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
Law of Substitution.--By the careful study of the action of Chlorine,
and of Nitric Acid, upon various organic substances, a remarkable series
of compounds has been discovered, containing a portion of Chlorine or
of Peroxide of Nitrogen in the place of Hydrogen. The peculiarity of
these substances is, that they strongly resemble the originals in their
physical, and often in their chemical properties. It might have been
supposed that agents of such active chemical affinities as Chlorine and
Oxide of Nitrogen would, by their mere presence in a body, produce a
marked effect; yet it is not so in the case before us. The primitive type
or constitution of the substance modified remains the same, even the
crystalline form being often unaffected. It seems as if the body by which
the Hydrogen had been displaced had stepped in quietly and taken up its
position in the framework of the whole without disturbance. Many compounds
of this kind are known; they are termed by chemists "substitution
compounds." The law invariably observed is, that the substitution takes
place in equal atoms: a single atom of Chlorine, for instance, displaces
one of Hydrogen; two of Chlorine displace two of Hydrogen, and so on,
until, in some cases, the whole of the latter element is separated.
In illustration of these remarks, take the following instances:--Acetic
Acid contains Carbon, Hydrogen, and Oxygen; by the action of Chlorine
the Hydrogen may be removed in the form of Hydrochloric Acid, and an
equal number of atoms of Chlorine be substituted. In this way a new
compound is formed, termed _Chloracetic Acid_, resembling in many
important particulars the Acetic Acid itself. Notice particularly that
the peculiar properties characteristic of Chlorine are completely masked
in the substitution body, and no indication of its presence is obtained
by the usual tests! A soluble _Chloride_ gives with Nitrate of Silver a
white precipitate of Chloride of Silver, unaffected by Acids, but the
Chloracetic Acid does not; hence it is plain that the Chlorine exists in a
peculiar and Ultimate state of combination different from what is usual.
The substance we have been previously considering, viz. Pyroxyline,
affords another illustration of the Law of Substitution. Omitting, for
the sake of simplicity, the number of atoms concerned in the change,
the action of concentrated Nitric Acid upon ligneous fibre may be thus
explained:--
{ Carbon
Cotton _or_ { Hydrogen + Nitric Acid
{ Hydrogen
{ Oxygen
equals
{ Carbon
Pyroxyline _or_ { Hydrogen + Water
{ Peroxide Nitrogen
{ Oxygen
Or in symbols:--
CH{11}O + NO{5} = C (H{n-1}NO{4}) O + HO
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