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oe

JOURNAL AND PROCEEDINGS

OF THE

ROYAL SOCIETY

OF NEW SOUTH WALES

FOR

1950

‘INCORPORATED 1881)

ee

VOLUME LXXXIV

Parts I-IV LAMSON,
eet ( JUN 22 1954
EDITED BY \

IDA A. BROWNE, D.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, August 17, 1951

CONTENTS
VyLUME LYXXIV

Part I*

TITLE PAGE. :

OFFICERS FOR 1950- 1951

NOTICES

List OF MEMBERS

AWwaRpbs, ETc. :

REPORT OF THE COUNCIL

BALANCE SHEET

OspiTruARY NOTICES a oe a

Art. I.—Presidential aasese By Harley Wood.

The Work of the Society
Astronomy in Australia

Art. II.—Dalton- Songs Area, N. S.W., Barth Teter & Nios 1949. By Gi F.
Jokhik

Art. IIT. Bp atisdians Gomplores: of miner Hors Part TE The ene tion of Botasaiard
Chloropalladite II with o-Methyl yee Benzoic Acid. By 8S. E. Livingstone,
R. A. Plowman and J. Sorensen er ee mit = ae ae

ArT. IV.—Nitrogen in Oil Shale and Shale Oil. XII. The Volumetric Determination
of Basic Nitrogen in Shale Oils. By Geo. E. Mapstone

ArT. V.—Nitrogen in Oil Shale and Shale Oil. XIII. An Aussie Method for
Determining ea eee. in Oil Shale and Similar Materials. By Geo. E.
Mapstone

Art. VI.—Studies in the Cheney of Plats Gomplaren. Bare II. Sone Properties
of Tetrammine Platinum II Fluorides. By R. A. Plowman.

Art VII.—Studies in the Chemistry of Platinum Complexes. Poe ath Guidanon
of the Tetrammine Platinum II Fluorides. By R. A. Plowman an a

Art. VIII.—Occultations Observed at Byeney era ke es Se 1949. By Wie EE:
Robertson .

Art. I[X.—The Geology of the Gangaandia piste N. 8. W. Bart me The Gannaen
Cowra-Woodstock Area. By N. C. Stevens

ArT. X.—The Five Properties Concerned in the Transport of tie heres (ortodant
Agent. By R. C. L. Bosworth

Art. XI.—The Mechanism of the Fischer Tadole Synthesis, By Pe H. Gore G. K.
Hughes and E. Ritchie

Art. XII.—The Permian Rocks of fe > Manning Macleay 1 Broce) New: South. Wales.
By A. H. Voisey ae 7

Part Il;

Art. XIII.—The Chemistry of Osmium. Part IV. The Preparation and Resolution
of the Tris 0,Phenanthroline Osmium IT Ion. re BB be N. A. Gibson and
HC. Gyarfas ae

ArT. XIV.—On the Grading Me Dine ore near Chstiontieh New South Wales. By
D. 8. Simonett

ArT. XV.—The Ghenseeny of unin: Part V; The Reioe Peteneinls of ne Tris
2: 2’-Dipyridyl Osmium IT/ITI and the Tris 0,Phenanthroline Osmium eae ee
By F. P. Dwyer, N. A. Gibson and E. C. Gyarfas

ArT. XVI.—The Chemistry of Osmium. Part VI. The Use of ae oO, Phenkntheobns
Aurea II Perchlorate as an Internal Redox Indicator. By F. P. eh and

. A. Gibson af a,

en! ae —The Besontial Oil of Boeken crentieet (De oni ee Be iv R. Pentold

and F. R. Morrison

ArT. XVIII.—Heard Island. Gaoeranke ana Glenielens By N ne Pape

* Published February 7, 1951.
} Published February 21, 1951.

87
92

CONTENTS

Part III*

Art. XIX.—Rank Variation in the Central Eastern Coalfields of New South Wales.
By J. A. Dulhunty, Nora Hinder and Ruth Penrose ay :

ArT. XX.—Studies in the Chemistry of Platinum Complexes. Part IV. Oxidation of
Ions of the Tetrammine Platinum II meas with a oe Peroxide. By S. E.
Livingstone and R. A. Plowman .. ae sa

Art. XXI.—Coordination Compounds of Copper. Part II. Compounds Derived from
Copper (I) Iodide. By C. M. Harris a a a ve a

Art. XXII.—The Chemistry of Osmium. Part VII. The Bromo and Chloro Pentammine
Osmium III Series. By F. P. Dwyer and J. W. Hogarth

Art. XXIIT.—The Chemistry of Iridium. Part V. The Oxidation of Iridium III Salt
Solutions. By F. P. Dwyer and E. C. Gyarfas

Art. XXIV.—Physical perc aaa on weirs sai of pam By
L. E. Maley ape

Art. XXV.—Tables for Nearly Parabolic Elliptic Motion. By Harley Wood
Art. XXVI.—Tables for Hyperbolic Motion. By Harley Wood |
Arr. XXVII.—An Occurrence of eae Structure in New South Wales. By T. G.

Vallance

Part IV;

Art. XXVIII.—Liversidge Research Lecture. Energy Transactions in Homeothermic
Animals. By Hedley R. Marston : ms a Si ae ae fe

Art. XXIX.—Halogenostannates (IV) of Some sas ae Cations. mati J. R. Anderson,
S. E. Livingstone and R. A. Plowman : sis she bus

Arr. XXX.—Palladium Complexes. Part II. Bridged Compounds of Palladium with
o-Methylmercaptobenzoic Acid. By 8. E. Livingstone and R. A. Plowman. . ‘

ArT. XXXI.—The Chemistry of Osmium. Part VIII. A Note on the Wea of
Ammonium Hexachlorosmate IV. By F. P. Dwyer and J. W. Hogarth

ArT. XXXII.—The Essential Oils of Zierta Smithit (Andrews) and its Various Forms.
Part II. By F. R. Morrison, A. R. Penfold and Sir John Simonsen

Index to Volume LXXXIV

* Published May 30, 1951.
+ Published August 17, 1951.

Page

99

107

165,

169

184

188

194

196

Le

a te ie FOR
aad (INCORPORATED 1881)

PART I (pp. i-xxvii, 1-67, Plates I and II)
sag a \s aS OF { s A
Bee ue eo VOL. LXXXIV ; SAE aie

_ Containing List of Members, Report of Council, Balance Shigek:
_ Obituary Notices and Papers read in April and May, 1950.

\y

4 , '

Beg in. ic th bn Gog (O BRITED (BY

BS et ida A. BROWNE, D.Sc.

f

i a } _ Honorary Editorial Secretary

; -

f : | > : 3 ay
Pein ~ F TER,

| ‘THE AUTHORS OF PAPERS ARE ALONE RESPONSIBLE FOR THE
__ STATEMENTS MADE AND THE OPINIONS EXPRESSED THEREIN

Pee he SYDNEY _ |
PUBLISHED BY THE SOCIETY, SCIENCE HOUSE
‘GLOUCESTER AND ESSEX STREETS: aN i

CONTENTS ©

VOLUME L¥EXKIV a

Part I
Page
TiItLE Pacer ie, ie cK t Be: ot aah fa p, a eh i-
OFFICERS FoR 1950-1951 wt oe ait a ys Ne ie fe eee
NoricEs io a ay ep i: ae ys La ny i » oa iv
List oF MEMBERS - we Siew aes Pep oN Ye ie Ae run ee v-
AWARDS, ETc. ay hs Me a % ee at oe ae oe oi 5 a
REPORT OF THE COUNCIL f eS af i s ie a a oe
BALANCE SHEET .. He zs se ee i i Ke a a <a
OxsituaRy NOTICES fi fs hi. tl i wis is ag ane eh | ah "ie —
Art. I.—Presidential Address. By Harley Wood.
The Work of the Society .. ¥ : ae: a ai an ae 1
Astronomy in Australia ya is ua ey ha A a oe 3
Art. II.—Dalton- omnes a? N.S.W., Earth Tremors of March, oe. By G. F,
Joklik .. ; ‘ : oe eee: "|
Art, II1.—Palladium doksse ae of Thioethers. Part I. The Reaction of Potassium
Chloropalladite II with o-Methyl es Benzoic Acid. a S.. E. :
R. A. Plowman and J. Sorensen wary, S29
Art. [V.—Nitrogen in Oil Shale and Shale Oil. XII. The Volumetric Determination
of Basic Nitrogen in Shale Oils. By Geo. E. Mapstone oe a oe 4 ao
Ant, V.—Nitrogen in Oil Shale and Shale Oil. XIII. An Approximate Method for
Determining Pyridine Nitrogen in Oil Shale and Similar Materials. By Geo. E.
_Mapstone Ai ee i. ey “s re es a Ht EE ~. syat
Art. VI.—Studies in the Chemistry of Platmum Complexes. Part II. Some Preneie
of Tetrammine Platinum II Fluorides. By R. A. Plowman. : 38
Art, VII.—Studies in the Chemistry of Platinum Complexes. Part III. Oxidation
of the Tetrammine Platinum II Fluorides. By R. A. Plowman .. 41
Arr. VIII.—Occultations Observed at Bs ei eee aE 1949. By W. H.
Robertson a rae Apa 8
Art. [X.—The Geology of the Canowindra District, N.S.W. Part II. The Canowindra-
Cowra-Woodstock Area. By N. C. Stevens —.. She 46
Art. X.—The Five Properties Concerned in the Transport of the Active Corrodant
Agent. By R. C. L. Bosworth .. oe SS bi 56 <2 cc ee i,"
ArT. XI.—The Mechanism of the Fischer Indole haraips By P, A: hae G. K. ;
Hughes and E. Ritchie o 09

Art. XII.—The Permian Rocks of the le Macleay Pes New South Wales.
By, A. H. Voisey: 2. ; 64

JOURNAL AND PROCEEDINGS

OF THE

ROYAL SOCIETY

OF NEW SOUTH WALES

FOR

1950

(INCORPORATED 1881)

——$—$$———— —__—___——

VOLUME LXXXIV

Part I

EDITED BY

Ida A. BROWNE, D.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

A | JUN 27 1951

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Royal Society of New South Wales
OFFICERS FOR 1950-1951

Patrons:
His ExcELLENCY THE GOVERNOR-GENERAL OF THE COMMONWEALTH OF AUSTRALIA
THe Rr. Hon. W. J. McKELL, P.c.

His EXcELLENCY THE GOVERNOR OF NEW SoutTH WALES,
LIEUTENANT-GENERAL JOHN NORTHCOTT, c.B., M.v.o.

President :
F. R. MORRISON, 4.4.¢.1., F.C.S.

Vice-Presidents :

R. O. CHALMERS, 4.s.17.c. | D. J. K. OCONNELL, S.J., M.Sc., F.R.A.S.
H. O. FLETCHER. | H. W. WOOD, M.sc., A.Inst.P., F.R.A.S.

Honorary Secretaries :

R. C. L. BOSWORTH, m.sc., D.se. (Adel.), | IDA A. BROWNE, D.sc.
Ph.D. (Camb.), ¥F.A.C.1., F.Inst.P. |

Honorary Treasurer :
C. J. MAGEE, D.sc.agr. (Syd.), M.sc. (Wis.).

Members of Council:

K. E. BULLEN, m.a., B.Sc. (N.Z.), M.A. C. St. J. MULHOLLAND, B.sc.
(Melb.), Ph.D., Sc.D. (Camb.), F.R.S. P. M. ROUNTREE, m.sc. (Melb.),

H. B. CARTER, B.v.sc. Dip.Bact. (London).

H. A. J. DONEGAN, 4A.8.7.c., A.A.C.1. W. B. SMITH-WHITE, m.a. (Cantabd.),

G. K. HUGHES, B.sc. B.Sc. (Syd.).

R. J. W. Le FEVRE, D.Sc., Ph.D., F.R.1.C. N. R. WYNDHAM, o.p., m.s. (Syd.),

C. E. MARSHALL, Ph.D., D.Sc. F.R.C.S. (Hng.), F.R.A.C.S.

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.

fd) he yur ath the sum of £ to the Royvat Society oF NEw SoutH WALEs,
Incorporated by Act of the Parliament of New South Wales in 1881, and I declare that the receipt
of the Treasurer for the time being of the said Corporation shall be an effectual discharge for the
said Bequest, which I direct to be paid within calendar months after my decease,
without any reduction whatsoever, whether on account of Legacy Duty thereon or otherwise,
out of such part of my estate as may be lawfully applied for that purpose.

[Those persons who feel disposed to benefit the Royal Society of New South Wales by Legacies
are recommended to instruct their Solicitors to adopt the above Form of Bequest. ]

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
- 1D Agee. LXVIII (1920 to 1934) ,, 25/- ,,
3 LXX 5, “Ee Xext (1936 to’ 1948)" o2b)-= ©
9 LXXXIII onwards » 30/- "

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

Royal Society of New Sonth Wales

as at April 1, 1950

P Members who have contributed papers which have been published in the Society’s Journal. The numerals
indicate the number of such contributions.

{ Life Members.

Elected.

1944
1938

1935
1898
1941
1948
1948

1930

1919

1935
1949
1924
1934
1937
1949
1946

1919
1947

1933
1926
1940
1937

1916
1920

1939
1948

1946
1933

P32
2
1

Bal
2
y
2

i eel |

Bak

ees)

P 29

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, 1.8., Registered Surveyor, Box 57, Orange, N.S.W.

Anderson, Geoffrey William, Bsc., 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.

Back, Catherine Dorothy Jean, m.sc., The Women’s College, Newtown.

Backhouse, James Roy, m.sc. Syd., Lecturer, Sydney Technical College ;
p.r. Fowler-avenue, Bexley North.

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.mnst.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.

Ball, Reginald Arthur, Industrial Chemist, 25 George-street, Sydney.

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.v.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. Ovon., The University Chemical Laboratory,
Cambridge, England.

Birrell, Septimus, 17 Appian Way, Burwood.

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.se. (Hons.), Industrial Chemist, 12 Culworth-avenue,
Killara.

Blaschke, Ernst Herbert, 6 Ilistron 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.)

vi

Elected.

1920 P 9 | Booth, Edgar Harold, M.c., D.sc., F.Inst.p., “‘ Hills and Dales,’’ Mittagong.
(President, 1935.)

1939 P 24 Bosworth, Richard Charles Leslie, m.sc., p.sc. Adel., Ph.p. Camb., F.A.C.1.,
F.Inst.P., c.o. C.S.R. Co. Ltd., Pyrmont; p.r. 41 Spencer-road, Killara.

1948 Boyd, Eric Harold, B.A., B.Sc., Dip.Ed., F.P.S., The King’s School, Parramatta.
1948 Boyd, Joan, B.Sc. Hons. Lond., Dip.zd. Lond., The King’s School, Parramatta.
1938 Breckenridge, Marion, B.sc., Department of Geology, The University of Sydney ;

p-r. 19 Handley-avenue, Thornleigh,

1949 1h oy Brewer, Roy, B.Sc. Syd., Research Officer, Division of Soils, C.S.I.R.O.; p.r.
Block 1, Section 56, O’Connor, Canberra, A.C.T.

1946 Pel Breyer, Bruno, M.D., Ph.D., M.A., F.A.C.1., Lecturer in Agricultural Chemistry,
Faculty of Agriculture, University of Sydney, Sydney.

1919 Piel Briggs, George Henry, D.Sc., Ph.D., F.Inst.P., Officer-in-Charge, Section of
Physics, National Standards Laboratory of Australia, University Grounds,
Sydney; p.r. 13 Findlay-avenue, Roseville.

1942 Brown, Desmond J., M.se. (Syd.), Ph.D. (Lond.), D.1.c., Department of Medical
Chemistry, Australian National University, 183 Euston-road, London,
N.W.1.

1945 Brown, Norma Dorothy (Mrs.), B.sc., Biochemist, 2 Macauley-street, Leich-
hardt.

1941 Brown, Samuel Raymond, A.c.a. Aust., 87 Ashley-street, Chatswood.

1935 Bd Browne, Ida Alison,p.sc.,Senior Lecturer in Paleontology, University of Sydney.
1913 P 23 |{Browne, William Rowan, D.sc., Reader in Geology, University of Sydney.
(President, 1932.)

1947 Buchanan, Gregory Stewart, B.Sc. (Hons.), Lecturer in Physical Chemistry,
Sydney Technical College ; p.r. 19 Ferguson-avenue, Thornleigh.

1940 Buckley, Lindsay Arthur, B.sc., 29 Abingdon-road, Roseville.

1946 Bullen, Keith Edward, M.A., B.sc. N.Z., M.A. Melb., Ph.D., Sc.D. Camb., F.R.S.,
Professor of Applied Mathematics, University of Sydney, Sydney, N.S.W.

1898 {Burfitt, W. Fitzmaurice, B.A., M.B., Ch.M., B.Sc. Syd., F.R.A.C.S., ““ Radstoke,”’
Elizabeth Bay.

1926 Burkitt, Arthur Neville St. George, M.B.; B.sc., Professor of Anatomy in the

University of Sydney.

1938 P 2 |tCarey, Samuel Warren, D.Sc., Professor of Geology, University of Tasmania,

Tasmania.

1948 Carroll, Dorothy, B.A., B.Sc., Ph.D., D.1.c., Secretary, Linnean Society of New
South Wales, Science House, 157 Gloucester-street, Sydney.

1903 P 5 |t{Carslaw, Horatio Scott, Sc.D., LL.D., F.R.S.E., Emeritus Professor of Mathe-

matics, University of Sydney, Fellow of Emmanuel College, Cambridge ;
Burradoo, N.S.W.

1945 Carter, Harold Burnell, B.v.sc., Officer-in-Charge, Wool Biology Laboratory,
17 Randle-street, Sydney.

1944 Cavill, George William Kenneth, m.sc., c/o Department of Organic Chemistry,
The University, Liverpool, Great Britain.

1913 P 4 |}{Challinor, Richard Westman, F.R.I.C., A.A.C.1., A.S.T.C., F.c.S.; p.r. 54 Drum-
albyn-road, Bellevue Hill. (President, 1933.)

1933 Chalmers, Robert Oliver, A.s.T.c., Australian Museum, College Street, Sydney.

1940 Chambers, Maxwell Clark, B.sc., c/o Coty (England) Ltd., 35-41 Hutchinson-

street, Moore Park; p.r. 58 Spencer-road, Killara.
1913 P 21 |tCheel, Edwin, 40 Queen-street, Ashfield. (President, 1931.)
1935 1a 74 Churchward, John Gordon, B.Sc.Agr., Ph.D., 1 Hunter-street, Woolwich.

1935 Clark, Sir Reginald Marcus, K.B.E., Central Square, Sydney.

1938 Clune, Francis Patrick, Author and Accountant, 15 Prince’s-avenue, Vaucluse.

1941 Cohen, Max Charles, B.sc., 80 ‘‘ St. James,”’ Stanley-street, Sydney.

1940 Cohen, Samuel Bernard, M.sc., A.A.c.1., 74 Boundary-street, Roseville.

1940 Je 4 Cole, Edward Ritchie, B.sc., 7 Wolsten-avenue, Turramurra.

1940 Po Cole, Joyce Marie, B.Sc., 7 Wolsten-avenue, Turramurra.

1948 Cole, Leslie Arthur, Company Executive, 21 Carlisle-street, Rose Bay.

1940 Collett, Gordon, B.sc., 27 Rogers-avenue, Haberfield.

1948 Cook, Cyril Lloyd, m.sc., 176 Ben Boyd-road, Neutral Bay.

1946 Cook, Rodney Thomas, A.s.T.c., 10 Riverview-road, Fairfield.

1920 Cooke, Frederick, c/o Meggitt’s Limited, Asbestos House, York and Barrack-
streets, Sydney.

1945 Coombes, Arthur Roylance, A.s.T.c. (chem.), 14 Georges River-road, Croydon.

1913 P 5 |tCoombs, F. A., F.c.s., Instructor of Leather Dressing and Tanning, Sydney
Technical College ; p.r. Bannerman-crescent, Rosebery.

Elected.
1933
1940
1919

1909
1941
1921

1948

1940
1919
1906
1913
1928

1947
1948

1943
1937

1948
1924

1934

1945
1949
1934

1949

1940
1944
1908
1935
1949

1909

1940
1940
1933

1949
1949

1932
1905
1940
1943
1940

1944
1945

Pt

1
Pl

2

3
P 14
P 49
Py 2
Pt
Pez

Corbett, Robert Lorimer, Scot Chambers, Hosking-place, Sydney.

Cortis-Jones, Beverly, M.sc., 62 William-street, Roseville.

Cotton, Frank Stanley, D.sc., Research Professor in Physiology in the University
of Sydney.

{Cotton, Leo Arthur, M.A., D.Sc., 113 Queen’s Parade East, Newport Beach.
(President, 1929.)

Craig, David Parker, ph.D., Chemistry Department, University College, Gower-
street, London, W.C.1., England.

{Cresswick, John Arthur, A.A.C.1., F.c.Ss., 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.

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.

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, D.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.sc., 21 Steward-street, Leichhardt.

Eisinger, Erich, “ 1ng.”’ Austria, 24 Cooper-street, Double Bay.

Elkin, Adolphus Peter, M.a., Ph.D., Professor of Anthropology in the University
of Sydney. (President, 1940.)

Ellison, Dorothy Jean, M.Sc. (Hons.) N.Z., Science Teacher, Abbotsleigh,
Wahroonga; p.r. 51 Tryon-road, Lindfield.

Emmerton, Henry James, B.Sc., 1 Rosedale-road, Gordon.

Erhart, John Charles, Chemical Engineer, c/o “Ciba” Coy., Basle, Switzerland.

tEsdaile, Edward William, 42 Hunter-street, Sydney.

Evans, Silvanus Gladstone, a.1.a.a. Lond., A.R.A.1.A., 6 Major-street, Coogee.

Everingham, Richard, 3 The Bastion, Castlecrag.

{Fawsitt, Charles Edward, D.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, Palzontologist, Australian Museum, College-street,
Sydney.

Flinter, Basil Harold, 75 Elizabeth Bay-road, Elizabeth Bay.

Follett, Frank William, Managing Director, Adastra Airways Pty. Ltd. ;
p.r. 74 Hopetoun-avenue, Vaucluse.

Forman, Kenn. P., M.1.Refr.E., Box 1822, G.P.O., Sydney.

{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., 1540 High-street, Malvern, 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.), p.M.p. (Hamburg), Dental Surgeon,
158 Bellevue-road, Bellevue Hill.

Vii

Elected.

1948
1935
1939
1926

1942
1947
1947
1940
1948

1945
1947

1949
1936
1949
1948
1938
1946

1948

1947

1934
1892

1949
1940
1905
1936
1934
1948
1949
1946
1934
1919
1945
1938
1936
1928

1948
1916

1941

bg bg
we bo

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.

Garretty, Michael Duhan, D.sc., 477 St. Kilda-road, Melbourne, §.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.

Gordon, William Fraser, B.Sc. Syd., Industrial Chemist ; p.r. 176 Avoca-street,
Randwick.

Goulston, Edna Maude, B.sSc., 83 Birriga-road, Bellevue Hill.

Gover, Alfred Terence, M.com., 32 Benelong-road, Cremorne.

Gray, Charles Alexander Menzies, B.Sc., B.E., 75 Woniora-road, Hurstville.

Griffiths, Edward L., B.Sc., A.A.C.I., A.R.1.C., Chief Chemist, Department of
Agriculture ; p.r. 151 Wollongong-road, Arncliffe.

Gutmann, Felix, Ph.D., F.Inst.P., M.1.R.E., N.S.W. University of Technology,
Broadway, 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, Norman Frederick Blake, m.sc., Chemist, 154 Wharf-road, Longueville.

tHalloran, Henry Ferdinand, L.s., A.M.I.E.Aust., F.S.I.Eng., M.T.P.1.Eng., 153
Elizabeth-street, Sydney ; p.r. 23 March-street, Bellevue Hill.

Hampton, Edward John William, 4.s.T.c.; p.r. 1 Hunter Street, Waratah,
N.S.W.

Hanlon, Frederick Noel, B.sc., Geologist, Department of Mines, Sydney.

{Harker, 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, A.s.T.c., Demonstrator, Chemistry Department, Sydney
Technical College; p.r. 12 Livingstone-road, Lidcombe.

Harris, Henry Maxwell, B.sc., B.E., Assistant Engineer, W.C. & I.C., 25 Prospect-
road, Summer Hill.

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.I., 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. corner
Bungaloe-avenue and New-street, Balgowlah.

Hill, Dorothy, m.sc. Q’ld., Ph.p. Cantab., Geological Research Fellow,
University of Queensland, Brisbane.

Hirst, Edward Eugene, a.M.1.E., Vice-Chairman and Joint Managing Director,
British General Electric Co. Ltd.; p.r. “‘ Springmead,”’ Ingleburn.

Hirst, George Walter Cansdell, B.sc., A. MALE. (Aust.), ‘‘ 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.1.E. Aust., Consulting and
Designing Engineer, 81] Frederick- street. Rockdale.

Howard, Harold Theodore Clyde, B.sc., Principal, Technical College, Granville.

ix

Elected.

1938 Pe Hughes, Gordon Kingsley, B.sc., Department of Chemistry, University of
Sydney, Sydney.

1947 Py ih Humpoletz, Justin Ernst, B.sc. Syd., 21 Belgium-avenue, Roseville.

1923 P 3 (|ftHynes, Harold John, pD.Sc., B.Sc.Agr., Biologist, Department of Agriculture,
Box 36a, G.P.O., Sydney ; p.r. “ Belbooree,’’ 10 Wandella-avenue, Rose-
ville.

1943 Iredale, Thomas, D.Sc., F.R.I.c., Chemistry Department, University of Sydney,
p-r. 96 Roseville-avenue, Roseville.

1942 P il Jaeger, John Conrad, M.A., D.sc., University of Tasmania, Hobart, Tasmania.

1909 P 15 Johnston, Thomas Harvey, M.A., D.Sc., 0.M.Z.S., Professor of Zoology in the
University of Adelaide. (Cor. Mem., 1912.)

1949 Joklik, Gunther F., B.Sc., c.o. Bureau of Mineral Resources, Canberra, A.C.T.

1935 P 6 | Joplin, Germaine Anne, B.sc., Ph.D., 18 Wentworth-street, Eastwood.

1948 Pil Jopling, Alan Victor, B.sc., B.E., 28 Cliff-street, Manly.

1930 Judd, William Percy, 123 Wollongong-road, Arncliffe.

1935 Kelly, Caroline Tennant (Mrs.), Dip.anth., ‘“‘ Eight Bells,” Cast Hill.

1940 Kennard, William Walter, 9 Bona Vista-avenue, Maroubra.

1924 Lea Kenny, Edward Joseph, Geological Surveyor, Department of Mines, Sydney ;
p.r. 17 Alma-street, Ashfield.

1934 Kerslake, Richmond, A.Ss.T.c., A.A.c.I., Industrial Chemist, 29 Nundah-street,
Lane Cove.

1948 Kimble, Frank Oswald, Engineer, 16 Evelyn-avenue, Concord.

1943 Kimble, Jean Annie, B.sc., Research Chemist, 383 Marrickville-road, Marrick-
ville.

1920 Kirchner, William John, B.se., A.A.c.1., Manufacturing Chemist, c/o Messrs.

Burroughs Wellcome & Co. (Australia) Ltd., Victoria-street, Waterloo ;
p.r. 18 Lyne-road, Cheltenham.

1948 Knight, Oscar Le Maistre, B.z. Syd., A.M.1.C.E., A.M.1.E.Aust., Engineer, 10
Mildura-street, Killara.
1948 Koch, Leo E., ph.p., D.se. (Cologne), Department of Geology, The University

of Sydney; p.r. 39 Bond-street, Mosman.

1939 Pt Lambeth, Arthur James, B.Sc., ‘‘ Naranje,’? Sweethaven-road, Wetherill

Park, N.S.W.

1949 Lancaster, Kelvin John, B.sc., 43 Balfour-road, Rose Bay.

1936 | Leach, Stephen Laurence, B.A., B.Sc., A.A.C.1., British Austrahan Lead Manu-
facturers Pty. Ltd., Box 21, Bio. Concord:

1946 Lederer, Michael, 67 Edgecliff-road, Bondi Junction.

1947 Le Fevre, Raymond James Wood, D.Sc., Ph.D., F.R.1.c., Professor of Chemistry,

Chemistry Department, University of Sydney, Sydney.

1936 Piz Lemberg, Max Rudolph, p.phil., Institute of Medical Research, Royal North
Shore Hospital, St. Leonards.

1920 Le Souef, Albert Sherbourne, 3 Silex-road, Mosman.

1929 P56 (|{Lions, Francis, B.Sc., Ph.D., A.R.1I.Cc., Reader, Department of Chemistry, Uni-
versity of Sydney. (President, 1946-47.)

1942 Lippmann, Arthur 8., m.p., 175 Macquarie-street, Sydney.
1947 Lloyd, James Charles, B.Sc. Syd., N.S.W. Geological Survey, 41 Goulburn-street,
Liverpool.

1940 Pescd Lockwood, William Hutton, B.Sc., c.o. Institute of Medical Research, The
Royal North Shore Hospital, St. Leonards.

1906 tLoney, Charles Augustus Luxton, M.Am.soc.Refr.E., National Mutual Building,
350 George-street, Sydney.

1949 Loughnan, Frederick Charles, ‘“‘ Bodleian ’’, 26 -Kenneth-street, Longueville.

1947 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. 5 Berrima
Flats, 12 Mulwarrie-avenue, Randwick.

1943 {Luber, Daphne (Mrs.), B.sc., 98 Lang-road, Centennial Park.
1945 Luber, Leonard, Pharmacist, 80 Queen-street, Woollahra.
1948 Pig Lyons, Lawrence Ernest, B.A., M.Sc., Lecturer in Chemistry, The University

of Sydney ; p.r. 13 Albert-road, Strathfield.
1942 . Lyons, Raymond Norman Matthew, m.sc., Biochemical Research Worker,

P 4

2
Po

1
Pian
P 12
P 1
P 25
P 28
Pr 2
Pe

Maccoll, Allan, m.sc., Department of Chemistry, University College, Gower-
street, London, W.C.1.

McCarthy, Frederick David, Curator of Anthropology, Australian Museum,
Sydney; p.r. 10 Tycannah-road, Northbridge.

McCoy, William Kevin, Analytical Chemist, c/o Mr. A. J. McCoy, 39 Malvern-
avenue, Merrylands.

McElroy, Clifford Turner, 147 Arden-street, Coogee.

McGregor, Gordon Howard, 4 Maple-avenue, Pennant Hills.

McInnes, Gordon Elliott, Department of Geology, The University of Sydney;
p.r. 46 Laycock-street, Bexley.

tMcIntosh, Arthur Marshall, “‘ Moy Lodge,” Hill-street, Roseville.

McKenzie, Hugh Albert, B.sc., 52 Bolton-street, Guildford.

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. Leeds, 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.

Marshall, Charles Edward, Ph.D., D.sc., Professor of Geology, The University
of Sydney, Sydney.

Martin, Cyril Maxwell, Chemist, 22 Wattle-street, Haberfield.

May, Albert, Ph.p., M.A., 94 Birriga-road, Bellevue Hill. '

Maze, William Harold, m.sc., Registrar, The University of Sydney, Sydney.

Meares, Harry John Devenish, Technical Librarian, Colonial Sugar Refining
Co. Ltd., Box 483, G.P.O., Sydney.

{Meldrum, Henry John, B.A., B.Sc., Lecturer, The Teachers’ College, University
Grounds, Newtown; p.r. 98 Sydney-road, Fairlight.

Mellor, David Paver, D.sc., F.A.C.1., Reader, Department of Chemistry, Uni-
versity of Sydney; p.r. 137 Middle Harbour-road, Lindfield. (President,
1941-42.)

Micheli, Louis Ivan Allan, M.sc., Ph.D., Research Chemist, Jordan House,
Jordan Terrace, Bowen Hills, Brisbane.

Millership, William, m.sc., Chief Chemist, Davis Gelatine (Aust.) Pty. Ltd.,
15 Shaw-avenue, Earlwood.

Morrison, Frank Richard, A.A.C.1., F.c.S., Deputy Director, Museum of Tech-
nology and Applied Science, Harris-street, Ultimo.

Morrissey, Matthew John, B.A., A.s.T.c., Auburn Street, Parramatta.

Mort, Francis George Arnot, A.A.c.1., Chemist, 110 Green’s-road, Fivedock.

Mosher, Kenneth George, B.Sc., Geologist, c.o. Joint Coal Board, 66 King-street,
Sydney.

Moye, Daniel George, Geologist, 6 First-avenue, Snowy Mountains Hydro-

Electric Authority, Cooma, N.S.W.
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.
t{Murphy, Robert Kenneth, Dr.iIng., 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.

Elected.
1943

1935
1945

1938
1920
1947
1948
1940

1935
1947
1921

1920
1949
1948
1938
1935
1946
1943

1919

1949
1896
1946
1921
1938
1945
1927
1918

1945
1893

1935

1922

1940
1919
1936
1947

Pel
age

xl

Nicol, Alexander Campbell, a.s.T.c., A.A.c.1., Chief Chemist, Crown Crystal
Glass Co.; p.r. 200 Paine-street, Maroubra.

Nicol, Phyllis Mary, m.sc., Sub-Principal, The Women’s College, Newtown.

Noakes, Lyndon Charles, Geologist, c/o Mineral Resources Survey, Canberra,
A: Cc®.

Noble, Norman Scott, D.sc.agr., M.Sc., D.I.c., c/o C.S.I.R., 314 Albert-street,
East Melbourne, Vic.

P 4 |tNoble, Robert Jackson, M.sc., B.Sc.Agr., Ph.D., Under Secretary, Department of

P 25
P 4
Pill
P 75
1 edge |
P 2
Pol
P’'3

6
iPe2
P 3

Agriculture, Box 364, G.P.O., Sydney; p.r. 324 Middle Harbour-road,
Lindfield. (President, 1934.)

Nordon, Peter, A.S.T.C., A.A.C.1., Chemical Engineer, 39 Tahlee-street, Burwood.

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., 8.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, D.Sc. Syd., Ph.p. Camb., Lecturer and Demonstrator
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.)

Penrose, Ruth Elizabeth, B.sc., 92 Baringa-road, Northbridge.

Perry, Hubert Roy, B.sc., 74 Woodbine-street, Bowral.

Phillips, Marie Elizabeth, B.sc., Botany Department, University, Manchester,
13, England.

Philips, Orwell, 55 Darling Point-road, Edgecliff.

Pinwell, Norman, B.A. (Q’land), The Scots College, Bellevue Hill.

Plowman, Ronald Arthur, B.sc. Lond., A.S.T.C., A.A.c.I., Analytical Chemist,
21 Harris-street, Normanhurst.

Poate, Hugh Raymond Guy, M.B., ch.m. Syd., F.R.c.S. Hng., L.R.c.P. Lond.,
F.R.A.C.S., Surgeon, 225 Macquarie-street, Sydney; p.r. 38 Victoria-road,
Bellevue Hill.

Poggendorff, Walter Hans George, B.Sc.Agr., Chief of the Division of Plant
Industry, N.S.W. Department of Agriculture, Box 364, G.P.O., Sydney.

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., 68 Wharf-road, Gladesville.

Powell, Charles Wilfrid Roberts, F.R.1.C., A.A.C.1., Company Executive, c/o
Colonial Sugar Refining Co., O’Connell-street, Sydney ; p.r. ‘‘ Wansfell,”’
Kirkoswald-avenue, Mosman.

Powell, John Wallis, A.s.T.c., A.A.C.I., 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.z., B.Sc., Teacher of Physics, Sydney Technical
College; p.r. 8 Wattle-street, Killara.

Priestley, Henry, M.D., Ch.m., B.Sc., 54 Fuller’s-road, Chatswood. (President,
1942-43.)

Proud, John Seymour, Mining Engineer, 4 View-street, Chatswood.

{Purser, 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, Bureau of Mineral Resources, Geology
and Geophysics, 485 Bourke-street, Melbourne, C.1, Victoria.

Ralph, Colin Sydney, B.sc., 24 Canberra-street, Epping.

Ranclaud, Archibald Boscawen Boyd, B.sSc., B.E., 57 William-street, Sydney.

Randall, Harry, Buena Vista-avenue, Denistone.

Ray, Nancy Evelyn (Mrs.), Plastics Manufacturer, 14 Hedger-avenue, Ashfield.

xl
Elected.
1947
1931
1935
1947
1946
1947
1947
1939

1939
1933

1940

1949
1935
1940
1948
1940

1948
1945

1945
1920

1948
1946
1940
1949

1933
1936

1948
1938
1936
1948
1945
1945

1948
1943
1933
1940
1947

1919

aoRas)

18

Ray, Reginald John, Plastics Manufa$ urer 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.a.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.

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.

Robertson, William Humphrey, B.sc., Astronomer, Sydney Observatory,
Sydney.

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.p., 48 Cambridge-avenue,' Vaucluse.

Ross, Jean Elizabeth, B.sSc., Dip.Ed., 5 Stanton-road, Haberfield.

Ross, Leonard Paul, B.sc., 137 Burwood-road, Enfield.

Rountree, Phyllis Margaret, m.sc. Melb., Dip.Bact. Lond., Royal Prince Alfred
Hospital, Sydney.

Sampson, Aileen (Mrs.), Sc.Dip. (A.S.T.c., 1944), 9 Knox-avenue, Epping.

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.

See, Graeme Thomas,. Analytical Chemist, 2 Skipton Flats, corner Mount and
Dudley-streets, Coogee.

Selby, Esmond Jacob, pip.com., Sales Manager, Box 175 D, G.P.O., Sydney.

Sellenger, Brother Albertus, St. Ildephonsus College, New Norcia, W.A.

{tSharp, 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, p.sc., F.A.C.1., 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, 1 Rocklands-road, Wollstonecraft.

Smith-White, William Broderick, m.a. Cantab., B.sc. Syd., Department of
Mathematics, University of Sydney ; p.r. 28 Cranbrook-avenue, Cremorne.

Southee, Ethelbert Ambrook, 0.B.E., M.A., B.Sc., B.Sc.Agr., Principal, Hawkes-
bury Agricultural College, Richmond, N.S.W.

Elected.

1949

1916
1914

1948
1900

1942
1916
1918

1919
1920
1941

1948

1915

1944
1946
1946
1919
1935

1923
1940
1949
1943
1949
1921
1935

1933

1903

1948
1943
1919

1913

1944
1921

1919

xl

Stanton, Richard Limon, B.sc., Teaching Fellow in Geology, The University
of Sydney, Sydney ; p.r. 42 Hopetoun-avenue, Mosman.

Stephen, Alfred Ernest, F.c.s., c/o Box 1158 HH, G.P.O., Sydney.

tStephens, 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.se., 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., Professor of Biochemistry, The University of
Sydney, Sydney.

Stone, Walter George, F.S.T.C., F.A.C.1., Chief Analyst, Department of Maes.
Sydney ; p.r. 26 Rosslyn-street, Bellevue Hill.

tSullivan, Herbert Jay, Director in Charge of Research and Technical Depart-
ment, c/o Lewis Berger & Sons (Australia) Ltd., Rhodes; Box 23, P.O.,
Burwood ; p.r. “‘ Stonycroft,” 10 Redmyre-road, Strathfield.

tSutherland, George Fife, a.r.c.sc. Lond., 47 Clanwilliam-street, Chatswood.

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.

Swanson, Thomas Baikie, M.sc. Adel., c/o Technical Service Department,
Icianz, Box 1911, G.P.O., Melbourne, Victoria.

Swinbourne, Ellice Simmons, Organic Chemist, A.S.T.C., A.A.C.I., 1 Raglan-
street, Manly.

{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. 12
Wood-street, Manly.

Thomas, Andrew David, Squadron Leader, R.A.A.F., M.sc., A.Inst.p. 17
Millicent-avenue, Toorak, Melbourne, E.2., Vic.

Thomas, Ifor Morris, m.sc., Department of Zoology, University of Adelaide,
Adelaide, S.A.

Thompson, Nora (Mrs.), B.sc. Syd., c/o Australasian Petroleum Coy., Port
Moresby, Papua.

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.
Tommerup, Eric Christian, M.Sc., A.A.C.1., Queensland Agricultural College,

Lawes, via Brisbane, Queensland.

Toppin, Richmond Douglas, 4.R.1.c., 51 Crystal-street, Petersham.

Tow, Aubrey James, m.sc., No. 5, “‘ Werrington,’’ Manion-avenue, Rose Bay.

Trebeck, Prosper Charles Brian, A.c.1.S., F.com.a., Hng., A.F.I.A., A.A.A., J.P.,
3 Honda-road, Neutral Bay.

Turner, Ivan Stewart, M.A., M.Sc., Ph.D., Lecturer in Mathematics, University
of Sydney; p.r. 120 Awaba-street, Mosman.

Vallance, Thomas George, 57 Auburn-street, Sutherland.

Vicars, Robert, Marrickville Woollen Mills, Marrickville.

Vickery, Joyce Winifred, M.sc., Botanic Gardens, Sydney; p.r. 17 The
Promenade, Cheltenham.

Voisey, Alan Heywood, p.sc., Lecturer in Geology and Geography, New
England University College, Armidale.

tVonwiller, Oscar U., B.sc., F.Inst.p., Emeritus Professor of Physics in the
University of Sydney ; Bice = Eightbells,” Old Castle Hill-road, Castle Hill.
(President, 1930.)

Walker, Donald Francis, Surveyor, 13 Beauchamp-avenue, Chatswood.

Walker, James Foote, Company Secretary, 11 Brucedale-avenue, Epping.

Walkom, Arthur Bache, p.sc., Director, Australian Museum, Sydney; p.r.
45 Nelson-road, Killara. (Member from 1910-1913. President, 1943-44.)

\t{Wardlaw, Hy. Sloane Halcro, D.sc. Syd., F.A.c.1., c/o Kanematsu Institute,

Sydney Hospital, Macquarie Street, Sydney. (President, 1939.)
Warner, Harry, A.Ss.T.c., Chemist, 6 Knibbs-street, Turner, Canberra, A.C.T.
tWaterhouse, Gustavus Athol, D.sSc., B.E., F.R.E.S., F.R.zZ.S., c/o Mrs. Millett,
Illoura-avenue, Wahroonga.
Waterhouse, Lionel Lawry, B.E. Syd., Lecturer and Demonstrator in Geology
in the University of Sydney.

X1V
Elected.
1919
1944
1911

1921
1947

1921

1947
1949

1946
1943

1928
1949
1942
1949
1945
1943
1940
1936
1906
1916

1946

1948

Elected.
1949

1949
1914
1946
1915
1912
1948 °
1948
1946

Ping

fe)
P 12

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.)

Watkins, William Hamilton, 8B.Sc., Industrial Chemist, 57 Bellevue-street,
North Sydney.

t{Watt, Robert Dickie, M.a., B.Sc., Professor of Agriculture in the University of
Sydney ; p.r. 64 Wentworth-road, Vaucluse. (President, 1925.)

Watts, Arthur Spencer, ‘“‘Araboonoo’’, Glebe-street, Randwick.

Webb, Gordon Keyes, A.F.1.A., A.C.1.S., Accountant, c/o Max Wurcker (1930)
Pty. Ltd., 99 York-street, Sydney.

Wenholz, Harold, B.sc.agr., Director of Plant Breeding, Department of Agri-
culture, Sydney.

Werner, Ronald Louis, Industrial Chemist, 25 Dine-street, Randwick. |

Westheimer, Gerald, B.Sc., F.S.T.C., F.1.0., Optometrist, 727 George-street,
Sydney.

Weston, Margaret Crowley, B.A., 41 Bulkara-road, Bellevue Hill.

Whiteman, Reginald John Nelson, M.B., Ch.M., F.R.A.C.S., 143 Macquarie-street,
Sydney.

Wiesener, Frederick Abbey, M.B., Ch.M., D.O.M.s., Ophthalmic Surgeon, Bram
Hall, Jersey-road, Strathfield.

Williams, Benjamin, A.s.T.c., 97 McMichael-street, Maryville, N.S.W.

Williams, Gordon Roy, B.sc.

Williamson, William Harold, Hughes-avenue, Ermington.

Willis, Jack Lehane, B.sc., Flat 5, *‘ Narooma’’, Hampden-street, North
Sydney.

Winch, Leonard, B.sc., 26 Boonah-street, Griffith, N.S.W.

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. (President, 1949.)

t{Woolnough, Walter George, D.Sc., F.G.S., c/o Mr. W. L. Woolnough, ‘“‘ Calla-
bonna ’’, & 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, Sydney.

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, rF.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, 1949-50.

1890 Henry Harvey Dare.
1916 Walter John Enright.
1879 Joseph Foreman.

1891 Robert Thomas McKay.
1941 Dansie Thomas Sawkins.
1909 Charles Josiah White.

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 EK. 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.S. 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.)
1937. ‘“‘ Some Problems of the Great Barrier Reef.’’ By Professor H. C. Richards, D.Sc. (Tus
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. (THis
JouRN., 1940, 74, 283.)
1941. “The Climate of Australia in Past Ages.”’ By C. A. Sussmilch, F.G.S. (THis Journ.,
1941, 75, 47.)
1942. ‘* The Heroic Period of Geological Work in Australia.”” By E. C. Andrews, B.Sc.
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.Se., 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. 8. Summers
D.Se.
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.
1949. ‘‘ Metallogenetic Epochs and Ore Regions in Australia.’”” By W. R. Browne, D.Sc.

AWARDS OF THE CLARKE MEDAL.

Established in memory of
The Revd. WILLIAM BRANWHITE CLARKE, .a., F.R.S., F.G.S., etc
Vice-President from 1866 to 1878.

The prefix * indicates the decease of the recipient.
Awarded.
1878 *Professor Sir Richard Owen, kK.0.B., F.R.S.
1879 *George Bentham, c.M.G., F.R.S.
1880 *Professor Thos. Huxley, F.R.s.
1881 *Professor F. M’Coy, F.R.S., F.G.S.
1882 *Professor James Dwight Dana, LL.D.
1883 *Baron Ferdinand von Mueller, K.c.M.G., M.D., Ph.D., F.R.S., F.L.S.
1884 *Alfred R. C. Selwyn, Lu.D., F.R.S., F.G.S.

Xvil

Awarded.
1885 *Sir Joseph Dalton Hooker, 0.M., G.c.S.1., C.B., M.D., D.C.L., LL.D., F.R.S.
1886 *Professor L. G. De Koninck, m.p.
1887 *Sir James Hector, K.C.M.G., M.D., F.R.S.
1888 *Rev. Julian E. Tenison-Woods, F.G.S., F.L.S.
1889 *Robert Lewis John Ellery, F.R.S., F.R.A.S.
1890 *George Bennett, M.D., F.R.c.S. Hng., F.L.S., F.Z.S.
1891 *Captain Frederick Wollaston Hutton, F.R.S., F.G.S.
1892 *Sir William Turner Thiselton Dyer, K.C.M.G., C.I.E., M.A., LL.D. Sc.D., F.R.S., F.L.S.
1893 *Professor Ralph Tate, F.L.s., F.G.S.
°1895 *Robert Logan Jack, LL.D., F.G.S., F.R.G.S.
1895 *Robert Etheridge, Jnr.
1896 *The Hon. Augustus Charles Gregory, C.M.G., F.R.G.S.
1900 *Sir John Murray, K.C.B., LL.D., Sc.D., F.R.S.
1901 *Edward John Eyre.
1902 *F. Manson Bailey, C.M.G., F.L.s.
1903 *Alfred William Howitt, p.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 (Natura]
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.O., 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.B.S.
1924 *Joseph Henry Maiden, 1.s.0., F.R.S., F.L.S., J.P.
1925 *Charles Hedley, F.L.s.
1927 Andrew Gibb Maitland, F.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 =. 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, p.sc., F.c.s., Department of the Interior, Canberra, F.C.T.
1934 *Edward Sydney Simpson, D.Sc., B.E., F.A.C.1., Carlingford, Mill Point, South Perth, W.A.
1935 *George William Card, a.R.S.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., LL.B., 9 Ivanhoe-parade, Ivanhoe, Victoria.
1938 *Professor H. C. Richards, p.sc., The University of Queensland, Brisbane.
1939 *C. A. Sussmilch, F.G.s., F.s.T.c., 11 Appian Way, Burwood, N.S.W.
1941 Professor Frederic Wood Jones, M.B., B.S., D.Sc., F.R.S., Anatomy Department, University
of Manchester, England.
1942 William Rowan Browne, D.sc., Reader in Geology, The University of Sydney, N.S.W.
1943 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.4.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, pD.sc., Director, Australian Museum, Sydney.
1949

Rupp, Rev. H. Montague, 24 Kameruka-road, Northbridge.

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
1949

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.

No award made.

Xvil

AWARDS OF THE EDGEWORTH DAVID MEDAL.
Bronze Medal.

Awarded annually for Australian research workers under the age of thirty-five years, for
work done mainly in Australia or its territories or contributing to the advancement of Australian
Science.

1948 Giovanelli, R. G., M.sc., Division of Physics, National Standards Laboratory, Joint
Sydney. Award.
Ritchie, Ernest, m.sc., University of Sydney, Sydney.
1949 Kiely, Temple B., p.sc.agr., Caroline-street, East Gosford.

AWARDS OF THE SOCIETY’S MEDAL AND MONEY PRIZE.
Money Prize of £25.
Awarded.
1882 John Fraser, B.a., West Maitland, for paper entitled ‘“‘The Aborigines of New South
Wales.”
1882 Andrew Ross, m.p., Molong, for paper entitled ‘‘ Influence of the Australian climate and
pastures upon the growth of wool.”

The Society’s Bronze Medal.

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.a.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.a.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, t.s., Parramatta, for paper entitled ““ The Aboriginal Rock Carvings and
Paintings in New South Wales.”

1895 C. J. Martin, D.sSc., 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.

1949 Elkin, Adolphus P., m.a., Ph.D., Sydney, in recognition of his valuable contributions to
the field of Anthropological Science.

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. Burrirt, 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.p., ch.m., 185 Macquarie Street, Sydney.

1932 Charles Halliby Kellaway, m. a 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 Physies. University of Sydney.

B

XVill

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.

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 Zinc Company of Australasia, Ltd., Collins Street,
Melbourne.

1933 W. J. Young, D.sc., M.sc., University of Melbourne.

1940 G. J. Burrows, B.Sc., University of Sydney.

1942 J.S. Anderson, B.sc., Ph.D. (Lond.), A.B.C.S., D.1.c., University of Melbourne.

1944 F. P. Bowden, pPh.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, 1950.

PRESENTED AT THE ANNUAL GENERAL MEETING OF THE SOCIETY, 5TH APRIL, 1950
(RULE XXVI).

The membership of the Society at the end of the period under review stood at 361, an increase
of seven. Twenty-nine new members were elected during the year. However, 13 members
were lost by resignation, and three, who were in arrears with subscriptions, were removed from
the register. Six members have been lost to the Society by death since Ist April, 1949 :

Henry Harvey Dare (1890).
Walter John Enright (1916).
Joseph Foreman (1879).
Robert Thomas McKay (1891).
Dansie Thomas Sawkins (1941).
Charles Josiah White (1909).

Professor Sir Howard Florey, M.B., B.S., B.Se., M.A., Ph.D., F.R.S., and Professor F. M.
Burnet, M.S., Ph.D., F.R.S., were elected to honorary membership of the Society at the annual
meeting on 6th April, 1949.

During the year eight General Monthly Meetings were held, at which the average attendance
was 39. Forty-four papers were accepted for reading and publication by the Society—an increase
of five from the previous year.

It has been the policy of Council to favour a broadening of the scope of the General Meetings
and to encourage members other than the authors of papers to play an active part. In pursuance
of this policy a portion of the time at general meetings has been devoted to ‘‘ Notes, Exhibits
and Questions ”’.

During the year the following questions have been answered :

4th May:
‘“Why do stars twinkle and planets not ?”’, by Professor O. U. Vonwiller.

Ist June:

** When a number is raised to the fifth power, why is the figure in the units place the same
as in the original number ?’’, by Dr. R. L. Aston.

7th December :
‘** How are earthquakes located at a distance ?’’, by Rev. D. J. K. O’Connell.
On the 7th September, also, the following exhibit was discussed :
“Crystal of Synthetic Rutile’, by Dr. D. P. Mellor.

At the meeting held on 2nd November, the President announced that the Council of the
Society had felt that there was need to organise an activity which would give members and their
friends a better chance to meet and talk with one another than was possible at the ordinary
formal meetings, and he welcomed members and their friends to the Conversazione.

The evening was devoted to Exhibits and Films of Scientific Interest, and this arrangement
had been made possible through the courtesy of the following :

Australian Museum,
Department of Agriculture,
Museum of Technology and Applied Science,
National Standards Laboratory.
Sydney Technical College,
University of Sydney :
Chemistry Department, and
Geology Department.

At the meeting held on Ist June the following addresses were given :

‘* Notes on a Recent Journey to Europe ”’, by Professor O. U. Vonwiller.

‘Visits to Observatories in Europe and America ’”’, by Rev. D. J. K. O’Connell.
BB

xx REPORT OF COUNCIL.

As has become customary, one meeting was devoted to the commemoration of great scientists.
This meeting was held on 7th September, and at it the following addresses were given :

‘‘ Goethe’s Work and its Significance in the Twentieth Century ”, by Professor R. B. Farrell.

‘““ Edward Jenner and Vaccination ’’, by Professor E. Ford.

‘* Life and Works of Pierre-Simon ce Laplace ”’, by Mr. H. H. Thorne.

Lecturettes given during the year were as follows:

3rd August :

“The Response of Marsupials to Pathogens ’”’, by Dr. A. Bolliger.

** Wolf’s Creek Meteorite Crater”, by Mr. R. O. Chalmers.

Five Popular Science Lectures were delivered during the year and were appreciated by
members of the Society and the public:

19th May: ‘“ The Study of Earthquakes ”’, by Professor K. E. Bullen.

18th August: ‘‘ Radio Astronomy ”’, by Mr. J. G. Bolton.

15th September: ‘“‘ Sex Control in Animals’”’, by Dr. C. W. Emmens.

20th October: “‘ The Australian and American Arnhem Land Expedition of 1948”, by

Mr. F. D. McCarthy.
17th November: “‘ War Surgery through the Ages’”’, by Dr. N. R. Wyndham.
The Annual Dinner of the Society was held at the Sydney University Union on 30th March,
_ 1950. There were present 89 members and friends.
The Section of Geology, whose Chairman was Dr. G. D. Osborne, and Honorary Secretary
Mr. N. C. Stevens, held five meetings during the year, at which the average attendance was 15
members and seven visitors. The activities were :
29th April: Address by Dr. G. D. Osborne and Mr. J. 8. Proud, entitled ‘“‘ Occurrence and
Probable Genesis of Asbestos at Wood’s Reef, near Barraba, N.S.W.”’

20th May: Discussion on ‘‘ The Geology and Mineral Resources of Tasmania ’”’, led by
Dr. W. R. Browne. Mr. R. O. Chalmers showed exhibits from mining centres of
western Tasmania.

16th September: Address by Dr. L. E. Koch entitled ‘‘ On Pyrophyllite, its Mineralogy,

Minerogeny and Economic Prospects in Australia’’. The address was accompanied
by an exhibit of specimens.
21st October: Address by Mr. N. C. Stevens entitled “‘ The Geology of the Canowindra
District, N.S.W.”

18th November: Notes and Exhibits by Miss F. Quodling, Mr. F. N. Hanlon, Mr. H. O.
Fletcher, Mr. R. O. Chalmers, Dr. D. Carroll, Dr. L. E. Koch, Mr. T. G. Vallance, Mr.
W. H. Williamson, Mr. N. C. Stevens and Dr. G. D. Osborne.

The Council of the Society held twelve ordinary meetings during the year, at which the
average attendance was 13.

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.

On Science House Extension Committee the Society was represented by Drs. A. Bolliger
and R. L. Aston.

The Clarke Memorial iectare for 1949 was delivered by Dr. W. R. Browne on 16th June,
the title being ‘‘ Metallogenetic Epochs and Ore Regions in Australia ”’

The Clarke Memorial Medal for 1950 was awarded to Dr. Ian Mure Mackerras, Director,
Queensland Institute of Medical Research, Brisbane, in recognition of his distinguished work
on Diptera of the Australian region.

The Medal of the Royal Society of New South Wales for 1949 was awarded to Professor
A. P. Elkin in recognition of his valuable contributions to the field of Anthropological Science.

The Edgeworth David Medal for 1949 was awarded to Dr. Temple BENE: Kiely for his .
research work in Plant Pathology.

The James Cook Medal was not awarded for the year 1949.

During the year several scientists from overseas visited the Society’s rooms and were enter-
tained by the President and Council. Among these were :

Sir Geoffrey I. Taylor, M.C., F.R.S., Fellow of Trinity College, Cambridge, and Yarrow
Research Professor of the Royal Society. (llth May, 1949.)

Professor H. 8. W. Massey, F.R.S., Goldsmid Professor of Mathematics at University College,
University of London. (26th September, 1949.)

Dr. G. M. Lees, M.C., D.F.C., of the Anglo-Iranian Oil Co. Ltd. Dr. Lee was accompanied
by Dr. Davies. (9th December, 1949.)

REPORT OF COUNCIL. xxl

During his visit to Sydney, Dr. Lees delivered a lecture entitled ‘‘ The Oilfields in the Middle
East ’’. The lecture, which was given under the auspices of the Royal Society of New South
Wales and the University of Sydney, was given on 9th December, 1949.

On 12th January, 1950, the Society arranged a public lecture by Professor Sidney Chapman,
Sedleian Professor of Natural Philosophy at the University of Oxford. The subject was
** Aurore ”’,

The first Pollock Memorial Lecture, sponsored by the University of Sydney and the Royal
Society of New South Wales, was delivered by Professor T. M. Cherry of the University of Mel-
bourne, on 28th October, 1949. The subject of the lecture was “ The Flow of Gases ”’.

The financial position of the Society, as disclosed by the annual audit, is not a satisfactory
one.

The greatest single increase in the Society’s expenses has been that of printing. The cost
of production of the Society’s Journal has increased from £12 per 16 pages, 1940, to £2 per page
in 1950, and is still increasing. This, together with a steady increase in the number of papers
accepted for publication, has meant that the Journal is now by far the costliest item on the
balance sheet. The Council is fully alive to the threat to the Society’s finances implicit in these
trends, and desires to place the position clearly before members. Council believes that any
curtailment in the publication of meritorious papers purely on the grounds of cost would be a
retrograde step.

The scientific standing of the Society is linked with the quality of the papers published in
its Journal. On the other hand, consideration of present costs makes it imperative for the
Editor to impress upon authors the need for the utmost conciseness in expression. Council has
found it necessary on several occasions this year to return papers to authors with a request for
abbreviation. However, there is a limit to the extent to which any subject matter can be
abbreviated and still remain intelligible, and a major subject for the deliberation of the incoming
Council will be concerned with ways and means of meeting the rising cost of publication.

The Society’s share of the profits from Science House for the year was £400.

The grant from the Government of New South Wales of £400 has been received. The
continued interest of the Government in the work of the Society is much appreciated.

Original Manuscripts, Maps, etc.—At its meeting held on 27th July, 1949, Council decided
that manuscripts, maps, etc., be made available to authors six months after publication.

The Library.—The amount of £38 4s. 8d. has been spent on the purchase of periodicals and
£57 lls. 6d. on binding.

Exchange of publications is maintained with 399 societies and institutions, an increase of
12 over the previous year.

The number of accessions entered in the catalogue during the year ended 28th February,
1950, was 3,060 parts of periodicals.

The number of books, periodicals, etc., horrowed by members, institutions and accredited
readers was 346. ;

The Society sold a number of bound volumes of early editions of The Sydney Morning Herald
to the Library Board of Queensland for the sum of £86 10s.

Among the institutions which made use of the library through the inter-library borrowing
scheme were: Australian Paper Manufacturers, Bureau of Mineral Resources, Colonial Sugar
Refining Co. Ltd., Commonwealth Observatory, C.8.I.R.O., National Standards Laboratory,
Division of Fisheries, Division of Food Preservation, Division of Industrial Chemistry, Division
of Tribophysics, Elliotts and Australian Drugs, Forestry Commission, Melbourne University,
M.W.S. and D. Board, New England University College, N.S.W. Department of Agriculture,
Division of Wood Technology, Plant Research Laboratory, Public Library, N.S.W., Public
Library, South Australia, Standards Association of Australia, Sydney Hospital, Sydney Technical
College, Sydney University, Taubman’s Ltd., University of Western Australia, Zinc Corporation.

HARLEY WOOD,
President.

XxXll BALANCE SHEET.

THE ROYAL SOCIETY OF NEW SOUTH WALES.
BALANCE SHEET AS AT 28th FEBRUARY, 1950.

LIABILITIES.
1949.
£ Lis
141 Accrued Expenses :
26 Subscriptions Paid in Advance
Life Members’ Subscriptions — Amount carried
90 forward
Trust and Monograph Capital Funds (detailed
below)—
Clarke Memorial .. sits re ts Mowe Gore w
Walter Burfitt Prize oye ae ee .. 1,090 12
Liversidge Bequest : aie ran si 733 «5

7,245 Monograph Capital Fund _ ae < .. 98,620 3

26,082 ACCUMULATED FUNDS
Contingent Liability—In connection with perpetual

leases.
£33,584
ASSETS.
1949.
£ DR
440 Cash at Bank and in Hand
Investments — Commonwealth Bonds ‘and Inscribed
Stock, ete.—at Face Value—
Held for—
Clarke Memorial Fund a on cai .. 1,800 0
Walter Burfitt Prize Fund fe 3 te .- 1,000 0O
Liversidge Bequest .. oie AS oa 36 700 0
Monograph Capital Fund .. a a .. 3,000 0
General Purposes... ie ais is .. 4,660 0
11,160
24 Prepayment .. Fe eit bie BY ois
Debtors for Subscriptions a a a4 sf 57 17
— Deduct Reserve for Bad Debts és he sh 57 U7

14,746 Science House—One-third Capital Cost ..
6,800 Library—At Valuation : sxe
379 Furniture—At Cost—less Depreciation
27 Pictures—At Cost—less Depreciation
8 Lantern—At Cost—less Depreciation

£33,584

H OO Ol

7,401 2

25,579 11

£33,591

SS)

tN
(as)
s™)
ps D2

11,160 0

oo

14,835 4

£33,591

6,800 0
360 0
26 0
Toad

5 10

ooooF

5 10

BALANCE SHERT.

Xxili

TRUST AND MONOGRAPH CAPITAL FUNDS.

Clarke
Memorial.
Sr Ss
Capital at 28th February, 1949 .. 1,800 0 0
Revenue—
Balance at 28th February, 1949 160 4 7
Interest for twelve months 64 14 0
224 18 7
Deduct Expenditure 67 17 6
Balance at 28th February, 1950 £157 1 1

ACCUMULATED FUNDS.

Balance at 28th February, 1949

Add Decrease in reserve for bad depts

Less—

Deficit for twelve months (as
shown by Income and Ex-
penditure Account) ae :

Amount written off re James Cook
and Edgeworth David Medals. .

Bad Debts written off a

Walter Monograph
Burfitt Liversidge Capital
Prize. Bequest. Fund.
£ gs. d. fo" gs. 7d. fo Ss.
1,000 0 0 700 0 0 3,000 0 O
55 17 5 LiAQo 3 520 18 4
34 15 0 25 15 0 99 5 0
90 12 5 33 5 3 620 3 4
£90 12 5 £33 5 3 £620 3 4
£ s. d.
26,081 18 2
27 8 O
£26,109 6 2
£436 3 7
7110 4
22 1 O
—— 529 14 11
£25,579 11 3

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, 1950, 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, 20th March, 1950.

HORLEY & HORLEY,

Public Accountants.

XXIV BALANCE SHEET.

INCOME AND EXPENDITURE ACCOUNT.
Ist March, 1949, to 28th February, 1950.

—
cen}
xe
[e.)
Ne}
—_
is}
re
-
Ou
i=)

pA ae > Se
640 To Printing and Binding Journal—Vol. 82 Avs -. LOOL 45re0
468 _,, Salaries a ; ae ae 520 0 11
133_—Ci,, Library—Purchases and Binding se a ae 113 4 8
103. —«,,:~“Printing—General .. : a, i vp 101 12 0
97 ,, Miscellaneous : te Ni e. ut re 68 2. -2
74 ,, Postage and Telegrams vie ee 57.14, 2
55 ,, Rent—Science House Management Conmnitioe, a 54.1 PY
— ,, Entertainment Expenses .. Lee Ns ar ae 16° ..S he
37. ~=«g, “Cleaning ne a om ay te ee ae 36) O10
23 ~=,, Depreciation Be 23 oF a ay Pa 21 4,0
22 +4, Telephone .. aN xe zig at om Al, 14 01 Sit
23. ,, Insurance, '.). le an a Be i aa 23) 1305
19 ,, Audit.. a ae ae a a he a 18.48.09
9 ,, Electricity .. ve oe A ies Bes a 417 6
2 ,, Repairs ant Bi xa nA ae ae oe 12 US
» Reprints—
Expenditure .. ate up 0) S104 VOL 16
Less Received aN ae a, Si ie
56 _———_—— 22-19. :3
,, Annual Dinner—
Expenditure .. ate mee Wb --) £98; 4.04
Less Received ae ae ng 69 14 9
39 ——______— 18 9 7
1,800 2,106 15 11
228 ,, Surplus for Twelve Months naa ar, te as —
£2,028 £2,106 15 11
1948-9. 1949-50.
£ ; 5 Bs ads
586 By Membership Subscriptions ay oe = ah she ws 599 0 6
400 ,, Government Subsidy .. da en as ae oe 400 0 O
391 ,, Science House—Share of Surplus Hs me a An aie 400 0 0O
156 ~,, Interest on General Investments ee eas ee ate wus 161 13 2
478 ,, Proceeds Sale of Old Library Books ae ne ea Bs 89 17 8
5 ,, Other Receipts .. ats a oa i Lhe bo O
12. ,, Proportion of Life Members’ Subscriptions a ahs a 9 0 0
2,028 1,670 12 4
— , Deficit for Twelve Months we a bee spunea te 436 3 7

£2,028 £2,106 15 11

Obituary

Henry Harvey Dare, a member of this Society since 1890, was born at Goulburn on
August 25th, 1867, and died at Sydney on August 20th, 1949. He was educated at Sydney
Grammar School and Sydney University, where he graduated as Bachelor of Engineering in
1888 and Master of Engineering in 1894, having been awarded a University Medal with each
degree. After a short period on the staff of Sydney Observatory he entered, in 1895, the Public
Works Department of New South Wales. He was responsible for the design of many public
works. His last position with the Public Works Department was that of Chief Engineer for
National Works and Drainage. When the Water Conservation and Irrigation Commission was
constituted in 1913, he was appointed Chief Engineer to the Commission, and in 1915 Engineering
Commissioner. He retired at the end of 1934.

The completion of Burrinjuck Dam, the construction of Wyangala Dam, works on the
Murrumbidgee Irrigation Area and the establishment of Coomealla Irrigation Area, as well as
the investigations of many of the proposals for water conservation throughout the State, were
carried on under his direction. These have had a large influence on the development of Australian
rural areas.

He was the New South Wales representative of the River Murray Commission from its
inception in 1917 and a consultant on many major water supply works throughout Australia and
New Zealand.

He was a member of a board appointed in 1918 to enquire into the extension of the water
supply for Sydney, which recommended the construction of the Cordeau, Avon and Nepean
Dams. The increase in average daily water consumption in Sydney from 41 milljon gallons in
1918 to 131 million gallons at present is sufficient to show the magnitude of the works in which
he played an important part.

Mr. Dare was of retiring disposition and was held in high respect and esteem by all who
knew him, especially by the staff who came under his control. He took an active part in the
affairs of the professional bodies to which he belonged, and was a member of the Council of The
Institution of Engineers of Australia, which awarded him the Peter Nico] Russell Medal. His
death terminates the career of one of Australia’s outstanding civil engineers.

WALTER JOHN ENRIGHT, who died on September 27th, 1949, was born on March 10th, 1874,
at West Maitland, N.S.W. After two years in his father’s auctioneering business he entered the
legal profession, and graduated B.A. in 1893. It was while pursuing his University studies that
he came under the influence of Professor David, being in one of the latter’s first geology classes
in the early nineties. The tmpress of Professor David on Enright’s life was indelible, and although
he was a very successful lawyer, becoming known throughout the Hunter River Valley, he never
lost his love for geology, and indeed for many branches of natural history.

He was an amateur scientist of distinctly high calibre. His observations in various fields
of natural science were accepted by professional scientists, and he was constantly appealed to by
those seeking information about local geology, entomology, forestry, ichthyology and
anthropology.

He wrote several useful original articles on some of these branches of science, and was instru-
mental in promoting research in many areas by assisting the work of the pioneers in various
parts of the State, but particularly in the Hunter-Manning regions... His great energy, wide
knowledge, tact and public spirit led to his assuming a leading place in his community, and he
was actively associated with many worthy causes, especially with scientific and educational
conferences or expeditions that were arranged in the northern part of the State. He played a
dominant réle in the whole organization of the visit to the Maitland district of Section C of the
British Association in 1914.

He travelled widely in Australia and in the South-west Pacific, and his journeyings were
always fruitful in scientific observations and in collection of exhibits.

Walter Enright will perhaps be best remembered by a host of friends of all classes because
of his unfailing generosity and characteristic readiness to offer his services for any purpose to
facilitate the work and promote the happiness of others.

He was elected a member of this Society in 1916.

RosBertT THomas McKay was born on December 31st, 1865, and died August 10th, 1949.
He had a distinguished career as a civil engineer and administrator of engineering projects.
After a period of training he qualified under the Mining Act of New South Wales and was appointed
surveyor of the Engineering Branch of the Department of Public Works, New South Wales.
From 1896 to 1902 he was Resident Engineer of the Sydney and Suburbs Sewerage Scheme

Xxvil OBITUARY.

and he was responsible for a number of important works carried out during his term of office.
He was principal officer of the Interstate Royal Commission on the Murray River (1902-1903)
to enquire into the allotment of waters as between New South Wales, Victoria and South Australia
for the purposes of water conservation, irrigation and navigation, and the report of this
Commission has served as a basis for the many negotiations which have taken place since on this
important problem. His expert knowledge in this matter was recognized by an invitation to
address a Premier’s Conference. He made a special study of riparian rights, the control of
water by the Crown and the supply and distribution of artesian water.

From 1905 till 1911 he was Engineer and Executive Member of Water Conservation, Irrigation
and Drainage Board, and was associated with many irrigation projects throughout the State,
particularly on the Murray, Lachlan and Murrumbidgee Irrigation schemes. He was subse-
quently Chief Assistant Hydraulic Engineer for the State of Queensland and later Chief Engineer
for the Geelong Water Works and Sewerage Trust and Engineer for Wheat Storage in connection
with the bulk handling of wheat. His final important public post was that of Engineering
Member and Deputy President of the Sydney Harbour Trust from 1922 to 1930.

He was an advocate for using the waters of the Snowy River to supplement the flow of the
Murrumbidgee and to provide a supply to Sydney. He was one of the earliest pupils of Sydney
High School and throughout his life took a great interest in the school, being very active in
assisting its advancement, particularly at the time when its new buildings were erected at Moore
Park. After his retirement from the Sydney Harbour Trust he undertook private practice as a
consulting engineer. He was a member of the Council of the Advisory Committee of the Institu-
tion of Civil Engineers for many years and occupied the position of Chairman of the Council for
six years.

He had been a member of the Royal Society of New South Wales since 1891.

JOSEPH FOREMAN was born on August 23rd, 1852, at Pemberton, near Wigan, in Lancashire,
England, and was trained in his father’s profession of medicine at Edinburgh and at London,
qualifying as a surgeon at Guy’s Hospital in 1873.

He then became Medical Officer on S.S. Bonny, conveying troops to Sierra Leone to the
Ashanti War, and in the following year was appointed Medical Superintendent on the ship Baron
Aberdare, taking some hundreds of immigrants to Auckland, New Zealand.

He stayed in New Zealand as Medical Officer at Waimate, in the Bay of Islands, from August,
1875, until 1877, when he came to New South Wales, and for the next two years he practised in
the Richmond River district.

In 1879 he set up in practice in Sydney and became interested in various medical, cultural
and industrial societies, including this Society.

He was appointed Surgeon on the Medical Staff of the N.S.W. Volunteer Forces in 1881.
Later in the same year he visited Europe, where he studied under the famous Berlin surgeon,
Augustus Martin, and also obtained further experience at the London Hospital for Women.

On his return he became Sydney’s first specialist in obstetrics and gynecology and was
appointed Honorary Surgeon at the Royal Prince Alfred Hospital, retaining his association with
that institution until his death. He was also on the Honorary Staff of the Royal Hospital for
Women, and Lecturer on Diseases of Women in the University of Sydney until 1920. Students
who attended his lectures recall his precise, calm and dignified manner and his stress on meticulous
cleanliness, tidiness and punctuality.

Besides achieving eminence in his chosen profession, he had an interest in farming and on
his retirement from active medical practice, when over 70 years of age, he invested in pastoral
properties at Cooma, Condobolin and Meadow Flat, near Bathurst. In 1948 the proceeds of the
sale of some of these properties (£20,000) were devoted to the foundation of fellowships in connec-
tion with Royal Prince Alfred Hospital.

At the time of his death on January 15th, 1950, Dr. Foreman was the oldest member of
this Society, having been elected in 1879.

CHARLES JOSIAH WHITE, a member of this Society since 1909, was born in 1881 at Wollongong,
N.S.W., and received his early education at Wollongong.

He began his life-work in the teaching profession as a pupil-teacher at Gerringong and later
at Wollongong. In 1902 he entered the Teachers’ Training College at Fort Street Model School.
After a distinguished undergraduate career in the University of Sydney, he graduated Bachelor
of Science in 1907 with the University Medal for Chemistry, of which he was the first recipient,
and Bachelor of Arts in 1908.

On the completion of his University course he was appointed Lecturer-in-Charge of Science
at the Teachers’ Training College, Sydney, and in this position he exercised a great influence on
the teaching of science in the secondary schools of New South Wales until his retirement in 1945.

He died on July 31st, 1949.

OBITUARY. XxXvV1l

DansiE THOMAS SAWKINS, a member of this Society since 1941, was born on August Ist,
1880, at Muswellbrook, N.S.W., and died on March 22nd, 1950.

After his early education at Maitland he graduated from Sydney University as Bachelor of
Arts with the University Medal for Mathematics in 1899, and Master of Arts in 1902. As James
King of Irrawang Travelling Scholar he went to Cambridge, England, and graduated a Wrangler
in 1904.

From 1904 to 1907 he was a schoolmaster in England; he then went to Siam and
the Federated Malay States as a surveyor for five years, and on his return to New South Wales
he worked as a surveyor in the State service for about five years.

Between 1917 and 1938 he was Statist to the Board of Trade and the Industrial Commission.
He became Lecturer in Statistics at the University of Sydney in 1922 and in 1924 was appointed
Peter Nicol Russell Lecturer in Geodesy. In 1938 he joined the full-time staff of the University
of Sydney as Reader in Statistics.

He published a large number of papers on various aspects of statistics both in Australia and
abroad, three of which appear in the Journal and Proceedings of this Society.

tad

ee ee
ke baa

et

PRESIDENTIAL ADDRESS

By HARLEY WOOD, M.Sc.

Delivered before the Royal Society of New South Wales, April 5, 1950.

THE WORK OF THE SOCIETY.

The Annual Report of our Society indicates a year of useful activity. The
usual monthly meetings were held, except for the one in July, which was cancelled
owing to power restrictions. In August an afternoon meeting was held in the
Geology Lecture Theatre at the University. The meetings of May, June,
October and December were devoted mainly to the presentation of original
papers and to lecturettes in the form of answers to questions brought forward
by members. At the August meeting we had two lectures by members of the
Council; the September meeting commemorated the centenaries of Goethe,
Jenner and Laplace, and the November meeting took the form of a conversazione,
at which there were films and exhibits of scientific interest. Sitting, as I have
done as your President, on the dais in front of the meeting, I have not been able
to avoid noticing that the number of members who attend varies as the amount
of material of general interest on our agenda. When we have devoted our
attention entirely to the presentation and discussion of original papers, the
audience has been just comfortably over the number we need for a quorum,
whereas at the September and, especially, the November meetings our hall was
well filled. In this respect the introduction into our meetings of questions by
members has certainly proved a satisfactory way of finding interesting topics
and speakers who might not otherwise have come forward. Naturally, many
authors who present papers to the Society are anxious to have them discussed
at a meeting, but, in view of experience while [ have been in the chair, and
indeed, observation for some years past, I believe that all such presentations
should be as nearly popular as possible. In most cases our audience can only
have a very few specialists in the subject of a paper, and it is necessary for authors
to speak more at the level of the unsophisticated majority. It should usually
be possible to explain the background of a piece of research in such a way that
most of us can understand the kind of contribution which is being made.

The Clarke Memorial Lecture for 1949 was delivered by Dr. W. R. Browne,
who spoke on ‘‘ Metallogenetic Epochs and Ore Regions in Australia’. During
the year there were five popular science lectures. All of these produced satis-
factory audiences and, in three cases, the hall was full to overflowing.

Two years ago the Council of the Society decided to institute a series of
monographs, and this year the first one to be accepted was presented by Dr.
G.D. Osborne. It is entitled ‘‘ The Structural Evolution of the Hunter-Manning-
Myall Province ”’. )

It is my pleasant duty to thank the members of the Council, and indeed
the general membership of the Society, for the cooperation I have received
during the year and for their goodwill, which has made it a pleasure to preside
at our meetings. My thanks are due especially to the Honorary Executives
who have carried on the work with such devotion. Dr. Bosworth has kept able
hands on the management of the Society’s affairs. Mr. Smith-White, as editor,
Dr. Bolliger as treasurer and Mr. Hanlon as librarian have given without stint
time, energy, and in each case more than ordinary skill.

Cc

2 HARLEY WOOD.

We live in an age when man is bewildered by his own technical achievement.
Science has placed in his hands a power altogether beyond the dreams of our
forefathers—a power that may be used for good or for destruction. The atomic
physicist has already demonstrated the destructiveness of his contribution, but
has only just begun to tame his monster so that it may be used for the service of |
society. The biological scientist, not to be outdone, insists that he has weapons —
available which can strike a blow no less terrible than the atomic bomb.

The questions posed by the enhanced possibilities for purposive destruction,
important as they are, represent only a part of the problem that is being thrust
on mankind. We have seen more clearly than ever before that, in a few genera-
tions, man can use up the resources of power which nature in past ages has
gathered from the sun and stored beneath our soil. We know that a few
generations of misuse can so reduce the fertility of that soil that the precarious
existence we now wring from it, and we must not forget that for the bulk of
mankind it is precarious, will be endangered.

The suggestion is often made that certain weapons of war should be
outlawed ; but war is the negation of law and it is not conceivable that a nation
would allow itself to be defeated, leaving unused a weapon which might bring
victory. According to recent press reports, Einstein has stated his belief, and
I think he is right, that the real alternative is that the political leaders of the
world will be deterred from war for a period long enough for the world to evolve
some sort of central government. In the past, the tendency has been for larger
groups of mankind to be formed by the amalgamation of smaller ones. One
group might conquer its neighbour, or combine with it through the fear of a
third power, and throughout history the powerful interest that has compelled
loyalty of different groups to common leaders, has been the threat of some
external aggressor. Now that the enemy is recognized to be war itself, surely
we can feel and foster a loyalty to mankind as a whole.

Science now has prestige, responsibilities and, especially, dangers that it
had not before. The characteristic of science is that every hypothesis should
undergo the searching test of discussion and comparison with observation, and
we have come to realize that, even such larger advances as the invention of the
quantum theory are only scaffoldings on which to unify the knowledge already
gained before proceeding to build further. Science distinguishes real advances,
which provide tests to which observation can be directed and to which they
stand up, from those which cannot be applied in a way which will test their
truth, and it implies a complete freedom of thought and of criticism, and the
display for criticism of all ideas within the realm of human knowledge. It is
by such means that knowledge advances. Now the advancement of knowledge
and the greater dissemination of it are essential if humanity is to be freed from
the chains placed upon it by want and fear. We all know that the power over
nature he now wields has produced a tendency to place restrictions on the
scientist and on free interplay of scientific discussion and criticism. This applies
in almost all countries of the world at present, and most members will be able to
recall cases of men of science having their activities restrained in some way or
other. Well publicized examples of interference with the freedom of science
have occurred in many countries. <A characteristic of this age is its science and
technology, and one phase of this is that many of the most alert and able minds
of the time are being attracted to science. One can observe signs that, if science
were to lose that freedom in which such alertness can flourish, it would begin to
wither for want of support. It has been freely stated that, despite advantages
offered in the way of opportunity for research and in the way of equipment
of the very best kind, the best scientists are not attracted to government
laboratories dealing with the development of weapons of war ; and if the attitude

PRESIDENTIAL ADDRESS. 3

of the community becomes further unfavourable to the work of science there
will be little attractiveness left in it.

In such a background our Society has an opportunity and a duty to provide
a forum for the discussion among scientists of matters of general interest which
affect them in their professional work. An example of this sort of discussion
was the symposium on ‘‘ The Education of a Scientist ’’, which we held in 1948
and which aroused considerable interest, but I believe that we should occasionally
have discussions on more controversial, and probably more vital, matters.
On the other hand we need to foster the penetration of the scientific outlook
into our Australian community and, while we now do this in some degree by
our popular science lectures, it will be readily admitted that there is a great
need for work which is more explicitly directed towards improving the prestige
of science.

Wherever I have been as your representative I have found our Society held
in high esteem. It is the only society in New South Wales which unites all of
the sciences ; other organizations are limited to one science or group of sciences
or by being professional associations, whose proper care is for the status of their
members. -

Of the various organizations to which I have belonged this is the one of
whose usefulness I feel most convinced and the association with which affords
me most satisfaction.

We must continue our work despite the difficulty of the times, indeed, in
some respects, because of it. We must endeavour more consciously, on the
one hand, to foster public interest in science and to make known the value of
science and scientific research in the economy and in the culture of our country
and, on the other hand, to provide more and more a meeting-ground for the
various specialist sciences and for the scientists who practise them.

ASTRONOMY IN AUSTRALIA.
THE HISTORY OF ASTRONOMY IN AUSTRALIA.

Astronomy was closely associated with the beginning of British settlement
in Australia. The idea of using the observation of a transit of Venus to determine
the distance of the Sun was first suggested by Kepler, and again with more
practical detail by Halley in his report of the observation of a transit of Mercury,
which he saw at St. Helena in 1677 and published with his Catalogue of Southern
Stars. It was important that this constant, the fundamental unit of the Solar
System, should be determined with all practicable accuracy and the scientific
- world was anxious to make use of the transits of Venus in the eighteenth century,
sending on each occasion expeditions to distant parts of the world. For this
reason James Cook was despatched to Tahiti to make observations there. The
transit was observed on April 13, 1769, and the published results (Green and
Cook, 1771) although not as precise as had been hoped, because of unexpected
observational difficulties, nevertheless did yield an improved value of the solar
parallax.

On this scientific expedition Cook made the exploration of the east coast
of Australia which led to the foundation of the colony in 1788. With Captain
Phillips’ first fleet, too, there was an astronomer, Second Lieutenant William
Dawes. One of his duties was to establish a post from which he was to attempt
to observe the expected return of a comet.

Among the comets which had been discussed by Halley were two observed
in 1532 by Appian and in 1661 by Hevelius. Having calculated that they had
similar orbits, Halley conjectured that they were identical and that a new return
would occur about 1790. This was discussed by Maskelyne (1786). The
anxiety to observe this object was quite natural because at this stage the only

4. HARLEY WOOD.

predicted return of a comet which had been verified was the famous one of
Halley, and the only other body added by observation to the classical members
of the Solar System was the planet Uranus. Several writers who refer to this
matter mention that Dawes made no observation of this comet, and indeed,
that no purely scientific observations were known to be produced from his
observatory. They do not appear to add, however, that this is quite natural,
since the comet was also not observed in the northern hemisphere where it should
have been seen to better advantage, although at a later stage. In any case,
Halley’s conjecture was probably wrong, as the observations of the earlier
comet are from the viewpoint of orbit computation not satisfactory, and com-
puters differ a good deal as to the real character of the orbit of the comet of
1532. Dawes, too, could scarcely have been expected to undertake other
astronomical work since, as well as being charged with the care of a small garrison,
he was a very active member in the survey and exploration of the young colony.
Besides other maps prepared later, he made a sketch of an area of the southern
shore of Sydney Harbour as early as July 1788, on which his observatory is
marked, its position being noted as longitude 151° 19’ 30” and latitude
—33° 52’ 30”.

When Sir Thomas Brisbane was appointed Governor of New South Wales
the British Government had already decided to establish an observatory at the
Cape of Good Hope and so there was no opportunity for him to persuade his
government to establish with public funds another observatory in the southern
hemisphere. He determined himself to erect an observatory near to Government
House in Parramatta. He arrived in Sydney in November 1821, and his
instruments were set up in time to observe the solstice in December. His
interest in the scientific culture of New South Wales is shown by the fact that
before the end of 1821 he became president of the newly formed Philosophical
Society of Australia, which was the predecessor of the Royal Society of New
South Wales. The success of the work at Parramatta is shown by the fact that
the three workers in the Parramatta Observatory, Brisbane himself, Dunlop
and Rumker, all received the Gold Medal of the Royal Astronomical Society.
One important piece of work done at Parramatta Observatory was the observa-
tion of Encke’s Comet on its first predicted return in 1822. This was only the
second case of a predicted return of a comet being verified, although several
other comets had periodic orbits attributed to them by this time. After
Brisbane’s departure Parramatta Observatory was carried on, first by Rumker
and then by Dunlop, but was finally closed in 1847.

Sir William Denison became Governor General in 1855, having previously
been Governor of Van Diemen’s Land, and it was due to his representation that —
the present Observatory was established. William Scott was appointed on the
recommendation of the Astronomer Royal and arrived in Sydney in November
1856. The present building was started in 1857 and observations commenced
in June 1858. Scott was honorary secretary of the Royal Society of New
South Wales from 1867 to 1874 and honorary treasurer for several years. He
joined in 1856 when it had newly assumed the title ‘‘ Philosophical Society of
New South Wales ’’, and was the oldest member of the Society before he died
in 1917. Indeed, astronomy in New South Wales has. always been closely
associated with our Society, and besides the influence of Brisbane it may be
mentioned that of the six directors of the Observatory five have held executive
positions in the Society and four have been president or held office equivalent
to the presidential status.

As its share of an international plan to catalogue the positions of stars to a
faint magnitude over the whole sky, Sydney Observatory undertook responsibility
for the zone between south declinations 51° and 65°. In recent years most of
the work of the Observatory has been associated with this Astrographic Catalogue,

PRESIDENTIAL ADDRESS. 5

somewhat more than half of which is now published and in the preparation of
which several meridian catalogues have been prepared. Sydney Observatory
has also published work on double stars and occultations of stars by the Moon.

Williamstown Observatory was founded in 1853 when R. L. J. Ellery was
appointed by the Government of Victoria but it was dismantled in 1863 and the
instruments were moved to Melbourne. Among the instruments Melbourne
Observatory acquired was an 8” meridian circle installed in 1884 and the 48”
reflector installed in 1869. Melbourne Observatory was closed as a State
institution by the Victorian Government in 1944. Several valuable catalogues
of star places based on meridian observations were left and are being prepared
for publication by the Commonwealth Observatory. It may be possible to
make arrangements to complete at Sydney Observatory the Melbourne section
of the Astrographic Catalogue from —64° to the South Pole. As comment on
the closure of Melbourne Observatory, I would say that it has since been necessary
to provide telescopic demonstrations for educational purposes and to carry on
certain other services of the old Observatory, and so the financial saving made
by the decision to close the Observatory by no means equals the whole of the
expenditure which was formerly made on it.

In 1855 Charles (later Sir Charles) Todd was appointed Superintendent of
Telegraphs and Astronomical Observer for the colony of South Australia ;
and in 1874 the Adelaide Observatory was erected and provided with instruments.
It has issued a series of publications on Jupiter, carried on some meridian
observations and maintained observations of variation of latitude, which are
part of an international cooperative plan. Most of the Adelaide Observatory
buildings have now been demolished to make room for a school and it is intended
to make the University responsible for future astronomical work.

Perth Observatory was founded in 1896 when W. E. Cooke was appointed
Government Astronomer for Western Australia. In 1900 Perth undertook a
share of the Astrographic Catalogue between —31° and —41° and its published
work consists of meridian catalogues associated with reference stars for this work,
and various volumes of the Catalogue, most of which has been published.

Although we are discussing chiefly professional astronomy, no account of
the subject in Australia would be complete without mention of John Tebbutt,
who worked as an amateur from about 1854 until 1904, maintaining at Windsor
an observatory which became known throughout the world. He made altogether
over 350 contributions to scientific journals, largely observations of comets,
minor planets and double stars. Astronomy has had many celebrated amateurs.
If we exclude those who became and worked mich as professionals, John Tebbutt
would rank very high indeed among the contributors to astronomical science.

Two further astronomical observatories have been established in Australia
in this century. Riverview College Observatory was established by the Society
of Jesus as a seismological station in 1908, with Father E. F. Pigot as first
director, and in 1931 began astronomical observations. Valuable contributions
are being made to astronomy by this Observatory, particularly important being
the study of variable stars of the southern skies.

After careful testing of conditions on Mt. Stromlo, a few miles west of the
Australian capital at Canberra, it was decided to establish an observatory
there and a staff was appointed which began work in Canberra in 1925 and
observations on Mt. Stromlo in 1926. Thus was established the strongest
astronomical institution that Australia has had. It was called the Common-
wealth Solar Observatory, but has now been renamed the Commonwealth
Observatory to correspond more with its wider purpose. In its comparatively
short life it has become an important contributor to research in a widening field
of astronomical endeavour. The 48” telescope, formerly at Melbourne, is being
modernized at Mt. Stromlo and soon a 74” reflector will be working beside it.

6 HARLEY WOOD.

ASTRONOMY AS AN OPPORTUNITY TO AUSTRALIAN SCIENCE.

For any country there are always subjects of research which represent a
special obligation or, in some cases, a special opportunity. Thus unless we in
Australia investigate the meteorology of our country and its natural resources,
we will leave a gap in information which is important, not only for ourselves, but
as part of a world picture. <A president of our Society, in his address four years
ago, pointed out that we are under an obligation to study Australia’s marsupial
fauna. For Australians there is a similar obligation to astronomy. The object
of my address is to point this out and at the same time to show that northern
astronomers planning work in the southern hemisphere should consider coming
to Australia. Because the great bulk of the wealth and population of the world
must always remain in the northern hemisphere and, because there are important
parts of the heavens not visible from the latitudes of Europe, North America
or Asia the countries of the southern hemisphere can make a contribution to
astronomical science more than proportional to the resources used, when
compared to the efforts of northern astronomers. The study of the structure
of the star-system in which our Sun is situated, or of the organization of the
systems of which ours is but one, is impeded if the knowledge of a large area of
the sky is comparatively incomplete. There is ample evidence of the need for
astronomical research in the southern hemisphere to be brought in line with that
of the north, and of the great opportunities which exist this side of the equator
in the fact that observatories of many northern countries have expensive branch
observatories in southern foreign lands. By far the greatest power of equipment
is in the northern hemisphere. Of reflecting telescopes equal to or exceeding
36” in aperture, there are 27 in: the world, of which four are in the southern
hemisphere and only one in Australia. Of the refractors 24” or more in aperture,
there are 26 in the world, six in the southern hemisphere and none in Australia.

To indicate the ways in which Australia can contribute towards astronomical
research, let us first list the objects of study towards the understanding of which
research is directed. These are:

1. The structure of the Solar System ;
2. The physical constitution of members of the Solar System ;

2

3. The physics of the Sun, which, of course, might be included as a member
of the Solar System or as a particular star, though the study of the Sun
is So important that it deserves a heading of its own ;

4. The structure of the Galaxy and of other star systems ;

5. The physical constitution of individual objects in the Galaxy including,
for example, stars and the gaseous nebule ;

6. The structure of the Universe.

Until the end of last century the emphasis in effort was mostly on the first
two of these subjects ; but in this century the fourth and fifth have become of
dominant importance, and it is likely that as time goes on the last one will advance
beyond the pioneering stage and assume a greater place in the thoughts of the
working astronomer. In the year books of the Carnegie Institution of
Washington of almost fifty years ago concern was expressed at the lack of data
on the southern skies as compared to those of the north, and ways of improving
the situation were discussed. It was pointed out that the positions and proper
motions of southern stars were required to facilitate the study of the motion of
the Sun and the then newly discovered streaming of stars. (We now recognize
other important systematic motions requiring study.) The important positional
work done by the expedition to San Luis, the work of the Cape Observatory
over a long period and the zone catalogues of the La Plata Observatory have
improved this position very greatly and the data in the General Catalogue is not

PRESIDENTIAL ADDRESS. wk

yet fully discussed. However, it is necessary still to remember that observations
must go on and that the resources of positional astronomy in the south remain
below those of the northern hemisphere. At Sydney Observatory we are
planning to continue positional work. By re-photography of the astrographic
zones and comparison of the new plates with old ones, reliable proper motions
should be obtainable ; we will be mounting a new specially designed photographic
lens on the astrographic telescope. The pioneering stage is now over and only
observations of the highest quality will make a useful contribution. Fifty
years ago it was also pointed out that the southern hemisphere was seriously
behind in observations of stellar parallax and of double stars, and in capacity
to make such observations. This position has been largely improved by the
work of the Cape Observatory, the Bosscha Observatory at Lembang, the Yale
University Observatory station at Johannesburg, the Union Observatory,
Johannesburg, and the Lamont-Hussey Observatory of the University of
Michigan. It was remarked, too, that the knowledge of radial velocities of the
southern objects was falling behind the knowledge of those of the northern
hemisphere, and that photometry of the stars of the southern sky was very much
needed ; and these deficiencies remain.

Among the most fundamental of the data required to study the galactic
system are well determined magnitudes for the stars concerned. Careful
observations have been made for a long time; for example, William and John
Herschell made determinations more than 100 years ago and so we would expect
there to be a great body of reliable data; but actually our knowledge of stellar
magnitudes is much below the needs of astronomy and there is much work to
be done in the northern hemisphere and the south is still very far behind. It is
hard to imagine observational astronomy in a condition where there will not be a
need for a substantial amount of photometric work on the stars. The apparently
slow progress made in developing reliable stellar photometry is due to the
difficulty of the observations which have to be made, and only gradually have
the number and complexity of the systematic errors revealed themselves. At
first, the photometry was done visually and astronomers relied upon the eye
to integrate the visible light of the stars in making comparisons of brightness
between them. A similar principle was used when photographic magnitudes
became common, but the stars, being of different temperatures and having
their energy distributed through their spectra in different ways, are affected
differently by the atmosphere, by the instrument, by the method of observing,
or the personality of the observer, and so gradually it became necessary to evolve
a more precise definition of magnitude which did not involve the allowance for
so many variables. In recent years, the emphasis has come to be on mono-
chromatic photometry, where only a narrow range of the spectrum of the star is
used and where we can rely upon the atmosphere and the instrument affecting
the light in a similar way for different stars. This gradual improvement in
photometric method means that for modern needs much of the work has to be
revised ; indeed, in the southern hemisphere it has to be revised almost from
the beginning. Work of this kind has been undertaken in observatories in
South Africa and our own Commonwealth Observatory. There will be need
for the magnitude-system to be extended to faint magnitudes, for the number
of stars per square degree to various magnitude limits to be determined so that
statistical methods may be applied to them in order to study the structure of
the galaxy. The discovery and examination of transparent areas of the Milky
Way is expected to yield important clues concerning its structure. By methods
such as the study of the continuous spectrum of the stars at Greenwich, or as
monochrometric photometry at different wave lengths at Mt. Wilson, the colours
of the stars in the southern sky need to be studied to extend the work which
has been done in the northern hemisphere. It will soon be necessary to follow

8 HARLEY WOOD.

the northern workers into the infra-red region and it seems that the examination
of continuous spectra of variable stars (particularly eclipsing ones) might yield
some results of interest. This kind of work is valuable not only in studying the
stars themselves but also in studying the inter-stellar material through which
the light from the stars has to pass before it reaches us. Some of the light is
absorbed by the material and the way in which it affects the colours of the stars
has already taught us much about the distribution, density and nature of this
material ; mostly, however, in northern hemisphere areas. Exploratory work
on the spectrum lines arising from inter-stellar absorption is also much needed.

When we go beyond the galaxy there is need to find the total magnitudes
of nebule in the southern hemisphere which are beyond the reach of the northern
observers, and to determine isophotal lines and make detailed spectral and
photometric examination of resolved objects, particularly variable stars. In this
connection it should be remembered that the Magellanic Clouds are the nearest
of the star systems which can be surveyed as a whole from the outside and the
study of them by all the methods which may be available should yield results of
importance, not only in studying these systems but also, more fundamentally,
in increasing our knowledge of the way in which the star systems behave.
Statistical data on their stars, having regard to magnitude, spectral class and
position in the system, are needed together with values of stellar motions, based
upon radial velocity measures, and possibly on proper motion measurements ;
for, if stars of the Magellanic Clouds have high systematic motions, it might be
possible for them to be measured, although, if the motions are not substantial
they will be very difficult to disentangle from the systematic motions of reference
objects among the stars of our own galaxy. In addition to the important and
widely interesting topics I have already mentioned, it should be remembered
that many other problems need to be studied over the whole sky and require
observation from both hemispheres. For example, research on meteors is more
advanced in the northern hemisphere than in the south in spite of the valuable
work of an amateur group in the Royal Astronomical Society of New Zealand.
Most of the work of observing minor planets can be done from the northern
hemisphere but there is still a need for cooperation from southern observers in
observing minor planets which culminate well south of the equator at opposition.
or when the effects of parallax have to be examined or eliminated. The new
lens at Sydney will be suitable for this kind of observation.

So far the most important deficiencies in apparatus in the southern
hemisphere have been in the direction of large astrophysical equipment. This
will be partly offset now that the Radcliffe telescope of Oxford University has
been put into commission in South Africa and the 74” telescope at Mount Stromlo
will be due in a few years.

Recently, the National Geographic Society (of America) and the California
Institute of Technology have sponsored a project for mapping the whole of the
accessible area of the heavens with the 48-inch Schmidt camera of Mount
Palomar. Each section of the sky will be photographed once in red light and
once in blue light. This will provide a survey which should uncover many
interesting objects for detailed examination by the great reflectors and give
important material for statistical work. There have been no Schmidt cameras
in the southern hemisphere but this will be partly remedied now that the
instrument operated by Harvard, Dunsink and Armagh Observatories is
becoming available. Mount Stromlo, too, may adapt the 48” telescope to
carry a Schmidt camera. As at least one of these is to be fitted with an objective
prism another southern hemisphere deficiency will have been mitigated. There
is no telescope corresponding to the 20” astrographic telescope at the Lick
Observatory in the southern hemisphere; nor, as far as I know, is there one
projected. One of the purposes of this instrument was to refer the system of

PRESIDENTIAL ADDRESS. 9

stellar motions to the galaxies beyond our own and, unless the data becomes
available for the southern part of the sky, this investigation might easily strike
difficulties when the interpretation of the results is to be made.

One thing that must be remembered is that, although there are some men
like Eddington and Russell whose powerful ideas enable them to contribute
greatly to their science, nevertheless most of the important contributions to
astronomy, such as the resolution of the nearer nebule into stars earlier in
this century, come from workers with powerful equipment and the most valuable
contribution that southern workers can make is by observation. We must
therefore see that our observatories have adequate and up-to-date equipment.

ON THE CHOICE OF SITES FOR OBSERVATORIES.

Having established that opportunity is good for astronomical work in the
southern hemisphere, we need to decide whether there are suitable places for
it in Australia. Let us list the requirements.

1. The site should be satisfactory from the meteorological point of view,
having a good proportion of clear sky, a low average wind velocity, and a low
average daily temperature range. Strong winds tend to cause instruments to
vibrate and lead to lack of homogeneity of the atmosphere from an optical point
of view, and a large temperature-range causes expansion and contraction of
instruments, which is particularly undesirable in large optical parts.

2. A site some miles away from big industrial plant, or from a situation
where such plant could come, is preferable ; for example, a large deposit of iron
or coal might prove a bad neighbour.

3. Adequate supplies of electricity and water and accessibility by road or
rail transport would be necessary, since, if they were not available, provision of
them would take too much of the resources of all but the most ambitious schemes.

4, Living conditions for staff should be good and this implies reasonable
proximity to town and educational facilities ; this is now recognized as desirable,
even if only scientific efficiency is taken into account.

5. The atmosphere at the site should have a standard of transparency
which is high and constant relative to varying position in the sky or to time.
This is necessary for almost any work, and particularly for photometry. The
background sky brightness should be low for photography with fast instruments.
The meteorological corona must be low for some work.

6. For work requiring good image quality, such aS measuring double stars
or examining planetary detail, the seeing conditions require to be of high average
quality.

These are very stringent requirements and much trouble is often taken to
discriminate between available sites. Of course, a lot of the work can be done
at the desk by examining meteorological and other statistical records, but it is
necessary, in particular cases, to make quantitative estimates in the field of
quality of the atmosphere before establishing a large and expensive institution.
Sometimes, of course, considerations other than purely scientific suitability have
to be taken into account. An observatory associated with a university should
be near enough to the university for students to doe observational work without
the handicap of too much travelling.

It is also desirable that the site should be at least some distance from the
sea, since, according to Middleton (1941) sea salt nuclei, even in smaller numbers,
are more effective in limiting visual range than dust or combustion nuclei.
Moreover in eastern Australia the coastal areas are inferior from the point of
view of freedom from cloud. Regarding seeing conditions, it seems established

10 HARLEY WOOD.

that there can be deficiencies which are very localized, as well as wide regional
characteristics, and it would be indeed unwise to establish an observatory at a
place where the topography showed marked lack of symmetry, as by the sea
Shore or on the slopes of mountains. In such places frequent diurnal winds are
likely to be destructive of good seeing. Places at which there is a strong
frequency of wind coming from higher topography should also be avoided,
unless they have been tested. The bad effect this has on seeing conditions has
been noted at many places.

It is always considered desirable to situate observatories at a considerable
- height above sea level in order to have below the observer a good deal of the
atmosphere, including the part which, being least transparent and most subject
to turbulence, interferes most with good optical quality of the air. The actual
site should be somewhat above the surrounding landscape, in order to lift it
above the ground haze, and above any dust which might be raised with particles
large enough to fall quickly in the air. Elevation above the surrounding
landscape also reduces the diurnal range of temperature. Another advantage
is that the air should tend to settle downwards on the top of a hill at night.
This should bring the haze level down at night and the gradual settling of the
air should be favourable to good seeing conditions. In regard to atmospheric
pollution from towns: it is well to remember that the effect is carried a good
many miles to the lee of its source, and situations, whose prevailing winds might
carry such pollution towards them must be regarded as unfavourable. The
situation of the observing site above the surrounding topography will be of value
towards eliminating this effect. However, when selecting a site for daytime
observation, it might be preferable to avoid a hilltop about which air might tend
to rise and produce undesirable optical effects.

On both sides of the equator there are high pressure zones which should be,
and indeed have been, found very favourable for astronomical observation.
In these zones the incidence of cloud is much lower (Brooks, 1930) and frequent
Stability or slow settling conditions in the atmosphere favours good seeing.

At the 1948 meeting of the International Astronomical Union it was
suggested that an international observatory should be established and located
between 10° and 40° south latitude. The requirements for the sites suggested
were that it should be noted for its fine seeing, preferably at an altitude of
between 6,000 and 10,000 feet, with not less than 225 clear nights per year and
no two-month period more than fifty per cent. cloudy. It was admitted that
these specifications might be very hard to satisfy, and, although in Australia
there would be excellent sites found, the altitude requirement would be a very
restricting one. I am inclined to think that the value of an altitude above two
to four thousand feet could easily be overrated, provided that tests of seeing and
transparency gave satisfactory results. The absorption (photographic, see
Buisson et al., 1930) caused by passage horizontally through 3,000 feet of the
atmosphere at altitude 1,000 feet would be about 0-04 magnitude and this is a
substantial proportion of the absorption at a good astronomical site where the
extinction coefficient might be 0:15 mag., and the absorptive capacity of the
atmosphere is much greater in its lower layers and varies rapidly with height
(Middleton, 1941). It will be seen that only very large increases in altitude of
the place will affect the result very materially after, say, 3,000 feet. Australia
is very favourably situated in the southern hemisphere, having the largest part
of its area in the latitude zone most likely to be favourable, and having large
areas with good freedom from cloud. The northern limit for placing the
observatory should be more like 25° south latitude, since any further north
would place at too great a zenith distance the part of the sky which is most
completely inaccessible to northern countries and which it is most essential to
observe.

PRESIDENTIAL ADDRESS. 11

AUSTRALIAN METEOROLOGY FOR ASTRONOMICAL OBSERVATION.

We can now apply the considerations of the previous section to Australia.
Figure 1 is a previously unpublished map of ‘‘ Clear and Cloudy Days ”’, which
is included by kind permission of the Director of Meteorological Services (of
Australia). I have also to thank Mr. C. J. Wiesener of the Meteorological Bureau
at Sydney for assistance with climatological material. It is divided into regions
over which the cloud regime remains much the same. By a clear day is meant
one which is judged to be equal to or less than two-tenths cloudy, and by a
cloudy day one equal to or greater than eight-tenths cloudy. The number of

Fig. 1.—Clear and Cloudy Days in Australia.

clear days recorded in each quarter (the first including December, January and
February) is given for each region in the first column and the number of cloudy
days in the second (bracketed) column.

Another map which is sometimes used to find places which should be free
from cloud is one showing the average annual number of days of rain. Such
maps are available in a publication by the Meteorological Branch (1945) or by
T. G. Taylor (1920). There are large areas in Australia which have less than 30
days of rain in the year but in the areas where living is congenial it might easily
be necessary to be satisfied with 60 days. According to the data given by
Brooks (1930) a location averaging four-tenths cloudy is a favourable one and,
indeed, one as good as this is not likely to be found outside the zones of maximum
pressure on either side of the equator. It may be mentioned that when places
were being selected for the Harvard stations for observation of meteors it was

12 HARLEY WOOD.

Quarter Quarter Quarter Quarter
Region. Dec., Jan., Feb. Mar., Apr., May. June, July, Aug. Sept., Oct., Nov.

] 12 (31) 40 (15) 68 (5) 42 (6)
2 35 (12) 46 (10) Di aa) 50 (5)
3 39 (7) 51 (12) 7p bess Ch) 67 (3)
4 45) (5) 43 (9) 46 (9) 54 (6)
5 43 (8) 45 (10) 50 (11) 52 (4)
6 23 (15) 17 (28) 10 (30) 15 (23)
7 55 (10) 44 (16) 32 (25) 43 (17)
8 27 (14) 25 (17) 26 (15) 28 (15)
9 43 (10) 50 (8) Bo. 19) 54 (7)
10 32 (12) 27 (17) 17 (19) 24 (16)
11 48 (11) 41 (12) 29 (15) 39 (12)
12 15 (18) 9 (22) 3 (27) 7 (23)
13 42 (8) 36 (14) 21 (22) 33 (16)
14 14 (21) P3025) 9 (27) 11 (25)
15 10 (19) 24 (9) 45 (7) 27 (4)
16 27 (16) 38 (11) 56 (9) 47 (5)
17 8 (19) 10 (14) 26 (10) 16 (5)
18 14 (13) 24 (11) 42 (10) 30 (5)
19 VS) 15 (18) 30 (18) 22 (16)
20 34 (13) 44 (12) 51 (14) 46 (9)
21 34 (10) 40 (7) 52, (13) 49 (10)
22 24 (17) 24 (18) 21 (19) 29 (10)
23 ¥3. (17) 15 (17) 18 (14) 15 (15)
24 30 (18) 26 (27) 34 (18) 36 (17)
25 36 (8) 35 (8) 32 (16) 37 (11)
26 15 (23) 210 (22) 30 (16) 22 (18)
27 30 (18) 25 (19) 22 (22) 26 (14)
28 39 (7) 39 (13) 24 (26) 31 (14)
29 8 (22) (23) 7 (21) 7 (23)
30 14 (24) a7) 7 (28) 9 (27)
Bul 44 (9) oor) 20 (24) 28 (14)

agreed (Whipple, 1949) that an average of about ‘‘ 5-5 hours of clear sky per
night is within a few per cent. of maximum clear sky available in North America.”’

Figure 2 is a map of Australia showing the average daily range of
temperature. It should be easy to choose a place in any of the districts otherwise
suitable for astronomical work that has a mean daily range of temperature less
than 25 degrees, although it must be recognized that the need of a low
temperature range is somewhat antagonistic to that of clear skies. However,
the requirement of an elevated position does favour a low temperature range.

In regard to wind, little can be said unless specific localities are being
examined. In general, the southern part of Australia is subject to westerly
winds in the winter time and the northern parts have predominantly south-
easterly winds, especially in the autumn and winter. The parts of New South
Wales on the western side of the Blue Mountains have a high percentage of calm
weather.

The altitude of any district which needs to be considered can, of course, be
found approximately from atlases and larger scale maps, which are available
from government departments responsible for survey work, and there is no
need for the information to be given here.

I believe that the air over Australia is distinguished by high clarity. I
have made a few measures of atmospheric extinction during the past year,
although not as many as I had hoped, as the period I had set aside for it proved
cloudy. A small camera and a guiding telescope were mounted equatorially
on a portable stand, the guiding being done by hand without a driving clock.
To photograph stars down to the fifth magnitude an exposure of 15 seconds
was used. The plate was calibrated by photographing a number of stars near

PRESIDENTIAL ADDRESS. 5 es

the zenith with a wide range of magnitude and, when these stars were compared
with another group photographed on the same plate at a low altitude, the effect
of the atmosphere on the apparent brightness of the lower stars was obtainable.
The star images were compared by medium of what has come to be called rather
elegantly a “‘ fly spanker ”’.

The results were analysed with the usual formula for atmospheric extinction
My =m, —k(sec 2—1)

where m, is the magnitude at the zenith, m, the apparent magnitude, z the zenith
distance, and k is the coefficient of extinction determined to give values of m,
consistent with the tabulated values for the various stars. The list of stars

Fig. 2.—Mean diurnal temperature range (average maximum—

average minimum) in degrees Fahrenheit. This map and

Fig. 1 are published by courtesy of the Director of Meteorological
Services.

selected for observation were all in spectral classes B and A, so that it could be
hoped that errors in the estimated photographic magnitudes would not affect
the result seriously ; and this does appear to be the case, especially when the
extinction stars are very low and the effects of absorption larger than any error
likely to occur. Even if the magnitudes used were not reliable and see z not a
sufficiently good approximation for the air mass in the formula, a comparison
between sites would be obtained if the same methods and the same stars were
used.

14 HARLEY WOOD.

The following table gives the results which were obtained.

| No. of
Place. 1) “Wong, on) ) Pat. 90) |e ielershit: 7% Month. Nights. k
| Oo / ro) / Ft.
Orange... re fp LA NE) 33 «18 2,900 Dec., 1949 3 0-19
Sydney Obs. PLS Da L233 eo 2 150 | Dec., 1949 2 0-47
Toronto, N.S.W... | 151 30 |—33 0 | 50 | Jan., 1950 | 0-40
Sugar Loaf Trig. | | |
Station .. Se oR (30) | Seer ot as ele sd) | Jan., 1950 1 0-28

| | | | |

No comment is necessary on these results except that the values are satis-
factorily low, especially as they are in the ordinary photographic wave-lengths.
A result similar to the one at Orange was obtained by Woolley and Gascoigne
(1948) during their work on the magnitude of the Sun at Mt. Stromlo; this
compares favourably with the values at the Lick and Mt. Wilson Observatories
(Fath, 1935). The observations at Sydney were made when the sky appeared
clear of industrial smoke as well as cloud.

As regards seeing conditions, it must be admitted that our knowledge is not
sufficient, but astronomers and surveyors have given good reports of conditions
in inland areas. H.C. Russell was enthusiastic about seeing conditions on the
mountains west of Sydney, C. J. Merfield commented favourably on conditions
at Wee Waa, New South Wales, and W. F. Gale on the seeing conditions at
Armidale. Others who have worked in the country, and with whom I have had
nights at the telescope in Sydney, have often remarked on the superiority of
their atmosphere even on nights regarded as quite satisfactory.

Even such a brief review as this indicates that Australia has localities almost
certain to be outstanding as astronomical stations. The districts of Canberra,
Armidale, Warwick, Toowoomba and Alice Springs all promise well and if field
tests were to be made it would be interesting to compare such an inland town of
New South Wales as Dubbo with the others. Observations could also be made,
where reasonable transport facilities exist, in regions 4, 5, 7, 9 and 21 of Figure 1 ;
Cue in Western Australia would be one. As far as freedom from cloud is con-
cerned, these areas would be among the best in the world. Canberra has the
advantage of having already a flourishing observatory and the Australian
National University. These would be of much value to a research institution,
as its staff would have the benefit of contact with others working in similar
fields and of library facilities beyond those maintained within the institution
itself. Of the meteorologically favourable sites, Mt. Stromlo is one of the
farthest south, not only in Australia but in the southern hemisphere, with the
south celestial pole highest. Armidale is on an extensive plateau with altitudes
of more than four thousand feet available close at hand, and is the home of the
New England University College. The claim of other places would rest chiefly
on their meteorological advantages, or their ability to provide a high frequency
of good seeing conditions.

EDUCATION IN ASTRONOMY.

One thing in which astronomy lags in Australia is in education. It is a
strange deficiency, for the general public seem very interested and many hundreds
visit Sydney Observatory each year. Astronomy is not mentioned in the
calendar of several of our universities, and in most, only the astronomy used in
connection with surveying is formally taught. At Sydney, it is one of the

PRESIDENTIAL ADDRESS. 15

choices available to students of mathematics after taking a first degree. Of
course, a little astronomy necessarily appears in some other courses, such as
physics and geography, and a number of Australian physicists have shown
interest in astrophysical applications of their subject. In New South Wales,
astronomy has recently been introduced into the secondary schools as a part of a
general science course. In many universities in other countries, not only in
America, England and Germany, but also in countries which have material
resources of the same order as those of Australia, such as Holland or Argentina,
astronomy may be taken as a full subject. It has played an exceedingly
important part in the history of science, in the growth of scientific method, and
in the development of the ideas we have of the universe and the place of world
in it; as, for example, by the re-orientation of man’s ideas at the time of
Copernicus. Once again at the present time I believe a similar re-orientation,
possibly attended by less bitterness, is taking place, as astronomy pioneers
what may prove to be a knowledge of the structure of the universe as a whole.
The discovery of gravity and of the finite velocity of ight came from astronomy ;
and, although the only material which reaches our laboratories from outer space
comes in the form of meteorites, one of the elements was first discovered on the
Sun by an astronomer. We should not be content while there is no professor
or lecturer in astronomy in an Australian university, as for example there is
one in meteorology at Melbourne. Apart from the fact that astronomy deserves
in its own right a place in tertiary education, some training at that level is
necessary in order to equip teachers who will be undertaking teaching at
secondary level.

In other countries the association between an observatory and a university
has been found stimulating to both institutions, if indeed, an observatory run
by a university can be regarded as a separate institution. Many of the
observatories of the world are organized in such association, among them being
the university observatories of London, Cambridge, Oxford and Glasgow in
Great Britain, and nearly all of those of the United States of America. Most
of these universities make available courses of study which leave the student
with a thorough knowledge of astronomy and, if his inclinations and abilities
are so directed, with technical equipment to engage in independent research.
The University of Leiden, in Holland, is a famous one of these; and many
Dutch astronomers occupy high positions in observatories all over the world.
Another university which, to judge by its published plan of studies, gives a very
complete and satisfying course in astronomy is the Argentine National University
of La Plata, which also has a first rate observatory associated with it. Although
I have been speaking of astronomy as a whole, I would like particularly to stress
the need for teaching and research in fundamental astronomy, rather than in
astrophysics, which appears to be able to look after itself very well. Now ifa
university department were being established in any subject it would be natural
to consider whether its staff, by nature of the organization of the department
and of the subject being studied, would have sufficient opportunity to do research
work ; and since fundamental astronomy has fallen somewhat into the back-
ground let me repeat that there are abundant opportunities in this field.
Observations of good quality are needed for comparison with the ephemeris
positions of various bodies for continual improvement of the astronomical
constants ; and, on the theoretical side, we must remember that the theories
we have are based on observations of the motions of the planets only over a
period of a few hundred years and the stability of the Solar System has so far
only been studied with simplified assumptions, which may be justifiable in
making a first approximation, but not in aiming for a definitive result. The
researches of Poincaré form a wealth of material which has never been properly
exploited. H. R. Morgan (1946) and G. M. Clemence (1947) in emphasizing

16 HARLEY WOOD.

the importance of fundamental astronomy give many examples of recent or
much-needed work in this field. Sir Edmund Whittaker (1949) in his article
for the celebration of the centenary of the birth of Laplace last year, said :

‘‘ It is, in my opinion, to be regretted that at the present time, professional
pure mathematicians ... devote their attention to artificial examples con-
structed by themselves, instead of trying to solve the vastly more interesting
problems of pure mathematics that are presented to us by nature. The remark-
able properties of the expansions of Celestial Mechanics have never, so far as I
know, been investigated by any of the pure mathematicians who specialize in
questions regarding convergence of series.”’

To illustrate the activity that does exist, we may point to many recent
researches in dynamical astronomy, as for example on the two body problem
involving subjects such as apsidal motion of binary stars and the distribution of
mass within them. LHinstein and Infeld have only recently produced the theory
of the double stars within the framework of relativity theory and the new
knowledge being gained of the atmospheres of close binary stars shows that these
give us a problem in dynamics which includes a close examination of the way
in which stellar masses might vary and the effect that this would have on the
evolution of the binary systems.

I do feel that, although Australia is doing work of which we may be proud,
we should look forward to even wider grasping of the opportunities which
undoubtedly exist. For this, one of the basic needs is a vital school of astronomy
associated, if possible, with an observatory.

REFERENCES.

Brooks, C. E. P., 1930. Mem. R. met. Soc., 1,127.

Buisson, H., Jausseran, G., and Rouard, P., 1930. C.R. Acad. Sci., Paris, 190,808.

Clemence, G. M., 1947. J.R. astr. Soc. Can., 41, 290.

Kath, E. A., 1935. Lick Obs. Bull., 17; 121.

Green, C., and Cook, J., 1771. Philos. Trans., 61, 397.

Maskelyne, N., 1786. Philos. Trans., 76, 426.

Meteorological Branch, Department of the Interior, Australia, 1945. Maps of Average Monthly
and Annual Rainfall, Australia. .

Middleton, W. E. K., 1941. Visibility in Meteorology. University of Toronto Press, Toronto.

Morgan, H. R., 1946. Popular Astronomy, 54, 2.

Taylor, T. G., 1920. Australian Meteorology. Oxford University Press.

Whipple, F. L., 1949. Sky and Telescope, 8, 90.

Whittaker, E. T., 1949. Math. Gaz., 33, 1.

Woolley, R. v. d. R., and Gascoigne, S. C. B., 1948. Mon. Not. R. astr. Soc., 108, 491.

DALTON-GUNNING AREA, N.S.W., EARTH TREMORS
OF MARCH, 1949.

By G. F. JOKLIK, B.Sc.
With four text-figures.

Manuscript received, December 15, 1949. Read, April 5, 1950.

I. INTRODUCTION.

On March 11th, 1949, severe earth tremors were felt in the Dalton area,
and, less severely, over a considerable portion of New South Wales. These
were succeeded in the epicentral area by numerous aftershocks during the
following fortnight.

As officers of the Bureau of Mineral Resources, Geology and Geophysics,
Canberra, G. M. Burton and the writer were detailed to investigate the tremors,
and left Canberra on the first day of their occurrence. The greater part of the
week devoted to the investigation was spent in the Dalton area. A recon-
naissance embracing an area within a radius of some 40 miles of Dalton was
also carried out with a view to determining the regional distribution of intensities,
and the Chief Geologist circularized post masters and police officers stationed
at fourteen N.S.W. towns from which some information about the tremors was
to be expected.

On the party’s return G. M. Burton was detailed to another field project
and was thus unable to participate in the compilation of this paper.

II. GENERAL DESCRIPTION OF THE EARTH TREMORS.

The first shock, which appears to have been the heaviest in all areas affected,
and which caused most of the reported damage, occurred at 8.31 a.m. (a), on
Friday, 1ith March. A strong aftershock was felt at 9.30 a.m. (b), and an even
more noticeable one shook the epicentral area at 1.33 p.m. (c), causing further
damage. The last severe aftershock took place at 11.24 p.m. on Wednesday,
March 16th (d). These four principal shocks were the only ones noted by
observers more than seven miles from the epicentral area, and shock (b) was
felt only in a limited area in a southerly direction from the epicentre.

No preliminary phase preceding the main shock was reported anywhere.
Shock (a) was very abrupt, and the most reliable estimates of its duration were
approximately five seconds. Durations of the same order were assigned to the
other principal shocks. The intensity of the main shock in the epicentral area
was estimated as VIII on the modified Mercalli scale (see p. 25). The intensity
gradient was very steep in all directions away from the epicentre.

The relatively dense population of the epicentral area facilitated the
investigation. For almost ten days after the main shock this area was subjected
to frequent slight aftershocks, none of them sufficient to cause further damage,
although their abruptness caused considerable uneasiness amongst the local
inhabitants. During the two or three days succeeding the main shock the
aftershocks occurred at roughly half-hourly intervals, and less frequently during
the latter part of this period.

D

18 , G. F. JOKLIK.

IIT. INSTRUMENTAL DATA.

Riverview Observatory, Riverview, N.S.W., and Brisbane Observatory
both recorded the tremors. Unfortunately these are both situated on approxi-
mately the same azimuth from the epicentre. For the information given below
in Table 1, the writer is indebted to Father D. O’Connell and Mr. P. F. Rhein-
berger, of the Riverview Observatory.

TABLE l.
Data from Riverview Observatory.
Distance from | Azimuth from
Date. E.S.T. Riverview. Riverview.
1949— h: m. Ss. Kim.

March 11.. 8 31 36 190 240°

13 aR 54 190 240°
March 16.. 23 25 24 190 240°

The distance and azimuth measurements correspond with an epicentre in
the Dalton—Gunning district. The many small aftershocks mentioned in the
preceding section were not recorded at Riverview. They appear to have been
near-surface phenomena, most of them being accompanied by considerable
sound effects.

On the morning of 13th March the party was favourably stationed in a
two-story building under a corrugated iron roof at Yass for recording a series of
tremors which were felt between 6.15 a.m. and 6.40 a.m. Details of the climax
of this set of tremors, which occurred at 6.31 a.m., are recorded in. Table 2.

TABLE 2: ;
Details of Tremors at 6.31 a.m., 13th March, 1949.

Duration of *
Tremor
(secs.) .. 20 20 40 65 85 60 60 25| |20

Interval
(Sees.) 5). &i: 45 30 25 10 10 15 30 40

The actual peak is marked with an asterisk, and at that stage a slight
bumping of the floor was felt ; all the other shocks were gauged by the trembling
of the corrugated iron roof. It is seen that, as the climax is approached, the
shock period increases. Inversely, the interval between successive shocks
decreases. Past the climax, the reverse holds.

IV. EFFECTS OF THE EARTH TREMORS.
(a) Damage to Property.

In all, some 150 persons were interviewed, and the properties of most of
these were inspected. Press reports drew attention to damage in the township
of Dalton itself, but it was found that landholders to the immediate east suffered
more heavily.

Damage in the epicentral area included such items as heavily cracked
walls, collapse of chimneys, collapse of timber stacks, shifting of heavy machinery,

1 Published with the permission of the Director, Bureau of Mineral Resources, Geology and
Geophysics.

DALTON-GUNNING AREA EARTH TREMORS OF MARCH, 1949. 19

collapse of poorly constructed walls, destruction of parapets, bursting of concrete
water-tanks, breakage of pictures and property stacked on shelves, etc. The
most spectacular damage was of course caused in the most poorly built structures.
In the township of Dalton all the more modern buildings with the exception of
one concrete edifice escaped serious damage. The Royal Hotel, which had
previously been condemned, and the two churches, both very old buildings,
received the greater publicity. In these three it was found, upon removal of

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o Hilers (4-5) DALTON-GUNNING AREA N.S.W. ‘

Showing distribution, on moditied Mercalli scale, of
seismic intensities during earth srremors of ANarch, 19-49,

SCALE OF MILES

2 ed ' a oO [3 4 6

Buresu of Mineral Fesources N 64 =|
Geology £ Geophysics, August (249

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the plaster, that the walls were built of irregular granite and sandstone blocks
the interstices between which had been filled with mortar, wood, and even
paper. Numerous chimneys collapsed in the township, but here again it was
found that the cement in most cases had crumbled.

The heaviest, though not the most spectacular, damage was inspected at
the properties of O. E. Newman, J. Medway, I. Butt, J. McCabe and at the

Dalton Cemetery (see Fig. 1). These define approximately the epicentral
area.

DD

20 G. F. JOKLIK.

At the property of O. E. Newman, sawmiller, the earth tremors produced
almost continuous rumblings for several days. A heap of sawdust was over-
thrown to the east, producing a complex pattern of fractures. Heavy wooden
posts supporting the roofs of sheds moved relative to the earth, and the wheels
of heavy machinery moved up to six inches in relation to the ground. In an
outhouse the basement bricks were shifted by several inches. The brick fire-
place was cracked, and all chimneys collapsed.

J. Medway’s station homestead is a modern solidly-built brick house on
good foundations. Cracks up to one-quarter inch in width, generally at a height
of eight to nine feet above the ground, damaged the walls of every room, and
large sheets of plaster were removed. Doorways built in a north-south direction
were distorted ; most objects had indeed been displaced to the north relative
to the ground, suggesting that the shocks travelled north to south. Two
concrete 2,000 gallon water tanks were fractured at the base, causing one of
them to drain completely.

The house of J. McCabe was partly destroyed. It is situated on deeply
weathered granite, and is built of loosely-cemented granite blocks. It is
suggested that, had the building been of better construction, damage would
have been slight.

Undoubtedly the heaviest damage to property was observed at the Dalton
Cemetery. Two granite pyramids, four feet high, had been rotated through 20°
in a clock-wise direction. Some slabs had been cracked, and in numerous
graves the side-stones had moved away from the tombstone by three inches.

Outwards from the epicentral area damage was found to fall off rapidly.
Outside a seven-mile radius from Dalton it was confined to an occasional fallen
vase or bottle, and inhabitants mostly reported only the rattling of windows and
crockery, and swaying of suspended lamps.

The results of the survey of the damage caused by the tremors suggest the
following observations with regard to |

(a) the suitability of different building materials in the Dalton area ;

(b) the influence of the geological foundation on damage to buildings.

Faulty or poor construction is naturally associated with the greatest
damage—it was this which led to the exaggerated press reports which followed
the tremors. Solid and preferably deep foundations were found to be important.
In houses of sound construction, the following materials are listed in their order
of greatest resistance to shock, according to the present party’s field observations :

(1) Fibro cement,

(2) Weatherboard,

(3) Brick,

(4) Concrete.

In the township of Dalton a concrete cottage which had not even been
completed was damaged beyond repair. On the other hand C. Holgate’s:
homestead, although within the epicentral region, showed very little damage ;
it is built of weatherboard on good foundations. Damage to effects within the
house was severe.

The two main rock types in the Dalton area are massive granite and
Paleozoic slate. Generally houses built on granite suffered more than those on
slate. For example, the house of J. McCabe, built on granite, was partially
destroyed, whereas that of E. L. McCabe, only 600 yards distant, on slate, suffered
only slight damage. Two explanations could be given. The first is that the
granite, with its deep zone of weathering, provides a less sound foundation than
does the compact cleared slate. The second is that the granite, through its
rigidity, transmits shock more abruptly than the slate, which, by virtue of its
cleavage, is elastic and absorbs some of the shock.

DALTON-GUNNING AREA EARTH TREMORS OF MARCH, 1949. 21

(b) Surface Effects.

These included displacement of granite boulders, cracks in the ground, and
slippage in alluvial banks.

On a granite hill only a few hundred yards east of O. Newman’s house the
following phenomena were observed: a granite block measuring 2’ x3’ x 2’
was displaced horizontally about three inches. Another block, 2’ x1’ x1’
moved down an inclined plane a distance of six inches. Half a mile south-west
of O. Newman’s house a block measuring 14’ x 8’ x10’ moved along an inclined
joint plane, ploughing up the ground and damaging a tree. J. McCabe also
reported movement of granite boulders near his house.

Only one crack in the ground was observed, namely on O. E. Newman’s
property. The trend of the crack was east-west, its length some 18 feet, width
one-quarter inch, and the northern side had been displaced to the east a distance
of about one-eighth inch. Many inhabitants reported earth cracks which
opened during the principal shocks and closed immediately afterwards.

Several slippages of the banks were observed in the creek separating the
properties of J. and E. L. McCabe. This dry watercourse is deeply entrenched
in thick alluvium and detrital granite. Further minor slippages of this kind
were noted in the creeks which spring from the western foot of Bald Hill, two
miles east of Dalton.

V. GEOLOGY, PHYSIOGRAPHY AND THEIR RELATION TO THE POSITION
OF THE EPI-CENTRAL AREA.

No geological map of the Dalton area was available, and a geological sketch
map (Fig. 2) was accordingly compiled from field observations and aerial
photographs.

Massive granite, which forms portion of the Gunning batholith, outcrops
to the south and west of Dalton. Tertiary basalt flows cap all prominences
to the north and west. The country rock is early Paleozoic slate containing
beds of shale, sandstone and quartzite. David (1932) assigned an upper Silurian
age to these rocks, but the maps published by the N.S.W. Mines Department
indicate an Upper Ordovician age. The deposits are of deep-water marine origin
and are, apparently, unfossiliferous.

Although the main portion of the granite is massive, definite granitized
beds were observed at three localities. The most prominent one follows the
chain of hills which trends in a northerly direction through the property of
J. McCabe. To the north, roughly a mile to the east of Bald Hill, this
granitized bed appears to be faulted out. It is found along the Gunning—Dalton
road four miles to the south of Dalton. From the east and west of it, the
Paleozoic slate grades into mica schist, strongly banded gneiss, and finally, into
a thin band of massive granite.

A similar granitized bed is found along the Gunning—Bialla road, one mile
north of the Crookwell turn-off. A remarkable feature of these granitized beds
is that the kurrajong tree grows selectively on them. They bear little other
vegetation. This peculiarity is apparently related to the original granitized
horizons which appear to be offset in places, apparently by faults. This fact
has significance in connection with the situation of the epicentral area.

The regional strike of cleavage and bedding is nearly north-south. In
detail, variations from this direction are common. The pitch of subsidiary
folds is generally to the north.

The western face of Bald Hill is traversed by a strongly mineralized shear-
zone, in which the place of the slate is taken by slickenslided phyllite. There
is no reason to believe that the shear-zone is connected with any present-day
fault-action. |

22 G. F. JOKLIK. i

An excellent view is obtained from the summit of Bald Hill. Dalton is
situated near the centre of a physiographic basin, some 15 miles in radius. Bald
Hill is the highest eminence in a chain of hills which traverses the basin in a
north-south direction. The range slopes steeply to the east and west and the
faces could actually be termed scarps.

a - chm
N17. 7 443
CN Ve VNG { SS

/
Ae

‘
/
.
~NI
-“7~
SNe

—}) \YHallam fay

ee pel ey er

An
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+
+

+
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-

SS
—— er te
= Z ta ee
7 \ t
—— =e es eee
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A 5 heh Rea
—- _ ~ ae + + + + + +
aad ar] a ‘ cc Oana! Setu/ aps aR
ere ee 4- —¢ 7 Mima Gu haa Tee ae
= and: ea BI ae NON Te Niele ry fe) a inate:
YAlchin (4) — — i ee oN ip, Le Pater ene
—- —— { Wy an Nee 1 Leh ae he
.

—— —— (— € ~ = NGL Nee Oe Ce ie

2 r = = — — nel bie

aa =a (7-8) *

= 4 =
cana 7 Tar == DALTON = =
Na A it ee eee
Sa aa — 480 &
— 70 wcRAe — —_ —_ — —— — 2
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+
po = == — ——7 —— et ee =
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— need es BE 20 Ee LS el + + ¢ e +
— — —— — Sure NC Hoare (6-7) + +) ¢
e) ce” ct, ) Vener oe

ee pee ss pes peak oe; iy '* e ¢ «¢ +\ ¢ +
— — SS, — ct ca + + aa + e
ay 3

GEOLOGICAL SKETCH MAP
DALTON AREA, NSW

from Aerial Photographs and from fielJ observations.

SCALE OF MILES
a) mo t 3

=” CY an LRN fac fh IER MIEN) OMe IPs, ek Cn TRI ey Nis Tastee EME Cay AIR ete ahd ok Geolagica/ GSouncarres
Tertiary E
Fossiliferovs Freshwater Sediments a, Fau/ts
¢ 7) Seiamic Intensity on modified! Mercalli Scale
Granite } Devonian om Roade
owe, Railways
Sediments & Metamorehx Pocks ewe tee ee
CArtly Shetes & Siatea) eo s Homes treads

Bureau of Winere/ Pescurces, Geolagy & Geonhyercs, Aug, 040. N64~-2

Fig. 2.

The theory is here advanced that the Bald Hill range forms an unstable
block which is out of isostatic adjustment with its surroundings, and its efforts
to reach isostatic equilibrium are the primary cause of the seismic disturbances
in the Gunning—Dalton area.

Except where actual offsetting of the granitized bed was observed, the
faults shown on Figure 2 are inserted on physiographic and air photograph

23

DALTON-GUNNING AREA EARTH TREMORS OF MARCH, 1949.

evidence only. Close field examination would be necessary to confirm them.

There is little reason to doubt, however, that the ‘‘ horst ” is complexly faulted.

os
Sis
aus
S bp
a
eee)
Pw
ss les.
y+
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77)
=

The fact that the chief evidence for some of the faults
shows that movement must have taken place in recent times.

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Y NYNEINOO
(r-&) (r-

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that such movements are the means by which the ‘

towards isostatic equilibrium

found here.

massif ’’ is proceeding
earth tremors is to be

, and that the cause of the

It has been stated that this eminence

one further point of evidence in favour of the theory that the

Bald Hill chain is a young upthrust block.

There is

24 G. F. JOKLIK.

stands alone in a physiographic basin of considerable radius. To the north and
east of Dalton, however, some elevated terrain does exist, and, as is seen from
Figure 2, Tertiary basalt forms cappings to it. The base of the basalt is found
everywhere at the same altitude, and it seems that the lava was poured out
over a peneplain.

Several of the hills in the Bald Hill chain have an altitude considerably in
excess of the general basalt level, others are lower, yet nowhere is any sign of
basalt found on them. The explanation could be that post-basalt uplift has
caused removal by erosion of the lava sheet.

VI. CAUSE OF THE TREMORS AND DEPTH OF FOCUS.

The cause of the tremors experienced in March in the Dalton—Gunning area
appears to have been movement along faults in the Bald Hill block. Slight
shocks have been felt at roughly six-monthly intervals as far back as the local
inhabitants can remember. The process thus seems to be continuous, but at
intervals of ten to twenty years relief is given to some residual stresses probably
involving movement of greater magnitude.

A shallow focus is indicated by the distribution in time of the tremors
and by the rapid falling-off in intensity away from the epicentre (see Figs.
1 and 2). In the case of a deep-seated or even intermediate focus, the Mercalli

Epicentre, E (m) ad G ww)

h

F (focus)

Fig. 4.

values VIII to V (see p. 25) would be expected to cover a far larger area if the
seismic disturbance were severe or, if slight, the higher values would be absent
and the gradient far less steep. Also the block-faulted Bald Hill chain is not a
sufficiently large tectonic unit to have very deep-seated roots.

It has been mentioned that sound effects were prominent throughout the
disturbance, which also indicates a near-surface origin for the shocks. Most
of the inhabitants, in describing the tremors, spoke of ‘‘ claps of thunder ”’ and
‘‘ reports of artillery ’’. The abruptness of the movements supports the same
idea. Instead of strong trembling or swaying, the motion took the form of
sudden jolts ; the former could be expected in a case of deep-focus disturbances,
but the latter was the case even in all the innumerable after-shocks.

A rough determination of the focal depth was made by Oldham’s method
(Holmes, 1946, p. 364). The intensity is expressed in terms of numbers on the
modified Mercalli scale (see p. 25). As these are not absolute quantities, an
error is introduced.

In Figure 4
m is the intensity at the epi-centre £,
m is the intensity at any other point G,
h is the depth of focus.

DALTON-GUNNING AREA EARTH TREMORS OF MARCH, 1949. 25

2
Then ge int 0.
m

In the present case, let H be a point midway between O. E. Newman’s
house and the Dalton cemetery, and let G be at Cullerin (see Fig. 2).

Then Ua cy eee 6
m 2x8
O41 H25

Now (Fig. 1) h=d tan 0
and @=19-38 Km. =19-8x0-8821
==A7 D>) Kam:

From this the depth of focus would be of the order of fifteen to twenty
kilometres, a value which agrees well with the description of the tremors so far
given.

VII. THE ISOSEISMAL MAPS.

Throughout this report use is made of the modified Mercalli Scale of Earth-
quake Intensities. For convenience, a brief summary is included (Holmes,
1946, p. 363).

Intensity.
I ( <10) Instrumental, detected only by seismographs.
II ( >10) Very feeble, noticed only by sensitive persons.
iit ( >25) Slght, felt by people at rest.
IV ( >50) Moderate, felt by people in motion.
Vv ( >100) Rather strong, people are wakened, bells ring.
vi { >250) Strong, slight damage.
VII ( >500) Very strong, cracking of walls, general alarm.
VItl (>1,000) Destructive, chimneys fall.
IX (> 2,500) Ruinous, houses begin to fall.

xX (>5,000) Disastrous, many buildings destroyed.
XI (>7,500) Very disastrous, few structures left standing, ground fissured.
XII (> 9,800) Catastrophic, total destruction, objects thrown into air, ground badly
twisted.

The numbers in brackets refer to the maximum acceleration of the ground
in mm. per sec. per sec.

Figure 1 shows that the isoseismal contours take the form of ellipses where
major axes trend in a north-north-westerly direction. They are, in other
words, elongated approximately parallel to the Bald Hill chain which appears
to be the ‘‘ seat”? of the tremors.

An anomaly is seen to the north-west of the epicentre, in which direction
the intensity values fall off abnormally steeply. Figure 2 suggests no geological
explanation. Two possible explanations are that:

(1) a portion of the block-fault system opposite the properties of J. Toohey
and J. Alchin did not take part in the recent movements, or

(2) that the houses of these two landholders were unaffected by the tremors
due to some favourable local geological conditions.

The regional map, Fig. 3, showing the distribution of seismic intensities
over south-eastern N.S.W., has mainly statistical value. Information was
partly obtained by correspondence. Inspection of the map shows that any
attempt to contour on this regional scale would have failed, the low Mercalli
values are distributed in too irregular a manner, and mostly correspond, in the
writer’s opinion, to local geological conditions or to different conditions of
observation.

26 G. F. JOKLIK.

VIII. SErsmic HISTORY.

The first earth tremor recorded from the Dalton—Gunning—Yass area
occurred in 1885. Since then Riverview Observatory has recorded many
pronounced and slight shocks, and local inhabitants have felt numerous minor
tremors which were not strong enough to register at the Riverview.

The last tremors sufficient to cause damage shook the Gunning—Dalton
area in 1934. The present party collected information concerning these, and
an attempt is made to correlate them with those of March, 1949.

In Table 3 are listed, for comparison, the maximum amplitudes, recorded
at Riverview, for the main tremors of 1934 and 1949.

TABLE 3.
Comparison of 1934 and 1949 Earth Tremors.

G.M.T. Max. Amplitude
Date. (N.-S Movement)
(lu=0-001 mm.).
h m. Ss
1934—
November 10 .. oe 23 47 40 40u.
November 18 .. ie 21 58 42 200u
November 19 .. ss 07 10 16 10u.
November 21 .. ie 06 32 07 80u
1949—
March 10 on oe 22 31 36 170u
March 11 Sie te 05 33 54 34u.
March 16 ae hi 15 25 24 Tu.

The figures show that the phase of November, 1934, was more severe and
sustained than that of March, 1949. When the local inhabitants were questioned
regarding the relative severities, some gave the opinion that the 1934 tremors
had greater force, others indicated those of 1949. The 1934 tremors were
felt more severely at Gunning, and the Riverview Observatory gives the azimuth
of these tremors as 235° and that of the recent ones as 240°, showing that the
position of the epicentre for the 1934 tremors was to the south or south-east
of that of the 1949 disturbance.

As an example may be quoted the houses of A. J. Sumner, two miles west
of Gunning along the Gunning—Dalton road (see Fig. 1). In 1934 the building
then in use was so severely damaged that it had to be abandoned. A new
house, admittedly of a construction more suited to withstanding shock, was
built only two hundred feet from the old one, and during the recent tremors
only one chimney was damaged. No additional damage was suffered by the
old house.

Enquiries indicated that during the 1934 tremors the zone of greatest
damage ran through Sumner’s property parallel to the recent epicentral zone.

It is suggested that the cause of both disturbances lay in the Bald Hill
fault system. It has been proposed that this system acts in the manner of an
active horst, and the theory is now advanced that, whereas in 1949 mainly the
western side sought relief, it was the eastern flank which gave way to stress in
1934.

X. CONCLUSIONS AND RECOMMENDATIONS.

The obvious recommendations are that detailed geological mapping be
carried out in the area to investigate more closely the possible cause of the

DALTON-GUNNING AREA EARTH TREMORS OF MARCH, 1949. 27

tremors, and that intending builders be made aware of the risk of using unsuitable
materials for construction.

Regarding dam construction in the Australian Capital Territory and
southern N.S.W., it is not thought that seismic disturbances in the Gunning—
Dalton area so far experienced need have any influence on future plannings.
The shallow focus and rapid falling-off of intensity indicate that outside a
limited radius no damage to such structures is likely.

XI. REFERENCES.
David, Sir T. W. E., 1932. Explanatory Notes to accompany a New Geological Map of the
Commonwealth of Australia.
Holmes, A., 1946. Principles of Physical Geology (Nelson), p. 364.
Milne, J., and Lee, A., 1939. Earthquakes and Other Earth Movements. (Kegan Paul.)

PALLADIUM COMPLEXES OF THIOETHERS.

Part I. THE REACTION OF POTASSIUM CHLOROPALLADITE IL WITH
O-METHYL MERCAPTO BENZOIC ACID.

By 8. E. LIVINGSTONE, A.S.T.C.,
R. A. PLOWMAN, B.Sc., A.S.T.C.
and J. SORENSEN, A.S.T.C.,

Manuscript received, March 7, 1950. Read, April 5, 1950.

Amongst the complex compounds formed in the platinum and palladium
series those with ammonia and organic sulphides are usually analogous and
comparable in properties. Chelating groups such as glycine are well known,
and by using this compound cis and trans forms of diglycine palladium IT have
been prepared (Wardlaw, Sharratt and Pinkard, 1934).

In the sulphide series, compounds of platinum II with S-ethyl thioglycollic
acid (C,H;.S.CH,.;COOH) have been prepared (Beilstein) but to our knowledge
no reaction of this type of chelating molecule with palladium ITI has been reported.

This investigation deals with the interaction of o-methyl mercapto benzoic
acid (1), which functions as a bidentate group, and potassium chloropalladite.
Interaction of 2 moles of (1) with 1 mole of K,PdCl, yielded bis (o-methyl
mercapto benzoato) palladium II, (2), sparingly soluble in cold water and
organic solvents. This compound appeared stable in water and could be
recrystallised from boiling water. In the presence of hydrochloric acid, however,
the rings were readily opened and the dichloro compound (3), sparingly soluble
in water and dilute acid, was formed. Recrystallisation of (3) from boiling
water yielded the monochloro compound (4) formed from (3) by the expulsion
of 1 mole of hydrochloric acid and the closure of one ring system. With 1 mole
of sodium hydroxide in aqueous solution, closure of the second ring occurred,
regenerating (2). Tentatively, trans structures have been assigned to these

compounds.
os CHs
@: KoPaCig Oe4
COOH ee x
ie)

tH
YN
oe COOH dl
CH

i COOH CHS Coon

EXPERIMENTAL.
(1) o-Methyl mercapto benzoic acid.
o-Mercapto benzoic acid, prepared as in Organic Syntheses, was methylated with (CH,),SO,
in alkaline solution. MRecrystallised from alcohol-water. M.pt., 168-5-169°C. (Beilstein, —
168-169° C.).
Found: S, 18:9%.
Calculated for C,H,0.8: 8S, 19-06%.

LIVINGSTONE, PLOWMAN AND SORENSEN. 29

(2) Bis (o-methyl mercapto benzoato) Palladium II.

K,PdCl, (1-9 g. =0- 006 mole) in 12 mls. of H,O was added to the cold solution of (1) (1-95 g.=
0-012 mole) in 20 ml. of H,O and 8 mls. of 2N NaOH. Crude bis (o-methyl mercapto benzoato)
palladium II precipitated and became crystalline on standing. Yield, 2-5 g. Recrystallised
from boiling H,O as canary yellow compound consisting of small needle-like crystals, with an
acid reaction to litmus paper, and sparingly soluble in cold water and organic solvents. Dried
over P,O;; M.pt. 192—194° C. (decomp.).

Found: Pd, 24-2%; 8S, 14-4%.

Calculated for C,,H,,0,S,Pd: Pd, 24-19%; 8S, 14-54%.

(3) Dichloro bis (o-methyl mercapto benzoic acid) Palladium II.

5:8 g. of (2) were dissolved in the minimum quantity of boiling water (850 ml.) and 50 ml.
of conc. HCl added. The yellow solution became dark red and deposited a red-brown crystalline
compound. On cooling, a further quantity of (3) crystallised (yield 5-45 g.) in well formed
tetragonal prisms, amber in colour and giving an acid reaction on moist litmus paper. The
substance decomposed but did not melt at about 240° C.

Found (on separate preparations, dried over P,O;) : Pd, 20-8%, 20-6% ; Cl, 14-0%, 13-7%.

Calculated for C,,H,,0,8,.PdCl,: Pd, 20-76; Cl, 18-80%.

(4) Monochloro (o-methyl mercapto benzoato) (o-methyl mercapto benzoic acid) Palladium II.

1-5 g. of (3) were dissolved in boiling H,O (650 ml.). On cooling crystallisation did not
occur and the solution was concentrated at the boiling point to 300 ml. On cooling (4) deposited
as fine, bright orange prisms (yield, 1-1 g.), M.pt. 199° C. (decomp.), with an acid reaction on
moist litmus paper. °

Wound ~°Pd, 22+4%; Cl, 7-1%.

Calculated for C,,H,,;,0,8,PdCl: Pd, 22-34%; Cl, 7-42%.

Regeneration of Bis (o-methyl mercapto benzoato) Palladium II.

0:55 g. of (4) were dissolved in 60-70 ml. boiling H,O containing 11-5 ml. N/10 NaOH
(=1 mole of NaOH to | mole of (4)). After concentrating to 40 ml., (2) crystallised on cooling
in bunches of thin, yellow needles. Yield, 0:35 g. M.pt., 194°.

Found: Pd, 24-1%.

Caleulated for C,,H,,0,8,Pd: Pd, 24-19%.

SUMMARY.

The reaction of the sodium salt of o-methyl mercapto benzoic acid (=SOH)
with K,PdCl, yields the palladium compound Pd(SO),, yellow crystals. In
the presence of dilute HCl the Pd-O links are easily broken, forming the dichloro
and monochloro compounds, (SOH),PdCl,, amber crystals, and (SOH)(SO)PdCl,
orange crystals, from which the original compound Pd(SO), is regenerated by
the action of NaOH.

ACKNOWLEDGEMENT.
-The authors wish to thank Dr. F. P. J. Dwyer and Mr. E. O. P. Thompson
for their interest and help during the course of this work, and Miss J. Fildes for
micro sulphur analyses.

REFERENCES.

Beilstein, 1928. Handbuch der Organischen Chemie. First Supplement, 3,95. Julius Springer,
Berlin.

Blatt, A. H., 1943. Organic Syntheses, 2, 580. John Wiley and Sons, London.

Pinkard, F. W., Sharrat, E., and Wardlaw, W., 1934. J.C.S., 1012.

Chemistry Department,
Sydney Technical College.

E

NITROGEN IN OIL SHALE AND SHALE OIL.

XII. THE VOLUMETRIC DETERMINATION OF BASIC NITROGEN IN
SHALE OILS.

By GEO. HE. MAPSTONE, M.S8c., F.A.C.I., A.R.LC., F.Inst.Pet.
Chief Chemist, National Oil Pty. Lid., Glen Davis, 6W, N.S.W.

Manuscript received, December 19, 1949. Read, April 5, 1950.

INTRODUCTION.

One of the characteristics of shale oils is the presence of basic nitrogen
compounds. If these are present in sufficient quantity they may be determined
as the decrease in volume of the oil on washing with a dilute mineral acid.
However, this method is sensitive to only 0-05-0-1 per cent. of bases by volume
(which is the same order as the tar base content of some of the samples), and,
moreover, the result is adversely affected by the polymerization of the pyrroles
present in the oil (Mapstone, 1948a) and by vapour losses from the volatile
samples. In any case the volume of the tar bases is not a direct measure of the
basic nitrogen content of the oil as the nitrogen content of the bases decreases
with increasing boiling point. A search was therefore made for a more accurate
yet simple method.

ACIDOMETRIC METHOD.

Various indicators were examined for their suitability for the acidometric
determination of the weakly basic tar bases in aqueous solution. Purified
samples of tar bases were analysed for total nitrogen by the modified Kjeldahl
method (Mapstone, 1948)), and for basic nitrogen by dissolving various amounts
in standard sulphuric acid and back titrating with standard sodium hydroxide
solution using the different indicators. Screened methyl orange was thus shown
to be the most suitable (Table 1), xylene cyanol FF as the screening agent
giving sharper endpoints than methylene blue.

TABLE 1.

Comparison of Indicators for Acidometric Determination of Nitrogen
Content of Tar Bases.

(Results as Percentage Nitrogen by Weight.)

|
Method. Sample A. | Sample B. | Sample C.
Kjeldahl... 8-20 8-69 10-62
Back titration of acid solution
using—
Screened methyl orange .. 8-19 8-74 —
Bromthymol blue .. Ai 8-11 8-46 —
Methyl orange as 7-60 7-88 —
Screened methyl] red ie 6-62 8-36 —_
Methyl red _ .. : ne 6-46 7-80 —
Phenolphthalein ais ne — — 1-09

NITROGEN IN OIL SHALE AND SHALE OIL. 31

Several hydrocarbon samples were extracted several times with standard
acid and then water washed, the extracts and washings being bulked and aliquots
titrated. The results thus obtained were satisfactory but sometimes the
extraction was incomplete or sharp separation of the oil and acid was difficult
so further work was carried out to overcome these difficulties.

Two INDICATOR TITRATION.

A technique was sought to determine the weakly basic tar bases by the use
of a two indicator titration analogous to that frequently employed for the
determination of weak acid such as phosphoric and carbonic acids.

Preliminary experiments showed that screened methyl orange could be
used as one indicator. Since the bases were slightly alkaline to phenolphthalein
(Sample C, Table 1), and the orange colour of the acid extracts of all but the
least discoloured samples interfered with the observation of that endpoint, the
requirements of the second indicator were that its colour change be from colour-
less or yellow in acid solution to blue or green in alkali, and that its pH range be
somewhat higher than that of phenolphthalein. Of those indicators which
came close to these requirements thymolphthalein was found to be the most
suitable.

Aliquots of a solution of a known weight of redistilled tar bases (from the
gasoline) in dilute hydrochloric acid were rendered alkaline to thymolphthalein
by the addition of an excess of barium hydroxide solution, followed by titration
with standard hydrochloric acid, first to the thymolphthalein endpoint, and
then to the screened methyl orange endpoint. (This procedure was adopted
to prevent the colour of the screened methyl orange from interfering with the
other indicator.)

The results, when expressed as the basic nitrogen content of the bases,
were high but reproducible. This was found to be due to the need of a blank
titration to allow for the wide pH range between the two endpoints (3-7-9-5).
This blank ranged from 0-2 to 0-4 ml. of 0-1N acid depending on the volume
of the solution being titrated. When this allowance was made the basic nitrogen
content (10-82%) was in close agreement with the total nitrogen content
(10-62%) as determined by the modified Kjeldahl method.

The method worked satisfactorily for the determination of the bases from
the gasoline but was not suitable for the higher molecular weight bases from
the light recycle oil from the cracking plant, as the precipitation of the bases
interfered with the observation of the endpoint. This interference, some
‘features of which suggested that the precipitated bases may have extracted the
indicator from the solution, was overcome by the addition of sufficient methyl
or ethyl alcohol (generally about half the volume of the solution) to prevent the
precipitation. This was further assisted by keeping to a minimum the total
volume of the solution being titrated.

EXTRACTION OF BASES FROM OIL SAMPLES.

In general it was found that two washes with hydrochloric acid were sufficient
to extract all the bases from an oil sample provided that an excess of acid was
present in each extract. With sulphuric acid it was necessary to have at least
a 50 per cent. excess presumably because of the relatively weak second
dissociation constant. The concentration of acid employed was relatively
unimportant as long as there was an excess present at the last two, or preferably
three washes. For samples containing less than 0-1 per cent. of basic nitrogen
by weight 100-250 ml. samples could be conveniently extracted with 0-1N
acid, but higher tar base concentrations were more conveniently extracted with
approximately normal acid.

s

a2 GEO. E. MAPSTONE.

The technique found most suitable for an unknown sample was to extract
a measured volume of the sample (100-250 ml.) with successive portions of 40,
20, 20, and 10 ml. of approximately 1N hydrochloric acid. (If the sample were
known to have a low tar base content 0-1.N acid could be used.) The extracts were
bulked and made up to 100 ml. with distilled water; 10 ml. aliquots were
rendered alkaline to thymolphthalein by the addition of a slight excess of barium
hydroxide solution after the addition of 20-25 ml. of methyl or ethyl alcohol
(necessary only with samples heavier than gasoline or with a very high tar base
content). The solution was then titrated with 0-1N hydrochloric acid till the
colour of the thymolphthalein was just discharged ; four drops of the screened
methyl orange were added and the titration continued to the second endpoint.
If the second part of the titration required less than 5 ml. of acid it was repeated
with a larger aliquot. A blank titration was then carried out using an equal
volume of distilled water in place of the acid extract. The basic nitrogen content
of the oil sample was then calculated as:

1-4N (T-B)A
V.D.E.

where T'=ml. acid required between indicators for aliquot,

B=ml. acid required between indicators for blank,

N=normality of acid,

A=ml. of aliquot titrated,

E=final volume of acid extract (normally 100 ml.),

V=mi. of oil sample taken,

D=density of oil sample.

=per cent. by weight of basic nitrogen in sample

TABLE 2.

Basic Nitrogen Content of Some Shale Oil Fractions.
(Results of Duplicate Analyses.)

Basic Nitrogen.
Sample. (Percentage by Weight.)
Crude shale naphtha 0-016, 0-017
Cracked shale gasoline—
: 0-0399, 0-0401
LE: pe yee ae 0-0266, 0-0270
Topped gasoline—
| Abas: 2 0-0633, 0-0637
od Ia ie 0-0760, 0-0769
Recycle light oil—
1 NA hs 0-439, 0-431
II 0-655, 0-655
II ae 0-448, 0-451
Crude shale oil 0-146, 0-146

OXIDIZED OIL SAMPLES.

On standing oil samples tend to oxidize and discolour. Part of this colour
was extracted by the acid and interfered with the observation of the
thymolphthalein endpoint. Distillation of the oil samples before extraction
was found to overcome this difficulty, the colouring materials being left in the
distillation residue (0-5-1-0 ml.) which was shown to contain a negligible amount
of bases. Discoloured samples were therefore redistilled before analysis.

NITROGEN IN OIL SHALE AND SHALE OIL. 33

CRUDE OIL SAMPLES.

Because of its wide boiling range crude shale oil could not be redistilled
before analysis and the colour of the acid extract seriously interfered with
observation of the thymolphthalein endpoint even when sufficient alcohol
had been added to prevent precipitation of the bases, though it did not interfere
significantly with the phenolphthalein endpoint. Further work showed that,
with the crude oil bases, both these indicators gave the same endpoint, and that
direct titration of the acid solution gave more consistent results. The crude
Shale oil tar bases were therefore determined in the acid extract by titrating
alternate aliquots with standard carbonate-free alkali (e.g. barium hydroxide)
to phenolphthalein and screened methyl orange endpoints, the tar bases being
equivalent to the difference between the two sets of titrations.

Titration of the acid extract to the first permanent precipitate of tar bases
required from 0-1 to 0:4 ml. more alkali than titration to the screened methyl
orange endpoint and, by not diluting the acid extract before titrating the
difference between the two methods of determining the excess acid could be taken
as 0:2 ml. of 0-1N alkali when titrating 5-10 ml. aliquots. In this manner
it is possible, if necessary, to make both the necessary titrations on the same
aliquot.

SUMMARY.

A simple volumetric method has been derived for the determination of the
basic nitrogen content of shale oil samples, based on a two-indicator titration
of an acid extract.

ACKNOWLEDGEMENTS.

The author wishes to acknowledge with thanks the assistance of Mr. F. B.
Benfield in carrying out part of this work, and the permission granted by the
management of National Oil Pty. Ltd. for the publication of this paper.

REFERENCES.

Mapstone, G. E., 19480. Tus JOURNAL, 82, 135-144.
-——_-——— 1948b. Ibid., 82, 129-134.

NITROGEN IN OIL SHALE AND SHALE OIL.

XITI. AN APPROXIMATE METHOD FOR DETERMINING PYRIDINE NITROGEN
IN OIL SHALE AND SIMILAR MATERIALS.

By Go. EK. MAPSTONE, M.Sc., F.A.C.I., A.R.1.C., F.Inst.Pet.
Chief Chemist, National Oil Proprietary Limited, Glen Davis, 6W, N.S.W.

Manuscript received, March 3, 1950. Read, April 5, 1950.

INTRODUCTION.

Various workers have observed that, for the determination of the nitrogen
in pyridine type compounds by the Kjeldahl method, additional digestion time
was required after the mixture cleared (e.g. Shirley and Becker, 1945 ; Cole and
Parks, 1946). It was previously suggested by the author that this time factor
might be able to be used as the basis of an approximately quantitative method
for the determination of pyridine rings in an unknown material (Mapstone,
1948a). This paper presents the results of work carried out to test this
hypothesis. Although they do not bear out their initial promise of an accurate
quantitative method, it is felt that, as a qualitative and approximately quanti-
tative method, they may be of interest.

Work DONE.

The apparent nitrogen content of a number of nitrogen compounds of known
structure was determined by the modified Kjeldahl method (Mapstone, 1948)
for various times of after-boil (i.e. digestion beyond that required for the digestion
mixture to clear). The results obtained (Table I) indicate that, in most cases,
the oxidation was nearly complete after an after-boil of half an hour. At the
end of one hour only those containing a pyridine nucleus or a reduced pyridine
nucleus were incompletely oxidized. Of these, only pyridine itself was incom-
pletely oxidized after two hours after-boil.

The proportion of the pyridine nitrogen evolved as ammonia after one
hour’s after-boil ranged from 60 per cent. for pyridine to 91 per cent. for acridine
and isoquinoline. As a first approximation the proportion of the nitrogen
evolved appeared to be a function of the amount of substitution in the molecule,
but it was not possible to derive any quantitative relationships.

Somewhat similar results were obtained with the much milder digestion
conditions obtained by not adding sodium sulphate to the sulphuric acid (Table I),
to increase the temperature of the digestion, the pyridine ring compounds
yielding from four to 42 per cent. of their nitrogen as ammonia with two hours’
after-boil. Quinine (which contains both a pyridine and a quinuclidine nucleus)
yielded 64 per cent. and piperidine gave 54 per cent. of its nitrogen in the same
time. The other compounds examined which were not completely oxidized
under these conditions were indole and its derivatives (80-92 per cent.) and
some of the tertiary amines (69-100 per cent.).

APPLICATION OF RESULTS.
Since only pyridine type compounds were not completely oxidized with an
after-boil of one hour in the presence of sodium sulphate, this method can be
used for indicating the presence of pyridine rings in an unknown material.

3D

NITROGEN IN OIL SHALE AND SHALE OIL.

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SLOOGOUd ANV AIVHS
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36 GEO. E. MAPSTONE.

The three-fold range form nine to 28 per cent. of pyridine nitrogen not evolved
from the samples (other than pyridine itself) means that it cannot be used for
accurate quantitative work though roughly quantitative results could be obtained
by assuming that one-sixth (16-66 per cent.) of the pyridine nitrogen remained
undigested under these conditions. The error in determining in this manner the
pyridine nitrogen content of the samples tested is also listed in Table I. This
method (Method A) gave errors ranging from —52 to +21 per cent. with the
exception of the case of pyridine. itself.

In the absence of added sodium sulphate, some materials other than
pyridine compounds were incompletely oxidized by an after-boil of two hours.
The error obtained by assuming that only one-quarter of the pyridine nitrogen
was evolved under these conditions and neglecting other types of compound is
also listed in Table I. This method (Method B) gave errors ranging from —52
to +40 per cent.

When applied to complex unknown samples, these approximate methods
must be used with caution. The pyridine nitrogen content of crude shale oil,

oil shale and petroleum coke, as determined by these two approximate methods,
is given in Table II.

TABLE II.

Calculated Proportion of Pyridine Nitrogen in Various Samples.
(Results presented as percentage of total nitrogen content.)

Proportion of Pyridine Nitrogen.
Total x
Sample. | Nitrogen. |
| | Method A. Method B. Known.
Oil shale ats ee is 0- 8939. 7 | 12% | 12% Unknown.
Petroleum coke of Sue 1-630% 6% 31% Unknown.
Crude shale oil a a 0-520% 36% 44% Approx. 30%.

By both methods of calculation, the pyridine nitrogen content of the crude
shale oil is slightly greater than the known basic nitrogen content of the oil
(Mapstone, 19485), but the small difference is well within the range of error
observed with the pure pyridine compounds.

With the crude oil, and more particularly with the petroleum coke, Method B
gave higher results than Method A. This may possibly indicate the presence
of indole or stable tertiary amine structures in addition to the pyridine rings
in these materials. The pyridine nitrogen content of the oil shale by either
method was calculated to be 12 per cent. of the total nitrogen content. Since
both methods give the same result the figure can be taken as of the correct order
with a reasonable degree of confidence.

DISCUSSION.

This work confirms the relatively slow oxidation of the pyridine nucleus
under the conditions of the analysis, as previously shown by the isolation of
pyridine carboxylic acids from the Kjeldahl digestion products of coal (Beet
and Belcher, 1938). The very slow attack of sulphuric acid on pyridine was
shown by the fact that, even after two hours’ after-boil in sulphuric acid without
added sodium sulphate or one and a half hours in its presence, some pyridine
was still distilled with the ammonia on rendering the mixture alkaline. This
factor similarly affected the results with piperidine, most of which appeared to
be initially oxidized to pyridine, and explains the relatively high results obtained

NITROGEN IN OIL SHALE AND SHALE OIL. Oo

with both these materials after short digestion periods. Since the pyridine
was first converted to a non-volatile and slowly oxidized compound, it is likely
that the slowness of the oxidation is due to the difficulty of the further oxidation
or sulphonation of pyridine sulphonic acid. The substitution of the pyridine
nucleus as in its homologues and benz-derivatives appeared to facilitate the
oxidation process as shown by the fourfold range of unoxidized material remaining
after an hour’s after-boil in the presence of sodium sulphate.

The reasons for the variations observed in the results appear to be mainly
due to the effect of the molecular structure but it is probable that other factors,
such as the rate of heating etc., are involved. For example, Crossley (1935)
found that maximum nitrogen figures were obtained with the minimum heating
rate to give the minimum “‘ clearing’”’ time, though no such relationship was
observed in the author’s previous work on the determination of the nitrogen
content of oil shale and shale oil (Mapstone, 1948a). In the work reported
in this paper, the heat input to the digestion was controlled to cause the sulphuric
acid vapours to reflux in the bottom of the neck of the digestion flask, and was
therefore approximately constant. It was noticed, however, that several-fold
variations of the clearing time were sometimes obtained though the heating rate
appeared to be constant.

Another factor in the application of the results is the absolute accuracy of
the analytical method upon which the approximate methods of calculation are
based. Duplicate analyses normally checked within one per cent. of the total
nitrogen content for the complete digestion, but the accuracy was somewhat
poorer when the digestion was incomplete. Assuming that the average accuracy
of the analyses was two per cent. of the total, the possible error of the estimate
of the pyridine nitrogen content of an unknown sample is twelve per cent. of the
total nitrogen content. This possible source of error is somewhat reduced if the
duplicate analyses check well with one another, a feature of the analysis of some
materials but not of others.

SUMMARY.

Approximately five-sixths of the pyridine ring nitrogen in a sample are
oxidized after an after-boil of one hour under standard conditions of the Kjeldahl
method, the complete digestion requiring between one and a half and two hours.
No other type of nitrogen compound examined interfered, so, in addition to
being a qualitative method for detecting pyridine rings in an unknown substance,
it can be used as the basis for a very approximate quantitative method. Similar
results can be obtained by eliminating the sodium sulphate from the digestion
mixture, but some other compounds interfere.

ACKNOWLEDGEMENTS.

The author wishes to acknowledge with thanks the assistance of Mr. R. M.
Gascoigne in providing specimens of some of the chemicals analysed, the technical
assistance of Mr. R. J. Dibley in carrying out this work, and the permission
granted by the Management of National Oil Proprietary Ltd. for the publication
of this paper.

REFERENCES.

Beet, A. E., and Belcher, R., 1938. Fuel, 17, 53.

—_-___—_————————— _ 1938. Mikrochemie, 24, 145.

Cole, J. C., and Parks, C. R., 1946. Ind. Eng. Chem., Anal. Ed., 18, 61-62.
Crossley, H. E., 1935. J. Soc. Chem. Ind., 54, 367-369T.

Mapstone, G. E., 1948a. THis JouRNAtL, 82, 129-134.

—-—--—_—_————._ 1948b. Ibid., 82, 135-144.

Shirley, R. L., and Becker, W. W., 1945. Ind. Eng. Chem. Anal. Ed., 17, 437-438.

STUDIES IN THE CHEMISTRY OF PLATINUM COMPLEXES.

PART II. SoME PROPERTIES OF TETRAMMINE PLATINUM II FLUORIDES.

By R. A. PLOWMAN, B.Sc., A.S.T.C. (Chem.).

Manuscript recewed, March 7, 1950. Read, April 5, 1950.

In the previous communication (Plowman, 1949) the preparation of the
fluorides and hydrogen fluorides of the tetrammine platinum II type was
described. This communication reports the decomposition of these compounds
on heating.

The results indicate that each tetrammine decomposes in a characteristic
manner, which is related to the nature of the coordinating molecule attached
to the platinum atom. The results can be represented thus :

140-150° C.
[Pt(NH3),](HF 5). _, [Pt(NH;),]F,+2HF +t
[Pt{C,H,(NH,).}, |(HF,) Lo Tenet. NH,) Jdshrp. HH
170-200°
[Pt(C;H5N),|)(HF 3). _, Simultaneous loss of HF and pyridine.

In the ethylenediamine compound the remaining mole of hydrofluoric acid
is held strongly, and on heating to higher temperatures no further evolution
could be detected. The stability of this compound compares with the compound

F.H,0
HF,

acid and acetone (Plowman, loc. cit.).

The hydrated and anhydrous tetrammine platinum II fluorides decomposed
completely at temperatures above 200°C. However, if the heating was con-
ducted cautiously, the evolution of some ammonia could be detected at temper-
atures of 180-200° C. Tetrapyridine platinum IT fluoride 3-hydrate commenced
to lose pyridine above 100°C. and at 140°C. the loss corresponded closely
with that of 2 moles of pyridine.

The above results are in reasonable accord with the known order of stability
of the platinum-nitrogen bonds and with the structures which could reasonably
be assigned to these compounds. Thus it is reasonable to expect hydrogen
bonding to occur in [Pt(NH,),]F, analogous to the type occurring in ammonium
fluoride which crystallizes with the Wurtzite structure (Wells, 1945). In metal
amines the difference in the electro-negativities between the nitrogen and
hydrogen atoms permits of a considerable portion of the positive charge on the
ion to be drained off to the hydrogen atoms (Pauling, 1948). Such a charge
distribution would favour hydrogen bonding and contributions from structures
such as

[Pt{C,H,(NH.,).}. obtained by crystallisation from aqueous hydrofluoric

| yt SL an l
— PHN He Be REP

as 4 se

STUDIES IN THE CHEMISTRY OF PLATINUM COMPLEXES. 39

would be expected in [Pt(NH,),|F,. With the replacement of one hydrogen
atom by an ethylene group such a symmetrical distribution would not be
expected, leading to greater stability of hydrogen fluoride groups in the structure.

The decomposition of the fluoride and hydrogen fluoride of [Pt(C;H;N),]++
indicate that stable compounds of the dipyridine series are formed. These are
being investigated further and will be reported in a communication on the
reaction of cis and trans [(C;H;N),Pt(OH),] with hydrofluoric acid.

EXPERIMENTAL.
All reactions involving fluorides were carried out in platinum vessels.

The Action of Heat on [PH{C,H,(NH,)o)o)(HF)>.

At 103° C. evolution of hydrofluoric acid perceptible and at 150° C. hydrofluoric acid was
issuing freely. A temperature of 165° was reached and the issue of hydrofluoric acid ceased after
a few minutes. The crystals had lost their clear appearance and were white and powdery.

Found: Loss in weight, 4-2%.

Loss of 1 mole of hydrofluoric acid requires 5-1% ; 2 moles, 10-2%. In another experiment
the compound was held at a temperature of 160—-170° for 9 hours and then raised to 190° for a
few minutes. Residue, pale yellow.

Found: Loss in weight, 6:6%.

In both cases residue increased in weight on standing almost regaining original weight.
These reactions correspond most closely to

A H,O
[Ptene,]|(HF,), —— [Ptene,]
150°

Between 190 and 200° C., decomposition was active, ethylene-ciamine is expelled and the
residue became grey and black. The evolution continued up to 250°, when if the residue was
now heated under a small flame decrepitation occurred.

The Action of Heat on [Pti(NH3),|(HF%)>.

At 150° C. for 1 hour, acid gas evolved and crystals lost clear appearance.

Found: Loss in weight, 10:0%.

At 140-150° C. and then temperature raised rapidly to 195°C. Residue started to blacken.

Found: Loss in weight, 10-1%.

Loss of 2 moles of hydrofluoric acid requires 11-7%.

Residue leached with water and crystallised by the addition of acetone.

Found: Pt, 58-9%.

Calculated for Pt(NH;),F,.1:5H,O; Pt, 59-45%.

At 140-150° C. until all hydrofluoric acid is expelled and then raised slowly to 170-180°C.
the evolution of some NH, was detected ; residue straw coloured.

Found: Loss in weight, 12-1%. |

If the residue was now cautiously and quickly heated over a free flame, further evolution of

NH, could be detected in the initial decomposition. Above 200° C., total decomposition started
evolving dense white pungent fumes, with acid reaction ; black residue.

The Action of Heat on [P1(C;H;N),|(HF2),.0°:5H.0.

At 100° C. the odour of pyridine was faint. At 130° C. a pale yellow colour was spreading
throughout the mass. At 185-190° C. the substance melted to a dark brown liquid; strong
odour of pyridine followed by pungent acid fumes. Reaction appeared to cease after about 1
hour, when the substance solidified to a dark amber vitreous mass.

40 R. A. PLOWMAN.

Found: Loss in weight, 25%.
Calculated : Loss for 2HF+0-5H,0, 8-2% ; loss for 2HF+0-5H,O+2C,H;N, 34:6%.
The residue was soluble in water, giving a dark amber solution. Preliminary investigations

have indicated that the solution contains a compound in which Pt:C,;H,N:F=1:2:2. The
compound is being investigated further and the results will be reported later.

The Action of Heat on [Pt(C;H,N),|F,.9H,O.
This substance readily loses 6H,O over P,O; (Plowman, loc. cit.). However, due to the
rapidity with which the trihydrate takes up H,O the 9-hydrate was used as a starting product.
(1) At 110° for 2 hours, odour of pyridine, and the residue was yellow and hygroscopic.
(2) At 140° for a further 2 hours, odour of pyridine and the residue was dark brown and
hygroscopic.
Found: (1) Loss in weight, 24% (110° C.); (2) loss in weight, 36% (140° C.).
Calculated : Loss for 9H,O, 22-8%; loss for 9H,O0 and 2C;H;N, 45%; loss for 6H,O and
2C;H;N, 37-4%.

SUMMARY.

The decomposition on heating of the fluorides and hydrogen fluorides of
[Pt(NH,),]**, [Pt(C;H;N),]*+, and [Pt{C,H,(NH,),},]++ has been described.
The hydrogen fluorides decompose in a characteristic manner depending on the
nature of the coordinating addenda attached to the platinum atom. With
[Pt(NH), |F, the temperature at which ammonia is lost and that at which total
decomposition occurs are too close to effect a possible preparation of a diammine
compound. However the compounds of [Pt(C;H;),]++ show evidence of.
decomposing to compounds of the dipyridine series.

ACKNOWLEDGEMENT.

The author is indebted to Dr. F. P. J. Dwyer for his interest and suggestions
during the course of this work.

REFERENCES.
Pauling, 1948. J.C.S., 1461.
Plowman, 1949. Tuis JouRNAL, 83, 216.
Wells, 1945. Structural Inorganic Chemistry. Oxford, p. 259.

Chemistry Department,
Sydney Technical College.

STUDIES IN THE CHEMISTRY OF PLATINUM COMPLEXES.
Part III. OXIDATION OF THE TETRAMMINE PLATINUM II FLUORIDES.

By R. A. PLOWMAN, B.Sc., A.S.T.C. (Chem.).

Manuscript received, March 7, 1950. Read, April 5, 1950.

In a previous communication (Plowman, 1949) the preparation of the
fluorides and hydrogen fluorides of the tetrammine platinum II type were
described. This communication reports the preparation of some platinum IV
compounds by oxidation of the corresponding platinum II types with hydrogen
peroxide.

The compounds |Pt( NH s)al/F, and [Pt{C,H,(NH,).}.]F, were oxidised
readily with hydrogen peroxide yielding the corresponding dihydroxo compounds,
[Pt,(NH;),(OH).|F,.0°-5H,O and [Pt,en,(OH),|F,3H,O as well defined,
colourless, crystalline substances soluble in water. Salts of the [Pt(NH3),(OH), |++
ion have previously been described (Mellor, 1937), but as far as is known the
fluoride has not previously been characterised. Compounds of the analogous
ion [Pten,(OH),|**+ do not appear to have been reported. Further investigation
is being carried out on the reactions of this ion and the results will be reported
in a separate communication.

When the above oxidations were carried out in the presence of concentrated
hydrofluoric acid, the ethylene diamine compound yielded [Pten,(OH)F |(HF,),
as a colourless crystalline compound, readily soluble in water. Oxidation of
the [Pt(NH,),]** ion in the presence of concentrated hydrofluoric acid yielded
[Pt(NH,),(OH),|(HF,). crystallising in colourless prisms, soluble in water.
The analytical results on this compound gave fluorine percentages that were
slightly high (ca. 2-3°%), whereas experience has shown that with a pure com-
pound the fluorine percentage is usually low (ca. 2-3%). This may be indicative
of the simultaneous formation of a compound analogous to that obtained with
the ethylenediamine compound, viz. [Pt(NH;),(OH)F](HF,),. When an
aqueous hydrofluoric acid solution of [Pten,(OH)F|(HF,), was evaporated to
complete dryness at the temperature of the water bath the residue approximated
in composition to [Pten,(OH),|(HF,),. Solution of this residue in hydrofluoric
acid (48%) and precipitation with acetone yielded a substance approximating
to the original compound, indicating the existence of the equilibrium

[Pten,(OH)F ](HF,),+H,O0[Pten,(OH), ](HF.2).+HF

The oxidation of [Pt(C;H;N),|F, with H,O, was not successful. The
oxidation of the [Pt(C;H;N),]+*+ ion with H,O, was made the subject of a
separate project, and preliminary investigations indicate that this ion is not
oxidised with hydrogen peroxide. The results of these investigations will be
reported in a later communication.

HXPERIMENTAL.
All reactions involving fluorides were carried out in platinum vessels.
(1) Dthydroxo bis (ethylenediamine) Platinum IV fluoride 0-5-Hydrate and 3-Hydrate.
pettyc,H,(NH,)},],F.-2H,O (Plowman, loc. cit.), 1-5 g.,in 10-15 ml. of H,O oxidised with
2 ml. of 30% H,O,. The solution was concentrated to | ml. on the water bath and on the addition
of methanol-ether, (1) was precipitated as the 3-hydrate in agglomerates of small, colourless

42 R. A. PLOWMAN.

crystals, very soluble in water, insoluble in acetone, alcohol and ether. Yield, 1-46 g.=86%.
Over P,O; 2:5 moles of H,O were lost, forming the 0-5 hydrate. The 2-5 moles of H,O were
regained on exposure to air.

Found (compound dried over P,O;): Pt, 49:1%; F, 9-3%; H,O (increase in weight on
exposure to air), 11:3%.

Calculated for (Pt!’{C,H,(NH,),},(OH),]F..0°5H,O : Pt, 49-29%; F, 9-6%;3 increase for.
2:5 H,O, 11-4%.

(2) Dihydroxo tetrammine Platinum IV fluoride, 0-5 Hydrate.

(ptll(NH,),JF..1-5H,O (Plowman, loc. cit.) 1-5 g. in 10-15 ml. H,O oxidised with 2 ml. of
30% H,O. The solution was repeatedly evaporated on the water bath until excess H,O, expelled.
Crystallisation occurred on evaporation and was completed by the addition of acetone. Yield,
1-56 g.=98% of (2) as clear colourless prisms soluble in water, insoluble in acetone, alcohol, and
ether. The compound commenced to decompose about 230° C. with simultaneous loss of NH,
and HF.

Found): (Pt, 757-09; 56-89, 55 1, LOG: a

Calculated for [Pt!¥(NH,),(OH),JF,.0-5H,O: Pt, 56-7%; F, 11-0%%.

(2) dissolved in cold H,O yielded a sparingly soluble sulphate with sodium sulphate.

Found (material recrystallised from hot H,O and dried over P,O,;): Pt, 49°-3%; 8S, 8:3%.

Calculated for [Pt(NH,),(OH).JSO,: Pt, 49°6%; 8S, 8-14%.

(3) Dihydroxo tetrammine Platinum IV hydrogen fluoride.

[pt!!(NH;),]F., 1-5H,O (Plowman, loc. zit.) dissolved in 2-3 ml. HF (48%) and the solution
oxidised by the addition of 3-4 ml. 30% H,O,. After evaporation [Pt'Y(NH,),(OH),](HF,),
crystallised in clusters of small jagged colourless prisms, with an acid reaction on litmus paper.
Yield, 2-06 g. Dried at 100° C. and finally over P,O;. Deliquescent.

Found’: “Pt;552-49, >) FB, 21-09%.

Dissolved in 3-4 mls. concentrated HF and recrystallised by the addition of acetone.

Found:: Pt, 51-7% 5 8, 20789:

Calculated for [Pt!”’(NH,),(OH),](HF,), Pt, 52-0%; F, 20-3%.

At 150°C. the compound lost HF, the loss being accompanied by some decomposition
(slight blackening).

Found: 2 hours at 150-160° C., lost 14-4%.

Calculated loss for 2 moles HF: 10:7%.

(4) Fluoro hydroxo bis (ethylenediamine) Platinum LV hydrogen fluoride.

pPptlic,H,(NH.),}]Cl,, 2-1 g.,in 10-15 ml. H,O was treated with excess of freshly prepared
Ag,O. To the filtrate excess HF was added and the solution evaporated to dryness on the
water bath. The residue, dissolved in 3-5 ml. of HF (48%), was oxidised with 1-0 ml. H,O,
(30%). A few seconds after the addition of H,O, a vigorous (almost violent) effervescence of gas
occurred and the temperature of the solution rose markedly. After evaporation on the water
bath to incipient crystallisation, crystallisation of the soluble compound was completed by the
addition of acetone. Washed with acetone and finally with ether. Yield, 1-76 g. of micro
crystals colourless and slightly deliquescent after drying over P,O;. The compound gave an
acid reaction with moist litmus paper.

Found (compound dried ovér P,O;): Pt, 45-7%, 45:0%; F, 21-5%.
Calculated for [Pt{C,H,(NH,),.!,(OH)F](HF,),: Pt, 45-59%; F, 22-1%.
Dissolved in concentrated HF and recrystallised in two fractions by the addition of acetone.

Found (on first fraction): F, 21-9%,; (on second fraction): F, 21-1%.

STUDIES IN THE CHEMISTRY OF PLATINUM COMPLEXES. 43

In a separate preparation, the solution after oxidation was evaporated to dryness on the
water bath and finally dried in the oven at 100—-105° C.

Hound: Pt, 45-69%; F, 18-6%. ‘

Calculated for [Pt{C,H,(NH,),}.(OH).](HF,)>: Pt, 45-7%; F, 17-8%.

Dissolved in 2-3 ml. HF (48%) and crystallised by the addition of acetone.

Hound = Pt, 45:7%; F, 20-3%.

At 120°C. the compound commenced to lose HF, and at 150-160° C. there was a steady
evolution of HF.

Found : 2 hours at 150-160° C., 4-9% loss; further 20 minutes at 165-180° C. (decomp.),
7:5% loss.

Calculated loss of 1 mole of HF: 4:7%.

The residue was deliquescent.

SUMMARY.

The preparation of some complex platinum IV fluorides and hydrogen
fluorides has been described. These are [Pten,(OH),.|F,0°5 and 3H,0O;
[Pt(NH,),(OH),|F2.0-5H,0 ; [Pt(NH,),(OH),|(HF.).; and [Pten,(OH)F](HF%)>.
All were prepared from the corresponding platinum II compound by oxidation
with H,O,. They are well defined, colourless crystalline compounds. The
[Pt(C;H;N),]++ ion was not oxidised with the same experimental conditions.

ACKNOWLEDGEMENT.

The author wishes to thank Dr. F. P. J. Dwyer for his interest and guidance
during the course of this work.

REFERENCES.

Mellor, 1937. Inorganic and Theoretical Chemistry, 16.
Plowman, R. A., 1949. THis JouRNAL, 83, 216.

OCCULTATIONS OBSERVED AT SYDNEY OBSERVATORY
DURING 1949.

By W. H. ROBERTSON, B.Sc.
(Communicated by the GOVERNMENT ASTRONOMER.)

Manuscript received, February 9, 1950. Read, April 5, 1950,

The following observations of occultations were made at Sydney Observatory
with the 114-inch telescope. A tapping key was used to record the times on a
chronograph, with the exception of number 195, which was an eye and ear
observation. No correction was applied to the recorded times, either for personal
effect or to allow for error in the Moon’s tabular longitude. The reduction
elements were computed by the methods given in the Occultation Supplement
to the Nautical Almanac for 1938 and the reduction completed by the method
given there. The necessary data were taken from the Nautical Almanac for
1949, the Moon’s right ascension and declination (hourly table) and parallax
(semi-diurnal table) being interpolated therefrom.

Table I gives the observational material. The serial numbers follow on
from those of the previous report (Robertson, 1949). The observers were
H. W. Wood (W) and W. H. Robertson (R). In all cases the phase observed
was disappearance at the dark limb. Table II gives the results of the reductions
which were carried out in duplicate. The N.Z.C. numbers given are those of
the Catalog of 3539 Zodiacal Stars for the Equinox 1950-0 (Robertson, 1940),
as recorded in the Nautical Almanac.

TABLE {[.
Serial NGC: | |
No. No. Mag. | Date. U.S; Observer.
hm Ss
187 647 5-5 Jian. al 13 32 56-4 R
188 797 | 6-3 vane 2 12 29 44-7 R
189 wal 6-1 Apr. 4 9 35 30-1 R
190 1365 | 6-1 Apr. 8 11 37)228 » R
191 1684 7-0 May 8 ll 31 29-4 WwW
192 1373 6-1 June 29 7 34 49-5 R
193 2063 6-7 Aug. 1 13 05 19-4 W
194 Zod 6-6 Aug. 3 8 35 10°3 R
195 2468 6-9 Aug. 4 9 47 33-0. WwW
196 2644 6-3 Aug) iD 12 14 38-3 W
197 2270 5-4 Aug. 30 8 19 20-8 W
198 2583 5:8 Sept. 1 9 10 13-6 W
199 3197 6-5 Nov. 26 W222. o2e5 W
200 545 4-2 Dec. 4 9 39 46-8 W
201 552 3-0 Dec. 4 10 26 41-3 WwW

OCCULTATIONS OBSERVED AT SYDNEY OBSERVATORY DURING 1949.

45

TABLE IT.
Coefficient of

Serial | Luna-

No. tion. Pp q p? Pq Q? As |) pAsc’ | q/Ac

Aw AS
187 ae +52 | +85 PAP +44 73 |—1-3 |—0-7 |—1-1 | + 4-0 | +0-95
188 322 +85 | +53 aes +45 28 |—2-4 |—2:-0 |—1-3 | +10-2 | +0-64
189 325 +92 | +39 85 +36 15 |—1-4 |—1-3 |—0-5 | +11-2 | +0-52
190 325 +34 | —94 12 —32 88 |—2-8 |—1-0 |+2-6;} + 0-1 | —1-00
191 326 +89 | —45 80 —40 20 j—1-0 |—0:-9 |+0-4 | + 8-6 | —0-82
192 328 +66 | —75 44 —50 56 |—0:-8 |—0-5 |+0°6/;} + 5-3 | —0-92
193 329 +69 | —73 47 —50 538 |—0-4 |—0°3 |+0°3 | + 4-9 | —0-94
194 329 +96 | —28 92 —27 8 |—0-6 |—0:°6 |/+0-2 | +11-7 | —0-52
195 329 +68 | +73 47 +50 538 |—2-5 |—1-7 |—1-8 | +10-4] +0-63
196 329 +83 | —56 69 —46 31 |—0-4 |—0:-3 |+0-2 | +11-0 | —0-56
197 330 +80 | —60 64 —48 36 |+0-4 |+0°3 |—0-2 | + 8-3 | —0-80
198 330 +68 | +73 47 +50 53 |—1-2 |—0-8 |—0°9 | + 9-3 | +0-71
199 300 +81 | —58 66 —47 34 |—0-6 |—0-5 |+0-3 | +13-9 | —0-22
200 333 +97 | —23 95 —22 5 |—1-7 |—1-6 |+0-4 | +13-6 | +0-06
201 BR +98 | —22 95 —22 5 |—2:-0 |—2:0 |+0:4 | +13-6 | +0-07
REFERENCES.

Robertson, A. J., 1940.

Robertson, W. H., 1949.

Astronomical Papers of the American Ephemeris, Vol. X, Part II.

THis JOURNAL, 83, 64.

Sydney Observatory Papers, No. 9

THE GEOLOGY OF THE CANOWINDRA DISTRICT, N.S.W.

PaArT Il. THE CANOWINDRA—CowRA-WO00DST0CK ARPA.
By N. C. STEVENS, B.Sc.

Teaching Fellow in Geology, The University of Sydney.
With Plate I and one text-figure.

Manuscript recewed, March 15, 1950. Read, April 5, 1950.

CONTENTS.
I. Introduction.
If. Physiography.
III. Paleozoic Strata.
IV. Structure—

Folding of the Paleozoic Strata.
Faults—

The Southern Continuation of the Columbine Mountain
Fault Zone.
Other Faults.

V. Intrusive Rocks—

The Garnetiferous Porphyry.
The Cowra Granodiorite.
Minor Intrusions.

VI. Summary and Acknowledgements.

I. INTRODUCTION.

The area considered lies immediately to the south of the district described
in Part I of this series (Stevens, 1948).

Previous geological literature concerning the district is confined to brief
notes (chiefly on mineral deposits) in some of the Annual Reports of the N.S.W.
Department of Mines; a report on the limestones near Canomodine and Walli
(Carne and Jones, 1919), and reports on dam sites on the Belubula River (Kenny,
1941 ; Mulholland, 1946). The latest regional map (1945) indicates the presence
of Lower Paleozoic and Devonian strata, invaded by granite, but the area had
not been previously mapped in detail.

The present paper is an attempt to explain the structure and stratigraphy
of the region, and to correlate it with that of the Cargo district. Detailed
accounts of the intrusive rocks will be reserved for later publications.

II. PHYSIOGRAPHY.

Two main streams drain the district—the Lachlan and Belubula Rivers.
They follow meandering east-west courses in valleys about 1,000 feet above
sea level, and join some distance to the west of the area considered. The divide
between them runs roughly east-west, and is generally 500-700 feet higher.

The Belubula River has cut steep-sided, and sometimes vertical, gorges
through the more resistant rocks (e.g. Silurian tuffs and cherts, and Devonian
quartzites and conglomerates). In these places the physiography is relatively
youthful ; elsewhere the country is more mature, especially where the river
flows through porphyry near Canowindra.

THE GEOLOGY OF THE CANOWINDRA DISTRICT, N.S.W. 47

Outcrops are generally poor near the Lachlan-Belubula divide, but become
better as the Belubula River is approached. The highest point in the area is
Malongulli Trigonometrical Station (The Sugarloaf), 2,109 feet above sea level.
It is not situated on the divide between the rivers, but owes its prominence to
the superior resistance of its quartzite capping. The quartzites of the Conimbla
Ranges and the granodiorite ridge between Cowra and Canowindra also form
marked physiographic features.

III. PALHOZOIC STRATA.
Ordovician.
Sedimentary rocks of Upper Ordovician age occur as narrow inliers between
Malongulli Trig. Station and Woodstock. They are elongated north-south and
are bounded on their western margin by a fault.

The rock types are mainly fine-grained sandstones and quartzites, some of
which have a slaty cleavage. The following graptolites were collected by
Mr. K. Sharp and the author (locality—one mile north of Woodstock, 810305*) :

Diplograptus calcaratus var. vulgatus.
Diplograptus rugosus var. apiculatus.
Dicellograptus forchammeri var. flexuosus.
Dicellograptus angulatus.

Dicellograptus cf. caduceus.
Clumacograptus bicornis.

Clumacograptus tubiliferus.

Clumacograptus cf. minimus.

Most of these rocks are in the zone of Dicranograptus clingani (the lower
part of the Caradocian of Britain).

Silurian.

The Silurian rocks of the Cargo district extend south across the Belubula
River towards Woodstock and Cowra. Slates, tuffs, cherts, limestones and
occasional quartzites and conglomerates are the main rock types, and these are
invaded by a garnet-bearing porphyry and the Cowra granodiorite. The
andesites and tuffs east of Woodstock and Walli are also thought to be of Silurian
age, equivalent to the Andesitic Series of Cargo. Thus, they would be the oldest
of the Silurian system in the district.

The series consists of andesites of several types, interstratified with tuffs
and breccias (as at Woodstock), slates and cherts. North-east of Woodstock,
the andesites have large, closely-packed felspar phenocrysts. They are
occasionally amygdaloidal as well, like those east of Canomodine Creek, Cargo.
Quartz-epidote veins and traces of copper minerals are again characteristic of
this series; and in this district several barytes deposits (Raggatt, 1925) are
associated with the andesites. Succeeding beds cannot be observed in this
area because of faulting.

In the ‘‘ Cranky Rock ”’ area, fine-grained crystal tuffs overlie the Cano-
modine limestone. The tuffs are interbedded with, and grade into, cherts and
Slates. South-east of ‘‘ Mountain View ’’, a high hill is composed of a con-
glomerate consisting of andesite pebbles. A similar rock has been noted on the
east side of Liscombe Pools Creek (801472). Strata which include red to
chocolate-coloured shales are adjacent to the garnetiferous porphyry south of
‘* Cranky Rock”. They have been noted in many other localities, both in this
district and to the north, at approximately the same stratigraphical horizon.

* Six-figure numbers are grid co-ordinates on the one-inch military maps, Canowindra and
Cowra. See also map (Plate I).

48 N. Cc. STEVENS.

Next in the sequence is the garnetiferous porphyry, most of which appears
to be a sill-like intrusive. It is generally conformable, though locally trans-
gressive.

Slates, tuffs and some quartzites overlie the porphyry to the west. Some
of .the tuffs resemble the porphyry in hand-specimen, but the fragments are
usually smaller and more closely packed than the phenocrysts of the porphyry.
No large felspars occur in the tuffs, which appear to have a greater percentage
of quartz in them.

East and south of ‘‘ Mountain View ”’ the strata are mainly slates (buff,
greenish and red), with some tuffs and thin limestone beds. One limestone bed
occurs at intervals along the west side of the porphyry belt of Liscombe Pools
Creek, and another on the eastern side. Fossils found north-west of Woodstock
(762350) and near ‘*‘ Malongulli”’ gate (788473) include Tryplasma, Halysites,
Favosites and brachiopods. Halysites, Favosites and bryozoa occur in a limestone
lens surrounded by porphyry and tuff on Liscombe Pools Creek (798470). These
limestones and the associated strata are younger than the Canomodine limestone,
and possibly younger than most of the tuffs which overlie it. (See text-figure.)

Correlation with the Cargo-Toogong District.

The first paper of this series (Stevens, 1948) expresses some doubt about the
stratigraphical position of the Canomodine limestone. Although very similar
to the parallel Cargo Creek belt, it seemed to occur at a higher horizon, separated
from the Cargo Creek limestone by tuffs and slates. On following the Canomodine
limestone south, it was found to be overlain by tuffs similar to those overlying
the Cargo Creek limestone to the north. Comparison of the sequence on the
Belubula River with that between the two limestones south of Cargo suggests
that the Canomodine and Cargo Creek limestones are equivalent, and that the
andesites and tuffs of Barrajin Trig. Station are equivalent to the Cargo Andesitic
Series (see Table I).

TABLE ff,

Comparison of the Silurian Sequences. (A) at the South-eastern End of the
Canomodine Limestone, (B) in the Cargo Creek Area.

Sequence A. Sequence B.

Canomodine limestone.

? Fault ?
4. Garnetiferous porphyry. 4. Garnetiferous porphyry.
3. Slates and cherts. 3. Slates and cherts.
2. Canomodine limestone. 2. Cargo Creek limestone.
1. Barrajin Trig. andesites and tuffs. 1. Cargo Andesitic Series.

Upper Devonian.

Western Area. The Upper Devonian rocks of the Mandagery Range and
Nangar Mountains (Stevens, 1948) continue south along the western boundary
of the area mapped beyond the Cowra-Grenfell Road.

In the Mandagery Range, quartzites are the dominant rock type, but further
south the proportion of interbedded shales and grits increases, giving rise to less
rugged country, especially where the Lachlan and Belubula Rivers have cut
through the series. As early as 1878, Wilkinson recognised Devonian rocks west
of Canowindra, but the southern extension of this series is shown on all previous
maps as Silurian. Wilkinson records Lepidodendron, Sigillaria and a “ small
bivalve shell’? from these rocks.

THE GEOLOGY OF THE CANOWINDRA DISTRICT, N.S.W. 49

Eastern Area. The Upper Devonian rocks of the Black Rock Range do not
continue far south of the Belubula River, as they are cut off by a fault. An
outlier of quartzite occurs east of the main belt, and on it Malongulli Trig. Station
is situated.

rh)

woz

~—
eS
pea)

A/
7
fA Af As

SEA LEVEL
EM 2
H

1 MILES

The oldest beds are quartzites showing evidence of shallow water deposition
in the form of ripple-marks and rain-prints. Etheridge (1909) records Lepido-
dendron, Lingula gregaria and fish-plates from these rocks. Some thin beds of
reddish shales occur within the quartzite series. Conglomerates follow, and
these are overlain by red shales and green mudstones with plant remains.

IV. STRUCTURE.
Folding of the Palzozoic Strata.

Ordovician. Owing to the poor outcrops, the structure of the Ordovician
rocks is uncertain, but from exposures one mile north of Woodstock it is probable
that the folding is closer than in the Silurian and that an unconformity exists
between them.

Silurian. Although the amplitude of the folds in the Silurian is much
greater than in the Ordovician, the intensity of folding in the former series
increases from west to east, as the major fault zone is approached. Angles of
dip steepen, become vertical and the strata overturn on the margins of the
porphyry upstream from ‘‘ Cranky Rock ’”’. Angles of dip are also very steep at
the porphyry boundary on the Canowindra-Cargo Road ; in the headwaters of
Binni Creek, and at the northern margin of the Cowra granodiorite.

The most striking major fold is the Cranky Rock plunging anticline, first
noted by Kenny (1941) in an unpublished report on the Cranky Rock damsite.
The structure in the Canomodine limestone is difficult to determine because
of its massive nature, strong cleavage (N. 20° W.), and lack of fossil bands.
It is possible that several minor folds exist within the limestone, as some have
been observed south, and on the flanks, of the main outcrop. The most con-
vineing proof of the fold is seen further south, where slates, tuffs and cherts dip
gently under the porphyry, and the beds outcrop in a broad arc; the fold
plunging gently south.

The garnetiferous porphyry follows the strike of the beds except in the
‘‘nose’’ of the fold. The irregularity in outcrop here suggests a fault, but it
may be due to a local transgression of the bedding planes.

South of the Cranky Rock anticline, another anticline emerges to the east
of Tenandra Creek. It appears to plunge north, as the porphyry margin curves
around, together with a change in strike. Minor synclines occur on the eastern
flanks of both anticlines.

To the east, near Liscombe Pools Creek, all dips are either to the west or
vertical, except for one near the major fault on the Belubula River. Over-

folding is likely in this area, and both folds and faults suggest pressure from the
west.

50 N. C. STEVENS.

Upper Devonian.

Western Area. Except near the Conimbla Mountains, the Upper Devonian
strata have not been followed far across their strike, but it is known that all the
rocks dip west on their eastern margin. A synclinal structure has been noted
west of Canowindra (Wilkinson, 1878).

The strike varies from N. 30° E. at Nyrang Creek to N. 30° W. north-west
of Cowra. The dip varies from 18° to 90°. An anticline and south-plunging
syncline are present between Conimbla Mountain and the Lachlan River; this
structure shows up well on aerial photographs, as the rock types are interbedded
grits, quartzites and shales.

Eastern Area. The synclinal structure of the Upper Devonian in the Black
Rock Range is cut off to the south by the southern continuation of the Columbine
Mountain fault, and the narrow strip of Upper Devonian west of Malongulli
Trig. Station dips steeply to the west. The outlier itself is in the form of a
syncline with gentle dips; almost a horizontal capping.

Faults.
The Southern Continuation of the Columbine Mountain Fault Zone.

North of the Belubula River the Columbine Mountain fault is joined by a
fault from the north-west, and for several miles south the fault can be traced
along the boundary of Silurian and Devonian rocks, the latter appearing to dip
under the former. The Upper Devonian rocks are nearly vertical near the fault,
and there is ample evidence of brecciation and shearing.

South of the point where the Upper Devonian rocks disappear Ordovician
strata occur east of the main fault, and due to lack of outcrops the evidence of
faulting is not as well defined. The main evidence for a fault along the western
margin of the Ordovician north of Walli lies in the contiguity of strata high in
the Silurian sequence and Ordovician rocks. However, some outcrops of iron
and manganese ore (due to deposition along fault planes) occur along this
boundary, aS well as in the Ordovician strata.

Further south, the position of the fault is hidden by soil cover, but has been
tentatively placed along the Ordovician-Silurian slate boundary. One mile
north of Woodstock an outcrop of manganese ore occurs at the boundary of
Ordovician sandy slate and Silurian sheared andesites. Faulting is clearly
indicated.

Other Faults.

Two transcurrent faults have been noted east of Canowindra, where
quartzite and slate beds have been displaced. A continuation of this line of
faulting may be represented to the south-west by a zone of shearing in the
porphyry and tuffs.

Minor faults displace a limestone lens and tuff beds near ‘‘ Malongulli ”’
gate, and signs of faulting occur between that locality and the head of Emu
Creek.

The steep and sometimes vertical dip of the Upper Devonian quartzites
along their eastern margin south-west of Canowindra suggests some faulting,
and it is further exemplified by displacement of beds W.N.W. of Cowra.

Consideration of the stratigraphy of the area between Cargo and the
Belubula River demands that, if the Cargo Creek and Canomodine limestones
are equivalent, either a fault exists along the north-east margin of the Cano-
modine limestone or that an overfolded syncline occurs between the two beds.

THE GEOLOGY OF THE CANOWINDRA DISTRICT, N.S.W. 51

V. INTRUSIVE ROCKS.
The Garnetiferous Porphyry.

The garnet-bearing porphyry previously seen near Toogong and Cargo
continues south, and is well-developed near Canowindra. The rock is fairly
uniform in appearance, except in shear zones. Idiomorphic phenocrysts of
altered plagioclase and biotite, and corroded quartz, are present in a fine-grained
groundmass.

The porphyry mass is mainly concordant, but tongues transgress the bedding
planes of the associated sediments. It is noteworthy that the porphyry is
restricted to the upper part of the Silurian, and has not been found invading the
Andesitic Series or the Upper Devonian rocks. Where the porphyry outcrops
strongly, large, rounded tors result; these are more pointed and elongated
where the rock has suffered shearing.

Certain phases exhibit a clastic nature under the microscope; but this
seems to be due to brecciation of an intrusive rock rather than evidence of a
pyroclastic origin. In many places the porphyry is intrusive into tuffs of a
similar mineralogical composition, and mapping of boundaries between the two
rock types is difficult.

Similar porphyries and tuffs extend south through Boorowa to Yass, where
three horizons of tuffs and similar intrusive porphyries have been recognised
(Brown, 1940).

The Cowra Granodiorite.

This intrusion has a north-south elongation and is nearly conformable
with the Silurian sediments, which dip towards it on the eastern side. It is
intrusive into these sediments, which have suffered only slight metamorphism.
On the western side, it is adjacent to the garnetiferous porphyry, but field
relations are obscured by soil cover.

In hand specimen the rock is fairly uniform throughout the mass except
for a narrow marginal phase (on the eastern side), which is a type of granite-
porphyry. The usual type of Cowra granodiorite is a mottled black and white,
phanerocrystalline rock with clear vitreous quartz, dull white felspars and
idiomorphic lustrous biotite. Red garnet is frequently present, often in or near
the margins of xenoliths. The latter are abundant, especially near the southern
end of the intrusion. Most of them have been completely recrystallised, but
some retain the banding of the original sediment.

Nothing is known of the age of the intrusion beyond the fact that it is post-
Silurian. It does not show any gneissic banding or marked orientation of
minerals, so it is probably younger than Late Silurian and is possibly of
Kanimblan age (Browne, 1929).

Minor Intrusions.

Most of the minor intrusions of the district occur near the major fault zone
through Walli and Woodstock. The largest of these invades Ordovician strata
south of Malongulli Trig. Station. The main rock type is a pyroxene lampro-
phyre, which weathers readily to a greenish-brown soil. This mags is intersected
by dykes of a peculiar red rock consisting of perthite, green pyroxene, zeolites
and quartz, with magnetite and apatite.

Further north, dykes of a finer-grained rock of similar mineralogical com-
position invade Silurian slates. It is considered that all these minor intrusions
are related to one another, and to the granophyres and monzonite-porphyries
of the Cargo district.

52 N. C. STEVENS.

VI. SUMMARY AND ACKNOWLEDGEMENTS.

Ordovician, Silurian and Upper Devonian strata have been folded into
plunging anticlines and synclines as in the Cargo district, of which the area
considered is the southern extension.

The Columbine Mountain fault zone has been traced south towards Wood-
stock and an account is given of the faulted area between Walli and the Belubula
River.

It has been shown that the garnetiferous porphyry, though locally intrusive,
is mainly conformable with the Silurian sediments, and has been folded with
them.

Introductory notes on the Cowra granodiorite are given, showing that it is
an elongated, sill-like intrusion, almost conformable with the Silurian strata.

The writer wishes to acknowledge financial assistance from a Commonwealth
research grant; also, some of the work was done during the tenure of a Deas-
Thomson scholarship in Geology at Sydney University.

Thanks are due to those members of staff of the Geology Department,
Sydney University, who have given me assistance ; also to Mrs. K. Sherrard for
determining the graptolites. The writer wishes to thank Mr. K. R. Sharp,
Mr. G. Packham and other students for their help in the field; Mr. and Mrs.
Whatmore of ‘ Malongulli’”’, and Mr. and Mrs. W. Ridout of Walli for their
hospitality.

VII. REFERENCES.

Brown, I. A., 1940. THis JourNaAL, 74, 312.

Browne, W. R.,°1929.. Proc. Linn. Soc. N.S.W., 54, xxii.

Carne, J. E., and Jones, L. J., 1919. Geol. Surv. N.S.W., Min. Res. No. 25.
Etheridge, R., Junr., 1909. Geol. Surv. N.S.W., Rec. 8, pt. 4, 308.
Kenny, E. J., 1941. Unpublished report, Geol. Surv. N.S.W.

Mulholland, C. St. J., 1946. Unpublished report, Geol. Surv. N.S.W.
Raggatt, H. G., 1925. Geol. Surv. N.S.W., Bull. No. 16.

Stevens, N. C., 1948. THis JouRNAL, 82, 319.

Wilkinson, C. S., 1878. A.R. Dept. Mines, N.S.W., 150.

EXPLANATION OF PLATE.
PLATE I.

Geological sketch map of the Cowra-Canowindra area. Letters pr, p, g, d, la refer to minor
intrusions related to porphyrite, garnetiferous porphyry, granophyre, dolerite and lamprophyre
respectively.

re

w

Journal Royal Society of N.S.W., Vol. LXXXIV, 1950, Plate I

Fa a 60 65 i) 85
i oo 6 = Vv fy WERE
ech WY v\ Nop tas \ - N
SYN 9
5 NS \vid S|] fe
KAA BS El [ess
Xoanky, Rock 2;
Ky VV I
ae
k= Nyrang

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ALN Y

Papi ur,

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PI/N/NZN/NIN

eS SSeS mKe a 3

=i

ze
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ty
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&

ne
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EXTAINININ| YS ©
ININININIS 2)
ANISISININ ie pik
WhO ge ais N\NREA SELES
LF KS

ya
WOODSTOCK S/S

LEGEND

CAINOZOIC = ALLUVIUM , TALUS

UPPER DEVONIAN - QUARTZITE,
CONGLOMERATE, ETC.

Be

SLATE es

TUFF, CHERT

LIMESTONE

ESN] ANDESITIC SERIES

ORDOVICIAN

— SILURIAN ——

GEOLOGICAL SKETCH Map
OF THE
COWRA = CANOWINDRA
AREA

GRANODIORITE

GARNETIFEROUS PORPHYRY

MINOR INTRUSIONS pr pe 4l3

= FAULTS

NSE

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THE FIVE PROPERTIES CONCERNED IN THE TRANSPORT
OF THE ACTIVE CORRODANT AGENT.

By R. C. L. BOSWORTH, Ph.D., D.Sc.

Manuscript received, March 27, 1950.° Read, May 3, 1950.

THE PROPERTIES INVOLVED IN DETERMINING THE RATE OF
CORROSION.

An analysis of the process of the corrosive loss of matter in the simple case
of a metal dissolving in a corrodant liquid without complications due to such
phenomena as pitting, dezincification or of bimetallic corrosion, has been recorded
in the three earlier papers of this series (Bosworth, 1949). The analysis revealed
that for a given metal, in a given corrodant and at a given temperature, there
are five properties concerned in determining the rate. These five properties,
with the symbols suggested for them in parentheses, are:

(a) the maximum corrosion rate (q),

(b) the conductance term ()j),

(c) the compliance term ({),

(d) the inertial term (&), and

(e) the electrochemical driving force (£).

The quantity q is the rate at which the corrosion process will proceed,
under the given conditions of temperature and pH, when the necessary
depolarizing agent is made instantly available wherever required. The quantity
4 is a measure of the effective driving force change with ease of accessibility to
the surface. K is a measure of the change of driving force with quantity of
metal corroded by unit volume of the corrodant and & is a measure of that
property which tends to maintain the reaction by maintaining the convective
flow of corrodant to the surface under attack once the reaction is proceeding at a
steady rate. &€ may be identified with an inertial (or inductive) term following
the claim by the author (Bosworth, 1946) that natural thermal convection
currents bestow an inductive character on the process of heat flow. €& then is a
property which indicates the magnitude of the opposition which the reaction
offers to any change in rate.

The analysis in the earlier papers gave the product of the two properties
K and #, viz. KE, but was not sufficiently complete to enable the two properties
to be separated. More recently, however (Bosworth, 1949a), the magnitude of #
for some of the systems studied has been obtained by polarization measurements
so that for these systems it is possible to derive all five of the physical properties
concerned in determining the rate of corrosion.

For example, for copper in 30% aqueous acetic acid at 20° C. we have, from
overvoltage measurements,

H=0-70 volt.
Previous measurements have given for this system
KE=1-20 mgrms. litres—1,

54 R. Cc. L. BOSWORTH.

so that
# =1-72 mgrms. litres“! volts.
Again, for copper in 60/40 acetic acid/acetic anhydride
H=1:-10 volts
KH=2-3 mgrms. litres—},
so that
K =2-09 mgrms. litres-! volts—}.

The other properties applying to these systems have all been recorded in
the earlier papers (Bosworth, 1949), so that now a complete list can be given.
Of these properties the value of K—the compliance term—and certain functions
derived from K are of particular interest. Prominent among these derived

properties are those having zero dimensions and those with the dimension of
time.

THE MAGNITUDE OF THE COMPLIANCE TERM.

The property & is a measure of the change in concentration of dissolved |
metal required to produce a unit change in the corrosion cell e.m.f. H. Mathe-
matically

where Cy is the concentration of the dissolved metal.

The variation of an electrode potential with the concentration C,. of the ion
concerned in the electrode reaction is given by the Nernst equation :

H=EK, a In (Oke

where R is the gas constant, F the faraday and n the valence of the ion.
At 20°C. this takes the value

B=n, 4° | Ce
ec
or ap = 40°3nCe jnmkp ih pple hos eyes ho 3 (2)

Since the concentration of the dissolved metal Cm is connected by some
stoichiometric relation with the concentration C, of the ion concerned in deter-
mining the corrosion cell e.m.f., such as

AC m=)dC ¢,
equation (1) may be transcribed to the form
Ki= 40° SNC 8 ts) Gi. Ue a er (3)

where A is the ratio of the equivalent weight of the dissolving metal to the
equivalent weight of the ion concerned in determining the corrosion cell e.m.f.

From the magnitude of K derived above we may thus obtain figures for the
quantity AnC,.. These figures are:

For copper in 50% aqueous acetic acid=0-043 milligrammes per litre.

For copper in 60/40 acetic acid/anhydride=0-052 milligrammes per litre.

Since An is not expected to be greatly different from unity, we conclude
that the concentration of the ion responsible for controlling the corrosion cell
e.m.f. is of the order of 0:05 milligramme per litre. This particular fact may be
used to eliminate certain mechanisms which might otherwise be postulated in
explanation of the corrosion reaction. Thus the active depolarizing agent

FIVE PROPERTIES IN THE TRANSPORT OF ACTIVE CORRODANT AGENT. 5D

cannot be copper ions in solution as the concentration of these ions is indeter-
minate in a fresh acid and much greater than 0-05 milligramme per litre in used
acid. Again the concentration of hydrogen ions even in the non-aqueous
solutions is many thousands of times greater than 0-05 milligramme per litre,
so that the hydrogen ions cannot be effective corroding agent. This leaves
dissolved oxygen as the only other obvious corroding agent. The concen-
tration of dissolved oxygen in a saturated solution of acetic acid at 20° C. is
about 0-2 milligramme per litre. It is not unreasonable to expect that the
somewhat lesser figures of 0-05 might represent at least the order of the magnitude
of the concentration of the dissolved oxygen in the vicinity of the surface under-
going corrosive attack.

From these considerations on the magnitude of the compliance term (K)
we are thus lead to the conclusion that it is, most probably, the dissolved oxygen
-in solution which is responsible for the chemical rate controlling step in the
corrosion process, and that, as this oxygen is used up by the corrosion process,
the effective corrosion cell e.m.f. is progressively changed by a factor determined
by the quantity AK. The fact that the supply of an oxidizing agent is necessary for
the maintenance of the corrosion of copper by organic acids has, of course, long
been known on thermochemical grounds, and it is at least noteworthy that a
purely physical analysis of the flow processes involved leads to the same
conclusion.

DIMENSIONLESS QUANTITIES DERIVED FROM THE COMPLIANCE TERM.

In problems involving heat flow in fluid systems the dimensionless ratio
known as the Prandtl number (Pr) has assumed great importance. Pr is the
ratio of the diffusion constant for momentum, or kinematic viscosity (y/9) to
the thermal diffusivity or thermometric conductivity (k/Cpe). The analogous
properties in the transport process involving the conveyance of the active
depolarizing agent is the ratio of the kinematic viscosity to the diffusivity of the
depolarizing agent (De).

Let us use the symbol Pe for this dimensionless quantity—the analogue of
the Prandtl number in corrosion problems.

We have

eD ae e)
All the properties concerned in equation (4) for the various systems studied
have been measured and we have for

Copper in 30% aqueous acetic acid a 9, ‘Pe=1-90
Copper in 60/40 acetic acid/anhydride mn 7 bG==1-96
Steel re ae 5 a ae ..) Pe=1-86
Brass - a eZ G

? 99 yy) ome,
Phosphor bronze in 60/40 acetic acid/anhydride .. Pe=2-08
The relative constancy of the values of this property is perhaps significant
and would appear to indicate that the transport of momentum and of the
depolarizing agents in these corrodant liquids is effected by a similar molecular
mechanism.
Another dimensionless quantity involving & is the expression
d3g& K? KH?
4j(1 —4/40)
which, as we have seen in the third paper of this series, plays a part in

the corrosion reaction analogous to that played by the Grashof group in the
natural convention of heat. Let us consider the possible variation of this

56 R. C. L. BOSWORTH.

quantity with change in temperature. &, as we have seen, is the larger the lower
the density of the original corrodant and thus is expected to increase slightly °
with increase in temperature. The quantity H, depending as it does on the
solubility of a gas in a liquid, will decrease rapidly with temperature increase.
£ will, in general, change but slightly with temperature. The quantity j/KE,
identified as a diffusion coefficient, and the viscosity will both change rapidly
with temperature following an exponential-reciprocal relationship. Thus Barrer
(1943) has written

y= Const eBArRE oe eo UA oes (3)
D=Const eee eee. eed. ebiec a cue weotehs lee (4)

Identifying 7/KH with D,, the diffusion coefficient for the active corroding
agent we find that the quantity j/K# is independent of temperature unless the
two activation energies of equations (3) and (4) are different. Accordingly we
expect that the temperature variation of

d®gé KH?

j(. —4/40)
will be largely dominated by the change in K and the quantity will thus assume
lower values at higher temperatures. We have seen, however, that at low values
of

degé K?H?

J (1 —4/40)

qd

j(1 —4/40)

will become practically a constant; or, except for values of gq approximating
tO qo, the product qd is expected to be practically constant, or the rate of loss of
matter from small cylindrical bodies by corrosion at high temperatures under
quiescent conditions is expected to be proportional to the length rather than to
the area. This particular phenomenon has already been noted in the third
paper of this series in connection with the corrosion of copper cylinders at
109%, C.

the quantity

TRANSIENTS IN CORROSION PHENOMENA.

We have seen that the flow of matter in corrosion phenomena involves
resistive, inductive and capacitative elements. Accordingly it is to be expected
that the corrosion process will show transient phenomena. It is, of course,
fairly common knowledge that the initial rate of corrosion may differ widely
from that attained in the same system after the lapse of time (Speller, 1935). It
now appears that we have, in some simple cases, a method of estimating the
‘¢ time constant ”’ for the corrosion process by analogy with what amounts to
an equivalent electric circuit. In the systems which have so far been studied
in this series the intensity of the convection current as estimated by the
magnitude of the dimensionless quantity

d3g& K?H?

J (1 —4/Q)
is relatively small and we may, as a first approximation, disregard the inductive
element and estimate the time constant in terms of the resistance and the
capacity.

Let us consider an area A under corrosion attack. Let V be the volume of
the corrodant. The corrosion rate g is now given by

Ay Nb vos aly
qq Aj

FIVE PROPERTIES IN THE TRANSPORT OF ACTIVE CORRODANT AGENT. 57

The corrosion cell e.m.f. (#) thus drives a mass current qA, or

Qoj A?
jJA+QV
so that the resistance term (f) is given by
(JA +4)V)H#
y ae teeta Seiya atts tek spake vee acess 5
Qoj A? ? ( )
The capacity term (C) is likewise given by
a Vetch ite ute rates bse dha eset Yate far gua lye Wid (6)
and the time constant (t) by
ai ey jA
epee pag TC (457) Sorecaic cv oeoso: Geoed «ito. GO cet. cic) -olcononn (7)
beseuler VA
ae +e7) EMEA IIA WENN. 4.0 (8)
The ratio e is equal to the depth of the layer of corrodant over the surface,

Mee Nc ; 1 ’
while j/q) is the measure of the intercept of the fl versus 2 line on the axis, or

a measure of the effective resistance of all factors concerned in determining
the rate of corrosion other than those involving cathodic polarization, the
measure being expressed in terms of the equivalent thickness (5) of the quiescent
layer of the corrodant. Equation (8) may thus be written

wa

7=5,(1 = Pe Tee ey We tree (8)

Expressions of a similar type for the resistance capacity time constants of
transport processes hold for all diffusional systems (Bosworth, 1949b). Since
values of D,. have been found for the various systems studied figures may be
found for different geometrical configurations. For 1/D.e we may take 200 sec. cms.
as a representative figure. For a metal covered to a depth of 1 cm. the time
constant is therefore of the order

400 seconds or 6-3 minutes.
For a surface covered to a depth of 2 cms. this becomes
1200 seconds or 20 minutes.
and one covered by 10 cms.
22,000 seconds or 360 minutes.

The time constant, while varying roughly as the square of the depth of
corrodant covering the surface under attack, is for any system of laboratory
dimensions, small in comparison with a day and experimental determinations
of the loss of weight over periods of five days or more should therefore not be
subject to significant errors arising from the initial condition of unsteady state
corrosion.

SUMMARY.

Corrosion of a metal by a corrodant liquid which attacks the surface
uniformly is controlled by five physical properties: (a) the maximum rate,
(b) a conductance term, (c) a compliance term, (d) an inertial term, and (f) the
electrochemical driving force. All five factors may be determined by methods
outlined in the previous papers.

58 R. GC. L. BOSWORTH.

In the case of copper in acetic acid the magnitude of the compliance term
is Shown to be dependent on the solubility of the corrodant for oxygen.

The rate of corrosion of a specimen freshly placed in a corrodant is expected
to show transient phenomena, and where the contribution of the inertial element
may be neglected the time constant for such transients is roughly proportional
to the square on the depth of immersion of the specimen.

REFERENCES.

Barrer, R. M., 1943. Trans. Farad. Soc., 39, 48-59.
Bosworth, R. C. L., 1946. Nature, 158, 309.
—_—__—___—___——. 1946. Phil. Mag., 37, 803-808.

—_—_—__—______—— 1949. The Influence of Natural Convection on the Process of Corrosion.
THis JOURNAL, 83, 25.
— 1949a. Anodic and Cathodic Polarization of Copper in Acetic Acid. THs
JOURNAL, 83, 124.
Speller, F. N., 1935. ‘‘ Corrosion, Causes and Prevention ”’, pp. 10 seq., 179 seq., 212. McGraw
Hill, New York.

THE MECHANISM OF THE FISCHER INDOLE SYNTHESIS.

By P. H. GORE,
G. K. HUGHES
and E. RITCHIE.

Manuscript received, April 11, 1950. Read, May 3, 1950.

The mechanism suggested by Robinson and Robinson (1918, 1924) for the
Fischer indole synthesis has been accepted as a satisfactory working hypothesis
for many years. Consequently the theory of Pausacker and Schubert (1949a,
1949b) that the reaction proceeds by the free radical mechanism summarised

below for the case of cyclohexanone phenylhydrazone, required careful
consideration.

WONH, HN SNH HN

Evidence along four lines was adduced in favour of this mechanism.

(a) It was found that a mixture of equal weights of cyclohexanone o-tolyl-
hydrazone and 2-methyl-cyclohexanone phenylhydrazone on cyclisation by
glacial acetic acid gave 11-methyl- and 8,11-dimethyl-tetrahydrocarbazolenines
and after dehydrogenation of the neutral fraction, carbazole and 1-methyl-
carbazole. These four products were formed in nearly equivalent proportions.
(It may be remarked here that a fifth product, 1,8-dimethyl-carbazole, also would
be expected in small amount according to both theories.)

60 GORE, HUGHES AND RITCHIE.

From this result it was concluded that the Fischer indole synthesis is an
intermolecular reaction and that homolytic fission of the N-N linkage occurs.

(6) From the cyclisation of cyclohexanone 2-chloro-5-methyl-phenyl-
hydrazone by dilute sulphuric acid, Pausacker and Robinson (1947) isolated
not only the expected product, 8-chloro-5-methyl-tetrahydrocarbazole but also
a small amount of a second substance to which the structure (I), with the name
12-hydroxy-7-methyl-1,2,3,4-tetrahydroisocarbazole given later (Barnes,
Pausacker and Schubert, 1949) was assigned. Other substances of this type
were subsequently obtained (Barnes, Pausacker and Schubert, loc. cit.).

OH

CH, N

(I)

It was claimed that the hydrolysis of the o-halogen in the substituted
phenylhydrazone could be readily explained by the free radical mechanism.
(c) The well-known facile cyclisation of methyl isopropyl ketone phenyl-

hydrazone may be explained, since the intermediate free radical (II) would be
stabilised by hyperconjugation as in (III).

CH, CH;
C—CH, é =CHOH
C—CH, igen
to a

(II) (III)

(d) The corresponding primary arylamines were produced in small amounts
in the cyclisation of the phenylhydrazone, o-methoxyphenylhydrazone, o-tolyl-
hydrazone and o-chloro-phenylhydrazone of cyclohexanone (Barnes, Pausacker
and Schubert, loc. cit.; Pausacker and Schubert, loc. cit. (b)).

These facts were explained by the equation ArNH +H-—-ArNH,.

However it can be shown clearly (1) that all of the evidence cited above
can be satisfactorily interpreted without recourse to a free radical mechanism
and (2) that there is convincing evidence that the cyclisation does not involve
free radicals.

(a) These results may be very simply explained by hydrolysis of the
hydrazones and recombination of the two hydrazines with the two ketones
(or hydrazone interchange without the participation of water) to form four
hydrazones, including cyclohexanone phenylhydrazone and 2-methyl-cyclo-
hexanone o-tolylhydrazone, not initially present, followed by intramolecular
cyclisation. While the experiments described below were in progress this same
explanation was suggested by Robinson and its possibility admitted by Pausacker
(1949 ; Pausacker and Schubert, loc. cit.), who then found that the cyclisation of
cyclo-hexanone o-tolylhydrazone in the presence of phenylhydrazine by glacial
acetic acid gave a product from which carbazole could be isolated after
dehydrogenation.

THE MECHANISM OF THE FISCHER INDOLE SYNTHESIS. 61

It has been known for many years that hydrazone interchange can occur
(e.g. Freer, 1899; Frank and Phillips, 1949; for a beautiful example of the
related case of semicarbazones, see Conant and Bartlett, 1932), and additional
examples pertinent to the question of the mechanism of cyclisation have now
been found. The experimental results may be summarised as follows :

(1) Acetone phenylhydrazone (1 mol.) and cyclohexanone (1 mol.) boiled
in glacial acetic acid for half an hour gave a 50% yield of tetrahydrocarbazole.

(2) Phenylhydrazine (1:2 mol.) and cyclohexanone 2,4-dinitrophenyl-
hydrazone (1 mol.) refluxed in glacial acetic acid for 24 hours gave an 18% yield
of tetrahydrocarbazole and a 25% yield of 2,4-dinitrophenylhydrazine.

(3) Cyclohexanone 2,4-dinitrophenylhydrazone (1 mol.) and acetone pheny]l-
hydrazone (5:3 mol.) refluxed in glacial acetic acid for 32 hours gave a 16%
yield of tetrahydrocarbazole.

(4) Benzaldehyde phenylhydrazone (1 mol.) and cyclohexanone (1 mol.)
boiled in glacial acetic acid for 25 hours gave a 5% yield of tetrahydrocarbazole.

Now in the proposed free radical mechanism the radicals C,H;NH and

C,H,.N would be very reactive since they would not be stabilised by a large
amount of resonance energy. Once formed, they would rapidly react further
and it is unlikely that they would recombine to an appreciable extent. Hence
according to this mechanism the critical step in determining whether a given
hydrazone will cyclise is the formation of free radicals. Under the conditions
used in the above experiments neither acetone phenylhydrazone nor cyclo-
hexanone 2,4-dinitrophenylhydrazone cyclises. Therefore the formation of
tetrahydrocarbazole in each of the experiments and the isolation of 2,4-dinitro-
phenylhydrazine in experiment (2) must result from a hydrazone interchange
and renders unnecessary the postulation of a free radical mechanism.

(b) This argument is valueless. The structures of the so-called tetrahydro-
isocarbazoles are uncertain and even if they had the structures assigned to them
it would still remain to be proved that they are formed from intermediates
involved in the normal cyclisation. Moreover it is by no means apparent how
the hydrolysis of the o-halogen in a substituted phenylhydrazone can be explained
by the free radical mechanism.

(c) The ready formation of indolenines and carbazolenines is to be expected
on the Robinsons’ theory also. It is well known that carbonium ions with the
formal positive charge on a tertiary carbon atom are formed more readily than
those with the charge on a secondary carbon atom.

(d) If free arylimino radicals were formed then by analogy with the
behaviour of other free radicals (Waters, 1946) they would be expected to react
mainly with the solvent thus:

ArNH+HX-—ArNH,+X

leading to the production of large, not small amounts of the primary arylamine.
It is well known that phenylhydrazine can function both as an oxidising and
reducing agent and it has also been found that by refluxing acetone phenyl-
hydrazone with dilute sulphuric acid aniline is produced in small yield, even
though cyclisation does not occur. Therefore the formation of primary aryl-
amines is satisfactorily explained by oxidation-reduction. In support of this
contention may be cited the fact that the cyclisation of cyclohexanone 2,4,6-
tribromophenylhydrazone gives comparatively high yields of 2,4,6-tribromo-
aniline and 1,3,5-tribromobenzene (Barnes, Pausacker and Schubert, loc. cit.),
Chattaway and Irving (1931) having shown that 2,4,6-trichlorophenylhydrazine
is readily oxidised to 1,3,5-trichlorobenzene.

Three further arguments against the free radical mechanism can be put
forward.

62 GORE, HUGHES AND RITCHIE.

(e) Free radical reactions in solution are generally far from ‘“ clean” and
usually do not give high yields (Waters, loc. cit.) By careful working a yield of
over 95% of tetrahydrocarbazole can be obtained by the glacial acetic acid
cyclisation of cyclohexanone phenylhydrazone.

(f) Free phenylimino radicals would surely combine to give at least a trace
of hydrazobenzene, which under the prevailing acid conditions would rearrange
to benzidine. Tests which detect 0-00003 g. of benzidine gave negative results
when applied to the appropriate fraction from the cyclisation of 39:5 g. of
cyclohexanone phenylhydrazone.

(g) Free radicals in glacial acetic acid solution would be expected to react
extensively with the solvent mainly by the reaction

X +CH,COOH—-CH,COO +HX
which would be followed by
CH,COO-—-CH, +CO,

and hence large amounts of carbon dioxide should be liberated. In a typical
experiment the yield of carbon dioxide was only 0-4 mol./mol. of hydrazone.
Moreover, it was found that when acetone phenylhydrazone was refluxed with
acetic acid carbon dioxide was slowly evolved. This means that part of the
carbon dioxide in the previous experiment was produced by a reaction not
connected with cyclisation. The remainder may have arisen from some free
radical reaction but in view of the very small amounts involved it is believed
that its production is unrelated to the cyclisation. Tentatively it is suggested
that it may be produced by thermal decomposition of the acetic acid, since much
of it is evolved rapidly during the short strongly exothermic cyclisation reaction.
It is thought that there may be present isolated points of high energy content
resulting in the rupture of the acetic acid molecule before the energy can be
otherwise dissipated.

EXPERIMENTAL.

Products were identified by m.p. and mixed m.p. with authentic specimens.

Formation of Tetrahydrocarbazole.

(1) A solution of acetone phenylhydrazone (4-1 g.; 1 mol.) and cyclohexanone (2-7 g. ;
1 mol.) in glacial acetic acid (25 ml.) was refluxed for half an hour and then cooled. Tetra-
hydrocarbazole (2:3 g.; 50%) m.p. 116-7° C. separated, and more was undoubtedly present in
the mother liquor since it is moderately soluble in glacial acetic acid.

(2) A solution of cyclohexanone 2,4-dinitrophenylhydrazone (5 g.; 1 mol.) and phenyl-
hydrazine (2 g.; 1-2 mol.) in glacial acetic acid (35 ml.) was refluxed for 24 hours (not con-
tinuously). The dark solution was diluted with water and then shaken with an equal volume of
ether, which took up the resinous material that had precipitated. After a few minutes orange
crystals began to separate from the ether extract. The material (2-3 g.; m.p. 184—92°C.)
which was collected after 18 hours was a mixture of cyclohexanone 2,4-dinitrophenylhydrazone
and 2,4-dinitrophenylhydrazine. The latter substance was obtained in pure form (0-9 g.; 25%)
by three crystallisations from alcohol. |

The ether mother liquor was washed with dilute acid and evaporated to dryness. The
residue on steam distillation (600 ml. of distillate) afforded tetrahydrocarbazole (0-55 g.; 18%).

(3) Acetone phenylhydrazone (18-4 g.; 5:3 mol.) and cyclohexanone 2,4-dinitrophenyl-
hydrazone (6-5 g.; 1 mol.) in glacial acetic acid (45 ml.) were refluxed for 32 hours and then
steam distilled. From the distillate 2,000 ml.), after acidifying with hydrochloric acid, tetra-
hydrocarbazole (0:65 g.; 16%) was obtained.

(4) A solution of benzaldehyde phenylhydrazone (2-4 g.; 1 mol.) and cyclohexanone (1:2 g. ;
1 mol.) in glacial acetic acid (45 ml.) was refluxed for 25 hours, and then steam-distilled. Tetra-
hydrocarbazole (0-1 g. ; 5%) was collected from the distillate (800 ml.).

THE MECHANISM OF THE FISCHER INDOLE SYNTHESIS. 63

Action of Dilute Sulphuric Acid on Acetone Phenylhydrazone.

The conditions were those used by Barnes, Pausacker and Schubert (loc. cat.). Pure acetone
phenylhydrazone (24-2 g.) free from aniline, was refluxed with water (65 ml.) and concentrated
sulphuric acid (7-2 ml.) for half an hour. After cooling, the reaction mixture was extracted with
ether, which on evaporation left unchanged acetone phenylhydrazone (4:0 g., 16%.) The
aqueous layer was made strongly alkaline and extracted with ether, the extract dried and the
ether removed. The residue was then fractionated under reduced pressure, the first few drops
only being collected. From this distillate aniline (0-36 g.; 2-4%) was isolated through its
hydrochloride and further identified through its 5-bromosalicylidene derivative. The residue
in the flask contained phenylhydrazine (about 4-5 g.; 29%), determined by oxidation with
Fehling’s solution, which does not attack acetone phenylhydrazone.

Cyclisation of Cyclohexanone Phenylhydrazone.

Glacial acetic acid (190 ml.) was refluxed vigorously for 15 minutes in a stream of carbon
di oxide-free nitrogen, then cooled and cyclohexanone phenylhydrazone (39-5 g.) added. Traces
of carbon dioxide were swept out, then the issuing gases passed through several gas wash-bottles
containing barium hydroxide solution and the acetic acid solution carefully brought to its boiling
point. At the moment of vigorous reaction carbon dioxide was evolved. When the reaction
had subsided refluxing was continued for half an hour. The barium carbonate (0-17 g.; Le.
0:4% mol. of CO,/mol. of hydrazone) was collected, washed and dried. The reaction mixture
on cooling deposited tetrahydrocarbazole (26-8 g.) and a second crop (8:2 g.; total 98%) was
obtained by éVaporating the mother liquor to half bulk and carefully adding water.

The second mother liquor was basified and shaken with an ethereal solution of the total
tetrahydrocarbazole. The brownish yellow extract was washed with water and then shaken with
dilute sulphuric acid (3 x 50 ml. of 3-2 N) when a slight amorphous brown precipitate (< 0-01 g.)
formed at the interface. Neither this precipitate nor any of the acid extracts gave a positive
test for benzidine with potassium dichromate or ferricyanide or carbon disulphide-bromine
water.

Action of Glacial Acetic Acid on Acetone Phenylhydrazone.

When acetone phenylhydrazone (18 g.) was refluxed in glacial acetic acid (195 ml.) in a
stream of pure nitrogen as above, barium carbonate (0-12 g.; 0-5%) was gradually precipitated
during 24 hours.

ACKNOWLEDGEMENT.

This work was carried out during the tenure of a Dunlop Research Scholar-
ship held by one of us (P.H.G.).

REFERENCES.

Barnes, C. S., Pausacker, K. H., and Schubert, C. I., 1949. J. chem. Soc.,- 1381.
Chattaway, F. D., and Irving, H., 1931. Jbid., 1740.

Conant, J. B., and Bartlett, P. D., 1932. J. Amer. chem. Soc., 54, 2881.

Frank, R. L., and Phillips, R. R., 1949. IJbid., 71, 2804.

Freer, P., 1899. Amer. chem. J., 21, 14.

Pausacker, K. H., 1949. Nature, 163, 602.

Pausacker, K. H., and Robinson, R., 1947. J. chem. Soc., 1557.

Pausacker, K. H., and Schubert, C. I., 1949a. Nature, 163, 289.

—— —— 1949b. J. chem. Soc., 1384.

Robinson, G. M., and Robinson, R., 1918. Jbid., 113, 639.
1924. Tbid., 125, 827.

Waters, W. A., 1946. The Chemistry of Free Radicals. Oxford University Press.

School of Chemistry,
University of Sydney.

THE PERMIAN ROCES OF THE MANNING-MACLEAY PROVINCE,
NEW SOUTH WALES.

By ALAN H. VOISEY, D.Sc.
‘With Plate II.

Manuscript received, February 20, 1950. Read, May 3, 1950.

INTRODUCTION.

In this paper is presented an account of the Permian rocks outcropping
in the region embraced by the valleys of the Manning, Camden Haven, Hastings
and Macleay rivers which will be called the Manning-Macleay Province. Details
of a number of sections have been published in a series of papers dealing with
smaller areas, but an attempt is now made to correlate the various beds
throughout the whole province.

For reference purposes and in order to show the occurrences of the major
units on a map it is suggested that the Macleay Series (Voisey, 1934), which
probably corresponds to the Lower Marine Series of the Hunter Vallty, may be
divided into three stages as follows :

Warbro Stage, consisting of micaceous mudstones with small proportions
of tuff, sandstone, shale, limestone and conglomerate, with a maximum
measured thickness of 1,640 feet ;

Yessabah Stage, comprising calcareous sediments (including the Yessabah
crinoidal limestone) and being very fossiliferous, with maximum
thickness of 1,260 feet; and

Tait’s Creek Stage, consisting of chocolate and grey shales, sandstones and
conglomerates with a maximum thickness of 500 feet.

This division, based on the lithology, is somewhat arbitrary and it is not
suggested that a detailed correlation with Osborne’s stages in the Hunter Valley
should be made. There are, however, a number of similarities between some
of the sediments and the faunas which indicate that the two sequences are of the
Same general age.

In a preliminary account of part of the province (Voisey, 1934) the name
‘“ Kempsey Series’ was given to the sedimentary strata around Kempsey.
Because of the paucity of outcrops subsequent evidence of age has only been
obtained in one place, a quarry beside the Kempsey-Telegraph Point road,
where marine Carboniferous shells were discovered. However, this information,
together with Professor L. A. Cotton’s discovery of Rhacopteris beside the same
road, and lithological resemblances of some of the rocks to those in known
sections, indicates that most, if not all, of the area shown as ‘‘ Kempsey Series ”’
on the map (Voisey, 1934, Plate X VI) should now be regarded as Carboniferous
and not Permian as previously suggested. On the accompanying map (Plate IT),
therefore, a possible fault separating Carboniferous and Permian beds is shown
running north-west from Kundabung.

MACLEAY SERIES.
Geographical Distribution.

The distribution of the three eee of the Macleay Series is shown on the
map (Plate II). No occurrences are known north of the Kempsey Area Fault

PERMIAN ROCKS OF THE MANNING-MACLEAY PROVINCE. 65

and none south of the Manning River Fault System. The chocolate or purple
shales of the Tait’s Creek Stage are revealed in road cuttings between Moparrabah
and Yessabah but further south they are inconspicuous. The crinoidal limestone
of the Yessabah Stage may be picked up at intervals beyond Dondingalong as far
as the old lime kilns near Kundabung. Since outcrops become fewer to the
south, the mapping of the continuation of the Permian beds is conjectural, being
based on the topography and the soil.

The limestone and its associates reappear some miles to the Peer of
Wauchope (Voisey, 1939b, 259). Together with Carboniferous strata they are
unconformably overlain by the Triassic sediments of the Lorne Basin, which
form the Broken Bago Range.

Limestone is recorded from a place five miles west of the village of Comboyne,
on the eastern side of a small tributary of Karagnine Creek, which flows into
the Ellenborough River. Carne and Jones (1919, 271) state that it is traceable
for some distance down the gorge. This belt continues southward to the
neighbourhood of Wingham and Taree (Voisey, 1938; 1939c).

Numerous isolated Permian outcrops have been mapped in the Kimbriki-
Mount George area, where they are separated from each other by the fractures
of the Manning River Fault System (Voisey, 1939a; 1939c).

Structural Relations.

The remains of the Permian deposits are preserved only in sunken areas
within a large fault-girt block, which has been depressed relatively to its sur-
roundings.

North of the Kempsey Area Fault Lower Paleozoic slates and phyllites
appear, all Upper Paleozoic sediments having been removed by erosion. Similarly
to the south, Devonian rocks are in contact with Permian and Carboniferous
strata, demonstrating a smaller but still important movement.

Within this main down-thrown block the Macleay Series outcrops along the
eastern limb of the Parrabel Anticline (Voisey, 1934) in synclines and small
faulted blocks.

A critical examination of each locality where a section has been measured
shows that only lower Permian rocks are present, and nowhere have the
equivalents of the Coal Measures or Upper Marine Series been recognised. The
question as to whether a much thicker Permian sequence ever existed over the
area must remain open.

The existence of the Triassic strata of the Lorne Basin (Voisey, 1939b)
lying with a relatively gentle dip on the upturned edges of Permian and Carbon-
iferous strata suggests that there was quite a long break between the onset of
the Upper Paleozoic orogeny and the formation of the freshwater lake. It
may be, therefore, that the early orogenic movements which caused the folding
of the older sediments took place a considerable time before the close of the
Permian period. As indicated in earlier papers (Voisey, 1939), 254 ; 1939c, 406)
the larger faults, the Kempsey Area fault and Manning River Fault system,
occurred late in the orogeny and were responsible for the lowering of the block
of already folded Upper Palzozoic sediments between them. The Triassic
lake formed in the depressed area perhaps a short time afterwards.

Stratigraphy.

Difficulties have been met in the field in the separation of the Kullatine
Series and the Tait’s Creek Stage of the Macleay Series since the Kullatine
tillites in places weather to a chocolate or reddish colour not unlike that of the
overlying shales (Voisey, 1936, 185). The calcareous matrix of the shales
containing glaciated pebbles at Yessabah and the marine fossils indicate that
these beds are related closely to the Macleay Series. In fact, the uppermost

66 ALAN H. VOISEY.

shales are interbedded with the limestones of the Yessabah Stage and these
also have a pink and sometimes purple colour. So close is the relation in this
locality that the separation of the Tait’s Creek and Yessabah Stages has to be
quite arbitrary. This point is emphasised because W. R. Browne has now
placed the Lochinvar shales in the Kuttung Series of the Carboniferous (Osborne,
1949, 207), and the Tait’s Creek shales have been compared with these
(Woolnough, 1911, 164).

Tait’s Creek Stage. The Tait’s Creek Stage is taken to include all beds
above the Carboniferous Kullatine Series and below the Fenestellide Mudstone
horizon (Voisey, 1934, 339).

There is a great variation in the nature of the sediments in this stage.
Between Willi Willi and Yessabah they are largely chocolate and grey shales
making up about 200 feet of the sequence, followed by 40 feet of green tuff. The
shales contain a number of pebbles, some glaciated.

At Dondingalong sandstones form the basal unit but contain two lenticular
bands of ‘‘ shell conglomerate ”’.

In the Manning District tuffs and tuffaceous sandstones close to the base
of the series also include a ‘‘ shell conglomerate ”’ of similar character containing
marine fossils, including Spirifer and Aviculopecten. This rock appears in
portions 117 and 118, parish of Taree, and portion 118, parish of Wingham
near Western’s Quarry. At Kimbriki and Mount George tuffs and banded
mudstones are several hundred feet in thickness and directly overlie the Carbon-
iferous tillites and tuffs.

Yessabah Stage. The division between this and the underlying Tait’s Creek
Stage is in each section placed where there is a definite increase in the amount of
calcareous material. This seems to occur at approximately the same point
throughout the province and represents some big change in the conditions of
sedimentation. In contrast with the underlying Stage, the Yessabah Stage
shows little lithological or faunal variation over an area representing probably
3,000 square miles of sea floor.

The Fenestellide Mudstones, which are generally well developed throughout
the province, pass upwards and in some places laterally into limestones. The
overlying Yessabah limestone has been used for the mapping of the whole
province. Its upper and lower limits vary slightly from place to place, usually
at the expense of the mudstones. The rock is coarsely crystalline and has been
described as a marble. Fossils are well preserved in spite of the texture. The
limestone varies somewhat in colour, usually being pink and purple in the
north and grey to bluish-grey in the south. Towards Kimbriki it passes into a
dark tuffaceous limestone losing much of its crystalline character.

The topmost unit of the Yessabah Stage is usually limestone, partly silicified,
which weathers to a spongy mass of silicified fossil remains. Where Cladochonus
nicholson is abundant, as at Willi Willi, macaroni-like masses occur.

Warbro Stage. <A distinct change in lithology from limestones to micaceous
mudstones and tuffs is recognisable in most localities. There is generally a
sudden break in slope stratigraphically above the silicified limestone, the Warbro
Stage sediments forming the lower ground.

Owing to the softness of the mudstones outcrops are infrequent, among the
best being those in the cliffs beside the Manning River at Kimbriki (Voisey,
1939a). These show the richly fossiliferous Linoproductus springsurensis and
Strophalosia jukesi beds to advantage.

The greatest variety of rock types in this stage is to be found in the parish of
Warbro between Willi Willi and Moparrabah, where tuffs, conglomerates,
mudstones and a band of limestone occur (Voisey, 1934, 339).

=e

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Journal Royal Society of N.S.W., Vol. LXXXIV, 1950, Plate II

OF THE

GEOLOGICAL

MANNING - MACLEAY
OF PERMIAN ROCKS

MAP

PROVINCE

|———

LEGEND
RECENT Ge)
PLEISTOCENE
TERTIARY
BASALT He

ALKALINE _INTRUSIVES. —
AND EXTRUSIVES ena se
TRIASSIC
PERMIAN
GRANITES & PORPHYRIES
SERPENTINE
WARBRO STAGE
YESSABAH STAGE
TAITS CRK. STAGE
CARBONIFEROUS
DEVONIAN
SILURIAN ?
WOOLOMIN SERIES

KOROGORO POINT

CRESCENT HEAD

RACECOURSE HEAD

<7 POINT PLOMER

LOWER PALAEOZOIC KZA
FAULTS — ae
Lee f PORT MACQUARIE
POSSIBLE FAULTS —-- . 28 E. ff j Cre
RAILWAY —_— I. Z SO SKENXA TACKING POINT

~CAMDEN HEAD

s\ DIAMOND HEAD

~cROWDY HEAD

ARRINGTON

MN.

VA WOLF

o
‘

Pe
ae

eet

PERMIAN ROCKS OF THE MANNING-MACLEAY PROVINCE. 67

Paleontology.

The fauna of the beds consists essentially of fenestellids, crinoids and
brachiopods, notably Linoproductus springsurensis and Strophalosia jukest.
Numbers of Spirifer, Martiniopsis, Dielasma, Productus and Platyschisma are
present as in most other Permian sections. Ptychomphalina and a number of
species of Aviculopecten occur in the Tait’s Creek Stage at Yessabah, while
EHurydesma cordatum, Aviculopecten mitchelli, Tceniotherus subquadratus and
Cladochonus nicholson are prominent in the Yessabah Stage. The identification
of the trilobite Phillipsia is noteworthy as it is not included in Osborne’s lists
from the Hunter River Valley.

Although Linoproductus springsurensis is well spread through the sequence
it forms two well-marked horizons, one below the Yessabah Limestone in the
Fenestellidz Mudstones and one in the Warbro Stage above the limestone.
The absence of this brachiopod and Cladochonus nicholsoni from the Hunter
Valley sequences and their abundance in the Manning-Macleay Province and in
Queensland suggest that there was a land barrier south of the Manning River.
This is also supported by the change in the character of the Yessabah Limestone
around Kimbriki and the fact that the Gloucester Coal Measures rest directly
upon the Carboniferous lavas in the Gloucester Trough (Voisey, 1940).

As full lists of fossils have been given in earlier papers (Voisey, 1936, 19394),
they will not be repeated here.

SUMMARY.

The Macleay Series in the Manning-Macleay Province, which corresponds
with part at least of the Permian Lower Marine Series of the Hunter River
Valley, has been divided into three stages on lithological grounds.

The sediments occur only in synclines and faulted blocks. Higher members
of the sequence, if any were developed, are no longer preserved. The fossils
Iinoproductus springsurensis and Cladochonus nicholsoni, which have not been
found in the Hunter Valley sections but are present in Queensland, together
with changes in lithology, indicate a land barrier between the Manning and
Hunter rivers in Permian times.

ACKNOWLEDGEMENTS.

I tender my grateful thanks to Dr. W. R. Browne for his help and inspiration
freely given over many years.

My thanks are also due to the Commonwealth Government for financial
help received from the Research Grant to the University of Sydney.

REFERENCES.

Carne, J. E., and Jones, L. J., 1919. Geol. Surv. N.S.W., Min. Res., 25.
Osborne, G. D., 1949. Proc. Linn. Soc. N.S.W., 74, 203.

Voisey, A. H., 1934. Jbid., 59, 333.

1936. Tuts JouRNAL, 70, 183.

1938. Proc. Linn. Soc. N.S.W., 63, 453.

1939a. Ibid., 64, 241.

1939b. Ibid., 64, 255.

——_—_——_—— 1939c. Ibid., 64, 394.

——_—_—_—_————— 1940. TIbid., 65, 192.

Woolnough, W. G., 1911. THis Journat, 45, 159.

¢

_ Seamer and Arundel Streets, Glebe, N.S.W. CG

1951 GES aaa

PART IL

JOURNAL AND PROCEEDINGS

att

COED OR ae Toye: SRY i a.

,OYAL SOCIET
| = OF NEW SOUTH WALES He
ae

(INCORPORATED 1881) _

PART II (pp. 68-98) |
OF
VOLULXXXIV:.

Containing papers read in June and: July, 1950

EDITED BY

Ida A. BROWNE, D.Sc.

Honorary Editorial Secretary

fas THE AUTHORS OF PAPERS ARE ALONE RESPONSIBLE FOR THE
_ STATEMENTS MADE AND THE OPINIONS EXPRESSED THEREIN

(7 oa ‘ " e

SYDNEY 4 x
PUBLISHED BY THE SOCIETY, SCIENCE HOUSE
GLOUCESTER AND ESSEX STREETS

1951

Part II

ree 3 a The Cheraictry of Osmium. Part IV. The Preparation and [aealgeenty
_ of the Tris 0,Phenanthroline Osmium II Ion. By F. BE He <3 ‘N. ye Gibson nd
_E. C. Gyarfas si on Ngee We

XIV. —QOn the Grading of Dune Sands near Castlereagh, New South Wales :
EAT Si Simonett © oe Ji beg wy ra fe Ne: ee 7

re
1

Ny ‘2: ae Dipyvidy Osmium T/T and the Tris 0, Phenanthroline Osmium NTL ‘ouples. nih
. ied F P. Dwyer, N. A. Gibson and | ee bP Gyarfas

“Osmium TI penises as an Tntedanh Redox Indicator, ee Ee ee Dwyer nd
Dae Gibson | a ig ay Shi Cea elie

ae

Ere!

By A. ites Penfold — iG

Journal and Proceedings of the Royal Society
of New South Wales

—

VOLUME LXXXIV

PART Il

JUN 27 195

THE CHEMISTRY OF OSMIUM.

Part [V. THE PREPARATION AND RESOLUTION OF THE TRIS
0,PHENANTHROLINE Osmium II Ion.

By F. P. DWYER, D.Sc.,
N. A. GIBSON, M.Sc., A.B.1.C.,
and (Miss) E. C. GYARFAS, M.Sc.

Manuscript received, April 24, 1950. Read, June 7, 1950.

Tris 2: 2’ dipyridyl osmium II bromide was prepared by Burstall, Dwyer
and Gyarfas (1950) by heating a mixture of ammonium bromosmate IV with
2:2’ dipyridyl at 280°C. The dark green complex ion Os(dipy)t+ was resolved
through the antimony] tartrate into stable optical enantiomorphs. The complex
ion was reversibly oxidized at approximately 0-9 volt to the red Os(dipy),+++
ion, which was also obtained in stable optical forms (Dwyer and Gyarfas, 1950).

The corresponding osmium II compounds with o,phenanthroline were
ultimately prepared by heating the base with ammonium bromosmate in
glycerol solution at 280-300°C. Mixtures of potassium hexachlor or hexa-
bromosmate IV or potassium hexachlorosmate III with phenanthroline in
aqueous alcohol could not be reduced to the compound. with hypophosphorous
acid in the same manner as the ruthenium compound (Dwyer, Humpoletz and
Nyholm, 1946). Heating of a mixture of excess base and ammonium bromosmate
in the absence of solvents, either with or without reducing agents such as
ammonium hypophosphite, sucrose, lactose or formaldehyde, gave only very
poor yields of the substance associated with osmium metal, and a large amount
of tarry carbonaceous matter.

The compound was isolated from the glycerol mixture, after dilution with
water, by addition of potassium iodide, and the sparingly soluble iodide was
crystallized several times to remove traces of a very dark brown impurity. The
very sparingly soluble perchlorate was obtained from the iodide by treatment
with sodium perchlorate, and the soluble chloride by treatment with silver
chloride. The salts crystallized in dark brown needles or flakes with a green
reflex. They dissolved in water to form intensely dark greenish brown solutions,
which were stable to strong acids and alkalis. In nitric acid the solutions
eradually became red as a result of oxidation to the ion Os(phenan),+++. The
potential of the reversible reaction was approximately 0-9 volt. The oxidized
solution, like the solutions of the ions Fe(phenan),+++ and Ru(phenan),ttt,
was not stable, and in the absence of excess oxidizing agent gradually became
brown by the re-formation of the original osmium II complex ion.

The resolution of the tris 0,phenanthroline osmium II ion was carried out
in a similar manner to the ruthenium, iron and nickel complexes (Dwyer and
Gyarfas, 1949), through the antimony] tartrate. The dextro-form separated as
the sparingly soluble antimonyl tartrate, which was transformed to the per-
chlorate. The levo-perchlorate was obtained by addition of sodium perchlorate
to the filtrate after the precipitation of the dextro-antimonyl tartrate. The
complex ion was optically stable in boiling water, like the corresponding
ruthenium compound. No rotation was observed in the Nap line, this wave-
length being close to an absorption maximum.

THE CHEMISTRY OF OSMIUM. 69

The pure perchlorates gave [«],22,=+3670° and —3570°. The corres-

ponding ruthenium and nickel complex perchlorates gave [o].23, = +1330° and
+1470° respectively.

The optical forms were oxidizable with ceric sulphate to optically active
forms of the osmium III complex Os(phenan),+++. It is hoped to be able to
isolate the enantiomorphous forms of this complex ion in the solid form.

The redox potentials of this complex and the dipyridyl analogue will be
discussed in a subsequent communication.

HXPERIMENTAL.
Tris 0,Phenanthroline Osmium II Iodide Trihydrate.

Ammonium hexabromosmate (2-1 g., 1 mol.) in glycerol (40 ml.) was heated to 80-90° C.
with stirring until the bromosmate had dissolved to a deep red solution. O,Phenanthroline
monohydrate (3:6 g., 6 mols.) was added gradually at 120° C. and the mixture maintained at this
temperature until the water was lost ; then the temperature was raised to 250-270 °C. whilst
the mixture was stirred with a thermometer, and this temperature was maintained for 20 minutes.
The dark brown mixture was cooled to below 100° C. and poured into 150 ml. of warm water.
The mixture was acidified with hydrochloric acid (3-5 ml. of 5N.) and potassium iodide added.
The dark greenish brown precipitate was washed with ether and ice water, and recrystallized
several times from hot water and potassium iodide.

The substance crystallized in black flat flakes and prisms, was very soluble in methyl alcohol,
but less soluble in ethyl alcohol and acetone.

Found: Os—18-0% ;° l=24-6%.
Calculated for Os(C,,H,N,)3I,.3H,O : Os=18-3%; I[=24-4%.

Tris 0,Phenanthroline Osmium II Chloride Octahydrate.

The iodide (1 g.) in hot water (50 ml.) was shaken for 15 minutes with excess of freshly pre-
cipitated silver chloride. After filtering from silver halide the dark greenish brown filtrate was
evaporated to 5 ml. on the water-bath and then to dryness over calcium chloride in a desiccator.
The substance crystallized in very dark brown prisms with a greenish reflex.

Hound. Os— 20-19% ; Cl=7-47%.
Calculated for Os(C,,H,N,.),Cl,.8H,O : Os=20-1%; Cl=7-50%.

Tris 0,Phenanthroline Osmium II Perchlorate Dihydrate.

The iodide (vide supra) (1 g.) in hot water (100 mls.) was treated drop by drop with sodium
perchlorate solution (10%) with scratching the sides of the vessel. The sparingly soluble per-
chlorate crystallized as a brown microcrystalline powder. It was very soluble in methylalcohol

Hound). Os—19-5% ; N=8-79%.
Calculated for Os(C,,H,N.;),(ClO,),.2H,0: Os =19-7%; N=8-70%.

d,Tris 0,Phenanthroline Osmium II d,Antimonyl Tartrate Trihydrate.

The iodide (1 g.) in hot water (50 ml.) was transformed to the chloride as above and the
solution cooled. Potassium antimony! tartrate (1 g., 3 mols.) in water (20 ml.) was added
gradually with scratching of the sides of the vessel. The antimony! tartrate of the dextro-form
was precipitated in fine brown needles. These were removed by filtration, washed with ice water
and then dissolved in cold 0:05N sodium hydroxide solution and after filtration reprecipitated
with acetic acid and a few drops of saturated potassium antimony] tartrate solution. This
purification was repeated three times. The substance was sparingly soluble in water to a greenish
brown solution, but easily soluble in dilute acids and alkalis.

A 0:006% solution in 0:01 NaOH gave «= +0-10° (1 dm. tube), whence bolle sey = +1700°.

Hound; Os=13:9%; N=6-18%.

Calculated for Os(C,,H,N,.)3(C,H,0,.SbO)..3H,O : Os=14:0%; N=6-20%.

H

70 DWYER, GIBSON AND GYARFAS.

d, Tris 0,Phenanthroline Osmium II Perchlorate Monohydrate.

The antimony] tartrate above was dissolved in cold 0° 05N sodium hydroxide and precipitated
with sodium perchlorate solution (10%). The resulting precipitate was crystallized several
times from hot water by the addition of sodium perchlorate. The substance crystallized in
small dark brown rods with a green reflex. It was more soluble than the d,/ perchlorate.

A 0:003% solution in water gave «=—+0- 11 (1 dm. tube), whence [a] 23, = +3670° and
[M],28, = +34,800°.

In the sodium D line no rotation could be observed.

The solution was optically stable at room temperature and at 100° C.

Found: Os—20-1°%; N—S8-930%%

Calculated for Os(C,,H,N.)3(C1O,),..1H,O : Os=20-°1% ; N=8-87%.

l, Tris 0,Phenanthroline Osmium II Perchlorate Monohydrate.

The filtrate from the precipitation of d, tris o,phenanthroline osmium II d,antimony] tartrate
(vide supra) was treated with sodium perchlorate solution and the resulting precipitate of the
levo-perchlorate crystallized several times from hot water with the addition of sodium per-
chlorate.

A 0-003% solution in water gave «=—0-10,° (1 dm. tube) whence [«];23, =—3570° and
[M],73, =—33,800°.

Found: Os=19:7%; N=8-95%.

Calculated for Os(C,,.H,N,.)3(ClO,)3.1H,O0 : Os=20-1%; N=8-87%.

SUMMARY.

Tris 0o,phenanthroline osmium II iodide was prepared by reaction between
0,phenanthroline and ammonium bromosmate in glycerol solution at 250—270° C.,
followed by dilution with water and addition of potassium iodide. The intensely
greenish brown solutions containing the ion Os(phenan),++ are reversibly oxidized
to the red Os(phenan),+++ at approximately 0-9 volt. The enanthiomorphous
forms were isolated through the antimony] tartrates, and the active perchlorates
gave [M],2 = +34,800° and —33,800°.

ACKNOWLEDGEMENTS.

The authors are indebted to Miss J. Fildes for nitrogen analyses and-one of
us (E.C.G.) to the Research Committee for an Assistantship.

REFERENCES.

Burstall, Dwyer and Gyarfas, 1950. J. Chem. Soc., 953.

Dwyer and Gyarfas, 1949. Tuts JouRNAL, 83, 174.
—_—_-_______———. 1950. J. Am. Chem. Soc. In Press.
Dwyer, Humpoletz and Nyholm, 1946. THis JouRNAL, 80, 212.

Department of Chemistry,
University of Sydney.

ON THE GRADING OF DUNE SANDS NEAR CASTLEREAGH,
NEW SOUTH WALES.

By D. 8S. SIMONETT, M.Sc.
With one map and three text-figures.

Manuscript received, April 12, 1950. Read, June 7, 1950.

In the western part of the Sydney Plain near the Nepean River at Castlereagh

lies a small field of fixed longitudinal sand ridges. In an earlier paper (Simonett,
1949) it was concluded that these dunes were built up by westerly winds with
sands derived from the Hawkesbury sandstone soils west of the Nepean; and
that sand movement followed vegetation destruction on the sandstone, probably
during the Early Recent arid period. It is now proposed to discuss the changes
in grading wrought on the source soils during the dune building.

Crest and trough samples (33) were taken from the western and eastern
parts of the dunes, respectively removed about 13 and 24 miles from the source:
Five source soil samples were collected, together with 13 from the “ Incipient
Dunes ”’, built up in advance of the main sand movement and composed of finer
sands. The location of the samples is given in Map 1.

Hawkesbury

Sandstone

16.17 18 Dunes

229 50 |

Present
River

” Lateritised
Drifts

EEE EEE
I Mile

All the analyses obtained by dry sieving* were plotted graphically to enable
ready comparisons of grain-size gradings ; of these, 36 representative samples
have been selected and plotted on a series of seven graphs.

* 100 grm. samples were taken, organic matter destroyed by boiling with hydrogen peroxide,
and after thorough dispersion and decantation of particles smaller than 0-02 mm. the sands
were oven-dried and sieved in a nest of Tyler sieves for 15 minutes on a Tyler “‘ Ro-Tap ” sieving
machine. The following meshes were used (apertures in millimetres) :

14 (1-168); 20 (0-888); 28 (0-589); 35 (0-417); 48 (0-295); 65 (0-208); 100 (0-147) >

150 (0-104); 200 (0-074).

{2 D. S. SIMONETT.

Bagnold’s (1941) method of plotting these results was selected} for, using
it he found that in naturally wind-blown sands ‘‘ outside a definite central zone
the grades to right and left of the peak (diameter) fall off each at its own constant
rate’’. To those wind-blown sands whose grading conformed to this simple

Crest

y Sane 25 3 #5) 36 8 1-0 15
Grain Diameter in mm.

i 22h e3 ye ha Bade CUE Bing C99: 1,40 a hee
R=Log,, of Grain Diameter d

arrangement of two straight lines inclined upwards, meeting at an apex, the top
of which was replaced by a small arc, he applied the term regular sands whether
the arrangement was symmetrical about the peak or not (loc. cit., p. 118).

+ The logarithm of the percentage-weight of sand per unit of the log. diameter scale is plotted
as ordinate against an abscissa of the log. grain diameter.

GRADING OF DUNE SANDS NEAR CASTLEREAGH, N.S.W. 73

Considering the grading of each group. The five source samples plotted
in Figure 1 show the same characteristic grading, the most distinctive features
of which are the marked irregularity on the coarse side and the gentle fall away
from the peak on the fine side with a slight steepening to the finest grades.

25° 3 4 §

Grain Diameter in mm.

The western group of sands, Figures 2 and 3, moved a mile to 14 miles, have
altered in grading to approach regularity, particularly about the peak diameter,
but on the coarse side the initial excess of sands of the range 0-888-1-16 mm.
over that of 0-589-0-888 has been but tardily removed (only samples 22, 24
(crest) and 28 (trough) show any significant reduction) and these are the eastern-
most samples of this group. The steepening in the finest grades of the parent

FA D. S. SIMONETT.

sand has, however, not only been removed, but has been replaced by a slight
flattening in the trough samples. Other than this little difference in crest and
trough grading is evident at this stage.

Z 25 63 pA 8
Grain Diameter in mm.

3 4. ‘5 6 > ‘8
R=1Log,, Of Grain Diameter

In the eastern sands (a further half to one mile removed from the source),
Figures 4 and 5, the changes which were barely evident in the western analyses
are pronounced, and a considerable difference in trough and crest grading is to

GRADING OF DUNE SANDS NEAR CASTLEREAGH, N.S.W. 75

be seen, the finer sands collecting on the ridges and coarse sands in the troughs.
From all the crests the excess of the penultimate grade over that retained on
sieve 28 has been eliminated ; but the curve is still kinked at this point. On
the other hand in only those trough samples farthermost from the source has
this occurred.*

The crest sands are near-regular on both fine and coarse sides of the grading
but the trough samples are not, for the slight flattening in the finest grades in
the trough samples of the western sands is now very marked in the eastern
trough sands.

The ‘‘ Incipient Dunes ”’ sands are essentially regular and lack both the
coarse side distortion and the fine side flattening of the true sand dunes (Figures
6 and 7).

DISCUSSION.

It seems evident from the analyses that although the rate of removal of the
initial distortion in the coarse grading of the source soils differed slightly in the
crest and trough samples (the former approaching regularity a little earlier
than the troughs) both required between two and three miles transport for such
removal.

These results are interesting when compared with work along similar lines
by Bagnold (1941) and Chepil (1946).

Bagnold (1941, 142-3), working with a regular sand distorted in the ultimate
fine and coarse grades by the addition of excess sand, found in the wind tunnel
that the excess in the finest grades was ‘‘ hardly (removed) at all in the accretion
deposits ’’ by wind action, whilst that on the coarse-side was rapidly removed.
On the basis of this experiment he concluded that ‘‘ the processes . . . which
tend to produce the logarithmic relation between the proportion by weight and
the grain diameter, are different on the fine and coarse sides of the grading,
though both must occur in the early part of the cycle of movement ”’.

Chepil (1946), working in the Canadian Wheat Belt, analysed sands piled
into small dunes resulting from drift from eroding cultviated fields of a quarter
to half a mile in length. He found that ‘‘ except for a few slight kinks, the two
arms of each curve are straight lines and agree, at least in essential features,
with the grading diagrams found by Bagnold for desert sand. Such marked and
consistent grading of drift material seems almost incredible in view of the fact
that the materials deposited in dunes were in the majority of cases the result of
a Single dust storm ’’ and concluded that ‘‘ a distance (of a quarter to half a mile)
was apparently sufficient for effecting an ultimate selection of the blown
materials ”’

A oreater distance was needed to remove the coarse-side distortion at
Castlereagh than would have been expected on the basis of Bagnold’s and
Chepil’s results. Comparing the diameter of the Castlereagh distortion (1-0 mm.)
with the latter (0-5-0-65 mm.) an even earlier removal than Chepil’s might have
been expected. Clearly some factor must have retarded the sorting. In part
the discrepancy with Bagnold’s experiment (loc. ctt., pp. 142-3) may be explained
by his use of a regular source sample distorted ‘only in the ultimate grades ;
1.e. one which would reach regularity very quickly. However, this argument
cannot apply to Chepil’s irregular source samples (Figure 8). It is more likely
that the answer lies in the amount of sand in movement, the speed of sorting
depending on the continuity of supply of irregular sand from up-wind. With

* With the exception of the most easterly trough samples from which the irregularity has
been shifted (16, 17, 18) all the trough samples retain the irregularity to a greater degree than
crest samples moved an identical distance. The following pairs of trough and crest samples
have been moved the same distance : all are less regular in the troughs than the crests :

ACTOR SU oe es) 62 IE ss Selb. 2: 13.

76 D. S. SIMONETT.

large volumes of sand available for movement fresh sand containing the coarse-
side irregularity would continually be moving over the areas in which this
coarse-side excess remained as residuals from earlier movement emphasizing
the irregularity and in effect shifting the removal-bed down wind. All the
evidence at Castlereagh points to large volumes of sand available (Simonett,
1949), a situation far less likely in the heavier wheat soils studied by Chepil.
The similarity of grading of ‘‘ Incipient Dune’”’ sample 39 moved half a mile
less than the other samples of Figure 6 (see also Map 1) supports this view. It
is possible that with certain initial gradings and large masses of sand for transport
the attainment of regularity may be even longer delayed than at Castlereagh.

The significance of the marked flattening in grading in the finest sands
of the eastern trough samples is not easily determined. We cannot regard it as
an unremoved initial irregularity, for the reverse was the case in the parent sand
where the grading steepened slightly to the finest grades. It is clearly a feature
produced on movement and appears to be fundamental to at least the early
process of grading of the trough samples.

The suggestion is made that this flattening, which it will be seen occurs in
sieves 150 (0:104—0-147 mm.) and 200 (0-074—0-104 mm.), may be due to the
fact that about this diameter (0-08 mm., Bagnold, loc. cit., p. 88) the fluid
threshold for grain movement is closest to the impact threshold, and thus
particles of diameter 0-10-0-15 mm. (Chepil, 1945, p. 404) are the most readily
eroded and maintained in saltation of all grades. Thus with greater wind
sorting at the crests any excess of the fine grades would tend to be directed
outwards to the troughs, where decline in wind velocity would favour deposition.

The concentration of fine grades of this diameter in the troughs is interesting
when compared with the peak diameters of the crest and trough sands of the
Simpson Desert seif dunes analysed by Carroll (1944) and Crocker (1946). They
found that the coarsest sands collected on the crests (peak 0:17 mm., one
0-35 mm.) and the finest in the troughs (peak 0-85-0-:9 mm.). On the other
hand at Castlereagh the eastern crest sands (peak load-sieve 48/0-295 mm.
31-36 %,) are finer than the trough sands (peak load sieve 35/0-417 mm.45-53 %).
Bagnold (op. ctt., p. 228) found the fine-crest-coarse-trough relationship to be
characteristic of the Libyan seif dunes and postulated it as general. Crocker
(1946) suggested that the reversal of the relationship in the Simpson Desert
sands may be due to their extreme fineness and their concentration about the
critical diameter of 0:08 mm. ‘They are undoubtedly much finer than the
Castlereagh sands or all the examples Bagnold gives of typical Libyan Desert
gradings.

On the evidence available at Castlereagh we cannot say that the extreme
fine-side distortion of the eastern trough sands is more than a feature of the early
part of the process of grading. However, the fact that the fine-side distortion
in the Castlereagh trough samples occurs in the same diameter range as the peak
diameter of the Simpson Desert trough samples suggests that it is more than an
early phase in the grading cycle and may be in fact fundamental to the whole
process. The reason for the concentration of these grades (0-08—0-15 mm.)
in the troughs appears to be bound up with the ease with which they are
moved ; gentle winds in particular capable only of moving sand on the crests
would ensure their selective migration to the troughs. |

Madigan (1946, p. 62) suggested that the concentration of these grades in
the troughs in the Simpson Desert was a post dune-fixation phenomenon—“ the
higher percentage of fine grades and clay particles in the two inter-ridge samples
aS compared with crests is probably due to the winnowing effect on the crests,
where under present conditions of no set lateral movement and secondary winds
from both sides the coarser fractions will tend to remain as residuals on the
crests and the crest sand to become more regular than that in the lanes. The

GRADING OF DUNE SANDS NEAR CASTLEREAGH, N.S.W. a

‘‘ smoking ”’ effect in strong lateral winds will carry the dust and fine particles
well down into the lee of the ridge, where it will remain’’. This process can
equally well take place during the dune-building and may be regarded as a
normal dune process.

With wide source sample gradings double maxima (one fine 0:08 mm., and
one coarse) should occur in the gradings of the lower slopes of seif dune plinths
in young deserts where the dunes are closely spaced. Thus in the grading of
sands from the Kalahari longitudinal dunes analysed by Lewis (1936) (Table 1)
the concentration of sands finer than 0:15 mm. in the lower slopes and troughs is
marked. The tendency to another peak in these gradings coarser than the
peak of the crest gradings is also evident.* On the other hand with narrow
source sands one or other of the maxima would be damped. The Simpson
Desert sands are low in coarse grains and lack a definite coarse maximum in
the troughs.

Geological time must be considered as a factor affecting gradings. In
young dune fields (Kalahari) with low, closely spaced dunes, fine grades will
mantle the lower dune slopes as well as the troughs ; but in old seif dune fields
long continued winnowing of steep-sided massive dunes, miles apart as in Libya,
would move all the fine grades into the sand sheet between the dunes. An
uncomplicated fine-crest-coarse-lower-slope grading relationship as described
by Bagnold would result on the dunes, the intervening sand plain consisting of
the very fine grades and residual very coarse grades.

No one simple general rule can characterize either rate of removal of
irregularities or the grading relationships on dunes. It may be misleading to
apply results obtained from wind-tunnel and field tests on removal of
irregularities, where sands were driven away from a source area, to desert areas
such as the Simpson where Madigan has shown that many of the dunes arose
ab initio from a sand sea. Equally, grading relationships on seif dunes will be
a function of origin (ab initio dunes or dunes trailing from a windward source)
grading of the source sands, and maturity of the dune system. The attempt
above to indicate the general types of gradings that are likely to occur in a
limited group of circumstances must be considered speculative ; a generalized
theory of dune grading must, however, take all the factors considered above
into account.

SUMMARY

The rate of removal of irregularities on the coarse side of the grading appears
to vary with the amount of sand in movement. Concentration of grades of the
diameter range 0:08-0:15 mm. in the troughs of the Castlereagh longitudinal
dunes and also in the troughs of desert young seif dune fields (Kalahari, and
Simpson deserts) appears to be a normal feature of the grading of closely spaced
seif dune fields. Grading relationships on longitudinal dunes will be a function
of the maturity of the system, the width of the grading of the source sands, and
the origin of the dunes (ab initio dunes arising in a sand sea, or dunes trailing
from a limited windward source).

ACKNOWLEDGEMENTS.
Grateful acknowledgement is made to Mr. H. J. Vogan, of the Civil
Engineering Department, University of Sydney, for the use of the Tyler
‘* Ro-Tap ” sieving machine.

* The results given in Table 1 (appendix No. 1 of Lewis’s paper) are mean analyses. About
200 samples were analysed from ten localities for crests, slopes and corridors of the dunes. Thus
30 groups of means are available, about six samples to a mean, assuming uniform sampling from
all localities. This lumping of analyses together must make one suspicious of the value of Lewis’s
results. However, since all ten groups possess roughly similar gradings, a certain amount of
value may be given to them, though they must be used with caution.

78

D. 8S. SIMONETT.
TABLE 1.
(After Lewis, 1936.)
Mechanical Analyses of Sands.
Kalahari Sand Dunes.
Mean of all Readings.
Percentages by weight retained on each sieve.
Number of Sieve. Passing
14 28 40) 48 65 90 115 150 150 Remarks.
1. Houmoed. Sind
Le zie 5 15 29 19 14 9 9 Slopes.
mate a 2 21 44 20 9 3 1 Crests.
2 5 10 9 16 15 13 12 18 Straats.
2. Lentlands Pan.
— —- 1 Sx: 29 24 22 9 7 Slopes.
— — -= 10 42 28 14 4 2 Crest.
—— — 6 19 27 18 15 7 8 Staat.
3. Kakolk.
— — 5 a 20 22 18 16 12 Slopes.
— — 4 22 31 2] 12 7 3 Crest.
a 8 16 6 10 12 13 14 21 Staat.
4. Abiquas Puts.
— --- 1 3 21 17 25) eb te 17 Slopes.
— —- = 4 25 25 24 13 9 Crest.
— — 2 3 12 11 17 18 37 Straat.
5. Albion.
— 2 12 9 16 18 18 12 13 Slopes.
— —- 6 13 27 23 18 9 + Crest.
3 2 9 9 ily 18 ity 11 14 = Straat.
6. Gemsbok Plains.
— — 2 ANY 38 19 14 6 4 Slopes.
= — 1 14 41 22 13 6 3 Crest.
- 2 9 21 25 13 12 8 11 Straat.
7. Bushmans Puts.
— 1 6 10 20 1b 19 13 14 Slopes.
— — 2 8 25 22 21 12 10 Crest.
— 3 10 11 ie) 14 17 12 16 Straat.
8. Tellery Pan.
— — 1 7 21 22 . 22 16 11 Slopes.
—- — 2 13 32 22 LN 10 4 Crest.
— 1 ° 6 10 18 16 16 17 16 Straat.
9. De Hoek.
=== = 3 6 22 21 23 12 13 Slopes.
— — — 6 40 24 21 6 3 Crest.
— 2 7 6 14 15 20 16 20 Straat.
10. Debinga.
— 5 15 9 10 ‘a 19 16 15 Slopes.
— 2 10 11 13 13 23 17 11 Crest.
2 12 16 6 i 8 18 15 16 Straat.

Sieve apertures in mms. are as below:
14 (1-168), 28 (0-589), 40 (0-381), 48 (0-295), 65 (0-208), 90 (0-150), 115 (0-

150 (0-102).

124),

I am especially indebted to Professor J. Macdonald Holmes, of the Depart-
ment of Geography, for his ever-ready help and advice, and to Dr. E. G. Halls-
worth, of the Faculty of Agriculture, University of Sydney, for helpful criticism.

GRADING OF DUNE SANDS NEAR CASTLEREAGH, N.S.W. 79

The field expenses occasioned in this work were met by a grant from the
Commonwealth Science Research Fund, University of Sydney.

REFERENCES.

Bagnold, R. A., 1941. The Physics of Blown Sand and Desert Dunes. Methuen, London.
Carroll, D., 1944. The Simpson Desert Expedition, 1939, Scientific Reports. No. 2, Geology—
Desert Sands. Trans. Roy. Soc. S. Aust., 68, 1, 49.
Chepil, W. 8., 1945. Dynamics of Wind Erosion. II. Initiation of Soil Movement. Soil
Sci., 60, 397.
—-——_—_—_—— 1946. Dynamics of Wind Erosion. VI. Sorting of Soil Material by the Wind.
Soi Sci., 61, 331.
Crocker, R. L., 1946. The Soil and Vegetation of the Simpson Desert and its Borders. Trans.
Roy. Soc. S. Aust., 70, 2, 235.
Lewis, A. D., 1936. Sand Dunes of the Kalahari. S.A. Geog. Journ., 19, Dec. 22.
Madigan, C. T., 1946. The Simpson Desert Expedition, 1939. Scientific Reports, No. 6,
Geology—The Sand Formations. Trans. Roy. Soc. S. Aust., 70, 1, 45.
Simonett, D. S., 1949. Sand Dunes near Castlereagh, New South Wales. Aust. Gieog., 5, 8, 3.

Department of Geography,
The University of Sydney.

THE CHEMISTRY OF OSMIUM.

Part V. THE REDOX POTENTIALS OF THE TRIS 2: 2’—DIPYRIDYL
Osmium II/III AND THE TRIS 0,PHENANTHROLINE Osmium II/III
COUPLES.

By he. DwvER Disc:
N. A. GIBSON, M.Sc., A.R.I.C.,
and (Miss) E. C. GYARFAS, M.Sc.

Manuscript received, May 10, 1950. Read, July 5, 1950.

Tris 2:2’ dipyridyl osmium II salts and analogous o-phenanthroline
compounds (Burstall, Dwyer and Gyarfas, 1950; Dwyer, Gibson and Gyarfas,
1950) are reversibly oxidized to the corresponding osmium III complexes. The
potentials of the two reactions have now been determined in order to complete
the iron, ruthenium and osmium triad of such complexes, as well as to ascertain
the suitability of the compounds as redox indicators.

The oxidized form of the dipyridyl compound was sufficiently stable to be
obtained in solution in known concentration, hence the potential could be
obtained by the standard method of allowing an electrode to come to equilibrium
in an equimolar mixture of oxidant and reductant. The oxidized form of the
phenanthroline complex, however, was unstable and rapidly underwent reduction.
This reaction has already been noted with the oxidized forms of the iron and
ruthenium complexes with o-phenanthroline (Dwyer and McKenzie, 1947;
Dwyer, Humpoletz and Nyholm, 1946). The potential of the phenanthroline
complex was determined by exactly half oxidizing a standardized solution of the
reduced form and observing the maximum potential attained on an electrode
(Dwyer, 1949).

Both systems were typically cationic, the potentials decreasing with
increasing ionic strength. At the same ionic strengths, the potentials of the
phenanthroline complex were slightly higher. This follows the same trend as
with the iron and ruthenium compounds. However, unlike the Fe and Ru
compounds, the stability of the oxidized form decreased with increasing acid
concentration.

With the completion of the potential investigations of the 2 : 2’ dipyridy]
and o-phenanthroline complexes with the members of the iron triad, it is
interesting to compare the potential changes consequent upon complex forma-
tion. The figures shown in detail in Table I are approximate, since corres-
ponding potentials of the simple bivalent/trivalent system and the bivalent:
trivalent complex system are not available in some instances at the same ionic
strength. The maximum potential change occurs with the ruthenium compounds,
from +0-085 volt for the Ru++/Ru*+++ couple to 1-31 volt for the Ru(phenan),t*/
Ru(phenan),+++ system, a change of 1-225 volts. The potential change conse-
quent upon the formation of the osmium compounds cannot be stated with any
degree of accuracy. The potential of the system Os++/Ost++ is unknown, and
probably cannot be determined directly, since disproportionation of the Os*t ion
can be expected to occur. With an estimated value of —0-25 volt, the change
is of the order of 1-13 volts for the formation of the phenanthroline complex.

THE CHEMISTRY OF OSMIUM. 81

TABLE [.
| Potential | Potential
Potential . | Dipyridy!] Potential Phenan. Potential
M++/Mt+++, | Complex. Change. Complex. Change.
Hes. es pOrworVit 1 SEI 096, V.2" | 0-346 V. bY ele dt 20: V2 0-370 V.
Ru .. ne +0-085? | +1-307 1-315 +1-314 1-325
Os. aA —0-25° +0-878 1-128 Pie Or Suile ee,

1Thermodynamic value, 0-771 V. (Latimer, 1940.)
2 Dwyer and McKenzie, 1947.

3 Backhouse and Dwyer, 1949.

4 Dwyer, 1949.

5 Estimated value.

Two general observations are noteworthy: the stability of the reduced form
is the greater with phenanthroline ; and of the oxidized form with dipyridyl.
The iron compounds in both oxidized and reduced states are less stable chemically
and optically than the ruthenium and osmium compounds.

EXPERIMENTAL.

The redox potential determinations were carried out at 25°C. in the
apparatus used for previous determinations (Dwyer, McKenzie and Nyholm,
1940). The saturated calomel electrode was calibrated against quinhydrone in
potassium hydrogen phthalate solution, pH 4-00, using a gold electrode. The
value of the potential accepted for the latter electrode was 0-4623 V. at 25° C.
The equimolar solutions of tris 2:2’ dipyridyl osmium II and osmium III
perchlorates were prepared by making 0-001 M solution of the reductant,
dividing into two portions, and oxidizing one portion with a slight excess of
chlorine. The excess chlorine was then expelled by a rapid current of air
saturated with water. The absence of chlorine was shown by taking 10 ml. of
the pink oxidized solution and adding one drop of the deep green reduced
solution. The consequent colour change showed that chlorine was absent.
Equal volumes of the oxidized and reduced solutions were then mixed. Water
and acid were subsequently added, so that the final solution was M/4000 with
respect to oxidant and reductant ion.

The tris o-phenanthroline osmium II perchlorate was prepared in saturated
aqueous solution, approximately M/1300, diluted with water and acid to twice the
volume, and potentiometrically titrated with 0-01 N potassium permanganate,
or in the first determination (with no added acid), with dilute chlorine water.
The volume of permanganate needed to half oxidize the solution was thus
obtained. Immediately following, another solution was prepared with added
acid and water and the calculated volume of permanganate so that the con-
centration of oxidant and reductant was M/5200 each. A platinum electrode
in the mixture was read each minute until the maximum value was obtained.
For acid concentrations of 0-05 N and 0:1 N the maximum was stable for more
than one and a half hours. With stronger acid the time of duration of the
maximum decreased, so that with 1 N acid the potential commenced to fall in
the first minute.

With the osmium dipyridyl system, the potential was stable for some hours
up to an acid concentration of 1 N, when a decrease of 35 mV. occurred in fifteen
hours. With the stronger acid concentrations 2 N, 3 N and 5 N, the potentials
decreased after a few minutes. The potentials observed are shown in Table IT.

&2 DWYER, GIBSON AND GYARFAS.

TaBLeE IT.
Acid Conc. Os(phenan),++/
(Normality). Os(dipy),+*+/Os(dipy),*** Os(phenan), +++
None added 0-877, V. 0-877 V.
0:05 0: 863, 0-863,
0-1 | 0-855, 0-859,
0-2 0-847, 0-856,
0-5 0-833, 0-842,
1-0 0-819, 0-822,
2:0 ~ 0-802 —
3:0 0-775 —
5:0 0:727 —
SUMMARY.

The redox potentials of the two systems tris 2: 2’ dipyridyl osmium I1/
tris 2:2’ dipyridyl osmium III, and tris o-phenanthroline osmium II/tris
o-phenanthroline osmium III have been determined. Both systems were
found to be typically cationic. The potentials respectively in 0-1 N hydro-
chloric acid were 0-8557 and 0-8593 volt.

REFERENCES.

Backhouse, J. R., and Dwyer, F. P., 1949. Tuts JouRNAL, 83, 138.

Burstall, F. H., Dwyer, F. P., and Gyarfas, (Miss) E. C., 1950. J. Chem. Soc., 953.
Dwyer, F. P., Gibson, N. A., and Gyarfas, (Miss) E. C., 1950. Tuis JourNAL, 84, 68.
Dwyer, F. P., and McKenzie, H. A., 1947. Jbid., 81, 93.

Dwyer, F. P., Humpoletz, J. H., and Nyholm, R. 8., 1946. Jbid., 80, 212.
Latimer, W. M., 1940. ‘‘ Redox Potentials.’’ Prentice Hall, New York.

Department of Chemistry,
Sydney University.

THE CHEMISTRY OF OSMIUM.

Part VI. THE USE oF TRIS 0,PHENANTHROLINE Osmium II
PERCHLORATE AS AN INTERNAL REDOX INDICATOR.

By F. P. DWYER, D.Sc.,
and N. A. GIBSON, M.Sc., A.R.I.C.,

Manuscript received, May 10, 1950. Read, July 5, 1950.

The first internal redox indicator for the titration of ferrous iron with
potassium dichromate was diphenylamine (Knop, 1924). Analogous com-
pounds—diphenylamine sulphonic acid and diphenyl benzidine—have been
recommended in order to overcome the relatively diffuse end-point and poor
stability of prepared solutions of the diphenylamine reagent. The redox
potential of all of these indicators is approximately 0-8 volt—hence the normal
ferrous/ferric potential (0-7 volt) must be lowered by the addition of phosphoric
acid or sodium fluoride in order to prevent the overlapping of the potentials of
the indicator and the iron system. Tris 2: 2’ dipyridyl ferrous sulphate and
later tris o-phenanthroline ferrous sulphate were recommended by Walden,
Hammett and Chapman (1931) as more suitable reagents. In strongly acid
solution (approximately 4 normal) the redox potentials of these indicators are
0:92 and 1:03 volt, and the titration of both the ferrous iron and the indicator
can be carried to completion. The reduced form of the indicator, however, is
unstable in acid of such high concentration, and the disappearance of the red
colour of the indicator, which signalises the end of the titration, can well be due
to decomposition. In solutions of lower acid concentration, the maximum
potential available from the dichromate is insufficient to effect the complete
oxidation of the indicator, the potential of which is higher in weakly acid solution
(1-102 volts in 0-1 N acid; Dwyer and McKenzie, 1947). A number of sub-
stituted dipyridyl complexes with ferrous iron were recently prepared by Smith
(1949), who suggested that the ideal redox indicator for the ferrous/dichromate
titration should have a potential of 0-85 volt.

Tris 2:2’ dipyridyl osmium II perchlorate and the corresponding
o-phenanthroline compound have been shown recently to be reversibly oxidized
at a potential of 0-86 volt in 0-1 N acid (Dwyer, Gibson and Gyarfas, 1950).
The colour changes accompanying oxidation were intense green to pink and
intense brown to pink respectively. The conditions for the use of these
substances as indicators for the ferrous/dichromate titration were determined
by the standard procedure of carrying out mixed potentiometric titrations of
ferrous sulphate and each of the osmium complexes as the perchlorate in sulphuric
acid of varying concentrations.

The titration in 0-1 N acid gave a satisfactory end point ‘‘ break ”’ for the
iron titration system, but not for either of the indicators (Fig. la). Both the
ferrous/ferric and the osmium II complex/osmium III complex systems are
cationic and the potentials fall with increasing ionic strength—but the decrease
is greater with the osmium complex system and as a result both systems tend to
merge. By the addition of either phosphoric acid or sodium fluoride in 1N
acid, both of these systems were satisfactorily separated.

84 : DWYER AND GIBSON.

It is to be noted that since the reduced form of the indicator is very much
darker than the oxidized form, the visual end point does not coincide with the
potentiometric end-point, but is about 30 to 50 mV. higher.

1-0
| ye
o
i)
>
=
uJ
(a)in NJIO H,SO,
a4
| (b)in N H,SO,
03 4
0: 2
0-0 0 30 12"9 16°0 20°0
mis. of K,Cr,O,
Fig. lL.
1-0
0
°
>
s
uw

N H,SO,+ N/2 PO;

“00 #0 8D 1270 16-0 20°
mis. of K,Cr, O,

Fig. 2.

Under the latter conditions both osmium complexes were shown to be
satisfactory indicators from the point of view of the potential. However, the

THE CHEMISTRY OF OSMIUM. 85

colour change of the tris 2 : 2’ dipyridyl compound in the presence of chromium
sulphate from deep green to a paler green was difficult to detect. The colour
change of the o-phenanthroline complex from yellow-green to blue-green was
well marked and easily detected.

In titrations involving 0-01 N potassium dichromate, the end point was
diffuse, but excellent with the 0-1 N reagent. From a series of titrations it
was found that with tris o-phenanthroline osmium II perchlorate the mean
error was 0:1%.

EXPERIMENTAL.

The Potentiometric Titration of Ferrous Sulphate and the Complex Osmium II
Perchlorates.

The titrations were carried out at 25° C., with a bright platinum electrode
in the redox assembly used in previous work (Dwyer, McKenzie and Nyholm,
1944). The ferrous sulphate solution ‘(10 ml., 0-01 N) was mixed with the
indicator solution (100 ml, 0-01M Os(dipy),(ClO,),H,O, or 0-:0078 M
Os(phenan),(ClO,),H,O), and the required volume of sulphuric acid (10 N).
The potassium dichromate (0-01 N) also contained the same concentration of
sulphuric acid. Typical curves are shown in Figs. la, 1b and 2.

The Estimation of Ferrous Iron with Tris 0,Phenanthroline Osmium IT Perchlorate
as Indicator.

Various volumes of standard ferrous sulphate solution were diluted with
sulphuric acid so as to produce approximately 100 ml. of normal acid solution.
Syrupy phosphoric acid (3 ml.) was added, and saturated (0-0078 M) tris
o-phenanthroline osmium II perchlorate (2 ml.). The mixture was titrated
with standard 0-1 N potassium dichromate solution. For comparison, the
titration was carried out also with diphenylamine solution (1%) as internal
indicator, using the recommended procedure (Vogel, ‘‘ A Text Book of Quanti-
tative Inorganic Analysis’’, Longmans, Green & Co., London, 1947). The
results are summarized in Table 1.

TABLE [.
i .

Mass Fe Fe Found Percentage Fe Found Percentage
Taken. (Os-(phenan).(C1O,),). Error. (Diphenylamine). Error.
0-0692 ¢g 0-0690 g. —0°3 0-0701 g. +1-3
0-1039 g 0-1039 g. 0-0 0-1047 g. +0-8
0-1385 g 0-1388 g. +0-2 0-1393 g. +0-6
0-1731 2g 0-1731 g. 0-0 0-1739 -g. +0°-5
0-2077 g 0-2077 g. 0-0 0-2088 g. +0°5
0-2770 g 0-2770 g. 0-0
0-3462 2g 0-3459 g. —0:-1

Mean Mean

0-1% +0°-7%

SUMMARY.

Tris o-phenanthroline osmium II perchlorate is recommended as an internal
redox indicator for the determination of ferrous iron with potassium dichromate.
The reagent, used in the form of its saturated aqueous solution, is stable. The
titration is performed in normal acid solution in the presence of phosphoric acid.
An accuracy of +0-1% is obtained.

I

86 DWYER AND GIBSON.

REFERENCES.

Brandt, W. W., and Smith, G. F., 1949. Analytical Chem., 21, 1313.
Dwyer, F. P., and McKenzie, H. A., 1947. Tuts JouRNAL, 81, 93.

Dwyer, F. P., Gibson, N. A., and Gyarfas, (Miss) E. C., 1950. IJbid., 84, 68.
Dwyer, F. P., McKenzie, H. A., and Nyholm, R. S8., 1944. Jbid., 78, 260.

Knop, J., 1924. J. Am. Chem. Soc., 46, 263.
Walden, G. H., Hammett, L. P., and Chapman, R. P., 1931. J. Am. Chem. Soc. 53, 3908.
Vogel, A., 1947. ‘‘ A Text Book of Quantitative Inorganic Analysis ’’, Longmans, Green & Co..,

London.

Department of Chemistry,
University of Sydney.

THE ESSENTIAL OIL OF BH#HCKEA CRENULATA (DE CANDOLLE).

By A. R. PENFOLD, F.A.C.1.,
and F. R. MORRISON, A.A.C.I.,
Museum of Technology and Applied Science, Sydney.

Manuscript received, May 10, 1950. Read, July 5, 1950.

The botany of this Myrtaceous shrub is described in Bentham’s ‘ Flora
Australiansis ’’, Vol. 3, pages 71-78. It is a small heath-like shrub with nearly
round leaves about } in. long, the edges of which are minutely crenulate. They
grow in irregular fashion around the stem, and give to the plant a distinctive
appearance. The plant, which has small white to pink flowers, occurs in patches
along the coast of New South Wales into Queensland, and on the Blue Mountains
of New South Wales. At one time it was very plentiful on most of the headlands
of our popular seaside resorts, extending from Broken Bay in the north to
Ulladulla in the south. Some of the localities between the north head of Port
Jackson and Cronulla, where collections were made during the past quarter of a
century, have since been cleared for building purposes. A pleasant odour of
terpenes, modified by linalool, is readily detected on crushing the leaves between
the fingers.

ESSENTIAL OIL.

Although the essential oil was examined first in 1921, its investigation has
been continued to the present time. Little difficulty was experienced in isolating
and identifying the principal terpenes, but the authors suspected others which
have defied identification. Repeated efforts, using fresh samples of oil distilled
from material collected from widely different localities during the past 27 years,
have merely confirmed the original results. Quite recently, fresh samples of
oil were distilled, but notwithstanding the use of improved methods of fractional
distillation, no additional terpene constituents could be identified. It was
possible, however, by the use of the Lecky-Ewell and Bower-Cooke fractionating
columns, to isolate and identify the alcohol linalool, whose presence, although
previously suspected, had not been established beyond doubt.

The essential oils from all consignments, obtained in yields of 0:2% to
0-36, varied in colour from a lemon tint to deep brownish yellow, and possessed
a pleasant, characteristic odour of the principal terpene constituents, modified
by that of the alcohol, linalool. The corks of the containing vessels were readily
bleached. On standing, many of the oils deposited yellow prismatic crystals of
the phenol ether beckeol, C,,;H,,O,, m.p. 103-104".

Although beckeol has been found in other Australian essential oils (Penfold,
1925) it was first isolated from the essential oil of B. crenulata in 1922 (Penfold
and Morrison, 1922). The chemical deportment and constitution of this unique
substance were described in a further communication to the Society in 1937
(Penfold and Morrison, 1937). Beckeol was synthesised simultaneously by two
groups of workers in 1940 (Ramage and Stowe, 1940; Hems and Tod, 1940).

The principal constituents, which have so far been identified, are as follows,
viz.: d-a-pinene, d- and dl-limonene, y-terpinene, cymene, linalool, sesqui-
terpenes and beckeol.

PENFOLD AND MORRISON.

38

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THE ESSENTIAL OIL OF BHCKEA CRENULATA (De CANDOLLE). 89

EXPERIMENTAL.
A total of 2532 Ib. of leaves and terminal branchlets was subjected to distillation in steam,
- and yielded crude oils possessing physical and chemical constants shown in the table.

The oil obtained from each consignment of foliage was separately investigated, but the results.
of one only have been selected for publication.

200 ml. of oil (Ulladulla sample, 23/9/40) were distilled at 10 mm., viz. :

be 20° | 20°
Fraction. B.p. | Vol. MI. diz aD hi.
1 To 60° | 108 0- 8576 E37 1° 1-4718
2 60-65° 52 0-8561 Te Sa 1-4737
3 65-70° | 17 0- 8592 SEO oe 1-4761
4 Residue | pas

The terpene fractions were allowed to stand over metallic sodium prior to fractional distilla-
tion through a Widmer column.

Fraction 1 was fractionated over sodium through a Widmer column at 759 mm. pressure.

| 15° 20° 20°
Fraction. B.p. Vol. M1. diz ooo MD
5 To 159° 6-0 0-8557 +39- 2° 1-4676
6 159-162° 12-0 0- 8600 +39-7° 1-4682
7 162-164° 19-5 0: 8576 +39: 5° 1-4686
8 164—168° 27-0 0- 8606 +38: 6° 1-4706
9 E68-175>) || 29-0 0-8533 +34-8° 1-4736

In view of the similarity of physical constants, fractions 5, 6 and 7 were mixed and frac-
tionated at 760 mm., viz. :

al: 20° | 120°
Fraction. B.p. Vol. M1. 15 *D D
10 156-157° 55 0+ 8578 440-89 | 41-4677
11 157-159° 10-0 0.8620 +.40-8° 1-4681
12 159-164° Ga5 0-8610 4+39-5° 1-4696

Fractions 8 and 9 were mixed with fraction 12, and distilled at 760 mm.

15° 20° 20°
Fraction. B.p. Vol. MI. 15 of) D

12a¢ 159-161° 7-0 0: 8601 +39-6° 1-4691
13 161-162° | 9-5 0- 8596 +39-1° 1-4699
14 162-164° 13-2 0- 8590 +38-8° 1-4703
15 164—166° 7-4 0- 8550 +38-9° 1-4711
16 166-168° 9-4 0- 8519 +37-0° 1-4726
16a 168-178° 11-6 0- 8528 +33-2° 1-4767

90 PENFOLD AND MORRISON.

Fraction 2 was mixed with fractions 16 and 16a and fractionated at 760 mm.

| 15° 20° 20°
Fraction. B.p. Vol. MI dis 7 =
16b 169-172° | 10 08538 433. 1° 1-4746
17 | 1722173 13 08533 +31-9° 1-4756
18 e821 75001 Vi 7 0- 8529 430-30 1-4776
19 176-177-5° | 10 | 0-8510 +28-4° 1-4782
20 | 1977-51789 12 | 0-511 +25-0° 1-4786
Residue | |

Fraction 3 was added to the residue from above distillation, and the mixture fractionated
over sodium at 760 mm.

|
| 15° 20° | 20°
Fraction. B.p. | Vol. MI. | dis 2D | ats
21 178-179° 7 0-8526 +22-0° 1-4784
22 179-180° 3 0-8540 +18-0° 1-4776

Determination of d-a-pinene.

Fractions 10, 11 and 12a on further fractionation yielded a specimen of boiling point
155-159°/760 mm., de 0-8610, an +40-8°. ny 1-4669. Oxidation with potassium per-
manganate solution gave a good yield of pinonic acid, m.p. 69-70° : fol, +91-6°; semi-
carbazone, m.p. 212°.

Fractions 13 and 14 were oxidised with neutral permanganate solution ; no crystalline
product could be isolated. The semicarbazone prepared from the resinous product had m.p.

212°. A mixed melting point with an authentic specimen of pinonic acid semicarbazone showed

no depression.

Examination for Presence of Camphene and (3-pinene.

Portions of fractions 2 and 15 respectively were oxidised with alkaline potassium per-
manganate solution, but products indicative of camphene and 6-pinene could not be isolated.

Determination of d-limonene and dl-limonene.

A fraction of b.p. 108°/100 mm. had d?°" 0-8486, n2”° 1-4803, ap +31°. Four ml. were
dissolved in amyl alcohol (4 ml.) and ethyl ether (8 ml.), cooled at —20°, and bromine (4g.)
in ether added slowly. After standing for one hour in a bath of acetone and solid carbon dioxide,
a yellow precipitate was obtained (0-9 g.). The precipitate was dissolved in chloroform and
reprecipitated with ethyl alcohol at room temperature. This treatment was repeated twice, the
crystalline bromide having m.p. 125-126°, unchanged in admixture with an authentic sample of
dl-limonene tetrabromide ; file +0° in chloroform.

The original chloroform-alcohol filtrate was cooled with acetone and solid carbon dioxide, a
precipitate being obtained, m.p. 98-100°, [a]? +46°, in chloroform. Purification with chloro-

form and ethyl alcohol as above yielded crystals of m.p. 103-4°, corresponding to d-limonene
tetrabromide.

Determination of y-terpinene and Cymene.

All fractions boiling above 175°/760 mm., on oxidation with potassium permanganate
solution (Penfold, 1925) gave good yields of the erythritol, C,)H,,(OH),, m.p. 237—238°, indicative
of y-terpinene.

THE ESSENTIAL OIL OF BACKEA CRENULATA (De CANDOLLE). 91

«6-dihydroxy-«-methyl-5-isopropylapidic acid, the oxidation product of «-terpinene, was
not isolated.

The unchanged oil, on oxidation with hot potassium permanganate solution, yielded
p-hydroxyisopropylbenzoic acid, m.p. 156°, which is indicative of p-cymene.

Determination of Linalool.

Portion (0-5 ml.) of a fraction of b.p. 74-80°/10 mm., d®” 0-8621, nZ” 1-4670, ap +6°,
was treated with xenyl carbimide at 100° for one hour. The urethane was isolated and, on
repeated recrystallisation from benzene, kad m.p. 83-84°.

Sesquiterpenes.

The results of fractionation indicated the presence of sesquiterpenes, but many experiments

failed to give crystalline derivatives. Fractions of b.p. 118-123°/10 mm., aye 0: 9158, ne 1-4870,

%p +8° and b.p. 123-132°/10 mm., d2>° 0-9145, n2>° 1-4835, ap +12°, respectively, gave the

characteristic purple colour in glacial acetic acid solution on treatment with bromine vapour.

SUMMARY.

The oil of Beckea crenulata (De Candolle) found growing on the coast of
New South Wales and southern Queensland yields from 0:2% to 0:36% of
essential oil containing 85% of terpenes, viz. d-«-pinene, d and dl-limonene,
-y-terpinene, cymene, together with linalool (10%), beckeol, sesquiterpenes,
and unidentified constituents.

ACKNOWLEDGEMENT.

We are indebted to Mr. K. G. O’Brien, B.Sec., Assistant Chemist, for a
complete investigation of the oil obtained from foliage collected at Wattamolla,
New South Wales, on October 22, 1947, using the distillation columns described
by Lecky and Ewell (1940) and Bower and Cooke (1943), and the technique of
distillation based on the methods of Sutherland (1948). This extensive investi-
gation confirmed the work recorded above. Linalool was isolated in a sufficient
state of purity to prepare the xenyl urethane. A detailed report of Mr. O’Brien’s
examination of the oil has been submitted to the University of Sydney as part
of a thesis for the M.Sc. degree.

REFERENCES.

Bower, J. R., and Cooke, L. M., 1943. Ind. Eng. Chem. Anal. Ed., 15, 290.
Hems, B. A., and Todd, A. R., 1940. J.C.S., 1208.

Lecky, H. S., and Ewell, R. H., 1940. Ind. Eng. Chem. Anal. Ed., 12, 544.
Penfold, A. R., 1925. Tuis Journat, 59, 351.

Penfold, A. R., and Morrison, F. R., 1922. Jbid., 56, 87.

——_—_—_—. 1987. Tbid., 71, 291.

Ramage, G. R., and Stowe, W. J. I., 1940. J.C.S., 425.

Sutherland, M. D., 1948. Univ. Queensland Papers in Chem., No. 34, 1.

HEARD ISLAND.
GEOGRAPHY AND GLACIOLOGY.

By A. JAMES LAMBETH, B.Sc.
With two Text-figures.

Manuscript received, March 23, 1950. Read, July 5, 1950.

CONTENTS.
Page

Geography—

Early History ws wi a ae 5 Oe

Position of the Island a oe as es eee iO

Description by is ee #5. mi pe OS
Glaciology—

Snow Line ae Mg arn se an aa eae(Oe

Glaciers ie a See =f ae nay ree

Retreat of Glaciers a ae ae We BH we pD

Ablation of Glaciers .. ne as RG his oo GS

Movement of Glaciers e sn a ae Oe

Types of Moraines .. We A a = i

Freezing of Bodies of Water Re es Bt, Pe he)

Snow Types .. : he am hs tS
Summary .. pte ah ah he te ae . sos
References .. oh + we Wes Au he =n aS

GEOGRAPHY.

Karly History.

Heard Island appears to have been sighted first by Captain Peter Kemp in
1833 (Mawson, 1935), but it was not until 1853 when it was rediscovered by
Captain Heard that the place became generally known. Darwin Rogers,
Captain of the Corinthian, was the first to land. The island was apparently
visited from time to time by sealers but prior to 1947 only four scientific
expeditions had called there.

The Challenger Expedition (1885) arrived on 5th February, 1873, and a
party spent several hours ashore at Corinthian Bay. The German Gauss
Expedition (Drygalski, 1908) in February, 1902, landed in the vicinity of Atlas
Cove. Aubert de la Rue (1929) in 1929 stayed eight days at Atlas Cove, living
in a hut erected there by the British Admiralty some years before. In November
of the same year the B.A.N.Z. Antarctic Expedition (Mawson, 1932) under the
leadership of Sir Douglas Mawson stayed several days at the same place.

On 11th December, 1947, the Australian National Antarctic Research
Expedition established a base camp on Rogers Head adjacent to Atlas Cove.

Position of the Island.

Heard Island lies in 73° 30’ E. longitude at 53° 05’ S. latitude, almost
halfway between Australia and South Africa. Kerguelen’s Land lies about 200
miles to the north-north-west, and the Antarctic Continent—MacRobertson
Land—is approximately 1100 miles to the south. The island is approximately
28 miles long and 12 miles broad, the longer axis lying in a N.W.-S.E. direction.

HEARD ISLAND. 93

It is the largest member of the McDonald Group, and McDonald Island lies
about 27 miles away to the north-west.

The surrounding seas abound with rocks and reefs; notable are the Shag
Islands and Wakefield Reef, situated respectively a few miles off the central
eastern and western coasts of Heard Island.

Description.

Heard Island is almost circular in plan, but is modified by two opposing
appendages. The coastline is precipitous ; rock cliffs and the vertical ice fronts
of glaciers alternate. These cliffs sweep rapidly upwards to form the mountain
mass known as Big Ben Range, which is almost completely snow and ice covered.
Several minor peaks are located here, e.g. Fremantle Peak (7800 ft.) and Campbell
Peak (7923 ft.), whilst the culminating peak is Mt. Mawson (9005 ft.). This
cone-shaped peak has a crater at the top and rises about 1000 ft. above the
semi-plateau-like top of Big Ben Range.

Cape Laurens is an imposing mass of small dimensions joined to the island
by a narrow tract of low land. The coast is composed of rock cliffs varying
from 100 ft. to 1000 ft. in height. The northernmost extremity is Red Island,
an extinct volcano (309 ft.), joined through a spit-like junction, thus forming a
tied island. The summits of Cape Laurens are snow fields and ice sheets, and
the spine-like Mt. Anzac is the highest point (2347 ft.). Lesser peaks are Mt.
Dixon (2316 ft.) and Mt. Olsen (2080 ft.).

The south-eastern end of the island is a spit-like structure about five miles
long, which swings away seaward after the manner of a tail. This area is low
lying and contains a shallow lake.

The coastline of Heard Island shows very little relief, consequently bays and
inlets are poorly developed. Atlas Cove is the best and is a fjord-like structure.
Corinthian Bay is a large semi-circular bay, as is also South West Bay. Beaches
occur; notable are Fairchild Beach and Long Beach, the low land at Atlas
Cove, and the boulder beaches of Spit Point.

The island is of voleanic origin and the grandeur and ruggedness are due to
the height and mass ef Big Ben Range and Mt. Mawson.

The map reproduced here (Fig. 1) is after that produced by the Expedition
during 1948.

GLACIOLOGY.
Snow Line.

Fully ninety per cent. of the area of Heard Island is covered with ice and
snow throughout the year.

The snow line varies according to the season. In December, 1947, it was
at 1000 ft., and remained stationary until the end of April, 1948, when it com-
menced to descend. By the Ist July, 1948, it had reached sea-level, where it
remained until lst September. At this stage it commenced to retreat and was
at approximately 200 ft. at the end of that month. In the middle of November
the snow line was at 500 ft., from which it retreated to 1000 ft., reaching this
level at the end of the first week in December, 1948.

There was little difference in the level between northerly and southerly
aspects.

Glaciers.

Glaciers on Heard Island may be discussed under two headings: those
situated on Cape Laurens and those on the island proper.

Those situated on Cape Laurens are small in size, due to the small area and
low altitude of the collecting grounds. Mt. Dixon is covered by a continuous
ice sheet, which descends to approximately 600 ft. Between Mt. Dixon and

94 A. JAMES LAMBETH.

Anzac Peak two glaciers rise, one flowing north, the other south. These descend
to approximately 500 ft., where they ablate amongst small piles of moraine.

_ HEARD ISLAND

Scale — Miles

Declination 48°40 W(I947)

Cape Arcona

Wakefield Reef 2

Fig. 1.—Key to Map of Heard Island. Minor Geographical Features.

Glaciers.

1. Mt. Dixon .. :. 2816-8: a. Unnamed.

2. Anzac Peak .. Se oats b. Re

3. Mt. Olsen... 2. 2080) ft: c. Jacka Glacier.

4. Mt. Drygalski fag HEQO ste. d. Baudissin Glacier..
5. North-West Cornice e. Schmidt Glacier.
6. Corinthian Head _.. 592 ft. f. Vahsel Glacier.

7. Melbourne Bluff 2 PALZOo Otte g. Abbotsmith Glacier.
8. Little Matterhorn .. 4856 ft. h. Gotley Glacier.

9. Fremantle Peak 6 7800 .4t. k. Unnamed.
10. Campbell Peak SU ROD ose mM. Le

11. North Barrier mn. Compton Glacier.
12. Round Hill wb) P2528 bit. p. Unnamed.

13. Searlet Hill .. 1410 1846 ft. r. Ae

14. South Barrier s. Challenger Glacier.
15. Sail Rock... A 56 ft.

16. Shag Island .. Me 301 ft.

17. Drury Rock Hie 122 ft.

18. Cape Lambeth Savi a tOO hae:

19. Long Beach
20. Cape Labuan i 130 ft.
21. Cape Lavett
22. Cave Bay

The eastern wall of these glaciers is an almost vertical cliff, which is a structural
geological feature, a fault scarp.

HEARD ISLAND. 95

Between Mt. Olsen and Anzac Peak and flowing east towards Atlas Cove
is the Jacka Glacier. This is the largest glacier of Cape Laurens and was
undoubtedly a hanging glacier to the former and now non-existent glacier
flowing northwards down Atlas Cove. This older glacier appears to have been
of the valley type with Cape Laurens forming the western wall. At the top of
the cliffs here is a typical alb formation, indicating the upper limit of the glacier.
As the course of this old glacier is intersected by a relatively recent geological
fault of large throw, it is evident that the retreat was caused by the lowering of
the collecting grounds.

The glaciers situated on the island proper rise from the heights of Big Ben
Range. Many reach the sea, but occasionally the front is land-based. Whilst
all of them show the effect of plucking action of ice on the underlying rock,
generally walls and sides of rock are wanting. It is frequently difficult to
determine the boundaries. Often these are low discontinuous mounds of highly
crevassed ice. The glaciers lack well defined cirques.

The course of the typical glacier is interesting. Rising on Big Ben Range,
the ice flows over the rim of the plateau through areas of intense crevassing.
The ice then enters a structure resembling an avalanch-shute, the top of which
is marked by a rock cliff normal to the course. Re-formation takes place .
between two lateral rock walls which are thickly encrusted with ice. Pinnacles
and aiguilles are common on these walls. The surface of the glacier now becomes
convex in profile and the lateral walls become insignificant. One glacier may
contain several of these amphitheatre-like structures. That these are not
cirques is indicated by the fact that the material entering is already blue ice.

The glaciers therefore resemble ice sheets modified by plucking action at
certain places. Consequently they are to be considered as belonging to the
Spitzbergen type.

Although many glaciers are sea-based, none is actually afloat. It was
considered that the ice foot was not far vertically below sea-level.

The total depth of ice is uncertain, but measurements taken on the fronts
of glaciers indicate that probably 150 ft. may be the upper limit. For example
the front of the Baudissin Glacier was measured at 110 ft. in August, 1948,
whilst the front of the Vahsel Glacier was 125 ft. thick in the same month.
Although the fronts are thinner than the main masses due to ablation, the
observations were taken when ablation was at a minimum.

Retreat of Glaciers.

Recent retreat of glaciers and evidence of loss of ice cover in the Antarctic
have been reported by Warner (1945) and Knowles (1945). The former has
evidence to show the loss of ‘‘ several hundred vertical feet ”’ of ice.

An indication of a similar recent diminution on Heard Island is afforded
by the terminal and lateral moraines of the Vahsel Glacier. The front of this
glacier abuts in part on to Cape Gazert, a small headland of bedded lavas.
Overlying these lavas are two terminal moraines, as indicated in Figure 1.
The terminal moraine situated immediately at the glacier front has an altitude
of approximately 125 ft., whilst a short distance away is an older and more
consolidated moraine of altitude 320 ft. approximately. The evidence indicates
a loss of at least 200 ft. vertical thickness of ice’ but little horizontal retreat
along the glacial path. The lateral moraine of the same glacier shows a similar
diminution, as shown in Fig. 2. The older moraine here has an altitude of
300 ft., which is approximately 220 ft. higher than the more recent moraine.

Ablation of Glaciers.

Dissipation of ice takes place by melting, by the action of the sea, or by
avalanching.

96 A. JAMES LAMBETH.

Melting takes place through the action of the sun, wind and rain. These
agencies are seldom significant above 1000 ft. During November, 1948, an
ablatograph was maintained on the north slopes of the Baudissin Glacier. The

b

N 5
fe) 400
Horizontal Scale —— yds.
(9) 300
Vertical Scale RAE PGs eae
Fig. 2.

Fig. 1 above. Section at Cape Gazert, indicating retreat of the Vahsel Glacier.

Fig. 2 above. Section near Erratic Poimt. The lateral moraine of the Vahsel Glacier,
indicating retreat.

a. Bedded lavas. d. Vahsel Glacier.
b. Old moraine. e. Redistributed moraine.
c. Active moraine.

Datum lines are at sea-level.

apparatus was at 125 ft. above sea-level, and the record concerns the ablation
of clear blueice. In general the ablation was greater during the hours of daylight
than during darkness, and rain, however cold, was more effective than sunshine,
which in turn was more effective than wind. The following condensed record
illustrates these points.

= ————

Typical Period Typical Period

Typical Period | of Light Fairly of Wind.
of Sunshine. Constant Rain. Overcast.
Decrease/Hour. | Decrease/Hour. | Decrease/Hour.

Average, Inches. | Average, Inches. | Average, Inches.

|
|

12 p.m. to 3 a.m. 0-00 | — 0-02
3 a.m. 4.2 6%alIm. 0-00 — 0-00
Gla 1.4 er 9) ca mas 0-03 | 0-15 0:00
9am. ,, 12 noon 0:05 0-14 0-02
12 noon ,, 3 p.m 0-12 | 0-20 0:00
o P.M O) pam 0-06 | 0-06 0-00
Ouplmt es 29 p.m 0-00 0-03 0-00
9 p.m.) 12" pim 0-00 | — 0-00

During the entire month ablation at this station from all causes averaged
0-02 in. per hour approximately.
The melt water finds its way into the ice through crevasses, sinks and
crevices, emerging as a torrent through a circular hole at the front of the glacier.
In hanging glaciers this water issues as a waterfall, but in the case of sea-based
types a discoloured stream enters the sea. In February, 1948, the glacial
stream from the Challenger Glacier was discernible two and a half miles to
seaward, whilst in February, 1949, sea water five miles off the south-eastern end

ry

HEARD ISLAND. 97

of the island was strongly discoloured. In this case the effect is due to a
coalescence of the streams as they are swept eastwards round the flanks of the
island by the westerly drift of wind and sea.

The sea is effective in the dissipation of glacial ice. The action is twofold.
The pounding of the waves causes undercutting at the foot, resulting in
avalanching of the front. Secondly, the deposition of salt spray on the lower
level ice causes deterioration of the surface and an opening of cracks and
crevasses, which later become lines of weakness along which the avalanches
Shear off.

Avalanches of this kind vary in size. On the Baudissin Glacier, where the
front averaged 100 ft. high, the falls were about 100 yards in length. The ice
which falls into the sea is well fragmented, so that large bergs do not result.

Movement of Glaciers.

Observations were carried out on the Baudissin Glacier between the months
September to December, 1948. The observation poles were at an altitude of
300 ft. approximately, about half a mile inland. The maximum movement
recorded was at the centre, where a movement averaging one foot per day was
recorded for the period 11th September to 20th October. In the period 20th
October to 8th December this had increased to a daily average of three feet.

Types of Moraines.

Land-based glaciers end in a terminal moraine ; in sea-based types shallow
water extends offshore for some distance. Lateral moraines are usually small
in size, due to the lack of well-defined walls. The lateral moraine on the north
side of the Vahsel Glacier is the largest on the island. It ends in the geographical
feature Erratic Point, which contains the largest erratics encountered. Several
of these are of the order of 1000 tons. The unusual development of this moraine
is due to the high, cliff-like wall, the North West Cornice, which contains the
glacier in the lower reaches.

The material deposited ranges from rock flour to boulders of the size
mentioned above. Large boulders are rare, the bulk of the material being less
than three feet in diameter. Whereas the bulk of material in lateral and medial
moraines is angular, the material of the terminal moraines contains a large
proportion of rounded and sub-rounded débris. Rounded débris weathers out
of solid ice high up on the glacial fronts, as well as issuing with melt water from
various tunnels. Scratched and soled pebbles are uncommon, but are more
abundant in lateral moraines than in terminal moraines.

Medial moraines are few and small in size ; noteworthy are the two medial
moraines of the Compton Glacier. Knob and kettle-structure on a small scale
occurs in the moraine of the glacier confronting Saddle Point.

An unusual feature is the large redistributed moraine of Atlas Cove. This
has been derived from waste of the Baudissin, Schmidt and Vahsel glaciers,
which converge at this point, and possibly in part from the old, now non-existent,
glacier flowing down Atlas Cove. The area is flat with a maximum elevation
of 60 ft. The débris has been modified by the action of wind and waves and alsa
by slumping, so that it assumes the nature of a plain.

Evidence of bodily shift of these sediments was provided by a stake in the
sediments between Corinthian Bay and Mt. Drygalski. This stake moved
fifteen feet in eleven months towards Corinthian Bay, thus indicating a spreading
by slumping towards deep water. When under the influence of the sea the
detrital material becomes subject to westerly drift and is worked round the
flanks of the island to the south-east end, where it is deposited in the lee. This
has caused the long thin tail-like spit to be built up.

G8 A. JAMES LAMBETH.

Freezing of Bodies of Water.

Freezing of the sea was noted on 30th July, 1948, and between then and
14th October freezing occurred on eighteen occasions. This was confined to
relatively quiet bodies of sea water and took the form of pancakes of ice and slush.
The freezing occurred most commonly on clear nights. The solid phase separated
at a temperature of 28-6° F., and was fresh. The most severe case of freezing
of the sea was noted on 15th September, 1948. :

Snow Types.

Snow falls at sea-level throughout the year; however that which falls
during summer is quickly dissipated and cold rain is more common. Falls
during the winter build up large drifts. An analysis of observations on snow
seen to fall about the base camp during the period 1st September to 1st December,
1948, showed that almost 90 per cent. could be classified as either stars, spicules
and rods, or frozen rain, the proportions being nearly equal.

Twice during this period snow was observed to accumulate with a preferred
orientation. On these occasions the factors were (a) the shape of the grains,
and (b) the influence of the wind. Both times the major axis of the grains was
very much longer than the two minor axes, so that the acicular type grains
lodged parallel to the surface of the ground and then orientated themselves
parallel to the direction of the wind.

SUMMARY.

Heard Island is a small precipitous volcanic island situated within the
McDonald Group at 53° south latitude in the Indian Ocean. The climate at
sea-level is sub-antarctic. The snow-line is at 1000 ft. during summer but
descends to sea-level in winter. During this latter period the sea was observed
to freeze. The island is almost completely glaciated and the depth of ice-cover
is in excess of 100 ft., although there is evidence to show that this depth was
formerly much greater. Descriptions of moraines and glaciers are given and
there are also notes on the ablation of ice and the types of snow.

REFERENCES.

Aubert de la Rue, E., 1929. ‘‘ Un Voyage d’exploration dans les mers Australes. Iles Heard,
Archipel de Kerguelen, ile St. Paul.”” Rev. de Geogr. Phys. et de Geol. Dynam. Univ. de Paris,
11, 97-146.
Challenger Expedition, 1885. ‘‘ Report of the Scientific Results of the Exploring Voyage of
H.M.S. Challenger, 1873-76.’ Narrative of the Cruise, 1, Pt. 1, 369.
Drygalski, E. Von, 1908. ‘‘ Geogr. von Heard Eiland.’? Deutsche Sudpolar Exped., 1901-3.
Bd. 11, Heft 3. Geog. u. Geol. 223-39.
Knowles, P. H., 1945. ‘‘ Glaciology of Southern Palmer Peninsular Antarctica.” Repts. of
the U.S. Antarctic Service Expedition, 1939-41. Proc. Amer. Phil. Soc. 89 (1), 174.
Mawson, D., 1932. ‘‘ The B.A.N.Z. Antarctic Research Expedition 1929-31.” Geogr. Jour.,
80, 105-6.
-— 1935. ‘‘ Some Historical Features of the Discovery of Enderby Land and Kemp
Land.” Geogr. Jour. 86, 526.
Warner, L. A., 1945. ‘‘ Structure and Petrography of the Southern Edsel Ford Ranges,
Antarctica.’ Repts. of the U.S. Antarctic Service Expedition 1939-41. Proc. Amer.
Phat. Soc.) 89 (1); 84.

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| AUSTRALASIAN MepicaL PUBLISHING Company L

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ISSUED MAY 30, 1951

PART Ill

VOL. LXXXIV

JOURNAL AND PROCEEDINGS

OF THE

ROYAL SOCIETY

OF NEW SOUTH WALES

fr ite. wy
y fir ey,

A oe iS Pee ;
FOR Y a a

1950 NAY | is i
(INCORPORATED 1881) Al %

ae Tigao

PART III (pp. 99-168)
OF
VOL. LXXXIV

Containing papers read during August to November
(inclusive), 1950, with Plate III

EDITED BY

IDA A. BROWNE, D.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, SCLENCE HOUSE
GLOUCESTER AND ESSEX STREETS

1951

CONTENTS
VOLUME LXXXIV

Part III

Art. XIX.—Rank Variation in the Central Eastern Coalfields of New South Wales.
By J. A. Dulhunty, Nora Hinder and Ruth Penrose ‘ ‘

Art. XX.—Studies in the Chemistry of Platinum Complexes. Part IV. Oxidation of
Ions of the Tetrammine Platinum II nes with se Aa actin Peroxide. By 8. E.
Livingstone and R. A. Plowman .. sep Ge

Art. XXI.—Coordination Compounds of Copper. Part II. Compounds Derived from

Copper (I) Iodide. By C. M. Harris

Art. XXII.—The Chemistry of Osmium. Part VII. The Bromo and Chloro Pentammine
Osmium III Series. By F. P. Dwyer and J. W. Hogarth :

Art. XXIII.—The Chemistry of Iridium. Part V. The Oxidation of Iridium IIT Salt
Solutions. By F. P. Dwyer and E. C. Gyarfas Z

Art. XXIV.—Physical pars ear on nes of namie a By
L. E. Maley aie

Art. XXV.—Tables for Nearly Parabolic Elliptic Motion. By Harley Wood
Art. XXVI.—Tables for Hyperbolic Motion. By Harley Wood

Art. XXVII.—An Occurrence of aM ieee haat Structure in New South Wales. By T. G.
Vallance : Ge “

Page

99

107
111
117
123

130
134

151

165

RANK VARIATION IN THE CENTRAL EASTERN COALFIELDS
OF NEW SOUTH WALES.

By J. A. DULHUNTY, D.Sc.,
NorA HINDER, B.Sc.,
and RUTH PENROSE, B.Sc.
With Plate III and two text-figures.

Manuscript received, July 10, 1950. Read, August 2, 1950.

INTRODUCTION.

Considerable variation has long been recognised in the nature and properties
of coal in the different coalfields situated around the margin of the Permian Coal
Basin in Central Eastern New South Wales. It is well known, for example,
that coals in the South Coast Field are very friable and ‘‘ dusty ’’ compared with
other fields and that they are characterized by low moisture contents, high
carbon contents, low volatile yields, and excellent coking properties. Coals
from the Northern, South-western and Western Fields are less friable, contain
more moisture and less carbon, give higher volatile yields, and, with some
important exceptions in the Newcastle-Swansea area, are more suitable for
gas-making and steam-raising than coke production. In the Ulan-Baerami
Field, situated between Mudgee and Muswellbrook, the seams are particularly
firm, with relatively high moisture contents, low carbon contents, high volatile
yields and very poor coking properties.

Such variations in the nature and properties of coal are due largely to rank
differences, or different degrees of metamorphic development. Type differences
play only a minor part in variations of properties as all the coals concerned
are of the same general type. The investigation recorded in this paper was
carried out with the object of obtaining quantitative data bearing on regional
variation of rank throughout the Upper Coal Measures of the Central Eastern
Coal Basin and on the metamorphic history of the area. Results also have
some bearing on the relationship between different chemical and physical rank
indices.

The coal-bearing strata of the Newcastle stage of the Upper Coal Measures
are continuous throughout all the coalfields. The Tomago Measures outcrop
only in the Northern Coalfield but the coal is generally similar in rank and type
to coal of the Newcastle Measures in the same section of the coalfield, and for
the purpose of the present paper coals of the two stages of the Upper Coal
Measures are considered together. The Greta or Lower Coal Measures also
outcrop on the Northern Coalfield but they contain coal of a somewhat specialised
type, which differs from coal of the Upper Coal Measures in nature and condition
of original plant material. In view of this and the substantial differences in
stratigraphical position, the Greta coal is not included with the Upper Coal
Measure coals in considering regional rank variation, but the relation of its
rank to other Permian coals is discussed separately. The Permian coals of the
Werris Creek-Curlewis-Gunnedah Coalfields are not included in the present
work as the coal-measure strata in that area form part of the Great Artesian
Basin, and the rank of the coal is not directly related to the tectonic history of
the Central Eastern Coal Basin.

I

APR2 8 1952

100 DULHUNTY, HINDER AND PENROSE.

Vitrain, which is coalified wood and bark, was used for the study of rank
variation so as to eliminate, as far as possible, the influence of varying pro-
portions of ‘* banded constituents’. Blocks of coal containing well-developed
vitrain bands were obtained from 48 collieries and fresh exposures of coal seams
in the different coalfields. In the case of each locality involving the area of a
colliery workings, or a fresh exposure of a seam in a railway tunnel or cutting,
pure vitrain was separated by hand from at least five or six different bands.
Aggregate samples so obtained were analysed to provide average results for
vitrain in each locality and to eliminate to some extent variations inherent in
the nature of the vitrains. The materials were crushed, sieved and water
saturated, then acid washed to remove as much adherent mineral matter as
possible. After complete removal of acid by prolonged soaking in water and
repeated washing, the samples were used for determination of carbon and
hydrogen by ultimate analysis; volatiles, fixed carbon and ash by proximate
analysis; and maximum inherent moisture by “ controlled vaporization of
adherent moisture ’’ (Dulhunty, 1947a). Results of the chemical and physical
determinations for the vitrains are recorded in Table I.

The ultimate and proximate analyses provide two sets of chemical-rank
indices. Values for maximum inherent moisture provide an index of physical
rank. The expression ‘‘ physical rank’ is used in relation to progressive
changes in the physical state of coal as it matures under natural metamorphism
(Dulhunty, 19476 and 1948). Itis concerned largely with the degree of physical
development of micelle or ultra-fine structure of the coal, and it has been shown
that this is closely related to values for maximum inherent moisture (Dulhunty,
19476; Hinder, 1949).

RELATIONS BETWEEN DIFFERENT RANK INDICES

Relations between results of proximate and ultimate analyses as chemical
rank indices and maximum inherent moisture as a physical rank index were
examined by plotting different properties against each other. In Fig. 1 carbon
was plotted against fixed carbon for each of the vitrains analysed. The points
fall in a relatively wide zone which rises across the diagram from left to right.
From the width of the zone it is evident that they are not closely related. Vitrains
with any given carbon content may vary in fixed carbon over a range of about
10 per cent. and those of any given yield of fixed carbon may vary in carbon
by about 8 per cent. The points fall towards the upper or lower limits of the
zone, or the carbon-fixed carbon ratio deviates from the mean, without any
apparent reason. The deviation is not related to geographical position or
stratigraphical horizons in the coalfields, nor is it related to physical rank of the
vitrains, or to the carbon-fixed carbon ratio of the coal seams in which the
vitrains occur. It may, however, be related to other factors, such as petrological
constitution, which remained to be investigated. It is also possible that
deviation of the carbon-fixed carbon ratio may be related to some variable factor
in the chemical constitution of the coal substance. In view of this, and the fact
that fixed carbon values vary with the conditions of determination, it would
seem that carbon content probably represents a more reliable and significant
index of chemical rank than fixed carbon. It is evident, however, that fixed
carbon may be regarded as a general indication of rank within the limits of
variation corresponding to the width of the zone in Fig. 1.

The relations between physical and chemical rank have been studied by
plotting values for maximum inherent moisture against carbon of vitrains in
all stages of metamorphic development (Dulhunty, 1948). Results showed a
zonal relationship with a well-defined maximum at about 68 per cent. carbon
and a minimum at about 89 per cent. carbon. The width of the zone, which
varies considerably with rank (as illustrated in the above references), is regarded

RANK VARIATION IN CENTRAL EASTERN COALFIELDS OF N.S.W. 101

TABLE I.

Results of Analyses of Vitrain Samples.

Percentage
Ash-Free M.I.M.
C.S. Dry Coal. Ash Percentage
Coalfield. Locality. Seam. No. Percentage| Ash-Free
Dry Coal. | Dry Coal.
C. F.C.
Sydney Ae NOoel 30 88-3 77°3 1-1 3-2
Helensburgh .. | No. 1 312 88-0 76-0 0-9 1-8
Clifton al iNOw dd 313 88:8 75°4 0:9 1-8
*Austinmer i UNO ek 314 88-9 73-0 0-8 2°3
South Bullt ~.. 22 Now | 445 89-7 72-3 itove 1-9
Coast —_. ——c“€— qe \q_ cml @ i i cqyy_[\—m eqcr
Bellambi by, Now 2 356 89-7 73°6 1-1 2-3
Corrimal .. | No. l 394 87-3 73°5 0:6 2-1
Keiraville wie | UNO, 2 444 88-3 710°4 Sod 2-0
Unanderra... | No. 3 439 88-4 73°5 Bip 1:9
Unanderra .. | No. 2 352-88 | 88-1 | 71-5 0-5 2-5
Dapto.. ped INO. 3 443 88-1 71°4 2-6 2-0
met South Berrima is Noss 347-8 84-8 67-8 4-7 4-1
Western = (| -——__|—__ |-—__ _ ]_ SS _ |]
Nattai De aNos3 681 84-9 66-8 222, 3°0
Katoomba .. | No. 1 671 82-4 67-8 2-9 3°0
Lithgow «2 | INO. 7 446 84-6 68-0 2-6 7°4
Lithgow 25, \ENoz 7 362 83-0 66-9 0:8 5-0
Lidsdale .. | No. 6 360 85:6 64:7 2-2 Me
Western Cullen Bullen No. 6 366-7 82-4 63°8 1-2 6:0
| Cullen Bullen No. 6 430 81-2 63-4 1-4 6-0
|) Se A eee ee
| Glen Davis .. | No. 1 667 S35 67s7 4-2 4-1
| Charbon ae WV INOsand 373 83°7 66°5 0:8 8-3
Kandos oe eNOS 7, 181 80-8 64-5 2-1 6-4
Ulan .. fry | UNO: 7 667 78°5 62-0 1-6 9-5
651 )
Wollar oe A NO:..6 653 82-4 63-5 1-6 11-3
Ulan- 656
Baerami (|_| —_—__—\——
Kerrabee vil INOSe6 666 78:3 65-6 2°5 10-9
Kerrabee vo NOs eG 673 80:0 66-7 1-9 11-8
Baerami So iaNOwro 672 79-2 66-5 0:6 9-0

102

Coalfield.

Northern

Greta

DULHUNTY, HINDER AND PENROSE.

Locality.

Muswellbrook. .
Liddell
Rix Creek

Rix Creek

East Maitland
East Maitland

West Wallsend

Adamstown

Whitebridge
Whitebridge

Redhead

Belmont

Belmont

Belmont

Swansea

Catherine Hill

Bay
Cessnock
Kearsley
Kearsley

Pelaw Main

Muswellbrook. .

TABLE I.—Continued.
Results of Analyses of Vitrain Samples.—Continued.

Seam.

Tomago
Measures

Tomago
Measures

Tomago
Measures

Tomago
Measures

Tomago
Measures

Tomago
Measures

Tomago
Measures

Victoria
Tunnel

Borehole

Victoria
Tunnel
Victoria
Tunnel

Borehole

Victoria
Tunnel

Great
Northern

Wallarah
Wallarah

Greta
Greta

Greta

Greta

Greta

C.S.
No.

675

174

447-52

172

363

364

169

353

Percentage

Ash-Free

Dry Coal.
C. F.C.
85-0 70-4
81-0 61-6
81-8 62-6
80-9 63-6
79-4 | 64-4
81-7 64-7
81-3 66-1
83-4 62-9
82-2 64-0
82-3 64-0
83-7 64-3
84-7 65-8
82-8 66-1
83-4 63-7
79-8 64-2
84-05 67:8
80-8 62-2
81-6 62-9
81-8 65-8
82-6 62-9
80-7 63-8

M.I.M.
Ash Percentage
Percentage} Ash-Free
Dry Coal. | Dry Coal.
1-9 4°3
3-1 4-0
2-0 4-6
4-4 6-0
0-7 4-9
Bed 4°7
1-8 5:6
51 3°9
3°0 4-4
2:5 4-6
3°4 4-0
0-5 3°9
2-2 4-4
2:4 © 4-8
5-6 6-1
7 5:8
1% 4-0
2-2 3°9
1-3 4-4
1-3 4-0
0-6 8-1

RANK VARIATION IN THE CENTRAL EASTERN COALFIELDS OF N.S.W. 103

as an indication of the extent to which the two forms of rank may become
separated in degree of advancement during metamorphic development. If a
point falls towards the lower limits of the zone, between 68 and 89 per cent.
carbon, it means that its physical rank is considerably in advance of its chemical
rank. Conversely, if a point falls near the top of the zone, between the same
limits of carbon, its chemical rank is in advance of its physical rank.

The relationship between chemical and physical rank for vitrains of the
Central Eastern Coal Basin is illustrated in Fig. 2. Owing to the limited range
in rank of the vitrains concerned (78—90 per cent. carbon), this diagram represents
only that portion of the zone where it approaches the minimum at 89 per cent.
carbon. It will be noted in Fig. 2 that there is a distinct crowding of points on

352,388
“443

0444

Fixep CARBON Z

CarRBoNn Z

Fig. 1.—Relations between Carbon and Fixed Carbon for Aggregate Vitrain Samples.

the lower side of the zone. From this it may be inferred that vitrains from the
majority of localities are considerably more advanced in physical rank than
chemical rank. The few vitrains which fall towards the upper side of the zone
are all from the western margin of the coal basin in the Western and Ulan-
Baerami Coalfields, suggesting that these were the only areas in which conditions
of metamorphism were such as to advance chemical rank more than physical
rank. These points which fall close to the lower limits of the zone are all from
the Maitland-Liddell-Cessnock section of the Northern Coalfield, suggesting the
existence of conditions capable of advancing physical rank more than chemical
rank. Such results may have an important bearing on prevailing conditions
of metamorphism in different parts of the coal basin and on the tectonic history
of the coal measures when more is known about the relative influence of various
metamorphic factors in the process of coalification.

REGIONAL VARIATION OF CHEMICAL AND PHYSICAL RANK.

In the study of regional variation of physical and chemical rank in the
Upper Coal Measures maximum inherent moisture and carbon were used

104 DULHUNTY, HINDER AND PENROSE.

respectively as indices of the two forms of rank. The area of the Central Hastern
Coal Basin and its arbitrary subdivision into coalfields, is shown on the accom-
panying map (Plate III). Localities from which vitrains were selected for the
investigation are indicated by small crosses numbered with the serial numbers
of vitrain samples in Table I, which supplies detailed chemical and physical
data. The values for carbon and maximum inherent moisture shown on the
map represent average results for vitrain in the vicinity of the places where the
figures appear. In each the average was obtained for all vitrains in an area
extending about halfway to the nearest place where another average is shown.
Average results of this kind were placed on the map as the printing of individual
results produced too much confusion, and because small local variations in
properties tended to obscure the general picture of regional variation.
‘¢ Isocarbs ”’ or lines indicating distribution of carbon content were drawn on the
map at intervals of 2 per cent. from 78 to 90 per cent. carbon. Similar lines

MAX. INHER. MoisT. 4

030

20352,388
o3l4% 0356)

2430
oz 04390313

CARBON Z

Fig. 2.—Relations between Carbon and Maximum Inherent Moisture for Aggregate
Vitrain Samples.

were drawn for maximum inherent moisture at intervals of 1 per cent. from
2to11 percent. These lines have been termed “‘ isomoists ’’ for the purpose of
the present paper.

Distribution of chemical rank illustrated by the isocarbs shows a general —
centre of metamorphism or maximum rank advancement in the vicinity of the
South Coast Coalfield. Rank decreases rapidly towards the South-western
Coalfield and somewhat less rapidly in the direction of the Northern Coalfield,
whilst in a north-westerly direction it decreases very slowly through the centre
of the coal basin. Rank also decreases through both the Western and Northern
Coalfields towards the Ulan-Baerami Field, where the coals of lowest rank are
situated. The centre of high rank on the South Coast is situated towards the
southern margin of the coal basin and does not coincide with the general centre
of sedimentation or the structural centre of the basin. Beyond the influence
of the high rank centre in the south, the isocarbs tend to follow the original shore
lines of coal-measure sedimentation. They also appear to be somewhat crowded
along the marginal areas leaving a large area in the central region where rank
variation is only slight.

Physical rank variation illustrated by the isomoists follows the same general
trends as the distribution of chemical rank. A centre of high physical rank with

an)
ues

Journal Royal Society of W.S.W., Vol. LXXXIV, 1950, Plate III

meeiwa fs

7 C-B30%

M-4:2
/ 7No Nperooene S
ele R Diy SS \ 80 3 if t
: aa Fox. Sad
“ip LE ‘ \ Ai ’
\i s

4

Suvcyeron’
Xe €-809—)
oy M-S:0N

> h at
J R/MAITLAND,

& l oe aaa SL)
r On

; : SE #3) SYDNEY

[LIEGE IN)D) =
—~—_— socanas

— — — |Somoists

4243 VITRAINS FROM UPPER COAL MEASURES

~
x30 - - GRETA - - ¢

C-83:2 AVERAGE FIGURES FOR CARBON 8
M-5-9 AND MAX. INHER MOIST. %

77> ==" RAILWAYS
30

—————
= SCALE MILES:
ye 8 \
1 \\

2 90

MOSS,

VALEG
\ A
84,i

KIAMA

Central Eastern Coal Basin of New South Wales, showing Rank Variation in Coals of tho Upper Coal Measures.

+i APG

oe
.
—
*
‘
;

ww

RANK VARIATION IN CENTRAL EASTERN COALFIELDS OF N.S.W. 105

low moisture values is situated in the vicinity of the South Coast Coalfield and
values increase aS rank becomes lower through the Western and Northern
Coalfields towards the Ulan-Baerami area, where the highest moisture values
occur in coals of the lowest rank. As in the case of chemical rank there is a
relatively rapid decrease in physical rank, or crowding of isomoists, along the
marginal areas of the basin and variation is slight in the central region.

Although the two forms of rank show the same general distribution in
relation to the coal basin there are some small but very significant differences
in rate of variation. In the Western and Ulan-Baerami Coalfields the isomoists
are far more crowded than the isocarbs indicating that physical rank decreases
more rapidly than chemical rank. This can be correlated with the conclusion,
based on the positions of vitrains in the zonal relationship between moisture
and carbon (Fig. 2), that in the Western and Ulan-Baerami Coalfields conditions
of metamorphism were such as to advance chemical rank more than physical
rank. If chemical rank is more advanced that physical rank then the rate of
change in physical rank on passing towards the Ulan-Baerami Field, will be
greater than change in chemical rank. This is so as the isomoists are more
crowded than the isocarbs in the Ulan-Baerami Coalfield. Similarly it was
concluded in discussing Fig. 2 that physical rank was more advanced than
chemical rank in parts of the Northern Coalfield, and it is evident trom the map
that isocarbs are somewhat more crowded than isomoists in that area. Another
example of correlation between rank distribution and the positions of vitrains on
the moisture-carbon diagram can be seen in the South-western Coalfield. In
this area isocarbs are more crowded than isomoists and the vitrains fall towards
the lower side of the zone in Fig. 2.

From the foregoing discussion and results it would seem to follow that
features such as relative crowding of isocarbs and isomoists or the different
rates at which physical and chemical rank vary from place to place, and the
crossing of isocarbs and isomoists must be related to differences in metamorphic
conditions or the predominance of different metamorphic factors which have
existed in various regions of the coal basin. As stated earlier, when moreis
known about the relative influence of different metamorphic factors during
coalification it is highly probable that much information about the geological
history of coal measures will be revealed by relations between the distribution
of physical and chemical rank, as illustrated by isocarbs and isomoists in Plate ITI.

STRATIGRAPHICAL VARIATION IN RANK.

In many coalfields of the world the coal seams exhibit a definite increase
in rank with depth from the surface. This is generally attributed to increase in
pressure and temperature with depth. In the Central Eastern Coal Basin of
New South Wales there is a general tendency for isocarbs and isomoists to follow
the original shore lines of deposition along the western and north-eastern sides
of the basin where rank increases on passing towards the central regions. This
is probably due to increases in depth of cover, but the principal trends in rank
variation are not related to depth of burial or thickness of the coal measures.
For example, rank decreases progressively from 84 per cent. carbon to 78 per
cent. carbon in a northerly direction along the western margin of the basin.
The centre of high rank on the South Coast is situated towards the southern
margin of the basin and cannot be correlated with either depth of burial or
thickness of coal measures. The highest and lowest rank coals occur in the
South Coast and Ulan-Baerami Coalfields respectively although depth of burial
in each case, and physiographic histories of the two areas, appear to have been
much the same.

Vitrain bands occur in the topmost beds of Triassic sandstone near Sydney.
The rank of the Triassic vitrains (about 86 per cent. carbon) is almost as high

106 ~ DULHUNTY, HINDER AND PENROSE.

as that of Permian vitrains (88 per cent. carbon), which occur some 3000 ft.
deeper in the same area. Also, the rank of the Triassic vitrain is much higher
than the Permian vitrains along the western and north-western sides of the basin.
The strata are practically undisturbed by folding or faulting in any of these
areas. It is possible that the high carbon contents of the Triassic vitrains near
Sydney may be due to coalification in a sandstone environment rather than the
general coal-measure environment in which the underlying Permian vitrains
were formed. If, however, their high carbon contents resulted from regional
metamorphic conditions, which appears likely, then some factors other than
depth must have produced the high-rank coals between Sydney and Wollongong
and those factors would appear to have operated in post-Triassic time. The
large number of igneous sills and dykes injected into the coal measures and
underlying marine beds along the South Coast may have elevated the general
temperature of the strata sufficiently to produce coals of higher rank than in
any other part of the coal basin. In general, however, it appears that rank
variation in the Central Eastern Coal Basin is not a simple consequence of depth
of burial, and cannot be related to folding or other tectonic disturbances in the
coal measures.

ACKNOWLEDGEMENTS.

In conclusion the authors wish to express appreciation of generous assistance
given by Colliery Proprietors and Managers in obtaining coal samples for the
investigation. They also wish to acknowledge assistance given by the Combined
Colliery Proprietors’ Association of New South Wales in providing the salary
for a Research Assistant during part of the investigation ; research facilities
provided from the Commonwealth Research Grant to the University of Sydney ;
and valuable discussion with Professor C. E. Marshall in connection with the
presentation of results.

REFERENCES.
Dulhunty, J. A., 1947a. THis JouRNAL, 81, 60.
metic 9475... Aust. Jour. Sei,'9, No. 4,1 133:
Se 1948. THIS JOURNAT. (G2. 265;
Hinder, Nora, 1949. Jbid., 83, 195.

y
a
.
t
»

STUDIES IN THE CHEMISTRY OF PLATINUM COMPLEXES.

Part IV. OXIDATION OF IONS OF THE TETRAMMINE PLATINUM II
TYPE WITH HYDROGEN PEROXIDE.

By 8S. E. LIVINGSTONE, A.S.T.C.,
and R. A. PLOWMAN, B.Sc., A.S.T.C.,

Manuscript recewed, June 23, 1950. Read, August 2, 1950.

Platinum (IV) compounds of the type [Pt(NH3),Y,|X, are, in general,
prepared by oxidation of the tetrammine platinum (II) ion, using a source of
the group it is desired to introduce as oxidising agent, when the compound of
quadrivalent platinum is formed, e.g.,

[Pt(NH3)4]** +Cl,——[Pt(NH3),Cl, }+*

When H,O, is used as oxidising agent in aqueous solution the corresponding
dihydroxo compound is formed.

[Pt(NH3),]** +H,O,——[Pt(N H3),(OH),.]**

Apart from salts of the dihydroxo tetrammine platinum (IV) ion, which
are well known, compounds in which the ammonia groups are replaced by
other coordinated groups do not appear to have been prepared previously.

In a previous communication it is reported that the attempted oxidation of
tetra pyridine platinum II fluoride with hydrogen peroxide was unsuccessful.
We have now made further attempts to oxidise the tetrapyridine platinum ITI
ion with hydrogen peroxide. Reaction of the chloride of this ion with aqueous
hydrogen peroxide under the same conditions used for oxidation of tetrammine
platinum ITI chloride does not appear to bring about oxidation and tetrapyridine
platinum (II) chloride can be recovered from the reaction mixture. An aqueous
solution of the perchlorate does not discolour potassium permanganate.

Compounds in which one or more of the pyridine groups in the tetra pyridine
platinum (II) ion are replaced by ammonia can be prepared.

Trans dipyridine diammine platinum (II) chloride reacts with hydrogen
peroxide, oxidation taking place to yield the corresponding dihydroxo platinum
IV chloride, from which other salts can be prepared by double decomposition in
aqueous solution. These are generally colourless, crystalline compounds,
moderately soluble in cold water and readily soluble in hot water. With
potassium chloroplatinate (II) and chloroplatinic (IV) acid the ion yields sparingly
soluble coloured compounds, the compound obtained from the chloroplatinate (IT)
being of uncertain structure, due to the possibility of simultaneous oxidation-
reduction occurring. It has thus been shown that analogous reactions with
hydrogen peroxide and the tetrammine platinum (II) ion occur when two of the
ammonia groups are replaced by pyridine molecules. The —OH groups are most
likely in the trans or 1:6 positions.

In the postulate of essential electrical neutrality of atoms (Pauling, 1948)
the charge on a complex ion is considered to be localised mainly on the peripheral
hydrogen atoms of hexaquo or hexammine ions. If the postulate is extended
to planar tetrammine ions of platinum (II) we can consider the greater portion
of the charge of 2+ located on the twelve hydrogen atoms in [Pt(NH,),]++

108 LIVINGSTONE AND PLOWMAN.

leaving the platinum atom with only fractional charge. With the tetrapyridine
platinum (II) ion such a charge distribution is less favoured resulting in a
numerically greater positive charge on the platinum atom. On the basis of this
postulate it would appear that these structural differences are somehow
intrinsically associated with the lack of reaction of the [PtPy,]++ with H,O,.
Replacement of two pyridine molecules by ammonia sufficiently alters the
structure as to permit reaction with H,O,.

The above example of the influence of attached pyridine groups on the
reactions of a complex ion is probably one of a general type. Thus it has been
shown (Friend and Mellor, 1947) that when trans-dichlorotetrapyridine cobalt
({11) chloride reacts with pyridine, reduction occurs and tetrapyridine cobalt
(II) chloride is formed, chlorine being liberated during the reaction. This
suggests that a complex cobalt ion with more than four attached pyridine groups
is incompatible with the increased charge required on the ion.

Evidence that, when the coordination number of a metal is satisfied by
pyridine molecules, the lower oxidation state is favoured has been demonstrated
by Dwyer and Nyholm (1942). These authors succeeded in preparing hexa-
pyridine rhodium (II) compounds, halogeno pentapyridine rhodium (II) and
other compounds in the pyridine rhodium (II) series. Attempts to prepare
similar compounds of rhodium (II) containing ammonia and ethylenediamine
were unsuccessful, only rhodium (III) compounds being obtained (private
communication from Dr. F. P. J. Dwyer).

EXPERIMENTAL.
1:6 Dihydroxo 2:4 dipyridine diammine Platinum IV Chloride 1-5 Hydrate.

Trans- [Pt(NH,;).(C;H;N).,|Cl,.H,O0 (Drew, Pinkard, Wardlaw and Cox, 1932) (1:0 g.)
was treated with 30% H,O, (6 ml.) ; oxygen was evolved and the temperature of the solution
rose to about 35° C. On standing crystals were deposited in well formed cubes with some tetra-
gonal forms present. Further crystallisation was induced by the addition of acetone. Yield
1-1 g. Recrystallised from hot water, yield 0:9 g., in small colourless tetragonal crystals of the
1-5 hydrate moderately soluble in water (about 6—7 g./100 g. at 5° C.). Over P,O, the water
of crystallisation was lost and regained on exposure to air.

Found (on air dry material): Pt, 37-6%; Cl, 13-8%.

H,O, 4:8, 5-6. (Lost 7m vacuo over P,O;.)

[Pt(NH3;).(C;H;N).(OH),]Cl,.1-5 H,O requires Pt, 37:6%; Cl, 13-7%; H,O, 5-2%.

1:6 Dihydroxo-2 : 4 dipyridine diammine Platinum IV Bromide 2—Hydrate.

The corresponding chloride, recrystallised from water (1:0 g.) was dissolved in minimum
quantity of hot water (5 ml.) and 0-7 g. of potassium bromide added. The clear solution was
cooled in ice water, when the less soluble bromide crystallised. Yield 1-0 g. Recrystallised
from hot water (7-5 ml.) as small colourless tetragonal crystals with (100) faces. The 2-hydrate
obtained was only moderately soluble in cold water (about 2-8 g. per 100 g. water at 5—-10° C.).
Over P,O,, 2 molecules of H,O were lost but are taken up again on exposure to air.

Found (on air dry material): Pt, 31-7%; Br, 26-1%; H,O, 5-6%. (Loss in vacuo over
P,O;.)

[Pt(NH,).(C;H;N),(OH),|Br,.2H,O requires: Pt, 31:6%; Br, 25-:9%; H,O, 5:°8%.

1:6 Dihydroxo 2: 4 dipyridine diammine Platinum (IV) Iodide 0-5 Hydrate.

Prepared from the corresponding chloride and potassium iodide in same manner as described
for the bromide. 0-8 g. of the chloride yielded 0:7 g. of the iodide, recrystallised from water.
The iodide was only sparingly soluble in water (about 0-5 g./100 g. H,O at 5° C.), moderately
soluble in hot water, from which it crystallised on cooling in colourless crystals of the 0-5 hydrate
with tetragonal form showing (100) faces. The water of crystallisation was lost over P.O;
and regained on exposure to air.

STUDIES IN THE CHEMISTRY OF PLATINUM COMPLEXES. 109

Found (on air dry material): Pt, 28-5%; I, 37-1%; H,O, 1-2%. (Loss in vacuo over
P.O 5.)
[Pt(NH3).(C;H;N),(OH). ]T,.0°5H,O0 requires : Pt, 28°59 ; I, 37-2% ; H,O, 1-3%.

1:6 Dihydroxo 2:4 dipyridine diammine Platinum (IV) Nitrate 1—Hydrate.

In an analogous manner to the preparation of the bromide and iodide, 1-0 g. of the chloride
with ammonium nitrate yielded 0-6 g. of the nitrate 1-hydrate, recrystallised from water. It
was sparingly soluble in water (about 3-8 g. in 100 g. at 5°C.), readily soluble in hot water,
from which it crystallised in colourless tetragonal prisms. Water of crystallisation was lost on
drying over P,O,; and regained on exposure to air. When heated the compound decrepitated.

Found (on air dry material): Pt, 34-49%; H,O, 3-1%. (Loss in vacuo over P,O;.)

[Pt(NH,).(C;H;N,).(OH).](NO3)..H,O requires: Pt, 34-6%; H,O, 3-2%.

1:6 Dihydroxo 2: 4 dipyridine diammine Platinum (IV) Perchlorate.

As before from the corresponding chloride and perchloric acid, 1-0 g. of the chloride yielded
0-6 g. of the perchlorate recrystallised from hot water. The perchlorate was only moderately
soluble in hot water and sparingly soluble in cold water (about 0-5 g./100 g. H,O at 5° C.), from
which it crystallised as colourless monoclinic needles and prisms. The anhydrous crystals were
not deliquescent.

Found: Pt, 31-4%.

[Pt(NH3;).(C;H;N).(OH), ](ClO,), requires: Pt, 31-4%.

Reaction of [Pi(NH;).(C;H;N).(OH).|++ with (PtCl,)~ and [PtCl,)~.

[Pt(NH;).(C;H;N).(OH), |Cl,.1:5H,O (0°49 g.) in a few ml. of water added to K,PtCl,
(0-4 g.) dissolved in the minimum quantity of water, gave an instantaneous precipitate which
consisted of small thin, pink coloured plates, resembling graphite in form.

Yield: 0:6 g.

Found: Pt, 51-1%.

Pt(NH3,).(C;H;N).(OH).PtCl, requires: Pt, 51-46%.

Similarly a solution of [Pt(NH;).(C;H;N),(OH).|Cl, in water with a solution of H,PtCl,
yielded an insoluble chloroplatinate (IV), in thin bright orange needles, sparingly soluble in hot
water, moderately soluble in hot concentrated hydrochloric from which the chloride crystallises
on cooling.

Found: Pt, 47-0%.

[Pt(NH,).(C;H;N).(OH),.]PtCl, requires: Pt, 47-0%.

Trans-dipyridine diammine Platinum (I1) Bromide 1—Hydrate.

Trans [Pt(C;H,;N),.(NH3).|Cl,.H,O (Drew, Pinkard, Wardlaw and Cox, 1932) (0-7 g.) was
dissolved in hot water (4 ml.) and 0-6 g. potassium bromide added. The bromide was precipitated
immediately ; yield 0-7 g. Recrystallised from hot water (6 ml.) as colourless tetragonal needles
and prisms. The hydrate obtained was only moderately soluble in cold water (2-7 g. per 100 g.
water at 15° C.). Over P,O; one molecule of H,0O is lost.

Found (on air dry material): Pt, 34-59%; Br, 28-6%; H,O, 2-94%.
[Pt(NH3;).(C;H;N).]Br..H,O requires: Pt, 34-59%; Br, 28-3%; H,O, 3-18%.

Trans-dipyridine diammine Platinum II Iodide.

Prepared from the corresponding chloride and potassium iodide in the same manner as
used for the bromide. 0-4 g. chloride yielded 0-33 g. of iodide, recrystallized from water. The
iodide was sparingly soluble in water (0-5 g. per 100 g. of water at 15° C.), moderately soluble in
hot water (about 4 g. per 100 g. water at 100° C.). It crystallized as anhydrous colourless tetra-
gonal prisms.

Found: Pt, 30-4%; I, 39-2%.

[Pt(C;H;N).(NHs3).]JI, requires: Pt, 30-49%; I, 39:6%.

110 LIVINGSTONE AND PLOWMAN.

Trans-dipyridine diammine Platinum IT Nitrate.

The nitrate was prepared from the chloride in a similar manner to the bromide and iodide.
0-6 g. of the chloride treated with ammonium nitrated yielded 0-6 g. of the nitrate, which on
recrystallization from water yielded 0:22 g. The nitrate was only moderately soluble in cold
water (about 6 g. per 100 g. water at 15° C.) but very soluble in hot water (about 40—50 g. per
100 g. at 100° C.), from which it crystallized in anhydrous colourless tetragonal needles and
prisms.

Found: Pt, 38-3%.
[Pt(NH3).(C;H5N).](NO3). requires: Pt, 38-2%.

Trans-dipyridine diammine Platinum II Perchlorate.

This was prepared by the addition of perchloric acid in a solution of the corresponding
chloride. 0-8 g. of the chloride yielded 0-57 g. recrystallized from water. The perchlorate
was only moderately soluble in hot water (about 6 g. per 100 g. water at 100° C.) and sparingly
soluble (about 0-4 g. per 100 g. at 15° C.) in cold water, from which it crystallized as colourless
monoclinic needles. The anhydrous crystals were not deliquescent.

Found: Pt, 33-1%.
[Pt(NH,).(C;H;N),](ClO,), requires: Pt, 33-2%.

Trans-dipyridine diammine Platinum II Chloroplatinate (IV).

A solution of [Pt(NH3).(C;H;N),]Cl, in water treated with a solution of H,PtCl, yielded an
insoluble chloroplatinate (IV). The product consisted of orange cubes, similar in shape to
fluorite. It was found to be insoluble in cold water, very sparingly soluble in hot water, and
moderately soluble in hot concentrated hydrochloric acid, from which the chloride crystallizes
on cooling.

Found: Pt, 49-0%.
[Pt(NH,).(C;H;N),]PtCl, requires: Pt, 49-0%.

SUMMARY.

The preparation of some compounds of the 1: 6 dihydroxo 2: 4 dipyridine
diammine platinum (IV) ion has been described. The compounds were colourless
crystalline compounds only moderately soluble in water. Coloured, insoluble,
crystalline compounds were formed when the ion reacted with the chloro-
platinate (II) and chloroplatinate (IV) ions. Attempted oxidation of the
tetrapyridine platinum (II) ion with hydrogen peroxide, under similar conditions
was unsuccessful.

ACKNOWLEDGEMENT.

The authors’ thanks are due to Dr. F. P. J. Dwyer for helpful discussions
during the course of this work.

REFERENCES.
Drew, Pinkard, Wardlaw and Cox, 1932. J.C.S., 1004.
Dwyer, F. P. J., and Nyholm, R. S., 1942. Tuis JourNnaL, 76, 275.
Friend, J. A., and Mellor, D. P., 1947. Tuts Journat, 81, 154.
Pauling, L., 1948. J.C.S., 1461.

Chemistry Department,
Sydney Technical College.

COORDINATION COMPOUNDS OF COPPER.

Part II. COMPOUNDS DERIVED FROM COPPER (I) IODIDE.

By C. M. HARRIS.

Manuscript received, July 31, 1950. Read, September 6, 1950.

Copper (I) halides readily dissolve in boiling concentrated solutions of the
corresponding alkali or ammonium halides to form complex halogeno-cuprates (I).
Recently the author employed this reaction (Harris, 1948) to isolate tetrammine
and bis-ethylenediamine copper (II) dihalogeno-cuprates (I) of the general
formula [Cu™(A),][CutX,], (A=NH,; 2A—C,H,(NH,), and X=Br and I).
With the chloro-complexes the ammonia compound was obtained as the mono-
hydrate [Cu™(A),][Cu!Cl,],.H,O and the ethylenediamine compound possessed
the formula [Cu™(C,H,(NH,),).]Cu',Cl;.

It has since been found that copper (I) iodide dissolves in a boiling con-
centrated solution of alkali or ammonium bromide forming a colourless solution
presumably containing the bromo-iodo-cuprate (I) ion.

aqueous Br-
CulsBrra > s| Calbrl>
dilution

Dilution decomposes the complex ion causing copper (I) iodide to be pre-
cipitated. That this solution does contain such an ion and is not merely a
mixture of the dibromo- and diiodo-cuprate (I) ions is supported by its reactions
with ammonia and ethylenediamine described later.

Addition of a solution containing the bromo-iodo-cuprate (I) ion to a
solution containing tetrammine copper (II) or bis-ethylenediamine copper (II)
ions yields, on cooling, black tetrammine copper (II) bromo-iodo-cuprate (I)
[(Cut4(NH;),][CutIBr], (I) and purple bis-ethylenediamine copper (II) bromo-
iodo-cuprate (I) [Cu™(C,H,(NH,).),][CutIBr], (II) respectively.

Water, particularly on heating, decomposes these compounds, forming a
deep blue and

[Cu™(A),] [CuBr], V2" pou™A),]+++2Br--+2Cu'l
Y

purple solution of tetrammine and bis-ethylenediamine copper (II) bromide
respectively and a white precipitate of copper (I) iodide. Addition of acid
decomposes the tetrammine ion as well according to the reaction

[Cu™(A),] (Cul Br],-+4H+ > Cut++2Br-+4AH++2Cul
1

providing a means of determining the copper (II) ion in the presence of copper (I)
since the addition of iodide ions liberates iodine equivalent to the copper (II).

Treatment of compound II with boiling concentrated potassium iodide
solution causes it to dissolve and, on cooling, brown prisms of bis-ethylene-
diamine copper (II) diiodo-cuprate (I) (Harris, loc. cit.) are deposited.

112 C. M. HARRIS.

Compounds I and II cannot be a physical mixture of the corresponding
dibromo- and diiodo-complexes since the diiodo-complexes liberate free iodine
(Harris, loc. cit.) on treatment with acid and these compounds do not. However,
the structures of compounds I and II in the solid state need not necessarily
contain discrete [CulBr]~ ions. They could contain both [CuBr,]~ and [Cul,]~
ions.

The reaction of the bromo-iodo-cuprate (I) solution with a limited amount
of ammonium hydroxide yielded, on cooling, an amminated copper (I) iodide
derivative, (Cul),.NH, (III), as white plates. On reacting a solution containing
the diiodo-cuprate (I) ion in a similar manner with ammonium hydroxide an
entirely different compound, Cul.NH, (IV), was obtained as yellow prisms.
This reaction supports the postulation of the bromo-iodo-cuprate (I) ion in
solution indicating that such a solution is not merely a mixture of [Cul,]~
and [CuBr,]~ ions since if this was the case it should yield the same copper (I)
iodide derivative with ammonia as a solution containing only [Cul,]~ ions.

Ethylenediamine fails to react with the bromo-iodo-cuprate (I) solution
to yield a copper (I) iodide derivative. On shaking the mixture in the presence
of air, oxidation takes place and purple prisms of compound II are deposited.
The diiodo-cuprate (I) solution reacts immediately with ethylenediamine to
deposit a cream microcrystalline compound, (Cul),.C,H,(NH,), (V). The
filtrate deposited brown prisms of a compound which was most likely bis-
ethylenediamine copper (II) diiodo-cuprate (I) resulting from oxidation of
copper (I).

The structure of compound III is unknown. Silberrad (1905) reported the
preparation of a green compound Cu,I,.NH,;.4H,O. Since the preparation was
performed in the presence of air in a strongly ammoniacal solution and the water
was determined by difference it is quite possible that this compound was an
oxidised copper (I) derivative in keeping with its colour.

Compound IV can be formulated as either the monomer [H,;N—Cul]°,
the dimer [Cu'(NH,).|[Cu'l,], or the tetramer [H,N—CulI],°. The last structure
is similar to the triethyl arsine derivative [Et,As—CulI],°, whose structure was
established by Mann, Purdie and Wells (1936) to consist of a central tetrahedron
of copper atoms surrounded by tetrahedral groups of iodine atoms and triethyl
arsine molecules. This structure would seem the most likely.

A number of alternative structures are possible for compound V also. It
may be formulated as the complex copper (I) cuprate (I), [Cut(C,H,(NH,),][Cu'l,].
This, however, seems unlikely, since apart from a lack of symmetry the
[Cut(C,H,(NH,),)]+ ion would involve considerable strain in the carbon-nitrogen
bonds if it was to possess the linear configuration which is associated with two
covalent copper (I) complexes (Wells, 1945). This view is supported by the
fact that no compounds containing the ethylenediamine copper (I) ion are
known. Compound V can be satisfactorily formulated with a tetrahedral
structure similar to the arsine derivative mentioned previously save that the
intramolecular bridging that would be required of ethylenediamine for the
existence of discrete tetrahedral molecules in the structure is unlikely from a
consideration of bond lengths and angles. An infinite three-dimensional
structure, however, would be possible with intermolecular bridging of the
tetrahedral units by means of the ethylenediamine.

Compounds corresponding to III and IV have previously been postulated
by Biltz and Stollenwerk (1921). They investigated tensimetrically the forma- —
tion of ammoniates with copper (I) halides and in the case of the iodide obtained
evidence for the existence of the ammoniates Cul.nNH, where n=0-5, 1, 2
and 3.

COORDINATION COMPOUNDS OF COPPER. 113

During the course of this work an attempt was made to form the diammine
(ethylenediamine) copper (II) ion, [Cu(NH,).(C,.H,(NH,),)]++, in solution and
isolate it as its diiodo-cuprate (I) derivative. This was not realised and on
reacting one mole of a copper (II) salt with one mole of ethylenediamine and a
limited excess of ammonium hydroxide followed by metathesis with a potassium
iodo-cuprate (I) solution an earth green mixture of tetrammine and bis-ethylene-
diamine copper (II) diiodo-cuprates (I) was obtained. The tetrammine com-
pound in the mixture was decomposed to copper (I) iodide by heating the mixture
at 100° C. to constant weight. From the loss in weight was calculated the
percentage of tetrammine compound present. The residue was treated with
concentrated potassium iodide solution to remove copper (I) iodide and the
bis-ethylenediamine compound that remained was filtered off and identified.

Compounds I-—V inclusive reduce silver nitrate solution to the metal instantly
in the cold due to the copper (I) present in their molecules and also give a
simultaneous precipitate of silver halide. They are insoluble in the usual
organic solvents and unstable to water.

Copper (I) iodide also dissolves to a small extent in boiling concentrated
ammonium and alkali chloride solutions presumably forming the chloro-iodo-
cuprate (I) ion. Attempts to isolate this ion as its bis-ethylenediamine copper
(II) derivative were unsuccessful due to the large amounts of ammonium or
alkali chloride that crystallised out on cooling the reaction mixture.

EXPERIMENTAL.
(1) Tetrammine Copper (II) Bromo-iodo-cuprate (I).

To diammine copper (II) acetate (1-6 g., 0-0074 g. mole (Horn, 1908)) dissolved in a solution
of ammonium hydroxide (1:3 ml. of 15 N) in water (25 ml.) was added acetic acid (0:3 ml. of
17N). After the addition of ammonium bromide (5-0 g.) the solution was heated to 80-85° C.
A boiling solution of copper (I) iodide (2-8 g., 0-015 g. mole) and ammonium bromide (30 g.)
in water (35 ml.) was added in a thin stream with constant stirring and the stirring continued
while the solution was cooled to 25°C. After immediate filtration the black microcrystals were
washed with 90% alcohol, followed by dry ether. The filtration and washing must be as rapid
as possible to avoid oxidation. Yield 2:4 g. (42%).

Found: Cu (total), 28-2: Cut+, 9-31; NHg;, 10:1%. 0-497 and 0-502 g. complex gave
0-623 and 0-631 g. of AgBr+AglI.

[Cu (NH,),][Cu'IBr], requires Cu (total), 28-36: Cut+, 9-45; NH, 10-13%. 0-497 and
0-502 g. complex give 0-625 and 0-631 g. of AgBr+Agl.

The compound is readily oxidised in the presence of moist air, assuming a greenish colour.
Water decomposes it instantly in the cold, according to the reaction given previously. It is
unaffected by alcohol, acetone and the usual organic solvents. A cold solution of silver nitrate
is instantly reduced by the compound to metallic silver with simultaneous precipitation of silver
halides.

(II) Bis-ethylenediamine Copper (II) Bromo-iodo-cuprate (I).

To a solution of bis-ethylene diamine copper (II) bromide monohydrate (2:5 g., 0-0069 g.
mole (Johnson and Bryant, 1934)) dissolved in water (30 ml.) was added ammonium bromide
(5-0 g.), and the solution was heated to 85°C. A boiling solution of copper (I) iodide (2-6 g.,
0-015 g. mole) and ammonium bromide (30 g.) in water (35 ml.) was added with constant stirring
and the stirring continued while the solution was cooled to 25°C. After filtration the compound
was washed with methyl alcohol followed by dry ether. Yield 4-6 g. (92%).

Found : Cu (total), 26-4; Cut+, 8-73%. 0-496 g. complex gave 0-474 g. AgBr+AglI.

[Cu™(C,H,(NH,),).][Cu'IBr], requires Cu (total), 26-3; Cut+, 8-77%. 0-496 g. complex
gives 0:479 g. AgBr-+AglI.

114 C. M. HARRIS.

The compound crystallises as purple prisms stable in air. Water decomposes the compound
more slowly than the corresponding tetrammine but completely on boiling in accordance with
the equation given previously. It reduces silver nitrate solution instantly in the cold to silver
with simultaneous precipitation of silver halides. Dilute acetic and sulphuric acid decomposes
the compound, according to the equation given previously to copper (I) iodide. (Found: Cu,
66:0; calculated: Cu, 66:6%.) The compound dissolves in boiling 50% potassium iodide
solution, from which brown prisms of bis-ethylenediamine copper (II) diiodo-cuprate (I) (loc. cit.)
is deposited on cooling. (Found: Cu (total), 23-4; calculated: Cu (total), 23-3%.) The
compound is unaffected by alcohol, acetone and the usual organic solvents.

(III) Monammine Bis-(Copper’ (I) Iodide).

To copper (I) iodide (2-0 g.) dissolved in a boiling solution of potassium bromide (35 g.)
in water (50 ml.) and cooled to 85° C. was added ammonium hydroxide (0:70 ml. of 15 N) with
vigorous stirring. The stirring was continued while the solution was rapidly cooled to 25° C.
After immediate filtration the compound was washed with 90% alcohol followed by dry ether.
The filtration and washing must be as rapid as possible to avoid oxidation. The ether was
removed under vacuum and the compound sealed from the atmosphere. Yield 0-8 g. (88%).

Found: Cu, 31:4; NH, 4:4; I, 63:8%. (Cu'l),.NH, requires Cu, 31:9; NH,, 4:3;
I, 63-8%.

The compound crystallises as lustrous pearly plates and is readily oxidised in the atmosphere
assuming a green colour. It is decomposed immediately in the cold by water, with the appearance
of the blue tetrammine copper (II) colour due to oxidation. A cold solution of silver nitrate is
instantly reduced by the compound to metallic silver, with simultaneous precipitation of silver
iodide. On heating at 100° C. to constant weight the compound (0-202 g.) loses its ammonia,
and copper (I) iodide (0-192 g.) (calc. 0-193 g.) remains. It is insoluble in organic solvents.

(IV) Monammine Copper (I) Iodide.

To copper (I) iodide (7-5 g.) dissolved in a boiling solution of potassium iodide (45 g.) in
water (30 ml.) and cooled to 75°C. was added ammonium hydroxide (2:5 ml. of 15 N) with
vigorous stirring. The stirring was continued while the solution was rapidly cooled to 25° C.
After immediate filtration the compound was washed with methyl] alcohol followed by dry ether.
The ether was removed and the compound sealed from the atmosphere. Yield 5-0 g. (61%).

Hound): (Cu, 303 >. NE 8-25 7) Gla.

Cu'I.NH, requires Cu, 30-6; NH,, 8-2; I, 61-2%.

The compound is decomposed by water similarly to the previous compound and gives the
same reaction with silver nitrate. It crystallises as yellow prisms, readily oxidised by the
atmosphere, when it assumes a green colour.

(V) Ethylenediamine Bis-(Copper(L) Iodide).

To copper (I) iodide (2:9 g., 0-015 g. mole) dissolved in a boiling solution of potassium
iodide (22 g.) in water (15 ml.) and cooled to 55° C. was added a solution of ethylenediamine
(0:40 ml. of anhydrous, 0-006 g. mole) and potassium iodide (5-0 g.) in water (5 ml.) at 55° C.
with stirring. After immediate filtration the compound was washed with methyl alcohol followed
by dry ether. Yield 2-6 g. (98%).

Round::) Cu; 28-7; (B)/ 57-69:

(Cu'l)..C,H,(NH,), requires Cu, 28-8; I, 57-5%.

The compound is insoluble in organic solvents and is stable in air. It crystallises as cream
micro-prisms and reduces silver nitrate in the cold to metallic silver with simultaneous pre-
cipitation of silver iodide. It is insoluble in cold water but decomposed readily on warming,
oxidation to bis-ethylenediamine copper (ITI) iodide taking place (see Morgan and Burstal, 1926).
The filtrate from the above preparation deposited a small amount of brown prisms which were
probably bis-ethylenediamine copper (II) diiodo-cuprate (I), resulting from partial oxidation
of some of the copper (1).

COORDINATION COMPOUNDS OF COPPER. 115

Reaction of Ethylenediamine with a Solution of the Bromo-iodo-cuprate (I) Ion.

To copper (I) iodide (1-0 g.) dissolved in a boiling solution of ammonium bromide (20.g.)
in water (20 ml.) and cooled to 60° C. was added a solution of ethylenediamine (0:15 ml. of
anhydrous) in water (5 ml.) containing ammonium bromide (5:0 g.) at 55°C. No precipitate
appeared on cooling to 30° C. but on shaking for 10-15 minutes purple prisms of compound II
were deposited. Yield 0:5 g. ,

Found: Cu (total), 26-4.
Calculated : 26-3%.

Attempted Preparation of Diammine (Hthylenediamine) Copper (II) Dwodo-cuprate (1).

To a solution of anhydrous copper (II) chloride (0-85 g., 0:0063 g. mole) in water (15 ml.)
was added ethylenediamine (0-62 ml. of 69%, 0-0071 g. mole) followed by ammonium hydroxide
(1:0 ml. of 15N). After the addition of potassium iodide (2-0 g.) the stirred solution was heated.
to 75° C. and to it was added in a fine stream a boiling solution of copper (I) iodide (2-4 g., 0-013 g.
mole) and potassium iodide (15-0 g.) in water (10 ml.). The stirring was continued and the
solution cooled to 25°C. After filtration the compound was washed with 90% alcohol followed
by ether. Yield 4-4 g.

Found: Cu, 23:8%.

Calculated for a 1:2 mixture of [Cu™(NH,),][Cul,], and [Cu™(C,H,(NH,).).][Cu'l,], :
Cu,- 238%.

The mixture, which was micro-crystalline, possessed an earthy colour with a green reflex.
Brown and dark green crystals could be distinguished under the microscope. The mixture
(0-511 g.) was heated to 100° C. to constant weight (0-468 g.). From the loss in weight (0-043 g.)
the amount of tetrammine copper (II) diiodo cuprate (I) (0-173 g.) present in the mixture was
calculated.

The residue was boiled with 50% potassium iodide solution (10 ml.) and on cooling to
30-40° C. the brown bis-ethylenediamine copper (II) diiodo-cuprate (I) was filtered off and
washed with 50% potassium iodide solution (5 ml.) followed by methyl alcohol and ether. Yield
0-29 g.

Found: Cu, 23:3%.
Calculated : 23-3%.

SUMMARY.

Copper (I) iodide dissolves in concentrated ammonium or _ alkali
bromide solution to form the bromo-iodo-cuprate (I) ion. Double decom-
position of solutions containing this ion with solutions of tetrammine and
bis-ethylenediamine copper (II) ions yields the corresponding tetrammine and
bis-ethylenediamine copper (II) bromo-iodo-cuprates (I) of general formula
[Cut%(A),][CuIBr],. Solutions containing the bromo-iodo-cuprate (1) ion give
with ammonium hydroxide a compound of empirical formula (Cul),.NH,,
whose structure is unknown. With ethylenediamine, however, partial oxidation
takes place and bis-ethylenediamine copper (II) bromo-iodo-cuprate (I) is
obtained. Similarly solutions of the diiodo cuprate (I) ion yields with ammonia
and ethylenediamine compounds of empirical formula Cul.NH, and
(Cul),.C,H,(NH,). respectively. Possible structures for these compounds are
suggested. Attempts to prepare diamine (ethylenediamine) copper (II) diiodo-
cuprate (I) were unsuccessful.

ACKNOWLEDGEMENTS.

The author wishes to thank Dr. F. P. Dwyer and Mr. R. A. Plowman for
their helpful advice and discussion.

116 Cc. M. HARRIS.

BIBLIOGRAPHY.
Biltz, W., and Stollenwerk, W., 1921. Z. anorg. Chem., 119, 97.
Harris, C. M., 1948. THis JOURNAL, 82, 218-224.
Horn, D. W., 1908. Amer. Chem. J., 39, 184.
Johnson, C. H., and Bryant, S. A., 1934. J. Chem. Soc., 1783.
Mann, F. G., Purdie, D., and Wells, A. F., 1936. J. Chem. Soc., 1503.
Morgan, G. T., and Burstall, F. H., 1926. J. Chem. Soc., 2022.
Silberrad, O., 1905. J. Chem. Soc., 87, 67.
Wells, A. F., 1945. ‘“* Structural Inorganic Chemistry.’”’ Oxford University Press, pp. 504-506.

Chemistry Department,
Sydney Technical College,
Australia.

THE CHEMISTRY OF OSMIUM.

Part VIL. THE BROMO AND CHLORO PENTAMMINE OSMIUM III SERIES.

By BE. BP. DWYER, D.Se:;
and J. W. HOGARTH, A.S.T.C.

Manuscript reecived, September 13, 1950. Read, October 4, 1950.

With the exception of the osmyl ammines OsO,(NH,),X,. (W. Gibbs, 1881),
no complex compounds of osmium containing ammonia, pyridine or ethylene-
diamine are known.

The curious substance potassium osmiamate K(OsO,N), a compound of
octavalent osmium has been prepared by treatment of osmium tetroxide with
ammonia and aqueous potassium hydroxide (Fritsche and Struve, 1847;
L. Brizard, 1900). It reacts with hydrochloric acid with the liberation of
chlorine and degradation to the sexavalent state to form K,(OsCI;N), which is
reducible with stannous chloride to potassium amino pentachloro osmate IV
K,(Os.NH,Cl;) (Werner and Dinklage, 1901).

Attempts to prepare osmium ammines by reaction of potassium hexachloro
or hexabromo osmate IV with aqueous ammonia led to hydrolysis, with the
separation, ultimately, of a black precipitate of (presumably) osmium dioxide.
Similarly, solutions of potassium hexachloro or hexabromo osmate III (Dwyer,
McKenzie and Nyholm, 1945 ; Dwyer, Humpoletz and Nyholm, 1946) darkened
in colour and also, ultimately, a black precipitate resulted. The molecules of
arsine in tris-dimethylphenyl arsine tri-bromo-osmium could not be replaced
by boiling the compound with alcoholic ammonia. Instead, partial replacement
of the bromine atoms by hydroxyl occurred (unpublished observations of
Barclay and Dwyer, 1948). By analogy with platinum, palladium, ruthenium
and iridium it appeared probable that direct ammination could not be achieved
in the tetravalent state, and consequently the osmium must be reduced to the
strongly reducing trivalent or bivalent states and then treated with ammonia
in the absence of both oxygen and water. It was thought possible that these
conditions could be realised simultaneously by heating a tetravalent osmium
compound in dry ammonia gas. If necessary, preheating of the gas could be
arranged to provide various pressures of hydrogen by thermal dissociation of
the ammonia. The initial experiments with potassium hexachloro and hexa-
bromosmate IV were not successful, either no reaction occurring or complete
reduction to osmium metal. However, with ammonium hexabromosmate IV,
a sublimate of ammonium bromide was observed to form at 260°. When
ammonia gaS was passed over the compound in a small porcelain boat at 280°
a further sublimate appeared with change of colour of the complex salt from dark
red to brownish, and at 300° more ammonium bromide appeared and a silvery
deposit of osmium remained.

The following changes appeared to occur :
(NH,),OsBr, > OsBr, +2NH,Br
OsBr,+NH,;-+H, — [Os(NH,);Br] Br, +NH,Br

[Os(NH,),Br]Br, "20s +NH,Br+NH,

K

118 DWYER AND HOGARTH.

The yields of the osmium ammine, however, were poor and the reaction difficult
to control. The initial experiments carried out in an autoclave with one or two
atmospheres pressure of ammonia were not successful. Eventually it was
found necessary to subject the ammonium bromosmate to 7 or 8 atmospheres
pressure for a short time and then reduce the pressure to 2 atmospheres. When
then heated at 285° for 14 to 2 hours a quantitative conversion to almost white
bromo pentammine osmium III bromide was found to have occurred. Although
much of the gas must have been consumed in the reaction, at the end, the
ammonia pressure was found to have barely altered. When the initial high
pressure was applied to the ammonium bromosmate it was found to have
dissolved to a red solution in liquid ammonia. With subsequent lowering of
the pressure the liquid boiled away but must have left a loose addition compound
(NH,),OsBr,.x.NH;, which is apparently transformed to the ammine. This
will be investigated further. Bromopentammine osmium JIII bromide
(Os(NH,);)Brsz, obtained as a light fawn coloured micro-crystalline powder by
precipitation of the aqueous solution, had powerful reducing properties, reacting
with silver nitrate to form a precipitate of the silver halide, and on warming
reducing the excess to metallic silver. With bromine water, oxidation and
precipitation of an orange osmium IV ammine resulted. These compounds will
be discussed in subsequent papers.

The iodide, [Os(NH,) Br] I, the nitrate [Os(NH,),Br].(NO3),, and the

perchlorate [Os(N H;),Br](ClO,), were obtained as light brown or fawn micro-
- erystalline powders by double decomposition. The reaction with silver chloride
gave a mixture of the hydroxy pentammine chloride, [Os(NH;);OH]Cl,, and
the bromopentammine chloride, [Os(NH;);Br]Cl,. The former compound was
transformed to chloropentammine osmium III chloride by treatment with
hydrochloric acid.

Morgan and Burstall (1936) noted a similar case of transformation of
chloro-hydroxy-tetrammine ruthenium III chloride to dichlorotetrammine
ruthenium III chloride.

Under 7-8 atmospheres pressure of ammonia gas, bromo-pentammine
osmium III bromide was found to dissolve to a greenish solution. Evaporation
of the liquid ammonia left a green substance, which appeared to be a mixture of
the original compound and the hexammine [Os(NH;),]Br,. The reaction is
being investigated.

Chloro pentammine osmium III chloride was obtained from ammonium
chlorosmate in the same way as the bromo compound. The almost white
microcrystalline powder had an acid reaction to litmus and partly replaced the
covalent halogen atom by hydroxyl on heating the aqueous solution.

[Os(NH,),CIJCl,-++-H,O > [Os(NH,),OH]Cl, + HCl.

The lability of the chlorine atom, due to its ionic character, made the preparation
of derivatives such as (Os(NHs);Cl)I, impossible. The chloro compound was
also more sensitive to atmospheric oxidation than the bromo compound. Speci-
mens of the solid after 10-14 days exposure to the atmosphere had little reducing
action on silver nitrate, and appeared to be almost completely transformed to
[Os(NH,),Cl]Cl,.OH.

During the preparation of the chloro pentammine compound, it was found
that, provided small samples of 0-1—0-3 g. of ammonium hexachlorosmate were
used, complete transformation to the white pentammine occurred—but with
larger amounts of the hexachlorosmate (0-5-1-0 g.) a mixture of white and |
yellow powders was obtained. The top crust and the edges of the reaction
product were usually white, whilst the centre was brownish yellow. ‘The yellow
product was insoluble in 0-5 N hydrochloric acid but soluble in water. From

CHEMISTRY OF OSMIUM. 119

the brownish aqueous solution it was precipitated easily with hydrochloric
acid and separated from the chloropentammine compound.

The formula of the anhydrous compound was found to be Os,(NH;),NHCI,,
I, or Os(NH;),NCI;, II. Three of the chlorine atoms were ionised, and on
treatment with cold sodium iodide, the substance [Os,(NH;),NHCI,]I, or
[Os(NH;),NCI,]I, was obtained. The yellow substance had no reducing action
on aqueous silver nitrate and thus presumably was a compound of Osmium IV.
On heating in the autoclave with ammonia gas at 300°C., it was partially
transformed to chloropentammine osmium III chloride.

ii i NH, NH,
NH; NH5 NH; H,
/
CIOs -NH—-05—CI Gi; CIOs _N=04—Cr Cl,
iH] | SNH, Ni, Hs
NH; NH, NH, NH
I 1

In the structural formula I, one Os atom is formally trivalent and the other
quadrivalent. However, both atoms would probably have the same valence
by reason of a resonance phenomenon. ‘This should lead to an intense colour.
The pale colour, especially of the solutions, is a possible objection to I. In
the structure II both atoms are quadrivalent, and this formula is to be preferred
by analogy with the nitrilo complexes K,[OsN.Cl;]. Owing to the difficulty of
carrying out hydrogen analyses in the presence of osmium, it is not possible to
distinguish analytically between I and If. The substance in aqueous solution
reacted acid, with darkening of colour on standing, due probably to replacement
of the covalent Cl atoms by hydroxyl.

Titration with silver nitrate potentiometrically also confirmed that three
chlorine atoms were ionised. The titration value, however, was a little high,
indicating that some of the covalent chlorine atoms were replaced. The con-
ductivity assuming formula IT, for 1 x10-3M and 2 x 10-4M solutions was found.
to be 499 mhos.

EXPERIMENTAL.

Bromopentammine Osmium ITI Bromide Monohydrate.

Ammonium bromosmate IV in two small platinum boats was suspended in the centre of a
still autoclave fitted with a steel needle valve, and pressure gauge. A steel tube led through the
head of the autoclave to near the bottom so that the ammonia gas could be used to sweep out
the air. The air was displaced at approximately 0-5 at. of NH, gas by allowing the head of the
autoclave to lift, then the head was screwed down and the full pressure of an ammonia cylinder
(90-115 Ib./sq. in.) applied for 20-30 mins. With excessive time of exposure to high pressure
the boats tended to fill with liquid ammonia and overflow. The pressure was then reduced to
2 atmospheres and the autoclave heated in an oil bath with the external temperature adjusted
to give 285°C. at the platinum boats. After 14-2 hours the autoclave was removed from the
oil bath and allowed to cool. The white powder left in the boats was ground up finely and
extracted with warm dilute hydrobromic acid (approx. 0-1 .N). The pale yellow solution was
filtered from a small amount of dark substance, and ammonium bromide added. The pentammine
precipitated as a pale fawn powder, and the precipitation was completed by cooling in ice. After
washing with 90% alcohol the substance was dried over calcium chloride. On heating, the

‘compound darkened considerably, leaving ultimately a deposit of osmium. It was insoluble in
alcohol and acetone, but easily soluble in warm water. The density was found to be 2:49. The

120 DWYER AND HOGARTH.

equivalent conductivities of 1 x 10-3? and 2 x 10-4 M solutions were found to be 248 and 229 mhos.,
showing the compound to be a ternary electrolyte. On treatment with a slight excess of silver
nitrate, followed by potentiometric titration with potassium chloride, almost all of the bromine
appeared to have precipitated.

Found: Br=42-1%.

Calculated: Br=30-02%. Total Br=45-03%.

The osmium analyses were carried out in a micro porcelain boat by heating 2-8 mg. of the
substance in oxygen-free ammonia gas up to a temperature of 460° C., and then weighing the
osmium metal. This procedure was not suitable for the perchlorate or nitrate for which a colori-
metric method (Dwyer and Gibson, 1950) was used.

Found: Os=35-6; N=13:-0; Br=44-93%.

Calculated for [Os(NH;),Br]Br,.1H,O : Os=35-68; N=13-11; Br=45-03%.

Bromopentammine Osmium III Iodide.

The bromopentammine bromide, in warm water, was treated with a little potassium iodide.
The substance crystallised as sparingly soluble dark yellow micro prisms on scratching the sides
of the vessel. ‘The compound was washed with alcohol and dried at 100° C.

Found: Os=31-1%.

Calculated for [Os(NH;);Br]I,: Os=31-23%.

Bromopentammine Osmium III Nitrate.

The bromopentammine bromide in warm water was treated with solid ammonium nitrate
when the sparingly soluble nitrate of the complex crystallised in brownish yellow prisms. It was
washed with 80% alcohol and dried at 100°. The substance decomposed at approximately
200° C. with a shght explosion and a black cloud of osmium metal.

Found: Os=39-3%.

Calculated for [Os(NH;),Br](NO,),: Os=39-7%.

Bromopentammine Osmium III Perchlorate Monohydrate.

This substance from sodium perchlorate and the bromopentammine bromide gave a brownish
yellow sparingly soluble micro-crystalline powder. It exploded on heating.

Found: Os=33:-27%.

Calculated for [Os(NH3;);Br ](ClO,),.H,0 : Os=33-24%.

Bromopentammine Osmium III Hexabromosmate IV Dihydrate.

A solution of potassium hexabromosmate IV in dilute hydrobromic acid was added to an
aqueous solution of the bromo pentammine bromide. The dark reddish brown microcrystalline
precipitate was washed with alcohol and dried at 100° C.

Found: Os=35-62%.

Calculated for [Os(NH3),Br](OsBr,.).2H,O : Os=35-86%.

Bromopentammine Osmium III Hexachloroplatinate IV.

A solution of chloroplatinic acid was added to an aqueous solution of the bromopentammine
bromide. The resulting orange yellow precipitate was washed with alcohol.

Found: Os+Pt: 46-15%.

Calculated for [Os(NH,),Br][PtCl, ]|.2H,O : 46-7%.

The Action of Silver Chloride in Bromopentammine Osmium III Bromide.

A saturated solution of the bromopentammine bromide at 35°C. was shaken with silver
chloride for 5 minutes and then filtered. The pale yellow filtrate was precipitated with alcohol
to yield a white colloidal suspension which was coagulated with concentrated hydrochloric acid.
(This also served to hold traces of silver chloride in solution as the acid H.AgCl,. Otherwise
these traces were precipitated as, presumably, the pentammine osmium salt of the acid.) The

CHEMISTRY OF OSMIUM. 121

pale fawn substance was washed with 90% alcohol and dried at 100°C It was very soluble in
water and reduced silver nitrate to the metal on boiling. Found: Os=46-2%. The bromo-
pentammine osmium chloride requires Os=44-:6%. Another specimen prepared by longer
shaking with silver chloride and allowed to stand overnight in the alcohol hydrochloric acid
mixture gave Os=48-1. The chloropentammine osmium III chloride hemihydrate requires
Os=48-68%. Tests on this sample for bromine gave negative results. It was not possible to
isolate the initial compound formed in the reaction between silver chloride and the bromo-
pentammine bromide, since it could not be induced to coagulate without adding some con-
taminating ion. Specimens allowed to coagulate by long standing had undergone oxidation
since they no longer reduced silver nitrate.

Chloropentammine Osmium III Chloride Hemihydrate.

Ammonium hexachlorosmate IV was heated in small platinum boats in ammonia gas as
for the bromo compound (vide supra), except that the temperature was raised to 290-295°. At
the end of the reaction the product consisted of a mixture of almost white material with a yellowish
incrustation. With small quantities of ammonium hexachlorosmate (0-1-0-2 g.) the yellow
material was almost absent. The mixture was ground up finely in a mortar and extracted three
times with small amounts (10-15 c.c.) of 0-5 N HCl and filtered. The dark coloured precipitate
was reserved (see later) and the pale yellow filtrate precipitated by the addition of alcohol.
The resulting very pale fawn coloured powder was washed with alcohol, redissolved in the
minimum of 0-5 N hydrochloric acid and traces of a yellow compound filtered off. It was then
reprecipitated with alcohol and dried at 100° C. The substance was much more soluble in water
than the bromo compound, the solution was acid (pH 4:5) due to partial replacement of the
covalent halogen by hydroxyl. On reprecipitation from water with alcohol : found Cl=19-95% ;
Os= 53-18%. Calculated for [Os(NH;);OHJCl,: Cl=19-54; Os=54-9%.

The chloropentammine chloride reduced warm silver nitrate to the metal rapidly but
specimens of the solid after two or three weeks failed in this reaction and hence must have under-
gone oxidation.

Found: Os=49-6, 49-04, 48-8, 48-6, 48-5, 48-8 (on different preparations); N=18-11;
Cl — 27-0,

Calculated for [Os(NH,),C1JCl,.4H,O : Os=48:67; Cl=27-25; N=17-91%.

Dichloro-octammine-u-nitrilo-diosmium Trichloride.

The residue from the extraction of the chloropentammine osmium IIT chloride with 0-5 N
hydrochloric acid was extracted with water at 40°C. The resulting brownish orange solution
was treated with hydrochloric acid, when it lost its brown colour becoming orange yellow and
depositing a brownish yellow crystalline precipitate. This was filtered, washed with hydro-
chlorie acid and alcohol and dried at 100°. The substance was found to be easily soluble in
cold water, becoming brownish on heating. The solution, which had an acid reaction, pre-
cipitated the solid on the addition of hydrochloric acid or chloride ion. It gave a precipitate
of silver halide on treatment with silver nitrate, but caused no reduction to the metal on boiling.

On standing over P,O, or heating at 130° C., two molecules of water were lost without visible
change in colour or form.

Found, undried substance: Os=50°5; N=16-:9; Cl=23-78%; H,O=4-2%.

Calculated for Os,.(NH,),N.Cl;.2H,O : Os=51:1%; N=16:93; Cl=23-85; H,O=4:-8.

Found, anhydrous substance: Os=53-1; N=17-5; Cl=25-05; Cl (ionised)=16-8%.

Calculated for Os,(NH,),N.Cl,: Os=53-7; N=17-79; Cl=25-07; Cl (ionised)=—15:-04.

Dichloro-octammine--nitrilo-diosmium Tri-iodide.

The chloro compound above, in water, was treated with a few drops of hydrochloric acid to
suppress hydrolysis and sodium iodide added. The resulting yellow brown precipitate was
filtered off immediately, washed with alcohol and dried at 100°.

Found: Os=38-6; N=12-9%. -

Calculated for [Os.(NH,),N.Cl,]I,: Os=38:8; N=12-81.

122 DWYER AND HOGARTH.

Di-iodo-Octammine-t-diosmium T'richloride.

The chloro compound in hot water containing hydrochloric acid was heated at 80° with
excess sodium iodide and cooled. The brownish yellow microcrystalline precipitate was washed
with hydrochloric acid and alcohol.

Found: Os=43:4; N=14-17%.
Calculated for [Os,(NH;),NI,|Cl,: Os=42:60; N=14-12%.

SUMMARY.

Ammonium hexabromo and hexachlorosmate IV reacted with ammonia
gas under pressure at 280-300° C. with the formation of bromopentammine
osmium III bromide, and chloropentammine osmium III chloride. These
compounds were pale fawn solids soluble in water to pale yellow solutions, which
reduced silver nitrate solution to the metal on boiling. The covalently attached
halogens were labile, especially in the chloro compound, whose aqueous solution
had an acid reaction due to the replacement of chlorine by hydroxyl.

The curious compound Os,(NH3),N.Cl;.2H,O formulated dichloro-
octammine-y-nitrilo-diosmium trichloride was formed during the reaction of
ammonium hexachlorosmate with ammonia.

ACKNOWLEDGEMENTS.

The authors are indebted to Miss E. C. Gyarfas and Mr. N. A. Gibson for
assistance with some of the analyses; to Richard Wildridge Pty. Ltd. for the
loan of the ammonia pressure gauge; and to Messrs. Patterson and Spooner
for some of the apparatus.

REFERENCES.

Brizard, L., 1900. Ann. chim. Phys., 21, 3738.

Dwyer, F. P., and Gibson, N. A., 1950. The Analyst, in press.

Dwyer, F. P., McKenzie, H. A., and Nyholm, R. S., 1945. Tuis JouRNAL, 79, 183.
Dwyer, F. P., Humpoletz, J. E., and Nyholm, R. 8., 1946. Jbed., 80, 242.

Fritsche, J., and Struve, H., 1847. J. prakt. Chem., 41, 97.

Gibbs, W., 1881. J. Am. Chem. Soc., 3, 238.

Morgan, G. T., and Burstall, F. H., 1936. J. Chem. Soc., 41.

Werner, A., and Dinklage, K., 1901. Ber., 34, 3702.

Department of Chemistry,
University of Sydney, N.S.W.

THE CHEMISTRY OF IRIDIUM.
Part V. THE OXIDATION OF IRIDIUM III SALT SOLUTIONS.

By F. P. DWYER, D.Sc.,
and (Miss) E. C. GYARFAS, M.Sc.

Manuscript received, September 15, 1950. Read, October 4, 1950,

This study has been undertaken as a preliminary to the investigation of
the fluorides of iridium, in which the bond Ir-F may be expected to be pre-
dominantly ionic. The nitrates, perchlorates and, to a lesser extent, the
sulphates, can be expected to be ionic and hence likely to give useful information
concerning the fluorides.

Little is known of the simple salts of tetravalent iridium such as the nitrate,
sulphate and perchlorate, attention having been confined almost exclusively
- to the covalent chloride and bromide, and to various complex compounds, of
which the hexahalogenates R,IrCl, are the best defined. It has been noted
very long ago (Le de Boisbaudron, 1883 ; Marino, 1904) that the yellow solutions
of iridium III sulphate, Ir,(SO,);, became green or blue on standing in air, and
the colour change has been ascribed to the existence of varying amounts of salts
in higher oxidation states. Similarly, the nitrate, prepared by dissolution of
iridium IIT hydroxide in dilute nitric acid, can be obtained as a yellow solution,
which rapidly becomes blue on standing or warming. Although the substance
responsible for the blue colour has not been isolated it has been generally inferred
that a higher oxidation state than trivalent iridium is present.

In the present work solutions of iridium III hydroxide in sulphuric, per-
chloriec and nitric acids have been potentiometrically titrated with a variety of
oxidising agents, or oxidised anodically and potentiometrically reduced. All
of the iridium III salt solutions were oxidisable by bromine water with the
development of a blue colour, discharged by the addition of ferrous sulphate.
After such oxidation and reduction, however, the solutions became extremely
sensitive to oxidation by air and became blue very rapidly. It could be shown
that the enhanced oxidisability was not due to catalysis by iron salts or bromide
ion, and hence must be ascribed to a new ionic species in the iridium III solutions.
As the acid concentration of the solutions was reduced, it was found that oxida-
tion became easier, whilst, on the other hand, if sufficient acid was present,
bromine failed to effect any oxidation. These observations suggested that the
easily oxidised ion is not the simple hydrated Ir+++ but probably an oxy or
hydroxy ion of the type IrOt or Ir(OH)++. This ion is formed directly by the
reduction of the blue oxidised solutions, or may occur by hydrolysis :

Jf Ir++++H,0 — IrO*++2H+
\ Ir++++H,0 — Ir(OH)++-+H+

The existence of ions of this type in solution is consistent with the occurrence of
basic salts such as Ir(OH)SO,, and the amphoteric character of the oxide,
Tr,O,

When titrated potentiometrically with cerium IV salts or potassium per-
manganate the resulting curves showed an initial very sharp rise in the potential

124 DWYER AND GYARFAS.

due to the oxidation of Ir"! to Ir’, followed by the usual flattening and a sharp
potential increase at approximately 1-27 volts. This signalised the end of the
reaction [rUl_+Tr!lV +e’, and the commencement of the reaction Ir!V—-IrV!+2e’.
The latter reaction was incomplete at the maximum potential available from
the oxidising agent.

However, if the oxidised solutions were reduced with ferrous sulphate quite
different curves were obtained, showing three potential breaks. The additional

0 5 ce.N/100 CelY 10 15
—_—_>
Se So al

15 10 cc.N/100 Fe 5 0
Fig. 1.

end point occurring at approximately 1-1 volts, as will be shown later, is not due
to reduction of Ir’! to the unknown valency state Ir’, but to an unstable form
of Ir'V, which arises only by reduction of Ir’! and cannot be obtained by oxidation
of IrH! (Curves I, II).

The anodic oxidation of iridium III salts in nitric, perchloric and sulphuric
acids gave progressively green, blue, violet, brown violet and finally brown
solutions. The last stage, which involved the formation of an iridium VI
compound, could be reached only in acid concentrations above 3 normal, with
high current densities on a clean polished platinum anode. In solutions of

THE CHEMISTRY OF IRIDIUM. 125

lower acidity the anode became covered with a brownish blue deposit ot (pre-
sumably) iridium trioxide and the oxidation of the solution stopped at the
violet stage of iridium IV, which was also the ultimate oxidation that could
be achieved with low current densities, or roughened electrodes.

It is significant that the brownish deposit on the anode was not formed
in strongly acid solution, and it is suggested that, in the presence of sufficient
acid, the oxide IrO, may react to form salts of the cation IrO,**

IrO, +2HCIO, -> IrO,.(C1O,),+H,0.

TITRATED RAPIDLY
1.3 CURVE IV.

237 % OXIDATION

CURVE III.

100 % OXIDATION

0.9

5 10 15 20 26 30
ec.N/100 Fell

Sa

Such salts are analogous to the osmyl salts OsO,.X,, and the well known uranyl
salts UO,.X..

When the violet solutions were titrated potentiometrically with ferrous
sulphate solution, the curves showed only one step due to the reduction of
iridium IV to iridium III (Curve III). The brown solutions, when titrated
rapidly, gave curves showing three steps ; but, if titrated very slowly, only two
steps (Curves IV, V). From the total percentage oxidation of the brown
solutions and the width of each of the steps (i.e. the titration value), it could be
shown that the first reduction step, in the rapidly titrated solutions, was from
iridium VI to an unstable form of iridium IV, and not to the unknown valency
state of five; the second, the reduction of the unstable form of iridium IV
to iridium III ; and the last step, the reduction of the stable form of iridium IV

126 DWYER AND GYARFAS.

to iridium III. In the slow titration, the potential break at the end of the
reduction of iridium VI was very much larger, and the step due to the reduction
of the unstable form of iridium IV disappeared.

Provided that the oxidation was not carried beyond 100 per cent. (i.e.
Ir!V) the unstable form of iridium IV could not be detected on the curves, and
where the oxidation was carried to the hexavalent stage, the width of the step
due to the unstable form was proportional to the amount of iridium VI present.
It is concluded, therefore, that the unstable tetravelent state can only arise
by reduction of the hexavalent state. The maximum oxidation achieved in
these experiments was 273 per cent.

1.5

1.3 TITRATED SLOWLY

CURVE V.
200 % OXIDATION

——>
co.N/100 Pell

Fig. 3.

If the assumption is made that the unstable form of quadrivalent iridium
carries the larger charge, and then the charge is reduced by hydrolysis to the
stable form of the quadrivalent state, the following scheme is consistent with
the results obtained.

IrO,++ (Brown) -+2H++2e’ >~ H,O+IrOt+t (Red violet)
IrO*+++H,O — [IrO.OH]*++H*t (Blue violet)

TrO++ +H+-+e’ — [Ir(OH)]*++ (Yellow)
(IrO.OH]++2H+-+e’ > H,O-+[Ir(OH)]** |
In weakly acid solutions the blue violet solutions of the stable form of quadri-
valent iridium yield a very fine precipitate of iridium dioxide.

{[IrO.OH]+ — IrO,+H*+

I

THE CHEMISTRY OF IRIDIUM. 12

The oxidation from Ir"! proceeds
Ir+++ + [IrOH]++ + [TrO.OH]+ > IrO,++

Although dark violet blue solid crystalline substances have been obtained
by the oxidation of iridium III nitrate, sulphate and perchlorate, none of the
preparations has been obtained in a pure state. The work on the isolation of
these compounds is proceeding.

In a subsequent paper the redox potentials of the Ir!/Ir!V and Ir!V/Trv!
eouples will be discussed.

EXPERIMENTAL.
Iridium ITI Salt Solutions.

Potassium hexachloriridate IV (1-2 g.) was dissolved in 50 ml. of water at 80° C. and whilst
hot treated with sodium hydroxide solution (0-40 g. in 50 ml. of water). The mixture was
adjusted with dilute alkali until faintly alkaline, and maintained near the boiling point to cause
the blue precipitate of hydrated iridium dioxide to granulate. This was removed by centrifuging,
washed with hot water until it commenced to peptise and then dissolved by heating with a
mixture of 20% sulphuric acid (20 ml.), 5% sulphurous acid (20 ml.), and water (30 ml.). The
mixture was boiled down to half the volume to expel all sulphur dioxide, and the greenish blue
solution of iridium III sulphate centrifuged to remove traces of undissolved iridium IV and
iridium III oxides.

>

The solution of the sulphate was diluted to 50 ml. with water, and, keeping the temperature
below 40° C., cold 10% sodium hydroxide was added until the initial precipitate of iridium IIT
basic sulphate and hydroxide was just dissolved. The greenish yellow solution of sodium
iridate III was cooled to room temperature, and the pH adjusted to approximately 6-5 with
dilute sulphuric acid. The yellowish precipitate was centrifuged and washed once with cold
water. By dissolving in cold normal sulphuric acid and making the volume to 200 ml. an approxi-
mately 0:01 M solution of the sulphate resulted.

The iridium III perchlorate was made in the same way, using normal perchloric acid to
dissolve the precipitate. The hydroxide was reprecipitated with sodium hydroxide and re-
dissolved. The last traces of sulphates were removed by the addition of a few drops of barium
perchlorate solution. The nitrate was prepared the same way. All of the solutions became
greenish and finally blue on standing. The nitrate became very dark blue in a few hours.

The iridium content in all solutions was found by evaporation of a known volume to dryness,
followed by ignition to the metal. Traces of sodium salts were washed from the ignited metal
with hot dilute hydrochloric acid.

The Potentiometric Oxidation of Iridium UI Salts.

The potentiometric set-up was similar to that used in previous work (Dwyer, Nyholm and
McKenzie, 1944). The mixture at 25° C. was stirred mechanically in a current of purified carbon
dioxide during the titration with approximately N/100 potassium permanganate, cerium IV
sulphate, nitrate or perchlorate as oxidising agents, or ferrous sulphate for the back titration of
the oxidised solutions. In all titrations the initially yellow or greenish yellow solutions became
green, blue and finally bluish violet. In the back titration, except in strongly acid solutions,
these colour changes were not entirely reversed, and a pale blue colloidal suspension of iridium
dioxide was left at the end.

Substantially the same results were obtained with all of the oxidising agents, at acid con-
centrations from 0-5 N to 6 N, showing a potential break at approximately 1-27 volts. From
the volume of oxidising agent used, this corresponded to the end of the oxidation tr 6 Se
(Curve I.) Further addition of oxidising agent involved only partial oxidation to the hexavalent
state.

The reduction curves with ferrous sulphate gave typical curves involving potential breaks at
1-27 volts, 1-1 volts and 0-9 volt. The break at 1-1 volts was usually poorly defined.

128 DWYER AND GYARFAS.

The Anodic Oxidation.

The anodic oxidation cell consisted of a small beaker (30 ml.) containing a cylinder of smooth
polished platinum, which fitted the beaker so closely that the inner side of the cylinder could be
considered as the effective anode surface. A small sintered glass crucible with the base removed,
and fitting loosely into the platinum cylinder, contained the platinum wire cathode. The solution
to be oxidised containing the appropriate amount of acid was placed in the beaker, and the
cathode chamber was filled with acid of the same concentration ; the levels in the two chambers
being adjusted so that the cathode level -was slightly higher. The solution being oxidised was
stirred with a rapid stream of fine carbon dioxide bubbles. When oxidation was complete, the
cathode was removed, the porous membrane washed out by allowing some of the cathode liquid
to percolate through ; then the rest of the cathode acid added, and the anode washed with a
little further acid. The solution was then made up to a specified volume.

The percentage oxidation achieved was determined by taking a known volume of solution,
diluting with water, adding excess potassium iodide, and titrating the liberated iodine with sodium
thiosulphate. From the known iridium content of the solution before oxidation, the calculation
can then be made. A small correction was necessary for the iridium deposited on the cathode.

In the sulphate solutions, persulphate was formed during the oxidation making the estima-
tion of the percentage oxidation impossible, whilst the nitric acid in the nitrate solutions inter-
fered with the titration by slowly liberating iodine. For these reasons, beyond qualitatively
establishing that the same products are formed in sulphate and nitrate solutions, the work has
been restricted to the perchlorate.

It was found that provided the current was more than 0:2 amp. (6 V. applied), or the current
density of more than 2-6 x 10-3 amp./sq. cm., the extent of oxidation was a function of the time
and the state of the electrode surface. With roughened electrodes, or electrodes that had been
used previously without cleaning, gassing occurred and the oxidation could not be carried much
beyond the Ir'’ state. The electrode between experiments was cleaned by making it the anode
in 5 N sulphuric acid and passing a current of 4—5 amps. for twenty minutes. Table I shows the
results obtained by oxidising in 4N perchloric acid with a current of 0-5 amp. (6-5 x 107%
amp./sq. em. of anode surface).

TABLE. ©.
0-0150 gm. of Ir in 10 ml. solution.

| | |
aossson, | | |
Time in | Cathode. | Total Ir. ~ N/100 Na,§,03.| Percentage | Percentage
Minutes. | Grammes. | Grammes. | Millilitres. | Oxidation. — IrVI,
| | er. cs ek berabafiel
a — |
|
10 0- 0006 | 0-0144 | 15-9 110 50"
20 0-0012 | 0-0138 | 24-2 175 37°5
40 0- 0022 | 0:0128 | 27:4 214 57-0
90 0-0029 0-012] | 29-3 242 71-0

The potentiometric reduction of the anodically oxidised solutions was carried out in the
assembly described above, with approximately N/100 ferrous sulphate solution. Typical
reduction curves of solutions oxidised to various stages are shown in Figures | to 3.

SUMMARY.

The oxidation of iridium ITI sulphate, perchlorate and nitrate with potassium
permanganate, or cerium IV salts yields bluish violet solutions, which probably
contain the cation [IrO.OH]*+. The anodic oxidation yields bluish violet
solutions, which contain the same ion, or the oxidation can be carried to the
stage of iridium VI, which exists in the solution as the brown ion IrOQ,**.

By examination of the potentiometric reduction curves of the brown
solutions, it is concluded that an unstable form of quadrivalent iridium, probably

THE CHEMISTRY OF IRIDIUM. 129

as the reddish violet ion IrO**, is the first reduction product of the ion IrO,**.
The unstable ion rapidly changes to the stable [IrO.OH]*, and can be obtained
only by the reduction of iridium VI.

REFERENCES.
Dwyer, F. P., McKenzie, H. A., and Nyholm, R. 8., 1944. THis JouRNAL, 78, 260.
Le de Boisbaudron, 1883. Compt. Rend., 96, 1336, 1406, 1551.

Marino, L., 1904. Zeit. anorg. Chem., 42, 213. See also Delepine, M., 1927. Zeit. Phys. Chem.,
130, 222.

PHYSICAL INVESTIGATIONS ON COMPLEXES OF
DIPHEN YLUTHIOCARBAZONE.

By L. E. MALEY, M.Sc.,
Department of Chemical Engineering and Chemistry Department,
Unwersity of Sydney.

Manuscript received, August 16, 1950. Read, October 4, 1950.

The object of this investigation was to study the interaction of metal
complexes of diphenylthiocarbazone with metal ions, in order that information
concerning the strength of the binding of the metal to the ligand, diphenyl-
thiocarbazone, and the extent of the exchange between metal ions in solution
with metal atoms bound to this ligand could be obtained.

Previous investigations by Maley and Mellor (1949) on the stability of a
series of metal complexes have shown that the order of the stability constants
for metal chelates with a series of ligands was independent of the chelating
organic molecules investigated.

If one metal complex is more stable than another of the same type, it should
be possible under suitable conditions for one metal to displace another metal
from a less stable complex.

The reaction

(ligand),Me, +Me, = (ligand)nMe,+Me,
should therefore proceed and displace the original metal Me, from its complex
if Me, forms a more stable complex with the ligand.

Diphenylthiocarbazone, which is acidic in character and forms chelates
with many metals, exists in both the keto and enol form.

keto enol

According to Fisher (1934) the keto form reacts with metal ions. The imino
hydrogen atom is replaced by the metal atom, which is then coordinatively
bound to the nitrogen. These complexes are soluble in organic solvents and as
a rule are coloured.

PHYSICAL INVESTIGATIONS ON DIPHENYLTHIOCARBAZONE. 131

The reagent diphenylthiocarbazone is itself insoluble in water and dilute
mineral acids but is soluble in chloroform, carbon tetrachloride, and alcohol.

A chloroform mixture of the uncombined chelate and the chelate combined
with the metal ion can be separated by a dilute aqueous ammonia solution
(0-02 M), which extracts the uncombined complex diphenylthiocarbazone leaving
the pure colour of the metal complex in the chloroform layer.

METHOD OF INVESTIGATION OF THE REACTION.

In the present investigation the following specific exchange reactions were
studied :

Zn(diphenylthiocarbazone) +Me = Me(diphenylthiocarbazone) +Zn
where Me=Cu, Co and Zn.

The extent to which this reaction proceeds from left to right was noted by
using radioactive ions. The zinc atoms in each case were labelled by using
radioactive zine solutions.

The reagent, diphenylthiocarbazone, which is a spot reagent and used for
determining metal ions in concentrations ly to 100y, 1s very sensitive to trace
metal ions and this factor necessitated the taking of special precautions to ensure
that all apparatus and reagents were free of zinc and other trace metals before
proceeding.

EXPERIMENTAL.
Reagents.

Diphenylthiocarbazone B.D.H. quality was used throughout and found free of oxidised
products.

Trace elements were eliminated from the pyrex glassware by thorough cleaning, washing
and testing it with diphenylthiocarbazone reagent until free of metal ions. No grease or lubricant
(other than water) or rubber fittings could be used on the separating funnels as all these were
found to contain a significant amount of zinc.

The distilled water and absolute alcohol and ammonia were redistilled several times in
pyrex glassware and the chloroform purified by distilling under a cover of aqueous solution of
sodium thiosulphate containing a little NaOH, drying the distillate over CaCl, and redistilling,

Preparation of Zinc Diphenylthiocarbazone.

It was prepared by adding diphenylthiocarbazone chloroform reagent (15 milligrammes in
100 ml. CHCl3) to the dilute 50y~ aqueous zinc chloride at pH 7:0. The excess reagent was
removed by extracting it with dilute (0-02 M) aqueous ammonia until the upper layer was water
clear.

The red complex remains in the chloroform layer. It was made up as required because the
colour fades on standing due to slow oxidation.

The formation of metal diphenylthiocarbazone is influenced by the hydrogen ion concentra-
tion of the aqueous solution [Fisher and Leopolidi (1934), Fisher (1934), Hibbard (1937), White
(1936) ].

The percentage of zinc ions extracted from an aqueous solution by a chloroform diphenyl-
thiocarbazone solution varies considerably with pH. The partition effect in dilute solutions
is illustrated by Fig. 1 (Hibbard, 1937).

The exchange reactions were therefore carried out experimentally at the constant pH of 7-0.

Alcoholic zine diphenylthiocarbazone was prepared by evaporating the chloroform solution
to a low bulk and then diluting with absolute alcohol giving a one-phase solution.
Exchange Reactions.
The alcohol zinc diphenylthiocarbazone was mixed with approximately an equal volume of
solution of the metal salt solution at the same molar concentration and at pH 7-0, so that
[Zine complex ]

[Metal salt conc. ia

12 L. E. MALEY.

The zine complex was then separated from the metal solution by adding CHCl,. The CHCl,
layer was washed with water and the water layer washed with CHCl,. Both layers were then
diluted, an aliquot portion taken, evaporated and dried on a glass counting plate and their
respective radioactivity measured on a Geiger Muller counter with a scale of eight using a 6 tube
with a two-inch lead shielding and a thin mica window.

No self adsorption corrections were needed due to the relative high energy of the B and y
rays emitted from Zn* 65 used, and, due to its relatively long half life of 250 days, no decay
corrections were required.

Due to the fact that emission of radioactive radiations follow statistical laws of random
processes the statistical probable error in the recorded activity is given by Poisson’s Term,
0:6745+/ 41, where A! is the number of events recorded.

The activity of the sample was then determined as follows :

Average sample+background count=B-+0-6745 +/ B

Average sample count = B—A+ V (0-67451/B)?-+(0: 6745/4)?

where A is the average background count.

1004

Zn h
EXTRACTED

30 5

! @ 3 4 5. 6 %. 8.9. 10) Atle

The concentration of the metal ions in the aqueous phase was determined by separating the
water layer, converting it into the diphenylthiocarbazone complex in chloroform and using a
Klett photometer to determine its concentration.

In the copper and cobalt exchange reactions copper sulphate and cobalt nitrate solutions
were added to the zinc complex solutions and allowed to stand several hours. The separation
was then effected as above by adding chloroform and the activities of the two layers
were measured. In both cases the activity of the aqueous solution increased to 100% of the
original complex activity, indicating a complete exchange of the zinc atoms in the complex with
the copper and cobalt ions.

The reaction between zinc atoms in the complex and zinc ions in solution was studied in the
first instance by using active complex and inactive zinc ions, and secondly inactive complex and
active zinc ions.

The relative concentrations of the zinc in both layers were then compared with the corres-
ponding activities and were found to agree.

PHYSICAL INVESTIGATIONS ON DIPHENYLTHIOCARBAZONE. 133

The exchange rate for the zinc-zinc exchange was very rapid in the alcoholic aqueous solution
and within the minimum time required to separate the solutions } to | minute the activity of the
aqueous layer reached 50% of the total activity, which means there is a 100% exchange of the
zine ions in solution with zinc atoms in the complex.

ACKNOWLEDGEMENTS.

The author wishes to thank Dr. D. P. Mellor, of the Chemistry Department,
University of Sydney, for his interest in and helpful discussions on the work ;
Dr. W. Rogers, of the McMaster Laboratory, Sydney, for the use of the counting
equipment ; and Dr. T. G. Hamilton, University of California, Berkeley, for the
supply of Zine 65* from the Crocker Laboratory 60” cyclotron, which enabled
this work to be undertaken; also, Dr. T. H. Oddie, Commonwealth X-Ray
and Radium Laboratory, Melbourne, for his advice on handling the radiation
material, and the University Commonwealth Research Committee for a Research
Agsistantship.

SUMMARY.

There is a rapid exchange between zinc ions in solution with zinc atoms in
zinc diphenylthiocarbazone and the zine atoms are held by relatively weak
bonds to the ligand.

Copper and cobalt metals form relatively stronger bonds with the ligand
and are more stable than the corresponding zinc diphenylthiocarbazone complex.

REFERENCES.

Fisher, H., 1934. Z. Angew. Chem., 47, 685.

Fisher, H., and Leopolidi, 1934. Z. Anal. Chem., 97, 385.
Hibbard, P. H., 1937. Ing. Eng. Chem., 9, 127.

Maley, L. E., and Mellor, D. P., 1949. Aust. J. Sci. Res., A 2, 92.
White, W. E., 1936. J. Chem. Education, 13, 369.

TABLES FOR NEARLY PARABOLIC ELLIPTIC MOTION.*

By HARLEY WOOD, M.Sc.

Manuscript received, February 20, 1950. Read, November 1, 1950.

In this article tables are given for the representation of nearly parabolic
elliptic Keplerian motion based on the formule of a previous paper (Wood,
1950a).

Equation (9) of that paper may be written

gine et /2u. seen aa
e3/21)3 s

D,=6k(1 +e)? "q-* t= (1 +e) 6p +u6)

where & is the Gaussian constant, e the eccentricity, e=(1—e)/(1+e), n=4y/4q,
A=4%/q and %, Yo are the rectangular coordinates in the plane of motion with
the 2 axis directed towards perihelion. When the place in the orbit is known,
and hence one of the alternatives

u=(sin B)/e?=y9/q=(r sin v)/q

calculable, this formula may be used to calculate perihelion time. The coefficient

of w*,
6 —A
| €3/2143 j

is given in Table 1 with argument ¢1!/2u. The table was calculated to nine
decimal places using the series when ¢!/*u4<0-20 and thereafter the Table of
Arc sin x prepared by the ‘‘ Mathematical Tables Project ’’ (1945). The values
of A, and the remaining functions of this article, were calculated at ten times the
interval given and then sub-tabulated to the interval of the table, the intention
being that errors should not exceed 0-52 unit of the last recorded place.

In order to provide for iterative computation of u from equation (1) and of
velocities facilities are given for convenient calculation of

aD 6 1
264

du. e/(1l—eu
1—(1—ep2)1/2
eu2(1 —ep.?)1/? | :

a Geer ae
1=6) eu2(1 —ep)t/?

=6(1 +e) +u26)

is given in Table 1 and a correction to an approximate value of u may be obtained
by the formula

Ap={D,—6(1 +e). —Ap?}/{6(1 +e) +L}. MP ee (2)

—* This paper is printed with the aid of a grant from the Commonwealth Scientific Publications
Committee.

TABLES FOR NEARLY PARABOLIC ELLIPTIC MOTION. 135

For obtaining » from the known elements of the orbit tables are given for
the use of formule (23) of the previous paper. Repeating these in a form
adapted to the present purpose we have

D=[12k(1 +e)!/2q-3/?e]t
where
e—1+y,e+y.e7+....,

12k=0- 2064 2519, c is obtained from Table 2 and the coefficient of ¢in the square
brackets can be computed for the whole orbit.

Also
D= Veg 268s ick Sind ence sa ee (3)
and
? +9125" +-Jost?G? + Goe%o? + .. . ‘|
a +zs82o" “+Ggge%o4 +...
= Oe aa
Now writing
J =1+9,9¢07 +G4eo4 +95g82o®+....,
Y3 Jao
het e244 e+...
Joo Joe
and
—K =9o.E0" +-934¢°o* +9 4¢°o® + ative: verte
we have

p= (J hK Ae Re ee oe ee (4)

where # is a function of ¢ and yu defined by the equation.

Inserting the values of the coefficients we have

e7=1—0°8e —0-03428 57143e? —0-01980 9524e? —0-01323 43854
—0-00963 4e° —0-00742c® —0-0059e’,

J =1-:0—0:15e0? +0-00071 428572204 +0-00003 96825e%a®
+0-00000 24930408 +0-00000 016832°%o",

K = +0-00285 7143e0% —0-00112 69842204 —0-00005 1252¢3o°
—0-00000 2454408 —[0-000033¢°%o1°},

h=1:0e +0:57777 777822 +0-38600 28862? +0-28097 7689e4
—[2-2e5],

where the terms in the brackets are not determined like the others but are
empirical terms added to reduce the value of Rk. Their greatest effect on hk
within the range of the table is 40 units in the ninth decimal place. Using the
manuscript tables caleulated from the above series to two places beyond what is
recorded here, values of Rk were calculated from equation (4), uw first having
been obtained from equation (2). The ‘‘ Table of Values of R ” gives the values
found in units of the ninth decimal place, including errors of computation up to
two units involved in using the full nine figures. & is negligible in seven figure
work.

136 HARLEY WOOD.

Table of Values of R in Units of the Ninth Decimal Place.

-< 0-02 | 0-04 | 0-06 | 0-08 0-10
c*o Pe | | |

0-1 aay ai 0 0 +1
0-2 0 | eg) 5] 0 _9
0-3 0 | 0 | +1 0 —2
0-4 0 | 2 453 +2 ail
0-5 0 49 Iai +6 16
0-6 ae, Sai) | na | +6 415

The values of c and A are found, once for the orbit, from Table 2; co is
obtained from equation (3) using tables of parabolic motion (Wood, 1950b),
and J and K come from Table 3 with argument [e1/2c-!]ec. When second
differences are appreciable they may be allowed for by using the table with
argument n and /\,)’+/y,", published in the Nautical Almanac for 1937 and
reprinted in the Interpolation and Allied Tables.

Having uw, we require
Sat eee TuEre a .
which is equation 6 of the first paper. The quantity
2 ee
eis
is given in Table 1 with argument ¢?/2y.

The formule for the rectangular equatorial heliocentric coordinates are
then

A,
ie 5 5 maa +[Bele,
y =[Ay]— eae aL he Tee pis +[By]y,
Jag |e ea
2=[ z ye ae | U ZI {45
where A,, B,.. . have the same meaning as in the second paper (Wood, 1950d)

and the coefficients in the square brackets are precomputed.

As an illustration, using the conventional example from Gauss’ Theoria
Motus, we take

e=0-9676 4567, q=0-5829 751,
V—LOOn, tan v= —5-671282,
u=(r sin v)/q=2-3291 134.

The preliminary calculations of the constants required to compute either
perihelion time or an ephemeris place give

«=0-0164 4317, 6k(1-+e)3/2g-3/2 = 0-6399 971,
21/2—0- 1282 309, 6(1 +e) =11-8058 740,
c=0-9933 962, 12Kk(1-+e)!/2q-3/2e= 0-6462 248,

¢}/2e-1—0 -1290 833, h= 0-01660.

TABLES FOR NEARLY PARABOLIC ELLIPTIC MOTION. 137

For calculation of perihelion time we obtain
ct/2447— 0-2986 643, A =1:0424 100,
t=63-54399 days.
A many-figure calculation gives t=63-5439 858 days.

In calculating an ephemeris place with t=63-543986 days we obtain

€o =2:-3459 994, w=2-3291 135,
et /*¥g =0-3028 293, 1/94, —0 - 2986 643,
J =0-9862 502, N =1:-0233 538,
K =0-0002 525, A= —0-4106 856
and for comparison with the original data we give
tan v=y/A= —5 671281, v=100° 00’ 00”-01.
REFERENCES.

Mathematical Tables Project, 1945. Table of Arc sin x, Columbia University Press, New York.
Wood, H., 1950a. Tuis Journat, 83, 150. Also Sydney Obs. Papers No. 10.
——1950b. Tuis JourNnat, 83, 181. Also Sydney Obs. Papers No. 11.

———

138 HARLEY WOOD.

TABLE 1.

TABLES FOR NEARLY PARABOLIC ELLIPTIC MOTION. 139

TABLE 1.

0227,- 0025 0056 892
0231 0025 : 0057 662
0236. 0026 : 0058 437
0241 0026 3 ¢ 0059 218
0246, 0027 ; t 0060 004

0250, 0027 ; p 0060 795
0255, 0028 : 3) 0061 592
0260, 0028 : 0062 394
0265, 0029 2 0063 201
0270. 0029 : 0064 014

0275, 0030 ; 0064 833
02802 0030 ; 0065 656
02852 0031 ; 0066 485
02902 0032 6 0067 320
0296. 0032 ; 0068 160
0301, 0033 327 0069 005
0306" 0033 0069 856
0312. 0034 ; 4 0070 712
03172 0035 0071 574
0322, 0035 ; 0072 441

0328, 0036 | ; . 0073 313
0334. 0036 ; > 0074 191
0339, 0037 > 0075 O75
0345. 0038 ” 0075 964
03507 0038 . , 0076 858

0356. 0039 0077 758
oseat mracdocaeite 7 eS eanconerl
0374° 0041 : 8 0080 490
0380° 0041 ® 0081 412
380°

0386, 0042 | 0082 339
0392) 0043 ; 9 0083 272
0398" 0043 | : 5 0084 211
0404° 0044 5° 0085 154
04108 0045 2980" ; 9 0086 104

0416, 0045 98: 0087 059
0423 0046 . 0088 019
0429° 0047 ° . 0088 985
0435, 0048 | ; “0089 957
0442 0048 “0090 934

966
972
O77
983

0448_ 0049 « io 0091 917
0455, 0050 + g 0092 905
0461, 0050 * 0093 899
0468, 0051 * 0094 898

0475, 0052 ° 0095 903

988
994
999
1005
1011

0482, 0053 1: eg: 0096 914
0488) 0053 9 0097 930) p20
0495, 0054 : 0098 952,052
05027 0055 0099 9807025
0509, 0056 0101 013%,

0516 0056 . 0102 051

140

406
300
205
121
047

1894
1905
1916
1926
1936

983 946
929

1958
887 ‘a

1967
854.
9391978

1989
821
820
830
850
881

1999
2010
2020
2031
2041

922
974
037
110
194

2052
2063
2073
2084
2095

289
394
510
637
775

2105
2116
2127
2138
2148
)
9235159
082
2170
252
2181
433
6242191
2203
827
040
264
499
745

2213
2224
2235
2246
2257

002
270
548
838
139

2268
2278
2290
2301
2312

451
774
108
453
809

2323
2334
2345
2356
2367

176
554
944
345
757

2378
2390
2401
2412
2423

180

HARLEY WOOD.

TABLE 1.
e2u.

051 0-250
0961 ono -251
146c 2 -252
2025 253
2680 254
330 0-255
4031 a3 256
Tia 257
5651500 258
B55) noe 259
750 0-260
85175, -261
958... 262
OTsaae 263
189} og 264
313 0-265
Ve 266
a 267
[20s -268
S745 6. 269
020 0-270
Li9ase, 271
B43 272
aan 273
6891 549 274
871 0-275
059,465 -276
25ore 277
AZo ve 278
CT ae 279
868,__, 0-280
085,554 281
30845 282
bSiaee, 283
TSS 284
012 0-285
25S sore 286
blOseee 287
T60re 288
0335, 289
303 0-290
B19 soo 291
861i oe. 292
149) oo 293
Wee. 294.
743 0-295
0497305 -296
360) 916 297
O78 ot 298
OO2its. -299
332 0-300

A

0292
0294
0297
0299
0301

0304
0306
0309
0311
0314

0317
0319
0322
0324
0327

0329
0332
0335
0337
0340

0343
0345
0348
0351
0353

0356
0359
0361
0364
0367

0370
0372
0375
0378
0381

0384
0387
0389
0392
0395

0398
0401
0404
0407
0410

0413
0416
0419
0422
0425

0428

130s
6142434

0602446
2457
517
9857468
2480
465
956
458
972
497

2491
2502
2514
2525
2536

033

5812048

14122
2570
raul
3942983
2594
888
493
110
739
379

2605
2617
2629
2640
2652

031
695
370
057
756

2664
2675
2687
2699
2711
467
189
923
669
427

2722
2734
2746
2758
2769

196
978
771
577
394

2782
2793
2806
2817
2830

224
065
OLS
784
662

2841
2853
2866
2878
2889
551

2902
458 5914

3675 906
293
9397939
2950
182
145
120
108
108

2963
2975
2988
3000
3012

120

TABLES FOR NEARLY PARABOLIC ELLIPTIC MOTION. Aa,

TABLE lI.

0595 130. 307: 0326 5
0598 812. 20 0328
0602 : é 0330 !
0606 : 0332
0609 ae ; 0334

0613 7 0336
0617 430° 51 (0338
0621 196,73, 32115, 0340
0624 976: 32315, 0342
0628. 770: 2515, 0344

0632 5 , 3271,, 0346
0636 402°°7" 3: 0348 <
0640 23928?" : 0351
0644 0353
0647 956' 0355

0651 836... 0357 2
0655 731°°° 395, 0359 :
0659 6: , 34165, 0361
0663 564°”: 0363
0667 50350") 345855 0365

0671 4: _ 0367
0675 423°°° 350171 0370
0679 406275? 355 0372
0683 403°". 3544°* 0374 3:
0687 415°°1* 35657! 0376 515

0691 441... 3587.. 0378
0695 ** 3609°- 0380
0699 539°" ““ 0383
0703 610° 3653-~ 0385 26
0707 697 3675-~ 0387

O711 7 3697, 0389
0715 91577! “0391
0720 ae ~ 0394
0724 5 376455 0396
0728 355,,-. 37865, 0398

0732 5 ; , 0400
0736 2 OA03
0740 | eye: ° 0405
0745 “3 0407
0749 0409

0753 23,, 0412 ;
0757 > 0414
0762 0416
0766 pate 0419 |
0770 : , 0421

0775 0423 8:
0779 0426
0783 85 OA 0428
0788 ‘ 0430
0792 0433

0797 0435

142

043
470
912
371
845

4427
4442
4459
4474
4491

336
843
366
905
46]

4507
4523
4539
4556
4572

033
621
226
847
485

4588
4605
4621
4638
4654

139
810
498
203
924

4671
4688
4705
4721
4738
662
417
189
978
784

4755
4772
4789
4806
4824

608
448
305
180
072

4840
4857
4875
4892
4910

982
909
853
815
795

4927
4944
4962
4980
4997

792
807
839
890
958

5015
5032
5051
5068
D087

045

149°194

9712122

5141
4125158
510577
747
942
155
387
638

5195
5213
5232
5251
5268

906

HARLEY WOOD.

TABLE 1.
e2u,
608 0-450
988505 451
eae 452
Tish 453
th Oss 454
592 0-455
G14 -456
444i 457
g82e to -458
spied 459
783 0-460
2405 2. 461
Vee ce 462
1985100 -463
6865105 464
[S35 0-465
6895r04 -466
2035255 467
Tbe e -468
2565.5 469
795 0-470
344500 471
9005706 472
4665004 473
0405045 474
622 0-475
paler -476
$14) 0 477
Dae 478
040 5G" 479
667... 0-480
30250 -481
9465505 482
nous 483
261550, 484
932 0-485
61 ied -486
3005000 -487
998506 488
104s -489
420 0-490
1455/5, -491
879505 492
e228: 493
EVE ie 494
136 0-495
9065/0 -496
6865.00 -497
A755. oe -498
Tage 499
081 0-500

TABLES FOR NEARLY PARABOLIC ELLIPTIC MOTION.

412
715
040
388
757

6303
6325
6348
6369
6393

150

56D otE?

O020
6460
462046!
945°483
6506
451

6529
980-°>"
5390052

108° "6

6598
106 6692
328
973
642

6645
6669

3350698 |

6716
6740

Tou
555
343
155
991

051

6764
6788
6812
6836
6860
851
736
645
579
538

6885
6909
6934
6959
6983

O21 O09
530, ..
7033
5637058
621

7084
7057108
813,435,
948

7159
107

7186
293
503/210

7237
7407063
003

7289
292

7314
606
947/341

7368
315
709
129
576
050

7394
7420
7447
7474
7501

551

I
Oe

7128.

TABLE 1.
ely
968 0-550
3321
289 551
33833353
3355
320 one 554
685.077 0-555
Os
3492299 558
FEAD410
2593 04 559
680... 0-560
3433
ppeeeeee |! ee
O19°°2? 563
Aqge 0% 564
3478
956 0-565
3490
st |
A500 568
Tso ale 569
3536
519 0-570
3548
oss STM
1o7 573
SaaS iter
1719 3595 574
374. 0-575
3606
pease tae eee
3993630 578
3703642 579
3655
525 0-580
3666
pre veep
560202! 583
263° 00° 584
Tue tea baat
978.057 0-585
ee |
ely balloon 588
Oolecc: 589
Bh dad:
738 0-590
3790
gon |
Mees. 593
9793827 594
“3840
812. 0-595
3853
ae |
Ajoe?? 598
CN aoe 599
3905
205 0-600

3:

9283
46
Q29C

l-

0898
0902
0906
0909

091s.

0917
0921
0925
0929

0933

0937
0942
0946
0950

0954 :

0958
0962
0966
0970
0974

0979
0983
0987
0991

0995 ¢

1000
1004
1008
1012

1017 :

1021
1025
1030
1034
1039

1043 ©

1047

1052 ;
1056 68%

1061

1065
1070

1074 =

1079

1083 6

1088
1092
1097
1101
1106

jee

143

144

HARLEY WOOD.

TABLE 2.

TABLES FOR NEARLY PARABOLIC ELLIPTIC MOTION. 145

TABLE 3.

K 3 5 ig

“000 0000, . . 6250, . 0-000 0071,
0000, | . -999 6099" ' 00742
0000) -999 5944. °° 0077:
0000, | . -¢ f a 0080:

0000) : -999 56: 33 0083.

0001, )-999 5463. -000 0086,
0001) -999 5296," 0089
0001! ; -999 5 0093:
0002, “ 0096:
00025 - 9 0099

0003) : : ) ; 0103
* 003° | ; : 41970. 0106
0004, | : : 42% : 0110.
0005, : : O47. 0113)
0006; . ; 50, O17,
0006 | ; : UE O12),
0007, | 2 : ; 0124
0008, d ; : 0128
0009) ; ae 0 01321
0010, : . : 0136)

0011, ; 5 -000 0140
0013; 0144
0014, 22245 0148)
0015 ; 0152"

ul 21
0016, : : aw 0156 |

0018, . Ds ; 0160
0019, : ; 0165
0021, : : 3 0169,
0022+ ; ; 0173.

00245 ,; a 0178)

0026, ; ; | -000 0182,
0027 : 0187”
00295 0192)
00312 — si 0196.
00335 ; 0201?

0035, : : at 0206.
0037: : : 9 211°
00395 : : : 0216?
0041 ; 0221°

2 5
0043. ; : 269 0226.

0046, )-000 0231,
00485 : : : 0236?
0050° | ; : 0241?
0053, : 0246?
0055, | : “4 ae 0252,

0058, | 2 0257,
00607 ; { AN 0262°
0063; | : 0268°
0066, 0273°
00695 998 529950" 0279°

0071 | : -000 0285

146

HARLEY WOOD.

TABLE 3.
226 J K 226 J K

0-100 ‘998 5001... -000 0285. 0-150 0-996 6254, -000 0637
-101 998 4699. 0290? -151 +996 5802777 0646 2
-102 “998 4395... 0296, -152 -996 534877. 0654 ®
-103 “998 4087. 0302, -153 “996 4890/7. 0663
-104 -998 3777, 0308, -154 ‘996 4430/0, 0671 |

0-105 ‘998 3463, , -000 0314, 0-155 0-996 3967,,,, -000 0680
106 -998 314755) 0320, -156 -996 3500) 44 0689 ?
‘107-998 2827359 0326, 157-996 3031). 0697 8
-108 -998 250555 0332? -158 -996 255817" 0706 ,
-109 -998 2180550 0338, -159 “996 2083) ,° O715 ¢
0-110 “998 1851,.., -000 0344. 0-160 0-996 1605,., “000 0724 ,

iat -998 15205. 0350, -161 -996 112370) 0733
112-998 11855. 0357; 162 996 063975" 0742 of
113 -998 084837, 0363, -163 -996 0152) 5, O751 9
114 -998 05075), 0369, -164 “995 9661). 0760 5
0-115 “998 0164, -000 0376, 0-165 0-995 9168,,, -000 0769, ,
-116 -997 9817546 0382, -166 -995 867156 0779")
117 997 9468) 75 0389/ -167 ‘995 8172. 0° 0788 |
118 ‘997 9115.7. 0396, -168 ‘995 7670; 0% 0797, 5

119 -997 8760' 0402- -169 -995 7164 0807
359 7 508 9
0-120 ‘997 8401... -000 0409, 0-170 0-995 6656, ‘000 0816, ,
31 | “997 80405) 0416, 74 ‘995 61457. 0826,
“122 -997 7676... 0423. ay VP “995 5630? ? 0835, 5
hy XE} -997 7308), 0430 173 *995 511375) 0845, 5

-124 -997 6938° 0437/ -174 -995 4593 0855
374 fj 524 9
0-125 ‘997 6564... -000 0444, 0-175 0-995 4069... 000 0864.)
-126 -997 6188) 0 0451! 176 "995 35437, 0874.)
127 -997 5808). 0458, “i Uv “995 30147), 0884.
-128 997 5426, 0. 0465, -178 ‘995 24817 0° 0894,
-129 ‘997 5040300 0472¢ -179 “995 194620? 0904,
0-130 ‘997 4652, -000 0480, 0-180 0-995 1408, ,, “000 0914, ,
-131 -997 4261... 0487, -181 “995 086621 09245
-132 -997 3866.7 0494 -182 995 03227) 7 0934, )
-133 -997 3469), 0502, -183 *994 9775, — 09447)
- 134 ‘997 3068) 5 0509, -184 994 9224°?. 0954,
0-135 -997 2665,,, -000 0517, 0-185 0-994 8671... “000 0965, ,
-136 -997 2258 | 9 0525_ -186 “994 8115570 0975; ,
-137 ‘997 184975 0532) -187 “994 7555, 0985,,
-138 997 1437.5 0540, -188 ‘994 6993? 0996,
-139 -997 10217). 0548. -189 “994 6428, 0 1006,
0-140 -997 0603,,, “000 0556, 0-190 0-994 5859, _, -000 1017,,
-141 -997 0181,5, 0564 -191 “994 528877) 1027,
-142 996 975715, 0572, 192 994 47147" 1038,
-143 -996 932975. 0580, -193 “994 4136? 0° 1049,
-144 ‘996 889975, 0588, -194 “994 355670, 1059,
0-145 996 8466. “000 0596, 0-195 0-994 2973... -000 1070,,
-146 -996 80297, 0604. -196 -994 2387?) 1081,
-147 -996 7590/4 0612, -197 994 17975), 1092,
-148 996 7147/1 ° 0620, -198 “994 1205?) - 1103,;
-149 -996 6702) 2 0629, -199 994 0610700 1114),

0-150 -996 6254 -000 0637 0-200 0-994 0011 -000 1125

PE To)

0-200
-201
- 202
-203
-204

0-205
-206
-207
-208
-209

0-210
-211
-212
-213
-214

0-215
-216
-217
-218
-219

0-220
“221
*222
-223
-224

0-225
-226
-227
-228
-229

0-230
*231
-232
-233
-234

0-235
-236
-237
-238
-239

0-240
-241
-242
-243
-244

0-245
-246
-247
-248
-249

0-250

TABLES FOR NEARLY PARABOLIC ELLIPTIC MOTION.

QO:

-000

-000

-000

-000

-000

-000

-000

-000

-000

-000

000

TABLE 3.

K 626
1125,, 0-250
1136), -251
147), -252
1158, -253
1169,, -254
1181, 0-255
1192), -256
120475 -257
1215), -258
1226 -259
1238, 0-260
125075 -261
1261, - 262
127355 - 263
1285 - 264
1297, 0-265
1308), - 266
132075 -267
133255 -268
1344 -269

12
1356, 0-270
1369,, -271
138155 -272
1393.5 -273
= :
1405, 5 274
Leas 0-275
1430), -276
aoe oe Hy ie |
1455), -278
1467 -279
3
1480,, 0-280
149270 -281
1505.3 -282
1518), - 283
153155 -284
1543,, 0-285
1556, - 286
1569), -287
1582, -288
1595_* -289
13
1608, 0-290
1621,, -291
1634); -292
1648, -293
1661), -294
1674, , 0-295
1688, , -296
1701), -297
1715), -298
1728), -299
1742 0-300

144

K

-000

-000

-000

-000

“000

-000

-000

-000

-000

-000

-000

1742,,

5 3115
5 2176

5058
4157
3254
2347
1437

0525
9609
8690
7769
6844

5916
4986
4052

1238
0288
9339
8387
7433

6475
5015
4551
3585
2615 |

1643
0667
9689
8707
7723

6735
5745
4751
3755
2755

990
994
996
1000
1002

1753
0748
9739
8728
7713

1005
1009
1011
1015
1017

2 6696

1020
1024
1026
1029
1033

1564
0529
9491
8449
7405

5676
4652
3626
2597

1035
1038
1042
1044
1047

6358

Q-

-000

-000

-000

-000 ¢

-000

-000

-000

-000

-000

-000

000

HARLEY WOOD.

TABLE 3.

K

2480, |,

6358
5308
4254
3198
2139

1050
1054
1056
1059
1062

lOT7ees
0012
1069
8943
1071
7872
67981074
1077
5721
4641) hos
3558
1087
DAT
13891089
1092
0290
9195
8097
6996
5892

1080

1095
1098
1101
1104
1107

4785
3675
2562
1446
0327

1110
1113
1116
1119
1122

9205
8080
6952
5821
4687

1125

1131
1134
1137

3550
2410
1267
0121
8973

1140
1143
1146
1148
1152

7821
6666
5508
4347
3183

1155
1158
1161
1164
1166

2017
0847
5 9674
8498
7320!

1170
1173
1176

1178
1182

6138
4953
3766
2575
1381

1185
1187
1191
1194
LES

0184

1128

O-

K

-000 3330

3348

-000 3421

-000 3512

‘000 3605

-000 3699

-000 3794

‘000 3889

-000 3986

-000 4083

-000 4182

000 4281

TABLES FOR NEARLY PARABOLIC ELLIPTIC MOTION. 149

TABLE 3.

K 2 K

150

0

-000

-000

-000

-000

-000

-000

-000

-000

HARLEY WOOD.

TABLE 3.

K

-000

‘000 7596

O-

-954
*954
-954
»954
-954

-953
*953
-953
-953
-953

-953
-952
*952
-952
*952

*952
-952
-951
-951
*951

-951
-951
-951
-950
-950

-950
-950
-950
-949
-949

-949
-949
-949
-949
-948

-948
-948
-948
-948
-948

-947
-947
-947
-947
-947

-946
-946
-946
-946
-946

-946

0

-000

-000

-000

-000

-000

-000

-000

-000.

-000

-000

K

TABLES FOR HYPERBOLIC MOTION.*

By HARLEY WOOD, M.Sc.

Manuscript received, March 15, 1950. Read, November 1, 1950.

In this article tables are given for the representation of hyperbolic Keplerian
motion. They are based on the same formule, with the same numerical
coefficients, prepared and intended for use in the same way as those in the
previous article, ‘‘ Tables for Nearly Parabolic Elliptic Motion ”’ (Wood, 1951)
and so only a few remarks need be added.

In order to avoid the use of imaginary arguments and give these tables a
slightly different appearance from the previous ones we set «= —e=(e—1)/(e+1).
The arguments for the respective tables then become a?u, « and «2c.

A was calculated from the series when «?4<0-20 and thereafter by obtaining
sinh-1 «?u—=log{a?u+(au2+1)2! with the Table of Natural Logarithms of the
‘* Federal Works Agency ”’ (1941).

The signs of both h and K become negative for e>1 (« negative) but since
only their product appears in the formula they are tabulated as positive.

Using the manuscript tables to two places beyond what are recorded here
the values of & for the hyperbolic case were calculated from equation (4) of the
previous article, » first having been obtained from equation (2). The intervals
of « and «co at which this was done were the same as before and the greatest
value of & obtained was 8 units of the ninth decimal place. £& is again negligible
in Seven figure work.

REFERENCES.

Federal Works Agency Projects Administration, 1941. Table of Natural Logarithms, Volume ITI,
New York.

Wood, H., 1951. Tis JourNAL, 84, 134. Also Sydney Obs. Papers No. 14.

* This paper is published with the aid of a grant from the Commonwealth Scientific Publica-
tions Committee.

152

3

2

ore

O-

HARLEY WOOD.

TABLE 1.

ar
2

0-050
‘051
-052
-053
-054

0-055
-056
-057
-058
-059

0-060
-061
-062
-063
-064

0-065
-066
-067
-068
-069

0-070
-071
-072
-073
-074

0-075
-076
-077
-078
079

0-080
-081
-082
-083
-084

0-085
-086
-087
-088
-089

0-090
-091
-092
-093
-094

0-095
-096
-097
-098
-099

0-100

9993
9993
9993
9992
9992

9992
9992
9991
9991
9991

9991
9990
9990
9990
9989

9989
9989
9988
9988
9988

9987
9987
9987
9986
9986

9985
9985
9985
9984
9984

9984
9983
9983
9982
9982

9982
9981
9981
9980
9980

9979
9979
9978
9978
9978

9977
9977
9976
9976
9975

9975

894
372
902
470
911
559
639 920
928
711
937
774
946
828
954
874
911 268
972
980
959
989
970
998
972
9661006
1014
952
1023
929
1032
897
1041
856
8081048
1058
750
1066
684
1075
609
1083
526
4351091
1100
1109
226
Tas ey
109
1126
983
9491134
1143
706
1151
555
1159
396
1168
228
0511177
1185
1193
673
1202
471
1210
261
0491219
1227
815
1235
580
1244
336
1252
084
394 1260
1269
1277
278
1286
992
1294
698
3961302
1310

086

TABLES FOR HYPERBOLIC MOTION.

TABLE 1.
oF,

124 0-150
6275 -151
pL 152
61725 153
ee 154
588 0-155
067,57 -156
540, 157
009? -158
Ae 159
932 0-160
386.5) 161
835.7. 162
280,70 163
719205 164
154 0-165
584) 7) 166
O10. 167
430704 168
846205 -169
257 0-170
6637)" 171
06490 172
46193 173
853, 6 174
240 0-175
62205 -176
9990 177
372050 -178
74059 179
103 0-180
4625 -181
8150, -182
16407. -183
509 pe 184
848 0-185
S35. -186
BIS oe 187
8380.0 188
159} ce 189
474 0-190
786004 -191
O92 F 192
394. 193
6918 194
983 0-195
oie -196
bbS5, 197
Bante -198
105s, -199

Us eal
167) 397
440

1336
104
7611243

1352

409
049
680
303
919

1360
1369
1377
1384
1394

1401
124
1409
715
1418
297
9711426
1434

Sood
995
1451
544
1458
086
6191467
1475
144483
661
1491
1705 499
671

1507
164,516
648
125
594
054
507

1523
1531
1540
1547
1556

951
388
816
237
649

1563
1572
1579
1588
1595

054
450
839
220
592

1604
1611
1619
1628
1635

957
314
663
004
338

1643
1651
1659
1666
1675

663
980
290
592
886

1683
1690
1698
1706
L714

172

153

154

No) eo)
fo) >
ao fo)
or) =)
OOOO O © C0 © © CO © © C © OC

GO

eo)

~J

—
oO OW O ©

HARLEY WOOD.

TABLE 1.
N ou
O-

9901 951... | 0-250
9900 988 Oo. 251
9900 020 208 252
9899 047 07° 253
9898 070 O41 254
9897 089 .., | 0-255
9896 103 o°° 256
9895 113 20° 257
9894 118 2° 258
9893 119,098 259
9892 116 0-260
9891 108; 5 -261
9890 096,07 262
9889 0801035 263
9888 059/05, 264.
9887 034 0-265
9886 004; 0s4 - 266
9884 970195, 267
9883 932,045 268
9882 889,07. 269
9881 843 0-270
9880 7919 one 271
9879 736,000 272
9878 676) 00) 273
9877 612i poo 274
9876 543 0-275
9875 470; ny -276
9874 39310.) 277
9873 312) 05, .278
9872 226) 000 279
9871 136 0-280
9870 042 oon -281
9868 944005 282
9867 84111)" 283
9866 734,1), 284
9865 623,,,, | 0-285
9864 508115, -286
9863 388) 150 -287
9862 264,755 -288
9861 136,15 289
9860 004 0-290
9858 87a ta 291
9857 726,14. 292
9856 581117, 293
9855 4321175 294
9854 279 0-295
9853 12908, -296
9851 960,165 297
9850 794,100 298
9849 624,570 -299
9848 450 0-300

788
691
588
477
360

2097
2103
2111
2117
2125

235
103
964
818
664

2132
2139
2146

2160

504
337
162
981
792

2167
2175
2181
2189
2195
597
394
185
968
745

2203
2209
2217
2223
2230

515
277
033
782
524

2238
2244
2251
2258
2264

260
988
710
424
132

2272
2278
2286
2292
2299

833
528
215
896
570

2305
2313
2319
2326
2333

237
898
552
199
840

2339
2346
2353
2359
2366

474
101
722
336
943

2373
2379
2386
2393
2399

544
138
726
307
882

2406
2412
2419
2425
2432

450

2154:

450
272
089
903
712

1178
1183
1186
1191
1195

517
318
115
908
697

1199
1203
1207
1211
1215

482
262
039
811
580

1220
1223
1228
1231
1236

344
104
861
613
361

1240
1243
1248
1252
1256

105
845
581
313
041

1260
1264
1268
1272
1276

765
486
202
914
622

1279
1284
1288
1292
1296

326
027
723
415
104

1299
1304
1308
1311
1316

788
469
145
818
487

1319
1324
1327
1331
1335

152
813
470
124
773

1339
1343
1346
1351
1354

419
060
698
332
963

1359
1362
1366
1369
1374

589

TABLES FOR HYPERBOLIC MOTION. 155

TABLE l.

156 HARLEY WOOD.

TABLE 1.

324
887
447
003
556

3437
3440
3444
3447
3450

106
652
194
734
269

3454
3458
3460
3465
3467

802
331
857
379
899

3471
3474
3478
3480
3484

415
927
437
943
446

3488
3490
3494
3497
3500

946
442
935
426
913

3504
3507
3509
3513
3517

396
877
355
829
301

3519
3522
3526
3528
3532

769
234
697
156
612

3535
3537
3541
3544
3547

065
516
963
407
848

3549
3553
3556
3559
3561

287
722
155
585
012

3565
3567
3570
3573
3576

436
857
275
691
103

3579
3582
3584
3588
3590

513

TABLES FOR HYPERBOLIC MOTION.

TABLE 1.
2,

719 0-550
i240. 551
elena 552
ioienes 553
Teas, 554
721 0-555
Tidak 556
T0565 557
6942) 558
G8lene: 559
665 0-560
Bis a53 561
Dike 562
604,05 563
B19 ase 564
552 0-565
Boater 566
491 ee 567
4585.0 568
422 569
383,54) | 0-570
sy ee 571
3005044 572
20s a ar 573
2095044 574
160 0-575
10850. 576
0555 0°5 577
9992020 578
9425 4 579
882 0-580
S206 ae 581
Woe ae 582
6895 be 583
ale 584
550 0-585
478 ac 586
4035000 587
Sie 588
24ge07e 589
167 0-590
0845 055 591
999200 592
Dee 593
S206 594
732 0-595
6305 -a. 596
ees 597
4465500 598
See 599
246 0-600

157

246
143
038
931
822

2103
2105
2107
2109
2111

711
598
483
366
247

2113
2115
2117
2119
2121

126
004
879
753
625

2122
2125
2126
2128
2131

494
362
228
092
955

2132
2134
2136
2137
2140

815
674
530
385
238

2141
2144
2145
2147
2148

090
939
787
632
476

2151
2152
2155
2156
2157

319
159
998
835
670

2160
2161
2163
2165
2167

503
335
165
993
820

2168
2170
2172
2173
2176

644
467
289
108
926

2177
2178
2181
2182
2183

743
557
370
181
991

2186
2187
2189
2190
2192

799

158

O-

HARLEY WOOD.

TABLE 2.

—

—

O-

TABLES FOR HYPERBOLIC MOTION.

QO:

TABLE 3.
K “20
-000 0000, 0-050
0000 -051
0000, -052
0000, -053
0000, 054
-000 0001, 0-055
0001, -056
0001, -057
0002) -058
0002, -059
-000 0003, 0-060
0003, -061
0004, -062
0005, -063
0006, -064
-000 0006, 0-065
0007, -066
0008, -067
0009; -068
0010, -069
-000 0011, 0-070
0013, -071
0014, -072
0015, -073
0016, -074
-000 0018, 0-075
0019 -076
00217 -077
0022 -078
0024, -079
-000 0026, 0-080
0027, -081
0029, -082
00315 -083
0033, -084
-000 0035, 0-085
0037, -086
0039, -087
0041, 088
00433 -089
-000 0046, 0-090
0048, -091
00503 092
0053, -093
0055, -094
-000 0058, 0-095
0061, -096
0063, -097
0066, -098
0069, -099
000 0072 0-100

O-

159

K

-000

-000

-000

-000

-000

-000

-000

-000

-000

-000

000

0072,
0074,
0077,
0080

0083)

0087,
0090,
0093,
0096

+
0100,

0103,
0106
0110,
0114

3
0117,

0121,
0125.
01287
0132

4
0136,

0140,
Ol44)
0148,
0153

t
0157,

O161,
0165.
0170,
0174

5
0179),

0183
0188
0193),
0197,
0202.

5

0207
0212
0217
0222
0227

5

0232
0237
0243
0248
0253

0259
0264
0270
0275
0281

HS OS OO

for)

0287

160

-001
-001
-001
‘001
-001

-001
-001
-001
-001
-001

‘001
-001
-001
-001
-001

-001
-002
-002
-002
-002

-002
-002
-002
-002
-002

-002
-002
-002
-002
-002

-002
-002
-002
-002
-002

-002
-002
-002
-002
-002

-002
-002
-003
-003
-003

-003
-003
-003
-003
-003

-003

QO:

-000

-000

-000

-000

-000

-000

-000

-000

-000

-000

000

HARLEY WOOD.

TABLE 3.

K “20
0287, 0-150
0293 -151
0298, -152
0304, -153
0310, -154
0316, 0-155
0322, -156
0329, 157
0335 158
0341, 159
0347, 0-160
0354 -161
0360, -162
0367, -163
0373, -164
0380, 0-165
0386, -166
0393, -167
0400, -168
0407, 169
0414, 0-170
0421, 171
0428, 172
0435, 173
0442, -174
0449, 0-175
0456, -176
0464 -177
0471, -178
0479, -179
0486. 0-180
0494, -181
0501, -182
0509. -183
0517, -184
0524, 0-185
0532. -186
0540 -187
0548. -188
0556, -189
0564, 0-190
0572, -191
0581, -192
0589, -193
0597, -194
0606, 0-195
0614, -196
0623, -197
0631 -198
0640, -199
0649 0-200

QO:

K

-000

-000

-000

-000

-000

-000

-000

-000

-000

-000

000

0649
0657
0666
0675
0684

©o O © © CO

0693 9
0702 9
O711 9
0720, 5
0730 9

0739

TABLES FOR HYPERBOLIC MOTION.

161

TABLE 3.

“2G J K 026 J K
0-200 1-006 0011,,, 0-000 1161, 0-250 -009 3778,., 0-000 1830, ,
-201 -006 0613, hans -251 “009 4530/7 1845,
-202 —- -006 1218, °° 1185," -252 © -009 52857? 1860)?
-203 -006 1826576 1196, -253 -009 6043/°° 1875,-
204 == 006 2436774 1209; 254 009 6804/01 1890,-
0-205 1-006 3050,,, 0-000 1221,, 0-255 -009 7568,,, 0-000 1905,,
-206 —_-006 3667/5 12335 -256 -009 8335,0/ 192170
-207. -006 4287555 124575 -257 -009 9105.70 1936,
-208 -006 4909 3-7 12575 -258 -009 9878/7" 1952.8
-209 -006 5535550 1269; -259 010 0654/70 1967,
0°210 1-006 6164,,, 0-000 1282,, 0-260 ‘010 1433, 0-000 1983,,
-211 -006 6796). 1294, -261 -010 2215,0° 1998,
212 — -006 74307. 1307; 5 262 — -010 3000/3 201416
-213 —_-006 8068,1, 1319," -263 —-010 3788/0" 2030)
214 = -006 870977) 133235 264 = -010 4579/04 204675
0-215 1-006 9353,,, 0-000 1345,, 0-265 -010 5373,,, 0-000 2062, ,
-216 — -007 0000/44 1358; 5 -266 010 6170/57 207817
217 -007 06497" 1370) 5 -267 010 697057) 209477
218 -007 1302,°% 1383, 5 -268 O10 Wise, 211077
219-007 1958," 1396, -269 010 8579. 2126.7
0-220 1-007 2617,,, 0-000 1409,, 0-270 010 9388,,, 0-000 2143.,
221 -007 327877 1422, -271 011 0200.7 215917
-222 —_-007 394357" 1435, 272 ‘O11 10155), 2175.
223 -007 4611,0° 1449," 273 O11 1833555 2192) /
224 — -007 5282571 1462, 274 O11 26545) 22081,
0-225 1-007 5956,,, 0-000 1475, , 0-275 -O11 3478,,, 0-000 2225, ,
226 -007 663357 1489," -276 -O11 430555% 224277
227 -007 7312,05 1502; 277 “O11 5135... 2258, 0
228 -007 7995, 55 si; 4 278 ‘O11 5968°°- 2275,
229 -007 8681)00 1529, -079 “O11 680525" 2292, 7
0-230 1-007 9370,., 0-000 1543, , 0-280 “O11 7644.,, 0-000 2309, ,
ai -008 0062) foie -281 ‘O11 8486577 23267
-232 -008 0757, 50 1570, -282 ‘O11 9831570 23437)
233 -008 1454257 1584;7 283 -012 017925 2360;
234 = -008 2155/1 1598, 4 -284 012 1030.7) 2378),
0-235 1-008 2859,,, 0-000 1612,, 0-285 -012 1884... 0-000 2395, ,
-236 -008 3566/7" 1626; 1 -286 -O12 2742578 241257
237 -008 4276, 9 1640; 1 -287 -012 3602553 2430).
238 -008 4989/7" 1654," -288 “O12 446500° 2447, |
-239 -008 5705.55 1669, 3 -289 -O12 583127" 24657
0-240 1-008 6424,,, 0-000 1683, , 0-290 -012 6200,,. 0-000 2482, ,
-241 -008 7146/57 1697; -291 ‘O12 7072277 2500; 4
242 -008 7870,00 ee -292 -012 7948279 2518).
243 -008 8598," 1726, , -293 -012 88265/° 2536, -
-244 — -008 9329/7"! 1741; 294 = 012 970755 2558;
0-245 1-009 0063,,, 0-000 1755, 0-295 -013 0591,,, 0000 2571,,
-246 -009 0800/77 1770,- -296 -013 147950 2589; |
-247 -009 1540/1, 1785,, -297 -013 2369.5, 2608, 5
-248 -009 2283/75 1800,° -298 013 326200) 2626; °
-249 -009 3029/7) 1815), -299 013 415800 2644.5
0-250 1-009 3778 0-000 1830 0-300 -013 5058 0-000 2662 »

162

K

HARLEY WOOD.

TABLE 3.

K

-000 3668

369055
37127
37345.
375655

3779
380125
38230
384655
3868."

3891
39147

22
39360,

TABLES FOR HYPERBOLIC MOTION.

O-

TABLE 3.
K “26

-000 4858, , 0-450
4884, . -451
49095, -452
4935, -453
49610, -454
-000 4987, 0-455
50145, -456
5040... 457
50665, -458
5092,, -459
-000 5119,, 0-460
5145, -461
5172,, -462
5199, ., -463
5225 -464

hi
-000 5252, 0-465
5279... -466
5306, -467
533354 468
5361 469

Past
-000 5388... 0-470
541554 -471
5443... 472
5470, -473
5498 ~ 474

PAT
-000 55255. 0-475
955350 -476
558154 -477
5609.4 -478
563753 -479
- 000 5665, 0-480
56935. -481
572154 -482
575058 -483
577853 -484
-000 5806,, 0-485
583559 -486
5864. -487
589259 -488
592155 -489
-000 5950... 0-490
597959 -491
6008, -492
603759 -493
6066.) -494
-000 6096, , 0-495
6125.) -496
615555 -497
6184.) -498
6214, -499
000 6244 0-500

QO:

-000

‘000

-000

-000

-000

-000

163

K

‘000 6244

-000 6393

-000 6545

‘000 6699

000

164 HARLEY WOOD.

TABLE 3.

K e K

-000 9659...
9698.5
973759
977659
9815.5

9854
9894")
9933.)
9972"
00127)

0052.
0092")
0131*
o1715
02114)

0252
0292%°
03327)
03737,
04137,

0454
04957)
05364)
05774)
06184)

0659
07007!
meek
07414)
07837)
0824/°
0866
09087
095075
09927"
1034/5

1076
11184°
116145
12034°
1246/9

1288

es
1374/5
141775
146045

AN OCCURRENCE OF BOUDINAGE STRUCTURE IN
NEW SOUTH WALES.

By T. G. VALLANCE, B.Sc.
Commonwealth Research Scholar in Geology, Unwersity of Sydney.

With three text-figures.

Manuscript received, October 11, 1950. Read, November 1, 1950.

INTRODUCTION.

During an investigation of the geology of the Wantabadgery district, New
South Wales, certain masses of quartzitic material roughly elliptical in section
were observed interbedded with more argillaceous low-grade metamorphic
rocks in the vicinity of Mundarlo (for locality see Fig. 1, inset). The arrangement
resembles the structure called boudinage by Lohest (1909). Boudinage structures
have not often been reported by geologists, in Australia at any rate, and it was
therefore thought desirable to place the present occurrence on record. The aim
of this note is to record the new locality and to give a brief description of the
structure. Oriented specimens have been collected for the purpose of a petro-
fabric examination, but this has not yet been commenced.

GENERAL GEOLOGICAL RELATIONS.

The country rocks for the most part consist of rather thick interbedded
sandy and argillaceous beds believed to be of Upper Ordovician age, though
reliable paleontological evidence is lacking within the area examined. Sedi-
mentary types, corresponding to the pelites, psammopelites and psammites,
recognised by Joplin at Cooma (Joplin, 1942) and Albury, are present, but the
psammopelites are quite the most abundant. These sediments are now repre-
sented by phyllites, mica-schists, quartzites and quartz-rich granulites of epi-
metamorphic type. The terrain has been invaded by a mass of partly gneissic
biotite-granite, lithologically similar to the Cooma gneiss (Joplin, 1942), which
is considered to be of epi-Ordovician age. Within the contact areole of this
granite the argillaceous schists have developed conspicuous knots of porphyro-
blastic andalusite and cordierite.

At the present time the structure of the area is far from being clear. Field-
relations suggest that the bedded rocks have been tightly, almost isoclinally,
folded on axes generally parallel to the north-west—south-east strike of the
country. Dips are constantly steep, often nearly vertical, and the cleavage
developed in the argillaceous phyllites and schists is usually parallel to the
bedding.

THE BOUDINAGE STRUCTURES.

The boudins have been found in a restricted area along the dry creek in
Pors. 97, 98, 169, Parish of Mundarlo, Co. Wynyard. Most of them occur in the
banks of the creek, where it locally cuts across the strike of the country. All
the observed outcrops are within the zone of knotted schists (Fig. 1). The
structures appear only where there is a rapid alternation of psammitic and more
argillaceous beds and in the vicinity of the best-developed boudins the average
thickness of individual horizons is only about 2-3 inches. <A few boudin-like

N

166 T. G. VALLANCE.

blocks up to 8 inches thick have been observed in the same locality, but the
field-relations are not clear. This close bedding is in contrast with the greater
part of the sedimentary series in this region, where much thicker beds are the

UP) ORDOVICIAN (?)
Pelites, Psammopelites,
Psammites.
TERTIARY — RECENT
Alluvium.
camntTe

ie ° Y2

Fig. 1.—Geological sketch-map of the Mundarlo District.
Metamorphic zones shown thus: Zone of Knotted Schists (1);
Biotite Zone (2) ; Chlorite-sericite Zone (3). Boudinage occurrences

indicated by (B).

general rule. The material of which the boudins are composed is typically a
rather compact, fine-grained, slightly mottled cream to grey psammite. In thin
section it is seen to consist essentially of quartz and clinozoisite-epidote with a

Fig. 2.
(a) Typical arrangement of boudinage at Mundarlo. From a
photograph.
(b) The neck between two small boudins showing parallel cracks.
Psammite (A), Psammopelite (B), Knotted Schist (pelite) (C). The
black marks at the nodes of the boudins represent quartz veins.

general granulitic appearance. The original sediment was probably a calcareous
or marly sandstone, a relatively rare type in this region. It is interesting to
note that ellipsoids of epidosite have been recorded at Broken Hill (Browne,
1922). Their origin and significance are, however, not clear.

OCCURRENCE OF BOUDINAGE STRUCTURE IN NEW SOUTH WALES. 167

The Mundarlo boudins are strung out along the bedding and are only found
between more argillaceous bands. Figure 2a illustrates the best-exposed section.
The major axes are parallel to the bedding and are usually about twice or three
times as great as the minor axes, the average dimensions being about 4 inches
and 1-5 to 2 inches respectively. Each boudin is joined laterally to its fellow
by a narrow neck composed of the same material as the main body. Fractures
have developed within the necks, and towards the shoulders some of these cracks
are parallel to the margins of the boudins. An extreme case of this parallel
cracking is to be seen in Fig. 2b. These nodal fractures are always filled with
glassy quartz which usually does not enter the neighbouring beds. These
adjacent beds have a definite cleavage curved parallel to the margins of the
boudins. The effect is most marked at the nodal positions. The undulations
along the bedding caused by the alternate thickening and thinning of the
psammite band are evened out in the immediately contiguous horizons (above
and below). Rarely does the disturbance proceed appreciably beyond these
two beds.

Fig. 3.—Diagrammatic representation of the probable nature of the
Mundarlo boudinage.

The third-dimensional aspect of these structures is not altogether satis-
factory because the bedding-planes are not uncovered where the boudins outcrop.
However, several specimens of boudins have been removed with a geological
pick and they appear to be end-sections of elongated masses somewhat
similar to the barrels or ‘“‘ sausages ”’ of the classic boudinage of Lohest, but they
are very much more flattened than the type-specimens. Figure 3 gives a
diagrammatic view of the probable nature of the boudins. They seem to
trend almost horizontally along the bedding-planes, and are thus nearly normal
to the dip direction of the beds. The length of the boudins is unknown. A faint
striation roughly normal to the length of the boudins is a constant feature but
there is not much indication of lineation parallel to the flattened barrels. Similar
lineation down the dip has been observed on the s-surfaces of specimens from the
Same area, which, however, show no signs of boudinage.

DISCUSSION.

The term boudinage was first applied to regular, nearly cylindrical bodies of
sandstone lying in the bedding-planes of the Devonian strata in the Bastogne
district, Belgium. These cylinders or boudins are separated from each other
by sharp fractures, transverse to the bedding, and filled by spindle-shaped
quartz-veins. The adjacent less competent beds have flowed into the depressions
between the boudins, which appear as regular undulations on the bedding
surfaces. In more intensely metamorphosed terrains, such as Scandinavia,
boudinage structures have been recorded, but often they present certain modifica-
tions of the classical examples. The columns are commonly flattened with the

168 T. G. VALLANCE.

major axis of cross-section parallel to the bedding. The quartz septa between
boudins are more typically irregular in shape. Wegmann (1932) gives some
illustrations of such modified structures. As an extreme stage Corin (1932)
refers to the ‘* quartzites en amandes ’’ from the Ardennes, which were figured by
Gosselet (1888, Pl. V, No. 5). The structures described in the present note
rather resemble Gosselet’s examples, although they are not as extreme as the
‘‘ amandes ”’.

Several different explanations have been advanced to account for the
origin of boudinage. These have been outlined briefly by Read (1934), who,
agreeing with Corin and Wegmann, concludes that the arrangement was caused
by extension in alternating competent and incompetent beds. Cloos (1946)
tacitly accepts this interpretation. In his example of boudinage from Unst
Read (1934) proved that the extension of the beds was due to a compressive
force acting normal to the direction of stretching. Corin (1932), in his work,
attributed the effect to an oblique force, the component of which on the bedding-
plane was parallel to the direction of extension. In both cases, however, the
result of the extension is that the competent bands are broken by transverse
fractures whilst the less competent adjacent beds flow towards the gaps caused
by the bending in of the edges of the resistant blocks. Quartz is simultaneously
deposited in the fractures.

In the boudinage from Mundarlo a relatively great extension is indicated.
The original psammitic bands were fractured but the marginal parts of the same
beds were induced to flow past the ends of the broken blocks, which at the same
time moved apart. The attenuated necks thus produced are in sharp contrast
with the clear-cut fractures of the Belgian boudinage. It is possible that the
marked secondary flow bears some causal relation to the composition of the
‘‘ boudined ’”? beds. True quartzites are not common in the vicinity of the
boudinage and so no comparative estimate can be made of the influence of the
lime-bearing minerals in the boudins. The cause of the extension is not yet
certain. The most plausible suggestion is that the boudins occur on the limb
(or limbs) of a tight fold in which there was extension normal to the axis. If, as
seems likely, the folding was related to the metamorphism of the area, the
flowage of the beds may have been greatly aided by the increased pressure-
temperature conditions. However, many more data are required before any
reliable statement can be made.

SUMMARY.

An occurrence of boudinage structure in the Upper Ordovician of the
Mundarlo district, New South Wales, is recorded. The examples are small
but nevertheless indicate appreciable flowage. As far as it can be seen the
boudins lie parallel to the strike of the enclosing beds. The cause of the
extension which produced the structures is not certain.

REFERENCES.

Browne, W. R., 1922. Report on the Petrology of the Broken Hill Region, excluding the Great
Lode and its Immediate Vicinity. Mem. Geol. Surv. N.S.W., No. 8, Appendix 1.

Cloos, E., 1946. Lineation, a Critical Review and Annotated Bibliography. Geol. Soc. Amer.,
Mem. 18.

Corin, F., 1932. A propos du boudinage en Ardenne. Bull. Soc. Belge Géol., 42, 101.

Gosselet, J., 1888. L’Ardenne. Mem. Carte géol. dét. de la France.

Joplin, G. A., 1942. The Cooma Complex. Proc. Linn. Soc. N.S.W., 67, p. 156.

Lohest, M., 1909. De Vorigine des veines et des géodes des terrains primaires de Belgique.
Ann. Soc. Géol. Belgique, 36, B, 275.

Read, H. H., 1934. On the Segregation of Quartz-chlorite-pyrite Masses in Shetland Igneous
Rocks during Dislocation Metamorphism, with a Note on an Occurrence of Boudinage-
structure. Proc. Liverpool Geol. Soc., 16, 134.

Wegmann, C. E., 1932. Note sur le Boudinage. Bull. Soc. Géol. France, ser. 5, 2, 477.

" AUSMRALASIAN Mepicar, PuRLISHING Company Lineimn
Seamer and Arundel Streets, Glebe, N.S.W.

| = «OF NEW SOUTH WALES

oye i 1950

me ae eee. (INCORPORATED 1881)

|} ss PART “IV (pp. 169-201, xxix-xxxi)

ea ek OF
aa , ' VOL. LXXXIV

BE as Containing Liversidge Research Lecture, Papers read
eee aA es — 1950, and Index to Volume LXXXIV

te RS : EDITED BY

Re IDA A. BROWNE, D.Sc.

; He ETS. 3 ? Honorary Editorial Secretary

a |e Mist) ee THE AUTHORS OF PAPERS ARE ALONE RESPONSIBLE FOR THE copie | Bure
che | PN STATEMENTS MADE AND THE OPINIONS EXPRESSED THEREIN 2 Re ap
: 4 ; a: i ; ;
£& “f ‘ % e

SYDNEY {th
PUBLISHED BY THE SOCIETY, SCIENCE HOUSE Fea eects 1 ‘
_ GLOUCESTER AND ESSEX STREETS ore Fi: i

1951 igs cae We

on “XXvIIL. —Liversidge Research Lecture.
Animale: a Hedley Ry Bi : mi

a “4 : . ‘ , SAVE hae ‘i
XXIX. eles a dauhaies) (IV) of Some Complex Cations. By | Re Anderson, vf
EL painartae and R. A. Plowren St 9,2) A ee Nea du

* '

ry; “XXX, ee a Complexes.
co) oe ebtebenzote Acid. By 8. E. en aaa R. A Plowman. )

AR r. XXXI. Mierke Chemistry of Osmium. Part VIII. A Note on the Preparatio.
amonium Hexachlorosmate IV. By F. P. Dwyer and J. W. Pager

\ \

Wis, i

4) { ; y ish
Reo —The Essential Oils of Bebvig Smithii iaadieckiey ia its vanude Forms.
c eS F. R. Moetee: A. Rs Penfold and ie John Simonsen

N

ENERGY TRANSACTIONS IN HOMEOTHERMIC ANIMALIS.*
By HEDLEY R. MARSTON, E.R.S.

Mr. President and Members of the Royal Society of New South Wales,

I thank you for the honour of being selected by you to be the Liversidge
Research Lecturer for 1950. I had never an opportunity to meet Archibald
Liversidge, but I knew of his devotion to Science, and so was gratified when this
opportunity made it possible for me to help carry out the desires expressed in
his last testament. In this you will recall, Liversidge, with deep insight, set
down the reference that ‘‘. . . the lectures shall be such as will encourage research
and stimulate the lecturer and the public to think and acquire new knowledge
by research, instead of merely giving instruction in what is already known. . .”’
Your lecturer has been stimulated in the course of the preparation of this discourse
for you: if what it contains entices any one of you to use his special skill to
render more clear the chemical reactions that are responsible for energy transfer
in living organisms, the hopes of Liversidge will be met.

An exhaustive discussion of the field of knowledge that it would be desirable
to cover before we might be quite ready to consider what is now known of the
chemical reactions involved in the energy transactions of living processes is
not for this occasion, so I trust I shall be forgiven if the treatment of the subject
lacks the nicety of balance which may have been achieved had the facts we have
at our disposal justified more precise generalization.t But we shall, no doubt,
occasionally catch a glimpse, however faint, of the general laws of energy
exchange that operate in living material, and thus be encouraged to add to the
pattern of knowledge that is already taking shape.

In the somewhat dismal prospect revealed by Clausius’ conclusion that our
world is ever moving towards a state of maximum entropy, there is one bright
spot. Photosynthesis, by those autotrophic organisms which bear chlorophyll,
converts a part of solar radiation into chemical energy of high potential and
SO initiates a series of reactions which create order out of the monotony of the
more probable state that atoms of hydrogen, oxygen, carbon, nitrogen, etc.,
have long since assumed in the earth’s atmosphere and hydrosphere. The
continual renewal of life brought about in this way is a backwater contrary to
the flow towards the equilibrium implied in maximum entropy ; but this state
is transient—chemical reactions of living processes are poised precariously in a
medium of oxygen which, although for a while their main driving force, ulti-
mately consumes the organism that renders them possible, to degrade its ordered
substance again to Nature’s more probable state. Transient and somewhat
feeble this contra current, but it flows to a complexity of form in which stirs
thought, the mirror in which Nature views herself. We are tempted to dwell
here and ask questions. Uncertain ground this, however, and perilously near
the siren call of first causes. So on this occasion let us avoid it and devote our

* The Liversidge Research Lecture delivered November 15th, 1950.

+ I hope to be forgiven also for failing to mention the names of those responsible for the great
volume of experimental work drawn on during the preparation of this lecture. To acknowledge
even briefly those whose contributions have given form to this subject would call for a catalogue
of names that would increase many times the length of this paper.

O

APR 2 8 1952

edi
25 FO

170 HEDLEY R. MARSTON.

attention to phenomena—nowise less alluring to the curious—which may be
interpreted through experimental enquiry.

I propose to recall for you some of the phenomena associated with the
overall energy transactions that take place under conditions of relatively constant
temperature in the tissues of homeothermic animals ; to seek with you to learn
something of the efficiency with which these proceed; and then to view our
findings in the light of what is now known of the chemical reactions of inter-
mediary metabolism that give rise to the free energy utilized in the process of
living.

oe

HEAT PRODUCTION Kg. Cal,/24hr/w°”?

DAYS OF FASTING DAYS OF FASTING

Fig. 1.—The fall in the rate of heat production that supervenes on fasting is shown
by the performance of four sheep, of which two, Nos. 522B and 558, were fasted
after three months on a very high level of feeding, and two, Nos. 572 and 560, after
a similar period on rations which provided sufficient energy to meet only 50 per cent.
of their energy requirements.
The gradual fall in the rate of energy expenditure of Nos. 522B and 558 towards
the asymptote of the basal level is typical of well fed ruminants ; the slow recession
being due to the buffer effect of the voluminous rumen contents, which continues
to ferment and so to provide assimilable nutriment to the animal for several days
after the beginning of fasting. As carnivores and mixed-feeders rapidly digest
and assimilate their -food, the enhanced rate of heat production brought about
by the heat increment of the absorbed nutriments subsides within 12-18 hours
after feeding, and so the recession to the basal level is precipitate. Subsequent
to reaching the basal level, the rate of heat production of the resting animal remains
unaltered for a considerable period.
Sheep Nos. 572 and 560 were already in a state of malnutrition when the observa-
tions were commenced. As they were fasted from a low level of food intake, the
residual food in the rumen was small, and fermentation was complete in 48 hours,
and so the rate of heat production in these fell more rapidly to the low “‘ basal ”’
level, which is a consequence of inanition.
The respiratory quotient of each animal during the 24 hours over which its heat
output was estimated is reported at each point on the graphs.

It is not my intention to pause long in the dawn of the modern era of
nutritional physiology, but our thesis will be better founded if we recall Antoine
Lavoisier’s last great contribution to science—his discovery of a relationship
between the work performed by an animal and the oxygen it consumes—for
this was indeed the sunrise. Perusal of the memoir in which Lavoisier describes
the experiments that led to these conclusions still quickens the pulse, for he so

ENERGY TRANSACTIONS IN HOMEOTHERMIC ANIMALS. LTE

clearly delights in setting down his ideas. Here, in a manner quite foreign to
his earlier writings, he exults in his argument, then, to savour it, pauses a while
to philosophize, akin in style to that incorrigible moralizer Joseph Priestly ;
soon to take up the threads again to discuss the effects of the ingestion of food on
oxygen consumption—which incidentally will be our main concern—finally to
end with an excursion into politics, pleading men to caution in the threatening
storm of revolution, as if in anticipation of his own fate. This, the last and
greatest of his memoirs to the Academy, contains his confession of faith ; in it
he sets down two essential conditions for the advancement of knowledge—
freedom of thought and the quietness of the laboratory. In the light of his
ae he had beheld the vista and declared ‘“ La vie est une fonction
chimique ”’

Before we consider the classical theories of energy metabolism, and attempt
to set them more securely in the framework of existing biochemical knowledge,
we should recall the main phenomena associated with heat production in homeo-
thermic animals. At this stage our concern is neither with the energy expended.
in voluntary muscular movement nor with the processes that are influenced
through nervous and hormonal mechanisms when, in a cold environment,
radiation exceeds the amount of heat liberated in the normal course of the
animal’s metabolism. We seek at this juncture to learn something of the rate
of energy expenditure necessary merely to sustain life in the homeothermic
animal, and so are at pains to eliminate aS many variables as possible.

When the increased heat production that supervenes on consumption of
food has subsided, a warm-blooded animal, at rest in a neutral thermal environ-
ment, produces heat at a rate which for some days is tolerably uniform. During
prolonged fasting—while the organism is virtually living at the expense of its
own tissues—this basal rate of heat production recedes very gradually with
the onset of inanition, to increase abruptly, as a symptom of the cataclysmic
disorganization of the metabolic processes, immediately prior to death.

Some of the earliest observations, made over 100 years ago, ‘showed clearly
that this overall cost of living is not a direct mathematical function of the
animal’s size but is nearly proportional to its body surface. Literal acceptance
of the. Surface Law which was formulated from this observed relationship has
been responsible for no little confusion. The search for a parameter to facilitate
comparison of the metabolic behaviour of animals of different sizes was influenced
by the implication that radiation from the body surface determines the basal
rate of heat production. In consequence, elaborate measurements were made
of the areas of body surfaces in order to relate them to body weights so that—
questionable logic this—energy metabolism might be related to surface areas
computed from body weights. All this in search of a chimera, for any generaliza-
tion based on the assumption that equal areas result in equal heat losses is.
precluded by the widely different capacities of different parts of the body surface
to radiate heat. The Surface Law, in so far as it suggests a causal relationship.
between the physical surface of an animal and its basal rate of heat production,
is untenable.

There is, however, no question that basal metabolism varies exponentially
with body weight. In homeothermic animals a relationship of this sort is.
clearly essential. A few simple calculations of heat exchange will suffice to
indicate the necessity for the relatively great differences between the rates at
which heat is produced in small and large animals. A mouse, for instance, with
a basal rate of heat production per unit weight identical with that of an elephant
could not live as a warm blooded animal in a temperate climate unless—strange
fancy this—it were clothed in an envelope some 30 cm. thick of material with
the same specific insulation as fur; or conversely, an elephant with a metabolic

172 HEDLEY R. MARSTON.

rate per unit weight identical with that of a mouse could not exist in its native
habitat without a radiator of monstrous proportions. These are extremes in
the phylogenetic scale, but within small limits of deviation the same exponential
relationship holds for all homeothermic animals, of identical species and of
different species, whatever their size.

Some such relationship could not have been other than a prime criterion
which, in the course of Evolution, determined survival of the species. The
precision with which Natural Selection has poised the rate of metabolism and
has graded so nicely the subsidiary anatomical apparatus to fulfil its requirements
of fuel and oxygen is a subject for wonder. All seems so perfectly ordered, as
if one agency determines both the size and the metabolic rate of the animal ;

3900

N
12)
12)

100
RABBIT

Kg.Cal. / Kilo / 24hrs.

Ox
| ELEPHANT

‘01 “{ { 10 1400 1000 10000
Body Wt. Kilos

Vig. 2.—The relationship between body weight and the rate of heat production of

homeothermic animals under basal conditions is plotted. The points are mean

values of critical determinations. The logarithmic scale employed for the ordinate

of body weights tends to obscure small deviations from the smooth curve, but
there is no doubt of the overall exponential relationship.

for in such close harmony we are led to seek a single variable. . Our thoughts at
once fly to hormonal balance within the organism, and particularly to thyroxine
with its known profound effects on both heat production and metabolism of
protein, and incidentally on growth and development. But to follow such
thoughts at this stage would lead us to digress. We shall return to them later.

~ We may accept, then, that the energy costs involved in living under basal
conditions vary exponentially with the weight of the animal. Observation of
the metabolism of animals varying in size from that of a mouse to that of the
elephant suggest that the rate of heat production by mature animals under basal
conditions will not deviate far from 70 W®’ Kg. Cal. per 24 hours, where W (Kg.)
is the body weight of the fasting animal. As this is an empiric expression
determined from well observed experimental data, it implies no causal relation-
ships. It is subject to small intraspecific corrections for age, sex, etc., which
factors are known to influence metabolic activities.

ENERGY TRANSACTIONS IN HOMEOTHERMIC ANIMALS. 173

In these considerations of the overall heat production we are dealing with a
summation of the rates at which heat is produced by a number of different
organs which, having in the course of ontogenesis assumed distinct functions,
might be expected, a priort, to differ in their call for energy. Let us then examine
the contributions made by individual organs to the overall heat production.
A close estimate may be made of this from the rates of oxygen consumption
and carbon dioxide formation, and these may be assessed directly from the
rate of blood flow and the difference in composition of the arterial and venous
supply to individual organs. The rate of heat production in the visceral organs
is amazingly great. Under basal conditions, approximately 70 per cent. of the
total heat production of man, for example, originates in the heart, kidneys, liver
and brain, the combined weights of which constitute little over 5 per cent. of the
total body weight (vide Table 1). The relatively rapid rate of heat production

TABLE I.

Energy Dissipated by the Tissues of a 70 Kg. Man under * Basal’ Conditions.

Oxygen Consumption
Weight of Organ of Organ Heat Produced.
Tissue. and (Proportion Litres O,/24 hr. | Kg. Cal./24 hr./Kg.
of Body Weight). and (Proportion of | Tissue.
Total Oxygen
Consumption).
Whole body 70 Kg. 356 23-5
(100 per cent.) (100 per cent.)
Heart 0-33 Kg. 37 520
(0:47 per cent.) (10 per cent.) |
Kidneys .. 0-33 Kg. 31 | 440
(0:47 per cent.) (9 per cent.) |
Liver 1-6 Kg. 115 | 335
| (2-3 per cent.) (32 per cent.)
Brain | 1-4 Kg. 68-5 | 225
| (2 per cent.) (19 per cent.) |
| 3:66 Keg. 251-5 |
| (5:24 per cent.) (70 per cent.) |
Rest of body (by diff.) | 66-3 Kg. 105 | 7:4
| (94-7 per cent.) (30 per cent.) |
Muscles | 29-5 Kg. 58-5 9-2
(42 per cent.) (16 per cent.)

by the heart is not surprising—the work entailed in circulating the blood of a
man of 70 Kg. body weight, for example, accounts for approximately 45 Kg.
Cal./24 hr., which from the overall heat production implies a mechanical efficiency
of close to 25 per cent. And the kidneys have extraneous work to do. Here
again there is nothing to astonish us until we compute the free energy change
entailed in the transport of salts, urea and water between the blood plasma and
the urine, and find that the osmotic work necessary for the secretion of urine
amounts to little more than 1 per cent. of the energy liberated as heat by the
kidneys. Thus in the kidneys as well as in the liver and, curiously, in the brain,
relatively intense chemical work proceeds continually, even when the animal
is fasting and at rest. The chemical activity within these organs under basal
conditions accounts for about 60 per cent. of the total heat produced by the
animal. In comparison, the energy necessary to sustain the skeletal muscles
in a living condition is small, smaller in fact than is implied in Table 1, because,

174 HEDLEY R. MARSTON.

even when at rest, postural tonus involves some work. Why then this com-
paratively great intensity of activity in the visceral organs? What are the
reactions which expend fuel at such a rate? And what controls them so
precisely ?

Before we seek an answer to these questions we might with profit consider
briefly the phenomena associated with the increased heat production that
supervenes on feeding. Up to this stage our concern has been with the rate
of heat production under conditions selected in attempt to ensure a minimum
expenditure of energy. This basal rate, however, is not by any means a simple
expression of the minimum rate of free energy expenditure necessary to sustain

(Cal./24 hrs

BASAL METABOLISM

0.04 0.1 1.0 10 100 1000 4000
BODY WEIGHT (Kg) = Ww

Fig. 3.—The exponential relationship between the body weight and the rated heat
production of homeothermic animals under basal conditions is obvious from the
above figure. The heavy line is that of the expression M=70W°®7? in which M
is the rate of heat production in Kg. Cal./24 hr. and W is the body weight in Kg.
The expression, derived empirically from observed data, is the best fit over a wide
range of animals, the body weights of which extend from 20 gm. to 410° gm.
The significance of the second figure of the exponent is doubtful. The broken
lines are to indicate 10 per cent. deviation from the expression.

life in the organism. Such an assumption would imply that the combustible
energy of the materials drawn from the tissues of the fasting animal to support
the living processes is 100 per cent. efficient for this purpose. Clearly, when
considering energy transactions of this sort, we are dealing with two factors—
with the demands of the organism for energy and with the efficiency with which
these demands may be met by the fuel assimilated from the food or drawn from
the tissues. The term “ basal metabolic rate ’’ when applied to the heat produc-
tion of an animal under defined ‘‘ basal’ conditions is thus misleading if it is
interpreted to mean the minimum rate of energy demand, and it is particularly
confusing if used as a base when assessing the capacity of a foodstuff to provide
the animal with the energy necessary to support its living processes—lack of
appreciation of this point has resulted in a half a century of controversy. _
The fact that foodstuffs differ in their ability to induce extra heat production
in the animal organism was recognized early in the study of energy metabolism,

ENERGY TRANSACTIONS IN HOMEOTHERMIC ANIMALS. 175

but the failure to realize that heat production is an incident, not an end, of
metabolism, led, for a period, to the quite erroneous assumption that the function
of a ration which would maintain a state of energy equilibrium in an animal at
rest in a neutral thermal environment was merely to provide the energy necessary
for the maintenance of body temperature. There is, however, ample evidence
to show unequivocally that only a fraction of the combustible energy of a

120

0:73

110

hr./ W
So
(o>)

a
oS

HEAT PRODUCTION Kg. Cal. /24
Se
=)

0 20 40 60 80 100 120 #40 160 180
INTAKE OF AVAILABLE ENERGY Kg. Cal/24 hr/w°”®

Fig. 4.—The relationship between the intake of available energy, I, from a fodder
of constant composition, and the heat production, M, of sheep consuming it is
plotted together with the “ basal’ fasting rate, B, and the inanition basal, B’.
The available energy is the combustible energy of the fodder minus the sum of the
combustible energy of the fodder minus the sum of the combustible energy of the
feeces, urine and of the methane which is a product of fermentation in the rumen.

Above maintenance the heat produced by the animals is linearly related to the
energy which becomes available from the rations. A constant proportion of the
available energy—37 per cent. of it from this particular fodder—is dissipated as
heat without performing any useful work in the organism. This fraction is defined
as ‘“‘the heat increment’. Extrapolation of the relationship to zero intake
provides the term, $8, which may be tentatively defined as “ true basal heat pro-
duction ’’. This is 20 per cent. less than B, the rate of heat production of the
resting animal under “ basal ’’ conditions, and implies that the energy provided
by fuel drawn from the tissues is subject to a heat increment of 20 per cent. Thus,
below maintenance, the slope of the relationship between the heat production
and the energy available from the ration, alters. In this range, it is made up of
two factors, the heat increment of the fodder and the heat increment of the tissue
substances drawn upon to make up the energy deficit.

maintenance ration contributes to the quota necessary to sustain life, and that
the remainder merely adds to the heat production already sufficient to support
body temperature.

The heat increment—that quota of the total energy available from a
substance being metabolized which is dissipated as heat apparently without
serving any useful purpose in metabolism—has been considered to vary with
the level of feeding, for in the relationship between food intake and heat output,
there is an apparent difference above and below the maintenance level. Below

176 HEDLEY R. MARSTON.

maintenance, however, when the available energy of the fodder is insufficient
to provide for the energy requirements of the animal, the heat increment should
be considered to be made up of two variables—the heat increment of the fodder
and the heat increment of the tissue substance being drawn upon to make up
the net energy deficit—and so, if these differ, the capacity of the fodder to
provide useful energy would appear to alter abruptly as soon as energy
equilibrium is established.

To illustrate these points let us consider, very briefly, the relationship
between heat production and the intake of available energy, of sheep fed different
quantities of the same foodstuff. It might be well to recall that the determination
of the heat production of the ruminant entails special problems as by far the
greater proportion of the energy that becomes available to the animal from the

STEERS Salles

{10

Zz
OF
=o} {00
O
> = 90
(ayy £
a
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rN
a0
Fe
Pen
w 060
sees 75
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40 40
0 40 80 {20 160 200 240 280 0 20 40 60 80 100 120 440 160
INTAKE OF AVAILABLE ENERGY INTAKE OF AVAILABLE ENERGY

Ke. Cal./24hr/w °75 Ke. Cal./24hr/w?7>

Fig. 5.—The apparent constancy of 6, the point at which the linear relationship
between heat production of an animal and the energy which becomes available to
it from a fodder of constant composition, is illustrated by plotting two sets of
independently observed data, one from observations on sheep and one from
observations on cattle.

From the former, 6=54-5 Kg. Cal./W®% 73/24 hr. and from the latter B=51-8
Kg. Cal./W°73/24 hr., the difference being well within the standard error of the
observations.

8 is tentatively defined as “‘ true basal rate of heat production ”’ for the convenience

of assessing the relative heat increments of the available energy from various

fodders. The term “‘ basal ’”’ does not imply that 6 is a measure of the minimum

expenditure of energy necessary to support the living processes, but, in distinction

to its more general use to define the exogenous conditions under which heat pro-

duction is estimated, it connotes in this expression an endogenous constant common
to the metabolism of all foodstuffs.

carbohydrates in its fodder is derived from simple fatty acids produced by
fermentation in the paunch. The chemical changes involved in the formation
of these fatty acids through the activity of micro-flora are exothermic. The
amount of heat dissipated during fermentation is approximately 6 per cent. of
the combustible energy of the carbohydrates transformed. This quota of energy,
like that of the heat increment, is valueless in the economy of the animal, other
than when, in a cold environment, the amount of heat lost by radiation from the
body surface is greater than that produced in the normal course of metabolism—
under which circumstances, as a part of the overall heat increment, it spares,
calorie for calorie, the energy that would be called upon merely to provide heat
for the maintenance of body temperature. The heat production of the fed

ENERGY TRANSACTIONS IN HOMEOTHERMIC ANIMALS. Lay

ruminant is thus the sum of the heat produced as an end result of metabolic
processes of the animal itself and the heat evolved by the fermentative activity
of the microorganisms of its alimentary canal.

When the whole of the animal’s energy requirement is drawn from the
fodder, there is no reasonable doubt that the relationship between intake of available
energy and heat production is linear. The heat increment quota is thus a constant
proportion of the available energy—in this particular instance 37 per cent. of the
available energy is dissipated as heat in the chemical work necessary to prepare
the absorbed nutrients for their entry into the chain of events through which,
according to the supply and demand, they may either be launched into the
energy-producing cycles or laid down as body substance (Fig. 4).

Extrapolation of this linear relationship to the heat production axis should
allow a close estimate to be made of the overall amount of energy spent on the
physiological requirements of living, uninfluenced by the heat increment of the
materials oxidized to provide this energy. Thus the intercept, 8, which we
might call tentatively the ‘‘ true basal requirement ”’, is less than B, the actual
heat production under basal conditions (Fig. 4), by the heat increment of the
fuel drawn from the body substance—which from this estimate is close to 20
per cent. of the total heat dissipated during fasting.

Theoretically, within the limits of the W®’ exponential relationship between
metabolic rate and body weight, the value of 8 should be identical for all homeo-
thermic animals. There is only one set of independent observations in the
scientific literature that provides suitable data for testing this hypothesis—
that gathered from a fine series of critically conceived and meticulously observed
determinations of the heat output of bullocks fed at different planes on rations
of identical composition (Fig. 5). The intercept, 2, at which the extrapolated
regression of the heat production : available energy relationship cuts the heat
production axis in this case indicates a value 51-85 Kg. Cal./W® 7/24 hr. with a
standard deviation of 3-38; the value of @ derived similarly from experiments
with the sheep is 54:56 Kg. Cal./W® 7/24 hr. with a standard deviation of 2-30.
What then is implied in this apparently constant figure? We may be better
prepared in our attempt to answer this question if we recall something of what is
known of the transformations involving energy exchange that take place in the
course of intermediary metabolism.

We can be sure that free energy is not liberated in one burst when substrates
are oxidized within the cell. The abrupt gradient in the passage of electrons
towards oxygen that such an event would imply is lessened by an ordered series
of reactions, guided through the maze of thermodynamic possibilities by inter-
linked specific catalysts that convey, by transphosphorylations, part of the
free energy to compounds of relatively low molecular weight. From our present
state of knowledge it appears not improbable that adenosine triphosphate
assumes in this way the main role of carrier of energy within the cell, weaving
between the sites where free energy is rendered available by respiration, and the
sites where chemical work is to be done, bearing in the resonance of its pyro-
phosphate group a versatile means of energy exchange for the performance of
work within the cell—one is tempted to consider this resonance energy to be
universal currency in living matter.

During respiration within the cell, three steps are now known to be capable
of intervening between the liberation of two hydrogen atoms from the substrate
and their final combination with oxygen—the stages marked successively by
reactions with the co-enzyme pyridine-nucleosides, which occur at H’, potentials
about —0-32 v.; the reactions with the flavo-proteins, the protein complexes
of d-ribityl 6 : 7 dimethyl-iso-alloxazine nucleoside, which occur about —0-6 v. ;
and the reactions with the iron-bearing cytochromes, which occur about +0-39 v.

178 HEDLEY R. MARSTON.

A path such as this, in which each pair of electrons is intercepted three
times at intervals during their journey between the substrate and oxygen, would
impose a thermodynamic limit to the number of coupled reactions which could
be brought about. Thus, if this path were traversed, the transphosphorylating

/
E, at pH 7-0 AF Keg.Cal. for
2 electron transfer

[1 Atmosphere O92 50

+0:-6
-245 KCal.

+0-4
30

Cytochrome C

tg. -Cal-

-152 K.Cal. 20

6)
Flavo-protein
10
Hane -12-2 KCal.
Phospho-pyridine Oo
nucleotide
-O-'4

Pi

Fig. 6.—The free energy changes which would take place, when, during respiration
within the cell, two electrons, set free by a dehydrogenating reaction, pass from
the substrate, via phospho-pyridine nucleotide, flavo-protein and the cytochromes,
to oxygen, may be assessed from the above figure.

The scale of oxidation-reduction potential E’, at pH 7-0, which is a measure of the
free energy of the reactions involved, expresses, in volts, the difference of potential
between the system at pH 7:0 and the normal hydrogen electrode (pH=0). The
signs and the zero of this conventional scale are thus consequences of the mathe-
matical convenience in the selection of the normal hydrogen electrode potential
as a reference point. The chemical potential, i.e. the relative tendency for electron
flow, of these reactions decreases progressively as the potential of oxygen is
approached.

The scale of free energy changes is derived from the relationship, —Af=nF AE, in
which A f=the change in free energy in Joules, n=the number of electrons involved,
F=the Faraday, and AE=the potential difference in volts.

As the average resonance energy in pyrophosphate bonds, ~P, is close to 12
Kg. Cal./mole, which is equivalent to approximately 0-25 volt per two electron
transfer, four coupled reactions, each involving the production of one ~P, are
the thermodynamic limit if the above course is taken, one in the 0-26v. interval
between phospho-pyridine nucleotide and flavo-protein, one in the 0-33v. interval
between flavo-protein and the cytochromes, and a possible two in the 0-52v.

interval between the cytochromes and oxygen.

reactions which convert adenosine diphosphate to adenosine triphosphate and
thereby convey 12 Kg. Cal./mole in the resonance of the added pyrophosphate
group, would be limited to four, for each atom of oxygen consumed. Available
evidence suggests that only three such transfers are achieved. This would
imply the dissipation as heat of 30 per cent. of the free energy liberated by each

ENERGY TRANSACTIONS IN HOMEOTHERMIC ANIMALS. 179

dehydrogenation—the remaining 70 per cent. being converted to resonance
energy capable of performing work within the cell.

Some of you may recall that classical physiologists considered glucose ‘ the
preferred fuel’ for the provision of energy to the organism. Let us, then,
examine what is known of free energy changes which occur during oxidation of
a glucose molecule within the cell. Glycolysis, you will agree, is now reasonably
well understood to be a series of reversible reactions—extending in the animal
organism between glycogen and pyruvic acid—through which glucose passes

GLYCOGEN

\
GLUCOSE -1- PHOSPHATE
||

GLUCOSE GLUCOSE -6-PHOSPHATE
@ |

FRUCTOSE-6-PHOSPHATE

|| Geo

GA) —_—- FRUCTOSE -1,6- PHOSPHATE

ee

DIHYDROXY ACETONE PHOSPHATE PHOSPHOGLYCERALDEHYDE

OQ Ss || — Garey

1,3- DIPHOSPHOGLYCERIC ACID

{| —cmotase>

2 PHOSPHOGLYCERIC ACID

|| ——qeeiese

2 PHOSPHO-ENOL-PYRUVIC ACID

© == ||

PYRUVIC ACID

FRUCTOSE

Fig. 7.—The probable course taken by glucose during glycolysis within animal
tissues is indicated. The reactions between the links are reversible, the equilibria
being influenced primarily by the concentration of adenosine triphosphate, the
resonance energy of the pyrophosphate group of which is indicated by ~P. Con-
version of glucose to glucose-6-phosphate in which form it is introduced into the
glycolytic chain involves the expenditure of one ~P. The activity of hexokinase,
which effects this priming reaction, is subject to hormonal control.

before its degradation product, pyruvic acid, enters the main energy-producing
cycle where oxidation is completed. Admission of glucose into this chain of
events necessitates its preliminary conversion to the Robinson ester, glucose-6-
phosphate, by the intervention of the enzyme, hexokinase, and of adenosine
triphosphate—a synthesis which entails the expenditure of 12 Kg. Cal./mole.
from a pyrophosphate group to produce an ester-phosphate in which the
resonance energy is in the vicinity of 3 Kg. Cal./mole. This priming reaction is
thus exothermic and irreversible. Incidentally, the enzyme that affects it is
now known to be subject to hormonal control—hexokinase activity is apparently
poised between the inhibitory influences of anterior pituitary and adreno-
cortical hormones and the stimulatory influences of insulin.

Once glucose is introduced into the glycolytic chain as glucose-6-phosphate
its conversion through the Cori ester, glucose-1-phosphate, to glycogen, or its

180 HEDLEY R. MARSTON.

degradation via fructose-6-phosphate to the Harden-Young ester, fructose-
1, 6 phosphate—by means of phosphatase and the intervention again of adenosine
triphosphate, at this stage to convey a recoverable unit of 12 Kg. Cal./mole—
hence via the triose, phosphoglyceraldehyde, by dehydrogenation to 1,3-diphos-
phoglyceric acid, and then in turn through 2,phosphoglyceric acid and phospho-
enol-pyruvic acid to pyruvic acid, is apparently a matter of equilibria, influenced
by the relative concentrations of the reacting links, and of the availability of
adenosine triphosphate. The resonance energy of two pyro-phosphate groups
of adenosine triphosphate are expended in this series of changes and four are
recovered. Thus, during the degradation of a glucose unit from glycogen through
these reactions to two molecules of pyruvic acid, recovery in terms of the energy
transferred to pyrophosphate groups—7.e. in currency expendable on work
within the cell—is approximately 35 per cent. of the energy set free. The overall
recovery of energy from the glycolytic reactions if glucose itself is the starting
point is further reduced to approximately 20 per cent. by the cost of the priming
phosphorylation.* But the major part of the potential energy of the glucose
molecule (83 per cent. of it) is retained in the two molecules of pyruvic acid.
The overall cost, then, in preparing glucose for its excursion into the tricarboxylic
acid cycle is about 14 per cent. of its combustible energy. While: considering
these reactions in some detail I have perhaps tried your patience, but in recalling
them, my purpose is to stress that there are considerable expenses in terms of
energy which must be met before even ‘‘ the preferred fuel ”’ is converted to a
form in which it may be launched into the cycle which apparently is the main
convertor of energy in the living cell.

The reactions of the tricarboxylic acid cycle which aré now known—and
which possibly are the more important ones—are no doubt familiar to you all,
so I shall not try your patience further by discussing them in any detail. However,
it might be well to bear in mind that the path taken by electrons liberated from
some of the dehydrogenations in the respiratory cycle remains obscure. But
once launched into this cycle, the 2-carbon fragment from all metabolites might
be expected to yield the same amount of energy to phosphate bond resonance.

When discussing the coupled reactions that take place after electrons are
liberated by dehydrogenation of the substrate, we concluded that the highest
efficiency of energy transfer, which may be expected if the course suggested
were taken, could not exceed 80 per cent. and that from experimental evidence
available, which implies three transphosphorylations for each atom of oxygen
consumed in the tricarboxylic acid cycle, the efficiency would probably be
closer to 70 per cent. If this estimate is correct, oxidation of the two moles of
pyruvic acid would transfer to adenosine diphosphate approximately 360 Kg. Cal.
as resonance energy in pyrophosphate groups. Complete oxidation of a molecule
of glucose, then, would yield in this currency close to 55 per cent. of the total free
energy liberated—there is a net gain of 24 Kg. Cal./mole, it will be recalled, in
the glycolytic reactions through which the glucose molecule is degraded to two
molecules of pyruvic acid.t Thus it becomes evident that the net recovery of
energy in a state capable of performing work within living tissues, falls far short
of the total energy liberated during complete oxidation of a substrate.

* Conversion of one mole of glucose to two moles of pyruvic acid involves a free energy change
of —115 Kg. Cal. As the resonance energy, ~P, of the pyrophosphate group of adenosine
triphosphate is approximately 12 Kg. Cal., the net recovery of energy in this currency is about
24 Kg. Cal.—the total recovery being 4~P and the expenditure 2~P. The efficiency of the
reaction in terms of resonance energy is thus approximately 20 per cent.

+ Recovery of energy in the resonance of ~P (approx. 12 Kg. Cal./mole) on complete oxida-
tion of a mole of glucose during respiration within the cell would be: from glycolysis, 2~P ;
and from oxidation of the two moles of pyruvic acid arising from glycolysis, 30~P, i.e., 384 Kg.
Cal. from a total free energy change of 674 Kg. Cal.

ENERGY TRANSACTIONS IN HOMEOTHERMIC ANIMALS.

181

Although fats take a course which, as yet, is not as well charted as the one
taken by carbohydrates, their relatively low heat increment suggests that the
higher fatty acids are launched into the reversible channels of metabolism with

an efficiency comparable with that of glucose.

i
c=0

|
COOH
Pyruvic acid

-2H
-CO,
COOH COOH
f | |
| 2 CARBON “3 =
| cz=0 *H20 GH +H20
: . C COOH C-COOH
H mel
C-H aca td
| |
COOH COOH

oxalo-citraconic acid CiS-aconitic acid

“
-2H <— WW 5)
1S @
COOH COOH COOH
\ |
c=0 H-C-OH CH
{ et tO. il
H-C-H H-C-H 5 H
| {
COOH COOH COOH
oxal acetic acid malic acid fumaric acid

-2H -2H

SucCinic acid

Acetic acid—an important

-2H

COOH COOH

| |
H-C-OH C=O

| ee |
H-C-COOH H-C- COOH

| t
HCH HaCom

|
COOH COOH

iso-citric acid oxalo succinic actd

5
-CO>z.
3
COOH
|
COOH C=o
| {
H-C-H *H20 H-C-H
| |
HCH. C2 teH
| |
COOH COOH

«keto glutaric

Peay oe |

Fig. 8.—The known reactions of the tricarboxylic acid cycle through which

respiratory dehydrogenation of many substrates is effected, are set out.

Knowledge

of these reactions has been achieved, for most part, from studies, in vitro, with

tissue extracts and suspensions.

The yield of ~P from the transphosphorylating
reactions coupled to each stage of dehydrogenation is not yet clear.

Experimental

determination of the overall relationship between the amount of oxygen consumed
and the yield of ~P during cellular respiration suggests that the production of

3~P is achieved at each stage.
Fig. 6.)

The thermodynamic lhmit would be 4~P.

(vide

fuel for ruminants—is apparently a much more expensive unit to launch into
these channels, and for this reason is probably responsible for a major part of the

relatively high rate of heat production in the fed ruminant.

Propionic acid,

which is formed along with acetic acid during fermentation of carbohydrates in
the rumen, certainly has a materially smaller heat increment than that of acetic

acid.

182 HEDLEY R. MARSTON.

The heat increment of the available energy from protein is notoriously
high. Here, however, we might expect the costs entailed in the formation and
excretion of urea to be superimposed on the heat increments of the various
fragments that arise from the deaminized amino acids, some of which take the
metabolic course of the carbohydrates, some the course of the higher fatty
acids, and some, like acetic acid, a much more expensive course. The costs of
the chemical work necessary for the production of urea in the ornithine cycle,
and for the osmotic work necessary for its excretion, must be discharged with
the depreciated currency of resonance energy, and so are greater than thoge
implied from the overall free energy change.

Hitherto I have refrained from employing the classical term ‘‘ specific
dynamic effect’, which has been considered to be synonymous with ‘ heat
increment ’’. I have avoided it because it implies that the increase of heat
production which supervenes on the consumption of food is the result of a
stimulus to metabolism—of an increase in the demands for energy by the tissues
rather than a consequence of the costs entailed in the launching of the foodstuffs
into channels through which these demands may be fulfilled. But the term
and its implications may not lightly be dismissed when considering the effect
that protein ingestion exerts on the heat production of animals, for it is conceiv-
able that the dynamic equilibrium, which exists between the metabolic pool of
amino acids and the tissue proteins, may be influenced by the amino acids
arising from the ingested protein to an extent that might increase materially
the expenditure of energy necessary to sustain protoplasmic structure.

Let us consider, very briefly, the energy transactions involved in this
equilibrium, as they will serve, inter alia, to illustrate the relatively great losses
of energy entailed in the performance of the chemical work in living tissues.

We have discussed the evidence which renders it probable that resonance
energy of pyro-phosphate groups constitutes a most important currency for the
performance of work in living tissues. The exchange rates for conversion of the
energy liberated by respiration to this currency are obviously high, and—to
continue the metaphor—its purchasing power in terms of chemical work is,
more often than not, very low. For instance, the costs of synthesizing a peptid
bond between two amino acids, which effects a free energy increase of about
3 Kg. Cal./mole, involves the expenditure of the whole of the resonance energy
of the pyro-phosphate group of adenosine triphosphate, with the dissipation of
75 per cent. of it. Thus, synthesis of protein is a costly item in the economy
of the organism ; its efficiency in terms of the ‘‘ preferred fuel’? would not
exceed 14 per cent., and, in terms of the fuel absorbed from the intestinal tract of
ruminants, would be reduced further by the heavy losses involved in the high
heat increment. A considerable amount of energy is clearly necessary to
maintain the structure of protoplasm, for there is no doubt that the proteins in
living cells are in constant flux and that their apparent steady state is but a
reflexion of the relative rates of their degradation and resynthesis. From
experiments in which N15-tagged amino acids were fed to humans and to rats
there is eloquent evidence to indicate that the rate of protein turnover within the
tissues of a homeothermic animal in a steady nutritional state, varies with the
size of the animal. The ratio of the rates of protein synthesis per unit weight of
the rat and of Man, estimated by this means, is very close to 5 : 1—practically
identical with the relative rates of energy expenditure under basal conditions.
We have already concluded (Table 1) that the heat production within the liver
accounts for over 30 per cent. of the total heat production of Man under basal
conditions. The rate of protein turnover in the liver of Man, assessed from the
rate of loss of N15 from the blood-plasma proteins, which there is good reason to
believe are produced in the liver and are in dynamic equilibrium with the liver

ENERGY TRANSACTIONS IN HOMEOTHERMIC ANIMALS. 183

protoplasmic proteins, bears a similar relationship to the overall rate of protein
turnover. And the comparatively slow rate of protein turnover in the muscles
is closely parallel to their basal heat production.

These relationships can hardly be fortuitous. They suggest that the
mechanism which poises the basal rate of heat production might operate by
influencing the rate of protein turnover. But, in so far as the latter may be
estimated from exchange reactions, the energy cost of the syntheses necessary
to preserve the tissue proteins in a steady state is not of the same order as the
energy dissipation implied by the total heat production, even when the
depreciated rate of the currency which effects these syntheses is accounted for.
Nevertheless a common factor is suggested and we are impelled to seek it, for
knowledge of the mechanism involved would greatly clarify the central problem
of energy metabolism. Although many suggestive clues are available, no satis-
factory explanation of the mechanism through which the rate of heat production
is poised in homeothermic animals emerges from our present state of knowledge.
It is not yet clear whether the nervous and hormonal agencies primarily
responsible for the overall rate of heat production in the resting animal, exert
their influence by altering the demands of the tissues for energy, or by altering
the capacity of the fuel to meet these demands. The former influence could
operate by controlling the relative rates of the hydrolyses and syntheses which
determine the dynamic state of protoplasmic constituents. The latter could
operate by controlling the series of equilibria between the links of the chain of
intermediary metabolic events through which the universal currency of resonance
energy is produced. Direct hydrolysis of adenosine triphosphate, by phos-
phatase, with the dissipation of its resonance energy without performance of
chemical work could, in this way, alter very materially the rate of fuel
consumption.

In both of these effects enzyme systems would be involved, and there is,
already, unequivocal evidence in the case of hexokinase that some at least of
the known hormones exert their profound physiological effects by influencing
the activity of specific enzymes.

We might speculate without end, and progress little without experimental
evidence, however, and we must leave this question unanswered, along with
many of the others which have confronted us during our somewhat superficial
survey of energy metabolism. But, the course towards the solution of some at
least of the problems which have intrigued physiologists for more than a century
is now clear enough to invite the curious: and it is perhaps not too much to
expect that a great clarification of our knowledge of energy transactions in
living matter will soon be achieved.

In our excursion this evening, we have failed to discover any clue which
might help explain the high rate of energy dissipation that occurs in the brain.
We may, however, be reasonably sure that this expenditure is not directly
concerned with the elaboration of that tenuous secretion, thought. We may thus
take heart, for this final product of the ephemeral turbulence in the universal
flow towards maximum entropy apparently calls for extremely little expenditure
of energy.

Gentlemen, I thank you for your attention. If I have provoked rather
than diverted you, my task is fulfilled, for I have attempted to carry out the
reference set down by Archibald Liversidge and conveyed to me in your
invitation.

The Division of Biochemistry and General Nutrition,
Commonwealth Scientific and Industrial Research Organization,
University of Adelaide,
South Australia.

HALOGENOSTANNATES (IV) OF SOME COMPLEX CATIONS.

By J. R. ANDERSON, A.S.T.C.,
S. E. LIVINGSTONE, A.S.T.C.,
and R. A. PLOWMAN, B.Sc., A.S.T.C.

Manuscript received, November 8, 1950. Read, December 6, 1950.

Tin in the oxidation state of +4 is characterized by forming compounds
with halogens of the type SnX, and SnX,-. Compounds of SnX, that have
been examined have a tetrahedral structure and are presumably using sp*
bonds. For salts containing the SnCl,= ion the octahedral arrangement has
been confirmed for the K, Rb, Cs, NH, and Tl compounds (Wells, 1945).

Octahedral bonds from an element such as tin differ from those which
occur in a complex such as PtCl,=. This ion has d?sp? orbitals available and
these after hybridization give bonds of nearly maximum strength. Octahedral
d2sp? bonds for Sn involves the use of d orbitals with the same principal quantum
number as the s and p orbitals (Kimball, 1939). From the observed values of
interatomic distances in SnCl,= Pauling (1944) has assigned the octahedral
bonds to the 5s 5p? 5d? orbitals, use being made of the unstable 5d orbitals of
the valence shell itself.

The formation of the hexahalogenostannate ion takes place by reaction
of the SnX, molecule with excess halide ions

SnX,+2X- ——+ SnX,>-:

The reaction appears to take place more readily and the compounds formed are
more stable with the increasing electronegativity of the halogen. Thus the
fluoro and chloro-stannate ions are well defined and numerous compounds are
known (Mellor, 1927), but the bromo and iodo-stannates are not so well
characterized. ;

In this investigation we have prepared some chlorostannates and bromo-
stannates of complex cobalt cations and two iodostannates of complex ferrous
ions. These are listed below :

I. Tris(ethylenediamine) cobalt (III) bromide bromostannate (IV),
1-hydrate
Il. Trans-dibromo-bis-(ethylenediamine) cobalt (III) chlorostannate (IV)
III. Trans-dibromo-bis-(ethylenediamine) cobalt (III) bromostannate (IV)
IV. Tris(l:10 phenanthroline) iron (II) iodostannate (IV)
V. Tris(22’ dipyridyl) iron (II) iodostannate (IV).

They are all well defined, coloured, crystalline substances sparingly soluble,
but completely hydrolysed in hot water. Analogous types of compounds to
I, II and III have been previously reported : [Co en,]Cl.SnCl,.2H,O (McCutcheon
and d’Ouville, 1947) [Co en,Cl,] SnCl, (Spacu and Spacu, 1931), [Coen,Cl,] SnBr,
(Spacu and Spacu, 1932). We have repeated the preparation of these
compounds in order to compare them with the above. In contact with cold
water, it was found that the bromo-stannates decomposed more rapidly than
the corresponding chlorostannates, also decomposition was more rapid with

HALOGENOSTANNATES (IV) OF SOME COMPLEX CATIONS. 185

compounds containing the cation [Co en,]+*+*+ than with corresponding halo-
genostannates containing [Coen,X,]+ (EKn=ethylenediamine, X=Cl, Br).
The iodostannates IV and V did not appear to hydrolyse to any extent in
cold water, probably due to their insolubility. The only compounds containing
the SnI,= ion so far reported are Cs,SnI,, Rb,SnI, and [(CH,),As].SnlIg,
prepared by Auger and Karantassis (1925).

EXPERIMENTAL.
I. Tris(ethylenediamine) cobalt (III) bromide bromostannate (I V)—1-hydrate.

[Co en,;]Br,; was prepared by a similar method to that given for [Co en, |Cl, arch
1946). The product was dried at 120°C.

Found: Br, 50:05%.
Calculated for [Coen;]Br,;: Br, 50-07%.

Tris(ethylenediamine) cobalt (III) carbonate, prepared from [Coen,]Br, and Ag,COs,
was added slowly to a concentrated aqueous solution of H,SnBr,.8H,O and the mixture warmed.
Product was washed with ice cold HBr and dried at 110°C. No further loss in weight occurred
after drying over P,O,.

Bound; Sn, 12-59%); Br, 59°6%;. N,. 9°05%.
[Co en,]BrSnBr,.H,O requires: Sn, 12:69%; Br, 59-81%; N, 8-99%.

The orange tetragonal crystals are immediately hydrolysed in cold water to SnO, hydrate.
The compound cannot be recrystallised from HBr; it dissolves in HBr (5 g. requires 80 ml.
boiling 48% HBr) and yields [Co en,|Br,.3H,O on cooling.

Found: Br, 45:5%.
Calculated: Br, 45-0%.

II. Trans-dibromo-bis(ethylenediamine) cobalt (III) chlorostannate (IV).

Trans [Co en,Br,|Br.HBr was prepared by treating aqueous trans [Co en,Cl,]Cl with Ag,O,
filtermg and evaporating the filtrate to dryness with HBr (Mellor, 1935).

Found: Br, 63-65%.

Calculated for [Co en,Br,|Br.HBr: Br, 63-96%.

An aqueous solution of trans [Co en,Br,]Br.HBr was added to a solution of H,SnCl, in
concentrated HCl and warmed on a water bath. On cooling, bright green perfectly formed
rhomb shaped crystals were deposited. These were washed with HCl and dried at 110° C.

Found :~ Sn, 11-79%; Br, 32-89%; Cl, 20-2%; Co, 11-4%.

[Co en,Br,],SnCl, requires: Sn, 11-76%; Br, 31-67%; Cl, 21-08%; Co, 11-68%.

Hydrolysis in cold water is slow (4-} hour); the compound is soluble in 10% aqueous
solution of H,SnCl, from which it crystallizes on cooling.

Ill. Trans-dibromo-bis(ethylenediamine) cobalt (III) bromostannate (IV).

[Co en,CO,],CO, (reddish violet) was prepared by heating an aqueous solution of trans
[Co en,Cl, JC] with Ag,CO,—cf. Mellor, Inorg. and Theor. Chem., 14, 819—filtering and concentrat-
ing the filtrate. Titration with cold standard HCl gave an equivalent weight of 268 ; one replace-
able CO, group requires equivalent weight of 269-2.

[Co en,CO,],CO, was added to an excess of H,SnBr,.8H,O dissolved in a minimum quantity
of 48% HBr. At first the mixture remained reddish violet (cis form) (Mellor, 1935), but on heating
on a water bath for ten minutes the product became yellowish green (trans form). The compound
was washed with HBr and dried at 110° C.

Bound: sn, 9°2%% ; Br, 62°0%.; N, 8-62% ; Co, 8-75%.

[Co en,Br,],SnBr, requires: Sn, 9:31%; Br, 62-62%; N, 8-78%; Co, 9-24%.

2

186 - ANDERSON, LIVINGSTONE AND PLOWMAN.

Recrystallization from HBr (1 g. requires 60 ml. boiling HBr) is accompanied by a small
amount of decomposition.

Found: Sn, 8:-6%; Br, 61:0%.

The bright yellowish green cubes and prisms decompose in cold water, yielding SnO, hydrate.
somewhat more rapidly than the chlorostannate.

IV. Tris(1: 10) phenanthroline iron (II) iodostannate (IV).

Tris(1 : 10 phenanthroline) iron (II) iodide 1-hydrate was prepared from 1: 10 phenanth-
roline 1-hydrate (m.pt. 99° C.), FeSO,(NH,),SO,.6H,O, and KI in aqueous solution and recrystal-
hzed from water. —

Found: N, 9-84%; H,O, 2-14%.

Calculated for [Fe(C,,.H,N,)3]I,.H,O0: N, 9-68%; H,O, 2:08%.

1-0 g. [Fe(C,.H,N,.),3]1,.H,O was dissolved in methanol and added slowly, with stirring, to a
methanol solution containing 0:75 g. SnI, and 3 ml. 66% HI. The mixture was warmed to
50° C., stood half an hour, cooled in ice, then filtered, washed well with methanol and dried at
110°C. The product consisted of dark red prisms. Yield, 1-40 g.

Found: (Sn, 8-0%; £,51°6% ; No a27 0%.

[Fe(C,,H,N.),|SnI, requires: Sn, 8:04%; I, 51-56%; N, 5:69%.

Attempts to prepare this compound, using Nal in place of HI, failed. Products were
obtained which gave reproducible analysis figures, in which the N : I ratio was 1: 1 but the tin
content was high.

Found: Fe, 3-35, 3-30%; N, 5-07, 5-16%; Sn, 8-7, 8-7%; I, 46:5%. This gives
Fe: N: Sn: [=0-985 : 6-00: 1-20: 6-00.

Hence it appears that the presence of HI in the methanol solution is necessary to stabilize
the SnI,~ ion ; sodium iodide is unable to prevent some of the SnI,~ being converted to SnQ,.

V. Tris(2,2’ dipyridyl) tron (II) todostannate.

1 g. of tris(2,2’ dipyridyl) iron (II) iodide dissolved in methanol was slowly added to a
methanol solution containing 0-81 g. SnI, and 2-3 ml. 66% HI. After warming to 50° C. and
cooling, the reddish black crystals were washed with methanol and dried at 110°C. Yield:
1-25 g.

Hound: NouG-1o%, ; £..53-6%.

[Fe(C,,H,N.)3|SnI, requires: N, 5:98; I, 54-20%.

As with the 1: 10 phenanthroline compound when Nal was used in place of HI, a product
was obtained in which the percentage of tin was high.

Found: N, 5-10%; Sn, 9-5, 9-5%; I, 49:0%, 1.e. N: Sn: I1=5-50: 1-24: 6-00.

SUMMARY.

The chlorostannate and bromostannate of the complex cation [Co en,Br,]*,
the bromostannate of [Co en,]+++ and iodostannates of [Fe(ophen),]+*+ and
[Fe(dipy),|++ have been prepared as well-defined coloured crystalline compounds
(en=ethylenediamine ; ophen=1:10 phenanthroline; dipy=22’ dipyridyl).
With the trivalent cation [Co en,]+++ only a compound containing a mixed
anion—bromide + bromostannate—could be obtained. The analogous chloro-
stannate is similar. All the compounds are completely hydrolysed in hot water.
In cold water, the bromostannates decompose more readily than the corres-
ponding chlorostannates.

ACKNOWLEDGEMENT.
The authors are indebted to Dr. F. P. J. Dwyer for his interest and help
and for supplying the tris (dipyridyl) ferrous iodide, also to Mr. E. R. Cole for
the nitrogen analyses.

HALOGENOSTANNATES (IV) OF SOME COMPLEX CATIONS. 18

REFERENCES.

Auger and Karantassis, 1925. Compt. Rend. 180, 1845.

Fernelius, W. C., 1946. Inorganic Synthesis, 2, 221, 223. McGraw Hill, New York.
Kimball, G. E., 1939. J. Chem. Phys., 8, 188.

McCutcheon, T. P., and d’Ouville, E. L., 1947. J.A.C.S., 69, 989.

Mellor, J. W., 1927. Inorganic and Theoretical Chemistry, 7. Longmans Green, London.
—-————_——— 1935. Inorganic and Theoretical Chemistry, 14.

Pauling, L., 1944. The Nature of the Chemical Bond. Cornell University Press, New York.
Spacu, G., and Spacu, P., 1931. Bull. Soc. Stiinte Cluj, 5, 473.
—-—___ - —_____———_— ._ 1932. Bull. Soc. Stwnte Cluj, 6, 384.

Wells, A. F., 1945. Structural Inorganic Chemistry. Oxford Press.

Chemistry Department,
Sydney Technical College.

PALLADIUM COMPLEXES.

Part II. BRIDGED COMPOUNDS OF PALLADIUM WITH o-METHYL-
MERCAPTOBENZOIC ACID.

By 8S. E. LIVINGSTONE, A.S.T.C.,
and R. A. PLOWMAN, B.Sc., A.S.T.C.

Manuscript received, November 10, 1950. Read, December 6, 1950.

Mann and Purdie (1935, 1936) prepared bridged compounds of palladium
with trialkyl phosphines and arsines of the type

Se ea
a ae e,

where A=(C,H,),P and (C,H,),As.

These were prepared by the action of ammonium chloropalladate (IT)
on the dichloro-bis(tributyl-phosphine or arsine) palladium (II) compounds.
They reported difficulty with the corresponding reaction using the dialkyl
sulphide compound. Mann and Wells (1938) by X-ray examination showed
that the trimethyl-arsine analogue had the trans structure. They also prepared
similar compounds with —Br, —NO,, and —SCN in place of —Cl in the bridging
positions.

As part of the systematic examination of the bridged compounds prepared
by Mann e al., Chatt and Mann (1939) reported that compounds in which the
two arsine groups were contained in a chelate molecule did not react with
ammonium chloropalladate (II) to form bridged complexes.

In the previous communication (Livingstone, Plowman and Sorenson, 1951),
it was reported that o-methyl-mercaptobenzoic acid functioned as a chelate
group and formed with palladium the compound _bis(o-methyl-mercapto-
benzoato) palladium (II), I. Potassium chloropalladate (II) solution added
to the solution of I produced II from which the two molecules of water were
expelled at a temperature just below decomposition. If, on the other hand, the
procedure was reversed and a solution of I was added to potassium
chloropalladate (II) solution the product III was anhydrous. Moreover, II
consisted of deep orange tetragonal prisms of m.pt. 214° C., while the yellowish
brown tetragonal prisms of III had a m.pt. of 224° C.

The empirical formule of these compounds are (C,H,O,S)PdCl.H,O and
(C,H,O,S)PdCl respectively. It is almost certain that these compounds are
dimeric (Mann and Wells, 1938), but they are insoluble in organic solvents and
the molecular weights were not determined.

Assuming that the compounds are dimeric, there appears to be no alternative
formulation of ITI in which one chelate group is attached to each palladium atom.

PALLADIUM COMPLEXES. 189

This substantiates that the formation of the bridged compounds prepared by
Mann and his co-workers takes place thus :

Se ae SS oe ey
ea PS,

.

and ‘not

Pe =
ee + Ke Pa Cl, a eee Pd Se
owe Bo ee

There remains to consider the relationship between II and III. The
possibilities appear to be limited to

(i) dimorphous forms ;
(ii) alternate formulation of IL ;
(iii) structural isomers.

Both II and III are precipitated from boiling aqueous solution which
appears to obviate the possibility of dimorphous forms. Alternate formulations
of II are possible involving Pd—OH bonds and free carboxylic acid groups.
Finally, since the compounds contain two asymmetrical sulphur atoms, they
may be related as racemic and meso forms. On the limited amount of data
obtained it is impossible to decide which formulation is correct.

The compound II was also prepared by the slow addition (one week) of a
dilute aqueous solution of the sodium salt of o-methyl-mercaptobenzoic acid
to a large excess of an ice cold solution of K,PdCl,. Thus the bridged compound
was formed directly from the chelating acid without first precipitating out
bis(o-methyl-mercaptobenzoato) palladium (II).

Although practically insoluble in water and organic solvents, the bridged
compound ITI dissolved in sodium hydroxide solution, three equivalents being
required per mole of bridged compound. Acidification of this solution with
two equivalents of hydrochloric acid precipitated reddish brown crystals of a
new compound, IV, which has been formulated as containing mixed bridging
atoms.

A saturated aqueous solution of II which was only very sparingly soluble
in water was found to have a pH of 4-5-4-8, indicating that considerable
hydrolysis had taken place, possibly as given in Table 2. A suggested mechanism
of the reaction of IT with sodium hydroxide is given in Table 3. Compound II
was found to be soluble in a concentrated solution of potassium chloride (cf.
Chatt and Mann, 1939). However, no compound was isolated from the solution.

Heating of II with dilute hydrochloric acid yielded bis (o-methyl-mercapto-
benzoic acid) palladium (II), V (Livingstone, Plowman and Sorenson, 1951)._
A 0-:00025 M solution of V was found to have a pH of 3:6; this is the same pH
value as hydrochloric acid of the same concentration. This confirms that the
reaction, aS given in Table 4, takes place in solution, since recrystallization of V
from water yields VI (Livingstone, Plowman and Sorenson, 1951).

A bridged compound VII similar to III, but with bromine atoms in place
of the chlorine, was prepared by a similar method to that used for IIT.

190

Hp i TABLE /
CGZ00)
oa
c~ i PS
HT] {
(6) CH3

is (0-methy!-mercaptobenzoato) palladium (H)

ns 4
Ga SF ee

cae es St

i i cM,

Bis methyl mere fa benzoate) -u-monohydroxo -
monochlord- dipalladium (17)

LIVINGSTONE AND PLOWMAN.

CH3 0
| i]

5 cl A~
Te ee

a x Ns

ll |

0 CH3

IT 81s(0-methy/-mereapfobenzoalo)4 - aichlora -

dipallagium (1), 2-hydrate

£18 (0- methy/-mercapfo benzoate) - x -aichlore -
aipalladium (I)

we
~~

chy

8is(o- a es. =u -dbramo =
apaliadry

TABLE 2
cH 0 0
ieee: i p:
™ p47 ey +2H,0 es meet ee ¢ Hel
cH! See ) a Ee =
CMs H ch3
Ts
TABLE 3
ie 4 v3 0
~ ye ores Oe a CG Ny? + Hel
(4) 7
Cc NZ ae oe" re 7
y |
0 I cn, 0 ] CA3
| 3% On
a 0 see
y y
S Zz 0 5 cl on tNaCl
yi Honor! ee Ne, bot ina Veta 2
ES avin ae reer Paine gi 8
0 H cH; A cm +20
NE ie
1G
TABLE 4
H HO [
i He 0 PY: i
Q ra —_4t—_> r) 5 A
A Ore ey cy tHel
35 A Pe ai P ee ~, 3
Cl iI ;
| ¢ 7 On cH;
p41
chloro -b1s (0- ened Monochlora aN mercaptobenzeato)

apta benzore acid )-
palladium ( )

[a-methy! patsy) 120/¢ acid) palladium (f)

PALLADIUM COMPLEXES. 191

On substituting trans-dichlorodiammine palladium (II), trans-diglycine
palladium (II) (Pinkard, Sharratt, Wardlaw and Cox, 1934), bis (anthranilato)
palladium (II) VIII, and bis(o-carboxy-phenyldimethylarsine) palladium (IT)
IX, in place of bis(o-methylmercapto-benzoato) palladium (II) I, no reaction
with potassium chloropalladate (II) to form bridged compounds was observed.
Mann and Purdie (1935) were able to prepare bridged palladium compounds
with dichloro-bis(trialkyl-phosphine) palladium (II) and dichloro-bis (trialkyl-
arsine) palladium (II) but not with the corresponding sulphur analogues. From
these results it seems that the formation of u-halogeno compounds of palladium
is dependent on the nature of the attached ligand.

EXPERIMENTAL.

I. Bis(o-methyl-mercaptobenzoato) palladium (II).

Prepared by the reaction of potassium chloropalladate (II) on sodium o-methyl-mercapto-
benzoate (Livingstone, Plowman and Sorenson, 1951). A 0-0025 M solution of the compound
was found to have a pH of 4:2.

II. Bis(o-methyl-mercaptobenzoato)-u.-dichloro-dipalladium (LL) 2-hydrate.

(a) To a solution of bis (o-methyl-mercaptobenzoato) palladium (II) (1 g.) in boiling water
(180 ml.) was added, drop by drop over thirty minutes, an aqueous solution (40 ml.) of potassium
chloropalladate (II) (0-97 g.). After twenty minutes at the boiling point crystals began to
form. The deep orange tetragonal prisms were almost insoluble in hot water, only very slightly
soluble in boiling alcohol, but insoluble in organic solvents. Yield 1-1 g.; m.pt. 214°C.

When the compound, dried over P,O;, was heated in a closed tube, water was evolved at a
temperature just below the melting point.

Found: Pd, 32:6%; Cl, 10-8%.

(6) An aqueous solution (90 ml.) of sodium o-methyl-mercaptobenzoate (2:3 g.) was added
very slowly from a burette to an ice cold solution (270 ml.) of potassium chloropalladate (IT)
(15-6 g.). After six hours crystallization commenced ; the total addition took six days. The
product, washed with water and dried over P,O,, consisted of deep orange tetragonal prisms,
m.pt. 214°C. ; water evolved when heated to just below the melting point.

Wound: Pd, 32-6%; Cl,.10*-8%.
[(C,H,O,8)PdCl],.2H,O requires: Pd, 32-60%; Cl, 10-83%.

{II. Bis(o-methyl-mercaptobenzoato)-u.-dichloro-dipalladium (ff).

To an aqueous solution (50 ml.) of potassium chloropalladate (II) (0-48 g.) was added slowly
(20 min.) at the boiling point an aqueous solution (90 ml.) of bis(o-methyl-mercaptobenzoato)
palladium (IT) (0:5 g.). After ten minutes heating crystallization commenced. Yield 0:58 g.
The product, washed with water and dried over P,O,, consisted of pale yellowish brown prisms
of m.pt. 224°C. No water was evolved on heating to decomposition.

Found Pd, 34:2% ; Cl, -10-9%.
[(C,H,O,8)PdCl], requires: Pd, 34-49%; Cl, 11-46%.

IV. Bis(o-methyl-mercaptobenzoato) -.-monohydroxo-monochloro-dipalladium (IT).

Bis(o-methyl-mercaptobenzoato)-y-dichloro-dipalladium (II) 2-hydrate IT (1-00 g.) was
treated with 0-1 N NaOH solution. It required 42-3 ml. 0-1085 N NaOH to dissolve com-
pletely (i.e., exactly three moles of NaOH to two moles of Pd). To this solution was added
28-0 ml. 0-:1089 N HCl (i.e. two moles HCl to two moles of Pd). An amorphous brown pre-
cipitate formed, which, on standing overnight, crystallized into small reddish brown crystals
which appeared to be cubic. Yield, 0-68 g.

Hound: bd, sa-0% :.. Cl 6°0°,.

(C,H,O,8),Pd,OHCI requires: Pd, 35-55%; Cl, 5:98%.

192 LIVINGSTONE AND PLOWMAN.

V. Dichloro-bis(o-methyl-mercaptobenzoic acid) palladium (I1).

(a) A sodium hydroxide solution of bis (o-methyl-mercaptobenzoato) -u.-dichloro-dipalladium
(II) 2-hydrate II (0-7 g.) was treated with excess hydrochloric acid (2 N) and reddish brown
crystals were deposited, m.pt. 250° C.

Found: Pd; 20-89; Cl, 13:7%.

Calculated for (C,H,O,S).PdCl,: Pd, 20-76%; Cl, 13-80%.

The product could be recrystallized by digesting the mother liquor to yield reddish brown
pyritohedra of m.pt. 250° C.

(6) On treating II with hydrochloric acid (2 N) and digesting for half an hour at the boiling
point, reddish brown crystals were obtained, m.pt. 250° C.

Found: Pd, 21:0%.

A 0-00025 M solution was found to have a pH of 3:6.

VII. Bis(o-methyl-mercaptobenzoato)--dibromo-dipalladium (I1).

To a boiling aqueous solution (100 ml.) containing potassium bromopalladate (II) (1 g.)
and potassium bromide (0:5 g.) was added a hot aqueous solution (200 ml.) of bis (o-methyl-
mercaptobenzoato) palladium (II) (0-75 g.) over a period of 15 minutes. After 10 minutes
crystals began to form ; after a further 15 minutes heating the red brown crystals were filtered
hot, washed with hot alcohol, then acetone. Yield 0:85 g.

Found: Pd, 30°3%; Br, 22°6%.

[(C,H,O,8S)PdBr], requires: Pd, 30-16%; Br, 22-59%.

VIII. Bis(anthranilato) palladium (II).

The reaction of anthranilic acid with Pd™ has been investigated by Sheintsis (1939), who
determined the sensitivity, but apparently did not characterize the compound.

Anthranilic acid (5-5 g.) was dissolved in aqueous sodium hydroxide solution (1-6 g. NaOH)
and a solution of potassium chloropalladate (II) (6-5 g.) added in the cold. The yellow
crystalline product was washed with water and acetone and dried, m.pt. 245° C.

Found :))'Pd, 27-89, 3.uN; 739%
Pd(C,H,O,N), requires: Pd, 28-16% ; N, 7-39%

IX. Bis(o-carboxy-phenyl-dimethylarsine) palladium (I1) 2-hydrate.

o-Carboxy-phenyl]-dimethylarsine (1-20 g.)—-prepared by the method of Barclay and Nyholm
(1947)—-was dissolved in one equivalent of sodium hydroxide solution (30 ml.) and a solution
(10 ml.) of potassium chloropalladate (II) (1-25 g.) added. The mixture was warmed for five
. minutes, then cooled. The yellow product was washed with water and recrystallized from water,
m.pt. 178°C. When the compound, dried over P,O;, was heated, water was given off at a
temperature just below decomposition.

Found: Pd, 18:15%; C, 36-34%; H, 3-94%.
Pd(C,H,,O,As),.2H,O requires: Pd, 18-00%; C, 36-479; H, 4:08%.

SUMMARY.

Further investigations of the reactions of compounds of o-methyl-mercapto-
benzoic acid with divalent palladium have shown that it is possible to prepare
bridged halogeno compounds containing o-methyl-mercaptobenzoic acid as a
chelating molecule. The p-dichloro compound [C,H,0,SPdCl], was found to
exist in two forms, with different colours and melting points, one anhydrous and
the other hydrated. A corresponding dibromo analogue [C,H,O,.SPdBr],
was prepared in the anhydrous form. One of the chloro atoms in the u-dichloro
compound was replaceable by a hydroxo group to give a new complex
(C,H,O,8),Pd,OHCl, containing mixed bridging groups. Various reactions
of these compounds are discussed. Similar p-halogeno compounds were not
obtained with certain other ligands attached to the palladium.

PALLADIUM COMPLEXES. 193:

REFERENCES.
Barclay, G. A., and Nyholm, R. 8., 1947. Tuts Journat, 81, 77.
Chatt, J., and Mann, F. G., 1939. J.C.S., 1622.
Livingstone, S. E., Plowman, R. A., and Sorenson, J., 1951. THis JourNat, 84, 28.
Mann, F. G., and Purdie, D., 1935. J. Soc. Chem. Ind., 54, 814.
— —_—_—— 1936. J.CSN., 873.
Mann, F. G., and Wells, A. F., 1938. J.C.S., 702.
Pinkard, F. W., Sharratt, E., Wardlaw, W., and Cox, E. G., 1934. J.C.S., 1012.
Sheintsis, O. G., 1938. J. Gen. Chem. (U.S.S.R.), 8, 596.

Department of Chemistry,
Sydney Technical College.

THE CHEMISTRY OF OSMIUM.

Part VIII. A NOTE ON THE PREPARATION OF AMMONIUM
HEXACHLOROSMATE I[YV.

By F. P. DWYER, D.Sc.,
and J. W. HOGARTH, A.S.T.C.

Manuscript received, November 6, 1950. Read, December 6, 1950.

The alkali metal hexachlorosmates IV R,OsCl, can be prepared by heating
osmium tetroxide with hydrochloric acid. Chlorine is liberated slowly, some
of the volatile tetroxide is lost and the acid H,OsCl, results. A better method
(Wintrebert, 1903) involves the formation of osmyl-oxy nitrite by reaction
between the tetroxide and potassium nitrite. This substance, on addition to
boiling hydrochloric acid, gives the potassium salt. Despite the claims of
Wintrebert, the yield of potassium hexachlorosmate is never more than 40-50
per cent., reckoned on the weight of tetroxide used. The main source of the
loss appears to be in the simultaneous formation of the very soluble potassium
penta-nitro osmate III, with the osmyl-oxy nitrite.

Further, the decomposition of potassium osmyl-oxy nitrite is uncertain,
the best results being obtained by the very slow addition of the substance to
vigorously boiling acid.

Since the redox potential of the Os™/Os'Y system in hydrochloric acid is
0-532 volt (Dwyer, Humpoletz and Nyholm, 1947), it can be concluded that
ferrous salts should reduce osmium tetroxide in hydrochloric acid to the tetra-
valent stage and no further. When the reaction was carried out with ferrous
chloride in concentrated hydrochloric acid, a deep orange solution of the acid
H,OsCl, resulted. Addition of ammonium chloride then gave an almost quanti-
tative yield of analytically pure ammonium hexachlorosmate IV.

OsO, +4FeCl, +10HCl -> H,OsCl, +4FeCl, +4H,O

The alkali metal pentachlor-hydroxy osmates IV, R,[OsCl,OH], were
prepared by Krauss and Wilken (1924) from hydroxy-trichloro osmium IV.
This series of complex salts can be obtained by reduction of osmium tetroxide
with ferrous salts in controlled hydrogen and chloride ion concentrations.
Although the reaction appeared to proceed quantitatively, the final yield was
30 per cent. of the theoretical, owing to the solubility of these complex salts,
and the difficulty of removing ferrous and ferric salts. Only a trace of hexa-
chlorosmate was formed. The pentachlor-hydroxy compounds are not inter-
mediates in the formation of the hexachlorosmates. The ammonium salt
(NH,),OsCl;,OH could be boiled with concentrated hydrochloric acid in the
presence of ammonium chloride without any ammonium hexachlorosmate
resulting. This behaviour is similar to the ruthenium compounds R,[RuCl,.OH],
and confirms the observations of Mellor (1943) and Dwyer and Gibson (1950)
on the hydrolysis of the hexachlorosmates.

OsO, +4FeSO, +2H,S8O,+3HCl+2NH,Cl >
(NH,),OsCl,OH +2Fe,(SO,), +3H,0.

THE CHEMISTRY OF OSMIUM. 195

EXPERIMENTAL.

Ammonium Hexachlorosmate IV.

Osmium tetroxide (1-0 g.) was heated with a mixture of ferrous chloride hexahydrate (10g.)
and concentrated hydrochloric acid (30 ml.) in a stoppered flask on a water bath for 2 hours,
with occasional shaking. The tetroxide rapidly dissolved and the deep greenish coloured solution
became orange red. Ammonium chloride solution (20%—10 ml.) was added and the mixture
cooled in ice. The deep red crystalline precipitate was filtered and washed with 80% alcohol
and finally absolute alcohol. Yield: 1-6 g.; 94%.

Found: Os=43:-4%.
Calculated for (NH,),OsCl,: Os=43-35%.

Ammonium Pentachlor-hydroxy Osmate IV.

A mixture of osmium tetroxide (1-0 g.), ferrous sulphate (5 g.), concentrated hydrochloric
acid (3 ml.), sulphuric acid (10 N—4 ml.), ammonium chloride (0-5 g.) and water (15 ml.) was
heated on the water bath in a stoppered flask for two hours. After standing overnight, a very
small quantity of red crystals of ammonium hexachlorosmate had been deposited. After filtra-
tion the deep greenish red solution was treated fractionally with 20% ammonium chloride solution
to give a greenish brown precipitate of the pentachlor-hydroxy salt. Finally the solution was
treated with 2 g. of solid ammonium chloride and 10 ml. of concentrated hydrochloric acid and
evaporated nearly to dryness. Sufficient water was added to dissolve the ferric salts and the
mixture filtered to give a further crop of the substance. This was finally dissolved in the
minimum volume of warm water and precipitated by the addition of ammonium chloride. The
dark greenish brown crystals were washed with 90% alcohol. Yield: 0-5 g.; 30%.

Found :. Os=45-4%; Cl=42-19%.
Calculated for (NH,),[OsCl;,,OH]: Os=45-21%; Cl=42-19%.

SUMMARY.

Ammonium hexachlorosmate was obtained in almost quantitative yield
from osmium tetroxide by reduction with ferrous chloride and hydrochloric
acid, followed by addition of ammonium chloride. Ammonium pentachlor-
hydroxy osmate was obtained in a similar manner by using ferrous sulphate
as the reducing agent.

REFERENCES.

Dwyer, F. P., Humpoletz, J. A., and Nyholm, R. S., 1947. Tuis Journat, 80, 242.
Dwyer, F. P., and Gibson, N. A., 1950. Nature, 165, 1012.

Krauss, F., and Wilken, D., 1924. Z. anorg. Chem. 137, 360.

Mellor, D. P., 1943. THis JourRNAL, 77, 145.

Wintrebert, 1903. Ann. de Chim. de Phys., 28, 121.

Department of Chemistry,
Sydney University.

THE ESSENTIAL OILS OF ZIERIA SMITHII (ANDREWS) AND
ITS VARIOUS FORMS.

PART IT:

By F. R. Morrison,
A. R. PENFOLD
and SIR JOHN SIMONSEN.

Manuscript received, August 25, 1950. Read, December 6, 1950.

The results of examination of the essential oils of this small Rutaceous
shrub, which occurs in moist situations throughout New South Wales, Victoria
and Queensland, were first published in 1930 (Penfold, 1925). The oils proved
to be a very remarkable series, rich in the phenol ethers, safrole, methyl eugenol
and elemicin.

The variation in chemical composition, and the probable occurrence of
physiological forms, made it desirable for publication at that date to be restricted
to the results obtained with material growing in Queensland. These oils
consisted mainly of safrole with some methyl eugenol. The investigation has
been continued for over twenty-five years, but has only recently been completed.

One constituent of unusual interest was isolated from the essential oil
obtained from plants collected in New South Wales. This substance,
l- A\3-carene-5 : 6-epoxide (I) was investigated by Penfold, Ramage and Simonsen
(1939) and is closely related to l- A3-carene (II). It is thus the third substance
containing the carane ring to be found in nature.

CMe CMe
HC CH HC CH,
AN
ee
HC S HC CH
. \
CH—CMe, CH—¢CMe,
II

Carene-epoxide appears to be present in greatest amount in the plants
collected from the Bellinger River district of New South Wales. This is evident
from the levo-rotation of the crude oils distilled from that material.

Our botanical material was carefully examined by Mr. E. Cheel when
Curator of the National Herbarium, Botanic Gardens, Sydney, in 1927. Although
identified as Zieria smithii, Mr. Cheel .expressed the opinion that the Bellinger
River material differed sufficiently in morphological characters from the type
to be considered a definite form. Pending agreement by botanists, we propose
distinguishing the Bellinger River plant by naming it Zieria smithi variety
‘“ A’. The present paper deals with the chemistry of the essential oils obtained
from material collected in.various parts of New South Wales.

THE ESSENTIAL OILS OF ZIERIA SMITHII (ANDREWS) 197

The principal constituents so far identified are as follows, viz. :

Safrole, methyl eugenol, elemicin, d-«-pinene, /- /*-carene-5 : 6-epoxide,
linalool and eugenol. An unidentified alcohol, C,,H,,0, and nopinone (?)
are also present.

The phenol ethers occur singly or in admixture ; in some instances all three
occur together as observed with the oils obtained from the Bellinger River and
Lilyvale. The occurrence of the three phenol ethers, mentioned in varying
proportions in the foliage from different localities, is of unusual interest. Although
in some instances one particular phenol ether may predominate, namely safrole,
methyl eugenol or elemicin, to the extent of 80°%—90%, it is usually accompanied
by a small quantity of one of its associates.

The yields of oil varied from 0-5% to 1-2%, calculated on the freshly cut
leaves and terminal branchlets.

EXPERIMENTAL.

Three thousand five hundred and forty-eight pounds weight of leaves and terminal
branchlets, collected in various parts of New South Wales, were subjected to steam distillation.
The distillates were usually pale yellow oils, heavier than water, highly refractive, and they
possessed the characteristic odour of the phenol ethers, modified by that of carene-epoxide.

It was practicable, in the course of distillation of the leaves, to separate the portion of oil
lighter than water from the heavier-than-water fraction. This separation proved useful in
isolating and identifying the lower boiling constituents. A typical example is given under the
heading of l-/3-carene-5 : 6-epoxide in the appended table. Unless otherwise stated, the
chemical and physical constants were taken on the mixed distillates.

It would be impracticable to record the results of examination of the oils from each con-

signment. For the purpose of this paper one or two are selected as typical examples.

The oil from a consignment of leaves collected at Toronto, New South Wales, on 27th
January, 1925, was subjected to fractional distillation under reduced pressure, with the following
results, viz. :

100 ml. crude oil taken.

Volume Lon 20° 20°
B.P./10 mm. (M1.) dr 5° Ws oF
50- 90° ae te ne 20 | 0: 8677 1-4662 +37-2°
90-126° om ¥ a 20 | 1-0027 1-5092 ="
126-150° ie ne Sy 50 | 1-0652 1-5285 —0-55°
Residue Be ie sat 6 |

On redistillation, the following fractions were finally obtained :

BP: Volume. qe 20° 20°
(Ml.) 15° Ae Dy
153—-158°/766 mm. fe 10 0-8596 1-4653 +43-6°
50-100°/ 10 mm. .. ats 4 0-8829 1-4703 +23-4°
100-110°/ 10 mm. .. st 6 0-9640 1-4938 —3-4°
110-140°/ 10 mm. .. oe 14 1-0479 1-5253 —1-5°
140-150°/ 10 mm. .. i 30 1-0650 1-5294 +0°

MORRISON, PENFOLD AND SIMONSEN.

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THE ESSENTIAL OILS OF ZIERIA SMITHII (ANDREWS). 199

Determination of d-a-pinene.

2 Ml. of the fraction distilling at 153-158°/766 mm. on mixing with an equal volume of
l-~-pinene gave an excellent yield of pinene nitrosochloride, m.p. 109°, raised by recrystallization
to 115°. 8 ml. on oxidation with potassium permanganate (Penfold, 1922a), yielded pinonic
acid m.p. 69-70° [a}2°’ = +.90-1° (in CHCI,, C=3.3) The semicarbazone of the acid had m.p.

208°.

Determination of Safrole.

The fractions distilling at 100—110° and 110-140°/10 mm. were mixed together and placed
in a bath of solid carbon dioxide; the frozen mass was transferred to a Buchner filter funnel
surrounded by a mixture of ice and salt. By continued repetition of this process the principal
constituent, safrole, was separated, and purified by fractional distillation. It possessed the

following physical and chemical characters: b.p. 230—233°/762 mm., m.p. 11°, de 1- 1046,
fee 19375, 06° —0-2°.

10 g. of the safrole were oxidized with potassium permanganate in accordance with the
method described (Penfold, 1925, p. 87) and gave a good yield of piperonylic acid m.p. 228°,
both alone and in admixture with an authentic specimen.

Determination of Elemicin.

The fraction distilling between 140° and 150°/10 mm. was oxidized with potassium per-
manganate in alkaline solution in accordance with the procedure described by Penfold (19226).
Two acids were obtained, trimethyl gallic, m.p. 169-170°, and _ trimethyl-homogallic,
m.p. 119-120°, which placed the identity of the phenol ether as elemicin beyond doubt. Mixed
melting points showed no depression.

Leaves Collected at Terrigal, New South Wales.
Oil from a consignment of leaves collected at Terrigal on 15th February, 1924, was subjected
to fractional distillation under reduced pressure, with the following results, viz. :

100 ml. of crude oil, after removal of all alkali-soluble substances with 8% sodium hydroxide
solution, gave the following results on distillation :

BP: Volume. 15° 720 20°
(M1.) 15° D “Dp

| | [|

50— 60°/10 mm. 7 0: 8635 1: 4664 +39:-45°

60-105°/10 mm. 8 0-9488 11-4865 +21-5°
105-5-109°/10 mm. ans 26 1:0495 e 1-5140 +7°5°
109-5-112°/4-5 mm. an 45 1-0815 1-5261 +3:-:7°
Residue ms che 14 — — —

Determination of d-a-pinene.
Similar results were obtained with the first fraction as in the examination of the oil from
Toronto, 27th January, 1925.

Determination of Safrole.

Safrole was separated from the second and third fractions by the method described above,
and had m.p. 11°, a 11-1031, neo 1-5339, ap -+0-85°. It was converted to isosafrole by treat-
ment with sodium ethoxide in ethyl alcohol. The isosafrole subsequently isolated possessed
the following constants: b.p. 120-5—122°/10 mm., de. 1-123, ae 1-5740. It was oxidized
with chromic acid in glacial acetic acid solution to piperonal. The crude aldehyde was purified

through the bisulphite compound, and, on recrystallization from ethyl alcohol, had m.p. 37°,
both alone and in admixture with an authentic sample.

200 MORRISON, PENFOLD AND SIMONSEN.

\

Determination of Nopinone (?).

The first fraction, after washing with 50% resorcin solution, yielded 1 ml. of oil having
mht ie 1-4760. It was converted to the semicarbazone, which, after recrystallization from
ethyl alcohol, had m.p. 189-190°, both alone and in admixture with an authentic sample.

Found: C, 61:46; H, 9-07. ©,,H,,ON, requires: C, 61-53; H, 8-7.

The identity of this ketone requires confirmation, since it has not previously been found to
occur in nature. The rapid extermination of this plant in settled areas makes further collection
difficult.

Determination of Linalool and Unidentified Alcohol, C,)H,,0.

The presence of a small percentage of linalool in this oil was established by the preparation
of the xenyl urethane m.p. 83-85°, both alone and in admixture with an authentic
example (Penfold, Ramage and Simonsen, 1939).

An unidentified alcohol was characterized by the preparation of its 3 : 5-dinitrobenzoate,
m.p. 119° (Penfold, Ramage and Simonsen, 1939).

Minor Constituents.

Eugenol, to the extent of 2% of the crude oil, was isolated from the alkali-soluble substances
in the usual way, and the benzoate prepared. It had m.p. 69—70°, both alone and in admixture
with an authentic sample.

Volatile Acids—Acetic and Cutronellic (?).

Small amounts of volatile acids, both free and combined, were isolated after saponification
of the oil. Silver salt of water-soluble acid gave 63-8% Ag. C,H,0,Ag requires 64-67% Ag.
A volatile oily acid was obtained, the silver salt of which gave 38-52% Ag. C,)H,;0,Ag requires
38:99% Ag.

Determination of l- A3-carene-5 : 6-epoxide.

This substance was found to occur in the oils obtained from the leaves and terminal branchlets
collected from the Bellinger River district of New South Wales ; it is the principal constituent
of the fraction boiling below 100°/10 mm.

The fraction of boiling point 88—90°/17 mm., on digestion with alkali, or if heated with water
at 150°, gave geranic acid practically in quantitative yield. After removal of impurities such
as linalool and the unidentified alcohol C,,H,,0, referred to above, the oil gave figures on analysis
in close agreement with these required for C,,H,,0. This substance was I- Ay Camne; 5: 6-
epoxide, a colourless sweet elie oil having the constants, b.p. 83-85°/14 mm., de 0- 9454,

nee l- -4729, [x]546, —88°. Its structure and properties have been discussed elsewhere (Penfold,
Ramage and Simonsen (1939); Penfold and Simonsen (1942)).

Leaves Collected at Fernmount, Bellinger River, 12th July, 1926. Determination of Methyl Hugenol.
The crude oil, on distillation, yielded a fraction possessing the following constants :

5° ° °
B.p. 130-135°/10 mm., digs 1-0435, n20° 1.5274, 020° 1-5°

6 MI. on oxidation with potassium permanganate (Penfold, 1925) gave an excellent yield of
veratric acid m.p. 179-180°, unaltered in admixture with an authentic specimen.

Fractions boiling from 135-147°/10 mm. were found to consist principally of elemicin.
Oxidation with potassium permanganate in alkaline solution gave trimethyl] gallic acid, m.p.
169-170°, and trimethyl-homogallic acid, m.p. 119 to 120°. Mixed melting points showed no
depression.

The presence of safrole was not detected in this sample of oil.

SE ee

THE ESSENTIAL OILS OF ZIERIA SMITHII (ANDREWS) 201

SUMMARY.

The essential oils of Zierta smith, a Rutaceous shrub found growing in
moist situations throughout Queensland, New South Wales and Victoria, consist
principally of one or more of the phenol ethers, safrole, methyl eugenol and
elemicin. The oils obtained from plants growing in New South Wales contain
also d-a-pinene, J[- /A3-carene-5 : 6-epoxide, linalool, an unidentified alcohol
C,)H,,0, and nopinone (?)._ The chemistry of the latter oils is described in this

paper.

ACKNOWLEDGEMENTS.

Our thanks are due to the various collectors, both private and official, for
the many consignments of foliage used in the investigations, and to Imperial
Chemical Industries Ltd. for financial assistance.

REFERENCES.

Penfold, A. R., 1925. Turis JouRNAL, 64, 83.

———$ 1922a. Ibid., 56, 195.

19226. Ibid., 56, 128.

Penfold and Simonsen, 1942. J.C.S., 206.

Penfold, Ramage and Simonsen, 1939. J.C.S., 1496.

The Museum of Applied Arts Colonial Products Research
and Sciences, Sydney. Council,
The Imperial Institute,
South Kensington,
London.

(re ee Se ee re ee ew,

INDEX.

A
Page.
Anderson, J. R., Livingstone, 8. E.,
and Plowman, R. A.—Halogeno-

stannates (IV) of Some Line

Cations .. wie) SA
Annual Dinner of the Society . si OK
Annual Report xix
An Occurrence of Boudinage Structure

in New South Wales .. 165
Astronomy in Australia. Presidential

Address .. rat lye ny em
Authors, Guide to. eh ee LEV,
Awards of the Society .. a oe aN

B

Backea crenulata (De Candolle), The

Essential Oil of nf bu Be sed
Balance Sheet : 4 Wee cdi)
Bequest, Form of 1V

Bosworth, R. C. L.—The Five Properties
Concerned in the Transport of the
Active Corrodant Agent ; 53

Boudinage Structure in New South

Wales, An Occurrence of : 165
Burfitt Prize, Awards of the Walter. val
C

Cambrian Period in Australia. Clarke
Memorial Lecture for 1950. (See
Volume LXXXV.)_..

Canowindra District, N.S.W. Part ae
The Geology of the .. 46

Cherry, T. M., Pollock Memorial Lecturer xxi

Clarke Medal, Awards of st aie <i

Clarke Memorial Lectures XV

Clarke Memorial Lecture for 1950—The
Cambrian Period in Australia. (See
Volume LXXXV) ae

Coalfields of New South Wales, Bank
Variation in the Central Eastern .. 99

Commemoration of Great Scientists xx

Conversazione A xi

Cook Medal, Awards of ie Ja ames Xv1

Coordination Compounds of Copper.
Part II ah rly

Copper, Coordination Compounds of.
Part II oat we as Ager Ch

D

Dalton-Gunning Area, N.S.W., Earth
Tremors of March, 1949 He Sa we NE

Dare, H. H.—-Obituary Notice. XxXV

David Medal, Awards of the Edgeworth XVil

Page.
Diphenylthiocarbazone, Physical In-
vestigations on ie ee oo) i)
Distinguished Visitors .. aa OX
Dune Sands near Castlereagh, New
South Wales, On the Grading of .. 71
Dulhunty, J. A., Hinder, Nora, and
Penrose, Ruth.—Rank Variation in

the Central Eastern Coalfields of
New South Wales Dy 99
Dwyer, F. P., and Gibson, N. ‘A.—The

Chemistry of Osmium. Part VI.

The Use of Tris o, Phenanthroline

Osmium IT Perchlorate as an Internal

Redox Indicator a leo

Dwyer. ick ve. Gibson, N. A., and
Gyarfas, re ee

The Chemistry of Osmium. Part IV.
The Preparation and Resolution of
the Tris 0, Phenanthroline Osmium
II Ion 68

The Chemistry of Osmium. Part V.

The Redox Potentials of the Tris

2: 2’-Dipyridy] Osmium IT/IIT and

the Tris 0, Phenanthroline Osmium
IT/III Couples 80
Dwyer, F. P., and Gyarfas, E. C.—The
Chemistry of Iridium. Part V. The
Oxidation of Iridium ITI Salt Solutions

Dwyer, F. P., and Hogarth, J. W.—

The Chemistry of Osmium. Part VII.
The Bromo and Chloro Pentammine
Osmium III Series ..

The Chemistry of Osmium. Part VIII.
A Note on the Preparation of
Ammonium Hexachlorosmate IV

123

IPI

194

E

Earth Tremors of March, 1949, Dalton-
Gunning Area, N.S.W. L7
Edgeworth David Medal, Aone of the XV1l
Elkin, A. P., Society’s Medallist for
1949 oa xx
Energy Transactions in Homeothermic
RRA EEE eee Research Lecture,
1950 a 169
Enright, W. J. —Obituary Notice .. xxv
Essential Oil of Bockea crenulata (De
Candolle) : 87
Essential Oils of Zieri 1a Smithia (Andrew s)
and its Various Forms a
Exhibits X1x

F

Fischer Indole Synthesis, The Mechanism
Of, the? i,t He) ive yt Ne OD)
Foreman, J,—Obituary Notice. . «XXV1L

xxx INDEX.

G
Page.
Geology, Section of as a ee. ©
Gibson, R. A.—
See Dwyer, F. P., Gibson, R. A., and
Gyarfas, E. C.

See Dwyer, F. P., and Gibson, R. A.
Gore, P. H., Hughes, G. K., and Ritchie,
E.—The Mechanism oe the Miseher

Indole Synthesis oe re 59
Guide to Authors lv
Gunning-Dalton Area, N.S. W., ~ Earth

Tremors of March, 1949 be 17

Gyarfas, E. C.—See Dwyer, F. P., et al.

H

Halogenostannates (IV) of Some
Complex Cations ; 184

Harris, C. M. —Coordination Compounds
of Copper. Part II. Compounds
Derived from Copper (I) Iodide .. 111

Heard Island, Geography and Glaciology 92

Hinder, Nora.—See Dulhunty, J. A.,
et al.

Hogarth, J. W.—See Dwyer, F. P., and
Hogarth, J. W.

Homeothermic Animals, Energy Trans-
actions in. Cavers: Research
Lecture, 1950) 169

Honorary Membership. “New Members xix

Hughes, G. K.—See Gore, P. H., et al.

Hyperbolic Motion, Tables for pps lod

I
Tridium, The Chemistry of. Part V... 123

J

Joklik, G. F.—Dalton-Gunning Area,
N.S.W., Earth Tremors of March, 1949 17

K
Keily, T. B. rae aeewonh David Medallist
for 1949 a x
L
Lambeth, A. J.—Heard Island, Geo-
graphy and Rey. an oe, ue
Lecturettes oe huh: @-<
List of Members .. Vv
Liversidge Research Lectureship, Awards

of . XVili
Liversidge "Research Lecture “for 1950. —
Energy Transactions in Homeothermic
Animals : 6g
Livingstone, S. E., ‘and Plowman, eaves
Studies in the Chemistry of Platinum
Complexes. Part IV. Oxidation of
Ions of the Tetrammine Platinum IT
Type with Hydrogen Peroxide .. 107
Palladium Complexes. Part II.
Bridged Compounds of Palladium
with o-Methyl-Mercaptobenzoic Acid 188

Page.
Livingstone, S. E., Plowman, R. A.,
and Sorensen, J.—Palladium Com-
plexes of Thioethers. Part I. The
Reaction of Potassium Chloropalladite
II with o-Methyl Mercapto Benzoic
Acid mH 28
Livingstone, S. E. —See Anderson, J. Re
et al.

M

Mackerras, I. M.—Clarke Memorial

Medallist for 1950 ib xX

Maley, L. E.—Physical Investigations o on

Complexes of Diphenylthiocarbazone 130

Manning-Macleay Province, New South
Wales, The Permian Rocks of the .. 64
Mapstone, G. E.—

Nitrogen in Oil Shale and Shale Oil.
Part XII. The Volumetric Deter-
mination of Basic Nitrogen in Shale
Oil ee 30

Nitrogen in Oil Shale and Shale Oil.
Part XIII. An Approximate Method
for Determining Pyridine Nitrogen
in Oil Shale and Similar Materials... 34

Marston, Hedley R.—Liversidge Re-
search Lecture. Energy Transactions

in Homeothermic Animals .. .. 169
McKay, R. T.—Obituary Notice : gy.
Members, List of Vv

Morrison, F. R.—See Penfold, A. Rij and
Morrison, F. R.

N
Nitrogen in Oil Shale and Shale Oil.
Part XII Ae : ee 2)
Part XIII ai et ne .. 984
Notices oie seh nae af Beha i'g
O
Obituary Notices XXKV
Occultations Observed at Sydney Ob-
servatory during 1949 ae 44
Officers for 1950-1951 .. iil

Oil Shale and Shale Oil, Nitrogen in.—
See Mapstone, G. E.
On the Grading of Dune Sands near

Castlereagh, New South Wales ar i
Osmium, The hee of.
Part IV aa .. 68
Part Vv ar ste ae 7.80
Part VI fe Af 8 HOB
Part VII on oe is PIOTAT
Part VIII iA om fa .. 194
P

Palladium Complexes of Thioethers.
Part Eo. , A ne cnr aS

Palladium Complexes. Part II .. 188

Parabolic Elliptic Motion, Tables for
Nearly ., ff i .. 134

INDEX. Xxxl

Page.
Penfold, A. R., and Morrison, F. R.—
The Essential Oil of Backea crenulata
(De Candolle) .. 87
Penrose, Ruth.—See Dulhunty, J. ‘Au
et al.
Permian Rocks of the Manning-Macleay

Province, New South Wales A 64
Physical Investigations on Complexes
of Diphenylthiocarbazone .. 130

Platinum Complexes, Studies in the
Chemistry of—

Part Il ws ne aa Se Bite)
Part III an sh a eoree all
Part IV ar a as fl LOT

Plowman, R. A.—

Studies in the Chemistry of Platinum
Complexes. Part II. Some _ Pro-
perties of Tetrammine Platinum II
Fluorides ; 38

Studies in the Chemistry of Platinum
Complexes. Part III. Oxidation of
the Tetrammine Platinum II
Fluorides a Le ae .. 4:1

See Livingstone, R. A., e¢ al.

See Anderson, J. R., e¢ al.

Pollock Memorial Lecture si By)». 0.4
Popular Science Lectures ; xX
Presidential Address, by Harley wiped
The Work of the Society... ; ]
Astronomy in Australia iv ts 3
R
Rank Variation in the Central Eastern
Coalfields of New South Wales ee)
Report of the Council .. : 6b

Ritchie, E.—See Gore, P. H., et al.

Robertson, W. H.—Occultations Ob-
served at pygeey Sey es gure

1949 < 44
S
Sawkins, D. T.—Obituary Notice oe X XVI
Science House Management Committee,
Society’s Representatives .. RM? S.¢
Section of Geology Report ss <<

Simonett, D. S.—On the Grading of
Dune Sands near Castlereagh, New

South Wales... es aM Ae yell
Society’s Medal and ne Prize,
Awards of the .. aoe . XVil

Sorensen, J.—See Taemneetone) net E.,
et al.

Stevens, N. C.—The Geology of the
Canowindra District, N.S.W. Part II.
The Canowindra-Cowra-Woodstock

Area iv . 46
Studies in the Chemin of Pistinum
Complexes—
Part II a a nee yh Sls!
Part III Be i its eer a

Part IV us ot ae eu OF

Ah
Page.
Tables for Hyperbolic Motion .. lod
Tables for eae Parabolic oe
Motion .. 134
The Chemistry of Taian Part Vv Sa ps:
The Chemistry of Osmium—
Party — 1V. x, ess 5p a 08
Part Ai $2 a as a ou)
Part VI a fe ee Reims ts,
Part VII ae Ne es Bape la ly)
Part VIII io is .. 194
The Essential Oil of Baca crenulata
(De Candolle) .. : 87

The Essential Oils of Deere ‘Smithis
(Andrews) and its Various Forms.
Part II ee ae . 196

The Five Properties @oncomedl in tne
Transport of the Active Corrodant
Agent .. 53

The Geology of this iGaiowmiies Teeter
N.S.W. Part II. The Canowindra-

Cowra-Woodstock Area fe 46
The Mechanism of the Fischer Tadols
Synthesis a 59

The Permian Rocks of fie Manning-
Macleay Province, New South Wales.. 64

Thioethers, Palladium Complexes of—
Part I ae A ai aire!
Part II ae ae ie Pe Lets)

Vv

Vallance, T. G.—An Occurrence of
Boudinage Structure in New South
Wales... 165

Voisey, A. H.—The DSerien Ronks of
the Manning-Macleay Province, New
South Wales... o is .. 64

Ww

White, C. J.—Obituary Notice ib. 2.0NAl

Whitehouse, F. W.—Clarke Memorial
Lecture for 1950. The Cambrian
Period in Australia. See Volume
LXXXV.

Wood, Harley—
Presidential Address—

The Work of the Society .. 1
Astronomy in Australia 3
Tables for Deed Parabolic Elliptic
Motion ‘ Soloed
Tables for Haymarbelic! Motion .. L151
Z
Zreria Smith (Andrews) and its Various
Forms, The Essential Oils of. . .. 196

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