The Principles of Chemistry, Volume IIMendeleyev, Dmitry Ivanovich
Science
The Principles of Chemistry, Volume II
Mendeleyev, Dmitry Ivanovich
Argon; Chemistry; Periodic law
[3] The absorption of the oxygen of the atmosphere at a constant
ordinary temperature by a large surface of phosphorus proceeds so
uniformly, regularly, and rapidly, that it may serve, as Ikeda
(Tokio, 1893) has shown, for demonstrating the law of the velocity
(rate) of reaction, which is considered in theoretical chemistry,
and shows that the rate of reaction is proportional to the active
mass of a substance--_i.e._ _dx_/_dt_ = _k_(A - _x_) where _t_ is
the time, A the initial mass of the reacting substance--in this
case oxygen--_x_ the amount of it which has entered into reaction,
and _k_ the coefficient of proportionality. Ikeda took a test-tube
(diameter about 10 mm.), and covered its outer surface with a
coating of phosphorus (by melting it in a test-tube of large
diameter, inserting the smaller test-tube, and, when the phosphorus
had solidified, breaking away the outer test-tube), and introduced
it into a definite volume of air, contained in a Woulfe's bottle
(immersed in a water bath to maintain a constant temperature), one
of whose orifices was connected with a mercury manometer showing
the fall of pressure, _x_. Knowing that the initial pressure of the
oxygen (in air nearly 750 × ·0209) was about 155 mm. = A, the
coefficient of the rate of reaction _k_ is given, by the law of the
variation of the rate of reaction with the mass of the reacting
substance, by the equation: _k_ = (1/_t_)log(A/(A - _x_)), where
_t_ is the time, counting from the commencement, of the experiment
in minutes. When the surface of the phosphorus was about 11 sq.
cm., the following results were actually obtained.
_t_ = 10 20 30 40 50 60 minutes
_x_ = 10·5 21·5 31·1 40·7 49·1 57·3 mm
10,000 _k_ = 32 32 32 33 33 33
The constancy of _k_ is well shown in this case. The determination
takes a comparatively short time, so that it may serve as a lecture
experiment, and demonstrates one of the most important laws of
chemical mechanics.
[3 bis] Not only do oxidising agents like nitric, chromic, and similar
acids act upon phosphorus, but even the alkalis are attacked--that
is, phosphorus acts as a reducing agent. In fact it reduces many
substances, for instance, copper from its salts. When phosphorus is
heated with sodium carbonate, the latter is partially reduced to
carbon. If phosphorus be placed under water slightly warmed, and a
stream of oxygen be passed over it, it will burn under the water.
Public-domain text, read in full here on John Shaqi.
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