Aerosol Science. 1972, Vol. 3, 10p. 199 to 210, P e r g a m o n Press. Printed in Great Britain.

THE KELVIN EQUATION--A REVIEW

L. M. SKINNER and J. R. SAMBL~S*
Institute of Coastal Oceanography and Tides, Bidston Observatory, Birkenhead, Cheshire, England

(Received 30 November 1971)

Abstract--This review is concerned with the general history of the Kelvin equation (which relates
vapour pressure to surface curvature) during the hundred years which have elapsed since it was first
proposed. Included are considerations of the use to which it has been put and the testing of its validity.
In addition, the application of the idea underlying this equation to other phenomena, e.g. solubility,
is discussed.
INTRODUCTION
W. THOMSON, later Lord Kelvin, (1870), developed an equation which implied that the
vapour pressure of a material in thermodynamic equilibrium over a curved surface differs
from that over a plane surface. His derivation was based on the consideration of the equilibrium between a liquid, contained in a capillary tube, and its vapour. For a capillary rise
the equation took the form
Pr, r, = p ~

~pv
Pl --

[1- + - 1,]

Pv

(1)

where Pr,r' is the equilibrium vapour pressure over a surface with principal radii of curvature
r and r' (for a concave liquid surface), P~ is the equilibrium vapour pressure over a plane
surface, ~ the surface tension of the liquid and pv, p~ the densities of vapour and liquid
respectively. This equation is inexact insofar as it does not allow for the variation of vv with
pressure. A m o r e exact form, in which it is assumed that pv <~ 9. is:

of which (1) is evidently the first approximation, if the vapour is assumed to behave as a
perfect gas, then
pv
M,.
P
RT
where Mr is the molecular weight, R the gas constant and T the temperature. Further if
r = r' and the surface is convex (as for a droplet or a liquid with capillary depression) then
Pr=P~exp

[ r ~p~

"

In its approximate form the Kelvin equation has been readily accepted by scientists
because of the simple way in which it was derived and its inherent plausibility. It has been
used since its introduction to interpret m a n y experimental results, a discussion of which are
*Physics Department, Imperial College, London S.W.7.
199

200

L.M. Srdach~aand J. R. 5AMBLZS

given in section 3. Those experiments which have been performed in order to test its validity
fall broadly into two groups. These are (a) experiments on liquids contained in capillaries
and (b) experiments using small part/cles, often in the form of aerosols. These experiments
are considered in sect/on (4).
In the following section a brief review is given of theoretical considerations concerning
Kelvin's equation, included is Kelvin's original derivation (THOMSON, 1870, 1871).
REVIEW OF THEORY
Kelvin derived equation (1) by considering the equilibrium of a liquid contained in a
capillary tube s/tuated in a sealed vessel as shown in Fig. 1. Imagine that at a temperature,
7", equilibrium has been achieved. Hydrostatic considerations lead to
P,.

dh

"

where the terms in brackets are as given in Kelvin's original approximate form. Pr is the
vapour pressure over the curved surface, aNumed to be concave, having a radius of curva-

Fro. 1. Capillaryheld liquid in sealed vessel.

ture r. P is the equilibrium vapour pressure over a plane surface, p~ the vapour density
(which is a function of height) and g the acceleration due to gravity. According to Laplace
the pressure within the liquid surface is given by
Prl = Pr + 2.._y

(r is positive when liquid surface is convex).

Also,

P~,=P~+ fg,,dh [=P~ +gmh,]

so that
Pr +

2y
-r

P= + | " g
J

m dh

The Kelvin equation- a review

201

Since the change of vapour pressure with height is given by

dP = g p~, dh
then
Pr

(,,,-pv / \ (Pr-P4"

(o,-0_
4 d,,=
Pv /

P~

The term on the R.H.S. within the square brackets is Kelvin's original equation with
r=r'==r

If

Pv ~ pz
Pr

then

27

--=pl
r

[ dP
d

Pv

P=
Assuming the vapour to be a perfect monatomic gas,
PM~
Pr=

RT

Pr
and hence

27 = p l R T fj dP
r
M-r
P
P=

Integration gives
Pr = P~ exp

and Kelvin's original equation is the first approximation to this.

Following the original derivation came works by WARBURG (1886) who considered a
Carnot cycle involving the surface of a droplet, and GAUTZl~ (1888) who considered on a
molecular basis the vapour pressure equilibrium over a curved surface. These two approaches
yielded essentially the equation obtained by Kelvin. At about the same time an article
appeared by FITZGEgALD (1879) who compared the probability of escape of atoms from a
curved surface with that from a plane surface. From such a consideration he also derived
a similar equation which related vapour pressure to surface curvature.
PAWLOW (1909), was the first to employ the Kelvin equation for solid particles, assuming
them to be spherical. VOLMER (1939) derived a more exact equation for facetted "Wulff"
crystals. This can be written in the form
Vr~ = P,~,exp [ 27s

rs

Mr.l]
"psR T J

where P,~ is the vapour pressure over a solid having a Wulff shape and 7*/r* = 7/h" for
all cr faces, 7a being the surface energy of the atn face and h the perpendicular distance from
that face to the Wulff centre of the crystal. P=~ is the equilibrium vapour pressure over a
semi-infinite solid.

202

L.M. SKINNERand J. R. SAMBLES

It is apparent that equations (3) and (4) can be interpreted as r e p r i n t i n g a change in

latent heat of evaporation for atoms leaving a curved surface. Some workers have approached
the problem from this viewpoint, (e.g. SATI'ERLY, 1929) but no significantly different formulae have been obtained.
In (1900) OSTWALDapplied the anderlying principle of Kelvin's equation to consider the
phenomenon of the increased solubility of small crystals compared with large ones. The
equation he derived was later modified by FgEtmDLICH (1909) and then took the form

-R T,logs $2 =

27.[1

;,

r-,.

1]

;,,

where S1, $2 are the concentrations of solutions in equilibrium with particles of radii
r, 1 and r,~ respectively, ~, is the mean solid surface energy and p~ is the solid density. This is
clearly very similar to the Kelvin equation although referred to as the Ostwald, or Ostwald.
Freundlich formula. It is the three equations, (3), (4) and (5) which have been used to interpret many observed phenomena, for although other theoretical treatments have been given
they have not superseded these basic equations (see for instance JoN~:s, 1913 (a); LACMANN.
1962).
For a fuller account of these theories, reference may be made to the extensive work of
DEFAY e t al. (1966). This provides clear derivations and discussions of the various forms of
the Kelvin equation.
USE OF THE KELVIN, (OSTWALD) EQUATIONS
Various workers have used these equations for the consideration and interpretation of
such phenomena as the growth of large particles in solution at the expense of small ones, the
enhanced evaporation of small particles, the change of the vapour pressure and melting
point of capillary held liquids, the lowering of the melting point of small particles and the
need for a supersaturation of vapour (or the presence of nucleation centres) for condensation
to occur. The last mentioned phenomenon is probably the best known although of no direct
use in the testing of Kelvin's equation since condensation is a fluctuation, and not a strictly
equilibrium process. The other phenomena are, perhaps, less familiar.

a.

The enhanced solubility of small particles

The earliest experimental evidence produced in support of the Kelvin equation tended to
be of a qualitative nature and took, mainly, the form of observation of the selective growth
of crystals in saturated solutions, or the d/fferential growth of large drops or crystals at the
expense of smaller particles in their vicinity through the medium of the surrounding vapour.
It was suggested by O m m (1885) that ira mixture of crystals of d/ffrent sizes were in contact
with a saturated solution, then in order to minimise the surface energy, the small crystals
would pass into solution and recrystallisation would occur on the larger crystals. This
selective growth process was observed both by OSTWALD(1897, 1900) and HULE~r (1901,
1904), The differential growth of a large variety of substances was observed by BmELOWand
TRIMm.E (1927) in an attempt to confirm the Kelvin equation. Contamination and temperature fluctuations led to inconsistencies in their results. J o ~ s (1913 b) used Hulett's data
on enhanced solubility in an attempt to deduce the surface energy of the solid particles
observed. Following this, JONES and PARXmGTON (1915 a, b) studied both theoretically
(1915 a) and experimentally (1915 b) the solubility of small particles. THOMPSON(1921)

The Kelvinequation-- a review

203

deduced the interfacial tension between solid cementite and iron from the enhanced solubility of carbon in small particles of iron. DUNDON (1923), and DUNDON and MACK (1923)
performed an extensive series of experiments deducing the surface energies of various salts
from the enhanced solubility of small, ground particles (0.3/Lm dia.) using essentially
equation (5). However in 1926 a paper by BALAREVappeared in which it was pointed out,
quite rightly, that much of the earlier work (excluding apparently, DUNDON and MACK)
gave values of surface energies which were too high, due to the effects of impurities and
crystalline imperfections in ground powders (see also COHEN and BLEKKINGH, 1940;
BAUER, 1953). He also attempted to measure surface enetgy by enhanced solubility. Since the
early 1920"s a considerable amount of work on enhanced solubility has been done, much of
which revolved around the measurement of the heats of solution of small particles, a parameter clearly related to the enhanced solubility--see for example CENTNERSZWER and
KRUSTINSANS (1927), LIPSETT et al. (1927, 1928), BOYD and HARKINS (1942), JURA and
GARLAND (1952), BENSONand BENSON(1955), BRUNAUERet al. (1956), VAN ZEGGERENand
BENSON (1957), and BENSONand YUN (1967).
b.

The enhanced evaporation and vapour pressure of smallparticles

It follows directly from Kelvin's equation that small particles in vacuum should evaporate more rapidly than large ones, and equally, that large particles in their vapour will grow
at the expense of small ones. OSTWALD(1900)reported the differential growth of large liquid
sulphur drops at the expense of smaller ones in their vicinity, whilst SALOMON(1899) and
WHITAKER (1925) observed the growth of sulphur crystals from nearby supercooled drops
of liquid sulphur. The effect was also noticed by MCKEEHAN (1916) who carried out experiments on the evaporation of liquid mercury droplets. LJALIKOV(1940), observed the
growth of large mercury droplets at the expense of smaller ones, and in an elaborate experiment obtained agreement with Kelvin's equation for particles of about 1 tzm radius.
However he gave no discussion of errors with his results and so left in doubt the question
as to how good a confirmation this was. ROSENHA]Nand EWEN(1912) found that tile vapour
pressure of finely crystalline material was greater than that of coarsely crystalline and
KNACKE and SCHMOLKE(t956) observed an enhanced rate of evaporation for very thin films
of copper and silver, which were presumably in the form of small islands. PIuz (1964),
appears to have been the first to use the enhanced evaporation of small particles to deduce
a value for their surface energy. He observed, using a radioactive tracer technique, the
evaporation of small solid silver particles of less than 0-1 t~m dia. Interpreting his results
by means of the Kelvin equation, he obtained a mean surface energy value of silver of
6.00 J m-L a figure which is surprisingly high (see BUTTNERet al. 1952). WOODLANDand
MACK (1933) and SHERESHEFSKYand STECKLER(1936) observed the evaporation of small
liquid drops in a MILLIKAN(1917)type apparatus but their results merely indicated that
the vapour around the drop became saturated and the evaporation rate decreased as the
drop became smaller.
It was shown by KGHLER(1921, 1922), from work on the condensation of water vapour
from the atmosphere, that droplets of a salt solution could be brought into equilibrium with
the vapour from a plane liquid surface. This was caused by the salt lowering the vapour
pressure and the curvature raising the vapour pressure of the small particles, the two effects
balancing. The vapour pressure change for droplets of solution has been observed by GUDRIS
and KULIKOVA(1924 a, b) and LAMER and GRUEN (1952) in testing Kelvin's equation
(see section 4). Theoretical considerations of this change in vapour pressure with drop size

204

L.M. SgINN~a and J. R. SAMeLE

for solutions are found in the studies of VOLMER(1939), K6HLr~t (1950) and DEFAY et aL
(1966).

c. The lowering of the melting point of amalt particles

In 1909 PAWLOW deduced an equation relating the melting point of small particles to
surface curvature. He considered the equilibrium between solid and liquid spheres of equal
radius (HANSZ~, 1960, ~ n d s this to equal mass) in equilibrium through their mutual
vapour at a temperature T, which is essentially a triple point. Pawlow predicts a melting
point d~pendence on radius for which ATal/r where AT is the c h a a ~ in the melting point.
An attempt to confirm this experim~tally is described by PAWLOW (1910). Subsequently
TAKAGI (1954), BLACKUANand CUgZON (1959), PALATNIKand KOUI~nK(1960), GLADKICH
et al. (1966), WRONSKI(1967), P6CZA et al. (1969), BOIKOet al. (1969), and SAMaLES(1971)
have observed a change of the melting point of small particles and for small AT have found
a 1/r dependence. However this does not necessarily show that Pawlow's melting point
relation derived from the Kelvin equation is of general validity, as various other formulae
relating the melting point to surface curvature in the form AT.d/r have been derived using
different approazhes (see for example PIE. 1923; Rmss and WILSON, 1948).
d.

The change of vapour pressure and melting point for capillary held liquids
Experiments have shown that the vapour pre~ure over a capillary held liquid is different
to that over a plane surface. THOt~'s work (1930) is a classical example of an experiment to
measure directly the change in vapour presure for a liquid held in a capillary; see section 4
for a full discussion of this experiment. Work by S ~ Y
(1928), StI~eS~Fss:'l and
CARTER (1950), FOL~,'~ and S',-i~egESHe~K'Z(1955) and F~YAK~ (1962) all report the
lowering of vapour pressure for capillary held liquids which do not agree with Kelvin's
equation. It has been s ~ t e d
that this is due to an int..qagtion between the capillary walls
and the liquid surface. Anomalous results have also been reported by CHMUrOV(1948, 1949)
for the vapour pressure lowering in capillary spaces formed by placing two convex lenses
on top of one another. Of a related c ~
is the work on the vapour pressure of liquids
adsorbed on to porous bodies. A review paper by ANDeaSON as early as 1914 invoked the
use of the Kelvin equation, (though not so ~ e d ) in the interpretation of results on the
adsorption of vapour on gels and FosTeg (t932) obtained condensation isotherms which
were of a form derivable from Kelvin's equation. PATRICK (1925) stated that the Kelvin
equation did not explain results for pores of very small radius and similar conclusions were
reached by Pn~cl~ et al. (1949) and E ~
and WHITTON(t955). This is to be expected as
the macroscopic properties of the material being adsorbed probably changes for pores of
radius Jess than about 2/an.
The review paper by CAgl~N (1951), draws attention to the fact that it is erroneous to
correlate the vapour pressure over capillary held liquids to the pore radius. It is in fact the
radius of the liquid surface which should enter into the equations. This is clearly true and
thus any quantitative results which used, for instance, a B.E.T. technique to measure pore
radius and correlated this to increased vapour ptmsure would be suspect. Another paper by
C~N
(1953), also qumtions the sugge~on that the v a ~ u r pressure over a capillary held
solid differs from that over b ~ material. He cites the works of BgowN and FOSTER(1944)
and B^TCH~OR and F o s r ~ (1944) and questions their interpretation of the melting point
depression of a capillary held liqmds by the use of an equation which contains the vapour
pressure change over a solid (it should be noted that the experiments of Pluz 1964, BLACKMAN

The Kelvinequation-- a review

205

et al., 1968, and SAMBLESet al., 1970 show that the vapour pressure over a solid particle is
different to that over a semi-infinite solid).

A considerable amount of other work has been done on the decrease in vapour pressure
for capillary held liquids but, in general, Carman's argument that liquid surface radii should
be used makes any quantitative deductions about the Kelvin equation meaningless since
these radii cannot be measured except by the use of the equation itself. Again, the results of
many of the experiments which observe a change of melting point for capillary held liquids
may also be criticised in that the pore radii are used incorrectly to interpret the results. In
theoretical considerations of this effect various approaches have been made; for instance
KUBELKA(1932) considered a lowering of the freezing point, AT1, to be due to the free surface
of the liquid raising the free energy of the system. He obtained AT~I/r where 1/r is correctly
calculated by using the Kelvin equation in conjunction with measurements on the vapour
pressure over the adsorbed liquid. Unfortunately in the main, experiments consist of observation of freezing points of liquids in pores and supercooling effects may cast doubt on the
application of any equilibrium thermodynamic theory to the results, Many workers have
observed the lowering of the freezing point of adsorbed liquids, for example, JONES and
GORTNER (1932), CULBERTSONand WINTER(1941), HIGUTi and SHIMIZU(1952), HIGUTIand
YOSmTOMO (1952), PURI et al. (1957), HODGSON and MCINTOSH (1960), and BRUN et al.
(1971). PURl et al. (1954) gave a short review of much of the earlier work. More relevant to
Kelvin's equation is the work of PATRICK and LAND (1934), and PATmCK and KEMPER
(1938 a)---on the lowering of the melting point of solids in pores--although PATRICK and
KEMPER (1938 b) interpreted their results by using a vapour pressure equation unrelated to
the Kelvin equation. BROWN and FOSTER (1944) used vapour pressure measurements to
observe a change in the melting point of adsorbed ethylenediamine, calculating surface
curvature from Kelvin's equation as applied to solids, and the measured vapour pressure.
Among other papers dealing with this subject is the work by ANTONIOU(1964) who mentions
a triple point equilibrium obtainable via Kelvin's equation, but who is apparently unaware
that there may exist a triple point which varies with particle size.
SUCCESSFUL ATTEMPTS TO CONFIRM KELVIN'S THEORY
One of the first attempts at a quantitative verification was due to BACON(1905) and this
has some importance because he carried out the distillation experiment originally suggested
by THOMSON(1870, 1871). In this form of the experiment, four capillary tubes were enclosed
in a vessel containing a plane surface of a volatile liquid. One of the tubes was open at both
ends to act as a reference for the equilibrium capillary level and the others, closed at the
lower ends, were filled to various levels both above and below the reference level. According
to the Kelvin theory, when the system is in equilibrium the liquid level in all four capillaries
should be equal. Bacon, after observing the sytem for one year, concluded that the levels all
tended to that in the open ended tube; but that the approach to equilibrium was very slow.
GUDRIS and KULIKOVA(1924), investigated the evaporation of water droplets of radii
greater than 0-5 ~m in a MmLIKAN(1917) apparatus. Stokes law was used to calculate the
drop radii. They found that for drops evaporating in gases the evaporation of the drops was
impeded both by saturation of the vapour immediately around the drops and by contamination of the drops by the surrounding gas. However they also performed a series of experiments in which droplets of sugar solution were allowed to grow or evaporate in water vapour;
large drops were found to grow and smaller ones evaporated. By extrapolation the drop radius

206

L . M . SKINNER and J. R. SAMBLES

for no growth or evaporation was determined and that for these drops, the reduction of
vapour pressure AP due to the sugar content was equal to the increase due to the curvature
of the droplets. Thus
27 pv
AP _~ - - -r "pl
where r is the droplet radius. Their results are given in the following table.
Concentration of Solution
(%)

AP(mm)

2
3

l.l 10-2
2"0 10-~"

2~, po
r p,

(calculated)

1.2 10-z
1.8 10-z

These provided, for d r o p l ~ s greater than 0.5 ~m radius a confirmation of the approximate form of Kelvin's equation to an at.curacy of about 10 per cent. This experiment would
appear to be the first to give any real qtmntitativeexperimental evidence in support of the
Kelvin equation. Subsequmnt literature in this field does not seem to give sufficient credit
to these workers, especially for using the ingenious idea of balancing the vapour pressure
over a curved surface by means of a solution. It should be pointed out, however, that the
Millikan experiment necessitates charging the droplets thus modifying, perhaps, the surf'ace
energy. The authors investigated this and found no observable effect.
THeMe. 1930, performed th first experiment, using an elegant technique, which sucessfully measured the pressure difference between the vapour over a curved liquid surface and
that over a plane liquid surface. A schematic diagram o f the apparatus is shown in Fig. 2.
A very sensitive m a n o m e t e r ' M ' measured, by the use of interference fringes, the difference
in equilibrium pressures over the liquid surfaces in glass tubes ' A ' and 'B'. In 'B' a plane
surface was produced and in 'A" a number of surfaces o f different radius could be produced.

71
Fro. 2. Schematic of Thomds apparatus.

The Kelvin equation -- a review

207

These ranged from 290 to 820/~m. With the sensitive membrane manometer Thom~ observed pressure differences of the order of 10 -G N m -2 and his results show agreement to
5 per cent with the Kelvin equation. Clearly only the linear approximate form, i.e. equation
(1), was tested using such large capillary radii. As already mentioned in Section 3d similar
experiments by other workers were to follow with smaller bore capillaries but with little
success due to the interaction between the contained liquid and the capillary.
Perhaps the best known experiment to date which tested Kelvin's equation is that of
LAMER and GRImy (1952). Their experiments, similar in form to those of GUDmS and
KULIKOVA (1924 a,b), consisted in observing the equilibrium of vapour pressure between
aerosol droplets from a non-volatile liquid (dioctyl phthalate) in contact with vapour from
a bulk or master solution of some volatile substance, for example toluene, dissolved in the
non volatile liquid. The radii of the particles studied however were greater than 100 nm for
which the difference between the exponential and linear forms of Kelvin's equation is less
than 1 per cent under the conditions of the experiment. The data on particle radii, which
were measured by a light scattering technique, is only quoted to two figures in the paper
and unfortunately the lack of any discussion of errors leaves even the general accuracy
with which the approximate form was tested open to doubt. From the data it would appear
that an accuracy of not greater than 5 per cent was achieved.
With a view to testing the exact form of Kelvin's equation BLACKMAN et al. (1968)
carried out preliminary experiments in an electron microscope on the evaporation of small
particles of liquid lead and solid silver. If the Kelvin theory is correct then both small liquid
and solid particles evaporating into a vacuum should yield a radius versus time curve which
contains an exponential increase as the radius decreases becoming experimentally observable
for radii smaller than 20 nm (e.g. for lead evaporating at P~ ~_ 10-3 Nm-~). BLACKMAN
et al. demonstrated the general suitability of the technique of recording on micrographs the
evaporation of small metal particles held at high temperatures (vapour pressures of about
10-3 N m -2) and comparing the radius vs. time graph obtained with the theoretical curve
derived from Kelvin's equation.
This preliminary study was then followed by two extensive pieces of work by SAMBLES
et al. (1970) observing the evaporation of liquid lead and silver particles and by SAMBLES
(1971) observing the evaporation of liquid and solid gold particles. The final results of all
these experiments show very close agreement between the theoretically predicted evaporation
curves and those obtained experimentally. In fitting the theory to experiment the surface
energy was used as a parameter to show the accuracy of this fitting. For liquid lead, see
Fig. 3, the fit was better than 5 per cent about the bulk surface energy value measured for
lead by conventional techniques. For the solid silver particles studied, the mean surface free
energy was determined from the fitting of theory to experiment. The value obtained of
1.20 4- 0.06 J m -2 at 1005 4- 25k compares well with the values of BUTTNER et al. (1952).
Likewise for solid gold particles a surface energy value of 1.35 ~ 0-06 J m -~ at 1160 4- 10k
compares favourably with values obtained by other workers; a compilation of results on the
surface energy of solid gold is given by GAMBLES(1971). For liquid gold the fit of theory to
experiment gave a possible range in v of 7 per cent about that determined by macroscopic
techniques. Furthermore, results were also obtained which yielded data on the lowering of
the melting point of solid gold particles. This effect as discussed in Section 3c m a y be predicted by the consideration of a triple point vapour pressure equilibrium between a solid
particle and a liquid particle of the same mass (see HANSZEN, 1960).
Apart from these very recent experiments there appears to be no other work which deals

208

L.M. Sg.UcN~ and J. R. SAMaLES

0 . 4 3 8 5 J-m-Z

F~o. 3. Radius ~ t

30

]_ N

60

90

Time,

sec

time plot for an e~alm:nUi~ ~

120

150

-- the fullline is ~ I

et al., 1970). X marks the time of e~po~we of the first microgra~ having no ~

(see S~SLES

of the particle.

with the Kelvin equation for ~ r t i c l e s below 20nm radius. It is to be hoped that the technique
will be extended to other materials in an attempt to gain information about surface energy
values, particularly for solids, using the Kelvin equation to interpret the evaporation curves.
CONCLUSIONS
As La Mer and Gruen point out "'The general acceptance which equation (1) enjoys
rests on the cogency o f the Kelvin derivation and the success o f further theori~ ~
upon
it". Nevertheless a good deal o f effort has been expounded in attempts to test its validity.
It is however only within the last t w o d ~
with the advent o f the high ~
resolution
obtainable in the electron microscope, that sufficiently small particles, with which the
validity of the exponential form of Kelvin's equation could be demonstrated, have been
successfully observed.
Acknow/cdfft,ments.--We would like to thank Prof. M. Blackman and Dr. N. D. Lisgarten for their help in
the production of this paper.
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The Kelvin equation -- a review

209

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