JOURNAL OF COLLOID SCIENCE 13, 273-274 (1958)

WILHELMY'S PLATE AND YOUNG'S EQUATION

A. J. G. Allan*

Polychemicals Department, t~. I. du Pont de Nemours and Company,

Inc., Du Pont Experimental Station, Wilmington, Deleware
Received November 11, 1957

In his recent criticisms of the Young equation (1), Bikerman (2, 3) cites
the Wilhelmy plate method for surface tension (4) as evidence for his
argument• He refers to a diagram similar to Fig. 1 with "y~3representing the
surface tension of the solid, ~ 3 the interracial tension along the solid-

Fro. 1

liquid boundary, and 712 the surface tension of the liquid making an angle
with the solid. He states " A s Wilhelmy's method gives correct results,
• . . it may be concluded that the vertical component of "m is not compen-
sated by ~3 - ~/23but exerts a pull on the solid. Thus, Young's equation is
not in accord with observations."
First, it should be emphasized that the Wi]helmy plate method gives
correct results only when the contact angle is zero or when there is "no
contact angle" (5).
Secondly, it can be shown that the net pull on the vertical plate is not
caused by the liquid surface tension vector per se but b y the weight of the
liquid lifted in the meniscus by the spreading of the liquid up the plate.
T h e shape of a liquid surface in contact with a plane solid surface has been
frequently discussed (6, 7), and in the case of the ring method the weight
of liquid lifted b y the ring has been calculated (8) and an accurate relation
* Present address: E. I. du Pont de Nemours Co., Inc., Bush House, Aldwyeh,
London W.C. 2, England.
273
274 A,~LAN

for the surface tension also derived practically (9). The following cal-
culation for the weight lifted by the Wilhelmy plate is simple but does not
seem to have been stated explicitly.
If we assume that end effects can be neglected, the hydrostatic pressure
at a point P ( x , y) on the meniscus (Fig. 1) is given by

gpy = ~~', [11

where g = gravitational constant,

p = density difference across the fluid interface,
y -- height of the liquid surface above the plane surface of the
liquid at the point P, and
R = radius of curvature at the point P.
Now
1 _ ~ sin ~b [2]
R
where ~ is the angle to the horizontal made by the tangent to the meniscus
at the point P. Hence the volume of liquid v per unit perimeter of plate
length 21 is given by

v - - - f0~ y dx = f ~ 0 ~. sin_~ . d~, [3]

~90-0 pg tan ¢
where 0 is the contact angle of the liquid with the plate. Integrating [3] we
have
vpg = ,y cos 0 [4]
and the total weight lifted by the plate, vpg. 21, is thus 2-fl cos 0 and is
responsible for the net pull.
~EFERENCES
1. YOUNG, T., Phii. Trans. Roy Soe., p. 65 (1805).
2. BI~ERMAN, J. J., paper presented at meeting of the American Chemical Society,
Atlantic City, September, 1956.
3. B~K~.RMAN,J. J., "Proc. Second International Congress on S~rface Activity."
Butterworths, London, 1957.
4. WILHELMY,J., Ann. Physik 119, 177 (1863).
5. GANS,D. ~¢I., J. Phys. Chem. 49, 165 (1945).
6. POYNTING, J. i . , THOMSON, J. J., AND TODD, G. W., "Properties of Matter,"
14th ed., p. 180. Griffin & Co., 1947, London.
7. THOMAS,W. H., Nature 179,776 (1957).
8. FREUD, B. B., AND FREUD, H. Z., J. Am. Chem. Soe., 52, 1772 (1930).
9. HARKINS, W. D., AND JORDAN, H. F., J. Am. Chem. Soc. 52, 1751 (1930).