Lord Kelvin: An account of his scientific life and workGray, Andrew
Science
Lord Kelvin: An account of his scientific life and work
Gray, Andrew
Kelvin, William Thomson, Baron, 1824-1907
Another important result of equation (B), as applied to the liquid and
vapour phases of a substance, is the information which it gives as to
the density of the saturated vapour. When the two phases coexist the
pressure is a function of the temperature only. Hence if the relation of
pressure to temperature is known, dp⧸dT can be calculated, or obtained
graphically from a curve; and the volume v₂ per unit mass of the vapour
will be given in terms of dp⧸dT, the temperature T, and the volume v per
unit mass of the liquid. The density of saturated steam at different
temperatures is very difficult to measure experimentally with any
approach of accuracy: but so far as experiment goes equation (B) is
confirmed. The theory here given is fully confirmed by other results,
and equation (B) is available for the calculation of v₂ for any
substance for which the relation between p and T is known. It is thus
that the density of saturated steam can best be found.
We can obtain another important result for the case of the working
substance in two phases from equation (B). The relation is
∂L⧸∂T + c - h = L⧸T ... (C)
where c and h are the specific heats of the substance in the two phases
respectively, and L is the latent heat of the second phase at absolute
temperature T.
We shall obtain the relation in another way, which will illustrate
another mode of dealing with a cycle of operations which Thomson
employed. Any small step of change of a substance may be regarded as
made up of a step of volume, say, followed by a step of temperature,
that is, by an isothermal step followed by an adiabatic step. In this
way any cycle of operations whatever may be regarded as made up of a
series of Carnot cycles. But without regarding any cycle of a more
general kind than Carnot's as thus compounded, we can draw conclusions
from it by the dynamical theory provided only it is reversible. Suppose
a gramme, say, of the substance to be taken at a specified temperature T
in the lower phase, and to be changed to the other phase at that
temperature. The heat taken in will be L and the expansion will be
v₂ - v₁. Next, keeping the substance in the second phase, and in
equilibrium with the first phase (that is, for example, if the second
phase is saturated vapour, the saturation is to continue in the further
change), let the substance be lowered in temperature by dT. The heat
given out by the substance will be hdT, where h is the specific heat of
the substance in the second phase. Now at the new temperature T - dT let
the substance be wholly brought back to the second phase; the heat given
out will be L - ∂L⧸∂T.dT. Finally, let the substance, now again
all in the first phase, be brought to the original temperature: the heat
taken in will be cdt, where c is the specific heat in the first phase.
Thus the net excess of heat taken in over heat given out in the cycle is
(∂L⧸∂T + c - h)dT. This must, in the indicator diagram for the
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