DEPARTMENT OF THE INTERIOR

BULLETIN

OF THK

UNITED STATES

GEOLOGICAL SURVEY

No.

REPORT OF WORK DONE IX THE DIVISION OP CHEMISTRY 

DURING THE FISCAL YEARS 189l-'92 AND 18!»2->5»3

WASHINGTON

GOVERNMENT PRINTING OFFICE 

1893
LIBRARY CATALOGUE SLIPS.

United. States* Department of the interior. (U. S. geological survey.) 

Department of the interior j | Bulletin | of the | United 

States | geological survey j 110. 113 | [Seal of the department] | 

Washington | government printing office | 1893

*5

"£ Second title: United States geological survey | J. W. PowelJ,

*£ director | | Report of work done | in the' division of chemistry |

* during the | fiscal years 1891-;92 and 1892-'93 | i Frank Wigglesworth Clarke, chief chemist | [Vignette] | 

Washington | government printing office | 1893

80. 115pp.

Clarke (Frank Wigglesworth).

United States geological survey | J. W. Powell, director | | 

Report of work done | in the | division of chemistry | during the | 

fiscal years 1891-'92 and 1892-'93 | j Frank Wigglesworth 

Clarke, chief chemist | [Vignette] | 

Washington | government printing office | 1893

So. 115pp.

[UsiTKU STATES. Department f>f> the interior. (U. &. yevlogical survey.) 

Bulletin 113.]

United States geological survey | J. W. Povvell, director | | 

Report of work done | in the | division of chemistry | during the | 

fiscal years 1891-'92 and l892-'93 | | Frank Wigglesworth 

Clarke, chief chemist | [Vignette] | 

Washiagtou | government printing office | 1893

8°. 115pp.

[UNITED STATES. Department, of the interior. (U. is. yeoloyieal survey.) 

lUilletiu 113.]
ADVERT IS EM: EN T.

[Bulletin No. 113.]

The publications of tlie United States Geological Survey are issued in accordance with the statute 

approved March 3, 1879, which declares that 

"Tho publications of tbo Geological Survey shall consist of the annual report of operations, geological 

and economic maps illustrating the resources and classification of the lands, and reports upon general 

and economic geology and paleontology. The annual report of operations of the Geological Survey 

shall accompany tho annual report of the Secretary of the Interior. All special memoirs and reports 

of said Survey shall bo issued in uniform quarto series if deemed necessary by the Director, butotherwise in ordinary octavos. Three thousand copies of each shall be published for scientific exchanges 

and for sale at the price of publication; and all literary and cartographic materials received in exchange 

shall bo the property of tho United States and form a part of the library of the organization; and the 

money resulting fronvthe sale of such publications shall be covered into the Treasury of the United 

States."

On July 7, 1832, the following joint resolution, referring to all Government publications, was passed 

by Congress:

1 'That whenever any document or report shall be ordered printed by Congress, there shall bo printed, 

n addition to the number in each case stated, the 'usual number' (1,734) of copies for binding and 

distribution among those entitled to receive them."

Except in those cases in which an extra number of any publication has been supplied to the Survey 

by special resolution of Congress or has been ordered by the Secretary of the Interior, this office has 

no copies for gratuitous distribution.

ANNUAL REPORTS.

I. First Annual Report of the United States Geological Survey, by Clarence King. 1880. 8°. 79pp. 

1 map. A preliminary report describing plan of organization and publications.

II. Second Annual Report of the United States Geological Survey, 1880-'81, by J. }V. Powell. 1882. 

R°. Iv, 588 pp. 62 pi. 1 map.

III. Third Annual Report of the United States- Geological Survey, 1881-'82, by J. AV. Powcll. 1883. 

8°. xvHi, 564pp. 67 pi. and maps.

IV. Fourth Annual Report of tho United States Geological Survey, 1882-r83, by J. W. Powell. 1884. 

8°. xxxii, 473 pp. 85 pi. and maps.

V. Fifth Annual Report of the United States Geological Survey, 1883-'8-i, by J. W. Powell. 1885. 

8°. xxxvi, 469 pp. 58 pi. and maps.

VJ. Sixth Annual Report of tho United States Geological Survey, 1884r-'S5, by J. W. Powell. 1885. 

8°. xxix, 570pp. 65 pi. and maps.

VII. Seventh Annual Report of the United States Geological Survey, 1885-'86, by J. W. Powell. 1888. 

8°. xx, 656 pp. 71 pi. and maps.

VIII. Eighth Annual Report of the United States Geological Survey. 1886-'87, by J. "W. Powell. 1889. 

8°. i pt. xix, 474, xii pp. 53 pi. and maps; 1 p. 1., 475-1063 pp. 54-76 pi. and maps.

IX. Ninth Annual Report of the United States Geological Survey, 1887-'88, by J. W. Powell. 1889. 

8°. xiii, 717pp. 88 pi. and maps.

X. Tenth Annual Report of the United States Geological Survey, 1888-'89, by J. "W. Powell. 1890. 

8°. ?pt. xv, 774pp. 98 pi. and maps; viii. 123 pp.

XI. EleventhAnnualReportoftheUniteuStatesGoologicalSurvey, 1889-'90, by J. W.Powoll. 1891. 

8°. Jpt. xv, 757 pp. 66 pi. and maps; ix, 351 pp. 30 pi.

XII. Twelfth Annual Report of tho United States Geological Survey, 1890-'91, by J. W. Powell. 1891- 

8°. :pt. xiii, 675 pp. 53 pi. and maps; xviii, 576 pp. 146 pi. and maps.

XIII. Thirteenth Annual Report of the United States Geological Survey, 1891-'92, by J. W. Powell. 

1893. 8°. 3 pt. vii, 240 pp. 2 pi.

XIV. Fourteenth Annual Report of the United States Geological Survey, 1892-'93, by J.W. Powell. 

1893. 8°. 2pt.

1
II ADVERTISEMENT.

MONOGRAPHS.

I. Lake Bonnevjlle, by Grove I£arl Gilbert. 1800. 4°. xx, 438 pp. 51 pi. 1 map. Price $1.50. 

II Tertiary History of the Grand Canon District, with atlas, by Clarence E. Button, Capt. U. S. A. 

1882. 4°. xiv, 264pp. 42 pi. and atlas of 24 sheets folio. Price $10.00. '

III. Geology of the Cornstock Lode and the Washoo District, with atlas, by George F. Becker. 1882. 

4°. xv, 422 pp.' 7 pi. and atlas of 21 sheets folio. Price $11.00.

IV. Comstock Mining and Miners, by Eliot Lord. 1883. 4°. xiv, 451 pp. 3 pi. Price $1.50.

V. The Copper-Bearing Rocks of Lake Superior, by Roland Duer Irviug. 1883. 4°. xvi,464 pp. 

151. 29 pi. and maps. Price $1.85.

VI. Contributions to the Knowledge of the Older Mesozoic Flora of Virginia, by William Morris 

Foutaine. 1883. 4°. xi, 144pp. 541. 54 pi. Price $1.05.

VII. Silver-Lead Deposits of Eureka, Nevada, by Joseph Story Curtis. 1884. 4°. xiii,200pp. 16 

pi. Price $1.20.

VIII. Paleontology of the Eureka District, by Charles Doolittle Walcott. 1884. 4°. xiii, 298 pp. 

241. 24 pi. Price $1.10.

TX. Brachioporta and Lamellibranchiata of the Raritan Clays and Greensaud Marls of New Jersey, 

by Hubert P. Whitfleld. 1885. 4°. xx, 338 pp. 35 pi. 1 map. Price $1.15.

X. Dinocerata. A Monograph of an Extinct Order of Gigantic Mammals, by Othniel Charles Marsh. 

1886. 4°, xviii,243pp. 561. 50 pi. Price $2.70.

XI. Geological History of Lake Lahontan, a Quaternary Lake of Northwestern Nevada, by Israel 

Cook Russell. 1885. 4°. xiv, 288 pp. 46 pi. and maps. Price $1.75.

XII. Geology and Mining Industry of Leadvillc, Colorado, with atlas, by Samuel Franklin Eiumons. 

]886. 4°. xxix,770pp. 45 pi. and atlas of 35 sheets folio. Price $8.40,

XIII. Geology of the Quicksilver Deposits of the Pacific Slope, with atlas, by George F. Becker. 

1888. 4°. xix. 486 pp. 7 pi. and atlas of 14 sheets folio. Price §2.00.

XIV. Fossil Fishes and Fossil Plants of the Triassic Rocks of New Jersey and the Connecticut Valley, by John S. Newberry. 1888. 4°. xiv, 152 pp. 26 pi. Price $1.00.

XV. The Potomac or Younger Mesozoic Flora, by William Morris Fontaine. 1889. 4°. xiv, 377 

pp. 180 pi. Text find plates bound separately. Price $2.50.

XVI. The Paleozoic Fishes of North America, by John Strong Newberry. 1889. 4°. 340 pp. 53 pi. 

Trice $1.on.

XVII. The Flora of the Dakota Group, a posthumous work, b-y Leo Lesquereux. Edited by F. H. 

Kuowlton. 1891. 4°. 400.pp. 66 pi. Price $1.10.

XVIII. Gasteropoda and Cephalopoda of the Raritan Clays and Greeusand Marls of New Jersey, 

by Robert P. Wbittield. 1891. 4°. 402pp. 50 pi. Price $1.00.

XIX. The Penokee Iron-Bearing Series of Northern Wisconsin and Michigan, by Roland D.Irving 

and C. R. Van Hise. 1892. 4°. xix. 534 pp. 37 pi.

XX. Geology of the Eureka District, Nevada, with atlas, by Arnold Hague. 1892. 4°. 419pp. 8 pi.

In press:

XXI. The Tertiary Rhynchophorous Coleoptera of North America, by Samuel Hubbard Scudder.

XXII. A Manual of Topographic Methods, by Henry Gannett, chief topographer.

XXIII. Geology of the Green Mountains in Massachusetts, by Raphael Pumpelly, J. E. Wolff, 

T. Nelson Dale, and Bayard T. Putuam. '

lu preparation:

 Mollusca and Crustacea of the Miocene Formations of New Jersey, by R. P. Whitfield.

 Sauropoda, by 0. C. Marsh.

 Stegosauria, by 0. C. Marsh.

 Brontotheridaj, by 0. C. Marsh.

 Report on the Denver Coal Basin, by S. F. Emtnous.

 Report on Silver Cliff and Ten-Mile Mining Districts, Colorado, by S. F. Eramons.

 The Glacial Lake Agassiz, by Warren Upham.

BULLETINS.

1. On Hypersthene-Andesite and on Triclinic Pyroxene in Augitic Rocks, by Whitman Cross, with a 

Geological Sketch of Buffalo Peaks, Colorado, by S. F. Emmons. 1883, 8°. 42pp. 2 pi. Price 10 cents.

2. Gold and Silver Conversion Tables, giving the coining value of troy ounces of fine metal, etc. .computed by Albert Williams, jr. 1883. 8°. 8pp. Price 5 cents.

3. On the Fossil Faunas of the Upper Devonian, along the meridian of 76° 30', from Tompkins County 

New York, to Bradford County, Pennsylvania, by Henry S. Williams. 1884. 8°. 36pp. Price 5 cents.

4. On Mesozoic Fossils, by Charles A. White. 1884. 8°. 36 pp. 9 pi. Price 5 cents.

5. A Dictionary of Altitudes in the United States, compiled by Henry Gannett. 1884. 8°. 325 pp. 

Price 20 cents. 

C. Elevations in the Dominion of Canada, by J. W. Spencer. 1884. 8°. 43 pp. Price 5 cents.
ADVERTISEMENT. Ill

7. Mapoteca Geologica Americana. A Catalogue of Geological Maps of America (North and South). 

1752-1881, in geographic and chronologic order, by Jules Maroou and John Belknap Maroou. 1884. 

8°. 184 pp. Price 10 cents.

8. On Secondary Enlargements of Mineral Fragments in Certain Rocks, by R. D. Irving and C. R. 

Van Hise. 1884. 8°. 50 pp. 0 pi. Price 10 cents.

9. A report of work done in tho "Washington Laboratory during the fiscal year 1883-'84. F. W. Clarke, 

chief chemist T.M. Ch.itard, assistant chemist. 1884. 8 3. 40pp. Price 5 cents.

10. On tho Cambrian Faunas of North America. Preliminary studies, by Cluarlca Doolittle Walcott. 

1884. 8°. 74 pp. 10 pi. Price 5 cents.

11. On the Quaternary and Recent Mollusca of the Great Basin; with Descriptions of New Forms, 

by 11. Ellsworth Call. Introduced by a sketch of the Quaternary Lakes of the Great Basin, by G. K. 

Gilbert. 1884. 8°. 06 pp. 0 pi. Price 5 cents.

12. A Crystallographic Study of the Thinolite of Lake Lahoutan, by Edward S. Dana. 1884. 8°. 

34 pp. 3 pi. Price 5 cents.

13. Boundaries of the United States and of the several States and Territories, with a Historical 

Sketch of the Territorial Changes, by Henry Gannett. 1885. 8°. 135 pp. Price 10 cents.

J4. The Electrical and Magnetic Properties of the Iron-Carburets, by Carl Barns and Vincent 

Stroithal. 1885. 8°. 238 pp. Price 15 cents,

15. On the Mesonoio and Cenozoic Paleontology of California, by Charles A. White. 1885. 8°. 33pp. 

Pricti 5 cei'its.

16. On tho Higher Devonian Faunas of Ontario County, New York, by John M. Clarko. 1885. 8°. 

8fi pp. 3 pi. Price 5 cents.

17. On the Development of Crystallization in the Igneous Rocks of Washoe, Nevada, with notes on 

the Geology of the District, by Arnold Hague and Joseph P. Hidings. 1885. 8°. 44 pp. Price 5 

cents.

18. On Marino Eocene, Fresh-water Miocene, and other Fossil Mollusca of "Western North America, 

by Charles A. White'. 1885. 8°. 26pp. '3 pi. Price 5 cents. 

10. Notes on tho Stratigraphy of California, by George F. Becker. 1885. 8°. 28 pp. Price 5 cents.

20. Contributions to tho Mineralogy of the llocky Mountains, by AVhitman Cross and W. F. Hillebrand. 1885. 8°. 114pp. 1 pi. Price 10 cents.

21. The Lignites of the Great Sioux Rese.rvatiifn. A Report on the Region between the Grand and 

Moreau Rivers, Dakota, by Bailey Willis. 1885. 8°. 1C pp. 5 pi. Price 5 cents.

22. On Now Cretaceous Fossils from California, by Charles A. White. 1885. 8°. 25 pp. 5 pi. 

Price 5 cents.

23. Observations on the Junction between the Eastern Sandstone and the Keweenaw Series on Keweenaw Point, Lake Superior, by R. D. Irving and T. C. Chamberlin, 1885. 8°. 124 pp. 17 pi. 

Price 15 cents. ;>

24. List of Marine Mollusca, comprising tho Quaternary Fossils and recent forms from American 

Localities between Capo Hattorus and Cape Roque, including the Bermudas, by William Healy Dall. 

1885. 8°. 336pp. Price 25 cents.

. 25. The Present Technical Condition of the Steel Industry of the United States, by Phineas Barnes. 

1885. 8°. 85 pp. Price 10 cents.

26. Copper Smelting, by Henry M. Howe. 1885. 8°. 107 pp. Price 10 cents.

27. Report of work done in the Division of Chemistry and Physics, mainly during the fiscal year 

1884-'85. 1886. 8°. 80 pp. Price 10 cents.

28. The Gabbros and Associated Hornblende Rocks occurring in the neighborhood of Baltimore, 

Maryland, by George Huntington Williams. 1880. 8°. 78 pp. 4 pi. Price 10 cents.

29. On the Fresh-water Invertebrates of the North American Jurassic, by Charles A. White. 1888. 

8°. 41pp. 4 pi. Price 5 cents.

30. Second Contribution to the Studies on the Cambrian Faunas of North America, by Charles Doolittle Walcott. 1886. 8°. 369 pp. 33 pi. Price 25 cents.

31. Systematic Review of our Present Knowledge of Fossil Insects, including Myriapods and Arachnids, by Samuel Hubbnrd Scuddur. 1886. 8°. 128 pp. Price 15 cents.

32. Lists and Analyses of the Mineral Springs of the United States; a Preliminary Study, by Albert 

C.Peale. 1886. 8°. 235pp. Price 20 cents.

33. Notes on the Geology of Northern California, by J. S. Diller. 1886. 8°. ,23pp. Price 5 cents.

34. On the relation of tho Laramie Mollusean Fauna to that of the succeeding Fresh-water Eocene 

and other groups, by Charles A.-White. 1886. 8°. iU pp. 5 pi. Price 10 cents.

35. Physical Properties of the Iron-Carburets, by Call Barus and Vincent Strouhal. 1880. 8°. 02 

pp. Price 10 cents.

36. Subsidence of Fine Solid Particles in Liquids, by Carl Barus. 1886. 8°. 58pp. Price 10 cents.

37. Types of the Laramie Flora, by Lester F. Ward. 1887. 8°. 354pp. 57 pi. Price 25 cents.

38. Peridotite of Elliott County, Kentucky, by J. S. Diller. 1887. 8°. 31pp. 1 pi. Price 5 cents.

39. The Upper Beaches and Deltas of the Glacial Lake Agassiz, by Warren Upham. 1887. 8°. 84 

pp. 1 pi. Price 10 cents.

40. Changes in River Courses in Washington Territory due to Glaciation, by Bailey Willis. 1887. 

8°. 10pp. 4 pi. Price 5 cents.
IV ADVERTISEMENT.

41. On the Fossil Faunas of the Upper Devonian tbr Genesee Section, New York, by Heury S. 

Williams. 1887. 8°. 121pp. 4 pi. Price ]o cents.

42. Report of work done in the Division of Chemistry and Physics, mainly during the fiscal year 

1885-'86. F. W. Clarke, chief chemist. 1887. 8=. 152 pp. 1 pi. Price 13 cents.

43. Tertiary ami Cretaceous Strata of the.Tuscaloosa, Tombigbee, and Alabama Rivers, by Eugene 

A. Smith and Lawrence C. Johnson. 1887. 8°. 189 pp. 21 pi. Price 13 cents.

44. Bibliography of North American Geology for 18S(>, by Nelson H. Barton. 1887. 8°. 35 pp. 

Price 5 cents.

45. The Present Condition of Knowledge of the Geology of Texas, by Robert T. Hill. 1887. 8°. 94 

pp. Price 10 cents.

46. Nature and Origin of Deposits of Phosphate of Lime, by R. A. F. Penrose, .jr., with an Introduction by N.S Shaler. 1888. 8°. 143pp. Price 15 eenis. 

47. Analyses of Waters of the Tellowstone National Park, with an Account of the Methods ot 

Analysis employed, by Frank Austin Gooch and James Edward Whitfield. 1888. 8°. 84pp. Price 

10 cents.

48. On the Form and Position of the Sea Level, by Robert Simpson Woodward. 1888. 83. 88pp. 

Price 10 cents.

49. Latitudes and Longitudes of Certain Points in Missouri, Kansas, and New Mexico, by Robert 

Simpsoti Woodward. 1889. 8°. 133pp. Price 13 cents. .

50. Formulas and Tables to facilitate the Construction and Use of Maps, by Robert Simpson Woodward. 1889. 8°. 124pp. Price 15 cents.

51. On Invertebrate Fossils from the Pacific Coast, by Charles Abiathar White. 1889. 8°. 102pp. 

14 pi. Price 13 cents.

52. Subaerial Decay of Rocks ana Origin of the Red Color of Certain Formations, by Israel Cook 

Russell. 1889. 8°. 65 pp. 5 pi. Price 10 cents.

53. The Geology of Nantucket, by Nathaniel Southgate Shaler. 1889. 8°. 55 pp. 10 pi. Price 10 

cents.

54. On the Thermo-Electric Measurement of High Temperatures, by Carl Barns. 1889. 8°. 313 pp. 

incl. 1 pi. 11 pi. Price 25 cents.

55. Report of work done in the Division of Chemistry and Physics, mainly during the fiscal year 

1880-'87. Frank Wiggles worth Clarke, chief chemist. 1889. 8°. 90 pp. Price 10 cents.

56. Fossil Wood and Lignite of the Potomac Formation, by Frank Hall Knowlton. 1889. 8°. 72 pp. 

7 pi. Price 10 cents.

57. A Geological Reconnaissance in Southwestern Kansas, by Robert Hay. 1890. 8°. 49 pp. 2 pi. 

Price 5 cents.

58. The Glacial Boundary in Western Pennsylvania, Ohio, Kentucky, Indiana, and Illinois, by George 

Frederick Wright, wTth an introduction by Thomas Chrowder Chainberlin. 1890. 8°. 112pp. incl. 

1 pi. " 8 pi. Price 13 cents.

59. The Gabbros and Associated Rocks in Delaware, by Frederick D. Chester. 1890. 8°. 43 pp. 

1 pi. Price 10 cents.

60. Report of work done in the Division of Chemistry and Physics, mainly during the fiscal year 

1887-'88. F. W. Clarke, chief chemist. 1890. 8°. 174 pp. Price 15 cents.

61. Contributions to the Mineralogy of the Pacific Coast, by William Harlow Melville and Waldemar 

Linclgrai. 1890. 8°. 40pp. 3 pi. Price 5 cents.

62. The Greenstone Schist Areas of the Menominee and Marquette Regions of Michigan; a contribution to the subject of dynamic metamorphism in eruptive rocks, by George Huutington Williams; 

with an introduction by Roland Duer Irving. 1890. 8°. 241 pp. 16 pi. Price 30 cents.

63. A Bibliography of Paleozoic Crustacea from 1698 to 18S9, including a list of North American 

species and a systematic arrangement of genera, by Anthony W. Vogdes. 1890. 8°. 177pp. Price 

15 cents.

64. A report of work done in the Division of Chemistry and Physics, mainly during the fiscal year 

1888-'S9. F. W. Clarke, chief chemisjj. 1890. 8°. 60pp. Price 10 cents.

65. Stratigraphy of the Bituminous Coal Field of Pennsylvania, Ohio, and AVest Virginia, by Israel 

C. "White. 1891. 8°. 212 pp. 11 pi. Price 20 cents.

66. On a Group of Volcanic Rocks from the Tewan Mountains, New Mexico, and on the occurrence 

of Primary Quartz in certain Basalts, by Joseph Paxson Iddings. 1890. 8°. 34 pp. Price 5 cents.

67. The Relations of the Traps of the Newark System in the New Jersey Region, by Nelson Horatio 

Darton. 1890. 8°. 82 pp. Price 10 cents.

68. Earthquakes in California in 1839, by James Edward Keeler. 1890. 8°. 25 pp. Price 5 cents.

69. A Classed and Annotated Bibliography of Fossil Insects, by Samuel Hnbbard Scudder. 1890. 

8°. 101 pp. Price 15 cents.

70. Report on Astronomical Work of 1889 and 1890, by Robert Simpson Woodward. 1890. 8°. 79 pp. 

Price 10 cents.

71. Index to the Known Fossil Insects of the World, including Myriapods and Arachnids, by Samuel 

Hubhard Scudder. 1891. 8°. 744 pp. Price 50 cents.

72. Altitudes between Lake Superior and the Rocky Mountains, by Warren Upharn. 1891. 8°. 

229 pp. Price 20 cents.
ADVERTISEMENT. . V

*

73. The Viscosity of Solids, by Carl Barns. 1891. 8°. xii, 139 pp.' C pi. Price 15 cents.

74. The Minerals of North Carolina, by Frederick Augustus Genth. 1891. 8°. 119 pp. Price 15 

cents.

75. Record of "North American Geology for 1887 to 1889, inclusive, by Nelson Horatio Darton. 1891. 

8°. 173 pp. Price 15 cents.

76. A Dictionary of Altitudes in the United States (second edition), compiled by Heury Gannett, 

chief topographer. 1801. 8°. 303pp. Price 25 cents.

77. Tho Texan Permian aud its Mesozoic Types of Fossils, by Charles A. AVliite. 1801. 8°. 51 pp. 

4pi. . Price 10 cents.

78. A report of work done in the Division of Chemistry and Physics, mainly during tlio fiscal year 

1889-'00. F. AV. Clarke, chief chemist. 18D1. 8°. 131pp. Price 15 cents.

79. A Lute Volcanic Eruption in Northern California a'nd its Peculiar Lava, by J. S. Diller. 1891. 8°. 

33pp. 17 pi. Price 10 cents.

80. Correlation papers Devonian and Carboniferous, by Henry Shaler AVilliams. 1891. 8°. 279pp. 

Price 20 cents.

81. Correlation papers Cambrian, by Charles Doolittle AValcott. 1891. 8°. 447 pp. 3 pi. Price 

25 cents.

82. Correlation papers Cretaceous, by Charles A. "\VTiite. 1891. 8°. 273pp. 3 pi. Price 20 cents.

83. Correlation papers "Eocene, by William Bullock Clark. 1891. 8°. 173pp. 2 pi. Price 15 cents.

84. Correlation papers Neocene, by W. H. Dall and G. D. Harris. 1892. 8°. 349pp. 3 pi. Pricf 

25 cents.

85. Correlation papers Tho Newark System, by Israel Cook Russell. 1892. 8°. 344 pp. 13 pi. 

Price 25 cents.

80. Correlation papers Archean and Algonkian, by C. E. Van Hise. 1892. 8°. 549 pp. 12 pi. 

Price'25 cents.

90. A report of work done in the Division of Chemistry aud Physics, mainly during the fiscal year 

1890-'!)!. F. AV. Clarke, chief chemist. 1832. 8°. .77 pp. Price 10 cents.

91. Record of North American Geology for 1890, by Nelson Horatio Darton. 1891. 8°. 88pp. Price 

10 cents.

92. Tho Compressibility of Liquids, by Carl Barus. 1892. 8°. 90pp. 20 pi. Price 10 cents.

93. Some insects of special interest from Florissant, Colorado, aud other points in the Tertiaries of 

Colorado and Utah, by Samuel Hubbard Scudder. 1892. 8°. 35pp. 3 pi. Price 5 cents.

94. Tho Mechanism of Solid Viscosity, hy Carl Barns. 1892. 8°. 138pp. Price. 15 cents. " 

05. Earthquakes in California in 1890 aud 1891, by Edward Singleton. Holden. 1892. 8°. 31 pp. 

Price 5 ci-uts. 

90. Tho Volume Thermodynamics of Liquids, by Carl Barns. 1892. 8°. 100 pp. Price 10 cent*.

97. The Mesozoio Eehfnodermataof the United States, by William Bullock Clark. . 1893. 8°. 207 

pp. 5i) pi. Price 20 cents.

98. Flora of the Outlying Carboniferous Basins of Southwestern Missouri, by David White. 1893. 

8°. 139pp. 5 pi. Price 15 cents.

99. Record of North American Geology for 1891, by Nelson Horatio Dartou. 1892. 8°. 7.( pp. Price 

15 cents.

100. Bibliography and Index of the Publications of the U. S. Geological Survey, 1879-1892, by Philip 

Crevi'liug Warman. 1893. 8°. 495pp. Price 25 cents.

101. Insect Fauna of the Rhode Island Coal Field, by Samuel Hubbard Scudder. 1893. 8°. 27 pp. 

2 pi. Price 5 cents.

102. A Catalogue and Bibliography of North American Mesozoic Invertebrate, by Cornelius Breckinridgo Boyle. 1803. 8°. 315pp. Price 25 cents.

103. High Temperature AATork in Igneous Fusion and Ebullition, chiefly in relation to pressure, by 

Carl Barus. 1893. 8°. 57pp. 0 pi. Price 10 cents.

104. Glaeiatiou of the Tellowstone Valley north of the Park, by Walter Harvey AAreed. 1893. 8°. 

41 pp. 4 pi. Price 5 cents.

105. The Laramio and the overlying Livingston Formation in Montana, by Walter Harvey Weed, 

with Report on Flora, by Frank Hall Kuowlton." 1803. 8°. 08 pp. 0. pi. Price 10 cents.

106. Tho Colorado Formation and its Invertebrate Fauna, by T. W. Stanton. 1893. 8°. 288 pp. 

45 pi. Price 20 cents.

107. Tho Trap Dikes of the Lake Champlain Region, by James Furman Kemp and Veruou Freeman Marsters. 1893. 8°. 02pp. 4 pi. Price 10 cents.

108. A Geological Reconnoissance in Central Washington, by Israel Cook Russell. 1893. 8°. 108 pp. 

12 pi. Price 15 cents.

309. Tho Eruptive and Sedimentary Rocks on Pigeon Point, Minnesota, and their contact phenomena, by William Shirlcy Bayley. 1893. N°. 121 pp. 10 pi. Price 15 cents.

110. The Paleozoic Section in the vicinity of Three Forks, Montana, by Albert Charles Peale. 1893. 

8°. 56pp. 6 pi. Price 10 cents.

111. Geology of tho Big Stone Gap Coal Field of Virginia and Kentucky, by Marius R. Campbell. 

1893. 8°. 100 pp. 6 pi. Price 15 cents.

112. Earthquakes in California in 1892, by Charles D. Perriue. 1893. 8°. 57 pp. Price 10 ceuto.
VI ADVERTISEMENT.

113. A report of work done in the Division of Chemistry during the fiscal years 1891-'92aud 1892-'93. 

F. W. Clarke, chief chemist. 1893. 8°. 115pp. Price 15 cents. 

In preparation:

114. Studies in the Structure of the Green Mountains, by T. Nelson Dale. 

115 A Geographic Dictionary of Ehode Island, by Henry Gannett. 

116. A Geographic Dictionary of Massachusetts, by Henry Gannett.

 The Moraines of the Missouri Coteau, and their attendant deposits, by James Edward Todd.

 A Bibliography of Paleobotauy, by David "White.

STATISTICAL PAPERS.

Mineral Resources of the United States, 1882, by Albert Williams, jr. 1883. 8°. xvii, 813pp. Price 

50 cents.

Mineral Kesources of tho United States, 1883 and 1884, by Albert Williams, jr. 1885. 8°. xiv, 1016 

pp. Price 60 cents.

Mineral Resources of tho United States, 1885. Division of Mining Statistics and Technology. 1886. 

8°. vii, 57C pp. Price 40 cents.

Mineral Resources of the United States, 1886, by David T. Day. 3887. 8°. viii,813pp. Price 50 cents.

Mineral Resources of the TJnited States, 1887, by David T. Day. 1888. 8°. vii, 832 pp. Price 50 cents.

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To THE DIRECTOR OF THE

UNITED STATES GEOLOGICAL SURVEY,

WASHINGTON, D. C. 

WASHINGTON, D. C., January, 1x94:
DEPARTMENT OF THE INTERIOR

BULLETIN

UNITED STATES

GEOLOGICAL SURVEY

No. 113

WASHINGTON

GOVERNMENT PRINTING OFFICE 

1893

UNITED STATES GEOLOGICAL SURVEY

J. W. POW.ELL, DlKIiCTOn

REPORT OF WORK DONE

DIVISION OF CHEMISTRY

FISCAL YEARS L80 !-'<)!> AN]) l.t>9l'-'U3

KLIANK WIGGLESWOimi CLARKE

CHIEF CHEMIST

WASHINGTON

GOVE11NME"NT FEINTING- Ol-'lMCE

1803

CONTENTS.

Page. 

Letter of transmittal....................................................... 9

Tscheruiak's theory of the chlorite group and its alternative. By F. W. 

Clarke.................................................................... 11

The constitution of the lithia micas. By F. W. Clarke....................... 22

Experiments upon the constitution of certain micas and chlorites. By F. W. 

Clarke and E. A. Schueider ................................................ 27

Notes on the action of ammonium chloride upon silicates. By E. A. Schneider 

andF.W. Clarke......................................................... 34

The preparation and specific gravity of crystallized uranium dioxide. By W. 

F. Hillebrand............................................................. 37

A further example of the isomorphism of thoria and uranium dioxide. By W. 

F. Hillebrand ............................................................ 41

The composition of rowlaudite and macldntoshite. By W. F. Hillebrand.... 44

Zinc-bearing spring waters from Missouri. By W. F. Hillebrand............ 49

Josephinite, a new nickel iron. By W. H. Melville.......................... 54

A new meteorite from Hamblen County, Tennessee. By L. G. Eakins........ 61

On the catalytic action of aluminum chloride on silicic ethers. By H. N. 

Stokes.................................................................... 63

On the action of phosphorus oxychloride on aromatic silicic ethers. By H. N. 

Stokes.................................................................... 77

Note on benzyl silicate. By H. N. Stokes................................... 79

On amidophosphoric acid. By H. N. Stokes................................. 80

On some organosols. By E. A. Schneider ................................... 95

On the preparation of a pure hyclrosol of silver. By E. A. Schneider......... 99

Contributions to the knowledge of colloidal silver. By E. A. Schneider...... 102

Miscellaneous analyses-..................................................... 109

The Mount Joy meteorite ............................................... 109

A nickel-iron sulphide from Canada.....................................' 109

Beauxite from Alabama................................................. 109

Anorthite from Raymond, Maine ........................................ 110

Feldspars from Jones Falls, Baltimore, Maryland ......... .............. 110

Ottrelito from Maryland ................................................ Ill

Piedniontite from Maryland............................................. Ill

Zoisite from North Carolina............................................. Ill

Prehnite from Fassa, Tyrol. ...................................... ^..... . 112

Minerals from Italian Peak, Gunnison County, Colorado................. 112

Xeuotime from North Carolina .......................................... 112

Water of Caledonia Springs, Caledonia, New York....................... 113

Water from Nashville, Illinois ........................................... 113

Water of Soap Lake, Washington....................................... 113

Water from Ojo Caliente, New Mexico................................... 114

5

ILLUSTRATION.

Papo. 

Fl(i. 1. Apparatus used in experiments upon silicic others.... ................ 70

LETTER OF TRANSMITTAL

DEPARTMENT OF THE INTERIOR, 

UNITED STATES GEOLOGICAL SURVEY,

DIVISION OF CHEMISTRY, 

Washington, J). (7., October 7, 1893.

SIR : The accompanying- bulletin, like its predecessors, Bulletins 9, 

27, 42, 55, 603 64, 78, and 90, contains an account of the miscellaneous 

investigations carried out in the Division of Chemistry during the 

stated time. Hitherto these bulletins have been annual, but the present one, for various reasons, represents two years of work. A year 

ago, when the usual bulletin fell due, a great reduction was made in 

the resources of the division, the force was largely cut down, and 

the laboratory was removed to its present quarters in the building 

occupied by the main offices of the Survey. At the end of the fiscal 

year 1891-'92 several of the investigations intended for its bulletins 

were not quite complete, and as the year following was evidently to 

be one of much smaller output, it seemed best to finish the work on. 

hand and to consolidate, both years in one report.

In one other respect the present report differs from its predecessors. 

Hitherto, under the heading "Miscellaneous analyses," a large volume of routine work has been recorded. This work, however, finds 

its proper publication in the memoirs of the geologists and petrographers of the Survey, and it is now omitted from the report of this 

division. Only those miscellaneous analyses which directly pertain 

to the work of the chemical division appear in its published record. 

The physical investigations carried out by Dr. Barns also appear in 

separate form in several independent bulletins. 

Very respectfully,

F. W. CLARTvE,

Chief 

Hon. J. W. POWELL,

U. $. Geological fturvcy.

WORK DONE IN THE DIVISION OF CHEMISTRY 

IN 1891-92 AND 1892-93.

TSCHERMAK'S THEORY OF THE CHLORITE GROUP AND ITS

ALTERNATIVE.

BY P. W. (iL

Iii the micas, vermiculites, the clintonitc, group, and the chlovites, we 

meet a large number of minerals having similar properties. All are 

probably inonocliuic, all are commonly foliated in structure, and within 

certain limits they shade into each other in composition. Their external 

resemblances are very close, and it is therefore a fair presumption that 

they are also alike in constitution. A satisfactory explanation of their 

chemical structure ought to emphasize their obvious relationships and 

be sufficiently general to include all the individual species in a single 

definite theory. The problem is easily stated, but its solution can be 

effected only .by slow degrees. Like other similar problems, it must be 

solved by a series of approximations; and every step towards order is 

a gain, even though it be not absolutely final.

Among the men who have advanced our knowledge of these minerals, 

no one is entitled to higher credit than Professor Tschermak. His 

successive papers upon tlie mica, clintonite, and ehlorite groups have 

all been long strides forward; and whether his interpretations are ultimately confirmed or abandoned, they have none the less been of real 

service in the development of knowledge.

In his latest paper, 1 Professor Tschermak seeks to explain the chemical structure of the chlorites, and masses the available evidence most 

admirably. This group of minerals lie divides into two subgroups, 

called orthochlorites and ieptochlorites, respectively, and for each 

division a special explanation is offered. The orthochlorites, which 

include pennine, elinochlore, leuchtenbergite, prochlorite a.nd corundophilite, are simply represented as mixtures of two end products, serpentine and amesite; and so far as the mere ultimate composition of the 

minerals is concerned, the interpretation is quite satisfactory. On theoretical grounds it leaves something to be desired, as will appear later. 

The Ieptochlorites, however, or chlorites outside of the main series, 

are less easily handled: and for these, in addition to the serpentine

'Die Cliloritgrnppe. TI Tlicil, Sil/imgsl>. Akiid. (I. AV'i.ss. in Wien, 19 FeH. 1891.

11
12 LABORATORY REPORT, 1891-J92 AND 1892-'93. [BULL. 113.

and ainesite molecules, four other fundamental compounds are assumed, namely, two derivatives of amesite, strigovite, and chloritoid. 

Six types of molecule are, in all, adopted, which, by mixtures in various 

proportions, account for all the species. Written seiniempirically, 

these molecules are as follows:

Seipentine,

Amesite,

" 1st doriv.,

" 2d "

Strigovite,

ChJoritoid,

Sp.

At.

At'.

At".

St.

Ct.

MgSi2 07 . H2 . (MgOH),

Al2Si07 . H2 . (MgOH)s

Al2Si07 . H3 . MgOH

Al,Si07 . H<

SiOa. Al2Si07 . H2 . (MgOH)2

Al2Si07 . H . Mg

Of these compounds, four are represented by known minerals, 

although the amesite and strigovite formulae rest each upon a single 

analysis. Two, the molecules At' and At", are hypothetical. Empirically, all the chlorites of well-established character correspond in 

composition to mixtures of these six molecules; but a few of the allied 

minerals, such as epichlorite and stilpnomelaue, are unaccounted for. 

The latter are yet to be brought into line.

At a first glance the six molecules, as just written, appear to be 

remarkably alike in form. But when they are Avritten structurally, 

as Tschermak himself writes them, they become somewhat dissimilar. 

Serpentine is then represented as a salt of the acid H6Si2O7 . Amesite, 

with its two derivatives and chloritoid, appear as basic orthosilicates. 

Strigovite is given as a salt of the acid H4Si2OG . That is, three different silicic acids are involved in Tschermak's theory, and the first apparent simplicity of the scheme disappears. All of the six molecules, 

however, with the single exception of the nonaluminous serpentine, 

are supposed to contain the structural nucleus

-Ov 0-A1-0- 

>i< >0 -O/ XO-A1-Oto which the remarkable similarities of the chlorites may be due. 

Through chloritoid the chlorites become affiliated with the cliutonite 

group; but with the micas, at least as the latter have been interpreted 

by Tschermak hitherto, no special analogies of structure appear.

Now, admitting that Tschermak's theory accounts for the known 

facts as fully as he believes, the question arises whether his mode of 

interpretation is the only one possible. If it is, then the problem of 

the chlorite group is solved, and controversy is out of court. But if 

other schemes can be devised, representing the facts equally well, further investigation becomes necessary. Pending the acquirement of 

new experimental evidence, we may discuss rival systems upon philosophic grounds; and that which is simplest, most general, and best 

supported by analogies, should have preference. Ultimately, of course, 

the problem must be attacked by means of experiment, through which 

alone the questions at issue can be finally settled.
CLABKE.] THEORIES OF THE CHLORITE GROUP. 13

In several previous papers, some of them written in joint authorship with others/ I have sought to establish the hypothesis that the 

more complex silicates are merely substitution derivatives of normal 

salts. For instance, many minerals are easily and naturally represented as so derived from the normal aluminum compound Al4 (SiO,|)3 ; 

successive aluminum atoms being equivalently replaced by other atoms 

or groups. Among these minerals, the micas seem to form a conspicuous family, and with them are found the clintonite group and some 

vermiculites. To this family I shall recur later.

In two quite recent papers, Schneider and I have tried, by experimental methods, to obtain some positive evidence as to the nature of 

the chlorites. That our results are not final, and that Tschermak's 

criticism of them is perfectly legitimate, I cheerfully concede, and yet 

we have found clues which are not without meaning. The reaction 

between dry hydrochloric acid and the hydromagnesian silicates we are 

still investigating, and its actual'character and significance we hope 

to determine in due time. So far, however, in every case of a true 

chlorite examined by us, and in the case of serpentine also, we have 

found that the chemical constitution may be represented by a mixture of molecules of the general form Mg2 (SiO4 ) 2 E'4 , in which E' may 

be either A1H2O2 , MgOH, or H, with of course the usual equivalent 

replacements of aluminum and magnesium by ferric and ferrous iron. 

These molecules are evidently substitution derivatives of the normal 

compound olivine, when the ordinary formula of the latter is doubled 

and made Mg4 (SiO4 )2 . Since we do not know the true molecular weight 

of any metallic silicate, this doubling of the simplest possible formula 

is perfectly allowable, and a'reason for it will appear later. Here, 

then, for a few chlorites at least, is a scheme of interpretation quite 

unlike Tschermak's; and we have to determine whether it is equally 

exact and equally general.

Taking Tschermak's paper as a basis for comparison, and discussing 

at first only the analyses discussed by him, I find that all of his orthochlorite series, except coruudophilite and aniesite, reduce sharply to 

the above given type of. formula. Omitting aniesite, which will be 

separately considered further on, every orthochlorite may be written 

E"2 (Si04)2R/4, with various relations between the several components 

collectively represented by E'4 . In fact, Tschermak's formuhe and 

mine, although quite dissimilar, are curiously parallel, as the following scheme, based upon his classification of the orthochlorites, plainly 

shows. His arrangement of the subgroup is this:

Pci i nine.......................... .... ............ SpaAt.^ to SpAt

Clinochloro.......................... ............. SpAt to SpjAfci

Prochlorite ..*................................ ..... Sp.'Ats to Sp:!At7

Coruudophilite.................................... Sp.:At7 to SpAt.,

1 Bull. TL S. Geological Survey, Nos. 27,42, GO, 04, and 78.
14 LABORATORY REPORT, 1891- ?92 AND 1892- ?93. [BULL. 113.

Transforming these expressions, and, for brevity, writing A1H2O2 =A, 

aud MgOH=M, we Lave:

KpaAtj = Mgs(SiO,)s . A4M0H7 = uMg-,(Wi04 ) 2E'4 

SpAt = Mg3 (SiO«)s AaMsHj = " 

Sp,A.t, = Mg7 (Si04 ) 7 A6M5H3 = 

Sp3AtT = Mg,,(SiO4 )i3 AHM,oH3 =' 

SpAtt = approximate agreement only.

Iii the last case, corundophilite, Tschermak's formula agrees better 

with the actual analyses than any formula derived from, my system. 

The cause of divergence will be considered in connection with the 

structure of amesite, later. Although the difference is small it ought 

not to be ignored.

In general, then, the orthocLlorites maybe provisionally regarded as 

mixtures of the three typical or generic salts Mg2 (SiO4 )2A4 , Mg2 (SiO4 ) 2 

M4 , and Mg2 (SiO4 )2 H4 . Whether these compounds exist separately in 

the mineral kingdom is an open question, and one not easy to answer. 

To each of them there are approximations; ekmanuite, for example, is 

near Fe2 (SiO4 ) 2H4 in composition; but it is more probable that the 

chlorites proper are mixtures of intermediate salts. Some pennines, 

for instance, tall near the compound Mg2 (S.iO4 ) 2AMH2 ; and other like 

substances appear among the minerals which Tschermak places in the 

subgroup of leptochlorites. A consideration of the latter must precede 

further discussion of theory.

. According to Tschermak, the leptochlorites form three subgroups, as 

follows:

I. Daphnite .............................. At5At'fiSp

(Jluittiosifco ............................. AtaAt'jjSp

II. Metachlorite ...................'........ At( ;StoSp:i

Klementito............................. At^tjSp

Cronstedtito ........... ................ AtSt

Thuringite............................. AtSt

Eiival'ite .......... ..................... At-iSt,

Stdgovi to.............................. Sfc

III. Diabantitc ............................. Ct.iSp7

Aphrosiderite .......................... (Jt,iAt6Sp4 to Ct;iAttiSp4

Delessite .......... ................... .{Jt.jAt3SpB to CtSp

Ruinpfite............................... G^At'VSp

EpicLlorite, grengesite, nielanolite, etc., he regards as chlorites, but 

as not yet definable. The delessite from Friedrichsrodahe places provisionally in the first division of the leptochlorites, along with daphuite 

and chamosite. The formulae given are deduced from specific analyses, 

but when several analyses exist for a species a considerable variability 

becomes manifest, which must influence all attempts to fix the molecular structure.

Taking now the analyses as cited by Tschermak, a number of them 

reduce at once to the same type of substitution formula as that which 

I have assigned to the orthochlorites. Uniting like oxides, Fe2Os with 

A12O3? MgO with FeO, etc., we get at once the following expressions
CLARKE.] THEORIES OF THE CHLORITE GROUP. 15

from the analytical data. The name of the analyst follows the name 

of the species :

Daphuite, Zeynek ........................ Fe":in(SiO.|).,o . HuA^Msa

Cbamosite, Boricky ..................... . .Fe"«(Si.0.i)« . 1 l^iA^M^

Delessite, Pufahl ......................... Mg .((.(SiO-i)/ . HisA^M^z

Thnringito, Giutl ........................ . .Fe"4 i(SiO^)M . HuA-mMi,-,

" Keyser .................. ...... Fe'VSiO-Om . Hi.2A 5oM n

An approximation to close agreement with theory is evident at a. 

glance; but a better conception of the agreement may be obtained by 

calculation, using the following formula:

Daphuite ............................ ...... Fc.^iSiO^jA^FeOll),!!,

Cbamosite ................................. " " ''

( I Fe,(Sip4)2A,(PeOH),H, 

1 )elesaito ( Krietlnclisrodn,) ............... < 3 Mg.2 (Si04)i2A.-Mi H,

, . . ., . ( 3 Fe2 (Si04)jA8 (FeOH)iH, Tburiiigite.... .................... .....{ lp^gio;j;A^

To this list we may add the thuriugite from Lake Superior, analyzed 

by Pen field and Sperry, which becomes 5 Fe2 (SiO4 ) 2 (FeOH).,-f9 Fe^ 

(Si04 )2A4 . The analyses, reduced to typical form and to 100 per cent, 

as is usual, are as follows:

SiOj..........

A1A---------

FeO ..........

MgO..........

*

Zi'.yuuk. 

23-44

22 -OS

43 -41

............

11-07

100 -00

Chaiuositc. 

Jioricky.

25-17

18-41

45 -37

11-05

mo -oo

DH ess! to. .Thuriugite. 

J'ufiihl. Gin IT.

2!t -75 23 -58

20-58 25-11

19-42 40-08

17-53 ............

12-72 11-23

100 -00 100-00

Thnringito. 

Kcyser.

24-15

25 -44

11 -02

100-00

1'. &.*M.

24 -02

I'i -QQ

10-75

100-00

Calculated from the formula} just given they become:

SiOa...... .............................

Al,0,-------- -- -- --" -- - 

I?c0. ...................................

MgO........' ..........................

H.O. ............ ....:.......... ........

Daph. &. 

Chain.

°4 -39

20 -73

43 -90

10-98

100-00

Doless.

18-18

100-00

21 -54 

2H -54 

44. 31

11 -00 I 10-01

10.1-00 100-00

In -short, these chlorites are apparently compounds of precisely the 

same type as the orthochlorites. Daphnite and chainosite vary from 

theory by small amounts in opposite directions, the one having a 

trifling excess of an FeOH salt, the other an excess of an A1H2O2 compound, Closer agreements could not be reasonably expected.

In order to properly interpret the remaining leptochlorites, we must 

return to the fundamental idea of the substitution hypothesis. Start-
16 LABORATORY REPORT, 1891-J92 AND 1892- ?93. [BULL.IIS.

ing with the normal orthosalt, Ave get at once the following probable 

series of derivatives:

Oliviue.............................................. Mg4 (Si04 >2

( Mg:j(Si04 ),R'2

Ortkocklorites..................................... ^ Mg..(SiO4 ),R'4

[ Mg(Si04 )2R'6

In the first of these derivatives, the compound intermediate between 

the orthochlorite type and olivine, we find the key to most of the 

leptochlorites. Again, discussing the analyses mainly considered by 

Tschermak, omitting strigovite and rumpfite for separate inspection, 

we get the subjoined semieinpirical expressions:

Metachlorite, Zeynek.............. Fe"«5 (Si04 ) 4o . H^A4 iM20

Euralite, Wiik ...............Mg65(Si04 ) 5o . H5aA;j ,.M4

Diabantite, Hawes .............. Mgtw ( Si04 ) 56 . HMA.25M9

Klementite, Element ............Mg{il (Si04 ) 4 8 . H7As6Mr

Delessite, Hedclle'............ .Mg75 (Si04 )s7 . H:!9A;)8Mi-f-34 aq.

Croustedtite, Ludwig ............. Fe4i,(SiO4 )35 . A<«, nearly.

Apkrosiderite, Raminelsberg......... Fe54 (Si04 )4l . H3MHA44

Metaehlorite, at one end of this series, corresponds nearly to the 

orthochlorites; while aphrosiderite, at. the other end, approaches 

the composition Fe3 (SiO4 )2A4 . All the other minerals in the series fall 

between these extremes. Eeduced to general form, the expressions 

become :

Metachlorite....................... .4R"«(S'iO.1 ).jR'4 -f- lR":j(SiO4 ) 2A2

Euralite............................ 7

Diabantite .........................4

Klementite ......................... 1

Delessite ........................... 1

Cronstedtite........................1

+ 3

+ 2 

+ 4

Aphrosiderite.......................0 " +1

These ratios, of course, are not rigidly exact, but they vary no more 

from the analyses considered than the analyses of the different occurrences in any one species vary among themselves. In the last case, 

the actual analyses show small admixtures of the orthochlorite type; 

but the approximation is nevertheless quite close to theory. It will be 

seen that the value of B'2 in the second term of each expression is constant; that is, that we have either A1H2O2 or the corresponding ferric 

radicle; but the values of the first term are somewhat different. In 

nietachlorite, as in daphnite and chamosite, E/4 =A2ME[; in cronstedtite it is A4 , and in delessite it is H4 . In kleineutite we" liave 

E'4=A3M; in diabantite, 3K'4 =M4H8 ; and in euralite, 7E/4 =A22H6 . 

Such ratios, however, are difficult to fix sharply, because of the uncertainties in the water determinations. In Heddle's analyses, however, 

the water given off at 100° is distinguished from that retained at

'The delessite from Bowling Quarry. The samples from Dumbuck and Long Craig agree well 

wilh this.
CLAKKB.] THEORIES OF THE CHLORTTE GROUP. 17

higher temperatures, and the results are correspondingly favorable to 

theory. In his clelessite, for instance, the water becomes partly water 

of crystallization; and the mineral from Bowling quarry agrees well 

with the formula 2Mg3 (Si04 ) 2A,)? 2aq + Mg2 (SiO4)2H4 ; with about twosevenths of the magnesium replaced by ferrous iron. Calculating the 

composition of each mineral from the formula} given below, and comparing the results with the reduced analyses from which the expressions were derived, we can judge of the closeness with which the facts 

and the theory agree.

Metachlorite ..... . .4

Euralite ............ TMg^SiO^RV +_3Mg3 (Si04 )c,A2

Diabantito ......... 'UVlg.^SiO.,^!^ -f 3Fe3 (SiO.,)2A3

Klementite ......... Mg.,(Si04 ).2A3M +Mg3 (Si04 ) aA2

Delessite ........... Mg.^SiO^H* +2Mg3 (Si04 )2A2 , 2aq.

Cronstcdtite ........ Fe3 (Si04 )i(Fe" 'HA)4+4Fe3 (Si04 ).:(Fe" 'HA)*

Aplirosidcrite .........

SiOz . .............

AW),..... ........

Vc,03 .. ...........

Fc<) ..............

MgO. .............

H20 ..............

Gifi

A1,0S .- ...........

FeA .............

FoO ..............

MgO... ...........

H20- .............

Metaclilorito.

Found.

23-82 

20 -42

45-76

10-00

100 -00

Calculilted.

24 -57 

20-88

44 -23

10-32

100 -00

Ivleiiientite.

Found.

28-85 

30 -36

28-73 

12-06

100 -00

Calcu-" 

lated.

28-78 

30-57

28-78 

11 -87

100 -00

Euralite.

*»»>* i lated:

37 -74 38 -15 

18 -48 19 -45

30-91 

12-87

100 -00

29-24 

13-16

100 -00

Croiistedtite.

Found.

21 -18

35-74 

35-19

7-89

100-00

Calculated.

21 -56

34-48 

36-20

7-76

100 -00

Diabantite,

Found.

34-05 

12-80

26-32 

.16 -70 

10 -13

100 -00

Calculated.

34-34 

12-51

20-49 

16 -35 

10-31

100 -00

Aphrosidcrito.

Found.

24-54 

22-59

43-87

9-00

100-00

Calculated.

25 -31 

21 -52

45-57

7-60

100 -00

Bull. 113-

Si02 ...... ........

A1A-. ........ ...

MgO..............

H2 0. .............

Aq...............

Delessite.

Found.

34-00 

19-34 

30-24 

10-36 

6-00

100-00

Calculated.

33-83 

19-17 

30-08 

10-15 

6.77

100-00
18 LABORATORY REPORT, 1891-*92 AND 1892- ?93. [BOLL.JIS.

In reducing the data, and in calculating the formulae, I have commonly assumed E" to be all magnesium or all iron according as one or 

the other predominated. Only in diabantite the relation between the 

JFe and Mg was so simple that it seemed desirable to keep both in 

view. I have also used relatively simple ratios between component 

molecules, rather than the more complex terms which might give a 

clqser agreement between analyses and theory that is, when Mgy 

(SiO4 ) 2E/4 , and Mg3(SiO4 ) 2A2 stood actually in the relation of 11 to 10,1 

have computed on the basis of 1:1. Most of the divergences between 

''found" and "calculated" are due to this cause; but in the case of 

cronstedtite, which is least concordant of all, there is probably a small 

admixture of some more basic compound, of the character, possibly, of 

amesite.

There now remain to be considered, of all of Tschermak's typical 

chlorites, only strigovite, ruinpfite, amesite, and in part corundophilite. 

Of these, the first three depend each upon a single analysis, and the 

available evidence is therefore not conclusive. To strigovite, the general 

formula H4Fe"2Al2Si2On seems to apply; which, in the constitutional 

expression given to it by Tschennak has already been cited. This may 

also be written Fea (SiO4 )2 . H(A1H2O2 )( A1OH), which is of the orthochlorite type with the bivalent group A1OH in place of E'2 . In ruinpfite, 

which has the empirical formula H28Mg7Ali6SiioO65, the same group 

A1OH appears, and also a molecule of the form of the last derivative 

of olivine, Mg(SiO4 )2E'6 . In detail, rumpfite agrees very nearly with the 

composition

Mg2 (SiO4 ) 2A2H2 +2Mg(Si04 )2A2 (AlOH)2 ;

which gives with the 'analysis by Firtsch reduced as usual, the following comparison:

Si02 ..............

AlsOa. ............

Mo-O

HjO.... ..........

Ruinpfito.

ITOTlTld.

31-01 

42-02 

13-73 

33-24

100-00

Calculated.

30-20 

42-79 

13-42 

13-59

100-00

It must be remembered that in order to account for rumpfite, Tschermak assumed the existence of the constituent molecule At", which appears in none of his other chlorites. Both in his scheme and in mine 

the mineral is exceptional, and undoubtedly it needs further study. *

In amesite, which occurs with corundophilite, we find another chlorite of peculiar composition. It is the most basic member of the group, 

and contains more oxygen relatively to its silicon than any other chlorite known. Its formula, as written by Tschermak, is AloSiOr, H2 - 

(MgOH)2 , which is the equivalent of his serpentine molecule, with A12 

in place of MgSi. As we have no experimental evidence from which
CI.AHKE.] THEORIES OF THE CHLORLTE GROUP. 19

to reason, we may with equal propriety regard amesite as having the 

structure

when it becomes analogous in structure to tbe other chlorites, standing in a simila,r relation to them as that which the cliutonite group 

bears toward the micas. Ou this supposition the micas and chlorites, 

as has already been shown elsewhere/ form two parallel series of compounds, as follows:

Normal ovthosilicate,

Whence derive Micas Chlorites 

Muscovite, Al-(.Si(^)sll:t Aplm>siderite. 

Normal biotite, Al.(8iO.,).: Rr, Ortliochlorites, M«r..(SiOOR< 

" pldogopite, Al(SiO,),Kft

Clintonite, Al <9>R" Amosite,

In certain respects, this general scheme is not incompatible with 

Tschermak's views. The orthochlorites, for example, lie regards as 

mixtures of serpentine and amesite, representing the structure of those 

compounds in a special way. But if serpentine be written Mg2 (!SiO4)aJBT:,(MgOH), and amesite as I have just suggested, the theory of substitution is satisfied, and the orthochlorites may be classified as intermediate between the two end terms. Then, however, the Jeptochlorites fall less easily into line, and the slight gain in apparent simplicity 

in the ortho series is oifset by loss elsewhere. It is quite probable, 

however,, that corundophilite is a mixture containing amesite molecules; and the formula which I give the latter mineral is sustained to 

some extent by the fact that both minerals occur intimately associated 

with diaspore. At Chester, the only locality for either corundophilite 

or amesite represented by analyses, the chlorites are commonly found in 

seams with diaspore on one side and emery on the other. Hence the 

group A1H2O2 is at least as likely to be found in amesite as the inagnesian compound MgOH.

Still another analogy between the micas and the chlorites remains 

to be noted. In the phengitic muscovites, i'n some phlogopites and in 

the lithia micas, the ratio of silicon to oxygen is less than 1 : 4, and 

often approaches 1:3. This variability, as I have shown in my paper 

upon "A theory of the mica group," 2 is easily explained by supposing 

an admixture of molecules containing the group Si3O8 in place of SiO<. 

This equivalency is well recognized in the feldspar series; and among 

the micas it is forcibly emphasized by the existence of Lorenzen's polylithionite, in which the group Si3O8 replaces SiO4 entirely. Does this 

group occur in chlorites also 1?

At the end of his discussion of the leptochlorites, Tschermak dismisses a number of minerals as doubtful in character, either because 

of unsatisfactory analyses, or uncertainty in the material described.

J Bnll. U. S. Geological Survey, No. 00, p. 17. 

4 Bull. TJ. S. Geological Survey, No. 64.
20 LABORATORY REPORT, 189i-'92 AND 1892-J92. [BOLL! m.

Iii particular he names the species grengesite, hullite, melanolite, and 

stilpnomelane, to which he adds epichlorite. All of these minerals, 

together with epiphanite and possibly strigovite, may be reduced to 

typical form by assuming the presence of Si3O8 . For grengesite and 

hullite the analyses are not satisfactory, and the formulae deducible 

have therefore no weight. Strigovite has been already explained by 

assuming in it the group AIOH, but a reconsideration here is worth 

noting as offering an alternative formula to that previously given. 

The formulae, which I have obtained are as follows:

{ 4Fe3 (Si308 ) 3 (FeH3 03 ) 3H2 

............... ^ +3Fe.2 (SiO<).2 (FeH2 03 >>H3

t lFe2 (Si 308) 2 (FeH2 02 )3H2

--- --- --- j +3Fe.2 (Si04 ).2(FeH3 02 )oH,

( !Mgs(Si04 )3H< +lMgJ (Si308 )aH4 - - -{ +3Mg3 (8iO«MAlHilOi) a

r 3Fei(SiO< ) 2 (AlH.2 02 ):iH+ 

.............. A 3Fe3 (Si04)2 (AlH,0;)2

l+lFe3 (Si3 08 )i(AlH2Oi) 2

Stilpnomelane

Melanolite.

Epichlorite.

Strigovite

Epiphanite

Mg:,(Si3 08HAlH2 03 )2 

+3Mg3 (Si04 )2 (AlH,02 )2

Here we find stilpuomelane and melanolite are orthochloritic in type; 

epiphanite is equivalent to aphrosiderite, and the other species are 

intermediate like most of the leptochlorites. The analyses discussed 

are these:

Stilpnomelane from Antwerp, 1ST. Y., by Brush.

Melanolite, Somerville, Mass., by H. Wurtz.

Epichlorite, from the Hartz, by Bammelsberg.

Strigovite, Striegau, by Websky.

Epiphanite, Wermland, by Igelstrom.

The reduced analyses are as follows:

SiO2 ..............

Fe,03 ...... .......

FeO ..............

H20 ..............

SiO« ..............

A1A- ..-..--..

FoO ..............

MgO..............

^Q ..............

Stilpnomelane.

Found.

42-85 

24-74 

23-69

8-72

100 -00

Calculated.

41-80 

26-01 

23 -41

8-78

100 -00

Epichlorite.

Found.

43-94 

17-75

27-38 

10-93

100 -00

Calculated.

45-50 

16-58

28 -17 

9-75

100 -00

Melanolite.

Found.

34-25 

29-32 

26-48 

9-95

100 -00

Calculated.

33-46 

29 -74 

26-76 

10-04

100 -00

 Strigovite.

Fonnd.

29-51 

24-78 

36-05

'9-66

100 -00

Calculated.

30-20 

24-25 

36-24

9-31

100 -00
OFARKE. ] THEORIES OF THE CTTLORITE GROUP. 21

For epiphanite Igelstvom's analysis needs no reduction, if we calculate with a ratio of Mg: Fe:: 7: 5.

810^ ..............

AljOs...... .......

:FeO ..............

MgO..............

H20 ..............

Pound.

37-10

21 -13

20-00

14-03

7-83

100 -09

Csilnt. 

latcd.

37-60

21-34

18-83

14-64

7-53

100 -00

The agreements are sufficiently close to establish the validity of the 

hypothesis upon which the calculations rest, although they are not as 

good in all cases as might be desired. Still, the formulae offered bringsome order out of chaos, and are therefore entitled to consideration 

until something better is proposed.

As between Tschermak's theory and mine, both representing the 

known facts fairly well, experimental research must be the final arbiter. 

Until experiment has given grounds for decision either theory may 

properly be used as a guide. Mine is offered as a possible simplification of the problem 5 but both may be supplanted by something more 

general still. Neither theory exhausts all the possibilities of the question, and neither can claim to be much more than a step forward in the 

series of approximations by which the truth may be at last attained.
THE CONSTITUTION OF THE LITHIA MICAS.

BY F. W. CLARKE.

.n a series of papers published during the past eight or nine years,1 

1 have sought to develop the theory that the complex natural silicates 

are chemically to be considered as substitution derivatives of simple 

normal salts. For the micas in particular a theory has been worked 

out in detail, partly on general principles, and partly on the basis of 

experimental evidence, in which the starting point of the series is the 

normal aluminum orthosilicate, Al4 (SiO4 )3, with occasional replacements of the orthosilicic group by the feldspathic group Si;tO8 . Thus 

we have the following systematic scheme:

Normal salt........................................ Al^SiO-Os.

Muscovite ........................................ Al;3 (Si04 );iR/3.

Biotite ........................................... A].;(Si04)3R"<R's.

Fhlogopite ...................'..........'.......... A](Si04 ).iE"3E/j.

/°\R» 

C]intouite ........................................ Al Q/

\SiO.<=R'3

This scheme is modified, however, not only by the assumption that 

Si04 may be replaced by Si 3O8 , as in. the feldspars, but also by other 

considerations due to the presence of fluorine in many micas, etc. In 

the cases of the lithia micas, lepidolite, zinnwaldite, cryophyllite, polylithionite, etc., such, modification is absolutely necessary; and hitherto 

it has been covered by the supposition that the fluorine is represented 

by the univalent group A1F2 , among the components of E/.

Naturally, and almost necessarily, the development of any such 

theory is by process of evolution; in which, details held provisionally at 

first are replaced by simpler conceptions, rendered possible by the 

acquisition of new evidence. A simplification of this order is the purpose of the present communication.

Structurally considered, the lithia micas are all characterized byt two 

special features; an oxygen ratio lower than that of the orthosilicates, 

and the presence of fluorine. The first of these peculiarities has already

1 J-iiillof ins of the U. S. Geological Snrvcy, Nos. 27, 42, 55, CO, 64, and 90.

22
CLARICE.] CONSTITUTION OF THE LITHIA MICAS. 23

been explained by the presence of the group Si3O8 replacing SiO4 , and 

the second is now rendered intelligible by assuming that the clintouite 

type may also be replaced by a molecule of the structure

or its equivalent in the corresponding polysilicate. For example, in 

the polylithionite described by Lorenzen, SiO4 is entirely replaced by 

Si3O8 , and the assumption of the latter group is thus fully vindicated. 

The analogy of the feldspars was strong evidence in its favor; but now 

we have what may fairly be regarded as positive proof. Polylithionite 

may now be considered as a mixture of the two molecules

Al F and Al Si3 08=Na3K

s Li3

in the ratio 5:1; whence we get the following comparison between 

observation and theory:

Si02 ..............

A1208 ---------.--.

FeO. .............

K2 0 ..............

Mn,0. ............

LijO...... ........

F. ................

0-F.. ...........

Found, 

Loronzen.

r.n .oc

12 -57

 Q'l

5-37

7 -IN

9 '04

7-32

102 -11 

3 '08

99 '03

 Calculated.

59 -80

12-70

5-85

7-72

9-34

7-93

103 -34

100 -00

The small amount of ferrous impurity and the low summation of the 

analysis fully account for all the variations between the two columns 

of figures both as regards their magnitude and their direction.

In the light of the foregoing evidence, and of the mica theory in 

general, the lepidolites proper, such as occur in Moravia and in Maine, 

become easily explainable. All of their variations in composition are 

covered by the supposition that these micas consist of mixtures in 

different proportions, of two typical molecules; one, the compound 

A1F2 . Si3O8 . E'3 , with lithium as the principal, constituent of R/, and 

 the other a muscovitic molecule, Al 3 (SiO4 ) 3R'3, in which R' may be 

either K2H, or KH2. Two such mixtures may be considered here: 

first, the two molecules A1F2 . Si3O8 . Li3 and Al3 (SiO4 ) 3K2H, in the ratio 

1:1; and second, the three compounds A1F2 . Si3O8 . K3 ; A1F2 . Si3O8 . Li3,
24 LABORATORY REPORT, 1891-92 AND l892- ?93. iflott. il3.

and Al3(SiO4 ) 3KH2 , commingled in tlie ratio 1:2:2. These mixtures 

correspond to the following percentage compositions:

Si02 ..............

AL,03 ...... .......

K2 0 ..............

LijO....... .......

H,0 ..............

P.. ...............

First.

49-05

27-79

12 -81

0-13

1-22

5-18

102 -18 

2-18

100 -00

Second.

50-39

9f> -70

13-16

5-04

2-01

6-38

102 -08 

2-68

100 -00

For purposes of comparison with these figures, the following analyses of typical lepidolites are quite sufficient, as they cover all important variations: A, Eozena, by Berwerth. B, Schiittenhofen, by Scharizer. 0, Paris, Maine. D, Hebron, Maine. E, Norway, Maine. F, 

Eumford, Maine. The last four analyses are by Eiggs.

Si02 ..............

A1Z0S ....... ......

Fe,0s ....... ......

PeO ..............

MnO...... ........

CaO ..............

MgO. .............

T i r\

Na,20. .............

K20.. .......... .'..

RbaO. .............

Cs20. .............

HaO-. .............

P .................

A. * B.t

50 -98 49 -25

27 -80 25 -27

 05 -84

.......... -85

',

f. .CO ' f, -Q8

.......... -35

JO -78 1 13-85

:::::::::: ,! 

 90 1 -70

7 -88 5 -68

104 -33 103 -23 

3 -32 2 -39

101 -01 100 -84

c.

50-92

24-99

 30

 23

4-20

2-11

11-38

1-96

6-29

102-38 

2-04

99-74

D.

48-80

28-30

 09

 08

 10

 07

4 "49

 74

1 12-21

)

1 -73

4-96

101 -86

2-02

99-84

E.

49-52

28-80

 40

 24

 07

 1 '!

 02

3

.Q7

 13

8

-QO

3.73

 08

1 '72

5-18

102 -71 

2-18

99-53

F.

51-52

25-90

 31

 20

 10

 02

4-90

i-oe

11-0]

.QK

5-80

101 -89 

2-44

99-45

: Also contains 0 -05 t Also contains 0 -06 SnOj.

In the first of these lepidolites, the mineral from Eozena, a slight 

variation from the scheme must be assumed, due to the excess of 

fluorine and the low proportion of alkalies. These peculiarities are 

easily accounted for by supposing a small admixture of the molecule 

A1F2 . Si3O8 . Al, which corresponds to the type already indicated and 

which is justified by other evidence. In the mineral cookeite recently 

reanalyzed by Penfield ' we find what appears to be the vermiculite of 

the lepidolite series, with nearly all the alkalies but lithia removed

J Amer. Journ. Sci., May, 1893.
CONSTITUTION OP THE LTTHTA MICAS.

and with fluorine replaced by hydroxyl. Penh'eld's analysis of it 

reduces easily to the type

/on

Al OH

and iii detail to a mixture of the three molecules A1(OH) 2 . SiO4 .Li3 ; 

A1(OH)2 . SiO4 . H3 , and A1(OH)2 . SiO4 . Al, in the ratio 10 : 14 : 33. Eeduciug Penfield's analysis by uniting Fe with Al, the remaining bases 

with Li, and F with OH, and throwing cutwater lost at or below 300°, 

we get the subjoined comparison between observation and theory:

SiOi ..............

Al.,<)3 ... ..........

FcjO, ... .......

CaO ..............

K/) ..............

¥ 1 n

Li/) ..............

11,0 above 300°... 

!«'. ................

Found.

34-00

45-06

 45

 04

 14

 19

4-02

1-82

13 -14 

 40

99-32

Reduced.

35 -01

) 40-71

1 

1

) 4 -09

? 13 '90

100 -00

Calculated.

34-08

4G-53

4-50

14-23

100 -00

In the lepidolite from Jusehakova, analyzed by Eammelsberg, we 

find a connecting link between the lepidolites proper and the iron-lithia 

micas zinuwaldite and cryophyllite. The Jusehakova mineral is easily 

represented as a mixture of molecules like the other lepidolites, except 

that a portion of the typical A1P2 . Si3O8 . E'3 is replaced by a similar 

molecule A1F2 . Si3O8 . Mn Li. In detail it seems to contain the molecules Al3 (SiO4 ) 3 K2Hj AlF2 .SiO4 .Al; A1F2 . Si3O8 . Mn Li; audA!F2 . 

Si3O8 . Li2K, in the ratio 2:1:3:0. Calculating its composition upon this 

basis, we get the following comparison with Eanmielsberg's analysis:

-

SiO, ..............

A1,O3 -- - -- 

ilnO..............

K,O ..............

NaaO .............

H.,0 ..............

F... '..............

Cl ................

Found.

50 -26

21 '47

5-36

11 -08

 54

4-88

 66

8-71

1-16

lOi -12 

3-92

100 -20

I? educed.

50-26

21-47

5-36

5 5-14

 60

i 9-33

5

103 '30 

3'92

09-38

Calculated.

50 -33

21-39

5-26

11 -CO

 44

9-38

J03 -95 

3-95

100 -00
26 LABORATORY REPORT, 1891-J92 AND 1892-7 93. [BULL.

As for the iron-lithia micas, zinnwaldite and cryophyllite, a detailed 

discussion now would be premature, for the reason that alternative 

formulae, agreeing equally well with the recorded analyses, are possible. The complication is due to the iron, which may be regarded 

either as belonging to a molecule of the type A1F?.. Si:!O8 . Fe" E'; or 

to a biotitic molecule A12 (SiO4 ) 3 Fe'^E'z- The zinnwaldite analyses 

of Berwerth and Eammelsberg are easiest interpreted as representing 

mixtures of A1F2 . Si3O8 . Fe Li, and A1 3 (SiO4 ) 3 K3 , in the ratio 5:2, 

approximately. Cryophyllite, on the other hand, according ta analyses by Eiggs, is most simply represented by the composition A13X3KH2 , 

+2 Al2X3Fe2H2 ,+3 A1F2 . X . K3 , +4A1F2 . X . Li 3 , in which X corresponds to the two acid groups SiO4 and Si3O8 in the ratio 1:3. This 

interpretation is based in part upon the fact that cryophyllite occurs 

in margins upon plates of annite, which is a lepidomelane of the 

biotite type. The iron in cryophyllite, however, may also be regarded 

as present in the molecule A1F2 , Si 3O8 , Fe^E', as in ziunwaldite; and 

between this interpretation and the other there are no adequate 

grounds for deciding. Taking the formulae as given above, Eammelsberg's analysis of zinnwaldite and the mean of Eiggs's three analyses 

of cryophyllite compare as follows:

SiOa ..............

AI n

Fea03 ...... .......

1'eO...... .........

MnO..............

CaO... ............

MgO..............

~NTo l~\

K2 0. ...... ........

H2 0....... ........

I1 .................

Zinuwaldite.

Pound.

46-44

21-84 

1-27

10-10 

1-57

 18 

3-36

10 -58 

1-04 

7-62

104 -03

Calculated.

47-55 

21-19

13-60

2-84

]0-CO

7-18

103 -02

Cryophyllite.

Found.

51-86 

16-50 

2-98 

6 -Go 

 21 

 04 

 07 

4-89 

 79 

10-01 

'1-29 

7-08

102 -97

Calculated.

51-95 

18-13

7-52

4-71

12-26 

1-41 

6-94

102 -92

In general it seems highly probable that the lithia micas are all 

characterized by the presence of the groups A1F2 . X. E'3 , A1F2 . X.. E"E', 

and A1F2 . X. Al ; in Avhich X may be either SiO4 or Si3O8 , and with the 

fluorine replaceable by hydroxyl in the process of vermiculitizatiou. In 

the original form of the mica theory the group A1F2 was regarded as 

the equivalent of E' in a molecule of the muscovite type. It is now 

represented as belonging to a distinct molecule analogous to clintonite. 

So far as the evidence goes, this interpretation seems to be satisfactory; 

and it is an advance upon thje earlier scheme in the direction of simplicity.
EXPERIMENTS UPON THE CONSTITUTION OF CERTAIN MICAS

AND CHLORITES.

BY F. W. CLARICE AND E. A. SCIINEIDER.

Shortly after the publication of our first joint paper upon the constitution of the natural silicates, 1 we received from Mr. A. Lb'sch, curator of minerals in the Imperial School of Mines at St. Petersburg, 

some highly important material bearing upon our researches. Our 

work upon leuchtenbergite, it will be remembered, was defective, on 

account of impurity in the specimens at our disposal; and Mr. Lb'sch 

therefore sent us a supply of the perfectly pure mineral, selected with 

extreme care, and in the very best condition for study. To this gift he 

added four other minerals which he thought would be of interest to us, 

and upon these five specimens our present communication is founded.

The minerals and the analyses are as follows:

A. Xanthophyllite, var. Walnewite, from the Nikolai-Maximilian mine, district of 

Slatoust, Ural.

B. Clinochlore from the same locality. Green, broadly foliated, closely resembling the mineral from West Chester, Pennsylvania.

C. Leuchtenbergite from Slatonst.

.1). "Diallage serpentine" from the Kiver Polclnewaja, district of Syssert, Ural.

E. White mica from Mi ask, Ural.

SiOj. .......................

TiO... .......................

ALA............. ...........

FQ.{03 . ................ .....^

FcO.......... ..............

MnO. .......................

PI ("i

Mo-O

K20...... ...... ............

Na.,0 .......................

E ...........................

HjO, 105= ...................

Loss 0 F ..................

A.

16-85

42 -03

9 *}£

0-20

20-77

0-04

0 '12

100 '40

B.

30-84

1 Q *'}1

1 '94

1-08

34-38

0-55

12 -84

100 -43

C.

30-00

20-43

1-68

0-14

0-21

0 -55

0 -35

19 '81

100 -47

D.

1-25

1-56

1-52

0-37

0-21

0. 11

12 -15

90.77

E.

44 -17

1-2!)

0-20

o-io

10-00

1-14

o-oo

1 -00

l\ ''.'t

100. 88 

 37

1.00-51

' Bull. U. S. Gcol. Survey, Xo. 78.

27
LABORATORY REPORT, 1891-92 AND 1892-7 93. [BOLL. m.

The molecular ratios deducible from these analyses, rejecting water 

given off below 300°, and the chrornite contained in the serpentine, are 

as follows:

Si02 ........................

utoa ...... ..................

no .........................

R*0.... .....................

II .0 ........................

F...... .....................

A.

 281

 750

 247

B.

 516

. '192

 874

 TlT

c.

 500

 211

 801

 714

D.

 709

,nQO

1-022

E.

 736

 374

 004

 124

 230

 050

Hence we get the following empirical formulae, in which all R"'=A1, 

all B"=Mg, etc.

Waluewite.................................. ALf.Mgve

Clinochlore................................. A^JMoCT

Lenchtenbergite............................ A]j:MgC6

Serpentine..................................Al|Mgio2

Mica........................................Al75K26H«(Si04 )74 0,Fr>

The last of these minerals is evidently an ordinary muscovite, possibly 

a little altered, and Avill receive no farther consideration in this paper. 

The other minerals were examined more in detail, with very interesting 

results. As in our previous work, all experiments upon each mineral 

were made upon a uniform sample of the powdered material, so that 

direct comparisons with the analyses might be possible. The analyses 

themselves agree closely with the published analyses made by others, 

and are noteworthy only in the fractional determinations of the water.

Towards dry, gaseous hydrochloric acid, at the temperature interval 

3S3°-412°, the minerals under investigation were somewhat refractory. 

From the waluewite, after nine hours heating in the gas, only 0-22 per 

cent of lime and 0-10 per cent of magnesia were extractable by water. 

Hence we may fairly infer that the species contains practically no 

-Mg-OH groups, a result which is in accordance with theory, as will 

be seen later. The chlorites and the serpentine, however, gave anomalous results, as follows, there being two experiments on each:

Clinochlorc.

8i

7-34

13

5-48

Leuclitenbergite.

16-i

7-33

m

5-02

Sorpoiil.iiie.

28J

3 -CO

7

2-60

In each case the heating was continued to constant weight, but the 

amount of action was much less than in the American clinochlore and 

serpentines which we formerly investigated. The leuchtenbergite behaves much like the impure material discussed in our earlier paper, from 

which 6-29 per cent of magnesia was removable; but more than double 

that amount is required to represent the MgOH which must be present 

under any recognized theory.
CLABKE AND ? 

SCIJNEIDEK. 3 EXPERIMENTS ON MICAS AND CHLORITES.

The irregularities in all these data remain to be explained. So far 

the results have only qualitative value. In those minerals which must 

contain the group MgOH, some action takes place, but in variable 

amount. But the magnesium silicates which can not contain MgOH 

are practically unattacked, and so far all the evidence is harmonious 

and clear. Contrary to onr earlier expectations, however, we can not 

trust the dry hydrochloric acid reaction quantitatively, at leastuntilits 

conditions and its nature are more fully understood. We can determine 

when the group MgOH is present as an essential part of a silicate, but 

not its actual amount. Probably the hydroxyl is first replaced by 

chlorine, converting the group -MgOH into the chlorhydrin-like group 

-MgCl. The latter, by continued action of the gaseous acids is then 

possibly split off as MgCl2 , but with secondary reactions to which the 

anomalous and irregular results may be due. The question is still open, 

and we hope by further experiments to get at something more conclusive. 

The problemis, to measure basic hydroxyl by its replacement with chlorine; and there seems to be no good reason why it should not be solvable.

By strong aqueous hydrochloric acid the chlorites and the serpentine 

were easily decomposed; but by previous ignition they were split up 

into soluble and insoluble portions. This splitting up is, in the case of 

serpentine, already well understood, the products being, as Daubree 

has shown, olivine and enstatite. For the waluewite and the chlorites, 

however, the existing data were scanty, and accordingly new experiments were undertaken. In each case the powdered mineral was ignited 

over a blast for several hours. It was then digested with strong hydrochloric acid, and after evaporation to dryness and re-solution, the 

residue was filtered off. Then, after drying and ignition, it was boiled 

with aqueous sodium carbonate to remove the silica which had been 

released from the soluble silicates, and the final residue was weighed 

and analyzed. As this process was followed in our first investigation 

with the Pennsylvania ripiclolite, the results are included here for 

comparison with the Siberian material. The percentages of insoluble 

residue were as follows:

Waluowito.

43-90

Clinochlore.

17-56

10 -03

Lenclitenbergite.

19 '24

18 -05

Ripidolite.

19-74

18-49

In the second line the silica found in the residues, being presumably 

extraneous, is deducted. The composition of the residues is given 

below:

Si02 .-.- ..............

KjOs-.... .............

MgO. .................

CaO ..................

Waluewito.

2-34

 71 -12

100 -21

Clinochlore.

5-25

C7-20

100 -34

LouclitonTjorgite.

08-52

oc .19

99-80

llipidolite.

6

.QO

C7-81

25 -07

99.80
30 LABORATORY REPORT, 1891-92 AND 1892-93. [HULL. 113.

In these analyses the silica ranges from 0-93 to 1-25 per cent of the 

original mineral, and the re;, .linder has quite sharply the composition 

of spinel. This point was noticed in om- former paper, in the case of the 

West Chester ripidolite; but since then it has acquired new significance, 

and it is emphasized by the new analyses. Leaving the waluewite for 

separate consideration, it is to be noted that the three chlorites studied 

by us are all typical members of Tschermak's orthochlorite series; 

which, according to him, are mixtures of two end compounds, serpentine and amesite. How amesite may behave upon ignition we do not 

know, but serpentine splits up, as is well known, into olivine and enstatite, the latter being insoluble in hydrochloric acid. Under Tschermak's theory of the chlorites, a clinochlore of the composition SpAt, 

should, upon ignition, yield about 18 per cent of enstatite; or, in other 

words, the insoluble residue should contain at least one-third of all the 

silica in the mineral. Since no eustatite is actually formed, or practically none, it is plain that the three chlorites here considered contain 

no serpentine molecules; and hence, so far at least as these minerals 

are concerned, Tschermak's theory falls to the ground.

Approximately, but not exactly, the formation of spinel from the 

waluewite and the chlorites seems to follow a simple quantitative law. 

To illustrate this the empirical formula* may be reproduced here.

Waluewite ............................. Al^,

Clinochlore............................. Al:!8

LeiichtenbergUe........................Ah:

Ripidolite .............................. A138

Upon ignition, of course, water is expelled, and the ignited residue 

is empirically as follows:

Waluewite. ................................A18(;I

Clinoclilore ................................ A1 38

Leuohtenbcrgite ...........................Al n

Ripidolite ................................. Al Mgs6(SiO.,)anO.n

Here we have in each mineral an excess of oxygen over SiO^, and to 

that excess the amount of spinel residue is approximately proportional, 

thus:

Cliiioclilnro................. 10-013; 14'80

Loiichtenbcrgile............ 18'05 17'02

Eipiilulite .............,.'.-. 18-19 15-8:f

Considering the impurities in the original materials, and the unavoidable inaccuracies of manipulation, the agreement here is as close as 

could be expected. The calculation assumes that the excesses of 

oxygen represent, quantitatively, the amount of spinel formed, and all 

the errors of analysis are accumulated in the final result. If we deduct 

the spinel from the composition of each mineral, the soluble portion is
T} EXPERIMENTS ON MICAS AND CHLORITES. 31

expressible as a mixture of oliviue and niaguesian garnet; two species 

which are among the commonest progenitors of the chlorite group. 

That oliviue and garnet are actually formed is certainly not proved; 

but it seems highly probable that the chlorites studied do split up in 

the manner indicated, yielding water, spinel, garnet, and olivine as the 

tinal products of decomposition. Other chlorites may behave differently, and it is quite likely that the species or varieties rich in iron 

may diverge widely from the types considered here. Speculation upon 

this theme would be premature.

As to the chemical structure of the leuchtenbergite and clinochlore, 

the evidence now available is quite in harmony with the general theory 

of the chlorite group recently advanced by one of us. J Again including the Pennsylvania ripidolite, the three chlorites reduce to compositions as follows :

Clinochlore ..................... M

Leuchtenbergite ................ Mg49 (SiO ,)M( AlH.2O2 )«(MgOH).,7HM

Ripidolite ...................... Mg49 (Si04 )M(AlHa02 )38(MgOH)w H..7

Condensing, by union of the univalent factors, these become 

Clinochloro ................... ...... .............. Mg6o(Si04 )53R'jo5

Leuchtenbergite .................................. Mg49(Si04 ) 5oR'ioi

Ripidolite ........ ................ ............ ....Mg49 (Si04 )f)0R'io2

or, in general, all three examples have nearly identical composition and 

conform to the typical expression Mg2 (SiO4 )2B'4 , in accordance with 

the theory which represents them as substitution derivatives of the 

normal salt Mg4 (SiO4 ) 2 . We may interpret the minerals in detail as 

was clone in the case of our earlier discussion of the West Chester 

ripidolite, or we may regard them as mixtures of the two salts 

Mg2 (SiO4 )2 (AlH2O2 ) 2 (MgOH)lH and Mg2 (SiO4 )2 (AlH2O2 ),(MgOH)2H. 

In either case the juxtaposition of the groups A1H2O2 and MgOH 

renders the formation of spinel intelligible.

In the waluewite, or more properly xanthophyllite, we have the first 

example of a true brittle mica met with in the course of our investigations. Being the most basic known member of the clintouite series, it 

has peculiar interest, and it deserves a somewhat detailed discussion. 

In the empirical formula deduced from our analysis, Al86Ca24Mg52H50 

(SiO4 )28Oi74, the most noticeable feature is the great excess of oxygen 

compared with the possible hydroxyl and the small amount of SiO4 . 

This excess is accounted for in part by the general formula which we 

have heretofore assigned to the clintonite group,

\SiO4 _E 3

which formula, however, needs some extension along a new line. In 

that formula the group of atoms A1O2B" appears, an equivalent

1 See the first paper iu this Bulletin.
32 LABORATORY REPORT, 1891-'92 AND 1892-'93. [BULL. 113.

obviously of the group A1O2H2 ; and this group may fairly be repeated 

among the components of E'3 . With such a group the extreme member of the clintonito series should have the composition (AlO2E")4 SiO4 ; 

and a molecule of that type is theoretically capable of splitting* up 

into olivine and spinel in the ratio of 1:2, when each mineral is given 

its lowest possible formula:

(AlO2R//)4SiO4=E//2SiO4 +2E//Al2O4 .

In the case of xanthophyllite, if such a molecule is contained in it, 

the olivine formed should be partly monticellite. At Monzoni mouticellite is found associated with spinel, and brandisite, a member of the 

clintonite series, occurs in the same region. In fact, all three of the 

true cliutonite micas are commonly associated with spinel, a fact of 

much interest when considered in its relations to our experiments. In 

the light of tlie foregoing argument the composition of waluewite and 

its manner of decomposition by heat may be represented as follows:

5Al-0>Ca

\Si04EH2 .AlH202

+5A1

\Si04ir (A102Mg)3

\SiO4-(A102Ca) 3

These three molecules are all of the general type heretofore assigned 

to the clintonite series, and two of them are presumably capable of 

yielding spinel. Eeducing the original analysis to 100 per cent with 

consolidation of like bases as usual, we get the following comparison 

between experiment and theory, the calculated composition being in 

accordance with the structural formula above cited.

Si02 ........................

Al.f>a . ......................

CaO ........................

MgO........................

H20-.... ...................

Found, reduced.

16-97

44-14

13-50

20.92

4.47

100 -oo

43-96

Calculated.

17 'f!9

44-71

13-00

20-63

4-64

100 -00 

43-94

Eeckoned on a similar basis, cliutonite, according to the analyses 

published by Sipocz, may be written 

A1O2E". SiO4 . H3 + (A1O2E")4 . SiO4

and brandisite is of the same general character, with a small admixture 

of the first of the three xanthophyllite molecules given in our structural expression. Whether chloritoid is a true member of this group, 

seems to be uncertain; but if it is, its composition may be written 

AlO2Fe. SiO4 . H . A1OH; the last factor being a bivalent group related 

to the univalent A1O2H2 .
EXPERIMENTS ON MICAS AND CHLORITES. 33

As for the ultimate structure of the group AlO^K", it maybe written 

in two ways, thus :

 A1<°>R" or -R" 0 A1=O

The first form corresponds to the group A1(OH)? . the second to the 

formula commonly assigned to spinel,

Ttf^O A1=s °

MS<O-AI=O

In either case two of the groups A102B" coalesce to form one molecule 

of spinel, with removal of a single magnesium atom. Such a coalescence is easiest comprehended when the second form of the radical is 

chosen 5 but the first form is more harmonious with the constitution 

of the mica series in general. If the xanthophyllite compound 

(AlO2B")4SiO4 be regarded independently of the micas, it is most simply written as follows, with its splitting up into olivine and spinel as 

indicated :

0-Mg-0-Al=0 /OX.MU M(( .0-A1=0

Q /0-Mg-0-Al=0 «i£0>M« M°<0-A1=0

bl<0-Mg-0-Al=0 bI$Ov,Mir Mo^0-Al=0 \o-M-o-Ai=o \O>MS MS<O-AI=O

If, however, for the sake of preserving harmony with the mica formulae 

we adopt the first expression for A1O2B", then spinel would seem to 

have the constitution

Mg<^>Al 0 Al=0

Although the last formula is somewhat novel, it is not altogether 

improbable; but between it and its alternative we cannot yet certainly 

decide. Another open question is furnished by the chlorites, in which 

the formation of spinel may possibly be due to the presence of AlO2Mg 

groups. Upon this supposition, however, the chlorites do not reduce 

to simple formulae, and therefore the suggestion has slight value. 

Apart from all theoretical considerations, the spinel reaction, as it may 

fairly be called, is one of an entirely new order in mineral chemistry, 

and it opens up a noteworthy line of attack upon the difficult problems 

before us.

Bull. 113 3
NOTES ON THE ACTION OF AMMONIUM CHLORIDE UPON

SILICATES.

BY E. A. SCHNEIDBE AND F. W. CLARKE.

In our investigations relative to the constitution of the natural silicates, 1 the action upon them of dry hydrochloric acid gas has played 

an important part. The reaction, however, as heretofore described by 

us, is very slow, and the operations involved in its application are 

long and tedious. In each experiment the powdered mineral must be 

heated for many hours in the stream of gas, and from time to time it 

is taken out and weighed. After each weighing the powder is stirred 

with a platinum wire to expose a fresh surface to action, and it then 

becomes liable to the absorption of hygroscopic moisture from the atmosphere, which introduces into the work a possible, though small, 

source of error.

In the hope of simplifying the reaction, and of avoiding the possible 

error just indicated, the experiments shortly to be described were 

tried. The results as yet are not wholly satisfactory, at least from a 

theoretical point of view; but we believe them to be novel, and that a 

preliminary notice will not be quite without value.

It is well known that when ammonium chloride is heated to 350° it 

is dissociated into HCl+lSnEL,. If, therefore, the salt is heated to that 

temperature with a silicate, the reaction of the latter with dry hydrochloric acid should take place. It is, of course, conceivable that in 

some cases the ammonia might act also; but we have so far observed 

nothing which would show this to be the case.

Our method of procedure has been as follows: The powdered mineral 

was mixed with about ten times its weight of pulverized ammonium 

chloride and heated in a platinum crucible to a temperature above 

350°, but below the temperature at which dehydration takes place, 

until the added salt was completely volatilized. The residue was then 

leached out with water, and the portion rendered soluble was investigated. In some experiments the residue, before leaching, was treated 

with a second, and even a third, portion of ammonium chloride, in order 

to ascertain whether a single treatment was final. Our conclusions 

are best stated in connection with our results, which we subjoin with all

1 Bull. U. S. Geological Survey, No. 78; and ATner. Journ. Sci., Sept., 1891, and April, 1892. 

34
} ACTION OF AMMONIUM CHLORIDE UPON SILICATES. 35

necessary detail. In each, experiment approximately one gramme of 

mineral was taken.

Olivine (Mg^SiO^. From Fort Wingate, New Mexico. By treatment with ammonium chloride only 044 per cent of magnesia was 

rendered soluble ; i. e. ? converted into chloride. This result agrees with 

the data obtained upon heating olivine in dry hydrochloric acid gas. 

By aqueous acid the mineral is easily decomposed.

Serpentine (MgsB^Si^Og). The so-called "diallage" serpentine from 

the river Poldnewaja, district of Syssert, Urals. After a single treatment witli sal ammoniac 4-93 per cent of magnesia was dissolved out 

by water, but the residue contained a little oxychloride, representing 

less than one per cent more.

In a second experiment the serpentine, after heating with ten grammes 

of ammonium, chloride, was reheated with ten grammes more. Upon 

leaching, 14-30 per cent of magnesia went into solution. In a third 

experiment the mineral was thrice treated, and only 10-G3 per cent of 

magnesia became soluble. In the last case the residue was boiled with 

a solution of sodium carbonate, which took up 3-82 per cent of silica. 

This fact, the splitting off of silica during treatment with ammonium 

chloride, may possibly shed some light upon the nature of the reaction. The same serpentine was completely decomposable by aqueous 

hydrochloric acid, but only moderately attacked by the dry gas. The 

irregularity of the results is manifest, but as yet unexplained.

Clinochlore (Mg7Al3Hit SitOas). From Slatoust, Urals. A double heating Avith ammonium chloride extracted 2-12 per cent of .magnesia. A 

triple heating took out 3-80 per cent. The dry gas converted twice as 

much magnesia into chloride, but the mineral is much less attacked 

than the similar clinochlore from Pennsylvania.

Leuchtenbergite. From Slat oust. Identical in composition with the 

clinochlore. A triple heating with ammonium chloride took out 3-98 per 

cent of magnesia. The residue contained a little oxychloride. Gaseous 

hydrochloric acid converted 5-62 per cent of magnesia into chloride.

Xanthophyllite, variety waluewite (A134 Ca9 Mg20 H20 Siu Om). From 

the Nikolai-Maximilian mine, district of Slatoust. Practically unattacked either by gaseous hydrochloric acid or by dissociating ammonium chloride, but completely decomposable by aqueous acid. A 

triple heating with ammonium chloride took out 0-48 per cent of lime, 

and 0-61 of magnesia.

So far the silicates examined have all been characterized by the 

presence of magnesia. Two of them, olivine and waluewite, were not 

seriously attacked by the reagent, while the others were perceptibly 

affected. In the latter group the radicle Mg O H almost certainly 

occurs; from the two unattacked minerals it is absent. The reaction, 

therefore, is probably valid as a rough test for MgOH; but how far 

it is trustworthy remains to be ascertained. The evidence is so far 

not absolutely conclusive. In the following experiments the minerals 

studied were nonmagnesiau.
LABORATORY REPORT, 1891- ?92 AND 1892- 5 93. [BULL. 113.

Natrolite (A^SiaO^Na^H^. From Magnet cove, Arkansas. A triple 

heating with ammonium chloride took out 9-50 per cent of soda, out of 

a total percentage of 15-40.

Prehnite (Al2Si3O]2Ca2H2). From the Fassathal, Tyrol. A triple 

heating with salamnioniac removed 1-72 per cent of lime. The mineral 

contained 26-49 per cent of lime.

Wollastonite (OaSiO3 ). From Diana, New York.

Pectolite (Ca^NaHSiaOg). From Bergen Hill, New Jersey.

These minerals were so strongly attacked that the complete analyses 

are given to facilitate comparison.

Si02 ........................

CaO ........................

NajO. ...... ................

AljOs.FejOs ................

MgO...... ...... ............

MnO.......... ..............

H20 ........................

....... .....

Wollustouite.

50-05

47-10

1-13

 09

 45

98-82

Pectolite.

53 -11

33-88

8-62

 40

 81

3-04

99 -8.0

The wollastonite was twice and the pectolite three times treated 

with the ammonium chloride. Upon leaching with water the following 

constituents were dissolved out:

CaO ........................

NazO. ......................

MnO........................

Wollastonite.

36-98

Pectolito.

20-50

6-95

 54

Here the action is quite independent of hydroxyl in the minerals, for 

wollastonite is anhydrous,-and pectolite but slightly hydrated. By 

future experiments we hope to reach some explanation of the results 

here given, which may or may not indicate a complete breaking up of 

the silicate molecules. At present, however, we prefer to offer no solution of the problem.

Our chief purpose in these experiments has been to discover some 

reaction by which the basic hydroxyl of a silicate might be recognized 

and measured. We have not succeeded in carrying out that purpose; 

but the results obtained are novel and at least worthy of record. Incidentally we have also studied the action of dissociating ammonium 

chloride upon certain phosphates. Lazulite and turquois were scarcely 

attacked, except that a little copper was removed from the latter 

mineral. Upon dufrenite there was considerable action, some ferric 

chloride being volatilized, and still more being extractable by water. 

But these experiments were merely qualitative, and have no immediate significance.
THE PREPARATION AND SPECIFIC GRAVITY OF CRYSTALLIZED

URANIUM DIOXIDE.

BY W. E. HlLLBBBAND.

Wohler prepared uranium dioxide, UO2, as a black crystalline powder, by evaporating urauyl chloride, UO2C12, with excess of sodium and 

ammonium chlorides and fusing the dry residue. Uhrlaub l fancied 

that the substance thus obtained might contain nitrogen, and, on the 

strength of a very unsatisfactory determination of that element, he 

suggested UIO^OIB as its probable formula. This requires 2-05 per 

cent of nitrogen, Avhereas Uhrlaub found scarcely over 1 per cent in a 

single determination by the soda-lrne method. The tube softened to 

such an extent during the long ignition as to interrupt the operation 

before all the nitrogen had beeu. given off. Qualitatively the coinpound prepared. by Wohler's method gives off ammonia on fusion 

with potassium hydroxide, according to Uhrlaub.

In view of the presence of nitrogen in uraninite it became desirable 

to subject Uhrlaub's work to review, and the supposed oxynitride was 

therefore prepared a number of times by Wohler's method, varying 

proportions of sodium and ammonium chlorides being used. The 

fusion was made in all but one or two cases in a large covered platinum crucible over a multiple (15) burner, and in some instances special 

precautions were taken to ensure entire exclusion of air during the whole 

operation of fusion, which in no case was continued over forty minutes. 

The amount of pure uranyl chloride employed for any single reduction. 

while never accurately gauged, ranged from seven to twelve grammes. 

The platinum crucible was somewhat affected by the chlorine liberated, 

but not to a great extent.

Without going too closely into details of the numerous experiments, 

it may be said that the color of the product of reduction, after thorough extraction by hot water and a little weak hydrochloric acid, ranges 

from different shades of rich brown to a most brilliant black, according 

to the degree of fineness of the octahedral crystals and the percentage 

of dioxide which they contain. In degree as air has had access to the 

interior of the crucible does the percentage of dioxide diminish and 

that of trioxide increase, and this change involves an increase in the 

opacity, a decrease in the specific gravity, and a change of color in the 

pulverized crystals from brown to dull greenish black. If the brilliantly reflecting crystals are relatively large, as was often the case, the 

color is black to the unaided eye whether the oxide, UO3, is present in 

quantity or entirely absent, but under the microscope those free, or 

nearly so, from trioxide are deep brown by transmitted light, at least

1 Die Verblntlnngen einigor Metallo init Stickstoff, Inaugural Dissertation, Odttingen, 1801.

37
38 LABORATORY REPORT, 1891-*92 AND 1892-'93. [BUU..U3.'

on the edges. When air has been entirely excluded the reduction is 

practically quantitative, and neither water nor hydrochloric acid extracts 

more than traces of uranium.

Notwithstanding the most careful qualitative tests, no trace of ammonia could be obtained by fusion with potassium hydroxide from any 

of the products of different reductions, nor was a sufficient amount of 

gas obtained by the methods used for the liberation of nitrogen from 

uraniuite 1 jbo render qualitative tests for nitrogen applicable. A volume of 1 -5°° of gas was obtained from 1 -06 grammes of substance in 

one instance, but even this may have been of extraneous origin. It thus 

appears that the oxynitride of Uhrlaub has no existence. His nitride, 

TJ3N4, has not been examined, and it is improbable that any further 

work in this direction can be undertaken in the near future.

Nearly all'the preparations obtained were assayed for UO2, and in a 

few of them small quantities of insoluble matter and of platinum were 

estimated. Ignition in oxygen serves for all practical purposes for the 

estimation of TJO2 , 2 but titration by potassium permanganate in sulphuric-acid solution is most accurate if solution has been perfect. The 

following determinations of dioxide were all made by the latter method 

unless otherwise stated. For the careful specific gravity determinations I am indebted to Mr. L. Gr. Eakins. These have been reduced to 

water at 4° 0. and vacuo for the sake of better comparison. They are 

especially interesting as showing that the highest hitherto obtained 

specific gravity of uranium dioxide, 10-15, by Bbelmen, of the oxide 

prepared by ignition of uranium oxalate in absence of air, is much too 

low. The tabulation is in ascending order of. specific gravity, the first 

column giving the order of preparation of the sample:

No.

X...... ........

I..............

III..............

V[...... ........

V.... ..........

XI..............

VII..............

XII..............

IV..............

IX..............

n...... ........

vni....... .......

Specific gravity.

Tound.

10-18 

10-50 

10-67 

10-80

10-88

10-87 

10 -895 

10-94 

10-92 

11 -00 

11 -01

Temperature.

(?) 

19-1 

22-2 

23 

28-5

18-8 

22-2 

30-3 

20-5 

27-6 

20-2

Eeducetl 

to water 

at 4° C. 

'and 

vacuo.

10-15 

10-47 

10 -64 

10 -82 

10 -83

10-85 

10 -80 

10-88 

10-89 

10 -95 

10-98

UO2 peicent.

56-96 

G6-89

97 -69 

94 -Gl

97-02 

98-42 

86-05! 

99-38 

78 -97 !

99'10

97-9 by ignition in 

air.

No Pt. found.

Pt. found. 

77-46 by ignition in 

air. Pt. found.

'Bull. U. S. Geological Survey, No. 78, p. 56, 1889-1890. Chem. News, vol. 64, p. 245, 1891.

z lgnition beloiv redness in air is usually quite as eifectivo as strong heating in oxygen for the conversion of UOa to UsOs- For the conversion of large quantities, or of coarse powders, several oxidations, each except the last followed by reduction in hydrogen, may be required, but this ia also true 

when the ignition takes place at redness in oxygen.
CRYSTALLIZED URANIUM DIOXIDE. 39

The table calls for a few explanations. In. the first place, as to the 

effect on the specific gravity of the trifling amounts of platinum and 

silica found in some preparations. The silica (probably derived from 

the sodium and ammonium chlorides) never exceeded 0-05 per cent, and 

the proper correction for this amount raises the specific gravity by less 

than two units in the second decimal. On the other hand, the correction for the platinum sometimes found was insufficient to produce a 

maximum effect of more than two units in the same decimal place in 

the opposite direction. Their effect when found together is toward 

neutralization, and may in any-case be disregarded.

A second point relates to the remarkable results shown by Nos. TV 

and II, for which no explanation offers itself. That two of the samples 

possessing the highest specific gravity should contain only 86 and 70 

per cent of dioxide is, to say the least, surprising. They were among 

the earliest preparations made and were almost entirely consumed in 

various experiments before the anomaly was made apparent by examination of subsequent preparations, but the determinations of specific 

gravity in both cases and of UO2 in No. II had been duplicated; hence 

there is no ground for doubting their substantial accuracy. In fact, 

the low results for the dioxide led to making the subsequent preparations, for it was thought that with such a high specific gravity for a 

material containing only 79 per cent of UO2 the pure dioxide should 

possess a specific gravity much above 11. As the table shows, however, repeated efforts failed completely to secure such a result.

Still a third point may be mentioned in regard to Nos. X and I. The 

reduction in the case of X was made in an atmosphere of carbon dioxide 

derived from a cylinder of the liquid oxide, which, however, contained 

so much air that a large amount of oxidation took place. In both 

cases the greater part of the product was greenish to olive gray under 

the microscope, though the mass was metallic gray and brilliantly 

reflecting to the unaided eye. The greenish matter extinguished polarized light weakly but very distinctly, it was in flat plates of irregular 

outline, but sometimes showing a good angle, and the axis of extinction was such as to make the system apparently orthorhombic.

Besides this there was a good deal of black matter, like that of later 

reductions, but not well crystallized in octahedra. The green often 

contained inclusions of the black, and the appearance of both was but 

little altered by ignition in air. It is probable that Uhrlaub's experiments were made on material like this which had already suffered considerable oxidation, for he describes it as gray and iridescent after drying, but no ammonia could be obtained from the present material. The 

substance obtained by Zimmermann' in his preparation of alkaline 

uranates after short fusion in an open crucible was doubtless a similar 

mixture.

. 'Aim. <1. Chom., vol. 213, pp. 291-292, 1882.
40 LABORATORY REPORT, 1831-'92 AND 1892-'93. [BULL. 113.

No. XI was made from Joachimsthal nraninite Avithout preliminary 

separation of the numerous foreign substances known to occur in it, 

other than silica, lead, and sulphur. The silica was separated by evaporation to dryness after solution in nitro-hydrochloric acid and conversion into chlorides, the lead, bismuth, etc., and a small part of the 

arsenic were thrown out by hydrogen sulphide, and after boiling off 

the excess of this gas, the sulphuric acid was removed by barium 

chloride. Without removing the excess of the latter reagent the solution was then evaporated with sodium and ammonium chlorides and 

fused as usual. To avoid contamination with platinum a porcelain 

crucible is preferable to one of platinum, but is harder to heat. All 

the metallic chlorides which were not volatilized were then easily 

extracted by water and dilute hydrochloric acid, leaving the uranium 

dioxide in a state of great purity, as shown by examination and by the 

high specific gravity.

This mode of preparing the oxide is mentioned briefly in GineliuKraut, vol. n, part 2, p. 381, as applied by H. Hermann to the separation from pitchblende, but I have not had access to the original paper 

and can find no other reference whatever in chemical literature to this 

particular point. The Jahresberichte der Chemie, while quoting Hermann's paper, omits mention of this topic. The method as outlined 

above seems admirably suited for obtaining large or small quantities 

of the dioxide quickly and almost absolutely pure and in a beautifully 

compact and attractive condition. It is obtained at once entirely free 

from alkali and is especially well adapted for the preparation of those 

compounds of uranium which do not contain an alkali metal.

Summary, The results above detailed may be summarized as follows:

The oxynitride of uranium of Uhrlaub has no existence, or at least 

cannot be prepared in the manner described by him.

The specific gravity of crystallized uranium dioxide, UO2, is much 

higher than heretofore supposed, being not less than 10-95 and possibly as high as 11 at 4° 0. and in vacuo.
A FURTHER EXAMPLE OF THE ISOMORPHISM OF THORIA AND

URANIUM DIOXIDE.

By W. F. HlLLEBRAND.

Attempts to prepare something like au artificial uraninite by fusion 

of thoria, a urariinin compound, and lead oxide with borax proved 

ineffectual, but the results of further experimentation without lead 

oxide were of some interest. Without following the order of experimentation, they were as detailed below.

The fusions were made over a blast lamp in a small platinum crucible set in a protective mantle to increase the heat. It was immaterial 

which of the oxides of uranium was employed, since the higher ones 

began to suffer loss of oxygen as soon as fusion commenced, as could 

be observed by the continual appearance of bright spots on the surface, 

caused by the rising of gas bubbles. The heating was continued for 

from eighteen hours to two or three days, according to the amount of 

borax to be volatilized, the progress of crystallization being noted from 

time to time by dipping in and withdrawing a platinum rod and examining the cooled drop adhering to it. After formation of a copious 

crop of crystals the cooled melt was soaked in water and dilute acetic 

or hydrochloric acid, which in time effected separation of everything 

soluble. The residue consisted always of jet-black crystalline forms, 

generally grouped in trellis-like shapes and sometimes distinctly crystallized in octahedra.

Two crops of crystals made by fusing only the oxide UnO8 with 

borax gave the following results:

I. 5 g. TJ3O8, 5 g. borax glass. Duration of fusion, twenty-four hours. 

Sp. grav. of product at 17° C., 10-70, or 10-676 reduced to water at 

4° and vacuo.

Composition.

UO2 ........................................................ 94-50

UO3 ........................................................ 3-38

SiO 8 ........................................................ -06

NaaO....................................................... 36

98 -30 

41
42 LABOEATORY REPORT, 1891- ?92 AND 1892->93. [BULL. 113.

II. 5 g. U3O8 ,7 g. borax glass. Duration of fusion, twenty-four hours. 

Weight of product, 4 g. Sp. grav. at 20-6° C., 10-77, or 10-74: reduced 

to water at 4° and vacuo.

Composition.

UOj ........................................................ 95-25

U0y, etc .................................................... 4-75

100 -00

The result of long fusion of an oxide of uranium with borax is thus 

seen to be practically the formation of crystallized uranium dioxide. 

The loss shown is probably to be largely accounted for by boric oxide, 

existing either as sodium or uranium borate inclosed by the, crystals. 

The high specific gravity of the products is in conformity with the 

results communicated in the preceding paper on the preparation and 

specific gravity of crystallized uranium dioxide. The appearance of the 

crystals was in no wise changed by isomorphous admixture of thorium, 

but their solubility in nitric acid was markedly lessened as the percentage of this element increased, so much so that acid potassium sulphate had to be used to effect solution in one or two instances.

III. 7 g. UO3, 0-71 g. ThO2 , 7 g. borax glass. Sp. grav. 10-57 at 17-5° 

C. or 10-55 reduced to water at 4° and vacuo.

Composition.

Th03 ....................................................... 9-87

UO.;. ........................................................ 74 44

Q0;) ........................................................ 13 91

FeO........................................................ -07

......................... ........................... 38

98 -67

IV. 7 g. UA, 1'4 g. Th02, ! borax glass. Sp. grav. 10-51 at 1G-8Q C., 

or 10-49 reduced to water at 4° and vacuo.

Composition.

Th0 2 ....................................................... 17-25 .

UO3 ........................................................ 74-48

UO3 ........................................................ 6-71

FeO ........................................................ -09

NasO ....................................................... -34

SiO,........................................................ -16

99-03

V. 0-7 g. UO3.0-7 g. ThO2 ,3 g. bo^ax glass. Duration of fusion thirtysix hours. Sp. grav. not determined.

Composition

Th02 ....................................................... 47-6

UO2 ........................................................ 51-8

99-4
i:i!.i.EHKANu.] THORtA AND URANIUM DIOXIDE. 43

This UO2 was calculated from the weight of TJ3O8 found gravimetrically; there may have been UO3 present. Other constituents were not 

looked for.

VI. 1 g. U3O8 , 0-5 g. ThO2,0-5 g. PbO, 2 g. borax glass. This experiment is added to show the high percentage of thoria in the product.

Composition,

TliO, ....................................................... 65.7

UO, ........................................................ 15-9

U03 ........................................................ 16.8

PbO........................................................ -6

99-0

The results of these experiments furnish another proof of the isomorphism of thoria and uranium dioxide.
THE COMPOSITION OF ROWLANDITE AND MACKINTOSHITE.'

By W. F. HlLLEBRAND.

I. BOWLANDITE.

The specimen ot rowlandite, furnished by Mr. Hidden for analysis, 

was a portion of a mass somewhat resembling amorphous gadolinite. 

It had a glassy interior surrounded by an uneven thickness of reddish 

alteration substance, chiefly a carbonate, or carbonates, of the rare 

earths and lime. The glassy "rowlandite" showed, when broken up, 

reddish and dark stains in places, the latter being produced by minute 

black inclusions, perhaps of a titanium mineral. Numerous scarcely 

visible fissures, filled with foreign matter, traversed the glass. This 

rendered the selection of pure material an arduous task; the result of 

several days of labor, however, was a sample possessing a high degree 

of puri ty as shown by the microscope. A very sni all amount of impurity 

was still present, but much less, apparently, than the analysis seems 

to indicate. A slight cloudiness in some grains points to incipient 

change. Its density is the same as that found by Mr. Hidden, 4/513, 

at 15-5° C. The analysis is as follows:

Si02 . .............

"X"t

ThO..... .........

Ce4O3 ;. ......'...-.

La group .........

FeA.... .........

FeO ... ..........

MnO.-.. ..........

CaO...... ........

"MgO. .............

Alk...... ........

nao ..............

CO2 ...... ........

Fl ................

P.O,. ....... .--..-

25-77

 59

5-06

9-34 

47-70

 0!)

4 -39$

 70

 CO

1-58

 32

 24

 34

3-87

26-04

 04

 40

1-66

 24

Mean. 

20 -04*

 59

5 -06

9-34 Mol.W.336-8 

47 -70 Mol. W. 266 -2

 09

4-39

 07

 50

1-62

 28

 24

 34

3 '87

101 -12 

1-63

99-49

* Certainly more nearly correct than 25- 77, since the fluorine must have caused loss of silica on evaporation with hydrochloric acid.

1A mixture of undefinable earths with some uranium and a trace of titanium,

{Cerium dioxide can not be present, if at all, in more than trivial amount, for otherwise much less 

ferrous oxide would have been found. For the same reason the manganese can not be present as 

Mna03 .

§If the small and undetermined amount of uranium exists as dioxide, the ferrous oxide here given 

is correspondingly high, but the possible error can have no influence on the formula deduced.

'For the general description of these new minerals, by W. E. Hidden, see the Anier. Jour. Sci. for 

Aug. and Sept., 1893.
IIILLEBRAND.] ROWLANDITE AND MACKINTOSHITE. 45

111 calculating the molecular ratios a brief consideration sliows thatCaO 

and CO2 may be neglected, and likewise, so far as their effect on the general formula is concerned, the ThO2 and the group denominated X; also 

the trace of ferric oxide and the alkalies. For the present the water may 

also be disregarded. There result then the following molecular ratios:

d:r\

CeA. ......................

FeO...... ..................

MnO. .......................

MgO...- ....................

Fl ..........................

26 '04 - 60 

9 -34 336 -8 -0277 [

47-70 266-2 -1792 j

4-39 72 -06101

 67 " 71 -00941

1-62 40 -0405 J

3 -87 19

 4340

 2037

3 '91

2-00

1-00

1 84

These furnish the following empirical formula, after deductiug 10 

atoms of oxygen for 20 of fluorine :

Sl43'"R44"RllF2oO|r,l

The silica is in all probability as much as half a per cent too low 

through loss occasioned by the presence of fluorine. Furthermore, it 

is possible that the fluorine, estimated by the Berzeliau method, is a 

little too low; or, if not, that the small amount of water found is in 

part at least derived from hydroxyl replacing fluorine. The presumption is then strong that the composition of rowlandite is represented 

by the formula SiV'^/'EiiFzaOis,, or in simplified form Si4 '"R4 "RF2O14 .

Structurally this formula may perhaps be written in a number of 

ways, that which most readily suggests itself being

KF

'T="'R

'"KF

in which the mineral is to be regarded as a derivative of the acid 

H6Si2O7. Until, however, the whole group of rare earth silicates is carefully studied and their relations among themselves and to other better 

known silicates are ascertained, it would be premature to pronounce 

in favor of this or any other structural formula.

Reducing all the other earths to a hypothetical one having the 

molecular weight of the yttrium group as found, and the manganese and 

magnesia to their equivalents in iron, the composition of an ideal rowlandite would appear as in the first column below, while the second 

column shows the percentages required to conform to the above formula.

Si.................

T...... ...........

Fe...... ..........

]?1 ................

o...... ...........

Found.

12-73

6-50

4 "05

25-89

100 -00

Calculated 

for 

SiAFeFlsOu

12-93

50 -37

6-46

4 "39

25 -85 '

100 -00
46 LABORATORY REPORT, 1891-?92 AND 1892-'93. [BULL. 113.

The agreement is very close and becomes much more so if the suggested slight increase in silica and fluorine is allowed.

. II. MACKINTOSHITE.

Of the dull black mineral, named mackintoshite by Hidden, and supposed by him to be the parent of thoro-gummite but nine-tenths of a 

gram was available for analysis after careful hand-picking under the 

lens. It was almost entirely free from recognizable impurity and had 

a density of 543 at 21-4° C.

In powder the mineral is not entirely decomposed by any one acid so 

far as the necessarily restricted tests indicated. Sulphuric acid attacks 

it quite strongly, but the gelatinous silica set free protects a portion 

from further action. The addition of nitric acid then, however, causes 

speedy and complete solution. This behavior is perhaps susceptible of 

a different explanation, namely, that the mineral is not homogeneous, 

but consists of two different substances, the predominant one of which 

is decomposable by sulphuric acid, the other much less affected by it, 

but when once the latter has been opened up by removal of the former 

it is readily dissolved by nitric acid. Mtro-hydrochloric acid likewise 

dissolves it completely.

Considering that the limited sample had to be divided into three portions in order to estimate the constituents tabulated below, it is not 

perhaps surprising that the analysis should present a loss o°f three and 

one-half per cent. The presence of even the little phosphoric acid shown 

renders the analytical operations by which the silica and bases are 

determined extremely complicated, particularly when zirconia and 

yttria are present. Precipitates are then obtained which under similar 

conditions the other earth bases do not give, and thus separations and 

identifications are rendered more difficult and losses are almost inevitable. It is therefore not at all certain that the very considerable loss 

is to be sought in some constituent not enumerated; it is more probable 

that it should be distributed somewhat unevenly over a number of those 

given, silica and lead oxide excepted, they being without doubt nearly 

correct. The following observations, however, may be of importance 

in this connection. After sealing the tube in which was the sample 

serving for the estimation of the oxidizable constituents, a slow but long 

continued evolution of gas was observed, just as in the case of most 

uraninites when similarly treated, but owing to the very small quantity 

of powder in the tube only -15 gram it could not be proven that 

the gas was nitrogen and not OO2 . The latter it should not be, for 

thoro-gummite, the direct alteration product of the mineral, is free from 

it according to Hidden and Mackintosh's analysis. In any event its 

amount is probably very small.

With respect to the oxidizable constituents it was found to be 

impossible to secure complete solution of the powder in the tube, even 

after several days' heating with dilute sulphuric acid, owing presumably
llILLEBKAJfU.] ROWLANDITE AND MACKINTOSHITE. 47

to the above-mentioned protective action of .silica set free and o! 

thorium sulphate thrown out. The amount of oxygen consumed 

indicated 16 per cent of oxidizable bases counted as TJO2 ; it may be 

therefore that all the uranium exists in that form and the iron in the 

ferrous state, as they are given in the analyses which follow. Of these 

& was made on a small sample selected grain by grain with the utmost 

care, but it was evidently not much purer than the first lot. There is 

at most an indication that FeO, CaO, alkalies, P2O5 , and perhaps 

some water arise from impurities. Titanium, manganese, and fluorine 

are not present in the mineral.

SiOj...... ...................

UO,. ........................

Zr0.z t ...... .................

Th02 .....->

CMV----

V f\ ' *

TbO .............. ..--- -.- 

FeO

CaO. ............... ........

MgO...... ......... -...:...

K2 0. ........................

(Na, U).,0 ..................

vtos ...... ..................

H2 0 above 100° C-. .........

H.,0 below 100° C...........

a

13-90

22 -40

,QO

*45 -30

3-74

1 -If)

 59

 10

 42

 08

 67

4 -31

 50

96-50

I

1Q -0°

t21 -86

3-92

(I)

 44

 13

} -,

 40

 35

Tlipro-gummito (H. <feM.).

Si02 ................. 13-085

UO........ ........... 22-43

Th02 ................ 41-44

Po203 ---------------- '845

(Co, Y) 203 etc. ....... 6-69 (At. W. 135.)

PbO ................. 2-10

CaO ................. -41

P206 ...... ........... 1-19

H2 0 ................. 7-88

98 -325

* The precipitate by potassium byelroxide was pure white after long action of chlorine. It may, 

however, have contained a trace of cerium.

t Would be slightly increased by uranium which was not separated from the earths. 

J The estimation of iron miscarried, but the amount was unquestionably less than in a.

Taken by themselves these results are incapable of translation 

through the medium of molecular weights into any precise formula, 

but they become of interest when compared with the accompanying 

analysis of thoro-gummite by Hidden and Mackintosh. 1 It is then 

seen that the opinion of Mr. Hidden regarding the derivation of thorogummite from the present mineral was fully j ustified. It is in fact 

remarkable, considering the great molecular alteration that must have 

taken place, as determined by the totally different appearance of the 

two minerals, that so little loss of substance has occurred. Almost 

the sole change has consisted in an oxidation of uranous oxide and an 

increase in the hydration. These facts render not altogether safe the 

assumption above made that all uranium and iron in the new mineral 

exist there in the lower forms of oxidation, and they furthermore 

indicate that the black mineral itself may have already undergone

1 Amer. Jour. Sei.,
48 LABORATORY REPORT, 189t-*92 AND 1892-'93. [BULL. 113.

oxidation and hydration without this being manifest to the eye a 

supposition which is strengthened by the loss at 100° C. of half a per 

cent of water, and in fact by the intimate union which existed between 

the two minerals when received. -Such material alteration without 

corresponding physical evidence of it seems to be common among 

uraninites. The original condition of the mineral may then have been 

one in which uranium and iron were entirely in the lower state of 

oxidation and in which water was possibly absent. It is to be hoped 

that opportunity may yet be afforded for a more thorough examination 

of this mineral, which, though apparently allied to thorite and uranothorite, is distinguished from them chiefly by greater content in 

uranium and by a higher degree of basicity.
ZINC-BEARING SPRING WATERS FROM MISSOURI.

BY W. F. HlLLEBRAND.

Zinc salts have been observed in the waters from La Malou in the 

south of France, according to Doelter, 1 and in those of certain hot 

springs of New Zealand f perhaps also in those of other localities, but 

I have as yet been unable to find any data bearing upon their contents 

in such salts. Durand-Fardel's Dictionnaire des Eaux Mine>ales, 1860, 

fails to include zinc as a constituent of the waters of La Malou which 

had been analyzed up to that time. It is therefore improbable that 

this element is present there in any considerable quantity.

The spring waters herein described are, it is thought, unique, in that 

their chief salt constituent is zinc sulphate. The following information 

in regard to the location and surroundings of the springs from which 

they flow has been obtained from Mr. W. P. Jenney of the U. S. Geological Survey, who was led to suspect a peculiarity of composition 

from the strong metallic astringent taste left in the mouth after swallowing, and by the slimy white precipitate which covers the walls of 

the springs and all vegetable matter falling into the water about them.

On the road from Joplin to Seneca, in Newton County, southwestern 

Missouri, about a quarter of a mile north of Shoal Creek and four and 

a half miles southwest of Joplin is a low bluff, perhaps 18 feet high, 

formed by a portion of the Burlington chert beds. At the base of 

this bluff, in a shallow depression, is a series of springs extendiug for 

a distance of perhaps 150 feet and emptying their waters into the abovementioned depression, wherein a sluggish current is produced and a 

deposition of a slimy white precipitate takes place. They vary in size, 

discharging from one-half to 3 gallons of water per minute, and about 

30 gallons, or 150 to 160 liters, in the aggregate. So far as can be 

judged by the taste they vary also in composition,,some waters being 

much stronger than others.

The two samples analyzed were taken by Mr. James A. Beeves, of 

Jopliu, from springs about 90 feet apart, designated as the east 

spring and the west spring, which were not only the most powerful, 

but which also, judged by the taste, furnished the strongest water.

1 Allgcmeino cliemischo Miueralogie, p. 233.

2 Trans. and Proc. New Zeal. Institute, 1870, vol. in.

Bull. 113 4 49
50 LABOEATORY REPORT, 1891-*92 AND 1892J93. [BULL. 113.

The composition as given below is that of the water after having stood 

in sealed bottles for two or three weeks and having been then separated by filtration from a whitish flocculent deposit which was probably 

formed after collection of the samples, in which case the reported composition does not exactly represent tha,t of the water as it issued from 

the spring. As received the waters were clear and limpid above the 

sediment, they were neutral to litmus paper, and their density differed 

but little from that of pure water, that of No. 1 being 1-0006 at 20£° 0. 

The samples were too small and time was too valuable to admit of 

exhaustive examination or of duplication of determinations. The 

analyses are as follows:

Pb.... ............

Cu...... ..........

Cd................

Zn...... ..........

Fo...... ..........

Mn. ...... ........

Al....... .........

Mg........ .......

K.. ...............

Na...... ..........

Cl........ ........

so4 ...............

PA

SiOj. ...... .......

I.

East spring. 

Parts in 

1,000,000.

 9

 5

320-5

 6

O *}

 4

61-1

0 Q

2-5

3-6

2-6

43 -2-'

.13-7

539 -9

II. 

West spring. 

Parts in 

1,000,000.

?

132-4

 6

 5

 63-1

4-2

9 -^

3

.Q

2-0

987 -ft

56 -8*

15-7

572-3

* Calculated.

PbS04 ....... ...............

CuS04 . ...... ...............

CdS04 .- ....................

ZnS04 -- ....................

FeS04 ...... ................

MuS04 ...... ................

A12 (S04 ) 3 - ..................

CaS04 ......................

MgS04 .............. ........

K2S0 4 ...... ................

NaaS04.....................

NaCl .......................

CaCOj- .....................

Si02 --.... ..................

I. East spring.

Parts in 

1,000,000.

trace. 

 5 

 9 

297-7 

1-6 

'6-3 

2-5 

109.9 

19-0 

5-6 

5-9 

4-3 

72-0 

13-7

539-9

Percentage 

composition.

trace. 

 09 

 17 

55 -14 

 30 

1-17 

 46 

20.34 

3-52 

1-04 

1-09 

 80 

13-34 

2-54

100 -00

II. West spring.

Parts in 

1,000,000.

imdet. 

undet. 

1

327-0 

1-6 

G-6 

3-2 

85-8 

21-0 

5-6 

6-8 

4-3 

94-7 

15-7

572-3

Percentage 

composition.

nuclei, 

undet. 

? 

57-14 

 28 

1-15 

 56 

14.99 

3-67 

 98 

1-19 

 75 

16-55 

2-74

100 -00
HILLEBRAND.] ZINOBEARING SPRING WATERS FROM MISSOURI. 51

Besides the above tabulated constituents, the waters held a considerable quantity of organic matter, which was not estimated, a small 

amount of ammonia not exceeding one part per million and which if 

counted as sulphate would affect only slightly the relative proportions 

of calcium sulphate and carbonate, and in an unconcentrated state 

they gave no reaction with brucine or diphenylamine for nitrates or 

nitrites. Although cadmium was not found in the water from the 

west spring, it is possible, in view of the close similarity of the two 

waters, that it was somehow overlooked.

In analyzing these waters a peculiarity deserves to be mentioned, 

which may at the same time serve as a warning to any one who may in the 

future examine them. Although a portion of the calcium unquestionably 

exists as carbonate, as shown by the excess of bases over chlorine and 

sulphuric anhydride, it is nevertheless the case that all the carbon 

dioxide is expelled by simply boiling the water. The amounts found 

for the east and west springs respectively were 120-5 and 110-0 parts 

of OO2 per million. No more was obtained by acidifying the water. 

At the same time a precipitation of a zinc compound free from carbon 

dioxide and from calcium began to take place in the water as soon as 

the boiling point was neared, which soon ceased after ebullition set in. 

This precipitation furnishes the explanation of the total escape of carbon, dioxide, combined as well as free, from the unacidulated water; for 

as the calcium bicarbonate in solution becomes decomposed by heat the 

calcium carbonate at temperatures near the boiling point at once 

reacts with zinc sulphate, with the formation of calcium sulphate1, zinc 

hydrate or. a very basic sulphate, and carbon dioxide. A determination 

of total solid constituents by evaporation of the water to dryness 

would involve, therefore, a very serious error in addition to those 

usually encountered.

A few remarks are here necessary in connection with the above 

reaction, which in one particular is so contrary to the statements that 

have come under my observations in chemical and geological literature 

bearing on the reaction which takes place between zinc salts in aqueous solution and undissolved calcium carbonate at elevated temperatures. It is generally stated that a basic zinc carbonate is precipitated 

while calcium, sulphate goes into solution, except by Demar9ay, the 

discoverer of the reaction, who says1 that zinc oxide is thrown down. 

It is not to be supposed that soluble calcium in the form of bicarbonate 

would in any Avay affect this reaction except to hasten its completion. 

While a zinc carbonate is undoubtedly thrown down from a solution of 

the chloride by calcium, carbonate or by the bicarbonate, us I have 

satisfied myself by experiment, this does not seem to be the case with 

a solution of zinc sulphate. An experiment, tested by repetition, with 

zinc sulphate and calcium bicarbonate in about the proportions shown 

in the above waters, i. e., with insufficient carbonate to throw out all

1 Ann. d. Clieniie, vol. xi, p. 250, 1834.
52 LABORATORY REPORT, 1891-?92 AND 1892-?93. [BULL. 113.

the zinc, by observing which precaution no calcium carbonate can contaminate the precipitate, showed that the latter was absolutely free 

from carbonic acid and from calcium, but contained some sulphuric 

acid. If this is the normal reaction for the sulphate, it is the one to 

be chiefly considered by the geologist, for in nature the sulphate of 

zinc, and not the chloride, on which latter laboratory experiments seem 

to have been largely made, is the form in which that element is most 

likely to be found in solution.

The sediments from the bottles, which were very slimy, amounted 

when dried at 100° 0. to approximately 17-0 parts per million of the 

water from the east spring and to about 40-3 parts per million of that 

from the west spring. They contained thus dried not less than ]3 

per cent of water and organic matter, while the ignition residue was 

about three fourths silica, and the remainder zinc oxide with a little 

iron, alumina, and sulphuric acid. The sediments were undoubtedly a 

mixture of amorphous silica, with very basic sulphates of zinc, aluminum and iron, without calcium. They had in both cases probably 

formed after the water was bottled, for they continued to appear in 

that portion of the filtered water which was retained as a reserve till 

completion of the analysis. As the two waters were not analyzed 

simultaneously the analyses are not strictly comparable, for one had 

deposited more sediment than the other, but it is noticeable that the 

water richest in salts had also deposited more sediment, showing that 

the differences in the analyses are not solely or in the main due to the 

different lengths of time that had elapsed between bottling and analyzing, but to inherent differences in composition.

With the waters was sent in a separate bottle a sample of the precipitate deposited in the depression into which the springs emptied. 

It was contaminated by much decaying vegetable matter and admitted 

of no satisfactory quantitative examination, but after filtration and 

washing, qualitative tests showed it to be essentially the same as the 

deposit found in the bottles. Owing to its greater amount it was also 

possible to ascertain that cadmium, lead, and copper were to a certain 

extent concentrated in it.

The source of the metallic salt constituents of these waters is of 

course to be sought in one of the deposits of zinc blende so numerous 

in that part of Missouri and across the state boundary in Kansas^ 

although there are no known indications of zinc ores within a quarter 

of a mile of the springs and no large producing zinc mines within two 

miles of them. The limestones and cherts of the region supply the 

calcium and silica, and the organic matter, if not originally of surface 

origin, may well have come from oxidation of the bitumen which is 

found in quantity in the limestone. The permanent water level thereabouts is very near the surface, and it is not to be supposed that the 

particular waters imdpr discussion have come from a great depth or 

are other than surface waters. The amount of zinc sulphate in them,
ZINC-BEARING SPRING WATERS FROM MISSOURI. 53

however, is from two to tliree times as much as could have resulted 

under the most favorable conditions from oxidation of zinc sulphide 

either directly or indirectly by the sole agency of oxygen, carried down 

by surface waters. It is probable, therefore, that the ore bed whence 

the supply of metals is derived lies very near the surface, above the 

permanent water level of the country, where the atmospheric oxygen 

has direct access to it through porosity of the earth's surface. The 

powerful influence of oxygen thus acting on moist ore bodies, which 

have been exposed by the opening up of mines, in changing- the character of the waters of a region, is shown by E. Haworth1 in writing of 

the mine waters of the adjoining county of Oherokee in Kansas: "The 

well and spring waters before the mines were opened were tirst class, 

* * * But as soon as the mines were opened all was changed, and 

the older the mines the worse the water. Animals of all kinds began 

being seriously affected," etc. He ascribes the high contents of the 

waters in metallic salts solely to the greater amount of oxidation rendered possible by exposure of masses of ore in the mine workings and 

on the dumps to atmospheric action, and gives instances to show how 

rapidly they succumb to it. He gives also a qualitative analysis of a 

mine water drawn from near the bottom of a shaft 130 feet deep which 

was nearly full of water at the time, and also the total weight of solids. 

The latter was over four times as high as in the spring waters above 

described, and there were found, in addition to the constituents already 

enumerated, ferric and ferrous sulphate in large quantity and free sulphuric acid. Carbonic acid, alkalies, and copper are not mentioned by 

him.

i A contribution to the Geology of the lead and zinc mining district of Cherokeo County, "Kansas, 

presented to the faculty of tho Kanaaa State University, 1884, p. 34.
JOSEPHINITE, A NEW NICKEL-IRON.

BY W. H. MELVILLE.

History. Several months ago Prof. F. W. Clarke submitted to me 

for examination a quantity of magnetic pebbles which were sent to this 

office by Mr. William H. Hampton, of Portland, Oregon, and by subsequent correspondence with, this gentleman he obtained a larger amount, 

with full liberty to publish the results arrived at in the laboratory.

In the spring of 1891 Mr. Hampton discovered these pebbles in large 

quantities in the placer gravel of a stream in Josephine and Jackson 

counties, Oregon, which border on the south of Douglas county, where 

the nickel silicate 1 described by Prof. Clarke 'occurs. He analyzed 

with reference to nickel and iron an average sample of 20 pounds 

of the wash gravel from the placer diggings, and found that the metallic portion gave 60-3 per cent nickel and 26-7 per cent iron. From 

the nature of the gangue or stony portion Mr. Hampton concluded that 

these waterworn pebbles and bowlders for some pieces weighed over 

100 pounds "came from an eruptive dike somewhere in the vicinity." 

The locality of this dike was not at that time ascertained.

Physical characters. £\iz pebbles are irregular in shape, but approximate the form of ellipsoids. Their smooth surfaces, polished by the 

action of water, are colored in general greenish black, interrupted by 

bright areas of the grayish white alloy of nickel and iron. The former 

portions consist of siliceous matter, and when cut by a knife yield a 

dull and light gray powder, but broken fragments show greenish yellow and deep green colors and resinous luster resembling noble serpentine. With this is associated in. some pebbles a silicate whose 

hardness is between 5 and 6. It is compact and on the fresh fracture 

exhibits a light brown color and vitreous luster, while exposed surfaces 

are reddened by ferric oxide.

The texture of the metallic portion as it appears on fracture is granular. The metal is gray, malleable, and sectile, with hardness about 5.

The specific gravity of one lot containing forty-two pebbles was taken 

in a pycnometer at a temperature of 22° C. These pebbles ranged in 

weight from 0-3159 to 1-6447 grams, and were about the dimensions of

'Bull. U. S. Gcol. Survey, No. 60, p. 21, 1887-'88. 

54
MELVILLE.] JOSEPHINITE, A NEW NICKEL-IRON. 55

a pea. The largest pebble in my possession weighed 4-2847 grams, and 

the specific gravity of this was taken by suspending it from, a silk fiber. 

Two determinations furnished a mean specific gravity of 6-204.

The pebbles are strongly magnetic.

Analyses. The analyses were conducted with the aim of separating 

the pebbles into their proximate principles and also their ultimate 

constituents. Two different lots of about twelve grammes each were 

pulverized in a steel mortar, a delicate and tedious operation, owing to 

the extreme malleability of the nickel-iron. Two complete analyses 

of these samples were made. The ratio between the nickel and iron 

in the metallic state was ascertained by deducting from the total 

amounts of each of these elements those quantities which were found 

in other combinations. The ordinary method of fusion with sodium 

hydrate and subsequent treatment of the residue with concentrated 

nitric acid failed to give the true contents of the metallic portion in 

the pebbles, because the nickel iron was not passive in this acid. The 

ratio between the nickel and iron, however, could be obtained by this 

method.

The stony matter was freed as far as practicable from the magnetic 

parts by a fractional process that is to say, by the repeated use of an 

electro-magnet and by the decantation of the light particles suspended 

in water. The siliceous portion was then analyzed. A fresh sample 

was treated with diluted hydrochloric acid, and after repeated evaporations the soluble silica was separated from the insoluble residue and 

weighed. The insoluble residue was analyzed, and the percentage 

composition of soluble silicate was inferred from this analysis, the 

analysis of the total siliceous matter, and the total silica of the pebbles.

The mean composition of the pebbles is shown by the following numbers:

Nickel free, ISTi. ................... 

Cobalt, Co........................

Iron free, ITe. .....................

Chlorine, Cl ......................

HS0 below 100°C... ..............

H20 above 100° C- ................

C02 . ..............................

Per cent.

CO'45 

0'55

23 -22 

0-55

0 -12

0-50

0-23

0-04

12 -20

0-81

112

0-70

100 -55

Nickel combined ..................

Iron combined. ................... 

Snlphur ..........................

Per cent.

0-25

1-79 

0-22

0-04
56 LABORATORY REPORT, 1891-'92 AND l892-'93. [BULL. 113. ' <«

SiOj...... ..................

AljOj...... .................

J?e203 . .......... ............

(Ni,Co)0. ..................

CaO ........................

MgO ...................

Na30..-.;. .................

H20 above 100° V. ..........

Total 

silicate.

- 5-14

0-33

2-08

0-32

t-62

2-69

0-08

1-12

13 -38

Insoluble 

silicate.

0-23

0-03

-> 0 -04

0-06

0-14

0-50

Soluble 

silicate.

4-91

0-30

2-04

0-32

1-5(3

2-55

0-08

1-12

12-88

Composition .

oin *"

A1A-----'-----"----

Fej03 ...... .........

(Ni,Co)0...........

CaO................

MgO... .............

Na-jO- ..............

Insoluble silicate.

Per cent.

45-63 

G-58 

8-77 

undetera 

11-03 

28-01

100 -02

At. ratio.

3-04 

0.39 

0-33 

ined. 

0-39 

1-40.

2-51

Soluble silicate.

Per cent.

38-23 

2-34 

15-88 

2-49 

12 -14 

19-85 

0-35 

8-72

100 -00

At. ratio.

2-55 

0-14; 

0-60 

0-07' 

0.43 

0-99 

0-01 

0-97.

0-74 

2-47

Silicates. There are two silicates, then, the one soluble in hydrochloric acid being undoubtedly serpentine. This serpentine surrounds 

the metallic portion, and on polished sections its deep green color is 

well brought out. It has not penetrated into the metallic mass, and it 

would appear that the pebbles once formed a large aggregation and that 

fractures took place in directions of least resistance through the serpentine. Other characters of serpentine were noted its resinous-luster, its hardness of about 3, and its iufusibility. In the closed tube 

water was given off'. The atomic ratio of the combined bases and 

water to silica is 3 -2:2 -55 or 5:4, a ratio which is identical with that of 

serpentine. The ratio between bases and water, 7:3 instead of 3:2, is 

not the true ratio for these constituents in serpentine as it exists in the 

pebbles, because the analysis is calculated from figures obtained from 

material which was dried at 100° C. Again, the reddish brown coloration of this dried material indicated the presence of some impurity, 

probably .oxides, and this could not be eliminated. The water is, therefore, too low and the iron oxide too high.

The insoluble silicate, however, can not be so clearly made out. Its 

atomic ratio, SiO2 : base = 6:5, brings it nearer an orthosilicate than a 

uietasilicate. It is light brown, vitreous, hard, compact, and not 

cleavable.. It does not fuse before the blow-pipe. It is not so hard as 

olivine and its insolubility in acid excludes this mineral. In physical 

and pyrognostic characters and to some extent, also, in composition it 

agrees fairly with bronzite (enstatite). The probable silicates to occur
MELVILLE.] JOSEPHINITE, A NEW NICKEL-IRON. 57

in this association are pyroxene, olivine, enstatite, from which serpentine is derived, while a feldspar is not to be expected. I did not determine to which silicate the sodium-oxide belonged, owing to its small 

quantity and the small quantity of insoluble silicate in the pebbles. A 

mixture of a soda-lime feldspar and enstatite (or pyroxene) would answer the requirements of the ratio, but this is purely speculative. So 

far as the data go it is best to regard this silicate as an impure bronzite.

During attempts to purify the silicates it was noticed that on the 

removal of the metallic part by a neutral concentrated solution of either 

cupric sulphate or mercuric chloride that the silicate was more or less 

attacked. Magnesia was removed, and one analysis showed that out 

of 2-69 per cent MgO in the pebbles only 0-43 per cent remained in the 

purified silicate. Curiously no iron or lime was removed. Pulverized 

olivine and serpentine were each digested with copper sulphate on the 

Avater bath two or three hours i a yellow copper salt was deposited and 

a large quantity of magnesia was taken out of both silicates. A basic 

copper sulphate was produced, and the liberated sulphuric acid (S0;t) 

combined with magnesia to magnesium sulphate. In the presence of 

olivine or serpentine this treatment for the purification of the silicate 

is inadmissible.

Chromite. Under the microscope a minute quantity of black metallic grains can be seen in the siliceous portion, which do not precipitate 

copper from a sulphate solution. These grains consist of chromite 

with a very few strongly magnetic particles of magnetite. 0-04 per 

cent of chromium was found in the pebbles, while the per cent of chromium, corresponding to 0-12 per cent of chrome iron, is 0-030. The 

presence of chromite is naturally expected in the serpentine.

Magnetite. The few grains mentioned under chromite were dissolved 

by protracted heating in hydrochloric acid. Other particles of magnetite were not recognized with certainty.

Two magnetic pebbles were found among those which carried the 

large percentage of nickel, and a small amount of fibrous serpentine 

(not chrysotilej adhered to this magnetite. It is probable that magnetite occurs in the original deposit from which the nickel pebbles were 

transported. The high percentage of iron obtained by Mr. Hampton 

was probably due to the presence of some magnetite-pebbles in the 

average sample which he studied.

Pyrrhotite (troilite). The nionosulphide of iron could not be separated from the other principles with sufficient purity for analysis. The 

amount of this mineral, formula Fe7S8 , was calculated from the total 

sulphur, 0-22 per cent. Hydrogen sulphide was liberated in considerable quantity when the powdered pebble was treated with diluted 

chlorhydric acid. Millerite does not act thus.

Copper. The copper is not a constituent of the pyrrhotite, but belongs 

to the nickel iron. Copper minerals were not detected under magnifying power.
58 LABORATOEY REPORT, 1891-'92 AND !892- ?93. [BULL. 113.

Arsenic. Arseuious oxide was condensed in the cool parts of a tube 

through which air was allowed to pass, as also in all the tubes used for 

the determination of volatile matter. No sulphide of arsenic dissolved 

by digesting in the cold with ammonium carbonate, nor could niccolite 

(nickel arsenide) be detected. Arsenic forms a part of the metallic 

portion of the pebbles.

Chlorine. The chlorine was determined in a nitric-acid solution of 

the original powder, a blank experiment with the use of the same quantity of reagents being run parallel with that. In an aqueous solution 

were found iron, nickel, magnesium, sodium, and chlorine, and this fact, 

together with the small available quantity of chloride, caused the difficulty in determining with which element chlorine was combined. The 

presence of iron and nickel, since pyrrhotite carries nickel, can be 

accounted for in the aqueous solution by the easy oxidizability of the 

sulphide with free access of air. Green ferrous chloride could not be 

detected in the powder, nor any soluble salt possessing that color. The 

permanence of the pebbles in air is also a presumption in favor of the 

absence of lawrencite. Mckel chloride has not before been observed, 

but may possibly exist in these specimens. It is more probable that 

the chlorine is united with sodium 0-04 per cent requiring 0-026 per. 

cent Na or 0-035 per cent NazO. The magnesium is in the form of carbonate.

Water and volatile matter. The powdered substance in a platinum 

boat was heated in a glass tube in a stream of dry carbonic anhydride, 

and the water, both hygroscopic moisture and water of constitution, 

was weighed in a chloride of calcium tube. Another portion was heated 

in hydrogen gas, and hence the oxygen in the oxides was known, 

although this amount might have included some, if not all, of the oxygen combined with iron in the ferric state in the silicates. After burning in a current of dry air and then reducing in hydrogen the total loss 

was ascertained from the difference in weight of the contents of the 

boat before and after the operation. In all cases except when burnt in 

air a brownish cloud possessing an empyreumatic odor was driven off 

without leaving a brown black sublimate in the tube. It was a volatile organic substance whose nature was not discovered. The pulverized pebbles when treated with dilute hydrochloric acid at the temperature of the water bath gave the odor characteristic of the decomposition of a carbide, so that the volatile matter given in the analysis 

consists of organic matter, namely, combined carbon and probably a 

hydrocarbon. All loss arising from the volatilization of arsenic, sulph ur, 

and chlorine have not been included in the per cent given for volatile 

matter.
MKI-VILLK.] JOSEPHINITE, A NEW NICKEL-IRON. 59

Nickel-iron. Of special interest is tlie metallic portion. Two 

analyses gave .

Fe................

Ni.... ............

(1)

23-36

GO -47

(2)

23 '00

GO -43

At. ratio

0-41

1-03

From this ratio is deduced the formula Fe2Ni5 . 

The following table gives a comparison of a few examples of nickel- 

.iferous iron, which form an instructive series:

Catariuite.*

63-69

33 -97

1. 14:0-58

Fe2TsT i

Octibbehite.t

37-69

59-G9

0 -G6 : 1 -02

FejNi3

Awaruite.;

31 -02

G7-G3

0-55:1-17

2(FeNiJ)

Josephinito.

23 -22

GO -45

0-41:l-0:i

1MH.

* Enf yclopi'die chimique, TYemy, Metalloids, Tome ii, par M. Stanislas Mrviuior.

t Am. Jour. Sci., II, xxiv, p. 29:',, Taylor.

{Am. Jour. Sci., vol. xxxm, p. 244, G. IL F. Ulricli; analysis by W. Skoy. A. Solla described a 

nickel iron from the auriferous sands of tho stream Elvo, near JBiella, Piedmont; Fe 2G-G percent; Ni 

(Co) 75-2 per cent; formula (2FcNi3) = Fe2Nic . C. E. CXH, 171; also Am. Jour. Sci., Ill, p. 252,1891.

The question naturally arises whether the origin of these pebbles is 

cosmic (meteoric) or terrestrial. Catarinite and octibbehite have been 

considered meteoric falls, while awaruite has been traced from the 

drift in the Awarua river on the western side of the middle island of 

New Zealand to a "mountain of peridotite, an oUvine-enstatlte rock 

more or less serpentinized," and is undoubtedly terrestrial. In the drift 

are found gold, platinum, cassiterite, chromite, and magnetite. The 

placer gravel, in which josephinite is found, is like that of New Zealand 

with the exception of the occurrence of platinum1 and cassiterite so far 

as known at present.

There is one element, phosphorus, which is almost universally found 

in meteorites and combined with nickel and iron to form the mineral 

schreibersite, which has no representative among terrestrial minerals. 

After evaporating to dryness a nitric acid solution of a sample of the 

pebbles, and fusing the residue with sodium carbonate and potassium 

nitrate, phosphoric acid was not detected in the acid nitrate, and thus 

was proved the absence of phosphorus both as terrestrial phosphate 

and meteoric phosphide. In the published analysis of awaruite by W. 

Skey no phosphorus is given. Catariuite and octibbehite contain 0-05 

per cent and O'lO per cent respectively.

By etching with nitric acid Widmannstiitten figures can not be produced upon a polished surface of the nickel-iron. The metal seems to 

be homogeneous, and the little sulphide occurs in the fissures. Awaru1 Platinum occurs in tho region of Rogue river, Oregon.
60 LABORATORY REPORT, 1891- ?92 AND 1892-793. [BULL. 113.

ite is passive toward an acid solution of copper sulphate, and only with 

difficulty and long heating is the nickel-iron from Oregon completely 

dissolved with replacement of the copper in a sulphate solution. This 

passive state is uncommon with the ordinary nickel-iron of meteorites, 

but the high percentage of nickel may account for this property. Con- 

. centrated nitric acid dissolves the alloy.

Daubree l points out that meteorites and analogous terrestrial rocks 

differ in that the former contain in a reduced state certain substances 

which appear in the latter in the state of oxides. This idea could be 

extended to include inetamorphism in its broadest sense. Serpentine 

is rarely found in meteorites, although Wohler has recognized it in some 

carbonaceous meteorites. In the two cases of awaruite and josephinite, 

serpentine is the principal silicate, derived in the former from olivine 

and enstatite. Daubr£elite is metamorphosed into chrome iron, and 

this may possibly be the explanation of the origin of the latter: that the 

double sulphide of chromium and iron existed in the ferromagnesian 

silicates before or at the time of their serpentinization, and was then 

oxidized to chromite.

The evidence cited in the previous paragraphs points to the terrestrial 

origin of the pebbles which form the subject of this paper, and here the 

question of origin must rest till the nickeliferous iron is found in situ.

The name josephinite is given in honor of the county, its locality, in 

accordance with the custom in use for naming analogous substances.

1 Etudes synth6tiqnes de geologic exp6riinentale, par A. Daubvtio, 1879, p. 578.
A NEW METEORITE FROM HAMBLEN COUNTY, TENNESSEE.

BY L. IT. EAKiNS.

This meteorite, which was found in September, 1887, on a ridge about 

six miles WSW. from Morristown, Hamblen County, Tennessee, was 

first recognized and brought to notice by Prof. J. M. Safford, of Nashville, who in course of an inspection of a collection of iron ores recognized some fragments as undoubtedly meteoric.

Professor Safford at once took steps to secure these pieces, and visited 

the locality where they were found. Here he succeeded in finding a 

few more fragments, which had the appearance of having been buried 

in the soil and afterwards turned up by the plow. These various pieces 

now in Professor Safford? s possession have a total weight of about 36 

pounds, two of them weighing respectively 11 pounds and 13 pounds.

A specimen sent by Professor Safford to the U. S. National Museum, 

and now in its collection, furnished the material for this investigation.

Most of the pieces show much surface oxidation; a fresh fracture 

showing a gray color, with numerous metallic particles of nickel iron.

The analysis was made in the usual way for this class of meteorites, 

that is, by separating the metallic and siliceous portions, both by picking and by the magnet, and analyzing separately the nickeliferous iron, 

the silicates soluble in hydrochloric acid and those insoluble in the acid.

The metallic and siliceous portions of this meteorite are, approximately, equal in amount, the iron being quite malleable and unusually 

tough.

The analysis is as follows:

Nickclifurous iron.

Fe.......................................................... 90.92

Ni.......... ................................................ 7.71

Co.......................................................... .80

Cu ......................................................... trace.

P..................................... ..................... .19

S,.,........................................................ .04

99.66

61
62 LABORATORY REPORT, 1891-'92 AND 1892-'93. [DULL.

Siliceous portion.

SiQ, ............. .

Ah03 . ............

CrA-------------

FeO ..............

NiO ..............

MnO...... ........

CaO ..............

MgO...... ........

K2 0 ..............

Na20 .............

T> f\

Soluble in HCl.

Analysis.

1C -70 

8-33

4-88 

 39

519 

1-34

 4C

 25

37-63

Calculated 

to 100 per 

cent.

45-61 

22-62,

11-73 

1-06

14-09 

3-64

1-25

100 -00

Molecular 

ratios.

 700 

 222

 163 

 014

 252 

 091

 009

Insoluble in HCl.

Analysis.

ai-47

9-25 

 82 

0-55

 47 

2-24 

. 11 -16 

 02 

 12

62-10

Calculated 

to 100 per 

cent.

50-67 

14 '89 

1-32 

10-55

 76 

3-61 

17-98 

 03 

 19

100 -00

Molecular 

ratios.

 844 

 146 

 009 

 147

 010 

 064 

 449

 003

In calculating the analysis of the soluble portion to 100 per cent, the 

S and an amount of iron (.56 per cent FeO) sufficient to form FeS are 

first deducted.

In many stony meteorites olivine is a considerable constituent, generally forming the bulk of the soluble silicate; but in this case the 

analysis shows olivine to be present in but small proportions, if at all. 

It is interesting to see that both the soluble and insoluble portions have 

practically the same molecular ratios, the soluble portion reducing itself 

essentially to E A12 SiO6 , in which, E=Ca, Fe,- and the insoluble part-to 

the same formula, where E=Mg, Fej both being equivalent to aluminous enstatite or j>yroxene.

At the time this analysis was made it was impracticable to Supplement the work with the proper microscopical examination of sections, 

which doubtless, in conjunction with the chemical evidence, would have 

satisfactorily determined the minerals present. Without this microscopical knowledge, however, little that is definite can be said, except 

that there seem to be present two similar molecules, the one in which 

lime predominates being soluble, and the other, ma^nesian, being insoluble, in hydrochloric acid. The other alternative is to assume a complex 

molecule which is split into two sections by the action of the acid.
ON THE CATALYTIC ACTION OF ALUMINUM CHLORIDE ON SILICIC

ETHERS.

BY H. K. STOKES.

If a little powdered anhydrous aluminum chloride be added to some 

ethyl trichlorsilicate, SiC^OC^Hs), which is cooled by ice, it dissolves, 

but no reaction is observed; on removing from the ice, bubbles of gas 

soon appear, and the reaction often becomes violent, attended by heating of the liquid. The gas, which burns with green-edged flame and 

formation of hydrochloric acid, is obviously ethyl chloride. If now the 

liquid be gently heated it gradually becomes thick, then solid, and 

finally the entire amount of aluminum chloride sublimes unchanged.

If instead of trichlorsilicate, tetraethylsilicate, Si(O02H5)4, be used, 

the reaction is in many respects the same, including the formation of 

ethyl chloride and the thickening of the liquid; but if the test-tube be 

connected with a condenser, it is seen that much ethyl ether is also 

produced. It may also be noticed that a relatively much greater 

amount of aluminum chloride than in the first case is required to produce the solid residue, while, unless a very considerable quantity has 

been added, none sublimes out on further heating.

It will be shown below that the action of the aluminum chloride on 

the trichlorsilicate is a case of so-called catalytic action (this being 

defined as a change brought about by a substance which at the end 

remains unaltered), while its action on the tetraethyl ether is one which 

is purely proportional to the relative amounts of the reagents, the 

aluminum remaining finally in combination with silica. It will also be 

seen that the monochlorsilicate, SiCl(OC2H5 ) 3 , is intermediate in its 

behavior, a mere trace of aluminum, chloride being sufficient to carry 

the decomposition to an end, when all the aluminum is found in fixed 

form. From these observations may be deduced the explanation of 

each case, including the catalytic action of the chloride on the trichlorsilicate. The details of the experiments, which were roughly quantitative, will be found in a separate section.

The only hypothesis which explains the facts .observed is that in each 

case the substances react in a truly chemical sense, ethyl chloride and 

aluminum silicate compounds, Si O Al, being formed, but that in 

case of the chlorsilicates these bodies are exceedingly unstable, and

63
64 LABOKATORY REPORT, 1891-'92 AND 1892-J93. [BULL. 113.

decompose at once with regeneration of aluminum chloride, which is 

thus able to act again, and thus produce total decomposition when 

present even in traces.

The cause of this regeneration I take to be due, in part at least, to 

the tendency of the silicon to monopolize the oxygen, at the expense 

of the aluminum, forming Si=O, Si O Si, etc., wliereby the metal is 

unable to remain combined with oxygen as long as this tendency of 

the silicon is not fully satisfied. If it happens that the latter is partly 

combined with chlorine (silicon chlorine), it at once exchanges it for an 

equivalent of oxygen. This^ however, holds only in the aliphatic series 

of ethers, and in those cases where the chlorine is not the only constituent of the silicon compound. As I shall show elsewhere, silicon, 

when completely saturated with chlorine, as in silicon tetrachloride, 

does not show this tendency, neither does it exist in case of the 

aromatic silicates. From the latter, aluminum chloride, if in excess, 

takes all the oxygen and the silicon becomes completely chlorinated.

The formation of ethyl ether I can explain only by assuming in silicon 

a well-known property of carbon, which is manifested in the orthoethers of carbonic and other organic acids, namely, that the highest 

basicity is shown only when all the basic radicle are organic, while 

the metallic salts are of a lower degree of saturation, and the mixed 

organic metallic ortho-salts are so unstable as to be scarcely capable of 

existing under ordinary conditions. Assuming this analogy to exist, 

we should expect to find transformations like the following occurring : 

OR

O Q- OR /-./SiOsAl . -p n 2Sl 03Al=0<Si03Al+R2°'

Strictly speaking, the tendency is not to form, as in the case of 

carbon, meta compounds containing Si=0, the analogue of carbouyl, 

but groupings in which two silicon atoms are united by oxygen, Si 

O Si, or (SiO)a?. This tendency is so strong, as has been pointed out 

by others,1 that it is obviously the explanation of the fact that nearly 

all silicon compounds containing the analogue of carbon yl are not 

volatile, or volatile only at high temperatures, when by analogy with 

carbon, the reactions producing them should give volatile bodies of 

low molecular weight. This tendency to condensation and polymerisation by means of oxygen is the rule in the silicon series, and forms one 

of the most marked differences in the chemical behavior of these two 

elements, and the chief obstacle to producing by any simple means 

definite derivatives of silicic acid. I wish to be distinctly understood, 

therefore, as using the following formulas and equations only as typical 

ones reduced to the simplest possible form, the actual ones being vastly 

more complex and of almost infinite variety. Where E is used it stands,

1 e. g. Mendelejeff, Gruudlageu der Cheniio, deutsche Aufl., p. 767.
STOKES.] CATALYTIC ACTION OP ALUMINUM CHLORIDE. 65

for sake of simplicity, for ethyl. That the quantitative experimental 

results do not conform with absolute strictness to the theoretical explanation is not surprising, for aluminum chloride is an extremely reactive 

body, tending to produce all sorts of secondary changes, Avhile it is not 

to be expected that the transformations could be carried quantitatively 

ito an. end by heating the viscous and finally solid masses which result. 

Etliyl triclilorsilicate, SiCl;i(OR), is readily and completely decomposed by aluminum chloride, and the reaction is quite independent of 

the amount used, even a trace being sufficient. The products are 

ethyl chloride, free from ethyl ether, free aluminum chloride unchanged 

in amount, and finally a solid residue of the empirical composition 

SiO.Cl2 , but which in reality consists of a mixture of all sorts of complex silicon oxychlorides with free silica, the general result being 

expressed by the equation

a typical case of catalytic action.

These oxychlorides are for the most part not volatile, but undergo at 

a high temperature transformation into oxychlorides richer and those 

poorer in chlorine, 1 the result being that they lose weight on ignition. 

The reactions by which they can be formed in the present case are very 

numerous, and only a few typfcal ones are given. The first steps in 

the process are

SiCl;1 (OR)+AlCl:t =SiCl3 .OAlCL+KCl,

or

These bodies, being for reasons above given very unstable, at once 

react with fresh portions of trichlorsilicate :

SiCl3 .O. A1C12 + SiCln (OE) = SiCl3 .O.SiCl2 (OE) + A1C13 , 

and

Sicl3o >A101+SiC1^^

The regenerated aluminum chloride acts further, thus :

SiCl3 .O.SiCl2 (OE)+A1013 =!SiCl3 .O.SiCl2 .O.AlCl2 +ECl, 

which latter repeats the process, or may decompose thus: 

SlCl3 .O.SiCl2 .OAlCl2 =SiCl3 .O.SiO.01+AlCl3 ,

and so on in every possible way ad infinitum, the aluminum chloride 

being continually regenerated, while the tendency of silicon to such 

condensations leads to increasing size of the molecules, which tend to 

the limit (SiO.Cl2 ) x, but seldom reach it before a high degree of complexity is attained. The increasing viscosity of the liquid interferes 

with the complete conversion of EO into EC1 at a temperature below 

which other changes set in, which are manifested by more or less evolution of hydrochloric acid and gaseous hydrocarbons, with some carbonization. There is, however, always an excess of silicon chlorine,

1 Troost and Hautefeuille, Ann. cliim. phys. [5], 7, 469.

Bull. 113-^ 5
66 LABORATORY REPORT, *1891-'92 AND 1892-7 93. [BULL. 113.

which regenerates aluminum chloride, enabling it to act in minute 

amounts, and to reappear unchanged at the end.

It may be objected that these reactions are purely hypothetical, and 

that no such compounds as SiCl3 .O.AlCl2 have been shown to exist. In 

the following cases it will be shown that there is strong evidence of 

their existence, the aluminum being caught in the act, so to speak, and* 

found ultimately, not as chloride, but in combination with oxygen.

Etliyl monochlorsilicate, SiCl(OR) 3 . Aluminum chloride, in acting on 

this compound, produces a similar series of changes, even if used in 

relatively small amount, with this difference, that as there is not enough 

silicon chlorine to carry the regeneration through to the end, the aluminum remains finally as A12O3 , and probably also as A1C1, combined 

with silica. The process is also complicated in certain cases by the 

formation of ethyl ether, which was explained above.

If we suppose the aluminum chloride to act by contact or influence 

merely, the decomposition would be expressed by the equation 

SiCl(OK)3 +aAlCl3 =SiO2+RCl+R2O+#A1013,

and the result would be practically independent of the amount of 

chloride used, which could be finally recovered unchanged. It is found, 

however, that while a mere trace is sufficient to bring about total decomposition in nearly the sense of the last equation, by increasing the 

amount more ethyl chloride and less ethyl ether are formed; when a 

certain proportion is reached, the ethyl ether vanishes, and also up to 

this point all aluminum remains fixed in the residue. If more than this 

amount of chloride be taken, some remains unchanged, and may be 

recovered by sublimation. We may consider three distinct cases, with 

differing proportions of the reagents, namely, when

(>3:2 (1)

Si:AN =3:2 (2) 

(<3:2 (3)

The first case includes that where aluminum chloride is present only 

in traces, when the complete reaction, reduced to the simplest form and 

neglecting aluminum, would be

(a] SiCl(OR)3 =SiO2+RCl+R20. 

By increasing the proportion of chloride we have, for example,

20SiCl(OB)3 +2A1013=(SiO2 ) 2o(Al2O3 ) + 26ECl+17E2O, 

6SiCl(OR) 3 +2AlCl3=(SiO2 ) 6 (A12O3 ) + 12RC1+3R2 O, etc.

It will be noticed that the relative amount of R^O decreases and 

that of RC1 increases as we approach the ratio Si: Al=3:2. Reaching 

this point, which is case (2), we have

(1)) 3SiCl(OR)3+2AlCl3=(SiO2 ) 3 (Al2O3 )+9RCl.

The experiment shows that with this ratio no R2O is formed, and that 

all aluminum remains in fixed form in the residue. Any further in-
STOKES.] CATALYTIC ACTION OF ALUMINUM CHLORIDE. 67

crease in the proportion of chloride belongs under case (3), where 

Si : Al<3 : 2. For example, if the ratio be that of equality, or 3 : 3, we 

might have

(c) 3SiCl(OB)3+3AlCl3=(SiO2 ) 3 (Al2O3 )+AlCl3 .

In fact when this proportion is taken, unchanged aluminum chloride 

sublimes out of the residue. Owing, however, to the tendency of the 

silicon to monopolize the oxygen or to take the metasilicate form,«this 

proportion admits of another reaction :

01

°\

(d) 8iCl(OB)3+A1013 =Sio_2Al+3ECl,

O/ 

and

01

°\ 0 SiO_ Al = SiO < g > A1C1,

O/

the residue being a chloraluminum metasilicate, or at least some similar form in which the preference of silicon for oxygen before 0 chlorine 

is satisfied. The chlorine and aluminum in this form are practically 

fixed, as such a body as this would probably give off aluminum chloride, if at all, only at a high temperature, the effect being that the volatile chloride falls below the theoretical amount required by equation (c). 

Finally, if Si: Al = 1:2 

(e) SiCl(OR) 3 +2AlCl3 =SiO3Al2Cl4 +3RGl. 

If we write the formula of the product

OA1012

it appears that in this form also the aluminum might be fixed, but that 

if more chloride be present, leading to the formation of

SiCl(OA1012 ) 3 ,

such a body would, by virtue of the silicon chlorine present, decompose at once into A1013 and SiO(OA1012 ) 2 . Two atoms aluminum are 

therefore the most that can. possibly be held by one atom silicon reacting as monochlorsilicate; any further amount must remain finally as 

unchanged chloride. The stability of such bodies as SiO(OA1012 ) 2 is; 

Lowever, made improbable by the experiments, which show that even 

with the ratio 1 : 1 only a part of the aluminum remains fixed.

These equations do not explain the semicatalytic action of aluminum 

chloride in decomposing indefinitely large amounts of monochl or silicate. 

The reason is obvious when we consider that, as the experiments show, 

the greatest amount of aluminum which can be held fixed by 1 rnol. 

wt. monochlorsilicate, lies between § and 1 at. wt. (equations 6 and d). 

Any greater amount of monochlorsilicate will, by virtue of its silicon 

chlorine, regenerate aluminum chloride, and be destroyed thereby,
68 LABORATORY REPORT 189l-'92 AND 1892-'93. [BULL. 113.

until the above proportion is reached. At this i3oint further reaction 

results only in the sense of' b and d, the regeneration of the chloride 

ceases, and all aluminum remains fixed.

It will be observed that in tHese reactions the chlorine going to form 

ethyl chloride comes proximately from the aluminum chloride, but ultimately, in part, from the chlorsilicate, and that the equations 

Si013 (OE) = SiOCl2 + BC1, 

SiCl(OE)3 =SiO2 + EC1 -f B2O

are not strictly true, the aluminum acting as the agent by which 01 is 

transferred from Si to E. The hypothesis might perhaps be further 

tested by substituting aluminum bromide for the chloride. If the 

decomposition is due to influence only, Si013 (OE) should give SiO.012 , 

and EC1 and AlBr3 only, but on the above hypothesis SiO.012 with 

either EBr and A1C13 only, or a mixture of EC1, EBr, A1C13 and aluminum chlorobromides, according to the proportions and the nature of 

the intermediate products. As this would involve previously studying 

the question whether a direct interchange of chlorine and bromine 

might occur, the experiment was postponed.

Etliyl dichlorsilicate, Si012 (OE)2 , from similar considerations, should 

decompose thus 

SiCl2 (OE)2 = SiO2 + 2BCl,

and it is not possible to devise any probable redaction by which aluminum should remain permanently combined. Therefore the apparent 

catalytic action should be as obvious here as in the case of the trichlorsilicate. The experiments s were, however, defective, probably 

owing to impure material, and no satisfactory conclusion could be 

drawn from them.

Etliyl orthosilicate, Si(OB)4 . This body shows a radically different 

behavior from that of the chlorsilicates, the decomposition being 

Strictly proportional to the relative amount of aluminum chloride used, 

and in this lies the explanation of the whole series of observations.

We may consider the following cases:

(<3:4 (1) 

Si:Al}=3:4 (2)

(>3:4 (3)

the ratio 3:4 being that in which the aluminum chloride contains just 

enough chlorine to convert all ethyl into ethyl chloride. 

( it) 3Si(OE)4 +4AlCl3 =Si3O]2Al4 +12BCl.

From considerations mentioned while speaking of the.monochlorsilicate, it is obvious that this proportion may result in a certain amount 

of chlorine remaining combined with the aluminum up to the limit 

(&) 3Si(OE)4 +4AlCl3 =Si3O10Al4Cl4 -fSBCl+2B2O.

For practical reasons given below, the substances could not be made 

to react in this proportion, the result being a formation of ethyl ether,
STOKES.] CATALYTIC ACTION OF ALUMINUM CHLORIDE. 69

ethyl chloride, and sublimation of some unchanged aluminum chloride. 

For the same reason a reaction in the sense of case (!) was practically 

not to be brought about.

If the reaction were in any sense catalytic, it would follow that by 

reducing the aluminum chloride below the proportion Si:Al=3:4, the 

decomposition would still be complete, but the amount of ethyl ether 

would increase relatively, while that of ethyl chloride would decrease, 

the limit being, with a trace of aluminum chloride 

Si(OB)4 =SiO2 +2B2O.

The actual result was that while with Si: Al=3:l the decomposition 

was complete, and approximately in the sense

(c) 6Si(OB)4+2AlCl3 =(SiO2 ) 6 (Al2O;t)+6BCl+9B2O,

the slightest diminution of the amount of chloride below this ratio was 

followed by some of the silicate remaining totally unchanged. With. 

Si:Al=3:0.9 for instance, it was possible to recover some of it, and 

with Si:Al=150:l the merest trace of decomposition was discernible. 

This proportion in the case of the monochlorsilicate resulted easily in 

total decomposition. The only possible explanation of this difference 

is that in the case of the chlorsilicates the apparent contact action is 

due to constant regeneration of aluminum chloride by silicon chlorine. 

The tetraethyl ether contains no silicon chlorine, aluminum chloride is 

not regenerated, and therefore acts only in proportion to the amount 

originally taken.

An experiment was made which shows the peculiar stability of silicon 

tetrachloride as compared with the chlorsilicates. It was supposed 

that since

SiCl3 (OB)+trace AlCl3=SiO.Cl2 +BCl+trace A1013 ,

by adding to tetraethyl silicate some silicon tetrachloride in the proportion required by the equation

Si(OE)4 +3SiCl4 =4SiCl3 (OB),

the chlorine of the tetrachloride would regenerate aluminum, chloride, 

with the final result that solid silicon oxychloride and ethyl chloride 

would be formed. With even Si:Al=5:l and in sealed tubes at 100° 

no solid was formed. Only after heating at 170°, at which temperature the tetrachloride acts on the ether, did total decomposition occur. 

Anhydrous ferric chloride acts on both the tetraethyl silicate and the 

trichlorsilicate, but with much greater difficulty than aluminum chloride. Only at near the boiling point (1.05°) of the trichlorsilicate was 

any marked reaction, with formation of ethyl chloride, visible. The 

tetraethyl silicate reacted easily on heating, giving off ethyl ether and 

ethyl chloride and leaving a solid residue. The reactions were not 

further studied.
70 LABORATORY REPORT, ' 1891-J92 AND' 1892-'93. [BOLL. 113

Anhydrous zinc chloride is without action on the tetraethyl silicate 

at its boiling point (165°).

 EXPERIMENTAL DETAILS.

Only carefully fractioned silicates and freshly sublimed aluminum 

chloride were used. The apparatus and method of working were as 

follows:

A thin-walled glass tube of about 2 cm. diameter was drawn out into 

the shape shown in the figure. The constriction E served when necessary as a support for the small weighed test-tube G, in which the ethyl 

ether collected. Some aluminum chloride was placed in a boat, inserted 

into AB, and carefully sublimed over into CD in a current of dry' 

hydrogen. In this way it was obtained in a finely 

divided state, rendering solution more rapid. The 

hydrogen was then replaced by air, EC drawn out 

and melted off at J5, and the weight of the sublimed 

chloride determined to a centigram. CD was then 

placed in ice, the calculated weight of silicate or 

chlorsilicate introduced through F, the tube 6r inserted when necessary, and the apparatus attached 

to an inverted condenser which ended in a (J-tube 

with two cocks, placed in a freezing mixture, and 

serving to condense the ethyl chloride and any ethyl 

ether that might be carried over. By gently agitating 

the tube, the solution of the chloride was effected. On 

removing it from the ice, the reaction usually began

Fig. 1. Apparatus used in experiments upon silicic ethers.

of itself, and often had to be moderated by cooling. After the evolution 

of ethyl chloride had slackened, CD was gently heated, the ethyl ether 

then distilling and collecting in r. After the collection of ether had 

ceased, G was gently warmed, whereby practically all ethyl chloride 

was driven over, the ether condensing and running back. After 

removing 0, the point B was broken off and the residue heated in a. 

current of hydrogen until no further effect was observed, any aluminum 

chloride condensing in DE, or sometimes in part being carried over 

into the condenser. The hydrogen was then displaced, DF melted off 

at J>, when necessary, and all products determined by weighing. Some 

of the liquid in the (J-tube was brought'in to a graduated tube over 

mercury, and any ethyl ether determined by absorption with a drop 

or two of strong sulphuric acid, the residue being ethyl chloride.
STOKES.] CATALYTIC ACTION OF ALUMINUM CHLORIDE.

Etliyl trichlorsilicate. Taken Si013 (OK) 7-66 grams (3 mol. wts.) 

and A1C13 1-91 grains (1 inol. wt.).

On removing the ice from CD, the evolution of ethyl chloride began 

almost at once and the liquid grew so warm that cooling had to be 

resorted to to prevent the contents from boiling over. Presently a 

large quantity of a colorless, apparently crystalline substance separated, nearly filling the liquid. Its nature was not determined, but it 

was found to fuse on gently heating. After the evolution of ethyl 

chloride had moderated, its formation was promoted by a gentle heat. 

The liquid then became gradually thick, and finally almost solid. B 

AVUS then broken off, and the residue heated in a stream of hydrogen 

until no further sublimation of aluminum chloride was observed. 

Absolutely no ethyl ether was formed. The residue was somewhat 

discolored, solid, transparent, and frothy. As explained above, the 

reaction occurs in accordance with the equation

SiCl3 (OK) + ayAlCl3=SiO. C12 + EC1 + 0A1C1.,,

as is borne out by the following data, which in this, as in all following 

experiments, are given in percentage of the total material used:

Distillate, RC1..............

Pound.

46-3

20 '9

22-5

Calculated.

51-2

in .n

28-8

The results are naturally only approximate, but quite as near as 

could be expected. The viscosity of the liquid towards the end interferes with the smoothness of the reaction, and it is impossible to condense the ethyl chloride completely, or to prevent some being carried 

off by the current of hydrogen. If the reactions given are correct, 

the residue is not really SiO.012, but a mixture of oxychlorides in. 

which there remains a small amount of ethyl, which will not go off at 

a temperature below that at which carbonization and other secondary 

changes take place, and which are still greater in the cases below mentioned. Troost and Hautefeuille' have shown that the result of heating oxychlorides is an approximation towards SiO2 and SiCL,. This is 

doubtless the reason why in this case the weight of the residue is 

slightly too low and that of the sublimed aluminum chloride a little too 

high. The former, on extracting with alcohol, left a little silica in gelatinous form, while the latter was found to contain a small amount of 

volatile silicon compounds. In fact, the residue on heating in a test 

tube to redness gave off a considerable amount of volatile oxychlorides, but no aluminum chloride.

>Loc. cit.
72 LABORATORY REPORT, 1891-'92 AND 1892-'93. [BULL. 113.

In experiment 2 the proportions taken were the same and the observations essentially similar.

A1C13 (sublimed) ..........

RC1-. ............ .............

Fonud.

38-9

21-2

. 22-4

Calculated.'

51-4

10 '9

28-8

The residue consisted mostly of oxychlorides, soluble in alcohol, and 

considerable silica, insoluble in alcohol. A portion of the same residue gave 

Si. ................................

Found.

27-08

Calculated 

for SiO.CI2 .

24-35

The excess of silicon is due, as before, to a partial volatilization of 

oxychlorides with a low percentage of silicon. This residue also 

contained a very small amount of aluminum, which was completely 

extracted by alcohol, and therefore present as chloride, not as silicate 

or oxide. No ethyl ether was formed.

In experiment 3 the residual aluminum was determined in the residue after heating to dull redness in hydrogen. The amount found, 

calculated as chloride, was only 3-5 per cent of the total chloride 

used. A small amount was to be expected, as it is practically impossible to expel it completely from the solid frothy residue. The conclusion that the chloride remains unchanged at the end of the reaction 

may therefore be accepted without hesitation.

dichlorsilicate. This calls for the reaction

SiCl2 (OR) a +a?AlCl3 =SiO2 +2RCl+a;AlCl3 .

Two experiments were made, one with Si: Al=50:l, the second with 

Si: Al=3:1. In both cases the 'decomposition was readily brought 

about, in the first almost as easily as in the second, but only in the 

second could any aluminum chloride be recovered, and then not the 

whole amount used. A small amount of ethyl ether was also formed 

in each case. As there were reasons for suspecting the sample to contain monochlorsilicate (which would explain the discrepancy) and as 

no more was available the quantitative data are omitted.

Etliyl monocMorsilicate. Four experiments were made.in which the 

following proportions were observed:

(2) ' 

 (3) 

(4) -

Eor case (1) the following equations hold, according as the chlorine
STOKES.] CATALYTIC ACTION OF ALUMINUM CHLORIDE. 73

of the aluminum chloride fs completely given off as ethyl chloride, or 

as it remains in part as Q > A1C1.

(a) 3SiCl(OE) 3 + 3AlCl3 =Si3Al2O9 + 9KC1 + A1C13. 

(6) 3SiCl(OE)3 + 3AlCl3 =3(SiO3AlCl) + 9EC1.

' Taken, 6-21 grains ,SiCl(OE)3 and 4-19 grams A1013 , or equal mol. 

wts.

The course of the reaction was essentially the same as with the 

trichlorsilicate, except that no solid was deposited. The liquid became 

gradually thicker, with evolution of ethyl chloride, and then quite suddenly stiff at about 75°. On heating in a current of hydrogen, a considerable volume qf uucondensible hydrocarbon gas was given off, 

whereby some aluminum chloride was carried into the condenser .and 

receiver. This was collected and determined, The amount of aluminum fixed in the residue was also determined. No ether collected, and 

none could be found by absorption over sulphuric acid.

E20. ................. .... .-

Found.

37-5

7-3

3-5

Calculated 

for (a) .

28-4

5-4

13-5

Calculated 

for (6).

45-9

8-1

The reaction occurs, therefore, in a form combining (a) and (&), the 

residue probably consisting in part of aluminum silicates, in part of 

chloraluminum silicates.

. For case (2) where Si: Al=3:2, there are also two ultimate equations 

possible:

(a) 3SiCl(OR)3 +2AlCl3=Si3O9Al2 +9BCl. 

(&) 3SiCl(OR)3 +2AlCl3=Si3O8Al2Cl2+7ECl+E2O.

Taken, SiCl(OE)3 , 12-93 grams; A1C13 , 5-80 grams; or exactly 3:2 

mol. wts. The reaction was essentially similar to that in the last experiment, and^took place quite as readily as when more chloride was 

used. The same gradual thickening and sudden stiffening of the 

liquid were noticed. On finally heating to dull redness in hydrogen, 

gas was evolved, and a somewhat carbonaceous black vitreous residue 

was left, but no aluminum chloride sublimed. A small amount of ethyl 

ether was formed, which was determined by absorption.

RtO.... .....................

RCl.... .....................

Found.

36-0

6-1

2-5

33-5

Calctilated for 

(a).

32-7

6-2

67-3

Calciilated for 

(6).

39-1

C-2

8-6

52-3
74 .LABORATORY REPORT, 1891-'92 AND l892-'93. [BULL. 113.

Here, too, the reaction is intermediate between (a) and (ft), some 

E2O is formed, but all aluminum remains in the residue. 

Case (3), where Si: Al=3:l, also admits of- two equations:

(a) 6SiCl(OB)3 +2AlCl3 =Si6Al2O,5+12BCl+3B2 p. 

(&) 6SiCl(OB)3 +2AlCl3 =Si6Al2O 14Cl2 +10BCl+4B2O.

Taken, SiCl(OB) 3 , 14-72 grams; A1013 , 3-30 grams, or 3:1 niol. wt. 

The same thickening, and sudden stiffening at 75° were observed. The 

reaction began at the same low temperature, and was nearly as rapid 

as with more chloride. Ethyl ether collected in the tube G in abundance, and was identified by its boiling at 30°-35°. The solid residue 

was nearly colorless, and only on high heating did discoloration ensue. 

No chloride 'sublimed. The ether was determined by weighing that 

collected, arid absorbing* the small amount found in the distillate as 

before.

R2 0...... ................

Found.

43-1

20-0

Calculated 

for (a).

 ' 31-7

. 15-2

Calculated 

for (6).

38-4

22 '0

Although the residue was somewhat too large, the amount of ether 

shoAved that the reaction was mainly in the sense of ('&). 

^Case (4). In this experiment, 1 rnol. wt. aluminum chloride was made 

to act on 150'mol. wts. monochlorsilicate, or almost a mere trace of the 

former (taken, 13-38 grams silicate to 0-06 gram chloride). The facts 

noted were the same as in the other experiments, including the sudden 

solidifying of the residue. The only difference was that the reaction 

took place rather more slowly, owing to the small amount of chloride 

present, and that the residue left at red heat was of purplish color, 

showing very little carbonization. The ease with which the decomposition took place indicated that a much smaller amount of aluminum 

chloride would have-been sufficient. The ethyl ether showed the correct boiling-point.

The equation for a trace of aluminum chloride is practically

' SiCl(OR)3=SiO2+BCl+B2O. 

The actual results were:'

R2 0. ......... .............

RC1...... .................

Found.

30 '8

32-7

n

-9

Calculated 

for Si : 

Al=150: 1.

30-3

36-8

33-0

The amount of ether was 89 per cent of the theoretical.
STOKES.] CATALYTIC ACTION OF ALUMINUM CHLORIDE. 75

Tetraethyl silicate. Four experiments may be mentioned into which 

the following proportions entered :

3:4 (1) °

The hypothetical equations for (1) and (2) are given under the general considerations on the decomposition of the tetraethyl silicate (a, b? 

and c).

For experiment (1) were taken 5-95 grams Si(OE)4 , 5-09 grams A1013r 

or 3 : 4 mol. wts. It was not possible to cause the chloride to dissolve 

completely in this amount of ether, and the result was a mixture of 

varying composition, from which no definite result should be expected. 

The general course of the reaction was the same as in other cases. 

Some ethyl ether was formed, but a little aluminum chloride also Subliined, indicating an excess in one part of the mass and a deficiency in 

another.

In experiment (2) with Si:Al=3:l the -mixture evolved ether and 

ethyl chloride, and finally became solid, and on further heating gave 

off gases, but no aluminum, chloride. Only about one-half the theoretical amount of ether was obtained, the remainder appearing as hydrocarbon gas and empyreumatic substances.

In experiment (3) with Si:Al=3:0-9 it was noticed that some unchanged silicate distilled at the end of the operation. It appears,. 

therefore, that the least amount of .aluminum chloride required to effecttotal decomposition is 1 mol. wt. to 3 mol. wts. of the silicate. This 

is strikingly seen in the next experiment (4), which at the same time 

shows the radical difference in their behavior towards aluminum chloride of the silicates and chlor silicates.

Taken, 16.37 grams Si(OR)4 , 0-07 A1C13 , or 150: 1 mol. wts. Even on 

boiling strongly for an hour at about 165° no inarked reaction was 

noticed. The liquid remained clear and limpid, and not over 0-1 gram 

ethyl ether collected. At the end of an hour the silicic ether was 

distilled off unchanged, leaving but a trace of solid residue. It was. 

therefore clear that' only a trace had been decomposed, corresponding 

to the trace of chloride used.

The decomposition of monochlorsilicates by a trace of aluminum 

chloridernightperhapsbe utilized to obtain other ethers than ethyl ether. 

It is known that the continuous process for obtaining ethyl ether from 

alcohol by means of sulphuric acid does not apply to the alcohols above 

propyl alcohol. 1 Isobutyl alcohol, for instance, does not give a trace of 

isobutyl ether. The silicates of the monatomic aliphatic alcohols, as 

far as has been investigated, are easily prepared, and of all the chlorsilicates, the monochlorsilicates are the most easily made. By adding1 Norton and Prescott, Am. Chein. Jour., vol. 6, p. 241.
76 LABOEATORY REPORT, 1891- ?92 AND 1892-'93. [BULL. 113.

to 1 niol. wt. silicon tetrachloride 3 mol. wts. of the alcohol, boiling the 

product or heating to 170° under pressure, and finally distilling with a 

trace of aluminum chloride, a product should be obtained, consisting 

of a mixture of ether and chloride, which could be easily separated. 

From ethyl mouochlorsilicate 89 per cent of the theoretical yield of 

ethyl ether was thus obtained.

On the isolation of the intermediate products. Aluminum chloride is 

insoluble in carbon bisulphide; if, however, a mixture of about 1 vol. 

tetraethyl silicate and 4 vols. carbon bisulphide be boiled with some 

aluminum chloride, the latter liquefies and partly dissolves, while there 

is an evolution of permanent gas, presumably ethyl chloride. On 

decanting the warm liquid a considerable amount of oil separates. This 

oil is not volatile, and on heating gives a solid residue resembling that 

obtained by the direct action of the chloride on the silicic ether. The 

carbon bisulphide solution, if concentrated out of contact with moisture, deposits on cooling a mass of well-formed rectangular crystals,; 

or on evaporation in. vacuo over paraffin shavings leaves a perfectly 

dry crystalline mass. A portion of such a bisulphide solution was 

decomposed by ammonia and the ratio of Si: Al: Cl determined. It 

was found to be 1: 2-1: 3-9, or very .nearly 1:2:4, a result which may, 

of course, have been accidental. The oil which separates is soluble in 

a fresh portion of hot carbon bisulphide, but it appears readily to 

change, for a greater amount is required than that from which it separated, and by boiling out with small quantities of bisulphide a residue 

is left which is finally almost solid. These facts seem to indicate the 

possibility of isolating some of the intermediate products, but this 

has not yet been attempted.
,.ON THE ACTION OF PHOSPHORUS OXYCHLORIDE ON AROMATIC

SILICIC ETHERS.

BY H. N. STOKES.

In a paper on the action of phosphorus oxychloride on ethyl silicates 

and clilorsilicates l (chlorhydrines), I have shown that this reagent 

converts ethyl orthosilicate completely into ethyl chloride and silicopyrophosphoryl chloride, SiP2O6 012 , and that the ethyl orthochlorsilicates yield under the same conditions these bodies and silicon tetrachloride, the amount of the latter being proportional to the amount of 

chlorine in the silicon compound used, the trichlorsilicate yielding most, 

while tetra-ethyl silicate gives none.

4SiCl,(OC2H5 )+2POCl3=3SiCl4+SiP2O6Cl2 +4C2H5Cl. .

8i(O02H5 )4+2POOl3= SiP2O6012 +4C2H5Cl. 

It was not thought worth while to repeat these experiments with 

other silicic ethers of the aliphatic series, as similar results "were to be 

expected.

In view of the different properties in general of aromatic bodies, the 

action of phosphorus oxychloride on silicates of this class could not 

be foreseen. I have therefore treated phenyl orthosilicate 2 with phosphorus oxychloride, and have obtained results which show in a strikingmanner the difference between aliphatic and aromatic silicates. 

The proportion selected was that required by the equations 

Si(OC6H5)4 4-2POCl3=SiP2OfiCl2 4-4CGH5Cl,

or Si(OCG H5 )4 +2POOl3=Si014 +2PO(^1 0(;H5)2>

The mixture, after being heated three to four hours at 170°-1.SO° (the 

temperature at which tbe ethyl silicates react with phosphorus oxychloride), was distilled. No indication whatever of areaction could be discovered, the oxychloride being recovered unchanged, and proved to be absolutely free from silicon compounds. After being heated sixteen hours at. 

240°, the liquid was somewhat discolored, but perfectly clear. On fractioning, it was easily separated into silicon tetrachloride (b.p.59°), phos'- 

phorus oxychloride (b. p. 109°), and chloric!e of phenyl-phosphoric acid,.

1 Ainer. Chem. Journal, 13, 244; Ber. (1. chem. Ges., 24, 933. 

2 Hertkorn: Ber. d. chem. Gea., 18, 1079.

 ' .77
78 LABORATORY REPORT, 1891-'92 AND 1892- ?93. [BULL. 113.

POC12 (OC6H5 ) (b. p. 240°-243°), with a residue consisting of chloride 

of diphenyl-phosphoric acid, POC1(OC6H5 ) 2 , and phenyl phosphate. 

The fraction of b. p. 59° gave 

Si.........................

Calculated 

for SiCl4.

1C -47

Found.

16-24

The amount of tetrachloride was approximately equivalent to the 

quantity of phenyl silicate used, while the higher-boiling portions and 

the residue were found to be practically free from silicon, thus proving 

the conversion into tetrachloride to be complete. Not a trace of chlorbenzene or silico-phosphoryl chloride was formed.

It will be noticed that while the ether is completely converted into 

chloride, the reaction does not proceed strictly according to the second 

of the above equations, but that a mixture of phenyl phosphate with 

the chlorides of the two phenyl-phosphoric acids results, some of the 

oxychloride remaining unchanged.

By means of this reaction and that described previously, 1 it is easy 

to convert aromatic or aliphatic orthosilicates into silicon tetrachloride. 

The aromatic ethers, heated with phosphorus oxychloride, give'the tetrachloride directly ; the aliphatic ethers yield silico-pyrophosphoryl 

chloride, which is readily converted into silicon tetrachloride by heating with phosphorus peutachloride 2 at 100°. Phosphorus pentachloride, used directly, effects the transformation only with great difficulty. 

Friedel and Crafts 3 have shown that the pentachloride readily, converts ethyl orthosilicate into ethyl monochlorsilicate, SiCl(OC2H5):J . I 

have found that this reaction can not readily be pushed farther than 

the trichlorsilicate, SiCl3 (OC2H5 ). This body holds the ethoxyl very 

firmly, and even after heating many hours at 140° with pentachloride 

but little silicon tetrachloride is formed. If heated much higher, the 

pentachloride liberates chlorine, causing total destruction of the ether. 

Acetyl and beuzoyl chlorides effect complete conversions into tetrachloride, but only when used in large excess and on heating at over 

200° for a very long time.

I am studying the action of various metallic haloid salts, especially 

those of aluminum, on silicic ethers, and have observed a similar difference; aluminum chloride, for example, readily converting the aromatic ethers into silicon tetrachloride, while its action on aliphatic 

ethers is entirely different and much more complex, the products depending on the nature of the ether taken and the proportional amount \ 

of aluminum chloride used. The results will be described in a sepa- \ 

rate paper.

1 Amer. Cliem. Journal, 13, 248.

2 Ibid., 13, 247.

3 Ann. chim. phys. [4], 9, 14.
NOTE ON BENZYL SILICATE.

BY H. K. STOKES.

As is known, both ethyl alcohol and phenol, if perfectly anhydrous, 

produce with silicon tetrachloride the corresponding oH/io-silicates in 

nearly theoretical amount, the chief difference being that while ethyl 

alcohol acts violently, with? reduction of temperature, 1 phenol requires 

prolonged boiling for complete conversion into the ether, the evolution 

of hydrochloric acid being scarcely noticeable at ordinary temperature.2

Anhydrous benzyl alcohol, as was to be presumed, behaves towards 

silicon tetrachloride as an aliphatic alcohol, not as a phenol, violent 

action with fall of temperature occurring. The reaction is not smooth, 

however, as in the case of ethyl alcohol. A large amount, perhaps 

one-fourth, is converted into benzyl chloride, either by direct action of 

the hydrochloric acid evolved, or indirectly by action of the latter on 

the benzyl silicate. As a result, if the calculated amount of alcohol 

be taken, much remains unchanged, and the tetrachloride is largely 

converted into polysilicates. On distilling the mixture under atmospheric pressure, some benzyl silicate passes over, but this is completely 

broken up by one or two redistillations. The products of decomposition consist of water, toluene, stilbene, anthracene, and high-boiling 

products of undetermined nature. As no particular interest attaches 

to benzyl'silicate, no further attempt was made to isolate it.

This formation of benzyl chloride recalls the action of benzyl alcohol on boron trichloride, 3 when the chief product is benzyl chloride.

1 Ebelmen: Ann. Chern. (Liebig), 57,334.

2 Herlkorn -. Ber. d. chem. Ges. 18, 1679."

3 Conncler: Jour, prakt. Chem. [2] 18,396.

79
ON AMIDOPHOSPHORIC ACID.

BY H. K STOKES?

By replacing the hydroxyls of orthophosphoric acid successively by 

amido groups, three amides may be derived, namely, amidophosphoric 

acid, PO.NH2 (OH)2 , diamidophosplioric acid, PO.(NH2 ) 2 .OH, andphosphoryl triamide,0 PO(lsrH2 )3, and from these, by abstraction of water or 

ammonia, an imido acid, PO.NH.OH, an imido amide, PO.NB.KH2 , 

and a nitrile, POJsT. Of these, amido and° diamido phosphoric acids 

have not yet been described. In the dictionaries of Fehling 1 and of 

Ladenburg 2 the formula PO.NH2 .(OH)2 is given to a body described 

by Schiff 3 and called by him phosphaminsaeure. This rests on an error 

of the compilers, as Schiff gives to his acid the formula PO.KELOH, with 

which his analyses agree, while they differ widely from that of amidephosphoric acid. Moreover, as will be shown, amidophosphoric acid is 

a body of entirely different properties.

Schiff 4 also describes the triamide, PO(^H2 )3. Although his analyses agree quite well with this formula, the existence of the body is 

called in question by Gladstone, 5 who, in repeating Schiff 7 s method 

of preparation, treating phosphorus pxychloride with dry ammonia, was 

unable to replace the third chlorine atom at any temperature below 

that at which further decomposition occurs (above 300°). The correctness of the formula PO.NH.OH assigned by Schiff to his phosphamic 

acid is also questioned by Gladstone and Holmes, 6 who point out the 

general resemblance of its properties, as described, to those of pyrophosphodiamic acid, obtained by them. They regard it as a mixture 

of the latter with metaphosphoric acid. The identity of SchifPs acid 

with pyrophosphodiarnic acid (diainidopyrophosphoric acid) has also 

found acceptance in some handbooks.7

The imido amide, PO.(NH).NH2 , was described by Gerhardt 8 under 

the name phosphainide, and was obtained by treating, phosphorus 

pentachloride with dry ammonia and then with water. Its nature has 

not been questioned.

.'Nenes Haudwcirterbuch tier Chemie, 5, 423. 4 Ann. Chem. (Liebig), 101, 300. 

'Handworterbuch cler Chemie, 9, 100. 5 Jonrn. Chem. Soc., [2] 7, 18. 

3Ann. Chem. (Liebig), 103, 168. c Journ. Chem. Soc., [2] 2, 229, 235. 

'Gmelin-Kraut: Handbiich der auorg.Ghemio, 1,2 Abth.529; Graham-Otto: Anorg. Chem.(Michae1J8), 2, 401.

OAnn.chim.phys., [3] 18, 188. 

80
STOKES.] ON AMIDOPHOSPHORIO ACID. . 81

The body PO.N, described by Gerhardt 1 as biphosphainide, by 

Schiff 2 as monophosphamide, and by Gladstone 3 as phosphonitryle, is 

the final product of heating the triamide, the imidoainide, or the amido 

chlorides. Its constitution is not known, but is probably much more 

complex than is represented by the formula given.

In addition to the above, Gladstone and Holmes'1 have obtained a 

series of complex amides, derivable from pyro and tetra phosphoric 

acids.

The difficulty in preparing amido orthophosphoric acids lies in part 

in the impossibility of regulating the decomposition by water or acids 

of the products of the action of ammonia on phosphorus pentachloride 

and oxy chloride. Gerhardt's imidoainide and Schiff's triamide seem to 

be capable of giving ammonia and phosphoric acid only; at least no 

mention is made of intermediate products. The bodies derived from 

phosphorus oxychloride by partial replacement of chlorine by amido 

groups are so decomposed by water as to give the amidopyrophosphoric 

acids of Gladstone, and further action results in the separation of 

ammonia before the pyrophosphoryl group is broken up. The reason 

for this, as will be seen below, lies in the great ease with which amidophosphoric acid passes over into ammonium phosphate. As phosphorus 

pentoxideis a derivative of pyrophosphoric acid, it is not to be expected 

that it would give orthophosphoric amides with ammonia.

I have overcome these difficulties in part by acting with ammonia on 

phosphoric ethers, and in this way have obtained the primary amide, 

PO.KH2.(OH)2. Attempts to obtain other amides by the same method 

are in progress.

By dissolving the chloride of diphenylphosphoric acid, PO.C1. 

(OC6H5 )2, in alcohol and adding alcoholic ammonia, diphenylamidophosphate, PO.NH2 .(OC6H5 )2, a beautifully crystalline substance, is at 

once formed. This, on saponifying with ammonia or baryta, gives 

phenylamidophosphoric acid, PO.FH2 .(OC6H5 ).(OH), and with caustic 

potash or soda, amidophosphoric acid. The free acid, obtained by 

decomposing the lead salt by sulphuretted hydrogen and precipitating 

with alcohol, is a well characterized body, forming fine microscopic 

 crystals. It forms two series of salts, acid and neutral, of which the 

,acid salts are invariably, the neutral often, crystalline, and in many 

cases the forms are characteristic. Boiled in aqueous solution, either 

alone or with an acid, it decomposes almost instantly into ammonia and 

orthophosphoric acid. Its cold aqueous solution may be kept a short 

time without much decomposition, but quickly passes into primary 

ammonium orthophosphate. Dilute mineral acids in the cold effect the 

change much more rapidly, but in either case the first product is not 

orthophosphoric acid, but an acid or mixture of acids giving white

1 Ann. china, phys., [3] 18,188.

"Ann. Chem. (Liebig), 101, 304.

3 Jowr. Cbem. Soc., [21 7, 18.

«Quar. Journ. Chem. Soc., 3, 353; Jouni. Chem. Soc., [2J 2, 225; [2] 1, 1,290; [2] 6, 64,201; [2] 7,15.

Bull. 113 6
82 LABORATORY REPORT, 1891-792 AND 1892-'93. [BULL. 113.

amorphous precipitates with silver nitrate. At 100° the dry acid 

passes without loss of weight into an ammonium salt, giving a white 

silver salt. This is possibly metaphosphate, or a mixture of the different metaphosphates,

NH2

PO OH=P03 (NH4), 

OH

but the nature of the product has not yet been established. The acid 

salts on heating give off ammonia and leave metaphosphates. Such of 

the neutral salts as contain crystal water pass first into ammonium 

salts, and on further heating into pyrophosphates. The neutral silver 

salt, which is anhydrous, is an exception. At 180° it gives off one-half 

its nitrogen as ammonia, apparently forming a very stable pyrimidophosphate,

NH/PO(OAg)2 

* u\PO(OAgy

which stands a red heat without further change, or at least without 

loss of weight. Other salts which are especially characteristic are the 

acid sodium salt, almost insoluble in water, and the neutral magnesium 

salt, isomeric with crystallized ammonium magnesium phosphate. In 

the absence of any experimental evidence to the contrary, the constitu-

-JO-TT

tion of the acid is regarded as PO^Sx in accordance with the usually (un.)^

assumed structure of acid amides, rather than as P(KE)(OH)3, in harmony with the most recent views on the nature of organic amides.

DESCRIPTIVE PART.

ATTT

Diphenylamidophosphate, PO /QQ JT \ 1 mol. wt. phosphorus oxychloride and 2 mol. wts. phenol are boiled in a flask fitted with 

return condenser until no further evolution of hydrochloric acid occurs. 

The product is a mixture of PO(OCG H5 ) 3, PO.C1.(O06H5 )2, PO.C12 .(OC6H5 ) 

and unchanged oxychloride. It is not necessary to isolate the diphenylphosphoric chloride. The liquid is diluted with absolute alcohol, and 

alcoholic ammonia is added slowly, with cooling, to alkaline reaction. 

The product is mixed with several volumes of water, whereby ammonium chloride dissolves and crystalline amidophosphate separates, 

mixed with oily phenylphosphates. This is sucked out in a funnel as 

far as possible, washed with water, dried on porous plates to rempve 

the oil, again washed, dried and recrystallized two or three times from 

alcohol, or better, chloroform. The yield is about 35 per cent of the 

theoretical.

P................. *.................

Calculated for 

PO.NH2 .(OC6H5)S .

12-46 

5-67 5-70

Found.

12-37 

5-64 5-67
STOKES.] ON AMIDOPHOSPHOKIC ACID. 83

Phosphorus was determined as magnesium pyrophosphate after 

evaporating first with alkali, then with acid; nitrogen as ammonia 

after evaporating with hydrochloric acid; both as ammonium chloroplatinate and by titratiou, after distilling.

The ether fuses at 148°, and on cooling solidifies to a crystalline 

mass with a surface of brilliant facets. At 180° there is a very slow 

evolution of ammonia and phenol, which becomes quite rapid at 230°, 

when it is accompanied by sublimation of unchanged substance. The 

non-volatile product of decomposition is first an oil, later a solid substance containing phosphorus.

Phenylamidophosphoric acid, POOC6H5 . The free acid could not be

OH

obtained in the solid state. On decomposing the lead salt in the cold 

with sulplmreted hydrogen a solution is obtained which is not precipitated by alcohol. On evaporating in vacuo over sulphuric acid, the 

acid takes up water and is converted into the acid ammonium salt of 

phenylphosphoric acid, which contains only traces of amido acid, which 

were isolated as the silver salt described below.

Acid ammonium phenylphosphate is easily soluble in water, and crystallizes in long prisms. It also crystallizes from alcohol, in which it is 

difficultly soluble, as pearly rhombic plates or flat needles, fusing at 

140°-145° with decomposition. Silver nitrate gives a precipitate of 

radiating flat prisms, consisting of the neutral silver salt, (a) which is 

anhydrous. By neutralizing the filtrate with ammonia a further precipitate of the same salt (b) is obtained.

Ag ...............

Calculated 

«**°($$&

55-64

Found.

a.

' 54 -88

b.

55-44

Phenylphosphoric acid therefore resembles phosphoric acid in that 

its acid salts give directly the neutral silver salt, and differs from 

amidophosphoric acid, which gives either acid or neutral silver salt 

according as acid or neutral salt be used as precipitant.

Ammonium phenylamidopkosphate, PO O06H5, obtained by saponifyOKH4

ing the diphenyl ether with aqueous ammonia, is easily soluble in water, 

and the solution may be evaporated without decomposition.

Silver phenylamidophospJiate. PO OC6H5, from the ammonium salt,

OAg

after recrystallizing from water, forms scales or long, narrow, pointed 

plates of pearly luster. It is difficultly soluble in cold, moderately iu
84 LABORATORY REPORT, 189l-*92 AND 1892-J93. [BULL. 113.

boiling water, and has a strong tendency to separate as a crystalline 

scum on the surface. It is unaffected by light.

p.................

If. ................

Ag.......... ....

Calculated for 

PO(NH2) 

(OC6H6)(OAg).

11 -09

5-02

38-53 38-31

Found.

11-11

5-08

38-19

Barium phenylamidophosphate is formed by boiling the ether with 

baryta water until nothing crystallizes out on cooling, and removing 

the excess of baryta by carbon dioxide. It forms scales, is quite soluble 

in water, and resembles the silver salt in forming a crystalline scum on 

the surface.

Lead phenylamidophosphate, from the barium salt by lead acetate, 

forms brilliant scales, nearly insoluble in water.

Amidophosphoric acid, . The alkali salts of this acid are

readily obtained by saponifying the ether with a strong solution of 

caustic potash or soda. The chief difficulty in obtaining them pure is 

in separating them from the small quantity of phosphate formed at the 

same time. In the case of some of the salts this may be effected by 

methods mentioned below. The conversion into phosphate by boiling alkali is very slow. A weighed amount of ether was boiled with 

concentrated caustic potash, and the ammonia determined in the distillate by titration. An hour's boiling showed a decomposition of only 

3 per cent.

Acid potassium amidophosphate. POOR. If a lump of caustic potash be

OH

placed on some of the diphenyl ether and a few drops of water be added, 

a somewhat violent reaction occurs. On boiling with an excess of concentrated caustic potash the saponification is complete in ten minutes. 

The oily solution is acidified with strong acetic acid, care being taken 

to keep it cool with ice water. On adding several volumes of alcohol 

the acid salt is at once precipitated. It is purified by washing with 

alcohol, dissolving in a little water and reprecipitating by alcohol. It 

can not be recrystallized from hot water, as its solution is rapidly converted by heating into acid potassium ammonium phosphate. A weighed 

amount of acid potassium salt was dissolved in water and boiled ten 

minutes; -^ n. caustic soda was added in ex cess, and the solution again 

boiled to remove ammonia. The loss of alkalinity due to the escape of 

ammonia indicated that by ten minutes' boiling, 98 per cent of the amide 

was converted into ammonium salt. The same change occurs in a few 

days in the cold aqueous solution. The salt forms six-pointed stars, 

or sometimes rhombohedra, readily soluble in cold water, insoluble in
STOKES.] ON AMIDOPHOSPHORIC ACID. 85

alcohol. Tts solution is neutral towards litmus, methyl orange, and 

phenolphthalem. On ignition it gives off ammonia and leaves potassium metaphosphate. 

The analysis of two air-dried preparations (a and &) gave 

p.................

N...... ...........

Calculated for 

PO.NHj.OK.OH.

22-96 

10-39

Found.

a.

22-76 

10-26 10-20

b.

10-35

The loss on ignition gave 

NH3 . ...........

Calculated for 

PO.NH2 .OK.OH.

12-61

Found.

13-83

The excess found is due in part to a small amount of water which the 

salt retains, in part to a little acid potassium ammonium phosphate 

which can not be removed by precipitating with alcohol. The amount 

of ammonium salt may be determined by distilling off the ammonia with 

alkali solution, and determining it in the distillate, making a slight 

correction for the decomposition of the amide itself as above determined 

(3 per cent per hour). In this way the amount of ammonium salt in 

preparation (a) was found to be 4-75 and 5-10 per cent, in (b) 4-15 per 

cent. As the acid potassium salt is used for preparing other salts, this 

small amount of phosphate must be taken into consideration, as the 

latter would otherwise be contaminated with phosphate. Its presence 

may be obviated by methods below mentioned.

Neutral potassium amidophosphate is extremely soluble in water, and 

not appreciably decomposed by boiling.

Acid sodium amidophosphate, PO ONa-f-#H2OC?). This is prepared

OH

by boiling the ether ten minutes with strong caustic soda, cooling and 

acidifying with acetic acid. It separates at once without adding alcohol, as a crystalline powder, which is washed with dilute alcohol, dissolved in ammonia, and reprecipitated by acetic acid or carbon dioxide. 

It forms a heavy sandy powder consisting of well-defined crystals 

belonging to the hexagonal system, occurring sometimes as hexagonal 

plates or prisms without pyramids, occasionally as very symmetrical 

double pyramids without prism surfaces. It is scarcely soluble in cold 

water, insoluble in alcohol. If boiled with water it dissolves and is at 

once converted into acid sodium ammonium phosphate. The same 

change occurs slowly at ordinary temperature under water. Like all 

other amidophosphates, it is instantly converted into phosphoric acid 

by warm dilute acids. On ignition it loses ammonia, and leaves a
86 LABORATORY REPORT, 1891-792 AND 1892-;93. [BULL. 113.

vitreous residue of sodium hexatuetaphosphate. It contains small but 

varying amounts of water. The analysis of one preparation gave 

p ...........................

H ............ ..............

Calculated for 

PO.NH,ONa.OH 

+JH20.

25-11

11-36

82-54

Tound.

25-08

11 -49 11 -34

82-43

Other samples contained less water. This water is accounted for in 

part by the presence of a small amount of acid sodium ammonium 

phosphate, but the latter, when determined as in the acid potassium 

salt, was found to be only 2 to 2-5 per cent, while the whole amount of 

water present, if assumed to be in the form of ammonium salt, would 

make the amount 1C-8 per cent. The water is therefore present mainly 

as such. It does not act on the amido grottp at 100°, as the quantity 

of ammonia expelled by alkali after heating at this temperature is not 

increased, and there is no loss of weight. At 150° it reacts, converting a portion of amide into ammonium salt, which at the same time 

loses ammonia, the residue being found to contain less nitrogen. The 

acid sodium salt dissolves rather difficultly in excess of ammonia, 

probably forming the sodium ammonium salt; from this solution it is 

reprecipitated by carbon dioxide, or even by expelling the ammonia 

by an air current or spontaneous evaporation. In this respect it resembles the neutral phosphates containing ammonia.

Neutral sodium amidophosphatCj PO v , is readily made by treating caustic soda solution with excess of acid salt, the excess remaining undissolved. It forms bunches of needles or prisms, extremely 

soluble in water, but not deliquescent. By the action of carbon dioxide, even that in the air, it is decomposed into acid salt and sodium 

carbonate. Alcohol precipitates it as a sirup from aqueous solution.

Acid lithium amidophosphate is precipitated by lithium chloride from 

a strong solution of the acid potassium salt, in the form of difficultly 

soluble crystalline granules. On boiling it is converted into phosphates of lithium.

Acid ammonium amidophosphate is formed by decomposing either the 

acid or neutral silver salt with ammonium sulphide and precipitating 

by alcohol. It forms a beautiful network of needles, crossing at angles 

of 60°, and is very soluble in water, and permanent in the air. As it 

is formed by precipitating an ammoniacal solution by alcohol, it 

appears that the neutral salt is very unstable, if capable of existence.

Potassium ammonium amidophosphate is precipitated by alcohol from 

an ammoniacal solution of the acid potassium salt as a sirup, which 

is decomposed by washing with alcohol into acid potassium salt and 

ammonia.

Acid hydroxylamlne amidophosphate, obtained by precipitating a
STOKES.] ON AMIDOPHOSPHORIC ACID. 87

moderately strong solution of the acid potassium salt with hydroxylamine hydrochlorate, is difficultly soluble in water, and forms brilliant 

rhombic plates and prisms. Its crystallizing power is greater than that 

of any other salt obtained. A neutral salt could not be prepared.

The preparation of salts of the earths and heavy metals from the acid 

potassium salt is interfered with by the contamination of the latter with 

a small amount of phosphate. The contamination of the precipitate in 

the case of the salts is best avoided by adding to the ice-cold solution 

of the acid potassium salt, before precipitation, a very little dilute 

nitric acid, which effectively holds all phosphate in solution. In making neutral salts, it is not so easy to get rid of the phosphate ; the ways 

in which this was accomplished are given in special cases below.

Acid barium amidophosphate, PO OH ) Ba+2£H2O, is obtained by

 S

adding to an ice-cold solution of acid potassium salt, faintly acidified 

with nitric acid, barium chloride in excess. It thus forms a supersaturated solution, which crystallized only on rubbing with a glass rod. 

The precipitate is washed with a little water and alcohol. It forms 

groups of radiating microscopic plates, and once formed is quite difficultly soluble in water. On boiling its solution a scaly crystalline 

precipitate of acid barium phosphate, BaHPO4 , at once forms. It contains about 2£ mols. crystal water, the greater part of which is lost at 

100°, but this cannot be directly determined, owing to its tendency to 

pass into ammonium salt with loss of ammonia. On ignition it fuses 

to a glass of barium hexametaphosphate.

Loss (2XH3 -f2jH.jO) ..................

Calculated for 

Ba(P03NH3 ) 2 

+2iH20.

20-17

Found.

19 -82

The residue gave 

Ba. ...................................

P.....................................

Calculated for 

Ba(P03)s.

46-43

21-03

Found.

47-12

21 -38

Neutral barium amidopliosphate, + H2O. By mixing a

dilute solution of acid potassium salt with ammoniacal barium chloride 

solution, and filtering quickly from the small amorphous precipitate of 

barium phosphate, the salt soon crystallizes. It forms very characteristic hard and brittle rhombic plates, often with truncated angles, often 

superposed in coincident or partly turned position, sometimes also as.
88 LABORATORY REPORT, 1891-92 AND 1892-7 93.

fine prisms with many sharply denned faces. It is unchanged at 100°, 

but at 150° the crystal water is taken up to form ammonium salt, 

which at once loses ammonia, forming acid barium phosphate, which 

on ignition leaves a residue of pyrophosphate, giving off but little 

ammonia.

Calculated for 

NH2

"?0g>B»+H»(X

6-80

10 -40

Found.

6-84

10-70

The residue gave 

Ba..............................................

P...............................................

Calculated for 

Ba^O?.

61-17

13-84

Found.

61-80

14-44

The salt is very difficultly soluble in water. Its solution, or the 

liquid from which it has not yet crystallized, gives on boiling, even in 

the presence, of an excess of ammoniacal barium chloride, a scaly precipitate of acid barium phosphate.

Loss on ignition §H2O ......

Calculated for 

BaHP04.

3-86

Found.

4-65

The residue gave 

Ba............... ...........

Calculated for 

Ba2P207 .

C1-1C

Found.

61-76

The salt shows a peculiar behavior when formed in the presence of 

strong ammonia. By mixing a solution of the acid potassium salt with 

strongly ammoniacal barium chloride an amorphous precipitate is 

formed, which dissolves (excepting traces of phosphate) on'adding 

water. Strong ammonia reprecipitates it, and more water dissolves it. 

This process may be repeated several times. The solution soon deposits 

crystals of the neutral salt, and the precipitate itself soon turns to 

scales of the same substance. Filtered off and washed with ammonia, 

it gave on analysis figures corresponding to those of the neutral salt.

Acid calcium amidophosphate, obtained like the barium salt, is much 

less soluble than the latter, and forms spherical aggregations of needles.

Neutral calcium amidophosphate is formed like the neutral barium
STOKES.] ON AMIDOPHOSPHORIC ACID. 89

salt, but is much less soluble. Its crystallizing power is also much 

less. From very dilute solutions it separates gradually in the form of 

microscopic groups of flat-pointed prisms; from concentrated solutions 

as an amorphous precipitate which does not become crystalline, while 

from solutions of intermediate strength it is at first amorphous but 

gradually becomes crystalline.

. \ 

Acid magnesium amidopliosphate,

/ NH2 

B, ( POO1 

V 0-

POOH I Mg+34H2O. On mix-

/2

ing an ice-cold strong solution of acid potassium salt, acidified slightly 

with nitric acid, with magnesium chloride, nothing separates, even after 

many hours. On rubbing with a glass rod crystallization starts at 

once. Once separated it is almost insoluble in water, and forms microscopic granules consisting of radiating needles or prisms. It is insoluble in ammonium chloride. At 100° it retains 2 mols. water; on ignition it gives off ammonia and water, and leaves magnesium metaphosphate.

Loss (2NH3+3JH,0). .................

Calculated for M££°AT5)2 HJ Jti2U.

33-71

Found.

33-86

The residue gave 

Mg ...................

P.....................

Calculated for 

Mg(P03)2 .

13-18

34-10

Found.

12.85

33-88

Neutral magnesium amidopliosphate,

ira.

7H2 O. This salt

has the same empirical composition as crystallized ammonium magnesium phosphate, MgNH4PO4 +6H2O, but differs entirely in its properties. It forms at once on adding magnesia mixture to a solution of 

acid potassium salt, or better, by precipitating neutral sodium salt 

with a magnesium salt. Any phosphoric acid present is first thrown 

down by a little of the precipitant, either as magnesium or magnesium 

ammonium phosphate; even when phosphoric acid is in excess it is 

completely thrown down by magnesia mixture before any amidophosphate forms, and the change can easily be followed by observing the 

crystals under the microscope. From solutions containing ammonium 

chloride (as when magnesia mixture is used) it crystallizes in very 

characteristic plates, often nearly rectangular, but more frequently 

with truncated angles, forming oblong octagonal plates. In the absence of ammonium salts it forms thick prisms, in either case easily 

distinguishable from ammonium magnesium phosphate. It is difficultly 

but perceptibly soluble in water, and quite readily in dilute ammonium 

chloride solution, and may be separated from any accompanying am-
90 LABORATORY REPORT, 1891-'92 AND 1892-*93. [BULL. 113.

monium magnesium phosphate in this way. From its aqueous solution 

ammonia precipitates magnesium hydroxide. On boiling its .aqueous 

solution, ammonium magnesium phosphate is at once formed. It dissolves in acetic acid; from its solution in nitric acid, alcohol precipitates 

acid salt. Even when free from ammonium salt, caustic potash causes 

more or less evolution of ammonia in the cold. Over sulphuric acid it 

quickly loses most of its crystal water, but the last two or three molecules are given off very slowly, and constant weight could not be obtained. At 100° it loses somewhat more than 5 mols., but this can not 

be accurately determined, as at this temperature partial decomposition 

of the amide with loss of ammonia occurs, as shown by analysis of the 

residue. On ignition it leaves magnesium pyrophosphate.

p.....................................

N. .............. ......................

Mg ...................................

Calculated for 

MgPOjNHz 

+7H20.

12-67

5-73

9-79

54-70

Found.

12-59

6-53 6-27

9-77

54-79

Acid manganese amidopliospliate, prepared like the acid magnesium 

salt, forms faintly pinkish microscopic crystals or granular and lenticular forms. It contains crystal water, is difficultly soluble, and shows 

no tendency to form supersaturated solutions.

Neutral manganese amidopliospliate, from the neutral sodium salt, is 

an amorphous white precipitate.

Acid zinc amidophosphate is difficultly soluble in water; soluble in 

acetic acid and in ammonia. It crystallizes readily in small but finelyformed rhombic prisms with pyramids, or in hexagonal plates.

Neutral zinc amidopliospliate is an amorphous white precipitate perceptibly soluble in water. Both salts are converted into phosphate by 

boiling.

Cobalt amidopliospliates. The acid salt forms readily from the acid 

potassium salt with a cobalt salt after adding a drop of nitric acid. 

It is difficultly soluble in water; soluble in ammonia, and forms pink 

granules. The neutral salt is an amorphous pink precipitate.

Nickel amidopliospliates. The acid salt has a great tendency to supersaturation, and can only with great difficulty be made to crystallize. 

Once formed, it consists of minute crystalline granules, difficultly soluble in water. The neutral salt is an amorphous, nearly colorless precipitate, soluble in acetic acid and in ammonia.

Ferrous amidopliospliates. The acid salt, formed as above, crystallizes very readily in nearly colorless microscopic crystals, apparently of 

the regular system, and consisting of the dodekahedron, or combinations of cube and octahedron. It is nearly insoluble in water or ammonium chloride; soluble in ammonia. The neutral salt is a dirty 

greenish, amorphous precipitate, soluble in much water, in acetic acid, 

and in ammonia.
8TOKES.] ON AMIDOPHOSPHORIC ACID. 91

Ferric amidophosphates. Both acid and neutral alkali salts give, with 

a neutral solution of ferric chloride, white, amorphous precipitates, 

soluble in excess of amidophosphate and in ammonia; insoluble in 

acetic acid.

Aluminum amidophosphate. Neutral sodium salt gives, with alum, a 

white, amorphous precipitate, completely soluble in ammonia.

Chromic amidophosphate, from neutral sodium salt, is a very nearly 

colorless amorphous precipitate, soluble in ammonia on warming.

Cupric amidophosphates. The acid salt crystallizes in rosettes and 

dumb-bell-like forms, nearly insoluble in water. The neutral salt is an 

amorphous precipitate, slightly soluble in water> and converted into 

phosphate by boiling.

Mercuric amidophosphates. Neither acid nor neutral salts are precipitated by mercuric chloride. On boiling, mercuric phosphate is formed.

Cadmium amidophosphates. By mixing solutions of acid potassium 

amidophosphate and cadmium chloride, crystalline precipitates somewhat soluble iu water are obtained. These differ in form according as 

one or the other reagent is in excess ; with excess of cadmium chloride 

a, double salt is formed which gives off ammonium chloride on heating.

Lead amidophosphate. Acid potassium salt and lead acetate give a 

precipitate consisting of groups of radiating plates, slightly soluble in 

water, presumably acid salt.

Acid silver amidophosphate, PO OAg. This may be obtained by preOH

cipitating the acid potassium salt with silver nitrate, but, thus obtained, 

it contains too much silver (about 2 per cent), due perhaps to a small 

amount of neutral salt or to a trace of phosphate. By previously adding a very little nitric acid to the cold solution it is obtained pure. As 

it is somewhat soluble in water, the theoretical yield can not be obtained. It is also formed by dissolving the neutral salt in cold dilute 

nitric acid and precipitating by alcohol or by adding alcohol to a solution of the free acid and silver nitrate. It forms a heavy crystalline 

powder, consisting of short needles, or, oftener, of very thick, short, 

hexagonal prisms with pyramidal ends3 united into groups or tAvius; 

also, by precipitating with alcohol, as hexagonal stars. The forms are 

very characteristic. It is difficultly but appreciably soluble in water, 

easily in dilute nitric or acetic acid, and in ammonia; from the latter 

solution it crystallizes on evaporation. The aqueous solution is at once 

converted into phosphate by boiling. Light does not discolor it. The 

air-dried salt is anhydrous. Analysis gave :

p.................

Ag. ..............

NH 2 

Calculated for PO OAg. 

OH

15 -22 

52 -90

Found.

15 -23 

53 -35
LABORATORY REPORT, 1891-J92 AND 1892-*93. [BULL. 113.

On ignition it loses ammonia and leaves an easily fusible glass of silver 

hexametaphosphate.

Loss(N.H"3).......

NH 2 

Calculated for PO OAg. 

OH

8-36

Found.

817

Neutral silver amidophospliaie,

AJTJ

 n* s *s either

by adding silver nitrate and then ammonia to the nitrate from the acid 

salt, or (with much loss) by dissolving the acid salt in very dilute nitric 

acid and adding silver nitrate and ammonia. It forms at first a turbidity, which in a few moments turns to a quickly subsiding crystalline 

precipitate. The ammonia must be added cautiously and stopped as 

soon as the salt ceases to subside quickly. At this point a nearly white 

amorphous substance of unknown composition is formed, which remains 

in suspension and may be redissolved by a drop of nitric acid. Further 

addition of ammonia to the filtrate gives the same amorphous salt, 

which is faintly yellow and rapidly blackens in the light. It may alsoo 

be obtained from the neutral sodium salt, but this method is not to be 

recommended, as the product is slightly yellow. The best method is 

the first mentioned, and if very dilute solutions of acid potassium salt 

have been used nearly all the acid silver salt remains in solution and 

can be converted into neutral salt as described. The neutral salt forms 

characteristic microscopic rhombic plates, with angles of nearly 60°, 

often united to bunches. It is colorless and unaffected by light. The 

crystalline powder is soft, and can thus be distinguished from the acid 

salt, which is gritty. It is almost insoluble in water; soluble in nitric 

acid, from which solution alcohol precipitates acid salt; soluble in ammonia, and deposited unchanged on spontaneous evaporation. The airdried salt is anhydrous.

p .................

N. ................

Ag... ............

Calculated for PO.NH2 (OAg)j.

9-98

4-52

69-40

Found.

10 -03 9 -87

4-51

C9-18 6915

It remains unchanged at 150°; at 180° it loses weight, the loss corresponding to one-half the total nitrogen calculated as ammonia. On 

heating to constant weight at 180° 

Calculated for 2PO.NHa (OAg)s NHS.

2-74

Found.

2-82

The residue is brownish, but may be fused over the blast with but 

slight loss, whereby a little oxygen escapes, and a small amount of
STOKES-l ON AMIDOPHOSPHORIC ACID. 93

metallic silver is formed. In the above case this was weighed and 

found to be only 5-61 per cent out of a total of 69-40 per cent. The 

loss between 180° and red heat was 0-34 per cent, and this is exactly 

the amount of oxygen which would be given off by the silver oxide 

corresponding to 5-61 per cent silver. The residue on ignition consists, besides metallic silver, of a yellow glass, soluble in ammonia. 

Probably there is formed at 180° the silver salt of pyrimidophospkoric 

acid,

which is not decomposed by fusion. Attempt will be made to isolate 

the free acid.

If the salt be heated at once over the blast, without previous heating 

at 180°, the decomposition is markedly different, much more metallic 

silver being formed.

Calculated for 

JN as NH3 .

2-74

Found.

4-63

25-75

This amount of silver corresponds to 1*91 per cent oxygen, which, 

with 2-74 per cent ammonia, makes 4-65 per cent loss, the amount actually found. The formation of silver oxide is due to the liberated ammonia, which splits off silver oxide and water, forming a higher amide. 

The action of dry ammonia gas on the salt is scarcely appreciable at 

180°, as was found by experiment, hence the salt may be heated at this 

temperature without the ammonia which is given off liberating any considerable amount of silver oxide, as in the first case. At 200° and 

higher, dry ammonia forms large amounts of silver oxide and water, 

and therefore on heating rapidly, as in the second case, the liberated 

ammonia is able to act, and the large amount of silver formed is 

accounted for. The products of the action of dry ammonia on this'salt 

will be described in a future article, when it will also be shown that 

amidophosphates may be made from neutral silver phosphate in this 

way. Experiments towards forming other inorganic amides by this 

method are also in progress.

Free amidophosphoric acid. The isolation of the free acid is attended 

with difficulties, owing to its unstable nature. It has not yet been 

obtained perfectly pure, and the yield is always far below the theoretical. The silver salts may be decomposed by hydrochloric acid in the 

cold, and the solution precipitated by alcohol, but a deficiency of acid 

causes the solution to be contaminated with acid salt, and an excess 

destroys the amido acid completely, or at least prevents its precipitation. The decomposition of the silver salts by sulphureted hydrogen 

gives better, but unsatisfactory results. The best results are obtained
94 LABORATORY REPORT, 1891 -92 AND 1892-'93. [BOIL. 113.

by suspending the lead salt in a little ice water, and decomposing by 

sulphureted hydrogen. It is essential to have the latter in excess, as 

otherwise the solution contains some lead salt. The nitrate is run into 

four or five volumes of alcohol, whereby the acid is at once precipitated 

in the form of microscopic crystals. These consist sometimes of thick 

plates, sometimes of forms which appear to be cubes, but which are 

anisotropic. It is insoluble in alcohol, easily soluble in water, the solution having a sweetish taste. It gives no precipitate with silver nitrate, 

unless on addition of ammonia or alcohol. It evolves no ammonia with 

caustic alkalies, and is easily converted into the characteristic sodium, 

magnesium, barium, and silver salts, hence there can be no question as 

to its nature. It may be exposed to the air for a long time without 

change, but gradually alters, becoming pasty, in which condition it precipitates silver nitrate directly, and hence has become converted into 

an ammonium salt. The precipitate is white and amorphous, hence not 

phosphate. Its solution, if boiled but a moment, also gives a white 

silver precipitate, but, on boiling several minutes, it is completely converted into phosphate. It does not lose weight at 100°, but is slowly 

converted into ammonium salt, giving a white silver precipitate direct. 

Whether the product is one of the isomeric ammonium inetaphosphates 

has not yet been determined. At 150° it also loses nothing, but fuses 

partially, and on higher heating it gives off ammonia. The silver salt 

from the acid which has been heated just to fusion becomes pasty under 

boiling water, like silver hexarnetaphosphate. The free acid obtained 

as above did not give satisfactory results on analysis, and such data 

are therefore postponed.

The alcoholic filtrate from the free acid contains an abundance of 

ammonium salts, giving amorphous, white, silver precipitates.

The action of amidophosphoric acid towards indicators is not sharp. 

The free acid gives acid reaction, the acid alkali salts have neutral 

reaction, but no sharp transitions can be obtained either with litmus, 

methyl orange, or phenolphthalein. It also differs from phosphoric acid 

in the uniformity with which its acid alkali salts precipitate acid salts 

and its neutral alkali salts give neutral salts. No exception to this 

was observed. Soluble acid phosphates, as is well known, give, with 

silver and many other metals, precipitates of neutral salt.

The investigation will be continued in the directions indicated.
ON SOME ORGANOSOLS.

BY E. A. SCHNEIDEE.

It is well known that Graham succeeded in the course of his work 

on diffusion in substituting organic liquids for the water in colloidal 

solutions. I mention here only that he prepared colloidal solutions of 

silicic acid in alcohol, ether, and even in carbon bisulphide,1 Similarly to his nomenclature for water soluble colloids hydrosol for the 

water-soluble colloid, hydrogel for the coagulated colloid he formed 

names like alkosol and alkogel, glycerosol and giycerogel, etc.

After having investigated somewhat this field, it appears to me very 

probable that the water in colloidal solutions may be replaced by many 

organic liquids. Should we accept without reserve Graham's nomenclature we would find it difficult to form in all cases clear and euphonious names. I propose, therefore, to retain the excellent expressions 

"hydrosol" and "hydrogel" for the water-soluble and the waterinsoluble forms of colloids and to call the solutions of colloids in organic 

liquids "organosols," while adding the chemical formula of the colloid and that of the solvent in parenthesis. Graham's experiments on 

orgauosols have not been repeated so far as I can make out from the 

existing literature. For this reason alone it appeared to me desirable 

to extend them to the large class of colloidal inorganic sulphides, 

which have become known only recently, and also to colloidal silver. 

The preparation of such solutions appeared to me also desirable, 

because we may hope that a detailed investigation of their physical 

properties will shed some light on the nature of solution.

Oryanosol Au2S2 (Ethyl alcohol). Among the numerous known colloidal sulphides the best suited for the first experiments in this field 

appeared to be the colloidal sulphides of gold,2 which have already 

been studied by me. They possess the advantage over other sulphides 

that they are not subject to oxidation on contact Avith the air, an advantage which should not be underestimated, if the length of time which 

dialysis requires is taken into account.

The organosol was obtained by dialyzing an aqueous solution of auroauric sulphide mixed with alcohol into absolute alcohol. To 50 c. c.

1 Ann. de Chim. ot de Phys., 4 ser., 3,1864. 

"Berichte, XXIV, 2241.

95
96 LABORATORY REPORT, 1891-*92 AND 1892-'93. [BULL. 113.

of a solution which contained in the liter 1-514 grams Au2S2 and only 

traces of impurities (prepared by the action of potassium, cyanide on 

precipitated auroauric sulphide), 150 c. c. absolute alcohol were added; 

no sign of coagulation became visible. The mixture was poured into 

a parchment tube and the latter suspended in a tall narrow beaker 

which was filled with absolute alcohol. The dialysis was carried on 

under a bell jar which fitted air-tight on a ground glass plate. If an 

attempt is made to dialyze the hydrosol of the sulphide into absolute 

alcohol without mixing it first with a sufficient quantity of alcohol the 

contents of the dialyzers become coagulated and hardly any liquid is 

left in the dialyzer after the lapse of twelve hours, for the rapidity 

of diffusion of water through the parchment into absolute alcohol is 

much greater than the opposite movement.

After twenty-six days of dialysis, during which time the alcohol in 

the outer vessel was frequently renewed, a liquid was obtained which 

did not show any difference, so far as color and optical behavior are 

concerned, from the hydrosol of the auroauric sulphide.

The analysis of the organosol was carried out in the following manner: 100 grams were distilled from a fractionating bulb.at the temperature of the water bath; at the same time a stream of dry carbonic 

acid was conducted into the flask in order to accelerate distillation. 

The specific gravity of the distillate was determined very accurately 

by means of the pycnometer. The residue in the fractionating bulb 

was dissolved in aqua regia and the gold was determined in the usual 

way; 100 parts by weight of the organosol contained 

Parts by weight. 

C2H6OH .................................................. 98-90

Au2S2 ..................................................... 0-0676

H2O ...................................................... 1-03

99-99

Equal volumes of the hydrosol and of the organosol which contain 

the same quantity of auroauric sulphide do not show any difference 

in depth of coloration or transparency.

The organosol is very stable, apparently more stable than the hydrosol, which on standing a long time deposits sediment.

Organosol Au2S (Ethyl alcohol). Up to this time I have not succeeded in preparing a sufficiently concentrated organosol of aurous 

sulphide in alcohol; the probable reason is that the hydrosol.was not 

sufficiently pure. It was possible to mix the latter in all proportions 

with alcohol, but on dialyzing such a mixture coagulation always took 

place. The strongest alcoholic solution which I obtained by mixing the 

hydrosol with alcohol contained 99 per cent alcohol, but only 0-001 per 

cent aurous sulphide. Its color was yet perceptibly straw-yellow and 

it appeared clear in transmitted as well as in reflected light.

Organosol Ag. (Ethyl alcohol). I have prepared the organosol of silver in ethyl alcohol according to two methods. It can be obtained
SCHNEIDEB] ON SOME ORGANOSOLS. 97

easily and conveniently by the dialysis of the hydrosol into absolute 

alcohol.

The product of a twenty-seven .days' dialysis was analyzed with the 

following results: 100 parts by weight of the organosol contained 

Parts by weight.' 

.C.2H5OH .................................................. 99-30

Ag....................................................... 0-1716

H20 ..................................:................... 0-53

This organosol is completely opaque in layers 2 mm. thick. Diluted 

with a sufficient quantity of alcohol or water it appears in transmitted 

light chlorophyll green with a bluish tinge; on further dilution the 

color becomes yellow-green. It is perfectly transparent in transmitted 

light; viewed by reflected light it appears violet-brown and decidedly 

turbid.

It is worth while to mention that on distilling off the alcohol silver 

is deposited on the bottom of the fractionating bulb as a beautiful 

gold-colored mirror.

The succession of colors in the hydrosol, in the case of transmitted 

light, reminds one very much of Newton's rings, for here also the order0 

proceeds from brown-red to blue-green, while the thickness of particles 

is probably increasing. This analogy, however, is incomplete, for we 

are dealing here not with the colors of thin plates, but at the most with 

diffraction phenomena.

As far as the color of the solid colloid is concerned it can be 

explained by pure absorption. Still the peculiar correlation of the 

complementary colors hydrosol, red-brown; solid mirror of the same, 

blue-white; organosol, green; solid mirror of the same, golden-yellow 

is remarkable and needs further explanation.

If the probability is kept in view that it may be possible to explain 

the changes of color of the silver solution on the basis of well-known 

laws of optical physics, the assumption of allotropic modifications of 

silver, which has been made by Carey Lea, becomes unnecessary.

The organosol of silver in ethyl alcohol-may be also prepared in 

another very easy manner, which is interesting because it illustrates 

the general application of the laws according to which colloidal solutions are formed.

If to the silver hydrosol, as it is obtained according to Carey Lea's 

prescription, absolute alcohol is added, coagulation begins as soon as 

a certain degree of concentration is reached. The black finely divided 

precipitate is now separated from the solution by means of a Pasteur 

filter. It settles on the walls of the latter as a crust with a beautiful 

bronze luster. This precipitate is soluble in water as well as in absolute alcohol, because the original impurities have been reduced to a 

minimum.1

i

1 Compare article on the preparation of the pure hydrosol of silver, pages 99-101, this bulletin.

Bull. 113 7
98 LABORATORY REPORT, 1891-J92 AND 1892J93. [BULL. 113.

Two portions of 100 c. c. each of an organosol which had been prepared in this manner were subjected to analysis. The silver was 

coagulated with hydrochloric acid in alcoholic solution.

Previous to analysis the organosol had been allowed to stand for two 

months, and a sediment had separated out.

The analysis gave the following results:

Ag..........................

I.

grams. 

0 -1240

II.

grams. 

0 -1225

Consequently a hundred parts by weight of the organosol contain, 

if we assume that the strength of the observed alcohol has decreased 

owing to absorption of moisture from the air, to 99 per cent by volume:

&£..:.. .....................

Parta by weight.

I.

0 -1552

II.

0 -1533

Starting from the alcoholic organosols, it appears to me possible to 

prepare many organosols of the inorganic sulphides and of silver.
ON THE PREPARATION OF A PURE HYDROSOL OF SILVER.

BY E. A. SCHNEIDER.

Ill a previous coinumuicatioii on this subject the peculiar behavior 

of colloidal solutions of silver or, if we use Graham's terminology, of 

the hydrosol of silver, towards hydrochloric acid has been discussed. 1 

It was shown that on addition of increasing quantities of hydrochloric 

acid, increasing quantities of silver chloride were formed and that at 

the same time neither the liberation of oxygen nor of hydrogen was 

noticeable. In order to find a plausible explanation for these facts it 

was necessary to prepare first of all a pure solution of silver hydrosol. 

Neither Carey Lea 2 nor Prange 3 have worked with the pure substance 

and, in my former experiments, I also used impure solutions. After 

prolonged experiments I have been able to work out a method by which 

it is possible to prepare solutions that possess the highest degree of 

purity attainable with this class of bodies. Experience has taught us 

that it is not possible to remove the last traces of crystalloids from 

colloidal solutions; this applies particularly to the hydrosols of silicic 

hydrate and of ferric hydrate, as has been observed by Graham4 and 

other investigators.5 My method is founded chiefly on the application 

of the Pasteur filter, of unglazed porcelain, and on the behavior of the 

silver hydrosol towards alcohol. The material used at the outset is 

made, according to the excellent prescription of Carey Lea, in the following manner: We prepare (1) 500 c. c. of a 10 per cent silver nitrate 

solution; (2) 500 c. c. of a 30 per cent ferrous sulphate solution (150 

grams crystallized ferrous sulphate in 500 c. c. liquid); (3) 700 c. c. of 

a sodium citrate solution which is obtained by dissolving 280 grams 

crystallized sodium citrate in the necessary quantity of water. Any 

deviation from this prescription leads to very unsatisfactory results.

'Berichte XXIV, 3370.

* Am. Journ. of Science, 37, 481,1889.

3 Rec. des Trav. Chim. des Pays Bas, 9,125.

«The hydrosol of ferric hydrate which Graham prepared contained 1 E<I. hydrochloric acid to 30.3 

Eq. Ferric oxide. Ann. Chem. Pharm., 121, 46.

sBecquerel subjected some hydrosols to electrolysis. He remarks "During the experiment a rather 

considerable quantity of hypochlorous acid is formed, particularly from the solution of silicic acid; 

this shows that these solutions still contain chlorine, notwithstanding they are neutral. Ann. Chem. 

Pharm., 126, 303. Oonipte rendu, 56, 237.

99
100 LABORATORY REPORT, 1891-'92 AND 1892-793. [BULL. 113.

The ferrous sulphate solution is mixed with the citrate solution and 

the resulting liquid is poured into the silver nitrate solution j the 

whole should be well stirred. To exclude daylight, as Prange recommends, is entirely unnecessary. It is advisable to divide the solutions 

into five equal parts, because the handling of smaller quantities at a 

time is much quicker and easier.

After standing half an hour the colloidal silver has usually settled 

completely. The supernatant liquid should be drawn off as much as 

possible, which is perhaps done best by means of a pipette, and the 

solid colloid is now thrown on the filter.

With the proper use of the Bunsen pump and of the right kind of 

filters it becomes possible to remove the greater part of the mother 

liquor from the colloid, without losing much of the latter by passage 

through the filter. The magnificently blue-violet iridescent colloid 

should now be rinsed off from the filter by means of a stream of water, 

and instant solution takes place. If care is taken to use the water 

very cautiously solutions may be easily obtained which contain 20 

grams silver to the liter. Their color is dark brown-red ; viewed in reflected light they appear turbid, in transmitted light, however, in thin 

layers or if largely diluted, completely transparent.

The impure hydrosol which has been thus obtained is brought into a 

flask and absolute alcohol added to it, with continuous agitation, until 

coagulation of the silver particles becomes apparent. It is not necessary to wait until the precipitate has settled (this sometimes takes several days), for it may be filtered off by means of a Pasteur filter tube. 

The filter tube should be connected with a powerful Bunsen or Chapman pump capable of producing a vacuum of 10 to 20mm, and placed 

in a glass cylinder, which is filled from time to time 'with the solution. 

The pure colloid is now deposited as a magnificently iridescent crust 

on the exterior wall of the filter. After some time the effectiveness 

of the filter is impaired owing to the fact that its pores become clogged 

and it is necessary to rinse of the crust by means of a stream of water. 

This should be done after the filter tube has been taken out of the cylinder and after the pump has been allowed to work a few minutes until 

the crust appears entirely dry. It is unfortunately not possible to 

wash the solid colloid with dilute alcohol. Just as other colloids, particularly the metallic sulphides, on washing with water go into solution after removal of the crystalloids, so also the colloidal silver, when 

free from impurities goes into alcoholic solution.

It should be mentioned that instead of the Pasteur filter, paper filters 

may also be used. But in this case the filtering takes a very long time, 

since no pressure can be employed, and it becomes impossible to work 

with large quantities.

To explain the working of this method, it is sufficient to point out 

the very considerable solubility of the sesquisulphate of iron and of 

ferrous citrate in alcohol and the insolubility of colloidal silver which
SCHNEIDKR.] HYDROSOL OF SILVER. 101

still contains some of these impurities, in alcohol. The data which are 

given below illustrate the effectiveness of the method.

I. A hydrosol which contained in the liter 17-034 grams silver and 

0-362 gram iron, the latter in combination with sulphuric and citric 

acids, was treated as described above.

A. A hydrosol was obtained which contained in the liter 12-248 grams 

silver and 0-038 gram iron. Consequently the percentage of iron, calculated on the total amount of silver, has decreased from 2-12 to 0-31 

per cent.

B. By the same method, using, however, ordinary paper niters and 

another hydrosol, the original proportion of 100 Ag: 2-7 Fe was changed 

to 100 Ag: 0-33 Fe.

A number of other solutions were prepared according to the same 

method. Their contents of iron averaged from 0-3 to 0-5 per cent (calculated on the total amount of silver), and this percentage was rarely 

exceeded.

After this method was found to yield the silver hydrosol so nearly 

pure, it became possible to explain its peculiar behavior towards hydrochloric acid.
CONTRIBUTION TO THE KNOWLEDGE OF COLLOIDAL SILVER.

BY E. A. SCHNEIDEE.

If hydrochloric acid is added to silver hydrosol the precipitate which 

is instantaneously formed always contains, besides silver, varying 

quantities of silver chloride; a fact which has been mentioned in a preliminary notice on this subject.

Two possibilities may be considered in attempting to explain this 

fact: Either the hydrosol contains small quantities of a silver oxide 

compound, or the silver combines with the chlorine of the hydrochloric 

acid and hydrogen is set free.

The first assumption appeared the more plausible since an evolution 

of gas had never been noticed on addition of hydrochloric acid. In order 

to carry out iu the most approved way a test for silver oxy-cornpounds 

in the hydrosol, 75 c. c. of an almost absolutely pure preparation, which 

contained in the liter 12.248 grams silver and 0.038 gram iron, were 

distilled to dryness in a current of carbonic acid and the residue was 

heated to redness. The water which distilled off was collected in a 

well cooled receiver, and the gases, which were set free, in a eudiometer 

tube over caustic potash. In this way 4 c. c. (766 mm. B. and 16°) of a 

gas were obtained which yielded to pyrogallol only 0-6 c. c. We have 

here consequently to deal with air whose composition has been somewhat changed by absorption in the hydrosol. If we take into account;, 

the rather long time which the experiment required, then the capacity 

of the whole apparatus, and lastly the fact that the carbonic acid was 

prepared from marble, we are perfectly justified in ascribing a considerable part of the air collected to these sources of error.

At any rate by'this experiment the absence of silver oxy-compounds 

in the hydrosol is proved absolutely.

The possibility of the reaction Ag -f HOI = AgCl -f- H has now to be 

considered. For this purpose the electrochemical behavior of the hydrosol 

was investigated. In order to obtain some information concerning the 

accumulation of hydrogen on the silver particles which are coagulated 

on addition of hydrochloric acid, the degree of the hydrogen polarization was measured by means of a compensation method.

Two equally large insulated silver crucibles connected with each 

other by means of a siphon were filled with the liquid to be investi102
SCHNETDEU.] COLLOIDAL SILVER. 103

gated; the system was manipulated as indicated in the table below. 

The wires of the measuring apparatus were connected with the outside 

surfaces of the silver crucibles and care was always taken that no current passed the liquid, with the exception of the weak, instantaneous 

one, which was needed for the measurement. Changes of the contents 

of the silver crucibles were always effected while the chain was kept 

open. Jarring, etc., was avoided. In the table are given the time of 

the measurement, the observed electromotive force e (degree of the 

hydrogen polarization), and the actual change de of the latter, which is 

originated by hydrochloric acid in its action on colloidal silver.

Values of ih.e electromotive force p..

a.

HC1, left hand. .......................

HC1, both sides.......................

I.

HC1, left hand. .......................

Time in.

0

15

60

100

1.200

2, 600

0

HO

0

5

35

145

1,400

«x 10s volt.

81

+277

 18

t n

+376

382

38G

389

381.

364

+100

+icr,

161

161

157

146

Sex 10'.

0

358

370

0

+367

373

377

380

372

352

0

65

61

61

57

46

* These forces are to ho added to 370, hecause each electrode is already charged with hydrogen.

The tables are divided into two parts and the experiments supplement each other. In a the system was first filled with water, then 

hydrochloric acid was poured first into the left hand crucible and after 

the measurement into the right-hand crucible. The polarization is 

here tfe=O367 volts on the average. The system was then thoroughly 

cleaned and the silver hydrosol placed in it. Experiment 6 shows 

forces which first increase, then decrease, but which on the whole 

exceed but little the values found in experiment a. On the basis of 

this experiment we would hardly be justified in assuming that the 

coagulated silver particles are more strongly charged with hydrogen 

than the silver foil (crucibles) treated in the same manner.

Much more sensitive and decisive are experiments c, which were carried out thus: The system was first filled with hydrochloric acid and 

then the hydrosol was poured cautiously into the left-hand crucible. 

Here an increase of the hydrogen polarization amounting to O060
104 LABORATORY REPORT, 1891-J92 AND 1892-'93. [BULL. 113

volts is clearly discernible. From these experiments we can conclude : 

(1) That hydrogen must be accumulated on the silver particles j (2) 

that the quantity of hydrogen which thus condenses upon coagulation 

of the hydrosol with hydrochloric acid is a little larger than on silver 

foil; (3) that the silver particles which are charged with hydrogen 

gradually lose a part of their charge.

It was not possible to prove directly, that is, by collecting and measuring, the presence of hydrogen in the coagulated silver. Some experiments which were carried out in this direction, for instance 'amalgamation of the coagulurn with mercury under water, did not yield 

decisive results. The quantity of hydrogen in the silver must be consequently very small. From this we can conclude that the quantity of 

silver chloride which is formed according to the reaction

Ag+HCl=AgCl+H

can not be large. This result is somewhat surprising, since it contradicts all outward appearances. The freshly coagulated silver is spongy 

and voluminous, and reminds one vividly of amonium-ainalgarn.

It is evidently necessary to find an explantion for the formation of 

the larger part of the silver chloride without simultaneous liberation 

of hydrogen.

An old experiment, which Becquerel 1 had made while experimenting upon the photography of colors, together with some observations 

which had been gathered in the course of this investigation, facilitated 

this task.

In order to prepare thin layers of silver chloride very sensitive to 

light, Becquerel dipped polished silver plates into solutions of metallic 

chlorides such as ferric chloride. A reaction takes place in the following way : .

Ag+FeCl3 =AgCl+Fe012 .

In the course of my analyses of silver hydrosols I noticed that the 

richer they are in iron the more silver chloride is formed on addition 

of hydrochloric acid. The suspicion that the iron salts which are present may be the cause of the whole phenomenon was obvious.

An experiment proved the correctness of this assumption. Two 

portions of 100 c. c. each of a silver hydrosol which contained in this 

volume 1-6834 grams Ag to 0-0112 grams Fe2O3 were mixed with varying quantities of neutral ferric chloride solution.

I. 100 c. c. silver hydrosol were mingled with 5 c. c. ferric chloride 

solution (=0-1268 grams

Grams. 

Ag precipitated as metal ................................... 1'5566

Ag precipitated as chloride. ................................ 0-1248

1-6814

i Aim. d. Ghim et Phys., 3 serie XX\T, 448.
SCHNEIDER.] COLLOIDAL SILVER. 105

II. 100 c. c. silver hydrosol were mingled with 150 c. c. ferric chloride 

solution (=3-804 grams Fe2O3 ). The silver hydrosol was allowed to flow 

slowly into the chloride solution Avhile the whole was shaken.

Grains. 

Ag precipitated as metal.................................... 

Ag precipitated as chloride................................. 1-6800

1-6800

' These experiments also show the influence of mass action.

The color of the precipitated silver chloride was a beautiful pink-red 

shading into violet; a tint I had not previously observed in the case of 

this compound. The silver chloride thus obtained appears to be very 

sensitive to direct sunlight.

A number of analytical examples are now given in order to better 

demonstrate the, statements contained above.

Three portions of a strongly contaminated hydrosol, such as is 

obtained by the method of Oarey Lea, and one portion of a hydrosol 

purified by the alcohol method were coagulated each with varying 

quantities of hydrochloric acid. The precipitate obtained was thoroughly digested with ammonia, the ammoniacal extract boiled in order 

to drive off the excess of the reagent, and the solution ultimately 

acidulated with nitric acid. The filtrate from the silver chloride thus 

obtained gave in some cases, on addition of hydrochloric acid, a further 

weighable quantity of the same compound. This behavior indicates 

the presence of silver subchloride in the precipitate which is formed 

by hydrochloric acid in the hydrosol. The formation of this silver 

chloride can be explained by the action of the (nascent) liberated 

hydrogen on a part of the precipitated silver chloride.

ANALYSIS OF THE IMPURE HYDROSOL.

(a) 50 c. c. of the hydrosol were coagulated with 1 c. c. hydrochloric 

acid (Ipart fuming hydrochloric acid to 1 part water). The precipitate contained 

Ag......................................... 0-7641 g. 0-7641 g. Ag

AgCl....................................... 0-1082 g. 0-0814 g. Ag

AgCl'...................................... 0-0087 g. 0-0065 g. Ag

0 -8520 g. Ag

In the filtrate from the precipitate by hydrochloric acid were found 

Grama. 

FesOa...................................................... 0-0259

80s........................................................ 0-0099

0.0259 grams Fe2O3 correspond to 0-0464 grams AgCl if we start 

from the equation FeCl3+Ag=AgCl+FeClz . If we subtract this 

quantity (0-0464 grams) from the total weight of silver chloride 

present 0-1082 grams there remain still 0-0618 grains AgCl to be 

accounted for.

1 In the filtrate from the ammoniacal extract as previously described.
106 LABORATORY REPORT, 1891-92 AND I892-'93. [BULL. 113.

Now 0-0618 grams AgCl correspond to 0-0004306 grams H=4-81 

c. c. if we assume the equation

Ag+HCl=AgCl+H

to be true.

If we assume now that the coefficient of absorption of silver hydrosol for air is equal to that of water, 50 c. c. of the hydrosol must 

absorb 0-29 c. c. oxygen. This quantity is sufficient to oxidize 

0.00,00517 grams hydrogen = 0-57 c. c. to water.

Further, according to Bunsen 100 c. c. water at a temperature of 0° 

to 20° absorb 1-93 c. c. hydrogen. If we assume now again for the 

silver hydrosol the same coefficient of absorption as for water, 50 c. c. 

absorb 0-96 c. c. hydrogen.

Ultimately a quantity of hydrogen is used in order to form 0-0152 

grams Ag2Cl. Two molecules of silver chloride require one atom of 

hydrogen in order to form one molecule of silver subchloride, which is 

indicated in the analysis by 0-0087 grams silver chloride.

According to the equation 2x143-5: 1=0-0174 :#, the quantity of 

hydrogen which was used up to form silver subchloride = 0-0006 

grains = 0-70 c. c. Consequently we can subtract from 4-81 c. c. hydrogen 0-57 c. C.+0-96 c. C.+0-70 c. c.==2-23 c. c. hydrogen. There remain 

thus 2-58 c. c. hydrogen which have to be accounted for.

If we take now into account the electrochemical behavior of the 

hydrosol in presence of hydrochloric acid, which has made probable the 

accumulation of hydrogen on the silver particles; and if we consider 

further that the liquid contains citric acid and perhaps other easily 

reducible organic compounds, the absence of gas bubbles on addition 

of hydrochloric acid to the hydrosol need not appear strange.

I will bring forward a few more examples, but this somewhat complicated calculation will not be repeated in detail, for a new element of 

uncertainty has still to be taken into account. The coefficient of absorption of hydrochloric acid for air has not been determined experimentally so far as I know, and the question remains open whether or 

not hydrochloric acid may absorb more oxygen from the air than can 

be expected according to the well-known laws of absorption of gaseous 

mixtures by liquids.

(&) 50 c. c. of the same hydrosol were coagulated with 50 c. c. of fuming hydrochloric acid.

There was precipitated 

. Ag....................................... 0.7408 g.=0.7408 g. Ag

AgCl..................................... 0.1456 g.=0.1096 g. Ag

0.8504 g. Ag

(c) 50 c. c. of the same hydrosol were mixed with 150 c. c. fuming 

hydrochloric acid.
SCHNEIDER.] COLLOIDAL SILVER. 107

i

There was precipitated 

Ag....................................... 0.7406 g.=0.7406 g. Ag

AgCL.................................... 0.1499 g.=0.1121 g. Ag

0.8527 g. Ag

The hydrosol of this composition was purified according to the method 

described in a previous paper and analyzed by the same method as the 

crude hydrosol. The concentration of the purified hydrosol has naturally decreased owing to the process of purification to which it had been 

subjected.

(A) 50 c. c. of the hydrosol were mixed with 1 c. c. hydrochloric acid 

(1 part hydrochloric acid to 1 part water).

There was precipitated 

Ag....................................... 0.5715 g.=0.5715 g. Ag

AgCl..................................... 0.0479 g.=0.0360 g. Ag

AgCl* ................................... 0.0028 g.=0.0021 g. Ag

0.6096 g. Ag

In the filtrate from the precipitate by hydrochloric acid were found 

Fe2 0;! ................................................... 0-0027 g.

SO3 - -.................................................... trace.

0-0027 grams Fe2O3 correspond, on the basis of the equation Fe013 

+Ag=AgCl+FeCl2 , to 0-0048 grams silver chloride. , If we subtract 

this quantity from 0-0479 grams, representing the total quantity of 

AgCl, the hydrogen has to be accounted for which corresponds to 

0-0431 grams AgCl. This quantity of hydrogen weighs 0-0003 grams 

and its volume amounts to 3-35 c. c. From this volume we may substract 0-57 c. C.+0-96 c. c. hydrogen=l-53 c. c. hydrogen, as has been 

shown above. 1-82 c. c. hydrogen remain consequently to be accounted 

for. To form the subchloride of silver a certain quantity of hydrogen 

has been used up. Two molecules of silver chloride need one atom of 

hydrogen in order to 'form one molecule subchloride of silver, whose 

presence is indicated by the 0-0028 grams AgCl found in the analysis.

According to the equation 2 x 143-5: 1=0-00.56: #, the quantity of hydrogen which has been used up in the formation of subchloride of silver amounts to 0-00002 grams=0-22 c. c. Consequently the whole 

quantity of hydrogen whose functions can not be determined with certainty=l-60 c. c.

(B) 50 c. c. of the hydrosol were precipitated with 50 c. c. fuming 

hydrochloric acid.

There were thrown down 

Ag ........................................ 0-5639 g.=0-5639 g. Ag

AgCl....................................... 0-0628 g.=0-0472 g. Ag

0-6111 g. Ag

*In the aramoniacal extract as previously noted.
108 LABORATORY REPORT, 1891-'92 AND 1892->93. [BULL. 113. )

(C) 50 c. c. of the hydrosol were precipitated with 200 c. c. fuming 

hydrochloric acid. 

There were precipitated 

Ag ........................................ 0.5587 g.=0-5587 g. Ag {

AgCl...................................... 0-0729 g. =0-0548 g. Ag

AgCl *..................................... 0-0040 g.=0-0030 g. Ag

0-6165 g. Ag

If this particular case which has yielded the maximum of silver chloride is compared with the analogous case, in which we had to deal with 

the crude hydrosol, we can easily perceive that the proportion of the \ 

quantity of silver which is precipitated as silver chloride to the quan- \ 

tity of silver which is precipitated as metal is smaller in the hydrosol 

containing little iron than in the hydrosol containing much iron.

If this result is expressed in percentage calculated on the total 

quantity of silver the following numbers are obtained:

The hydrosol contained 3 per cent Fe2O3 .0-4 per cent Fe2O3 . v

There were precipitated as AgCl 13-1 per cent=9-3 per cent Ag.

Shortly expressed, the results of this and of the two other investigations pertaining to the silver hydrosol are:

1. The crude hydrosol can be purified by precipitation with alcohol 

and by dissolving again the precipitated colloid in water.

2. The almost pure colloid is soluble in absolute alcohol and forms an 

organosol.

3. The behavior of the silver hydrosol differs from that of ordinary 

finely divided silver not in nature but in degree.

4. This becomes evident from the electro-chemical behavior of the 

hydrosol on contact with hydrochloric acid. The finely divided silver 

becomes charged in a higher degree with hydrogen than silverfoil. 

The same follows from the behavior of the hydrosol towards ferric 

chloride. If the latter is present in sufficient quantity all the colloidal 

silver present is changed into silver chloride according to the equation

FeCl3+Ag=AgCl+FeCl2 . .

Under the same circumstances silverfoil is covered only, with a thin 

coating of silver chloride..

5. The peculiar differences in the color of the hydrosol, of the organosol (ethyl alcohol), and of the solid colloid are probably due to interference phenomena depending upon the size of the particles.

6. It is consequently unnecessary to assume an allotropic condition 

of silver so long as the physical properties of solid colloidal silver are 

not fully known.

* In ammoniacai extract as before.
MISCELLANEOUS ANALYSES.

THE MOUNT JOY METEORITE.

An iron found near Two Taverns post-office, in the neighborhood of 

Gettysburg, Pa.

[Analyzed by L. G. Eakins.]

Pe..... .........................

Ni. .............................

Co .............................

GU ...... .....................:.

p...............................

s...... .........................

93 '80

........................... 4-81

............................ -005

 10

........................... -01

99 -325

A NICKEL-IRON SULPHIDE FROM CANADA.

From the Worthiugton Mine, Sault Branch Canadian Pacific Bailroad, 25 miles west of Sudbury, Ontario. Grayish, with a cast of 

yellow. Not pyrrhotite. Possibly a mixture of pyrite and polydymite.

[Analysis by W. F. Hillebraiul.] 

Fe.......................................................... 38-36

Ni.......................................................... 4-57

Mn......................................................... -10

S........................................................... 45 11

SOa........................................................ '95

C02 ........................................................ *l-49 .

CaO........................................................ 1-91

MgO........................................................ -41

Insoluble................................................... 4-80

Moisture at 100°............................................ -55

98-25 

BEAUXITE FROM ALABAMA.

From near Jacksonville, Oalhoun county. Two samples A, red; 

B, white.

[Analyses by W. F. Hillebrancl. Lime, magnesia, and alkalies not looked for.]

Si02 .. .......................

TiOg........................

A1203 ... ....................

Ee,03 - ....... ...............

T> f\

A.

 65

20-43

10-25

2-53

41-00

25-25

100. 11

B.

 45

23-41

91 -na

2-52

48-92

2-14

98-52

' Calculated to saturate CaO.

109
110 LABORATORY REPORT, 1891- ?92 AND l892-'93, [BULL. 113. 

ANOETHITE FROM RAYMOND, MAINE.

White crystals, associated with idocrase, cinnamon gar-net, pyroxene, 

and scapolite.

[Analysis by W. H. Melville.]

Si03 ....................................................... 43-13

A12 03 ..-................................................... 30-95

Fe3 03 ...................................................... 1-04

FeO, MnO ................................................. traces.

CaO....................................................... 19-71

MgO....................................................... -31

KjO ........................................................ 1-29

NajOl................. .................................... -69

Li20 ....................................................... trace.

H2 0 at 100°................................................ -22

H2 0ignition............................................... 2-80

100-14

The locality is near the boundary between the towns of Baymoud 

and Gray, and is perhaps in the latter. It adjoins the northern end of 

Little Sebago lake.

FELDSPARS FROM JONES'S FALLS, BALTIMORE, MARYLAND.

[Collected by G. H. Williams; analyzed by W. F. Hillebrand. J

A, white albitej B, flesh-colored niicrocliue; C, greenish inicrocline.

SiO2 . ........ ...............

Al20g ...... ...... ...........

PegOg.......................

FeO... ...... ............

CaO ........................

SrO.......... ...............

BaO ........................

MgO........................

K20-. ......................

Na-zO .......................

Li20-... ....................

HjOatlOO0 .. ...............

A.

63-72

t22 -26

3-58

 00

 76

8-98

 09

 43

99.88

B.

65-06

U8-41

 26

 13

 04

14-30

1-60

 04

 26

100 -10

C.

 JtfiQ ^1

16-11

 9ft

 17

 23

 05

 03

12-99

1-27

 06

 26

99.85

* Quartz not wholly separated. t Including trace of iron.
ELKINS.] % MISCELLANEOUS ANALYSES. Ill 

OTTRELITE FROM MARYLAND.

Separated by G. H. Williams from the ottrelite-phyllite rock occurring at Liberty, Frederick county.

[Analysis by L. G. Eakius.] -

SiOi................. ..................................... 23-40

Ti08 ....................................................... 1-19

Al,03 -..................................................... 39-31

FftsOa....................................................... 5-14

FeO........................................................ 21-94

MnO....................................................... trace.

CaO.......................................-...'............ trace.

MgO ...................................................... 2-18

KaO ....................................................... -20

Na.2 0 .............................'......................... -20

1I20....................................................... 6-81 

PiO& ........................................ .............. trace.

100 -37 

PIEDMONTITE FROM MARYLAND.

From rhyolite found at Pine mountain, near Monterey station.

[Kecoived from G. H. "Williams; analyzed by W. F. Hillebraud; ooiituins a little admixed quartz.]

SiOa ...................................................... 47-37

AlaOa.........:........................................... 18-55

Ce20.,..................................................... -75

Other XfAi, mol. wt. © 295 ................................ 1 -28

Y^OS ..................................................... 4-02

Mn,03 .................................................... 6-85

MnO ..................................................... 1-92

PbO ...................................................... -14

CuO...................................................... -11

CaO ...................................................... 15-82

MgO...................................................... -25

K20 ...................................................... -68

Na.2 0 ..................................................... -23

Li3 0...................................................... trace.

H2O at 100°........................................... .... -14

H30 above 100° ........................................... 1-94

PaO6 ...................................................... trace.

100 -05 

ZOISITE FROM NORTH CAROLINA.

From James's mica mine, Yancey county. Color,.rose red.

[Analyzed by L. G. Eakins. Sp. gr. 3-352, 27°.]

SiO2 ...................................................... 38-98

A13O3 ...-..-.-....-..-.................................... 31-02

Ye.2Oz......... ............................................ 4-15

MnO...................................................... -23

CaO........'.............................................. 23-80

HaO ...................................................... 2-03

100 -21
112 LABORATORY REPORT, 1891-7 92 AND 1892-'93. 

PREHNITE FROM FASSA, TYROL.

[BULL. 113.

Analyzed by E. A. Schneider in connection with the experiments 

described on p. 36, of this bulletin.

Si02 ...................................................... 43-32

A1S03 -........................J........................... 25-50

FeaOs..................................................... trace.

CaO ...................................................... 26-49

H20, 105°................................................. -17

HgO,250°-300°............................................ -14

H2O ignition.............................................. 4 -70

100 -32 

MINERALS FROM ITALIAN PEAK, GUJNNISON COUNTY, COLORADO.

Analyzed by L. G. Eakins. A, pyroxene; B, garnet; C, epidote; 

D, scolecite.

Si02 - ........... ............

A120S .... ...................

Fe203 - .............. ........

FeO--.. ........ ............

MnO. .......................

CaO

MgO.... ....................

Xa..zO.. ........ ..............

H20....... ..................

F.. .........................

Sp.gr.......................

A.

47-53

9-88

 91

25-46

14-43

 30

100 -30 

3 -312, 16° -1

B.

36-88

10-34

17-51

34-85

 43

 21

100 -22

3

.791 -170 -9

c.

37-22

24.09

12-80

 79

 11

23-36

 06

1-61

 06

100 '10 

3 '452, 17° 

D.

45-90

26-51

14.17

13-79

100 -37

o .9,17 1 70 -9

XENOTIME FROM NORTH CAROLINA.

From the gold washings at Brindletowu.

[Analyses by L. G. Eakins.]

Si02 ..................................

Zr02 ..... .............................

uo2 . ...... ............................

ThOj.. ...............................

AfcOg. ......... .'......................

Fe203 . ^ ..............................

(LaDi)203 . ............................

(YEr)203, mol. wt. 260 ................

CaO...................................

P

f\

F... ..................................

H,0 ..................................

Sp.gr ................................

Green.

3-46

1 -01

4.10

 77

 65

 93

56 '81

 21

30-31

 06

 <\7

99-85 

4 -68, 24o -2

Brown.

3 '56

9 -10

1

.70

1 -V!

9 -70

 77

55 -43

 19

9Q .70

 56

1-49

100 -06 

4 '46, 24° -4
MISCELLANEOUS ANALYSES. 113

WATER OF CALEDONIA SPRING, CALEDONIA, NEW YORK.

[Analysed by TT. "N. Stokes.j

f'n

Mg.. ....................

K .........................

Na.. .....................

ci. ......................

coa ....:. ................

SiO...... ................

Parts per 

million.

............. ' 180-3

3 "2

.............' 98-3

...... .......i 3-6

.............'. 292-0

............. 206-1

.............. 7-6

/ 1038 -8

Per cent 

total solids.

17 -36 

'J-90 

 31 

9-45 

 35 

28 *17 

19 -85 

20-88 

 73

100 -00

WATER FROM NASHVILLE, ILLINOIS.

The "American Carlsbad Spring."

[Analysis by George Steiger. In parts per million.]

SiOs. .............

en '

r*f\

ci..... ...........

Al-A-------------

Ca..... ...........

Mg.. .............

2fa...... ..........

Found.

12-40

IfiCU KO

1 142 -12

°4'44

3-00

427-14

277 -32

680 -71

4262 -31

Percent 

total 

solids.

39-76

 57

 08

10-02

6-51

15-97

300-00

Hypothetical combination.

!ST aCl .............. 40-27

Na4S04 ........... 2052 -44

MgS04 ............ !!83-78

MgCOg.. ......... 701-97

CaC03 ............ 1067.85

A1203 ....... ...... 3-60

SiO, .............. 12-40

4262. 31

Per cent 

total 

solids.

 05

 48-15

9-01

16-47

25-05

 08

 29

100 -00

WATER OF SOAP LAKE, WASHINGTON.

[Stated in parts per million. Analysis by George Steiger. J

1 

i Found.

. . j

SiO* .......... ...J 113-00

SO,,. .... ........-! 4362-40

COg. .............. 9624-59

CI ................ 3526 -20

Ca ................ trace

TSTa......... :...... 10504-11

H (bicarbonate) . . 53 -42

i 28194 -57

Per cent 

total 

solids.

.40 

15 -47 

34-13 

12-50 

trace 

 04 

37-27 

 19

100 -00

I Per cent 

Hypothetical combination, j total 

i solids.

NaC1 !

N-iSO

N CO

NaHCO

MgHjCA 

Si02 ......

....... 6452 -76

........ 66-00

1 1 9 .fln

28194 -57

20-61 

22-89 

40-22 

15-65 

 23 

 40

.100 -00

Water strongly alkaline.. Contains about four parts per million 

of sediment, containing carbonate of lime with a little sulphur and 

organic matter. A good.deal of organic matter is in the water. 

Bull. 113 S
114 LABORATORY REPORT, 1891 J92 AND 1892-793. 

WATER FROM O.TO CALIENTE, NEW MEXICO.

A thermal spring near Taos. Sp. Or., 1 -00273,18° -4.

[Analysis by W. F. Hillebraud. In parts per million.]

[BULL. 113.

Si02 ..............

so4 .. .............

T>n

rrk *

B4 07 . ...... .......

a

-

F...... '..........

Fe-A*-- ..........

Alt03 ..... ........

Ca.. ..............

Sr ................

Mg.. .............

K.. ...............

Na..... ...........

Li ................

Found:

60-2

151-0

 2

2153 -5

4-2

231-4

5-2

1-6

 5

22-8

1-4

9

.K

31-4

995'.

3-4

3071 -4

Hypothetical combination.

LiCl... ........... 20-9

KC1 .............. 5D-9

NaCl- ............ 305-5

Na^S04 ........... 223-3

CagPA-- -. - - '3

CaFj.............. 10-7

CaC03 ............ 43-0

SrC03 ............ 2-4

MgC03 ...... ...... 33-2

Si02 . :............ 60-2

 $etOt . ............ 1-6

C02 bicarb........ 775-6

3y81) -4

Per cent 

total 

solids.

 A9 I

1 -76

9-01

 16

0-59

 "ill -40 04 4J |

 01 !

.'.)»>

1-27

- -07

 118

1-78

 05

 01

 " -88

- 100 -00

* State of oxidation unknown. Fej03 all in sedinieut.

The water also contains traces of arsenic, nitrates, iodine (*?), barium, 

and ammonium. No organic matter. Titanium), bromine, manganese, 

and sulphides were looked for but not found.
INDEX.

Page.

Aluminum chloride, catalytic action of, on 

silicic.ethers............................. C3-7C

Amidosphosphoric acid, paper on ......../. 80-94

Ammonium chloride, action of, upon silicates ..................................... 34-3G

Aiiorthite,analysis of...................... 110

JJeauxite from Alabama, analysis of ....... 109

Becquerel, cited...............'....-..-..... 104

Benzyl silicate, note on...................... 79

Caledonia spring, !Ncw York, analysis of 

 water from...................... ........ iw

Catalytic action of aluminum chloride on 

silicic ethers .............................. 68-7U

Chloritt'S and micns,.oxperiments upon constitution of .............................. 27-03

Chlorite group, theories of ................. 11-21

Clarke, F. W., papers by ................... 11,12

' Clarke, If. W., and E. A. Schiieider, papers 

by......................................... 27,31

Daubree, A., cited.......................... GO

Doeller,C.,cited ........................... 49

Eakins, L. G., papers and analyses by...... 01,

109,111,112 

Epidote, analysis of........................ 112

Fenling, cited.............................. 80

Feldspars, analyses of...................... 110

Fricdel and Crafts, cited ................... 78

Garnet, analysis of......................... 112

Gerliardt, cited............................. 81

Gladstone, cited............................ 81

Graham, cited.............................. 95,99

.Haworth, E.. cited.......................... 53

Hidden, W.E., cited........................ 44

Hillebraud, W. 1\, papers and analyses by. 37,

41,44,49, 109,110, 111, 114

Holmes, cited .............................. 81

Hydrosol of silver, preparation of......... 99-101

Josephinite, a now uiekel-iron, paper on.... 54-60

Ladenburg, cited........................... 80

Litbia micas, constitution of............... 22-26

Loach, A., acknowledgments to ............ 27

Mackintoshite, composition of ............. 44-48

Melville, W. H., papers by................. 54-110

Meteorite from Hamblen county. Tenn..... 61-62

Meteorite from Mount Joy, Pa., analyses of. 109 

Micas and chlorites, experiments upon the 

constitution of........................... 27- 33

Mount Joy, Pa., analysis of meteorite from. 109 

.Nickel-iron sulphide from Canada, analysis

of........................................ L09

O.jo Caliente, New Mexico, analysis of water

from ..................................... 114

Orgauosols, paper on........................ 95-98

Ottrelito, analysis of ..........*............. Ill

Phosphorus oxychloi idc, action of, 011 aromatic silicic ethers....................... 77-78

Piedmont ite, analysis of ................... Ill

Prehnite, analysis of....................... 112

Pyroxene, analysis (if...................... 1.12

Kowlaudite. composition of................. 44-48

Saflbrd, J.M., meteoric iron furnished for

analysis by .............................. 61

Schiff,'cited ................................ 80

Schiieider, E. A., papers and analyses by... 95,

102,112 

Seolecite, analysis of....................... 112

Schiieider, E. A., and F. W. Clarke, papers

by ....................................... 27,34

Silicates, action of ammonium chloride

upon.................................... 34-30

Silicic ethers, catalytic action of aluminum

chloride on .............................. 63-76

Silicic ethers.'action of phosphorus oxychloride on............................... 77,78

Silver, colloidal, paper OH ............... 102-108

Silver, hydrosol of ........................ 99-10.1

Soap lake, Washington, analysis of water of 113 

Steiger, George, analyses by................ 113

Stokes. H. N., papers and analyses by...... 63.77,

79, 80,113 

Thorium and uranium dioxido, isomorphism

of........................................ 41-43

Tschermak's theory of the chlorite group

and its alternative....................... U-21

Uranium dioxide, pieparation and specific

gravity of................................ 37, 40

Uranium dioxide, isomorphism of.......... 41-43

TJrlaub, cited............................... 37

Water, analyses of........................113,114

Xenotime, analyses of...................... 112

Zimniermann. cited ........................ 39

Zinc-bearing spring waters from Missouri,

paper on................................. 49-53

Zoisite, analysis of......................... Ill

115