Modified Phase Rule

No. 3564, FEB.
19, 1938 NATURE 331

A Modified Phase Rule Equation A similar behaviour is exhibited by an intermetallic
IT is well known that the Gibbs Phase Rule as compound with a submerged maximum, as, for
applied to equilibrated macro-systems subject to example,
changes of temperature, pressure and concentration AuSn, +t AuSn, + liquid ;
may be written in the form
but in this case the linkages involved are metallic.
P +F = C + 2, These transition processes are conveniently termed
where P is the number of phases, F the number of meritectic reactions (from meros, part ; tectic, melting)
degrees of freedom and O the number of components. to distinguish them from the ordinary peritectic
In applying the equation to physical and chemical reactions of solid solutions. Applying the equation
equilibrium, the number of components O is ta.ken to a binary system of two solid solutions undergoing
as the minimum number of independently variable peritectic reaction,
constituents in terms of which the equilibrium may ex +t + liquid,
be expressed in the form of a chemical equation. we have
The term 'number of components' has thus to bear
the brunt of the matter and assume a responsibility 4 + 0 + R = 2 + 2 - 0 ; and R = 0.
not shouldered by the equation itself. In fact, it is It is clear, therefore, that the peritectic transforma-
frequently necessary to write out a properly balanced tion of solid solutions does not involve the rupture
chemical equation in order to decide upon the number of chemical or metallic linkages.
of components in the system. Moreover, the equation The modified equation, while removing the bugbear
cannot be applied without making allowance for of the term component, is also of utility in other
certain restrictions when the phases approach directions and in my opinion is much more easy to
identity, as in critical phenomena., or when one of the apply than the customary equation.
substances is kept in a definite weight-ratio to some
other substance in the system, as in dissociation
s. T. BOWDEN.
University College,
phenomena. Cardiff.
In view of these difficulties it is perhaps desirable Jan. 17.
to state the Phase Rule in terms more readily compre-
hended by the ordinary chemist and metallurgist.
If we retain the original definitions of phases and
degrees of freedom and let C be the total number of Constitution of Heavy Water
chemical constituents (that is, actual chemical ON lines similar to the investigation by one of us
substances) present in the system we may write on ordinary water 1, 1, we have studied the Raman
band of heavy water (99·6 per cent D 2O) at different
P + F + R = C + 2 - r, temperatures ranging from 6° to 100° C. Within
where R is the number ofreversible chemical reactions this range, the principal band for this substance is
occurring in the system, and r, the restriction term, very broad and diffuse, extending in its Raman
is equal to the number of pairs of phases having the frequencies from 2,254 to 2,784 cm-1 • It shows a
same concentration or composition. This equation structure similar to that of ordinary water, having
may then be applied without reference to stoichio- at 30° C. three components merging into one another
metric chemical equations and without recourse to
any process of choosing components.
Thus in the thermal dissociation of calcium
carbonate :
CaCOs +t CaO + CO 2 ,
we have three constituents and one reversible
chemical reaction so that
3 + F + I = 3 + 2 - 0 ; that is, F = I.
-8216
Again, in the dissociation of ammonium chloride

NH.Cl +t NH 3 + HCl,
we have a reversible chemical reaction and also one - 3435
pair of phases (the solid phase and the gas phase)
with identical composition, so that
- 3582
2 +F + I = 3 +2- I ; that is, F = I.
The equation also leads to a clear differentiation
between physical and chemical change in transition
processes. We know, for example, that the system
Na 2SO, IO H 2O +t Na 2 SO, + liquid with their maxima at 2,394, 2,534 and 2,674 cm-1 •
containing three substances (decahydrate, anhydrous The one important characteristic of this band, as
salt and water) is invariant (that is, F = 0). Accord- compared to that of ordinary water which earlier
ingly, workers with this substance 3 ,',6 failed to record, is
4 + 0 + R = 3 + 2 - 0 and R = I. the difference in the relative intensities of the three
components. The accompanying microphotometric
The point is thus an incongruent melting point arising curves of the bands for the two types of water were
from the rupture or formation of chemical linkages. ta.ken at 30° C. It is clear from the curves that for
© 1938 Nature Publishing Group

Modified Phase Rule

Uploaded by

Copyright:

Available Formats

Modified Phase Rule

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Modified Phase Rule

Uploaded by

Copyright:

Available Formats

No. 3564, FEB.

19, 1938 NATURE 331

Again, in the dissociation of ammonium chloride

© 1938 Nature Publishing Group

You might also like