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To cite this article: S.R. Craxford , O. Gatty & J.St.L. Philpot (1933) LXXIV. The theory of
electrocapillarity.Part I. Capillarity , The London, Edinburgh, and Dublin Philosophical
Magazine and Journal of Science, 16:108, 849-864, DOI: 10.1080/14786443309462339
Article views: 27
Download by: [New York University] Date: 28 June 2016, At: 15:56
THE
LONDON, E D I N B U R G H , AND D U B L I N
PHILOSOPHICAL MAGAZINE
AND
JOURNAL OF SCIENCE.
[ S E V E N T H SERIES.]
Downloaded by [New York University] at 15:56 28 June 2016
NOVEMBER 1933.
PISTON I
Downloaded by [New York University] at 15:56 28 June 2016
PISTON 2
p,
Pl--P~ . . . . . . . (5)
or ~12= C1 C2
where C1 and C2 are the two principal curvatures of the
surface s12.
This definition, which defines the surface tension at
uny point, is in agreement with the previous work of
Laplace, Young, and others on surface tension. In the
case of an interphase of finite thickness a surface tension
could be defined by equation (4) for a n y appropriate
boundary in the non-homogeneous region between the
two phases, and ~2 could be regarded as the surface
tension in t h a t particular boundary to which dr12 and
ds~ both refer. I t is essential in this case t h a t they
refer to the same arbitrary boundary.
Now let some arbitrary boundary separating phases
1 and 2 be described in the non-homogeneous interphase,
and this boundary be produced, but so as to separate
phases 1 and 3, and be produced back further so as to
separate the piston from the walls of the containing
vessel and on till it finally intersects the outer edge of
piston 1. Let the total volume enclosed by this boundary
and the outer edge of piston 1 be V1.
Then [dvl~ --dvl =dV1]p,, T, w', ~, sk-
This is so because the condition s~ constant, which means
t h a t ds~=O, implies t h a t these particular parts of the
surface have undergone no increase of area, and therefore
have had no work done on them, and so sweep out zero.
volume.
862 Messrs. Craxford, Gatty, and Philpot :
Ids-.
,storing pressure is equal to V ~dvl # --(Pl--P2). For
virtual changes in which (Pl--P~) and ? are kept constant
the type of equilibrium is determined b y the sign of
The Theory of Electrocapillarity. 863
References.
(1) Bowden and Rideal, Proc. Roy. Soc. A, exx. p. 59 (1928) ; Erdey-
Grdz and Kromrey, Zeit. phys. Chem. A, civil p. 213 (1931).
(2) Philpot, Phil. Mag. (7) xiii. p. 775 (1932); Frumkin, Zeit. phys.
Chem. ciii. p. 55 (1923).
(3) Paschen, Ann. Phys. xliii, p. 568 (1891).
(4) Gouy, Ann. Chim. Phys. (7) xxix. p. 145 (1903).
(5) Frumkin, J. Russ. Proe. Chem. Soe. xlix. (1) p. 207 (1917);
Bodforss, Z. Elektrochem. xxxix, p. 121 (1923).
(6) Billiter, Ann. Phys. xi. pp. 902 & 937 (1903) ; Zeit. phys. Chem.
xlviii, p. 513 (1904).
(7) Bennewitz and Deliian~is, Zeit. phys. Chem. A, cxxv. p. 144 (1927) ;
Bennewitz and Kiichler, ibid. A, cliff, p. 443 (1931).
(8) Bennewitz and Schulz, ibid. A, cxxiv, p. 115 (1926) ; Bennewitz
and Bigalke, ibid. A, cliv. p. 113 (1931).
(9) Guggenheim, J. Phys. Chem. xxxiii, p. 842 (1929); ibid. xxxiv.
1a. 1540 (1930).
(10) Gibbs, ' Scientific Papers,' i.
(11) Butler, Proc. Roy. Soc. A, exxxv, p. 348 (1932).
(12) Langmuir, J. Chem. Phys. i. p. 3 (1932).
Physical Chemistry Laboratory, Balliol & Trinity Colleges, Oxford,
and the National Institute for Medical Research, Hainpstead.