Manuscript received, December 12, 1948. Read, April 6, 1949.
INTRODUCTION.
That the phenomena occurring at the interface between a fluid electrolyte and an electrode, usually solid, can be influenced by the mechanism available for the transport of ions in the fluid has been recognized since the days of Nernst (1904). Nernst introduced the concept of a diffusion layer as that of a quiescent fluid zone of definite thickness across which matter may be transferred only by molecular conduction and in which no convection currents occur. The bulk of the fluid outside the diffusion layer is assumed to be so well stirred up by convection as to be effectively at uniform concentration. It then follows that the rate of transfer to the interface is governed by the product of the concentra- tion difference across the diffusion layer, the diffusivity in the layer and the reciprocal of the thickness of the layer. Since the diffusivity is a specific property of the system concerned the diffusion layer thickness is the property which determines the influence of concentration difference on the rate of transfer.
The Nernst concept of a diffusion layer has been extended by Levich (1942, 1944, 1947) to that of a diffusion boundary layer defined by analogy with the boundary layers of hydrodynamics and of thermal convection. Agar (1947) has used this concept of a diffusion boundary layer treated as a Nernst diffusion layer in order to estimate the influence of the current density on overvoltage, and has applied his figures specifically to the deposition of iodine. His method is based on an assumed analogy between matter flow and heat flow both under conditions of natural convection and the final figures he obtains supports his initial assumptions. He makes no use of the analogy other than that of deter- mining boundary layer thicknesses and associated properties.
In a series of measurements on the rate of transfer of metal ions from solid metal to liquid electrolyte—or measurements of the rate of corrosion of certain metals by acids—under such conditions that all convection currents could reasonably be presumed to have been eliminated, the author (Bosworth, 1949) was led to infer a possible analogy between corrosive matter loss and convective heat loss from a lagged hot body geometrically similar to the one undergoing corrosion. It is clear that if this analogy could further be developed it would yield information on other properties concerned in the transport of matter as well as the diffusion boundary layer thickness. This, and the succeeding paper, will describe attempts to study the behaviour of corroding bodies under regulated conditions of forced and natural convection by the same method as that which has proved so successful in heat transfer problems; namely by the use of dimensionless quantities analogous to the Nusselt, Prandtl, Peclet and Grashof numbers.
THE TABLE OF ANALOGOUS PROPERTIES.
Table 1 below gives, on the left-hand side, a list of the properties and their units used in the treatment of forced and natural convection from a cylindrical E
R. C. L. BOSWORTH.
18
*;Aep ,UIp —
"7-90
"t-FOA 7-91] “SULIdUI
*;-O1pT] “SULISUT
*; OTP] “SUIISUT |
*,Sep “wip
*;Aep ;_‘uIp ‘sulidul
*;Aep “suLIsUr ‘sup *“suIp “1-4 OA ;-Aep ;_—‘Ulp ‘suidur "1-FOA ;-Aep ,-‘UIp ‘suTIsUL
‘SJOA | *;Aep ,_‘uIp ‘suIsun -;-Aep ,-‘UIp ‘SULISUZ |
910)
‘joquiAg
qgueporii00 jo AqtAIsnyyiq
‘Agrun Aq W_ osueyo
0} peramber oumnjoA yun | dod yuepori0o jo Aqquenty
‘euINjOA yun aod FUBPOIIOS FO Aqriyuen?y Ayisueqd
Aqaeis 09 ONp WoIyBIE]OOOV
: AYISOOST A, MOP jo o7BI sseyl
acn6G Surpo1109 jo y4sueT Apoq Surpoi109 Jo 10youreIGq
cere “TULA [[90 OATZOOTA (** 998i WOTSOII00 SuUTqTULI'T a 0481 UWOISOIIO(
‘Aqyrodoig
‘UOISOLION YIM poyoouuo0y sormazsdoig
‘7-008 ,“SUl0
come) fe}
t= Ove, c= UO s[B0
“ga "UO “STO *. "SUID “SUI
2°) o 1 Us “spo
',"008 “SUID ‘sostod *;008 ‘SsuLIS "suo "suo "1-0 o 1-908 jw “s[B@o 1T="0 o 1-988 g—"Wd “Ss[TBo 0 o
*;-'008 ,‘UIO ‘ST@O
910)
‘| @Iavy,
ge o_ QT y dd5 Qddo d dg (186)4 bu i | p 4 Y 0 Bb ‘joquikg
AYIATJONPUOD O1IZOWULOWIOY J,
uoisued xe
dYJOUINJOA Jo yuUETLoyyzooD
Aytoedeo yeoy o1aqournjo, “eUINJOA
qrun rod yeou jo Aqqueny
Aqisuog
(d -ysuog) Aqtoedvo yeoFT
Ayners 04 enp U0TZBIO[OIOV
AYISOOSTA
MOP JO O9B1 SSBI
Apoq yoy jo y4sue'T
Apoq yoy jo Joyowig ©
AyLatgonpuood [eUIoyT,
eoueyqIUISsUBL, eousIeyIp orngesodurey,
XN] 70H
*Aqyaodoig
‘sorytodoig [BULIOU,y,
INFLUENCE OF FORCED CONVECTION ON PROCESS OF CORROSION. 19
body. On the right-hand side the corresponding properties associated with the flow of the depolarizing agent to a corroding body are given with their units and suggested symbols. The units have been selected in such a way as to be con- sistent with the usual technical measurements of qg (the rate of corrosion) in milligrammes decimetres~? days—! or 8-64 x10° C.G.S. units. H (the corrosion cell e.m.f.) in volts has been taken as defining the fourth fundamental unit in this system. The complete set of corrosion properties will thus be measured in decimetres, milligrammes, days and volts or in d.m.d.v. units.
Two new quantities are introduced in this table, namely K and &, the former defined by
and the latter by
K is thus a measure of the capacity of the system for the corrodant, or the quantity in solution required to change the overall cell e.m.f. by one volt; and E, a dimensionless quantity, is defined as the change in density produced by unit change in the concentration of the corrodant. The diffusivity term D, is simply defined by analogy with the thermometric conductivity or thermal diffusivity.
EXPERIMENTAL MEASUREMENTS ON FORCED CONVECTION.
In these experiments the body of the metal corroded took the form of a cylindrical tube, being part of a pipe system through which the corrodant flowed at a measured rate. The test piece fitted flush into glass pipes of the same diameter so that no eddies were created by any discontinuity in the rate or direction of flow. The test piece was weighed before and after a measured time interval during which the flow rate (I’) has been maintained constant. From a series of such measurements on any one tube, g could be measured as a function of I’. Various tubes of copper, brass, phosphor bronze and mild steel of different lengths and diameters were used. The resultant g versus I’ curves were all of the same form. Very low rates of flow produced no increase in the rate of corrosion. Further increase in the flow rate resulted in a sharp increase in the rate of corrosion, but at still higher flow rates the rate of corrosion again became independent of the rate of flow. An increase in corrosion rate with flow rate has been recorded by Hatch and Rice (1945). In all the examples studied the velocity of flow required to give practically a stationary final corrosion rate were well within the region of laminar flow. Figure 1 gives some illustrative results obtained in the study of corrosion of a mild steel tube 10-0 cms. long and 0-33 cm. internal diameter, by a 60/40 acetic acid acetic anhydride mixture ; and Figure 2 similar results from a copper tube 15-6 ems. long and 0-454 em. internal diameter, both at 20°C. The group of curves shown in Figure 3 refer to the corrosion of copper tubes of the various lengths and diameters indicated on the legend, exposed to a 50% aqueous acetic acid solution. The tubes were prepared from a given batch of copper and were given an identical heat treatment and finally quenched in alcohol just before use. The corrosion rates for very fast and very slow rates of flow were independent of the diameters of the tubes. At inter- mediate rates the shorter and finer tubes corroded relatively faster than the longer and wider ones.
THE PROBLEM OF HEAT LOSS UNDER FORCED CONVECTION. The problem of the change in heat transmittance (h) with change in the velocity of flow in a pipe has been subject to considerable study and experi- mental results have been co-ordinated by means of dimensionless quantities.
R. OLA BOSWORTH.
20
=f
fo MGKMS SEC -
’
s FLOW RATE
- é Esese
/- Ard 2- Ne SWNIIW A/ TLEY NOS CFYOI
Pigs:
-WT
ELVA IDL’
77
SLY
NOV SOSY/ OID
IN
Fig. 2.
INFLUENCE OF FORCED CONVECTION ON PROCESS OF CORROSION, 21
For heat transference in the region of laminar flow McAdams (1942) gives the
expression
1/3 0-14
ey, on (22) 4) Poe Nila ik eS (3) ko kl Yw
where 7 is the viscosity of the fluid in the centre of the pipe and yy that at the
400
700
\ \ ° § " 2 OO k y § ty : N LEGEND. RK © @:0.027. ([+/:0 w 100 a ed 201057 (27-6 y © @: 0.02; Cl: 4-0 © 4-0-0845, ¢:/. 56. g ALL I) DECIMETERS. : & Ni
20 | “AO 30, FLOW RATE "f MGRYS SeCHW/ Fig. 3.
walls. The other symbols have the meanings outlined in Table 1. When convection is transporting not heat but the soluble products of corrosion there is no reason why the viscosity at the walls should be significantly different from that at the centre of the pipe. Equation (3) transposed to quantities concerned with corrosion will therefore take the form
gd aoe 1/3 ——=—_—. = 2°01] —— J] Hn... ce cee ee 4 j(1—4/%) jlo o
22 R. C. L. BOSWORTH.
where the symbols again have the meanings given in Table 1. Equation (4) may be rewritten as
1 1 dl 1/3 0 1/3 anearnien -498(") (xs)
LEGLIVD,
O MLD STEEL IW 60/40 ACID/AMHID | O COMER WY 60/40 ACID/ANHYO. ® PHOSPHOR IEE 7 60/40 Bee ye ad Se LE AQUEOUS
) ACETIC ACID @ 2455 WW 60/40 ACIDS AYA YO
12
a oe a Oe
Fig. 4.
INFLUENCE OF FORCED CONVECTION ON PROCESS OF CORROSION. 23
So that experimental results may therefore be fitted to this equation by plotting 3
\ 1/3 1/q versus 4 The results treated in this way are shown in Figure 4.
The experimental points for each system studied lie on a straight line, giving a positive intercept on the 1/q axis. The slopes of these lines are a measure of the
quantity ( an) Thus we have
a0,
9 \Hs (cea) eee nae) 13 a
=16-1 d.m.d.v. units (copper in 60/40 acetic acid-acetic anhydride).
=29-1 d.m.d.v. units (copper in 50% aqueous acetic).
=3-32 d.m.d.v. units (mild steel in 60/40 acetic acid- anhydride).
=7:44 d.m.d.v. units (phosphor bronze in 60/40 acetic acid- anhydride).
=26-1 d.m.d.v. units (brass in 60/40 acetic acid-anhydride).
The values of the densities p in d.m.d.v. units are :
1-056 x10° for 50% aqueous acetic acid and 1-060 x10° for 60/40 acetic acid acetic anhydride.
Using the values of 7 from the earlier paper, we may now compute the values of the product K# for the five examples above. An independent measurement of # (from over-voltage measurements or from the Gibbs’ free energy of the corrosion reaction) is necessary before we can derive the values of the capacity terms K. However, for many purposes the product K# is all that is required. Thus the coefficient of diffusion D. of the depolarizing agent is related to 7 and KH by the expression
De J decimetres? day~!
WEE —1-16 x10-? _ ems.? sec.-1. KE Values of KH and D. computed from the figures above are given in Table 2. TABLE 2, De in | KE in - Metal. Corrodant. dain. dix, Units. d.m.d.v. C.G.S. Units. Units. Copper .. .. | 50% aqueous acetic. 1-20 5:0 0-0058 Copper .. .. | 60/40 acetic acid-acetic an- 2-3 4-6 0:0053 hydride. Mild steel .. | 60/40 acetic acid-acetic an- 10:8 4-8 0-0056 hydride. Brass a .. | 60/40 acetic acid-acetic an- 1:5 4-] 0-0048 hydride. Phosphor bronze | 60/40 acetic acid-acetic an- 4-2 4-3 0-0050 hydride.
24 R. C. L. BOSWORTH.
It will be observed from this table that whereas the values of KE vary practically over a tenfold range the values of the diffusivities are, within the limits of an experimental error accentuated by the act of cubing, constant. It therefore appears that these observations lend support to a suggestion that the same depolarizing agent is concerned in all these cases. The absolute magnitude of the diffusion coefficient is considerably higher than those usually given by liquid systems. Thus Sherwood (1937) claims that the diffusivities of most organic and inorganic matter in liquids lie between 0-3 and 1-5 x10—° cms.? sece.—}, or about 3x10-? of the figures estimated above for the diffusivity of the depolarizing agent.
SUMMARY.
The rate of corrosion of metal tubes through which a corrodant liquid is caused to flow has been measured as a function of the rate of flow. The rate of corrosion increases as the flow rate increases but becomes practically stationary when the rate of flow is still quite low.
The variation of the rate of loss of matter with the rate of flow takes the same form as that for the rate of loss of heat from a geometrically similar lagged hot pipe through which a conducting fluid is caused to flow.
The diffusivity of the depolarizing agent, defined as an expression analogous to the thermometric conductivity, proves to be the same for all metals and corrodants studied, and is of the order 5 x10-% cms.? see.-1.
A table is given showing the properties concerned in the convective loss of heat together with the corresponding terms involved in the convective transfer of matter concerned in the process of corrosion.
REFERENCES.
Agar, J. N., 1947. Farad. Soc. Discussion, 1, 26-37. Bosworth, R. C. L., 1949. THis JouRNAL, 83, 8. Hatch, G. B., and Rice, O., 1945. Ind. Hng. Chem., 37, 752-759. Levich, B., 1942. Acta Phystochem., 17, 257. 1944. Ibid., 19, 117. 1947. Farad. Soc. Discussion, 1, 37-43. McAdams, W. H., 1942. Heat Transmission, p. 190. McGraw Hill, New York. Nernst, W., 1904. Z. Physik. Chem., 47, 52. Sherwood, T. K., 1937. Absorption and Extraction. McGraw Hill, New York.
THE INFLUENCE OF NATURAL CONVECTION ON THE PROCESS OF CORROSION.
By R. C. L. BOSWORTH, Ph.D., D.Sc., F.Inst.P.
Manuscript received, December 6, 1948, Read, April 6, 1949,
INTRODUCTION.
Two earlier papers (Bosworth, 1949a, 1949b) have traced a degree of © parallelism between heat loss by conduction and convection and matter loss by corrosion under conditions of forced convection and in circumstances in which all convection currents have been eliminated by the use of guard rings. The present paper extends this study to the consideration of natural convective losses from cylindrical bodies placed horizontally in a corrodant liquid. The convective heat loss from cylindrical bodies such as hot wires or steam pipes immersed in fluids has, on account of its economic importance, been subject to very considerable detailed examination. A fairly complete review of the findings in this field have been given by Lander (1942). For convective heat loss from horizontal cylinders the emittance q is related to the other physical variables by means of the dimensionless equation
gd —7(Eee cp B ) kO nk where the symbols have the meanings given in Table 1 of the previous paper (Bosworth, 1949b) and F( ) is a function which has been determined experi- mentally.
The methods of correlating experimental data expressed by means of equation (1) have been extended by analogy with the problems of the convective loss of matter by evaporation. Thus Sutton (1934), Powell and Griffiths (1939) and Pasquill (1943) have shown that losses by evaporation follows laws analogous to the loss of heat from similarly shaped hot bodies. The convective loss by corrosion, in a8 much as the rate is controlled by the conveyance of the active constituent to the surface and the removal of the products of reaction by con- vective currents set up as a result of the density changes produced by the reaction, appears to be quite analogous to the convective loss of water by evaporation with the simple difference that the convective current now flows downwards past the corroding body. If we transpose equation (1) over to properties concerned with corrosion according to Table 1 of the previous paper (Bosworth, 1949b) we get
Gd tes ( d3g&K2E? (2) jd 9/5) nj —9/4) 1G) OO. 0: 6 Ore) ai) 6) et 6 eis 8 8.6 oz 6.6.0 had EXPERIMENTAL.
The validity of equation (2) has been tested experimentally by placing a number of cylinders of different metals and different diameters in a horizontal position at a given depth (2 ems.) below the free surface of different corrodant liquids in such a way that the cylindrical and not the end faces could be attacked. After standing in a thermostat for a given time, ranging from 24 to 168 hours, the samples were removed and weighed and the corrosion rates (q) determined. The metals investigated included deoxidized copper, mild steel, phosphor bronze and a brass (37% Zn, 63% Cu).
ti
26 R. C. L. BOSWORTH.
Of the various factors which occur in equation (2), the values of j (the corrosion conductivity) and gq, (the maximum corrosion rate) have been deter- mined by experiments on the guard ring equipment (Bosworth, 1949a). The product K# has likewise been determined (for the systems studied) by measure- ments under conditions of forced convection (Bosworth, 1949b). Figures for y, the viscosity of the corrodant medium, are readily available, so that there remains only the quantity € to be determined before equation (2) may be put to an experimental test. This factor may be computed from observations of the density of the corrodant before and after a given quantity of each metal has been dissolved in a known volume. Samples of the corrodant were therefore collected after various measured masses of each metal had dissolved in a known volume and their densities were determined by pyknometer measurements in a constant temperature room.
RESULTS.
The results obtained from the study of corrosion from horizontal cylinders are summarized in Figure 1, in which the corrosion rates for various metals, in each of a number of selected corrodants at 20° and 70°, are plotted against the
\| |) ia
Se
, (rs).
BIA METER
»
CORROSION RATE
COPPER IN 60/40 ACETIC Ac/iO/ 4. COPPER WN GLACIAL ACETIC ACIO VT.
© AHN YORIDE AT 20°C. P1140 STEEL IN 60/40 ACETIC 70° C9 Lo, AT HALE SCH, is is O 4D SINNYORIDE Ted GY <CkOmATES Lk SCALE ) PP, ‘f7 WEOUS LIVE © Ge ar bee pad sacs dea? BRASS (IN GLACIAL ACETIC ACIO AT Wipe SA eels $s % 70°C (9 COORDINATES 47 HALF ICALE) A eras eee, GLACIAL (ACETIC ACID mao. g PHOSPHOR BRONZE (NW 60/40 ACETIC Te) in 50, OUS o AE fd Ber tae 9 ACID) ANHYORIDE AT 20° C.
COPPER iw S0f$0 ACETIC ACIo/ © SEAZENE AT’ ZO0°e
Bigs 1.
diameter of the specimen. In order to present as much data as possible on the one graph the scale for the q (or corrosion rate) axis referring to measurements at 70° C. is half that used for the measurements at 20° C.
It will be observed from the figure that for those systems in which the corrosive action is comparatively mild the rate of corrosion (in units of mass lost per unit area per unit time) varies only slightly with the diameter, and varies in such a way that the rate is somewhat faster for the smaller specimens. For
ODEN S/F Y¥
INFLUENCE OF NATURAL CONVECTION ON PROCESS OF CORROSION. 27
systems in which the corrosion rate is faster, such as mild steel at 20°C. or the copper alloys at 70° C., the variation of g with d (the diameter) is much more pronounced, so much so that for these systems the product qd (or the mass loss per unit length per unit time) is practically a constant. The one system examined with a very large value of 7 at room temperature (namely copper in 50% acetic acid 50% benzene) also gave a big variation of q with d, but one in the opposite direction, i.e. one in which the larger specimens corroded relatively faster than the smaller.
1070
ANH YORIDE.
=
=o sno ©
LEGESYD.
OC) BRASS + COPPER
O WD STEEL
® PHOSPHOK BROPMZE.
-000 *OO7 "OC28. CON CEN TRAFIO/T
Fig. 2.
The dimensionless quantity € referred to above is defined as the ratio of the density change produced to the concentration of corroded metal measured in units of mass per unit volume of corrodant. While some water was formed during the corrosion action, represented chemically by
M+2HAc+40,=MAc,+H,0, where M represents any divalent metal; the corrodants examined were hydro- Scopic in nature and care was necessary in order to prevent the condensation of additional water from the atmosphere with consequent dilution of the corrodant.
Figure 2 shows densities plotted against the concentrations for some of the FF
28 R. C. L. BOSWORTH.
systems studied. It will be seen that the different metals and alloys studied do not give significantly different results with respect to this property. The different fluids tested do however behave differently, the lower the density of the fluid the more pronounced the density change produced by dissolving a given small quantity of metalin it. The values of & from Figure 2, with the associated values of po, the original densities of the corrodants, are given in Table 1.
TABLE 1. Corrodant. Density o. ae Acetic anhydride ag 1-0674 Orig, 60/40 acetic acid- acetic. anhydride a 1-0602 Lhe) 50% aqueous acetic acid ; Se 1-0568 2:0 Glacial acetic acid 1g - ae 1-0524 3:0 50/50 acetic acid-benzene S we 0-9475 12-0
CORRELATION OF RESULTS ON NATURAL CONVECTION.
We have now found, in the case of four of the systems studied, all the data necessary in order to compute the magnitude of both of the dimensionless quantities in equation (2). These systems are: copper in 50% aqueous acetic acid, and copper, mild steel, brass and bronze in the 60/40 acetic acid —acetic anhydride mixture. In Figure 3 the data for these systems, each represented by distinctive points, are shown plotted as
qa log ———_ = (1 —4/40)
3 2 fi2 og ais. = :
nj (1 —4/4)
The full line shown on the figure is the curve for the corresponding dimensionless quantities involved in the loss of heat from horizontal cylinders by natural convection. This curve was taken from the paper by Lander (1942). The excellent agreement between the points, for the corrosive loss of matter by natural convection; and the curve, for the loss of heat from geometrically similar bodies by thermal convection, is a very clear indication that the phenomena involved are similar and the process which removes the products of corrosion from a surface and brings a continuous supply of the depolarizing agent is essentially the same as that involved in the removal of heat by the natural convection currents.
Data for correlation of all the curves shown on Figure 1 in terms of the dimensionless quantities shown in Figure 3 are not yet complete, mainly because sufficient independent values of KH are not available. However, if we assume that corrosion data would follow the heat convection curve over a wider range than shown above we may make certain interesting deductions the implications of which will be examined in a following paper. It has been shown that, for higher temperature corrosion, the product qd is practically a constant. In heat flow problems the corresponding quantity also becomes practically constant when the right-hand side of equation (1) is made less than about 10-4 (Bosworth, 1944). We conclude, then, that the condition gqd=a constant in a corrosion problem means that the right-hand side of equation (2) is very small. This might be effected, for example, by the value of K decreasing with increase in temperature, a fact which becomes significant when an attempt is made to interpret K in terms of the physical and chemical properties of the solution.
versus
INFLUENCE OF NATURAL CONVECTION ON PROCESS OF CORROSION. 29
CONCLUSIONS.
As a result of the study of mild stee Jand copper alloys in acetic acid and acetic anhydride mixtures under such physical conditions that the removal of the products of reaction from the corroding surface takes place in a closely defined manner, it is concluded that an analogy may be set up between the rate of matter loss by corrosion on the one hand and the rate of heat loss from a lagged hot body on the other. Further, when the physical variables concerned with each phenomena are expressed as dimensionless products corresponding to the Nusselt number and the product of the Grashof and the Prandtl numbers respectively, the same function expresses the relationship between the parallel sets of dimensionless products applying to both phenomena.
LEGLE/YD. QD COPPER 17 6040 ACETIC AC ANNYDHIDE Q COPPER 1 50%. AQUEOUS ACETIC ALD
©) MO STEFL IN 6040 Ab10/ APH YORIDE O BRASS iV 60/40 AC1Of AMM YDNIOE. © HoSPHI BRONZE IN bofto ACI ann YOR
This result suggests that a method for estimating the behaviour of large- scale metal members subject to corrosion could be established by setting up ah appropriate thermal model. However, it must be emphasized that the principles as developed in these three papers apply at the moment only to a restricted field of corrosion problems—namely to those in which bimetallic corrosion cells are absent and in which the products of corrosion do not form insoluble films and thus give rise to a type of restriction to the flow of matter, of which a counterpart is not realized in the convective flow of heat.
SUMMARY.
_ The corrosive loss of matter from a metal cylinder immersed horizontally in a corrodant liquid at a constant temperature has been measured for a number
30 R. C. L. BOSWORTH.
of specimens of different diameters. The metals investigated included mild steel, copper and various copper alloys; the liquids acetic acid and acetic anhydride mixtures. In most cases q (the corrosion rate) tends to increase as d (the diameter) is decreased and in some cases the product qd is practically constant.
When the dimensionless products of the properties involved in corrosion analogous to the Nusselt, Prandtl and Grashof numbers are set up, the functional relationship between them is shown to be the same as that applying to the convective loss of heat from geometrically similar bodies.
It is suggested, therefore, that under certain conditions the use of thermal models could be a useful tool in extrapolating corrosion data from small to large-scale equipment.
REFERENCES.
Bosworth, R. C. L., 1944. Tuts JouRNAL, 78, 220-225.
—______—__—_—_ ——— ]1949a. Tuis JOURNAL, 83, 8.
—______— —— 1949b. Tuis JOURNAL, 83, 17.
Lander, C. H., 1942. Jnst. Mech. Engrs. J. and Proc., 148, 81-112.
Pasquill, F., 1943. Proc. Roy. Soc., A 182, 75-95.
‘Powell, R. W., and Griffiths, E., 1939. Trans. Inst. Chem. Engs., 36, 125-143. Sutton, W. G. L., 1934. Proc. Roy. Soc., A 146, 701-722.
THE FORMATION OF MOBILE AND IMMOBILE FILMS OF OXYGEN ON TUNGSTEN.
By R. C. L. BOSWORTH, Ph.D., D.Sc., F.Inst.P.
Manuscript received, February 2, 1949. Read, April 6, 1949.
INTRODUCTION.
The contact potential method of studying the properties of films on metal surfaces has been developed into a tool suitable for both electro-positive and electro-negative films (Bosworth and Rideal, 1937; Bosworth, 1945). Since the contact potential difference between a covered and a bare surface is an easily measurable index of the fraction (0) of the surface covered, it can be used to record the changes in 0 which follow such surface processes as evaporation and condensation. This paper will be devoted to an application of the contact potential method to the study of the condensation of oxygen on tungsten.
An analysis by Roberts (1935, 1938) of the kinetics of adsorption with dissociation of a diatomic gas has shown that condensation proceeds far more slowly if the film formed is mobile than if the film formed is immobile, particu- larly when the interaction between the adsorbed atoms (or adatoms) is large. For the rate of change of 0 (with time) Roberts gave the expression ,
dpi 2 t2Po dee VET OG) ine testes aS rcal oaaeeretul (1) where ng is the number of spaces per unit area available for adsorption.
is the condensation coefficient.
is the pressure due to the molecules.
the mass of a single (diatomic) molecule. is the Boltzmann gas constant,
is the absolute temperature, and
(0) is a function derived by Roberts.
For an immobile film the function (0) takes the form (9) =1 —1-75(0 —0 -32156? —0 -083303 —0-017505) ...... (2)
For a mobile film (0), while practically the same as for the immobile film at low values of 0, decreases much more rapidly as 6 increases and, over the higher values of 0, assumes a value which depends on the interaction energy of the adatoms, being the smaller the higher this energy.
The fraction of the surface covered at which 0(0)movile becomes significantly less than the corresponding value of 0(9)immopile depends on the lattice arrange- ment on the surface. If each adsorption space on the surface has four near neighbours the value of 0 at which the difference becomes significant is a little less than 0-5. If the adsorption space has six near neighbours, this value of 0 is just under 0-33.
Many of the adsorbed films for which the property of surface mobility has been studied have shown immobility at low temperatures and mobility at higher temperatures (Bosworth, 1942). Accordingly it was considered desirable to study the condensation of oxygen on tungsten over a range of temperatures. Any occurrence of appreciable surface migration in times of the order of the
Wes se wa
32 | R. C. L. BOSWORTH.
interval between two successive collisions of a gaseous oxygen molecule at the same lattice point should mean a change in the kinetics of the condensation process at a temperature marking the inception of the surface migration. »
EXPERIMENTAL.
The apparatus used consisted of a tube for the measurement of contact potential differences of the type already described (Bosworth and Rideal, 1937). A sketch of the apparatus used has been given by Bosworth (1945a). In addition to the normal two crossed tungsten filaments the tube contained a barium oxide coated nickel filament which had been previously heated in an oxygen atmosphere in order to convert the coating into BaO,. When all the parts had been assembled the tube was exhausted, using a two-stage mercury diffusion pump; and all the metal parts, with the exception of the BaO, coated filament, were thoroughly outgassed. Sodium metal was then distilled into the vessel in order to produce a mirror on the glass walls, but not on the metal filaments, which were maintained hot during this process. The vessel was finally sealed off under vacuum.
Any desired oxygen pressure could now be maintained in the tube first by immersion in a liquid air bath and then by heating the BaO, coated filament with a known current. This produced an evolution of oxygen at a fixed rate ; and since every oxygen molecule striking the cooled walls was immobilized by the sodium film, this also resulted in a fixed oxygen pressufe which could be varied at will by varying the heating current to the oxygen-emitting filament.
The current-temperature curves for the two cross filaments were obtained by measuring the current-resistance characteristics at temperatures below 1000° K., and the current-brightness temperature curve (using an optical pyrometer) in the higher temperature range.
Contact potential differences were obtained by drawing the infrasaturation curve from emitter filament to collector filament. The former was maintained at a fixed temperature of the order 2500° K., while the latter was taken through a series of small external potential differences (from —2 volts to +1 volt) with respect to the central point of the hot filament. A string galvanometer with recording camera was used to follow rapid changes in the contact p.d. The method of working was as follows: A stable equilibrium film was allowed to build up on the collector filament and a series of snapshots of the galvanometer string taken with the camera, over a range of external applied potentials. <A suitable external potential was then selected so that the expected curve for the variation of the emission with change in the contact potential difference conse- quent on a change in the chemical nature of the surface film should lie wholly within the range of the camera. The oxygen pressure was adjusted to the desired figure by means of the current through the barium dioxide source and the collector filament was heated to 2200°C. to clean it. The camera drive was then set going. The collector filament temperature was then dropped to the figure at which condensation was to be studied by suddenly changing the heating current. Initially rapid changes in galvanometer current occurred and the camera was stopped when this change became substantially constant. Further records were then obtained by reflashing the collector filament and then dropping the temperature to some other point in the condensing range (90 to 1000° K.). As explained above, changes in the oxygen pressure could be effected by changing the heating current on the BaO, source. The relative pressures attained could be measured from the slope of the initial part of the condensation curve or from the whole of the condensation curve at 90° K., at which temperature condensation follows entirely the mechanism associated with the immobile film.
FORMATION OF MOBILE AND IMMOBILE FILMS OF OXYGEN ON TUNGSTEN. 33
EXPERIMENTAL RESULTS.
The results accruing from the various experimental runs were collected in the first instance in the form of records of the infrasaturation, emission versus time curves for the various experimental conditions studied. Using the known current-volts characteristic of the assembly, the curves were first changed to contact p.d. versus time curves and then by means of the relationship between the contact p.d. and @ found earlier for oxygen on tungsten films (Bosworth, 1945b) were finally converted to 0 versus time curves. Some illustrative curves of this nature are shown in Figures 1 and 2.
FIG. I.
{QO 6 < ) TIME (SECONDS)
Figure 1 refers to condensation at a fixed oxygen pressure of 1:1 x10-6 mms. of mercury and at a series of different temperatures. Curve A records the process of condensation at 90° K., curve B condensation at 540° K., curve C at 690° K., and curve D at 920° K.
Figure 2 refers to condensation at a pair of fixed temperatures, one each in the mobile and the immobile range, and at a series of different oxygen pressures. Curves AA record condensation at a pressure of 7-4 <10-* mms. of mercury, curves BB at 4:4 x10-® mms., and curves CC at 2:0 x10-® mms. In each case the heavy lines refer to condensation at 90° K. and the broken lines to con- densation at 830° K.
It will be observed that at about 0=0-5 or a little less the condensation proceeds the more slowly the higher the temperature at any fixed pressure, and more than proportionally slowly the lower the pressure at any fixed temper- ature. These results are not such as would be expected from the simple Roberts’ theory.
THEORY.
In the Roberts’ theory for the condensation of a completely mobile film the condensation proceeds the more slowly the lower the quantity (y) or e-V/*?, in which V is the interaction energy between a pair of atoms on the surface. V varies only slowly with the temperature. Accordingly y is expected to increase with an increase in temperature. Condensation on a completely mobile film is
34 R. C. L. BOSWORTH.
thus expected to proceed more rapidly at higher temperatures and this, as pointed out above, is not observed. However, a sudden onset of a mobility on the surface akin to a type of two-dimensional melting is also a phenomenon which has only been recorded in a few special cases. Much more usually the process of acquiring a state of surface mobility is more akin to a two-dimensional vaporization. On the picture given by Lennard Jones (1937) the mobile adatom is in a certain state of high energy and remains in that state for a finite time before being deactivated to return to the normal state of being fixed to a given lattice point. In this static condition the adatom remains, on the average, for a much longer time interval before being reactivated to the mobile condition. At any given instant the number of adatoms in the mobile state is only a small fraction of the total number. In considering the effect of activated mobility on the rate of condensation it would appear that the important factor is the prob- ability of a given adsorbed atom migrating to a neighbouring lattice point before that point suffers a collision from a component atom of a gaseous molecule. Higher surface temperatures are associated with more frequent activations to the mobile state and therefore at such temperatures the film behaves as though it
TIME. (SECONDS)
were more completely mobile in the Roberts sense. Again at lower pressures the time intervals between successive collisions become longer, so that the film also behaves as though it were more mobile.
At any fixed temperature and pressure the rate of condensation of a (truly) mobile film depends on the quantity y. 1 =e-VisT,
where V is the interaction energy between a pair of adatoms. Above a value of 6 of about 0-5 the rate of condensation becomes practically zero when y, is small. For oxygen on tungsten films we may estimate V from the figures given by Bosworth (1945) for the heat of evaporation of oxygen from nearly bare and from completely covered surfaces. These heats are respectively 154,000 and 66,000 calories per gramme molecule. Since each lattice point on the 110 surface plane has six almost equidistant neighbours, and further since dipole interaction as calculated by the Topping equation is negligible in comparison
FORMATION OF MOBILE AND IMMOBILE FILMS OF OXYGEN ON TUNGSTEN. 35
with the total interaction, we may neglect all interaction other than that between near neighbours and write )
__ 154,000 —66,000
mama it
=14,700 calories per gramme molecule.
V
For a temperature of 750° K., therefore, 7 becomes 0-000068,
at which figure the value of 9(9)mopniie becomes very small in comparison with 0(9)immopile-
We are now in @ position to attempt a computation, from the observed rates of condensation, of a number of adatoms which become mobile in a given
time. Let (7 represent the rate of growth of the film calculated from the im:
theory of immobile condensations for given conditions of 0, temperature and
external pressure and let Ga sas be the actual observed rate of growth under
the given conditions. In addition to the variables which enter into the deter-
mination of ae the observed rate of condensation also depends on the state of distribution of the adatoms on the surface at the moment when further condensation takes place. This distribution of the adatoms on the surface may be characterized by two limiting states ; a state «in which every atom is attached at the point at which it made the initial collision with the surface and a state 6 in which surface spreading forces have attained equilibrium with thermal
agitation. Condensation on a surface in state « will proceed at the rate Gi im-
Condensation on a surface in state 8 (provided 0>0-5) will proceed at a rate
which may be taken as negligibly small in comparison with ia . Surface im-
migration results in a change from the state « to the state 8, and will be assumed to follow a ‘ unimolecular ’”’ law, viz.
da 5 aa or a=l1—ext,
where a represents the fraction of the covered surface in the state a, and ¢, is effectively the time elapsing between two successive collisions at two neighbouring lattice points on the surface. This time depends on the rate at which gaseous molecules impinge effectively on the surface. For immobile condensation the data of Roberts shows that the integral
oa
o (8) attains the value of 1-0 at 02=0-52. Accordingly we take for ¢, the time taken for the film to build up from zero concentration to 0=0-52 under the given
external conditions and with the film immobile, i.e. condensation at low temperature.
36 R. C. L. BOSWORTH.
We may now write for the rate of condensation Dy ley a at ime dd — Pah eae (1 é xt) ala.
dd =x, Tilia
so long as (71) is not of a different order of magnitude to (7) . Thus
obs: im-
3 4 RELATIVE RATE OF CONDENSATION
we have for the relative rates of condensation
ay 4(@®) _,, (lana la Ne Ths
The value of ¢, may be read off from the curves shown on Figure 2 for the
three different pressures employed. A _ plot of wv ap versus at obs- dt im-
t, is given in Figure 3 for the three different values of 0, viz. 0-5, 0-6 and 0-7 at 830° K. These points fall on satisfactory straight lines passing through the origin. From the slopes the values of x may be read off. The values thus obtained are:
At 6=0:5, T=830° K., x=0-66 reciprocal seconds.
At 6=0:6, 7 =830° K., x=0-95 reciprocal seconds.
At 0=0-7, T=830° K., x=1-28 reciprocal seconds.
CALCULATION OF THE DIFFUSION COEFFICIENTS.
The values of x deduced above may be taken as measures of the times elapsing between successive activations of the same adatom to the mobile state, and thus may be related to the coefficients of surface diffusion (D) by the ex pression
D= 3x22, where A is the mean free path of the diffusing adatom and may be taken as the distance between two neighbouring points on the surface lattice. With the
FORMATION OF MOBILE AND IMMOBILE FILMS OF OXYGEN ON TUNGSTEN. 37
high interaction energy characteristic of the oxygen on tungsten films it is unlikely that a mobile adatom will move over several lattice points before deactivation. Once it has moved out of the range of immediate neighbours of any other adatom it is practically in a uniform field. Thus we have for the diffusion coefficient of oxygen on tungsten
D=38:7 x10-1%& ems.? see.—!.
At 830° K. the values of D are thus: Hor 0=0-5, D=2-45 x10-!® cms.” sec.—1. Hor G—0-6, D=3-5 x10-1® ems.? sec. 1, and For 0=0-7, D=4-8 x10-1* cms.? sec.—}. From other measurements of x it is possible to calculate D over a range of
temperatures and values of 0. For an activated process we expect D to vary with temperature according to a relation
D=D,e-b/T where D, is a constant and b is a measure of the activation energy concerned. Some curves showing log x plotted against 1000/7 are given in Figure 4. Curve A
refers to 0=0-4, curve B to 6=0-5, and curve C to 0=0-6. Values of the activation energy computed from the slopes of these curves are:
For 0=0-4, activation energy 0-52 electron volts.
For 0=0-5, activation energy 0-50 electron volts.
For 0=0-6, activation energy 0-47 electron volts.
For 0=0-8, activation energy 0-46 electron volts. These figures for the activation energy for surface migration are only a small
fraction of the corresponding figures for the heats of vaporization for these same films.
38 R. C. L. BOSWORTH.
SUMMARY.
The contact potential difference has been used to study the condensation of oxygen on tungsten. At low temperatures the process follows the kinetics expected by the Roberts’ theory of condensation with dissociation as an immobile film. At higher temperatures the condensation (once 0 has exceeded a value of about 0-4) proceeds the more slowly the higher the temperature or the lower the pressure. This is interpreted as due to the activation of some of the adsorbed oxygen atoms to a mobile state which proceeds the more rapidly the higher the temperature and the more completely the lower the pressure.
Calculation of the surface diffusion coefficient at 830° K. gives a figure of 2-5 x10-16 ems.? sec.—! at 0 =0-5, increasing with increase in 9 and an activation energy of 0-50 electron volts for 0=0-5, this time decreasing with increase in 0.
REFERENCES.
Bosworth, R. C. L., 1942. J. and Proc. Aust. Chem. Inst., 9, 134-142. ee) OA Da) ais) POURNALA | £ Os1Do- U2:
—____________ 19456. Tuis JOURNAL, 79, 190-195.
Bosworth, R. C. L., and Rideal, E. K., 1937. Proc. Roy. Soc. Lond., 162A, 1-32. Lennard Jones, J. E., 1937. Phys. Soc. Lond., 49, 140-149.
Roberts, J. K., 1937. Proc. Roy. Soc. Lond., 161A, 141-153.
1938. Proc. Camb. Phil. Soc., 34, 399-411, 577-586.
A NOTE ON THE SIGMA PHENOMENON.
By R. C. L. BoSWoRTH, Ph.D., D.Sc., F.Inst.P.
Manuscript received, March 3, 1949. Kead, April 6, 1949.
I. INTRODUCTION.
The sigma phenomenon, which has been described in some detail by Scott Blair (1938, 1944), is apparently of wide occurrence in the flow of semi-fluid pastes and slurries. In the method of studying the flow of such systems intro- duced by Schofield and Scott Blair (1930, 1931, 1935) we plot the mean velocity of the flow (U) against the stress (t) at the wall. If the one system is studied in a series of pipes of different diameters we get a series of straight lines, one for each tube diameter. Let us call the slope of these lines (dU/dt) a quantity o, and then proceed to plot o against AR, the radius of the tube. Were the fluid system studied to be Newtonian in behaviour, it would follow that the resultant plot would be a straight line passing through the origin and having a slope (do/dR) equal to 1/4 y, with y the viscosity. For systems exhibiting the sigma phenomenon the co versus # plots are reasonable straight lines, but they do not pass through the origin, but instead give a positive slope o, on the o axis. Thus for such systems we have
dU R de OO G, corte (1)
dt
In a paper by the author (Bosworth, 1947) it was shown that this equation had a form resembling that for the flow of a gas in a capillary at such a low pressure that slip flow was occurring, and it was further suggested that similar mechanisms for the transport of momentum from the fluid to the walls was operative. The peculiar properties of gas flow at low pressure are attributable to the fact that the carriers of momentum (viz. the moving molecules) travel through the system with mean free paths which are of the same order of size as the diameter of the tubes concerned. In seeking a similar mechanism for the transport of momentum in a semi-liquid slurry at atmospheric pressure it was suggested that the class of hypersonic longitudinal waves in the oscillatory motion into which the Debye theory of specific heats breaks up the thermal motion of condensed matter might contribute the momentum carriers with the long mean free paths. It will be the object of this paper to make an estimate of the magnitude of the sigma phenomenon in terms of the Debye distribution of frequencies. A similar estimate by the author (Bosworth, 1948) of the magnitude of the viscosity of normal liquids interpreted as a momentum transfer by transverse waves with mean free paths equal to the mean distance between two ‘‘ holes ”’ in the liquid has met with moderate success and will be used as a basis for the present calculation.
II. DERIVATION OF THE INTENSITY OF THE MOMENTUM FLOW.
Following the practice adopted in the earlier papers we will refer to the stream of acoustical radiation as a stream of ‘‘ phonons ”’ carrying quanta of energy and momentum given by the quantum rule. The energy per unit volume
40 ; R. C. L. BOSWORTH.
dH associated with longitudinal waves of frequency lying between vy and v+dv is given by Ath vedy ~ @3 ehv/kT—1 where ¢) is the velocity of propagation of the longitudinal waves. The number of phonons dnp per unit volume derived from longitudinal waves in the frequency range v to v-+dv (or phonons of class B) is expressed by the relationship
At v2dv dnp ~ 63 ehy/kT —1 @ je: fe je Nini -«: @ sie we = Kas (6 1m jehte) wliaite a itolin (3) The density of these same phonons (dop) is likewise given by _4rh vedv Pp ee ehy/kT _] @ jere ele) lollieulohie) « inelfolhoMioiicl citeMeitoncmenei eins (4)
While the number of phonons of class B striking unit area of the wall in unit time is + dnp C1, OF TT v?dv c@ ohvkT—1 A like number of phonons will leave the unit area of the wall in unit time in directions which are distributed according to the cosine law. <A certain fraction
Fig. 1.
of that number will cross the surface of an inner cylinder of radius r. If & is the inner radius of the pipe (Figure 1) then phonons from any given point on the wall will cross the inner cylinder so long as they make an angle 0 with the normal which is less than are sin r/R, in a plane normal to the direction of flow.
The fraction crossing the inner cylinder is thus are sin r/R cos 0 d0=r/R. O
If « is the absorption coefficient the number of phonons in unit’ time and from unit wall area which are absorbed between the radii r and r —dr (the shaded area in Figure 1) is then
a1 v2dy r
ce ehv/kT —] 3 R . e a( Rk —r)gdr.
A NOTE ON THE SIGMA PHENOMENON. Al
Let now wu be the local velocity of flow of the zone of fluid represented by the shaded area. Generally wis a function ofr. The momentum flow from unit area of the wall to an area r/R of the shaded zone and due to the phonons of class B now becomes
t~t wuhvdy r ct ehv/kT—1 R
The total momentum flow to the shaded area carried by all the phonons
arising from longitudinal waves thus becomes
mure-a(R—r)adr [Yo hvy3dy , te SIRE eae : ATE (5)
where v, is the limiting Debye frequency. For all temperatures considerably
e-a(R —r)gdr.
in excess of the Debye characteristic temperature hyp we may write approxi-
k mately ehy/kT —] =hy/kT, so that expression (5) becomes rere“ —r)ukPadr vo’ 6) Res Qorir tte set ee eects e ee But now v, is related to the number N of molecules in unit volume by
ON eed
cs ay ka =a} where c; is the velocity of propagation of the transverse hypersonic waves. As in the earlier paper, we assume that the Cauchy-Poisson relation holds between c,; and ¢, namelv that 5c¢? =—oCIe Se Maichietewecc.usteteuetrstien ic shiesisu.e tere. 6 ies (8) which on substitution in equation (7) gives
Vp? =0 +1886 Ma NG ec ucis tee er (9)
and this, on substitution in expression (6), gives for the momentum transferred per unit time to the shaded area
0-1414 ue-elR—radr feces R Cl This momentum flow yields a contribution (dt) to the stress exerted by the fluid on the walls, namely
dt =0-1414 ae fo epee aire 0) | aaa ee ee ae (10) 1 The total stress on the walls due to the longitudinal waves becomes R 7=0-1414 2 | Megat Td ois a (11) 1 O
Whenever sigma phenomena are in evidence there occurs considerable slip at the walls, thus w varies relatively slowly throughout the pipe except in the immediate vicinity of the walls. Under such conditions we may, without sensible error, take u outside the integral sign in equation (11) and replace it by U, the average velocity of flow in the pipe. Then we get
aUNkT f C)
7+=0-1414 e—a(k —r)dr
O
42 R. C. L. BOSWORTH.
=0-1414 vee CROCE ide Ua ie te a) sh oe ee (12) 1 as our final expression for the contribution to the stress on the wall due to the collision of photons originating from longitudinal waves.
Ill. THE MAGNITUDE OF oy. On differentiation of equation (12) we obtain dU 7-07 —— = CU te oka tk ee dt NkKT Now from equation (1) we have for o, Ge lana ~ R>0 dt OTe NE But since N is N/V where N is the Avogadro number and V is the molecular volume, and further since Nk is R, the ordinary gas constant, we get finally Gyp=7-07 oe eae (15) For aqueous solutions ¢; is of the order 1-5 x10° ems. sec.-t and at room temperature RT is 2-5 x10! ergs. Accordingly, for such solutions we have for o, the approximate value
6) = 4°24 X10-> V cms.*® seésic' dynes . - aoe (16)
This estimated value of oj may be compared with the experimental values of Schofield and Scott Blair (1930) for various aqueous pastes. Such a comparison would enable V, the effective molecular volume of the pastes, to be computed. In the table below the experimental values of oj and the estimated values of V obtained therefrom are given in tabular form.
Oo
FAB Tarieele
Effective Molecular Volumes Estimated from the Sigma Phenomenon. (Data of Schofield and Scott Blair.)
Percentage Oo Paste. Solids. (cms.? sec:4, dynes_,). V (Litres). Clay 2-36 0-33 ran) Kaolin us 37°2 O-ay 2-6 Plaster of Paris. . : 5-8 0-017 0-40 Barytes ap at 43-5 0-015 0-35 Subsoil : 33°5 0-0055 0-13
These molecular volumes are very large and are more nearly appropriate to a gaseous rather than a liquid system. ‘To the effusive transport of momentum resulting in the sigma phenomenon these slurries thus act as solutions which are very dilute on the molar basis.
SUMMARY.
The suggestion that the sigma phenomenon observed in the flow of certain slurries is due to the transport of momentum to the walls by the acoustical vibrations into which the Debye theory resolves the thermal energy of the molecules is examined quantitatively. It is shown, subject to the assumptions
A NOTE ON THE SIGMA PHENOMENON. 43
that the system is far above its Debye temperature and that the ratio of the velocities of the longitudinal and the transverse waves takes the Cauchy-Poisson value, that the value of o, is given by
Gq Oe OMe Vici aR where ¢) is the velocity of the longitudinal hypersonic waves and V is the effective molar volume of the slurry. Comparison of this equation with the measurements of Schofield and Scott Blair shows that V has a value of the order of a litre.
REFERENCES. Bosworth, R. C. L., 1947. Phil. Mag., 38, 592-601. ——___—___________. 1948. Trans. Farad. Soc., 44, 308-317. Schofield, R. K., and Scott Blair, G. W., 1930. J. Phys. Chem., 34, 248-262. a oo LOS eld. 355° 122-21 5:
1935. Ibid., 39, 973-981.
Scott Blair, G. W., 1938. ‘*‘ Introduction to Industrial Rheology’, J. and A. Churchill, London.
—--—____—___——— 1944. “‘ A Survey of General and Applied Rheology ”’, Pitman, London.
A NOTE ON THE ESSENTIAL OIL OF BACKHOUSIA ANISATA VICKERY AND THE OCCURRENCE OF ANETHOLE.
By H. . G. MCKEEN, AAC
Manuscript received, January 21, 1949. Read, April 6, 1949.
Although specimens from the myrtaceous tree Backhousia anisata Vickery, indigenous to the north coast of New South Wales, were collected as long ago as 1910, it has been confused with Hugenia ventenatu, and its taxonomic position was not established until recently by Vickery (1941).
On account of the strong aniseed-like odour of the crushed foliage it has received the vernacular name of ‘‘ Aniseed Tree ’’, and this observation has prompted officers of the Forestry Commission of New South Wales to enquire into the economic value of the oil as a possible substitute for anise oil. This Institution has undertaken the examination of the oil obtainable from this Species, and since a preliminary investigation shows promise of commercial value it has been decided to publish the results hitherto obtained. When further supplies of material become available, a more detailed examination of the oil will be made.
The examination so far shows that the foliage of this tree yields on steam- distillation 0-5°% of a pale yellow oil strongly resembling anise oil of commerce in respect both to odour and taste. The principal component of the oil is anethole (p-propenyl anisole), present to the extent of about 60%, as compared with about 80% for anise oil. However, it is considered that by rectification or by freezing, a commercial equivalent of anise oil could be prepared, and would provide a local source of anethole. The oil of B. anisata is considered by the author to be far superior to fennel oil.
EXPERIMENTAL.
Samples of foliage were supplied by the Forestry Commission of N.S.W. Two collections were made, one, received 4/7/46, from one restricted locality in the Bellenger River area of New South Wales; the other, received 11/11/46, was made up of foliage from three different and separated localities in the same area—Buffer Creek, Pine Creek and Kalang—the purpose of the second sample being to determine if the oil of this species is reasonably constant in composition to justify commercial exploitation.
Both samples consisted of leaves and terminal branchlets cut as for commercial distillation, and on steam-distillation they both yielded 0:5% of a pale yellow mobile oil, lighter than water and having a sweet taste and pronounced anethole-like odour. The oil froze readily to a crystalline mass on cooling in ice-water. The oils had the characteristics shown in the following table ; figures for the British Pharmacopceia specification for anise oil being given for comparison.
Preparation and Characterization of the Anethole.
Essential oil of B. anisata (47 g.) was frozen by cooling to about +5°. The crystalline mass was transferred to a chilled porous tile and pressed. By repetition of this process, 24 g. of white
A NOTE ON THE ESSENTIAL OIL OF BACKHOUSIA ANISATA VICKERY 45
1932 B.P. 4/7/46 - 1/11/46 Specifications. Sample. Sample. (Anise Oil). Specific gravity at 20°/15-5° a 0- 9826 0- 9806 0-980 to 0-994 Refractive index, at 20° ae o > els ¥53 1:5489 1:553 to 1-560 Optical rotation, 100 mm. tube a —1-15° —1-88° —2° to +1° Freezing point ie a ae 14-5° 12-0° Not below 15° Melting point .. a - ae 15-2° 13-2° Not below Lie Solubility in 90% V/V alcohol ~ Soluble in Soluble in Not more than 1 vol. 1 vol. 3 vols. Ester number, mg. KOH per gramme —- 15-4 — Ester number, mg. KOH/g, after acetylation .. 6 vs ee —— 87-6
crystals were obtained, melting at 21°-22° to a colourless oil of powerful anethole odour and taste, and having the following characters :
die rey eset et le) 992 ine ee ae eet) Glee 560s Xp Sf ie er .. Inactive.
On oxidation of a portion with potassium permanganate by the procedure of King and Murch (1925), an excellent yield of a solid acid (neutral equivalent, 152) crystallizing in needles from hot water, and melting at 183-184° (uncorr.), was obtained. The melting point was not depressed by mixing with an authentic specimen of anisic acid (neutral equivalent, 152 (cal- culated)).
A further portion of the material was oxidized by the method of Shoesmith (1923) and a pale yellow liquid of aubépin odour resulted. It yielded a p-nitrophenylhydrazone m.p. 161-5° (uncorr.) undepressed by admixture with p-anisaldehyde p-nitrophenylhydrazone.
It is therefore concluded that the compound is anethole.
ACKNOWLEDGEMENTS.
Thanks are due to the Director, Mr. A. R. Penfold, for permission to publish this note, and to Mr. R. J. Waijiles for assistance with the distillation of the leaf.
REFERENCES.
King and Murch, 1925. J. Chem. Soc., 127, 2640. Shoesmith, J. B., 1923. Jbid., 125, 2702. Vickery, Joyce W., 1941. Contrib. N.S.W. Nat. Herb., 1, 129.
The Museum of Technology and Applied Science, Sydney.
NITROGEN IN OIL SHALE AND SHALE OIL. VIIL. THE DETECTION OF TAR BASES.
GEO. EK. MAPSTONE, M.Sc., A.A.C.I., A.R.I.C., M.Inst.Pet.
Manuscript received, January 13, 1949. Read, April 6, 1949,
INTRODUCTION.
In connection with other aspects of this work it became necessary to develop an unambiguous test for the detection of tar bases in crude shale oil and its products.
The tar bases present in shale oil are principally pyridine homologues, though weakly basic pyrrole homologues are also present (Mapstone, 1948). Crude shale oil also contains a large proportion of non-basic nitrogenous com- pounds of unknown composition (Mapstone, 1949), but these were not of importance in the work described here. Tests carried out on the oil could indicate the presence of either pyridine homologues or of pyrroles, while tests on an acid extract of the oil would be mainly indicative of the pyridine bases because of the very low acid solubility of the pyrroles.
With strongly coloured samples, it was necessary to extract the bases with acid before applying the tests. A number of different tests were therefore examined for sensitivity for the detection of tar bases in solution in the lighter oils and in solution in dilute sulphuric acid as they were extracted from the darker coloured oils.
SAMPLES TESTED.
The tar bases present in the acid sludge from the treatment of cracked shale gasoline were considered to be sufficiently representative of those initially present in the gasoline to be used for this work. They were therefore isolated as described previously (Mapstone, 1947) and purified by distillation. They contained 8-69% of nitrogen by weight, and the bases present would be almost entirely pyridine homologues.
Since preliminary work indicated the probable presence of approximately 5 p.p.m. of tar bases in refined shale gasoline, another suitable tar base-free hydrocarbon solvent was required for the determination of the sensitivity of the various reagents. The highly purified n-heptane-isoctane blend used for the determination of the octane rating of motor fuels was found to give a negative test with all except a few of the reagents used. In the cases where a positive result was obtained the reaction could be attributed to other factors. A 1% solution of the bases in the heptane-octane mixture (hereafter referred to as gasoline) was carefully prepared and the more dilute solutions prepared from it by dilution with further gasoline.
A solution of the purified bases in dilute sulphuric acid was prepared by dissolving 1-0 ml. of the bases in 250 ml. of 0-097 N sulphuric acid. Titration of portion of the solution showed that the excess acid was 0:0637 N, giving an 0:0333 N solution of the bases. This solution was diluted with further portions of the 0-0970 N acid to give the more dilute solutions required.
The light recycle oil (boiling range 5% at 360° F., 95% at 520° F) from the thermal cracking of crude shale oil is dark brown in colour, and it was therefore
NITROGEN IN OIL SHALE AND SHALE OIL. 4G
necessary to extract the bases for detection. From the method of extraction and the boiling range the bases would be principally pyridine homologues together with any quinoline homologues that may be present. Fifty millilitres of the oil were washed with 200 ml. of 0:1061 N sulphuric acid. Titration of portion of the solution thus obtained showed that the excess acid was 0-0362 N, giving an 0-0699 N solution of the bases. This was diluted with further portion of the 0:1 N acid to give the more dilute solutions required.
With crude shale oil it was even more necessary than with the light recycle oil to extract the bases before detection. In the manner described for the light oil a 0-042 N solution of the bases from the crude shale oil was obtained in 0-1 N sulphuric acid.
Unless otherwise mentioned the tests on the hydrocarbon samples were carried out by adding two drops of the reagent to 5 ml. of the sample, and the tests on the acid extracts by adding four drops of the reagent to 1 ml. of the _ sample.
REAGENTS.
In deciding which reagents were to be tested, those which reacted with pyridine or quinoline or their homologues to give precipitates or developed colours were chosen. Since many alkaloids contain pyridine nuclei several ‘‘ alkaloid ’’ reagents were included. However, those alkaloid reagents which are based on concentrated sulphuric acid (e.g. Froehde’s, Mandelin’s and Erdmann’s reagents) were not examined because of the action of the acid on the olefines in the gasoline samples, and with the samples dissolved in dilute acid, the dilution of the reagent would render them ineffective.
From the nature of their reaction with the tar bases the reagents were somewhat arbitrarily subdivided into seven classes which are discussed in turn.
(1) Metal salts which precipitate the metal hydroxide.
Pyridine and quinoline and their homologues are tertiary amines and their aqueous solutions can be sufficiently alkaline to precipitate the hydroxides from the solutions of the salts of various metals (Perkin, 1935). The sensitivity of the tests with such reagents would therefore depend principally on the solubility of the hydroxide of the metal, and the ease with which it could be seen when precipitated. The reagents were prepared by adding dilute ammonia dropwise to the aqueous solution of the metal salt until a sight permanent precipitate was formed. The reagent solution was used after filtration.
Five per cent. solutions of ferric chloride, cobalt nitrate, nickel nitrate, cupric nitrate and zinc chloride and a saturated solution of potassium alum were prepared in this manner. Another mixed reagent was prepared by the addition of 3 ml. of 1% ammonium aurine tricarboxylate solution to approximately 80 ml. of the saturated alum solution. A slight red precipitate was formed and removed by filtration. It was thought that the dye would be adsorbed on any aluminium hydroxide precipitate and render it more visible and thus possibly increase the sensitivity of the alum reagent.
On carrying out the test on samples with higher tar base concentrations a precipitate was thrown down but, with the limiting concentrations a film was formed at the gasoline-reagent interface. If an excess of reagent was used (e.g. 2 ml. per 5 ml. sample) the cobalt and aluminium reagents gave positive results even in the absence of tar bases. It was therefore necessary to adhere strictly to the test conditions in order to obtain reproducible results. The sensitivities of these reagents are presented in Table 1.
GG
48 GEO. E. MAPSTONE.
TABLE l. Sensitivities of Reagents. Metal Salts which Precipitate the Metal Hydroxides.
Colour of Reagent. Precipitate. Sensitivity.?
Ferric chloride .. a .. | Red to yellow. 0-0001%. Cobalt nitrate .. a | ela Beyond 0-00005%. Nickel nitrate... ile -.'\| Greets. 0-0001%. Cupric nitrate .. oi .. | Green-blue. Beyond 0-00005%. Zine chloride... se .- | White, Beyond 0-00005%. Potassium alum : White. 0-001%. Alum plus ammonium aurine
tricarboxylate % .. | Reddish. 0-001%.
1 Sensitivity is quoted as the least percentage of tar bases (8-7% N) by volume which gave a positive test.
Because the reaction between these reagents and the tar bases involves the precipitation of the acid soluble hydroxides of the metals, they were applicable to the detection of only the free bases and could not be applied to the acid extracts.
(2) Acids which precipitate insoluble salts of the bases.
This group of reagents includes many which have been used for the separa- tion, isolation and identification of tar bases, and several “‘ alkaloid ”’ reagents. Because of their varied nature they are discussed separately. The sensitivities of the reagents are presented in Table 2
TABLE 2. Sensitivities of Reagents. Acids which Precipitate Insoluble Salts of the Bases.
Source of Bases. Gasoline. Light Oil. Crude Oil. Base dissolved in acid ae Gasoline 0-1N H,SO,. | 0-1N H,SO,. | 0-1N H,SO,. Chlorplatinic . . st: bie 0-1% Nil Nil 0-0001 N Chlorauric 0:05% Nil 0-00007 N 0-00003 N HCl in ether 0-00005% — — — HCl (concentrated) . 0:005% — — — Picric .. 0-001% Nil 0:02 N 0-0012 N Styphnic 0-19; Nil 0-015 N 0-0002 N Trinitro-m-cresol 0:05% Nil 0-015 N 0-0002 N Oxalic 0-01% — — — Tannic 0:2% Nil 0:03 N 0-003 N Phosphomolybdic 0-0005% Nil Nil 0-0002 N Phosphotungstic i. 0:05% | 0-003 N 0-00007 N 0:0002 N Silicotungstic ee .. | 0-005% p.p.pt. Nil Nil 0-002 N
0-00005% colour
The sensitivities are quoted as percentage of tar bases (8-7% N) by volume in the gasoline solution, and as normalitied in the dilute sulphuric acid solutions.
(a) Chlorplatinic Acid. This reagent precipitates the sparingly solubie platinichlorides of the bases and has been used extensively for this purpose. It is of interest that the earliest recorded isolation and separation of the tar
NITROGEN IN OIL SHALE AND SHALE OIL. 49
bases from shale oil involved the precipitation of the bases as their platini- chlorides which were separated by fractional crystallization (Williams, 1854, 1855). The reagent was prepared by dissolving 0-:0942 gm. of platinum in aqua regia, evaporating the solution to dryness on a water bath, dissolving in 2 ml. of hydrochloric acid and making up to 20 ml. with distilled water. A positive test was indicated by the formation of a yellow-brown precipitate.
(b) Chlorauric Acid. This reagent is sometimes used to give sparingly soluble amine salts for the separation or identification of tar bases. It was prepared by dissolving 0-1998 gm. of pure gold in aqua regia, evaporating the solution to dryness on a water bath, dissolving in 2 ml. hydrochloric acid and making up to 20 ml. with distilled water. A positive test was indicated by the formation of a yellow-brown precipitate.
(c) Hydrogen Chloride in Ether. Since the hydrochlorides of the tar bases are insoluble in hydrocarbon solvents, the addition of hydrochloric acid should precipitate the chlorides, and as the precipitate would be soluble in water the sensitivity of the test should be increased by the use of an etherial solution of hydrogen chloride. The reagent was prepared by saturating redistilled ether with hydrogen chloride gas. <A positive test was indicated by a yellowish or white cloudiness in the sample. An excess of reagent gave a positive test in the absence of tar bases. This test was suitable for hydrocarbon samples only.
(da) Hydrochloric Acid (Concentrated). This test was based on the considera- tions outlined in (c) above, but since it was an aqueous reagent it was not expected to be quite as sensitive. However, the reagent is always readily available and was therefore included for comparison. <A positive result was indicated by a white cloudiness in the sample.
(e) Picric Acid. This reagent is frequently used for the isolation, separation and identification of basic organic compounds. The reagent was used in the form of the saturated aqueous solution. <A positive result was indicated by the formation, of a yellow precipitate or a yellow film at the gasoline-reagent interface.
(f) Styphnic Acid. This reagent is frequently used instead of picric acid for the same purposes and gives similar results which are no doubt due to the similarity of structure (styphnic acid is 3-hydroxy picric acid). The test was carried out as with picric acid and gave similar results.
(g) Trinitro m-cresol. This reagent (3-methyl picric acid) was included for comparison. The test was carried out as with picric acid and gave similar results.
(h) Oxalic Acid. The oxalates of pyridine homologues have sometimes been used for their separation and identification. The reagent was used as a saturated aqueous solution. <A positive result was indicated by a white pre- cipitate or film.
(i) Tannic Acid. This reagent is commonly employed as an “ alkaloid ”’ reagent, and was therefore included in this series of tests. This reagent was used as a 10° aqueous solution. The formation of a brown precipitate indicated @ positive result.
(j) Phosphomolybdic Acid. This “ alkaloid ’’ reagent was prepared by the method of Hawke and Bergeim (1937). A positive result was indicated by the formation of a precipitate which was brown in higher concentrations and white in the lower concentrations. An excess of reagent gave a white precipitate even in the absences of the bases.
(k) Phosphotungstic Acid. This ‘“ alkaloid ’” reagent was prepared by the method of Hawke and Bergeim (1937). The test was carried out by adding two drops of the reagent to 5 ml. of the sample. A positive result was indicated by
50 GEO. E. MAPSTONE.
the formation of a precipitate the colour of which increased from orange-yellow to white with decreasing tar base concentration.
(l) Silicotungstic Acid. This “‘ alkaloid ”’ reagent was prepared by dissolving 2 em. of sodium tungstate in 10 ml. of hot water, adding 5 ml. of syrupy sodium silicate solution (s.g. 1-7), acidifying with 2 N nitric acid, diluting with 100 ml. of water, boiling and filtering. The clear filtrate was then acidified with 5 ml. of concentrated nitric acid. The tests were carried out using twice the usual proportion of the reagent. A positive test was indicated by the formation of a light brown precipitate or, in greater dilution, a pink colour in the gasoline sample.
(3) Alkali salts which precipitate a salt of the base.
(a) Potassium Ferrocyanide. This reagent is used for the detection of pyridine (Perkin, 1935) because of the low solubility of pyridine ferrocyanide. The reagent was used in the form of a saturated aqueous solution. <A positive result was indicated by the formation of a white precipitate with the lower boiling bases to deep brown precipitate with the higher boiling bases.
(b) Potassium Dichromate. This reagent is commonly used for the detection of quinoline (Perkin, 1935) because of the sparing solubility of quinoline dichromate. The reagent was used in the form of a saturated aqueous solution A positive result was indicated by the formation of a yellow-orange to dark brown precipitate, the colour increasing with boiling point of the bases.
(c) Potassium Triiodide. This “ alkaloid’? reagent was prepared by dissolving 2 gm. of iodine and 4 gm. of potassium iodide in 100 ml. of water. A positive result was indicated by the formation of a brown precipitate.
The results of these tests are presented in Table 3.
TABLE 3. Sensitivities of Reagents.
(a) Salts which precipitate a salt of the Base. (b) Reagents which precipitate a double salt of the Base. (c) Miscellaneous.
Source of Bases. Gasoline. Light Oil. Crude Oil. Bases dissolved in .. .. | Gasoline. 0-1N H,SO,. | 0-1 N H,SO,. | 0-1N H,SO,. Reagent : Potassium ferrocyanide . 0:5% Nil 0:03 N 0-005 N Potassium dichromate 0:01% Nil 0:03 N 0-004 N Potassium triiodide 0:05% 0-001 N 0-00001 N 0-0001 N Mercuric chloride 0:05% Nil 0-03 N 0-0002 N Mayer’s reagent 0-0005% 0-003 N 0-0007 N 0-0008 N Dragendorf’s reagent 0-00005% 0-0002 N 0-00001 N 0-0002 N Sodium hydroxide — 0-015 N 0-0035 N 0-0002 N Nessler’s reagent 0-001% 0-003 N 0-00002 N 0-000002 N
The sensitivities are quoted as percentage of tar bases (8-7% N) by volume in the gasoline solution, and as normalities in the dilute sulphuric acid solutions.
(4) Reagents which give an insoluble double salt of the bases.
The reagents discussed in this section could be classified in the previous section as the distinction is one of degree rather than type. The results are therefore presented with them in Table 3.
(a) Mercuric Chloride. With this reagent pyridine and quinoline and their homologues form complex mercurichlorides, usually of the form (BHCl),Hg(Cl,
NITROGEN IN OIL SHALE AND SHALE OIL. 51
but frequently the precipitated compound is more complex, e.g. 2-5 dimethyl pyridine gives the compound C,H,N.HC1.6HgCl, (Garrett and Smythe, 1902). The reagent was used in the form of a saturated aqueous solution. The forma- tion of a precipitate indicated a positive result. With the lower boiling bases the precipitate was white, but it was more orange-brown with the crude oil bases.
(b) Potassium Mercuric Iodide (Mayer’s Reagent). This ‘ alkaloid ” reagent was prepared by dissolving 2-7 gm. of mercuric chloride and 10-0 gm. of potassium iodide in 190 ml. of water. <A positive test was indicated by the formation of a precipitate, the colour of which was usually brown but, when near the limiting concentration of bases, was sometimes light brown, cream or even white.
(c) Potassium Bismuth Iodide (Dragendorff’s or Thresh’s Reagent). This ‘‘ alkaloid ’? reagent was prepared by the method outlined by Perkin (1935). A positive test was indicated by the formation of a red-orange precipitate, though the colour sometimes varied to red or brown.
(5) Reagents which open the pyridine ring.
The reagents discussed in this section cause the opening of the pyridine ring to give glutaconic aldehyde which forms brightly coloured Schiff’s bases with primary aromatic amines.
(a) Thionyl Chloride. Pyridine can be converted into 4-pyridyl pyridinium chloride on heating with thionyl chloride and on treatment with alkali, this gives glutaconic aldehyde and 4-aminopyridine. Feigl and Anger (1939) developed a test which they reported to be sensitive to five y of pyridine with a concentration limit of 1: 10,000 by condensing the glutaconic aldehyde with a-naphthylamine. All attempts to apply this test even to the pure shale tar bases or to pure pyridine yielded negative results.
(b) Cyanogen Halides. Cyanogen halides react with pyridine to give the unstable N-cyano-pyridinium halide which is readily hydrolysed to glutaconic aldehyde. This reaction has been applied to the colorimetric determination of traces of cyanides (Epstein, 1947) as well as pyridine (Barta, 1935) and the detection of alkaloids containing a pyridine ring (Shmuk, 1940, 1942). In this work the three cyanogen halides were tested and the product reacted with a saturated aqueous solution of aniline or a 1°% alcoholic solution of p-nitro-aniline, anthranilic acid, or «- or 6-naphthylamine. The mixture was acidified and the colour change noted. The cyanogen chloride solution was prepared by adding 5 ml. of a 1% chloramine T solution to 2 ml. of a1 N potassium cyanide solution, The cyanogen bromide and iodide solutions were prepared by adding bromine water or the potassium triiodide solution respectively to a 1 N potassium cyanide solution until there was a slight excess of the free halogen ; this was removed by the addition of a few drops of the cyanide solution. The test was carried out by shaking 5 ml. of the sample with 1 ml. of the cyanogen halide solution followed by the addition of 1 ml. of the amine solution. After the colour had been noted concentrated hydrochloric acid was added dropwise until no further change occurred. With the cyanogen chloride and bromide the tests were satisfactory, but iodine was precipitated on acidification of the tests with cyanogen iodide. The results are presented in Table 4.
(6) Salts which give co-ordination compounds with pyridine.
Pyridine is noted for the large number of co-ordination complexes which it forms with metallic salts, but in order that such compounds may be used for the detection of pyridine or its homologues, they should either be insoluble in or extractable from the reaction medium, and should be preferably strongly
GEO. E. MAPSTONE.
TABLE 4.
Sensitivities of Reagents.
Cyanogen Halides and Aromatic Amines.
Source of Bases. Gasoline. Light Oil. Crude Oil. Bases dissolved in .. ae Gasoline 0-1N H,SO, | 0-1N H,SO, | 0-1N H,SO, A. Cyanogen chloride with—
Aniline : Test y. to r.br. wh. to c. wh. to c. . toe. Sensitivity 0-75% 0-003 N 0-000001 N 0-000004 N p-Nitro-aniline : Test ee y. to or. y. conc: y- to ec. Venn C: Sensitivity 0:75% 0-015 N 0-000003 N 0-00001 N Anthranilic acid : Test y-. to r.br. wh. to ce. wh. to c. y- to ec. Sensitivity ~ 0:75% 0-002 N 0-000001 N 0-000002 N a-Naphthylamine :