10.1351 Pac196102010207
10.1351 Pac196102010207
KENNETH s. PITZER
f:..S = - i .L
i, j
giJaiaJ (I)
(2)
(3)
* I t should be noted that there is no limit upon the number of independent microscopic
processes. For example in a thermo-osmosis system there might be several different mem-
branes and each would have its characteristic heat of transfer for passage of matter. How-
ever, the number of fluxes required to describe the macroscopic system is fixed by the
number of components, etc. While Li's resultis identical with that given here, his use of a
square transformation matrix implies an unnecessary Iimitation of equal numbers of fluxes
in the two sets.
208
IRREVERSIBLE THERMODYNAMICS
At equilibrium all gradients Xi are zero and by the.rmodynamics all
ßuxes must be zero. Also for systems not at equilibrium S must be positive
regardless of the signs of the Xi. Consequently the ]i must change sign
with the xi and one expects a linear dependence of ]t on xi to be a good
approximation for small xi.
An arbitrary selection of ßuxes cannot be expected to yield those micro-
scopic processes which are actually independent of one another but we
postulate that such non-interacting processes exist in the region offirst-order rate laws.
Forthisspecial set ofßuxes, ]j, each ßux depends only upon its corresponding
potential gradient x;, hence
]j = L)Xj (4)
]i = 2 j
CXij]J (5)
and this transformation may be substituted into equation (3) for entropy
production
(6)
x; = 2 cxijxii
(7)
Su bsti tu tion of these results and the rate eq ua tions (4) for the independen t
processes into equations (5) yields
(8)
(9)
Ltk = 2 j
CXij(XkjLj (10)
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