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hydrochloric acid, so that the acid should be sat. with chlorine before the attempt is made
to measure the gaseous products of electrolysis. The vessel containing the acid is arranged
so that the acid about one electrode is connected with the acid about the other electrode by
a glass tube junction, 25 and an electric current is passed until the liquid in the chlorine
limb is sat. with chlorine. The two gas receivers are put into communication with the
electrolytic vessel by suitably turning the three-way stopcocks. The gas receivers have,
of course, been previously filled with liquid a sat. soln. of sodium chloride by placing a
dish of the liquid below each receiver and applying suction at the proper exit tube when
the three-way cocks are suitably turned. The gases collect in the tubes at equal rates.
The experiment shows that during the electrolysis of concentrated hydrochloric acid, the
volume of hydrogen liberated at the one electrode is equal to the volume of chlorine liberated
at the other electrode. Assuming that the hydrogen chloride dissolved in the water is
alone decomposed by the electric current, it follows that hydrogen chloride contains equal
volumes of hydrogen and of chlorine, and therefore also an equal number of atoms ; or
the formula is H X C1 X , where x is evaluated as before from the vapour density 36*5. This
demonstration of the composition of hydrogen chloride, though interesting as circumstantial
evidence, is not a proof unless supported by accessory evidence. A similar demonstration
applied to the analogous hydrofluoric acid would " prove " that hydrogen fluoride is a
compound of hydrogen and 'oxygen.

3. The synthesis of hydrogen chloride. The mixed gases obtained by the electrolysis
of cone, hydrochloric acid are passed through a stout glass explosion tube with a stopcock
at each end. The tower is packed with lime and glass wool to absorb the chlorine. Instead
of the tower, the exit tube may lead to the fume closet. When all the air is displaced, the
stopcocks are closed. One of the stopcocks may be opened while the corresponding end of
the tube is dipping under cone, sulphuric acid ; no gas enters or leaves the apparatus.
The tube and contents are exposed to sunlight or to the light from burning magnesium.
The face must be protected in case the tube should burst during the explosion. When the
tube is cold, open one of the stopcocks while the corresponding end is dipping under cone,
sulphuric acid ; no gas enters or leaves the tube. This shows that no change in volume
has taken place as a result of the explosion. It can be proved that the tube contains
nothing but hydrogen chloride by opening the tip of the tube under water. The hydrogen
chloride will be absorbed and water will rise and fill the tube except for a little air (or
perhaps a slight excess of hydrogen) which might have been present. This experiment
shows that one volume of hydrogen unites with one volume of chlorine to form two volumes
of hydrogen chloride.

Hydrogen chloride contains the eq. of half its volume of chlorine and half its
volume of hydrogen, or, by Avogadro's hypothesis, assuming the hydrogen and
chlorine each contain two atoms, one molecule of hydrogen chloride contains half
a molecule of chlorine, that is, one molecule of hydrogen chloride contains an atom
of chlorine and an atom of hydrogen. The formula is therefore HC1. This agrees
with the vapour density determination of hydrogen chloride which furnishes 36 '4 9
(H 2 =2). If the at. wt. of chlorine be 35'46, and of hydrogen T008 (0=16), it
follows that the formula for hydrogen chloride is HC1.

The detection and determination of the chlorides, bromides, and iodides.- A
soln. of silver nitrate produces a very sparingly soluble precipitate of silver chloride,
bromide, or iodide when added to a neutral or acid soln. of the corresponding acid
or salt. Silver chloride and bromide are white, silver iodide is pale yellow. The
precipitates are all virtually insoluble in dil. nitric acid, and in a soln. of potassium
cyanide or sodium thiosulphate. Silver chloride is easily soluble in aq. ammonia,
silver bromide is less soluble, and the iodide is but sparingly soluble. Ammonium
carbonate (sesqui- or bicarbonate) dissolves silver chloride fairly easily, but not
the bromide or iodide. Silver nitrate does not precipitate all the chlorine from
soln. of mercuric chloride unless a large excess of the nitrate is used. Stannous
chloride also reduces some of the silver to the metallic state ; the precipitate with
platinic chloride is yellow owing to the presence of some platinum. Green chromic
chloride also gives no precipitate with silver nitrate. Mercurous nitrate gives
white precipitate of mercurous chloride, a pale yellow precipitate of niercurous
bromide, and a yellowish-green precipitate of mercurous iodide respectively wrt!
neutral or acid soln. of chlorides,, bromides, or iodides. Soln. of lead acetate o
nitrate give crystalline precipitates in cold cone. soln. of the halides-
VOL. n.



210 INORGANIC AND THEORETICAL CHEMISTRY

and bromide are white and the iodide is yellow. The precipitates are fairly soluble
in hot water. Thallous sulphate, T1 2 S0 4 , gives a white precipitate in cone. soln.
of the chlorides, or bromides, and a deep yellow precipitate with iodides. Palladium
chloride, PdCl 2 , has no action on soln. of chlorides or bromides, but palladium
nitrate, Pd(N0 3 ) 2 , gives a brown precipitate, PdBr 2 , with bromides, but not with
chlorides ; both palladium salts give a very dark brown precipitate, PdI 2 , with
iodides. Mercuric chloride in excess gives no precipitate with chlorides or bromides,
but with iodides a scarlet precipitate, HgI 2 , is obtained. This precipitate is soluble
if the potassium iodide be in excess. Iodides alone are decomposed by ferric sulphate
with the liberation of the free halogen. A mixture of copper sulphate and sulphurous
acid added in excess to a cone. soln. of a chloride, bromide, or iodide, gives a pre-
cipitate of the corresponding cuprous chloride, CuCl, or bromide, CuBr, or iodide,
Cul. Stannous chloride can be used instead of sulphurous acid. A soln. of cuprous
chloride in an excess of ammonium chloride gives a white precipitate of cuprous
iodide, Cul. Dil. sulphuric acid (1 : 10) has no action on chlorides cold or hot ; it
has no action on cold soln. of the bromides or iodides, but gives off hydrogen bromide
or iodide respectively when heated. Cone, sulphuric acid partially decomposes
solid chlorides in the cold and completely when heated. Hydrogen chloride is
evolved. Silver and mercurous chlorides are decomposed with difficulty, the latter
gives off some sulphur dioxide as well as hydrogen chloride : 2HgCl-J-3H 2 S0 4
=2HgS0 4 -{-2H 2 0-|-S0 2 -|-2HCl. Bromides under similar conditions give both
bromine and hydrogen bromide ; and with iodides, iodine is formed and some
sulphuric acid is reduced to sulphurous acid : 2NaI-{-2H 2 S0 4 =Na 2 S0 4 +H 2
+H 2 S0 3 +I 2 ; and with an excess of hydriodic acid the sulphuric acid is reduced to
hydrogen sulphide : H 2 S0 4 +8HI=4H 2 0+H 2 S+4I 2 . If the chloride, bromide,
or iodide is mixed with sulphuric acid and manganese dioxide, there is an evolution
of chlorine, bromine, or iodine respectively. Free hydrochloric acid can be detected
in a soln. of a chloride by distilling the soln. with manganese dioxide alone, and
collecting the distillate in a soln. of starch and potassium iodide. A blue coloration
indicates that hydrochloric acid was present. Alkali chlorides or bromides are not
decomposed if melted with potassium dichromate ; but the iodides liberate iodine.
If a dry decomposable chloride is heated with a mixture of concentrated sulphuric
acid and potassium dichromate, reddish-brown vapours of chromyl chloride,
Cr0 2 Cl 2 , are evolved which condense to a brown liquid. This chloride is decomposed
by water forming chromic and hydrochloric acids : Cr0 2 Cl 2 4-2H 2 0=H 2 Cr0 4 +2HCl.
If treated with sodium or potassium hydroxide, a mixture of the alkali chloride, etc.,
is formed. If such a soln. be acidified and shaken with ether and hydrogen peroxide,
the upper ethereal layer will be coloured blue, and this coloration indicates chromium,
which in turn shows that a chloride was originally present. With bromides, bromine,
and with iodides, iodine ; but no chromium collects in the distillate. Chlorides,
bromides, or iodides when heated with a mixture of dil. sulphuric acid and potassium
dichromate give respectively free chlorine, bromine, or iodine. Chlorine water
with bromides liberates bromine, which can be recognized by the yellow or brown
coloration, particularly if shaken with a little chloroform or carbon disulphide in
which the bromine dissolves. Iodides behave similarly, but impart a rose or
violet colour to the chloroform or carbon disulphide ; bromine water liberates iodine
from iodides alone. Alkali nitrates and dil. sulphuric acid have no action on chlorides
or bromides, but with iodides, iodine is liberated, and this can be recognized by the
blue coloration it imparts to a soln. of starch. In /. Guareschi's test for bromine
(1912), 26 H. Schiff's reagent for the detection of aldehydes is made by just decolorizing
a soln. of magenta S (or rosaniline acetate, ^-rosaniline hydrochloride, Hofmann's
violet, etc.) by means of sulphur dioxide (or sodium bisulphite). A trace of bromine
gives an intense violet-blue coloration, iodine gives virtually no coloration, and
chlorine a brownish-yellow or red tint. The coloration shows with O'OOOOl grm.
of potassium bromide in O'l c.c. of soln. after treatment with 2 c.c. of 25 per cent,
chromic acid. The liquid is shaken with ether and the colour collects between the



THE COMPOUNDS OF THE HALOGENS WITH HYDROGEN 211

ethereal and aq. layers. In testing for bromine vapour, the reagent is best absorbed
on blotting paper free from starch, and this suspended over the liquid in which the
bromine is liberated by chlorine water, chromic acid, etc. The reaction is hindered
by nitrites which must be removed ; thiocyanates give no reaction or a faint rose
coloration. The colour given with aldehyde and the magenta reagent is reddish-
violet, and is not removed from the soln. by ether ; the colour is produced only in
soln., and not by the vapour of aldehyde.

Most insoluble chlorides are decomposed by boiling with a cone. soln. of sodium
carbonate : 2HgCl+Na 2 C0 3 =2NaCl+C0 2 +Hg 2 0, and the soln. of alkali chloride
is freed by nitration from the heavy metal. Silver chloride is not decomposed by
this treatment, but even it is decomposed by fused sodium carbonate. Silver
chloride may also be decomposed by treatment with cadmium or zinc in an acid
soln. Many chlorides of the non-metals are decomposed by water with the forma-
tion of hydrochloric acid : PCl 5 -f 4H 2 0=H 3 P0 4 +5HC1 ; carbon tetrachloride must
be heated with water in a sealed tube : CCl 4 +2H 2 0=C0 2 -f-4HCl. Many organic
chlorides are decomposed : (i) By heating in a sealed glass tube with silver nitrate
and cone, nitric acid L. Carius' process, (ii) By heating an intimate mixture
of the chloride with granular lime and subsequently extracting the mass with dil.
nitric acid, (iii) By heating the substance with a small piece of clean sodium,
or magnesium wire. The cold mass is extracted with water.

Chlorides, bromides, and iodides can be quantitatively determined by treatment
with silver nitrate, and, with suitable precautions, the precipitated halide is washed,
dried, and weighed. Chlorides in neutral soln. can be determined by F. Mohr's
volumetric process 27 by titration with a standard soln. of silver nitrate with a little
potassium chrornate or sodium phosphate as indicator. When all the chloride has
reacted with the silver nitrate, any further addition of this salt gives a yellow
coloration with the phosphate, and a red coloration with the chromate. In
J. Volhard's volumetric process, the chloride is treated with an excess of an acidified
soln. of silver nitrate of known concentration. The excess of silver nitrate is
filtered from the precipitated chloride, and titrated with a standard soln. of ammo-
nium thiocyanate, NH 4 CNS a little ferric alum is used as indicator. When the
silver nitrate is all converted into thiocyanate : AgN0 3 -f NH 4 CNS=AgCNS
+NH 4 N0 3 , the blood-red coloration of ferric thiocyanate appears.

A. du Pasquier 28 i n 1840 and M. J. Fordos and A. Gelis in 1842 indicated the
principle of the process for the volumetric determination of iodine by means of
sodium thiosulphate : 2Na 2 S 2 3 +I 2 =2NaI4-Na 2 S 4 6 , but the results were not
satisfactory. R. Bunsen used a standard soln. of sulphurous acid : H 2 S0 3 -f-I 2
+H 2 p=H 2 S0 4 -f2HI ) and indicated the precautions needed for accurate results.
The introduction of sodium thiosulphate in place of sulphurous acid by C. L. H.
Schwarz in 1853 proved of noteworthy benefit in analytical processes. A little
starch paste is used as indicator, and when the blue colour of the iodine is discharged,
the titration is finished. The process is used not so much for the direct determination
of iodine in iodine compounds, but rather in the indirect determination of such
substances as will liberate iodine when in contact with potassium iodide either by
direct displacement e.g. chlorinated compounds, chlorine, etc. or by reduction
in the presence of hydrochloric acid e.g. lead peroxide, chromic acid, manganese
peroxide, arsenic acid, ferric chloride, etc. Bromides can be oxidized and the free
bromine passed into a soln. of potassium iodide or into a soln. of arsenious acid of
known concentration. Alkaline arsenites are transformed by chlorine, bromine,
or iodine into arsenates : K 3 As0 3 +H 2 0+Cl 2 =KH 2 As0 4 +2KCl, the free halogen
can be titrated with a standard soln. of sodium thiosulphate, or the excess of
arsenious acid titrated with a standard soln. of potassium permanganate :
+5H 3 As0 3 +4HoS0 4 =3Ho04-2KHS0 4 +2MnS0 4 -f5H,As0 4 . The separation <
chlorides, bromides, and iodides is effected by removing the iodine with soir
reagent which does not interfere with the other two halides, and separating 1
chlorides and bromides by oxidizing reactions which break down the bromides but



212 INORGANIC AND THEOKETICAL CHEMISTRY

not the chlorides. For example, F. W. Kuster 29 distilled a mixture of the three
halides with a soln. of acetic acid and sodium acetate which expelled the iodine ;
then with a soln. of acetic and sulphuric acids to expel the bromine ; and finally
with cone, sulphuric acid to expel the chlorine. The methods usually employed
depend on the fractional oxidation of the mixture. Iodides are oxidized most
readily, and chlorides least readily. L. F. Kebler used cone, nitric acid, but the
result is more under control with dil. acid. There is a tendency to the formation
of iodic acid. J. von Liebig recommended oxidation with iodic acid, or potassium
iodate and sulphuric acid ; S. Benedict and J. F. Snell used a mixture of potassium
iodate and acetic acid with better results. Several other oxidizing agents have
been recommended lead, manganese, or barium dioxide ; alkali chromates,
permanganates, nitrites, hypochlorites, arsenates, or persulphates ; ferric salts ; etc.
The processes require a careful adjustment of the acidity of the soln. and on the
interruption of the reaction at the right time, otherwise the chloride might be
attacked. S. Bugarszky's method (1895) 30 is based on the action of potassium
di-iodate in dil. sulphuric acid soln. as symbolized by the equation : KH(I0 3 ) 2
+10KBr+llH 2 S0 4 =llKHS0 4 +5Br 2 +I 2 +6H 2 0. The iodine and bromine can
be distilled off in a current of steam, and the remaining chloride with the excess of
iodic acid. The soln. with the chloride is diluted, acidified with nitric acid, and
the chloride titrated by Volhard's process ; the bromine is absorbed in a reducing
soln. containing say phosphorous acid and boiled until all the iodine is expelled
and the bromine determined in the residue by Volhard's titration process. G. Deniges
liberated the iodine by treatment with sulphuric acid and ferric sulphate ; the
bromine by potassium dichromate ; and the chlorine was liberated from the residue
left after the removal of these two halogens. If a soln. of iodides, bromides, and
chlorides be boiled with ferric sulphate, the iodine which distils off can be collected
in a soln. of potassium iodide and titrated with sodium thiosulphate. The soln. is
cooled to 60 and a slight excess of potassium permanganate is added. The bromine
is all liberated, and it may be collected in ammonia. Chlorides alone remain in the
residue.

Silver chloride is converted into silver bromide by digestion with a soln. of
potassium bromide. Silver iodide is scarcely affected by this treatment. Silver
chloride and bromide are converted into silver iodide by digestion with potassium
iodide. Hence, F. Field devised an ingenious process for the determination of
chlorides, bromides, and iodides when all these are together. The soln. is divided
into three equal parts. The halogens in each are precipitated with silver nitrate.
The precipitate in one is washed, dried, and weighed. Let w be the weight of the
precipitate containing x of silver chloride, y of silver bromide, and z of silver iodide.
The precipitate in another portion is washed, digested with potassium bromide,
washed, dried and weighed. Let w z be the weight of the precipitate containing
187'8/143'34: of silver bromide derived from silver chloride, with y of the original
bromide and z of the original iodide. The third precipitate is treated with potassium
iodide in a similar manner. The weight w s of silver iodide contains 234'8ic/14:3'34
of silver iodide derived from the chloride ; 234 'Sy/l 87*8 derived from the bromide,
and z of the original iodide. Consequently, w^=x -\-y-\-z; w. 2 =].'3IOx-\-y-}-2 ;



Uses of the halide acids. The hydrochloric acid formed as a by-product in the
manufacture of sodium sulphate from sodium chloride is sufficient to meet com-
mercial requirements, and accordingly the acid is cheap. The largest amount of
hydrochloric acid or hydrogen chloride is used in the manufacture of chlorine and
chlorine products hypochlorites, bleaching powder, and chlorates. It is also used
in the manufacture of many of the metal chlorides zinc, tin, etc. This acid is also
used for general purposes in laboratories, in analytical and metallurgical work, in
the manufacture of colours. Smaller quantities are used medicinally. Hydro-
bromic acid or the bromides and hydriodic acid or the iodides are used medicinally,
in photography, and in analytical chemistry. Hydriodic acid is an important



THE COMPOUNDS OF THE HALOGENS WITH HYDROGEN 213

reducing agent.^ Hydrochloric acid is stored for transport in large glass balloons
or carboys, or in stoneware vessels. It cannot be stored in iron or lead vessels
because these metals are attacked by the acid.

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214 INOEGANIC AND THEORETICAL CHEMISTRY

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