History of Chemistry, Volume 2 (of 2): From 1850 to 1910Thorpe, T. E. (Thomas Edward)
History
History of Chemistry, Volume 2 (of 2): From 1850 to 1910
Thorpe, T. E. (Thomas Edward)
Chemistry -- History
The fact that all gaseous substances, however different their chemical
nature, conform in the main to certain simple “laws” indicates
the probability that their mechanical structure is similar and
comparatively simple. The so-called gaseous “laws”—the laws of Boyle,
Dalton, Gay Lussac, Avogadro, and Graham—are to-day explained on
the assumption that a gas consists of an aggregation of molecules,
moving incessantly in straight lines and with great rapidity. The
rate of movement of the particles is variable by reason of their
mutual encounters; at the same instant some are moving rapidly, others
more slowly. As already explained, to this ceaseless movement of the
molecules is to be ascribed the pressure they exert; the pressure which
a gas exerts on any containing surface is the aggregate effect of the
impact of its molecules. The law of Boyle states that the product of
the volume V and pressure P of a given mass of gas is invariable so
long as the temperature is unchanged: PV = constant. It was found
by Regnault, Magnus, Natterer, and Amagat that all gases, with the
exception of hydrogen, show a departure from Boyle’s law in the sense
that PV is less than theory demands. In the case of hydrogen PV is
greater than theory. This exception, however, is only apparent. Every
gas, if maintained above a certain temperature, shows, after a certain
pressure has been reached, a deviation in the same sense as that
exhibited by hydrogen.
The deviations from Boyle’s law are probably due to two causes: (1) to
the effect of cohesion among the molecules, whereby the volume, and
hence PV, is less than theory requires; (2) the molecules are not
mathematical points—they have a certain volume; hence, with increasing
pressure, PV is greater than theory demands. The effect of the molecule
having a certain magnitude will be clear from the following figure: Let
M be a molecule moving backwards and forwards within a certain space,
_a b_:
| M |
_a_ | | _b_
| • |
| |
Assume, now, we halve the containing space:
| M |
_a_ | | _b_
| • |
| |
It will be seen that M, since its volume is unchanged, will have less
than half the original distance to travel or, in other words, it
will strike the boundaries of the containing space _more_ than twice
as frequently in the same interval of time as before; hence P, and
therefore PV, becomes greater than Boyle’s law demands.
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