Joseph William Mellor.

A comprehensive treatise on inorganic and theoretical chemistry (Volume 2) online

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hydrogen fluoride and sulphur fluoride. Each bubble of sulphur dioxide led into
a jar of fluorine produces an explosion and thionyl fluoride, SOF 2 , is formed ; but
if the fluorine be led into the sulphur dioxide, there is no action until the sulphur
dioxide has reached a certain partial pressure when all explodes. If the fluorine
be led into an atm. of sulphur dioxide at the temp, of the reaction, sulphuryl fluoride,
S0 2 F 2 , is formed quietly without violence. Sulphuric acid is scarcely affected by
fluorine.

Fluorine does not unite with chlorine at ordinary temp. 0. Ruff and J. Zedner
also obtained no result by heating fluorine and chlorine at the temp, of the electric



12 INORGANIC AND THEORETICAL CHEMISTRY

arc. Liquid chlorine dissolves fluorine, but the dissolved gas escapes as the chlorine
freezes. It is inferred that the gases do not react at the low temp. 80 when fluorine
is dissolved in liquid chlorine because (i) the gases evolved when the soln. is fraction-
ally distilled showed no signs of an abrupt change in composition between 97 '32
per cent, of fluorine at the beginning and 0'63 per cent, at the end of the operation ;
(ii) on cooling a soln. of fluorine in liquid chlorine, there is a tumultuous evolution
of gas when the mixture freezes the solid is chlorine, the gas fluorine. Bromine
unites with fluorine at ordinary temp, with a luminous flame forming bromine
trifluoride, BrF 3 . Similar remarks apply to iodine, where the pentafluoride, IF 5 ,
is formed. The heat of the former reaction is small, the latter great. Liquid
fluorine, however, does not react with or dissolve bromine or iodine at 187, nor
does it liberate iodine from potassium iodide. In the presence of water, chlorine
reacts with fluorine forming hypochlorous acid ; and bromine, hypobromous acid ;
some chloric or bromic acid may also be formed, and part of the water is also decom-
posed by the excess of fluorine. If fluorine be passed into a 50 per cent. soln. of
hydrofluoric acid, there is an energetic reaction accompanied by a flame in the
midst of the liquid. The reaction of fluorine with gaseous or aq. soln. of hydrogen
chloride, bromide, or iodide, is accompanied by flame. Most of the haloids of the
metalloids are attacked with great energy by fluorine at ordinary temp.

Fluorine does not unite with argon even if a mixture of the two gases be heated
or sparked. Neither nitrogen or nitrous oxide, N 2 0, nor nitrogen peroxide, N0 2 ,
is attacked by fluorine at ordinary temp. 0. Ruff and J. Zedner also found no
reaction occurred at the temp, of the electric arc between fluorine and nitrogen.
Even at a dull red heat nitrous oxide remains unattacked by fluorine, but by
sparking a mixture of fluorine and nitrous oxide, a mixture of nitrous oxide, nitrogen,
and oxygen is formed, but no nitrogen oxyfluoride. 13 A little nitric oxide, NO,
unites with fluorine at ordinary temp. ; the reaction is attended by a pale yellow
flame, and a volatile oxyfluoride is formed ; but if the nitric oxide be in large
excess, it is simply broken down into nitrogen and oxygen, and the excess of nitric
oxide forms nitrogen peroxide. According to H. Moissan and P. Lebeau, if the
fluorine be in excess, at the temp, of liquid oxygen, a white solid is formed which,
as the temp, rises, changes into a colourless liquid, boiling above 80, and
which furnishes on fractionation nitroxyl or nitryl fluoride, N0 2 F. Fluorine
decomposes ammonia with inflammation ; and a mixture of the two gases explodes.
Phosphorus inflames in fluorine gas forming the pentafluoride, PF 5 , if the fluorine
be in excess ; and the trifluoride, PF 3 , if the phosphorus be in excess. Arsenic
forms the trifluoride, AsF 3 , with inflammation. Similarly with antimony ; but
bismuth is only superficially attacked. Both phosphorus and arsenic react with
incandescence with liquid fluorine, but antimony remains unaltered. Phosphorus
pentoxide, P 2 05, is decomposed at a red heat forming the fluoride and oxyfluoride ;
phosphorus tri- and penta-chloride are attacked with the production of flame ;
neither phosphorus pentafluoride nor phosphorus oxyfluoride is attacked. Arsenic
trioxide and arsenic trichloride are attacked. Arsenic trifluoride, AsF 3 , absorbs
fluorine, and the heat generated during the absorption led H. Moissan to suggest
that some unstable arsenic pentafluoride is formed.

Both boron and silicon unite with fluorine gas energetically and with incandes-
cence, forming in the one case boron trifluoride, BF 3 , and in the other, silicon totra-
fluoride, SiF 4 . Boric oxide and silica react energetically in the cold. Boron
trichloride, BC1 3 , at ordinary temp., and silicon tetrachloride, SiCl 4 , above 40,
both react with fluorine. Dry fluorine does not attack glass, for H. Moissan kept
dry fluorine in glass vessels for two hours at 100, without appreciable attack.
Hydrogen fluoride behaves similarly. The slightest trace of moisture is sufficient
to activate either gas. Dry lampblack becomes incandescent in fluorine ; wood
charcoal fires spontaneously; the vigour of the reaction is reduced at low temp.,
for horon, silicon, and carbon are not attacked by liquid fluorine. If powdered
charcoal or soot I.e. allowed to fall into a vessel containing liquid fluorine, the particles



THE HALOGENS 13

become incandescent as they drop through the vapour, but the glow is quenched
when the particles reach the liquid. The denser forms of carbon require a teni|>. of
50 to 100 before they become incandescent ; retort carbon requires a red heat ;
and the diamond is not affected at that temp. Soft charcoal is quickly ignited in
contact with the gas. The product of the reaction is usually a mixture of different
carbon fluorides, but if the temp, of the reaction be kept low, carbon tetrafluoride
alone is formed. H. Moissan 14 also found that fluorine acts on calcium carbide at
ordinary temp, giving calcium fluoride and carbon tetrafluoride. Carbon monoxide
and dioxide are not attacked in the cold ; carbon disulphide, CS 2 , inflames forming
carbon and sulphur fluorides ; carbon tetrachloride, CC1 4 , reacts at temp, exceeding
30 forming chlorine and carbon tetrafluoride ; cyanogen is decomposed at ordinary
temp, with the production of a white flame. According to W. L. Argo and co-
workers, the unlighted gas issuing from a Bunsen's burner is immediately ignited
by fluorine. According to B. Humiston, acetone in an open vessel takes fire ;
Chloroform forms chlorine, phosgene, and carbon fluorides. With phosgene, a
compound which appears to be carbonyl fluoride, COF 2 , was formed. The action
of fluorine on ethylene tetrachloride, C 2 C1 4 , is symbolized : C 2 Cl 4 -f2F 2 =C 2 F 4 -j-2Cl 2 ,
followed by C1 2 +C 2 C1 4 =C 2 C1 6 , and C 2 F 4 =CF 4 +C.

The metals are in general attacked by fluorine at ordinary temp. ; many of them
become coated with a layer of fluoride which protects them from further action.
These remarks apply to the metals : aluminium, bismuth, chromium, copper, gold,
iridium, iron, manganese, palladium, platinum, ruthenium, silver, tin, zinc. The
formation of a protective skin of fluoride renders it possible to prepare fluorine in
copper and platinum vessels at ordinary temp. Lead is slowly converted into the
white fluoride at ordinary temp. If the temp, be raised, nearly all the metals are
vigorously attacked with incandescence for example, with tin and zinc, the
ignition temp, is about 100, and iron and silver, at about 500. Gold and platinum
are slowly converted into their fluorides at about 500 or 600. The metals of the
alkalies and alkaline earths, thallium, and magnesium are converted with incandes-
cence into their fluorides. Many of the metals which in bulk are only attacked
slowly, are rapidly converted into fluorides if they are in a finely divided condition.
Thus fluorine forms a volatile fluoride with powdered molybdenum in the cold,
but a lump of the metal is not attacked ; tungsten is attacked at ordinary temp.,
and also forms a volatile fluoride ; electrolytic uranium, in fine powder, is vigorously
attacked and burns, forming a green volatile hexafluoride. If niobium (columbium)
or tantalum be warmed, the pentafluorides are formed. Liquid fluorine has no
action on many of the metals e.g. iron. If mercury be quite still, a protecting
layer of fluoride is formed, but if the metal be agitated with the gas, it is rapidly
converted into the fluoride.

The chlorides, bromides, iodides, and cyanides are generally vigorously attacked
by fluorine in the cold ; sulphides, nitrides, and phosphides are attacked in the cold
or may be when warmed a little ; the oxides of the alkalies and alkaline earths are
vigorously attacked with incandescence ; the other oxides usually require to be
warmed. The sulphates usually require warming ; the nitrates generally resist
attack even when warmed. The phosphates are more easily attacked than the
sulphates. The carbonates of sodium, lithium, calcium, and lead are decomposed
at ordinary temp, with incandescence, but potassium carbonate is not decomposed
even at a dull red heat. Fluorine does not act on sodium borate. Most of these
reactions have been qualitatively studied by H. Moissan, 15 and described in his
monograph, Lefluor et ses composes (Paris, 1900).

Atomic and molecular weight of fluorine. The combining weight of fluorine
has been established by converting calcium fluoride, potassium fluoride, sodium
fluoride, etc., into the corresponding sulphates. In illustration, J. B. A. Dumas
(1860) found that one gram of pure potassium fluoride furnishes T4991 gram of
potassium sulphate. Given the combining weights of potassium 39' 1, sulphur
32 -07, oxygen 16, it follows that if x denotes the combining weight of fluorine with



14 INORGANIC AND THEORETICAL CHEMISTRY

39'1 grams of potassium, 1 : 1*4991=2KF : K 2 S0 4 =2(39*l+z) : 174*27 ; or,
z=19.

H. Davy 16 made the first attempt in this direction in 1814 by converting fluorspar
into the corresponding sulphate. His result corresponds with an at. wt. 18*81.
J. J. Berzelius (1826) also employed a similar process and obtained first the value
19*16 and later 18*85. P. Louyet, in 1849, employed the same process, taking care
that the particles of fluorspar did not escape the action of the sulphuric acid by the
formation of a protective coating of sulphate. P. Louyet obtained 18' 99 with
native fluorspar, and 19*03 with an artificial calcium fluoride. In 1860, J. B. A. Dm HUB
obtained the value 18*95 with calcium fluoride ; S. de Luca (1860), 18*97 ; H. Mois.sun
(1890), 19*011. P. Louyet, J. B. A. Dumas, and H. Moissan also converted sodium
fluoride into sodium sulphate and obtained respectively the values 19*06, 19 '08,
and 19*07. P. Louyet and H. Moissan in addition converted barium fluoride into
the sulphate and obtained respectively 19*01 and 19*02 ; and P. Louyet's value,
19*14, was obtained with lead fluoride. 0. T. Christensen (1886) treated ammonium
manganese fluoride, (NH 4 ) 2 MnF 5 , with a mixture of potassium iodide and hydro-
chloric acid one mol. of the salt gives a gram-atom of iodine. The liberated iodine
was titrated with sodium thiosulphate. The value 19*038 was obtained. J. Meyer
(1903) converted calcium oxide into fluoride and obtained 19*035. D. J. McAdani
and E. F. Smith (1912) obtained 19*015 by transforming sodium fluoride into the
chloride. E. F. Smith and W. K. van Haagen obtained 19'005 by converting
anhydrous borax into sodium fluoride. E. Moles and T. Batuecas estimated the
at. wt. of fluorine from the density of methyl fluoride, and found 18*998 0'005
when the at. wt. of carbon is 12*000, and of hydrogen, 1/0077. The best
determinations range between 18*97 and 19*14, and the best representative value
of the combining weight of fluorine is taken to be 19. No known volatile com-
pound of fluorine contains less than 19 parts of fluorine per molecule, and
accordingly this same number is taken to represent the at. wt. The vapour
density of fluorine, determined by H. Moissan, is 1*31 (air=l), that is, 28*755
Xl*31=37*7(H 2 =2). The molecule of fluorine is therefore represented by F 2 .

Fluorine is assumed to be univalent since it forms fluorides like KF, NaF, etc.
with univalent elements and radicles ; CaF 2 , BaF 2 , etc., with bivalent radicles, etc.
As indicated in connection with hydrogen fluoride, etc., there is, however, the great
probability that fluorine also exhibits a higher valency in the more complex com-
pounds like KF.HF, AlF 3 .3NaF, etc. 17 This also agrees with J. Thomson's observa-
tions on the heat of the reaction between the acid and silica.

REFERENCES.

- 1 H. Moissan, Compt. Rend., 109. 861, 1889 ; 138. 728, 1904 ; B. Brauner, Zeit. anorg. Chem.,
7. 1, 1894 ; J. Sperber, ib., 14. 104, 374, 1897.

2 H. Moissan and J. Dewar, Compt. Rend., 124. 1202, 1897 ; 125. 505, 1897 ; 136. 785, 1903.

8 J. Sperber, Zeit. anorg. Chem., 14. 164, 1897.

4 J. H. Gladstone, Phil. Trans., 160. 26, 1870 ; Amer. Journ. Science, (3), 29. 57, 1885 ;
G. Gladstone, Phil. Mag., (5), 20. 483, 1885 ; J. H. and G. Gladstone, ib., (5), 31. 9, 1891 ;
F. Swarts, Bull. Acad. Belgique, (3), 34. 293, 1897 ; Mem. Cour. Acad. Belgique, 61. 1901 ;
C. Cuthbertson and E. B. R. Prideaux, Phil. Tran*., 205. A. 319, 1905.

6 H. Moissan, Compt. Rend., 109. 937, 1889 ; 0. de Wattcville, ib., 142. 1078, 1906 ; G. Salet,
Ann. Chim. Phys., (4), 28. 34, 1873.

6 P. Pascal, Compt. Rend., 152. 1010, 1911 ; Bull. Soc. Chim., (4), 9. 6, 1911.

7 W. Abegg and C. E. Immerwahr, Zeit. phys. Chem., 32. 142, 1900.

8 F. Kohlrausch, Wied.. Ann., 66. 785, 1898.

9 F. W. Skirrow, Zeit. anorg. Chem., 33. 25, 1903 ; M. G. Levi, Chem. Ztg., 30. 4508, 1906 ;
M. G. Levi and F. Ageno, Atti Accad. Lincei, (5), 15. ii, 549, 615, 1907.

10 H. Moissan and J. Dewar, Compt. Rend., 124. 1202, 1894 ; 136. 641, 785, 1903.

11 0. Ruff and J. Zedner, Ber., 42. 1037, 1909 ; G. Gallo, Atti Accad. Lincei, (5), 19. i, 295,
753, 1910.

12 H. Moissan and P. Lebeau, Ann. Chim. Phy., (7), 26. 5, 1902.
18 H. Moissan and P. Lebeau, Compt. Rend., 140. 1573, 1905.

14 H. Moissan, Le Jour electrique, Paris, 1897 ; London, 1904 ; Compt. Rend., 110. 276, 1890 ;



THE HALOGENS 15

B. Humiston, Journ. Phys. Chem., 23. 572, 1919; W. L. Argo, F. C. Mather?, B. Humiston, and

C. 0. Anderson, ib., 23. 348, 1919.

15 H. Moisaan, Ann. Chim. Phys., (6), 24. 224, 1891.

16 H. Davy, Phil Trans., 104. 64, 1814 ; J. J. Berzclius, Pogg. Ann., 8. 1, 1826 ; Ann. Chim.
Phys., (2), 27. 53, 167, 287, 1824 ; P. Louyet, ib., (3), 25. 291, 1849 ; E. Fremy, ib., (3), 47. 15,
1850 ; J. B. A. Dumas, ib., (3), 55. 129, 1859 ; S. de Luca, Compt. Rend., 51. 299, 1860 ; H. Moissan,
ib., 111. 570, 1890 ; O. T. Christenseri, Journ. prakt. Chem., (2), 34. 41, 1886 ; (2), 35. 541, 1887 ;
J. Meyer, Zeit. anorg. Chem., 36. 313, 1903 ; D. J. McAdam and E. F. Smith, Jouni. Amer. Chem.
Soc., 34. 592, 1912 ; E. Moles and T. Batuecas, Journ. Chim. Phys., 17. 537, 1919; E. F. Smith
and. W. K. van Haagen, The Atomic Weights of Boron and Fluorine, Washington, 1918.

17 C. W. Blomstrand, Die Chemie der Jetztzeit, Heidelberg, 210, 340, 1869 ; J. Thomson,
Wied. Ann., 138. 201, 1869 ; 139. 217, 1870 ; Ber., 3. 583, 1870. .



5. The Occurrence of Chlorine, Bromine, and Iodine

Chlorine. Chlorine does not occur free in nature, but hydrogen chloride has been
reported in the fumes from the fumeroles of volcanic districts, 1 Vesuvius, Hecla,
etc. D. Franco reported that the gases given off by the flowing lava of Vesuvius,
during solidification, contained much hydrogen chloride, and the same gas has been
found as an inclusion in minerals. Hydrogen chloride is also found in the springs
and rivers of volcanic districts e.g. the Devil's Inkpot (Yellowstone National Park),
Paramo de Ruiz (Colombia), Brook Sungi Pait (Java), the Rio Vinagre (Mexico),
etc. The latter is said to contain 0*091 per cent, of free hydrochloric acid which
is estimated to be eq. to 42,150 kgrms. of HC1 per diem. 2 J. B. J. D. Boussingault
supposes this acid to be derived from the decomposition of sodium chloride by steam.

Combined chlorine is an essential constituent of many minerals there are sal ammoniac
(ammonium chloride) ; sylvine (potassium chloride) ; halite (sodium chloride) ; chlorocalcite,
CaCl 2 ; cerargyrite or horn silver, AgCl ; calomel, HgCl ; terlinguaite, Hg 2 OCl ; eglestonite,
Hg 4 Cl 2 O ; molysite, FeCl 3 ; erythrosiderite, 2KCl.FeCl 3 .H 2 O ; rinneite, 3KCl.NaCl.FeCl 3 ;
kremersite, 2KC1.2NH 4 C1.2FeCl 3 .3H 2 O ; lawrencite, FeCl 2 ; douglasite, 2KCl.FeCl 2 .2H 2 O ;
sccechite, MnCl 2 ; cotunnite, PbCl 2 ; matlockite, PbCl 2 .PbO ; penfieldite, 2PbCl 2 .PbO ;
mendipite, PbCl 2 .2PbO ; laurionite, PbCl 2 .Pb(OH) 2 ; fiedlerite, 2PbCl 2 .Pb(OH) 2 ; rafaelite
or paralaurionite, PbCl(OH) ; nantokite, CuCl ; melanothallite, CuCl,.CuO.H 2 O ; hydro-
melanothallite, CuCl 2 .CuO.2H 2 O ; atacamite, Cu 2 Cl(OH) 3 ; percylite, PbCuCl(OH) 2 ; boleite,
3PbCuCl 2 (OH) 2 .AgCl ; foote'ite, CuCl 2 .8Cu(OH) 2 .4H 2 O ; tallingite, CuCl 2 .4Cu(OH) 2 .4H 2 O ;
atelite, CuCl 2 .2Cu(OH) 2 .H 2 O : cumenge'ite, 4PbCl 2 .4CuO.5H 2 O ; pseudobolite, 5PbCl 2 .4CuO.
6H 2 O ; phosgenite, Pb 2 Cl 2 CO 3 ; daubre'Ue, BiCl 3 .2Bi 2 O 3 .3H 2 O ; and in some Stassfurt
minerals, carnallite, KCl.MgCl 2 .6H 2 O ; bischofite, MgCl 2 .6H 2 O ; tachhydrite, CaCl 2 .2MgCl 2 .
12H 2 O ; boracite, MgCl 2 .2Mg 3 B 8 O 15 ; etc. Chlorine also occurs in mineral phosphates
e.g. it partially replaces fluorine in the chloroapatites pyromorphite, (PbCl)Pb 4 (PO 4 ) 3 ;
mimctite, (PbCl)Pb 4 (AsO 4 ) 3 ; and vanadinite, (PbCl)Pb 4 (VO 4 ) 3 . It occurs in pyrosmalite,
H 5 (Fe,Mn) 4 Si 4 O 16 Cl ; sodalite, Na 4 Al 3 Si & O 12 Cl, and other silicate minerals.

Chlorides occur in sea, river, and spring water, and small quantities in rain water.
The ashes of plants and animals contain some chlorides. The gastric juices of animals
contain chlorides as well as free hydrochloric acid. The 0'2 to 0'4 per cent, of free
hydrochloric acid in the gastric juices of man is thought to play an important role
in the digestion of food. 3 Sodium chloride occurs in blood and in urine ; flesh
contains potassium chloride ; while milk contains both of the alkaline chlorides,
with potassium chloride in large excess. According to R. Wanach, 4 blood contains
0*259 per cent, of chlorine, and serum, 0'353 per cent. ; and according to
A. J. Carlson, J. R. Greer, and A. B. Luckhardt, there is still more chlorine in lymph.
T. Gassmann found human teeth to contain 0*25 to 0*41 per cent, of combined
chlorine, and the teeth of animals rather less.

Bromine. J. H. L. Vogt 5 estimates that bromine occupies about the 25th
place in the list of elements arranged in the relative order of their abundance ; and
that the total crust of the earth has about 0*001 per cent, of bromine the solid
portion 0*00001 per cent. The ratio of bromine to chlorine is about the same in
sea water and in the solid crust, and amounts to 1 : 150. The ratio of chlorides to



14 INORGANIC AND THEORETICAL CHEMISTRY

39-1 grains of potassium, 1 : T4991=2KF : K 2 S0 4 =2(39'l-f2*) : 174*27 ; or,
z=19.

H. Davy 16 made the first attempt in this directionin 1814 by converting fluorspar
into the corresponding sulphate. His result corresponds with an at. wt. IS'tfl.
J. J. Berzelius (1826) also employed a similar process and obtained first the value
19' 16 and later 18'85. P. Louyet, in 1849, employed the same process, taking care
that the particles of fluorspar did not escape the action of the sulphuric acid by the
formation of a protective coating of sulphate. P. Louyet obtained 18' 99 with
native fluorspar, and 19*03 with an artificial calcium fluoride. In 1860, J. B. A. Dumas
obtained the value 18'95 with calcium fluoride ; S. de Luca (1860), 18'97 ; H. Mois.su n
(1890), 19'011. P. Louyet, J. B. A. Dumas, and H. Moissan also converted sodium
fluoride into sodium sulphate and obtained respectively the values 19'06, 19 '08,
and 19'07. P. Louyet and H. Moissan in addition converted barium fluoride into
the sulphate and obtained respectively 19 '01 and 19'02 ; and P. Louyet's value,
19*14:, was obtained with lead fluoride. 0. T. Christensen (1886) treated ammonium
manganese fluoride, (NH 4 ) 2 MnF 5 , with a mixture of potassium iodide and hydro-
chloric acid one mol. of the salt gives a gram-atom of iodine. The liberated iodine
was titrated with sodium thiosulphate. The value 19'038 was obtained. J. Meyer
(1903) converted calcium oxide into fluoride and obtained 19'035. D. J. McAdatn
and E. F. Smith (1912) obtained 19*015 by transforming sodium fluoride into the
chloride. E. F. Smith and W. K. van Haagen obtained 19*005 by converting
anhydrous borax into sodium fluoride. E. Moles and T. Batuecas estimated the
at. wt. of fluorine from the density of methyl fluoride, and found 18*998 0'005
when the at. wt. of carbon is 12*000, and of hydrogen, 1'0077. The best
determinations range between 18*97 and 19*14, and the best representative value
of the combining weight of fluorine is taken to be 19. No known volatile com-
pound of fluorine contains less than 19 parts of fluorine per molecule, and
accordingly this same number is taken to represent the at. wt. The vapour
density of fluorine, determined by H. Moissan, is 1*31 (air=l), that is, 28*755
Xl*31=37*7(H 2 =2). The molecule of fluorine is therefore represented by F 2 .

Fluorine is assumed to be univalent since it forms fluorides like KF, NaF, etc.
with univalent elements and radicles ; CaF 2 , BaF 2 , etc., with bivalent radicles, etc.
As indicated in connection with hydrogen fluoride, etc., there is, however, the great
probability that fluorine also exhibits a higher valency in the more complex com-
pounds like KF.HF, AlF 3 .3NaF, etc. 17 This also agrees with J. Thomson's observa-
tions on the heat of the reaction between the acid and silica.

REFERENCES.

- 1 H. Moissan, Compt. Rend., 109. 861, 1889 ; 138. 728, 1904 ; 13. Brauner, Zeit. anorg. Ch< m. t
7. 1, 1894 ; J. Sperber, ib., 14. 104, 374, 1897.

2 H. Moissan and J. Dewar, Compt. Rend., 124. 1202, 1897 ; 125. 505, 1897 ; 136. 785, 1903.

3 J. Sperber, Zeit. anorg. Chem., 14. 164, 1897.

4 J. H. Gladstone, Phil. Tram., 160. 26, 1870 ; Amer. Journ. Science, (3), 29. 57, 1885 ;
G. Gladstone, Phil. Mag., (5), 20. 483, 1885; J. H. and G. Gladstone, ib., (5), 31. 9, 1891 ;
F. Swarts, Hull Acad. Belgique, (3), 34. 293, 1897 ; Mem. Cow. Acad. Bdgiquc, 61. 1901 ;
C. Cuthbertson and E. B. R. Prideaux, Phil. Tram., 205. A. 319, 1905.

6 H. Moissan, Compt. Rend., 109. 937, 1889 ; C. do Wattcville, ib., 142. 1078, 1906 ; G. Salet,
Ann. Chim. Phys., (4), 28. 34, 1873.

6 P. Pascal, Compt. Rend., 152. 1010, 1911 ; Bull. Soc. Chim., (4), 9. 6, 1911.

7 W. Abegg and C. E. Immerwahr, Zeit. phys. Chem., 32. 142, 1900.

8 F. Kohlrausch, Wied. Ann., 66. 785, 1898.

F. W. Skirrow, Zeit. anorg. Chem., 33. 25, 1903 ; M. G. Levi, Chem. Ztg., 30. 4508, 1906;
M. G. Levi and F. Ageno, Atti Accad. Lincei, (5), 15. ii, 549, 615, 1907.

10 H. Moissan and J. Dewar, Compt. Rend., 124. 1202, 1894 ; 136. 641, 785, 1903.

11 O. Ruff and J. Zedner, Ber., 42. 1037, 1909 ; G. Gallo, Atti Accad. Lincei, (5), 19. i, 295,
753, 1910.

12 H. Moissan and P. Lebeau, Ann. Chim. Phi/*., (7), 26. 5, 1902.
18 H. Moissan and P. Lebeau, Compt. Rend., 140. 1573, 1905.

14 H. Moissan, Le Jour electrique, Paris, 1897 ; London, 1904 ; Compt. Rend., 110. 276, 1890 ;



THE HALOGENS 15

B. Humiston, Journ. Phys. Chem., 23. 572, 1919; W. L. Argo, F. C. Mathers, B. Humiston, and

C. 0. Anderson, ib., 23. 348, 1919.

16 H. Moissan, Ann. Chim. Phys., (0), 24. 224, 1891.

16 H. Davy, Phil. Tram., 104. 64, 1814 ; J. J. Berzelius, Pogg. Ann., 8. 1, 1826 ; Ann. Chim.
Phys., (2), 27. 53, 167, 287, 1824 ; P. Louyet, ib., (3), 25. 291, 1849 ; E. Fremy, ib., (3), 47. 15,
1850 ; J. B. A. Dumas, ib., (3), 55. 129, 1859 ; S. de Luca, Compt. Rend., 51. 299, 1860 ; H. Moissan,
ib., 111. 570, 1890 ; 0. T. Christensen, Journ. prakt. Chem., (2), 34. 41, 1886 ; (2), 35. 541, 1887 ;
J. Meyer, Zeit. anorg. Chem., 36. 313, 1903 ; D. J. McAdara and E. F. Smith, Jour.i. Amer. Chem.
tioc., 34. 592, 1912 ; E. Moles and T. Batuecas, Journ. Chim. Phys., 17. 537, 1919; E. F. Smith
and W. K. van Haagen, The Atomic Weights of Boron and Fluorine, Washington, 1918.

17 C. W. Blomstrand, Die Chemie der Jetztzeit, Heidelberg, 210, 340, 1869 ; J. Thomsen,
Wicd. Ann., 138. 201, 1869 ; 139. 217, 1870 ; Ber., 3. 583, 1870.



5. The Occurrence of Chlorine, Bromine, and Iodine

Chlorine. Chlorine does not occur free in nature, but hydrogen chloride has been
reported in the fumes from the fumeroles of volcanic districts, 1 Vesuvius, Hecla,



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