A Manual of Photographic Chemistry, Including the Practice of the Collodion ProcessHardwich, T. Frederick
Science
A Manual of Photographic Chemistry, Including the Practice of the Collodion Process
Hardwich, T. Frederick
Photographic chemistry; Photography
Observe therefore that free acids of all kinds must be excluded from the
fixing Bath, or, if inadvertently added, the liquid must be set aside for
some hours until the Hyposulphurous Acid has decomposed, and, the Sulphur
having settled to the bottom, the Bath has regained its original neutral
condition.[22]
[22] The chemical reader will understand the decomposition of free
Hyposulphurous Acid by the following equation:--S{2}O{2} = SO{2} and S.
b. _Decomposition of the Bath by constant use._--It has long been known
that a solution of Hyposulphite of Soda undergoes a peculiar change in
properties when much used in fixing. When first prepared it leaves the
image of a red tone, the characteristic colour of the reduced Silver
Salt, but soon acquires the property of darkening this red colour by a
subsequent communication of Sulphur. Hence a simple fixing Bath becomes at
last an active toning bath, without any addition of Gold.
This change of properties will be found more fully explained in the
abstract of the Author's researches given in the next Section (p. 156). At
present we remark only that it is due principally to a reaction between
Nitrate of Silver and Hyposulphite of Soda, attended with decomposition
of Hyposulphite of Silver (p. 130); and hence, if the prints are washed
in water before immersion in the Bath, the solution will be less quickly
liable to change.
Many operators state that the toning Bath having at first been prepared
with Chloride of Gold, no further addition of this substance will be
required. This no doubt is correct, but in such case the proofs will at
last be toned by Sulphur more than by Gold, and will not possess the
same stability; the Bath will also, after long use, be found to acquire
a distinct _acid_ reaction to test-paper, the acidity being due to a
peculiar principle generated by decomposing Hyposulphite of Silver, and
which is shown to have an injurious action upon the print (p. 158). To
avoid this the solution should be kept _neutral to test-paper_ by means of
a drop of Ammonia, if required; and when it begins to be exhausted, and
does not tone (quickly) a print from which the free Nitrate of Silver has
been removed by washing, a fresh quantity of Chloride of Gold should be
added.
c. _Tetrathionate in the Hyposulphite Bath._--The Author has shown that
the Tetrathionates, which are analogous to the Hyposulphites, have an
active sulphuretting action upon Positive prints (see the papers in the
next Section). Very fine colours can be obtained in this way; but toning
by Sulphur having been proved to be wrong in principle, the formulæ given
in the first two editions of this Work have been omitted.[23]
[23] The preparation of a toning bath by Tetrathionate, without Gold, is
described in the next Section, but it is not recommended for practical use.
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