II TEXTUAL REFERENCES 47

103. L Sutherland, Austral. J. Chem., , 319 (1954).

104. N N 4.hur4;a and A I Rusan4;, J. Colloid Interface Sci., 81, 97 (1981).
105. R S Hansen and T C Walla.e, / !hys. Chem., 63, 1085 (1959).
106. W D E Th42as and D J Hall, / Colloid Interface Sci., 51, 38 (1975).
107. D A Netzel, G H4.h, and T I Marx, / Colloid Sci., 19, 774 (1964).
108. R S Hansen, / !hys. Chem., 68, 01 (1964).
109. W D E Th42as and L P4tter, / Colloid Interface Sci., 50, 397 (1975).
110. C C Addis4n and T A Elli4tt, J. Chem. Soc, 1949, 789.
111. F H Garner and P Mina, %rans. Faraday Soc, 55, 1607 (1959).
11. J Van Ha;enbergh and P J44s, J. Colloid Interface Sci., 95, 17 (1983).
113. C Hsu and R E Apfel, J. Colloid Interface Sci., 10, 467 (1985).
114. R S Hansen and J Ah2ad, !rogress in Surface and Membrane Science, V4l 4,
A.ade2i. Press, New Y4rk, 1971.
115. H L4fgren, R D New2an, L E S.ri;en, and H T Da;is, / Colloid Interface Sci.,
98, 175 (1984).
116. S Hard and R D New2an, / Colloid Interface Sci., 115, 73 (1987).
117. M San4, M awagu.hi, Y-L Chen, R J Skarlupka, T Chang, G Z4graphi, and H
Yu, #ev. Sci. Instr., 5, 1158 (1986).
118. J C Earnshaw and R C M.Gi;ern, / !hys. D. Appl. !hys., 20, 8 (1987).
119. V B Fainer2an, R Miller, and P J44s, Colloid !olym. Sci., 22, 731 (1994).
10. R Miller, P J44s, and V B Fainer2an, !rog. Colloid !olym. Sci., 9, 188 (1994).
11. V B Fainer2an, A V Makie;ski, and R Miller, Colloids & Surfaces, A5 (1993).
1. J F Padday and D R Russell, J. Colloid Sci., 15, 503 (1960).
13. D G LeGrand and G L Gaines, Jr, / Colloid Interface Sci., 42, 181 (1973).
14. J l4ubek, Colloid !olymer Sci., 253, 99 (1975).


CHAPTER III
TIe NuLure und TIermodynumIcs oI IquId nLerIuces


It was 2ade .lear in Chapter II that the surfa.e tensi4n is a definite and a..urately
2easurable pr4perty 4f the interfa.e between tw4 liquid phases M4re4;er, its ;alue is ;ery
rapidly established in pure substan.es 4f 4rdinary ;is.4sity; dyna2i. 2eth4ds indi.ate that a
n4r2al surfa.e tensi4n is established within a 2illise.4nd and pr4bably s44ner [1 In this
.hapter it is thus appr4priate t4 dis.uss the ther24dyna2i. basis f4r surfa.e tensi4n and t4
de;el4p equati4ns f4r the surfa.e tensi4n 4f single- and 2ultiple-.42p4nent syste2s We
begin with ther24dyna2i.s and stru.ture 4f single-.42p4nent interfa.es and expand 4ur
dis.ussi4n t4 s4luti4ns in Se.ti4ns III-4 and III-5

1. One-Component Systems
A. Surface %hermodynamic Quantities for a !ure Substance
Figure III-l depi.ts a hyp4theti.al syste2 .4nsisting 4f s42e liquid that fills a b4x ha;ing
a sliding .4;er; the 2aterial 4f the .4;er is su.h that the interfa.ial tensi4n between it and the
liquid is zer4 If the .4;er is slid ba.k s4 as t4 un.4;er an a24unt 4f surfa.e dJl, the w4rk
required t4 d4 s4 will be y d A. This is re;ersible w4rk at .4nstant pressure and te2perature
and thus gi;es the in.rease in free energy 4f the syste2 (see Se.ti4n XVII-12 f4r a 24re
detailed dis.ussi4n 4f the ther24dyna2i.s 4f surfa.es`

The t4tal free energy 4f the syste2 is then 2ade up 4f the 24lar free energy ti2es the t4tal
nu2ber 4f 24les 4f the liquid plus G
s
, the surfa.e free energy per unit area, ti2es the t4tal
surfa.e area Thus

Be.ause this pr4.ess is a re;ersible 4ne, the heat ass4.iated with it gi;es the surface
entropy
m-1 NE-CMPNENT SYSTEMS

3


where S
s
is the surfa.e entr4py per square .enti2eter 4f surfa.e Be.ause
(dG/ dT)
P
= -S, it f4ll4ws that
ften, and as a g44d appr4xi2ati4n,
s
and the surfa.e energy E
s
are n4t distinguished, s4
Eq III-6 .an be seen in the f4r2

The t4tal surfa.e energy E generally is larger than the surfa.e free energy It is frequently
the 24re inf4r2ati;e 4f the tw4 quantities, 4r at least it is 24re easily related t4 24le.ular
24dels
ther ther24dyna2i. relati4nships are de;el4ped during the .4urse 4f this

4r, in .4njun.ti4n with Eq III-l,

Finally, the t4tal surfa.e enthalpy per square .enti2eter
s
is

III THERMDYNAMICS F LIQUID
INTERFACES

4
.hapter The surfa.e spe.ifi. heat C (the distin.ti4n between C* and C is rarely 2ade`, is
an additi4nal quantity t4 be 2enti4ned at this p4int, h4we;er It is gi;en by

The surfa.e tensi4n 4f 24st liquids de.reases with in.reasing te2perature in a nearly
linear fashi4n, as illustrated in Fig III-2 The near-linearity has sti2ulated 2any suggesti4ns
as t4 algebrai. f4r2s that gi;e exa.t linearity An 4ld and well-kn4wn relati4nship,
attributed t4 E4t;4s [3, is

where V is the 24lar ;4lu2e ne d4es expe.t the surfa.e tensi4n t4 g4 t4 zer4 at the
.riti.al te2perature, but the interfa.e see2s t4 be.42e diffuse at a slightly l4wer
te2perature, and Ra2say and Shields [4 repla.ed %
c
in Eq Ill-10 by (%
c
- 6` In either
f4r2, the .4nstant k is ab4ut the sa2e f4r 24st liquids and has a ;alue 4f ab4ut 21
ergs/ An4ther f4r2 4riginated by ;an der Waals in 1894 but de;el4ped further by
Guggenhei2 [5 is

Fig III-2 Variati4n 4f surfa.e tensi4n and t4tal surfa.e energy 4f CCIq with te2perature
(Data fr42 Ref 2`
n-1 ONE-COMPONENT SYSTEMS 5


where subs.ript m den4tes 2elting p4int and y is in dynes per .enti2eter [

There is a p4int 4f 4..asi4nal 2isunderstanding ab4ut di2ensi4ns that .an be illustrated
here The quantity y V
2
/
3
is 4f the nature 4f a surfa.e free energy per 24le, yet it w4uld
appear that its di2ensi4ns are energy per 24le
2
/
3
, and that k in Eq Ill-10 w4uld be in ergs per
degree per 24le
2
/
3
The ter2 "24le
2
/
3
" is 2eaningless, h4we;er, be.ause "24le" is n4t a
di2ensi4n but rather an indi.ati4n that an A;4gadr4 nu2ber 4f 24le.ules is in;4l;ed
Be.ause A;4gadr4s nu2ber is itself arbitrary (depending, f4r exa2ple, 4n whether a gra2 4r
a p4und 24le.ular weight syste2 is used`, t4 get at a rati4nal 2eaning 4f k 4ne sh4uld
.42pute it 4n the per 24le.ule basis; this gi;es k = 2.9 x 10"
16
ergs/degree-24le.ule
Lennard-J4nes and C4rner [8 ha;e p4inted 4ut that Eq Ill-10 arises rather naturally 4ut 4f a
si2ple statisti.al 2e.hani.al treat2ent 4f a liquid, where k is the B4ltz2ann .4nstant (13 x
10
-16
` ti2es a fa.t4r 4f the 4rder 4f unity

Equati4ns III-10 and III-11 are, 4f .4urse, appr4xi2ati4ns, and the situati4n has been
exa2ined in s42e detail by Cahn and Hilliard [9], wh4 find that Eq Ill-11 is als4
appr4xi2ated by regular s4luti4ns n4t t44 near their .riti.al te2perature

. %he %otal Surface Energy, E
s
If the ;ariati4n 4f density and hen.e 24lar ;4lu2e with te2perature is s2all, it f4ll4ws
fr42 Eqs Ill-10 and III-8 that E
s
will be nearly te2perature-independent In fa.t, Eq Ill-11
with n - 1 2ay be written in the f4r2


whi.h illustrates the p4int that surfa.e tensi4n and energy be.42e equal at 0 The
te2perature independen.e 4f E
s
generally h4lds f4r liquids n4t t44 .l4se t4 their .riti.al
te2perature, alth4ugh, as illustrated in Fig III-2, E
s
e;entually dr4ps t4 zer4 at the .riti.al
te2perature
Inspe.ti4n 4f Table III-l sh4ws that there is a wide range 4f surfa.e tensi4n and E
s

;alues It is 24re instru.ti;e, h4we;er, t4 .42pare E
s
;alues .al.ulated 4n an energy per
24le basis The area per 24le 4f spheri.al 24le.ules 4f 24le.ular weight M and radius r
is
where n is 11/9 f4r 2any 4rgani. liquids but 2ay be .l4ser t4 unity f4r 2etals [6]. A useful
e2piri.al relati4nship f4r 2etals is
6 III THERMDYNAMICS F LIQUID
INTERFACES


where is A;4gadr4s nu2ber nly ab4ut 4ne-f4urth 4f the area 4f the surfa.e spheres
will be exp4sed t4 the interfa.e; thus Eq Ill-14 be.42es A = /A^y
3
V
2
/
3
, where V den4tes
24lar ;4lu2e and / is a ge42etri. fa.t4r near unity Then, E
s
= AE
S
4n an energy per 24le
basis In Table III-l 4ne sees that the ;ariati4n in E
s
is 2u.h s2aller than that 4f y 4r E
s
.
Se2ie2piri.al equati4ns useful f4r 24lten 2etals and salts 2ay be f4und in Refs and
10, respe.ti;ely

Exa2ple We repr4du.e the entry f4r ir4n in Table III-l as f4ll4ws First E
s
-1880-
(1808` (-043` = 265 ergs/.2
2
Next, esti2ating V t4 be ab4ut 1 .2
3
/24l and taking / t4
be unity, A = (602 10
23
`/
3
(1`
2
/
3
= 31 10
8
.2
2
/24l when.e E' = (265`(31
10
8
`/(413 10

` = 20,100 .al/24l

ne 2ay .4nsider a 24le.ule in the surfa.e regi4n as being in a state inter2ediate
between that in the ;ap4r phase and that in the liquid Skapski [11 has 2ade the f4ll4wing
si2plified analysis C4nsidering 4nly nearest-neighb4r intera.ti4ns, if , and n
s
den4te the
nu2ber 4f nearest neighb4rs in the interi4r 4f the liquid and the surfa.e regi4n,
respe.ti;ely, then, per 24le.ule
An extensi;e .42pilati4n 4f y and dy/ d% data is gi;en by G 4r4si and E sz 4;ats,
J. Chem. Eng. Data, 26, 323 (1981`
b
E
s>
.42puted 4n a per gra2 i4n basis
.
Perflu4r42ethyl .y.l4hexane
III-l NE-CMPNENT SYSTEMS



where & is the intera.ti4n energy n this basis, the energy 4f ;ap4rizati4n sh4uld be
&i t j / 2. F4r .l4se-pa.ked spheres, n, = 12 and n
s
= 9 s4 that E
s
sh4uld be ab4ut 4ne-f4urth
4f the energy 4f ;ap4rizati4n (n4t exa.tly be.ause 4f /` n this basis the surfa.e energy 4f
2etals is s42ewhat smaller than expe.ted; h4we;er, 4;er the range in Table III-l fr42
heliu2 t4 ir4n, 4ne sees that the ;ariati4n in the surfa.e energy per area depends al24st
equally 4n the ;ariati4n in inter24le.ular f4r.es and 4n that 4f the density 4f pa.king 4r
24le.ular size

C. %he Effect of Curvature on Vapor !ressure and Surface %ension
A ;ery i2p4rtant ther24dyna2i. relati4nship is that gi;ing the effe.t 4f surfa.e
.ur;ature 4n the 24lar free energy 4f a substan.e This is perhaps best underst44d in ter2s
4f the pressure dr4p A! a.r4ss an interfa.e, as gi;en by Y4ung and Lapla.e in Eq II-
Fr42 ther24dyna2i.s, the effe.t 4f a .hange in 2e.hani.al pressure at .4nstant
te2perature 4n the 24lar free energy 4f a substan.e is

It is .4n;enient t4 relate the free energy 4f a substan.e t4 its ;ap4r pressure and,
assu2ing the ;ap4r t4 be ideal, G = G + #% n !. Equati4n III-1 then be.42es


where ! is the n4r2al ;ap4r pressure 4f the liquid, ! is that 4bser;ed 4;er the .ur;ed
surfa.e, and #
m
is the 2ean radius 4f .ur;ature (in a 24re exa.t ;ersi4n, the quantity y
/ #
m
be.42es y/ #
m
-(!-!) [19 Equati4n III-18 is frequently .alled the Kelvin equati4n
and, with the Y4ung-Lapla.e equati4n (II-`, 2akes the se.4nd funda2ental relati4nship
4f surfa.e .he2istry
F4r the .ase 4f a spheri.al surfa.e 4f radius r, Eq Ill-18 be.42es

4r if the 24lar ;4lu2e V is assu2ed .4nstant and Eq II- is used f4r AP
III THERMDYNAMICS F LIQUID
INTERFACES

8

Here, # is p4siti;e and there is thus an in.reased ;ap4r pressure In the .ase 4f water, !/!
is ab4ut 1001 if # is 10"
4
.2, 1011 if # is 10"
5
.2, and 1114 if # is 10~
6
.2 4r 100 The
effe.t has been ;erified experi2entally f4r se;eral liquids [20, d4wn t4 radii 4f the 4rder 4f
01 ji2, and indire.t 2easure2ents ha;e ;erified the el;in equati4n f4r #
M
;alues d4wn t4
ab4ut 30 [19 The phen42en4n pr4;ides a ready explanati4n f4r the ability 4f ;ap4rs t4
supersaturate The f4r2ati4n 4f a new liquid phase begins with s2all .lusters that 2ay gr4w
4r aggregate int4 dr4plets In the absen.e 4f dust 4r 4ther f4reign surfa.es, there will be an
a.ti;ati4n energy f4r the f4r2ati4n 4f these s2all .lusters .4rresp4nding t4 the in.reased
free energy due t4 the .ur;ature 4f the surfa.e (see Se.ti4n IX-2`

While Eq Ill-18 has been ;erified f4r s2all dr4plets, atte2pts t4 d4 s4 f4r liquids in
.apillaries (where #
M
is negati;e and there sh4uld be a pressure redu.ti4n` ha;e led t4
startling dis.repan.ies P4tential pr4ble2s in.lude the presen.e 4f i2purities lea.hed fr42
the .apillary walls and all4wan.e f4r the fil2 4f ads4rbed ;ap4r that sh4uld be present (see
Chapter X` There is r442 f4r an4ther real effe.t arising fr42 stru.tural perturbati4ns in the
liquid indu.ed by the ;i.inity 4f the s4lid .apillary wall (see Chapter VI` Fisher and
Israela.h;ili [19 re;iew 2u.h 4f the literature 4n the ;erifi.ati4n 4f the el;in equati4n
and rep4rt .4nfir2at4ry 2easure2ents f4r liquid bridges between .r4ssed 2i.a .ylinders
The situati4n is si2ilar t4 that 4f the 2enis.us in a .apillary sin.e #
M
is negati;e; s42e 4f
their results are sh4wn in Fig III-3 Studies in .apillaries ha;e been re;iewed by Melr4se
[20 wh4 .4n.ludes that the el;in equati4n is 4beyed f4r radii at least d4wn t4 1 FIM.
T4l2an [21 .4n.luded fr42 ther24dyna2i. .4nsiderati4ns that with suffi.iently .ur;ed
surfa.es, the ;alue 4f the surface tension itself sh4uld be affe.ted In re;iewing the subje.t,
Melr4se [22 gi;es the equati4n

where 5 is a 2easure 4f the thi.kness 4f the interfa.ial regi4n (ab4ut 5 A f4r .y.l4hexane
[23` and #
M
2ay be p4siti;e 4r negati;e (See als4 Se.ti4n III-2A`
This effe.t assu2es i2p4rtan.e 4nly at ;ery s2all radii, but it has s42e appli.ati4ns in
the treat2ent 4f nu.leati4n the4ry where the ex.ess surfa.e energy 4f s2all .lusters is
in;4l;ed (see Se.ti4n IX-2` An intrinsi. diffi.ulty with equati4ns su.h as III-20 is that
the treat2ent, if n4t 24delisti. and hen.e partly e2piri.al, assu2es a .4ntinu4us 2ediu2,
yet the effe.t d4es n4t be.42e i2p4rtant until .ur;ature .42parable t4 24le.ular
di2ensi4ns is rea.hed Fisher and Israela.h;ili [24 2easured the f4r.e due t4 the Lapla.e
pressure f4r a pendular ring 4f liquid between .r4ssed 2i.a .ylinders and .4n.luded that
f4r se;eral 4rgani. liquids the effe.ti;e surfa.e tensi4n re2ained un.hanged
n-1 NE-CMPNENT SYSTEMS

9

Fig III-3 C42paris4n 4f Eq ITJ-18 (s4lid line` with experi2ental results f4r .y.l4hex-ane
bridges f4r2ed between .r4ssed 2i.a .ylinders; the dashed line is the .al.ulati4n in.luding
Eq 111-20 (fr42 Ref 19`


d4wn t4 radii 4f .ur;ature as l4w as 05 n2 Christens4n [25, in a si2ilar experi2ent,
f4und the Lapla.e equati4n t4 h4ld f4r water d4wn t4 radii 4f 2 n2
D. %he Effect of !ressure on Surface %ension The f4ll4wing
relati4nship h4lds 4n ther24dyna2i. gr4unds [26, 2:

where A den4tes area In 4ther w4rds the pressure effe.t is related t4 the .hange in 24lar
;4lu2e when a 24le.ule g4es fr42 the bulk t4 the surfa.e regi4n This .hange w4uld be
p4siti;e, and the effe.t 4f pressure sh4uld theref4re be t4 in.rease the surfa.e tensi4n
Unf4rtunately, h4we;er, 4ne .ann4t subje.t a liquid surfa.e t4 an in.reased pressure
with4ut intr4du.ing a se.4nd .42p4nent int4 the syste2, su.h as s42e intert gas ne
thus in.reases the density 4f 2atter in the gas phase and, 24re4;er, there will be s42e gas
ads4rbed 4n the liquid surfa.e with a .4rresp4nding ;4lu2e .hange
Studies by Erikss4n [28 and ing and .4-w4rkers [29 ha;e sh4wn that ads4rpti4n
10 III THERMDYNAMICS F LIQUID
INTERFACES

d42inates ne 2ay als4 study the effe.t 4f pressure 4n the surfa.e tensi4n 4f s4luti4ns
[30, 31 and 4n interfa.ial tensi4ns As an exa2ple 4f the latter .ase, A V
s
was f4und t4 be
ab4ut 28 x 10~
9
.2
3
/.2
2
f4r the w-4.tane-water interfa.e [32

. Structural and Theoretcal Treatments of L6ud Interfaces
The surfa.e free energy .an be regarded as the w4rk 4f bringing a 24le.ule fr42 the
interi4r 4f a liquid t4 the surfa.e, and that this w4rk arises fr42 the fa.t that, alth4ugh a
24le.ule experien.es n4 net f4r.es while in the interi4r 4f the bulk phase, these f4r.es
be.42e unbalan.ed as it 24;es t4ward the surfa.e As dis.ussed in .4nne.ti4n with Eq Ill-
15 and als4 in the next se.ti4ns, a kn4wledge 4f the p4tential fun.ti4n f4r the intera.ti4n
between 24le.ules all4ws a .al.ulati4n 4f the t4tal surfa.e energy; if this .an be written as
a fun.ti4n 4f te2perature, the surfa.e free energy is als4 .al.ulable
The unbalan.ed f4r.e 4n a 24le.ule is dire.ted inward, and it 2ight be asked h4w this
.4uld appear as a surfa.e "tensi4n" A 2e.hani.al anal4gy is sh4wn in Fig III-4, whi.h
illustrates h4w the w4rk t4 raise a weight .an appear as a h4riz4ntal pull; in the .ase 4f a
liquid, an extensi4n 4f the surfa.e results in 24le.ules being br4ught fr42 the interi4r int4
the surfa.e regi4n
The next p4int 4f interest has t4 d4 with the questi4n 4f h4w deep the surfa.e regi4n 4r
regi4n 4f appre.iably unbalan.ed f4r.es is This depends pri2arily 4n the range 4f
inter24le.ular f4r.es and, ex.ept where i4ns are in;4l;ed, the prin.ipal f4r.e between
24le.ules is 4f the s4-.alled ;an der Waals type (see Se.ti4n VI-1` This type 4f f4r.e
de.reases with ab4ut the se;enth p4wer 4f the inter24le.ular distan.e and, .4nsequently, it
is 4nly the first shell 4r tw4 4f nearest neighb4rs wh4se intera.ti4n with a gi;en 24le.ule is
4f i2p4rtan.e In 4ther w4rds, a 24le.ule experien.es essentially sy22etri.al f4r.es 4n.e
it is a few 24le.ular dia2eters away fr42 the surfa.e, and the thi.kness 4f the surfa.e
regi4n is 4f this 4rder 4f 2agnitude (see Ref 23, f4r exa2ple` (Certain aspe.ts 4f this
.4n.lusi4n need 24difi.ati4n and are dis.ussed in Se.ti4ns X-6C and XVII-5`
It 2ust als4 be realized that this thin surfa.e regi4n is in a ;ery turbulent state Sin.e
the liquid is in equilibriu2 with its ;ap4r, then, .learly, there is a tw4-way and balan.ed
traffi. 4f 24le.ules hitting and .4ndensing 4n the surfa.e fr42 the ;ap4r phase and 4f
24le.ules e;ap4rating fr42 the surfa.e int4 the ;ap4r phase Fr42 the gas kineti. the4ry,
the nu2ber 4f 24les striking 1 .2
2
4f surfa.e per se.4nd is

F4r ;ap4r saturated with respe.t t4 liquid water at r442 te2perature, Z is ab4ut 002
24l/.2
2
se. 4r ab4ut 12 x 10
22
24le.ules/.2
2
se. At equilibriu2, then, the
e;ap4rati4n rate 2ust equal the .4ndensati4n rate, whi.h differs fr42
III-2 TREATMENTS F LIQUID
INTERFACES 11




the pre.eding figure by a fa.t4r less than but .l4se t4 unity (.alled the .4ndensati4n
.4effi.ient` Thus ea.h square .enti2eter 4f liquid water entertains 12 x 10
22
arri;als and
departures per se.4nd The traffi. 4n an area 4f 10

.4rresp4nding t4 the area 4f a single

water 24le.ule, is 12 x 10

se."
1
, s4 that the lifeti2e 4f a 24le.ule 4n the surfa.e is 4n the
4rder 4f a tenth 2i.r4se.4nd
There is als4 a traffi. between the surfa.e regi4n and the adja.ent layers 4f liquid F4r 24st
liquids, diffusi4n .4effi.ients at r442 te2perature are 4n the 4rder 4f 10
-5
.2
2
/se., and the
diffusi4n .4effi.ient 2` is related t4 the ti2e t f4r a net displa.e2ent x by an equati4n due t4
Einstein:


If x is put equal t4 a distan.e 4f, say, 100 then t is ab4ut 10~
6
se., s4 that, due t4 Br4wnian
24ti4n, there is a ;ery rapid inter.hange 4f 24le.ules between the surfa.e and the adja.ent
bulk regi4n
The pi.ture that e2erges is that a "quies.ent" liquid surfa.e is a.tually in a state 4f ;i4lent
agitati4n 4n the 24le.ular s.ale with indi;idual 24le.ules passing rapidly ba.k and f4rth
between it and the bulk regi4ns 4n either side Under a 2i.r4s.4pe 4f suitable 2agnifi.ati4n,
the surfa.e regi4n sh4uld appear as a fuzzy blur, with the a;erage density ;arying in s42e
.4ntinu4us 2anner fr42 that 4f the liquid phase t4 that 4f the ;ap4r phase
In the .ase 4f s4lids, there is n4 d4ubt that a lateral tensi4n (whi.h 2ay be anis4tr4pi.` .an
exist between 24le.ules 4n the surfa.e and .an be related t4 a.tual stret.hing 4r .42pressi4n
4f the surfa.e regi4n This is p4ssible be.ause 4f the i224bility 4f s4lid surfa.es Si2ilarly,
with thin s4ap fil2s, wh4se thi.kness .an be as little as 100 stret.hing 4r extensi4n 4f the
fil2 2ay in;4l;e a .4rresp4nding ;ariati4n in inter24le.ular distan.es and an a.tual tensi4n
between 24le.ules
A .ase .an be 2ade f4r the usefulness 4f surfa.e "tensi4n" as a .4n.ept e;en in the .ase 4f
a n4r2al liquid-;ap4r interfa.e A dis.ussi4n 4f this appears in papers by Br4wn [33 and
Gurney [34 The inf4r2al pra.ti.e 4f using surfa.e tensi4n and surfa.e free energy
inter.hangeably will be f4ll4wed in this text
1 n THERMODYNAMICS OF LIQUID
INTERFACES

A. Further Development of the %hermodynamic
%reatment of the Surface #egion
C4nsider a liquid in equilibriu2 with its ;ap4r The tw4 bulk phases a and d4 n4t
.hange sharply fr42 4ne t4 the 4ther at the interfa.e, but rather, as sh4wn in Fig III-5,
there is a regi4n 4;er whi.h the density and l4.al pressure ;ary Be.ause the a.tual
interfa.ial regi4n has n4 sharply defined b4undaries, it is .4n;enient t4 in;ent a
2athe2ati.al di;iding surfa.e [35 ne then handles the extensi;e pr4perties (G, E, S,
n, et.` by assigning t4 the bulk phases the ;alues 4f these pr4perties that w4uld pertain if
the bulk phases .4ntinued unif4r2ly up t4 the di;iding surfa.e The a.tual ;alues f4r the
syste2 as a wh4le will then differ fr42 the su2 4f the ;alues f4r the tw4 bulk phases by
an ex.ess 4r defi.ien.y assigned t4 the surfa.e regi4n
The f4ll4wing relati4ns will then h4ld:
V4lu2e : V = V
a
+ V
0
Internal energy
. E = E
a
+ E
0
+ E
Entr4py . S =S
a
+ S
(i
+ S
a
M4les : n, = n f + nf + nf
(111-
24`
(111-
25`
(111-
26`
(111-
2`

We will use the supers.ript a t4 den4te surfa.e quantities .al.ulated 4n the pre.eding
assu2pti4n that the bulk phases .4ntinue un.hanged t4 an assu2ed 2athe2ati.al di;iding
surfa.e F4r an arbitrary set 4f ;ariati4ns fr42 equilibriu2,




ffl-2 TREATMENTS F LIQUID INTERFACES 13
where c and c
2
den4te the tw4 .ur;atures (re.ipr4.als 4f the radii 4f .ur;ature` and C| and C
2

are .4nstants The last tw4 ter2s 2ay be written as (C + C
2
)d(c + c
2
) + (C -
C
2
)d(c - c
2
), and these plus the ter2 ydA gi;e the effe.t 4f ;ariati4ns in area and
.ur;ature Be.ause the a.tual effe.t 2ust be independent 4f the l4.ati4n .h4sen f4r the
di;iding surfa.e, a .4nditi4n 2ay be put 4n C and C
2>
and this 2ay be taken t4 be that
C +C
2
= 0 This parti.ular .4nditi4n gi;es a parti.ular l4.ati4n 4f the di;iding surfa.e su.h
that it is n4w .alled the surface of tension.
F4r the .ase where the .ur;ature is s2all .42pared t4 the thi.kness 4f the surfa.e regi4n,
d(c - c
2
) 0 (this will be exa.tly true f4r a plane 4r f4r a spheri.al surfa.e`, and Eq 111-28
redu.es t4

Be.ause


where G is the Gibbs free energy, it f4ll4ws that



(Equati4n 111-31 is 4btained by differentiating Eq 111-30 and .42paring with Eq 111-29`
At equilibriu2, the energy 2ust be a 2ini2u2 f4r a gi;en set 4f ;alues 4f S and 4f ,-, and


but

s4
Equati4n 111-34 is the sa2e as w4uld apply t4 the .ase 4f tw4 bulk phases separated by a
2e2brane under tensi4n y.
If the surfa.e regi4n is displa.ed by a distan.e dt


n THERMDYNAMICS F LIQUID
INTERFACES

14

Equati4n n-38 is the Y4ung-Lapla.e equati4n (Eq II-`
The f4reg4ing ser;es as an intr4du.ti4n t4 the detailed ther24dyna2i.s 4f the surfa.e
regi4n; the 2eth4d is essentially that 4f Gibbs [35, as re;iewed by T4l2an [36, 3 An
additi4nal relati4nship is


where x den4tes distan.e n4r2al t4 the surfa.e and the p4ints a and -a lie in the tw4 bulk
phases, respe.ti;ely F4r a plane surfa.e, P* P*
3
, and


Here, P is the bulk pressure, whi.h is the sa2e in b4th phases, and p is the l4.al pressure,
whi.h ;aries a.r4ss the interfa.e

Returning t4 the 2atter 4f the l4.ati4n 4f the di;iding surfa.e, the p4siti4n defined by (Ci
+ C) = 0 is in general su.h that n
a
+n&, .al.ulated by assu2ing the bulk phases t4 .4ntinue
up t4 the di;iding surfa.e, will differ fr42 the a.tual n. That is, e;en f4r a single pure
substan.e, there will be a n4nzer4 surfa.e ex.ess r that .an be p4siti;e 4r negati;e This
.4n;enti4n, while 2athe2ati.ally .4n;enient, is n4t pleasing intuiti;ely, and 4ther
.4n;enti4ns are p4ssible f4r l4.ating the di;iding surfa.e, in.luding 4ne su.h that the surfa.e
ex.ess is zer4 In fa.t, the quantity 8 in Eq IH-20 is just the distan.e between this di;iding
surfa.e and the surfa.e 4f tensi4n and is p4siti;e f4r a dr4p This general subje.t has been
dis.ussed by irkw44d and Buff [38, Buff [39, Melr4se [22,40, Mandell and Reiss [41,
and als4 by Neu2ann and .4-w4rkers [42-44 Neu2ann and .4-w4rkers ha;e de;el4ped a
generalized hydr4stati. treat2ent
m-. TREATMENTS F LIQUID
INTERFACES 15

4f .apillarity that is ;alid f4r highly .ur;ed surfa.es [45 and ha;e sh4wn that in the .4ntext
4f this the4ry the free energy re2ains in;ariant t4 a shift in the di;iding surfa.e
[46
. Calculation of the Surface Energy and Structure of Interfaces
The fun.ti4n 4f ther24dyna2i.s is t4 pr4;ide phen42en4l4gi.al relati4nships wh4se
;alidity has the auth4rity 4f the laws 4f ther24dyna2i.s the2sel;es ne 2ay pr4.eed
further, h4we;er, if spe.ifi. 24dels 4r additi4nal assu2pti4ns are 2ade F4r exa2ple, the
use 4f the ;an der Waals equati4n 4f state all4ws an analysis 4f h4w P - p in Eq 111-40
sh4uld ;ary a.r4ss the interfa.e; T4l2an [36,37] 2ade an early .al.ulati4n 4f this type
There has been a high degree 4f de;el4p2ent 4f statisti.al ther24dyna2i.s in this field
(see Ref 47 and the General Referen.es and als4 Se.ti4ns XV-4 and XVI-3). A great
ad;antage 4f this appr4a.h is that 4ne 2ay deri;e ther24dyna2i. pr4perties fr42
kn4wledge 4f the inter24le.ular f4r.es in the fluid Many physi.al syste2s .an be
appr4xi2ated with 24del intera.ti4n p4tential energies; a widely used syste2 .42prises
"attra.ti;e hard spheres" where rigid spheres 4f dia2eter b intera.t with an attra.ti;e
p4tential energy, u
m
(r).

The hard-sphere treat2ent als4 suggested a relati4nship between surfa.e tensi4n and the
.42pressibility 4f the liquid In a 24re .lassi. appr4a.h [48, the equati4n

relates the internal pressure 4f the liquid, (dE/ dV)r, t4 the surfa.e tensi4n where b is the
side 4f a .ube 4f 24le.ular ;4lu2e The internal pressure .an be repla.ed by the expressi4n
(a%/ f i - !), where a and 0 are the .4effi.ients 4f ther2al expansi4n and 4f .42pressibility
and ! is the a2bient pressure [49

The .lassi. the4ry due t4 ;an der Waals pr4;ides an i2p4rtant phen42en4l4gi.al link
between the stru.ture 4f an interfa.e and its interfa.ial tensi4n [50-5]. The expressi4n


relates the surfa.e tensi4n t4 the square 4f the gradient in the equilibriu2 density pr4file
a.r4ss the interfa.e The equilibriu2 density pr4file is that 2ini2izing the free energy 4f
the interfa.e The para2eter 2 is f4und fr42 the inter24le.ular f4r.es in the fluid, 4r in
24re pre.ise the4ries, fr42 the dire.t .4rrelati4n fun.ti4n fr42 statisti.al 2e.hani.s [53].
If 4ne f4ll4ws the attra.ti;e hard-sphere 24del 4f ;an der Waals, a si2ple result f4r m is
16 IT! THERMDYNAMICS F LIQUID
INTERFACES



ne pr4ble2 with this treat2ent is that it negle.ts higher-4rder ter2s depending 4n higher
242ents 4f u
m
that be.42e undefined f4r sl4wly de.aying intera.ti4n p4tentials (see
Pr4ble2 III-9`
The gradient 24del has been .42bined with tw4 equati4ns 4f state t4 su..essfully 24del
the te2perature dependen.e 4f the surfa.e tensi4n 4f p4lar and n4np4lar fluids [54 Wid42
and Ta;an ha;e 24deled the surfa.e tensi4n 4f liquid
4
He near the X transiti4n with a
24dified ;an der Waals the4ry [55
An4ther statisti.al 2e.hani.al appr4a.h 2akes use 4f the radial distributi4n fun.ti4n
g(r)
t
whi.h gi;es the pr4bability 4f finding a 24le.ule at a distan.e r fr42 a gi;en 4ne
This fun.ti4n 2ay be 4btained experi2entally fr42 x-ray 4r neutr4n s.attering 4n a liquid
4r fr42 .42puter si2ulati4n 4r statisti.al 2e.hani.al the4ries f4r 24del p4tential energies
[56 irkw44d and Buff [38 sh4wed that f4r a gi;en p4tential fun.ti4n, &(r)


where, as sh4wn in Fig III-6, e4 is the p4tential energy at the 2ini2u2 and a is an
effe.ti;e 24le.ular dia2eter; the tw4 para2eters .an be 4btained fr42 the internal
pressure 4f a liquid 4r fr42 the n4nideality 4f the ;ap4r ne .al.ulati4n al4ng these lines
ga;e y f4r arg4n at 843 as 151 ergs/.2
2
[5 as .42pared t4 the experi2ental ;alue 4f
132 ergs/.2
2
The irkw44d-Buff appr4a.h has been applied t4 ethan4l-water 2ixtures
[58 and 24lten salts [59

The statisti.al 2e.hani.al appr4a.h, density fun.ti4nal the4ry, all4ws des.ripti4n 4f
the s4lid-liquid interfa.e based 4n kn4wledge 4f the liquid pr4perties [60, 61 This
appr4a.h has been applied t4 the s4lid-liquid interfa.e f4r hard spheres where experi-
2ental data 4n .4ll4idal suspensi4ns and the4ry [62 b4th indi.ate yb
2
/ k%= 06; this
;erifies that n4 attra.ti4n is ne.essary f4r a s4lid-liquid interfa.e t4 exist The adhesi;e
sphere and Lennard-J4nes (Eq 111-46` s4lids ha;e als4 been studied [61, 63 In


where p is the a;erage density and & den4tes d&/ dr. A widely used and su..essful f4r2
f4r &(r) is that due t4 Lennard-J4nes:


n-3 RIENTATIN AT INTERFACES 63













Fig III-6 The Lennard-J4nes p4tential
fun.ti4n



the Lennard-J4nes syste2 the influen.e 4f the dis4rdered phase density is e;ident with the s4lid-
;ap4r interfa.ial tensi4n greatly ex.eeding that ab4;e the triple p4int where a s4lid .4exists with
a liquid

Tw4 si2ulati4n 2eth4ds-M4nte Carl4 and 24le.ular dyna2i.s-all4w .al.ulati4n 4f the
density pr4file and pressure differen.e 4f Eq 111-44 a.r4ss the ;ap4r-liquid interfa.e [64, 65
In the f4r2er 2eth4d, the initial syste2 .4nsists 4f N 24le.ules in assu2ed p4siti4ns An
inter24le.ule p4tential fun.ti4n is .h4sen, su.h as the Lennard-J4nes p4tential, and the
p4siti4ns are rand42ly ;aried until the energy 4f the syste2 is at a 2ini2u2 The resulting
.4nfigurati4n is taken t4 be the equilibriu2 4ne In the 24le.ular dyna2i.s appr4a.h, the N
24le.ules are gi;en initial p4siti4ns and ;el4.ities and the equati4ns 4f 24ti4n are s4l;ed t4
f4ll4w the ensuing .4llisi4ns until the set sh4ws .4nstant ti2e-a;erage ther24dyna2i.
pr4perties B4th 2eth4ds are .42puter intensi;e yet widely used
In Fig III- we sh4w a 24le.ular dyna2i.s .42putati4n f4r the density pr4file and pressure
differen.e P - p a.r4ss the interfa.e 4f an arg4nlike syste2 [66 (see als4 Refs 6, 68 and
.itati4ns therein` Si2ilar .al.ulati4ns ha;e been 2ade 4f 6 in Eq 111-20 [69, 0 M4nte Carl4
.al.ulati4ns 4f the density pr4file 4f the ;ap4r-liquid interfa.e 4f 2agnesiu2 h4w stratifi.ati4n
penetrating ab4ut three at42i. dia2eters int4 the liquid [1 Experi2ental 2easure2ent 4f the
transverse stru.ture 4f the ;ap4r-liquid interfa.e 4f 2er.ury and galliu2 sh4wed stru.tures that
were indistinguishable fr42 that 4f the bulk fluids [2,
3

3. Orentaton at Interfaces
There is 4ne re2aining and ;ery signifi.ant aspe.t 4f liquid-air and liquid-liquid
interfa.es t4 be .4nsidered bef4re pr4.eeding t4 a dis.ussi4n 4f

HI THERMDYNAMICS F LIQUID
INTERFACES

18

Fig D3- (a) Interfa.ial density pr4file f4r an arg4nlike liquid-;ap4r interfa.e (density in
redu.ed units`; z is the distan.e n4r2al t4 the surfa.e, (b) Variati4ns 4f P-p 4f Eq BI-40
(in redu.ed units` a.r4ss the interfa.e [Fr42 the thesis 4f J P R B Walt4n (see Ref 66`


the beha;i4r and ther24dyna2i.s 4f s4luti4n interfa.es This is the 2atter 4f 24le.ular
4rientati4n at interfa.es
The idea that unsy22etri.al 24le.ules will 4rient at an interfa.e is n4w s4 well
a..epted that it hardly needs t4 be argued, but it is 4f interest t4 4utline s42e 4f the hist4ry
4f the .4n.ept Hardy [4 and Harkins [5 de;4ted a g44d deal 4f attenti4n t4 the idea 4f
"f4r.e fields" ar4und 24le.ules, 24re 4r less intense depending 4n the p4larity and
spe.ifi. details 4f the stru.ture rientati4n was treated in ter2s 4f a prin.iple 4f "least
abrupt .hange in f4r.e fields," that is, that 24le.ules sh4uld be 4riented at an interfa.e s4
as t4 pr4;ide the 24st gradual transiti4n fr42 4ne phase t4 the 4ther If we read
"intera.ti4n energy" instead 4f "f4r.e field," the prin.iple .4uld be rew4rded 4n the ;ery
reas4nable basis that 24le.ules will be 4riented s4 that their 2utual intera.ti4n energy will
be a 2axi2u2
A s42ewhat 24re quantitati;e de;el4p2ent al4ng these lines was gi;en by Lang2uir
[6 in what he ter2ed the pr/nc/p/e af /ndependent sarface act/an. He pr4p4sed that,
qualitati;ely, 4ne .4uld supp4se ea.h part 4f a 24le.ule t4 p4ssess a l4.al surfa.e free
energy Taking ethan4l as an exa2ple, 4ne .an e2pl4y this prin.iple t4 de.ide whether
surfa.e 24le.ules sh4uld be 4riented a..4rding t4 Fig III-8a 4r b. In the first .ase, the
surfa.e presented w4uld .42prise hydr4xyl gr4ups wh4se surfa.e energy sh4uld be ab4ut
190 ergs/.2
2
, extrap4lating fr42 water In the se.4nd .ase, a surfa.e energy like that 4f a
m-4 THE SURFACE TENSIN F
SLUTINS

19


hydr4.arb4n sh4uld pre;ail, that is, ab4ut 50 ergs/.2
2
(see Table III-l` This is a differen.e
4f 140 ergs/.2
2
4r ab4ut 30 x 10"
14
ergs per 24le.ule Sin.e k % is 4n the 4rder 4f 4 x 10"
14

ergs per 24le.ule, the B4ltz2ann fa.t4r, t xp(-&/ k`, fa;4ring the 4rientati4n in Fig l &-
Sb sh4uld be ab4ut 10
5
This .4n.lusi4n is supp4rted by the 4bser;ati4n that the a.tual
surfa.e tensi4n 4f ethan4l is 22 ergs/.2
2
4r n4t ;ery different fr42 that 4f a hydr4.arb4n
Lang2uirs prin.iple 2ay s4und rather pri2iti;e but, in fa.t, it is widely used and useful
t4day in 4ne 4r an4ther (4ften disguised` f4r2

There is, 4f .4urse, a 2ass 4f rather dire.t e;iden.e 4n 4rientati4n at the liquid-;ap4r
interfa.e, 2u.h 4f whi.h is at least i2pli.it in this .hapter and in Chapter IV The 2eth4ds
4f statisti.al 2e.hani.s are appli.able t4 the .al.ulati4n 4f surfa.e 4rientati4n 4f
assy22etri. 24le.ules, usually by intr4du.ing an angular dependen.e t4 the inter24le.ular
p4tential fun.ti4n (see Refs 6, 68, as exa2ples` Wid42 has applied a 2ean-held
appr4xi2ati4n t4 a latti.e 24del t4 predi.t the tenden.y 4f AB 24le.ules t4 ads4rb and
4rient perpendi.ular t4 the interfa.e between phases 4f AA and BB [8 In the .ase 4f
water, a 24le.ular dyna2i.s .al.ulati4n .4n.luded that the surfa.e dip4le density
.4rresp4nded t4 a tenden.y f4r surfa.e-H gr4ups t4 p4int t4ward the ;ap4r phase [9

4. The Surface Tenson of Solutons
A. inary Solutions
The prin.ipal p4int 4f interest t4 be dis.ussed in this se.ti4n is the 2anner in whi.h the
surfa.e tensi4n 4f a binary syste2 ;aries with .42p4siti4n The effe.ts 4f 4ther ;ariables
su.h as pressure and te2perature are si2ilar t4 th4se f4r pure substan.es, and the 24re
elab4rate treat2ent f4r tw4-.42p4nent syste2s is n4t .4nsidered here Als4, the .ase 4f
i22is.ible liquids is taken up in Se.ti4n IV-2
A fairly si2ple treat2ent, due t4 Guggenhei2 [80, is useful f4r the .ase 4f ideal 4r
nearly ideal s4luti4ns An abbre;iated deri;ati4n begins with the free energy 4f a spe.ies

where a, is the abs4lute a.ti;ity, a, = / g/ , where Af, is the 24le fra.ti4n 4f
m THERMDYNAMICS F LIQUID
INTERFACES

0
spe.ies i (unity f4r pure liquids`, and g
t
deri;es fr42 the partiti4n fun.ti4n Q
t
. F4r a pure
liquid 1, the surfa.e tensi4n 2ay be written as

4r

where the surfa.e is ;iewed as a tw4-di2ensi4nal phase 4f 24le.ular state .4rresp4nding t4
#f and o is the 24le.ular area Thus, the w4rk 4f bringing a 24le.ule int4 the surfa.e is
expressed as a AG using Eq 111-4 The sa2e relati4ns are then applied t4 ea.h .42p4nent
4f a s4luti4n

where
s
den4tes the 24le fra.ti4n in the surfa.e phase Equati4ns 111-50 and IH-51 2ay
be s4l;ed f4r
s
x
and
2
, respe.ti;ely, and substituted int4 the require2ent that iVf +
2
=
1 If it is assu2ed that o = = a2, 4ne then 4btains

Hildebrand and S.4tt [81 gi;e an expansi4n 4f Eq 111-53 f4r i a
2
.
Guggenhei2 [5 extended his treat2ent t4 the .ase 4f regular s4luti4ns, that is,
s4luti4ns f4r whi.h

and, in .42binati4n with Eq 111-49

where / den4tes the a.ti;ity .4effi.ient A ;ery si2ple relati4nship f4r su.h
IU-4 THE SURFACE TENSIN F
SLUTINS

21
where j8 is a se2ie2piri.al .4nstant
Figure III-9a sh4ws s42e data f4r fairly ideal s4luti4ns [81 where the s4lid lines 2, 3,
and 6 sh4w the atte2pt t4 fit the data with Eq 111-53; line 4 by taking a as a purely
e2piri.al .4nstant; and line 5, by the use 4f the Hildebrand-S.4tt equati4n [81 As a further
exa2ple 4f s4luti4n beha;i4r, Fig 111-96 sh4ws s42e data 4n fused-salt 2ixtures [83; the
d4tted lines sh4w the fit t4 Eq 111-55

An extensi;e f4r2alis2 f4r ;ari4us types 4f n4nideal s4luti4ns by has been de;el4ped by
Prig4gine, Defay and .4-w4rkers using a latti.e 24del all4wing f4r intera.ting 24le.ules 4f
different sizes [82 Nissen [84 has applied the appr4a.h t4 24lten-salt 2ixtures, as has
Gaines [85, Reiss and Mayer [10 de;el4ped an expressi4n f4r the surfa.e tensi4n 4f a
fused salt, using their hard-sphere treat2ent 4f liquids (Se.ti4n IH-2B`, and ha;e extended
the appr4a.h t4 s4luti4ns The sa2e is true f4r a statisti.al 2e.hani.al 24del de;el4ped by
Eyring and .4-w4rkers [86 G44dis2an [8 has .422ented 4n ;ari4us treat2ents f4r
24lten-salt 2ixtures
The the4reti.al treat2ents 4f Se.ti4n III-2B ha;e been used t4 .al.ulate interfa.ial
tensi4ns 4f s4luti4ns using suitable intera.ti4n p4tential fun.ti4ns Thus Gubbins and .4-
w4rkers [88 rep4rt a 24le.ular dyna2i.s .al.ulati4n 4f the surfa.e tensi4n 4f a s4luti4n 4f
A and B 24le.ules 4beying Eq 111-46 with CO,BBAO,AA = 04 and

We ha;e .4nsidered the surfa.e tensi4n beha;i4r 4f se;eral types 4f syste2s, and n4w it
is desirable t4 dis.uss in slightly 24re detail the ;ery i2p4rtant .ase 4f aque4us 2ixtures If
the surfa.e tensi4ns 4f the separate pure liquids differ appre.iably, as in the .ase 4f al.4h4l-
water 2ixtures, then the additi4n 4f s2all a24unts 4f the se.4nd .42p4nent generally
results in a 2arked de.rease in surfa.e tensi4n fr42 that 4f the pure water The .ase 4f
ethan4l and water is sh4wn in Fig III-9. As seen in Se.ti4n III-5, this effe.t 2ay be
a..4unted f4r in ter2s 4f sele.ti;e ads4rpti4n 4f the al.4h4l at the interfa.e Dilute aque4us
s4luti4ns 4f 4rgani. substan.es .an be treated with a se2ie2piri.al equati4n attributed t4
;4n Szyszk4wski [89,90


where yo is the surfa.e tensi4n 4f water, is a .4nstant .hara.teristi. 4f the h424l4g4us
series 4f 4rgani. .42p4unds in;4l;ed, A is a .4nstant .hara.teristi. 4f ea.h .42p4und,
and C is its .4n.entrati4n This equati4n 2ay be deri;ed 4n the basis 4f the Lang2uir
ads4rpti4n equati4n (see Pr4ble2 III-8 and Se.ti4ns XI-1A and XVII-3`
regular s4luti4ns .42es fr42 Prig4gine

22 III THERMDYNAMICS F LIQUID
INTERFACES


ffl-4 THE SURFACE TENSIN F
SLUTINS

23
The type 4f beha;i4r sh4wn by the ethan4l-water syste2 rea.hes an extre2e in the .ase
4f higher-24le.ular-weight s4lutes 4f the p4lar-n4np4lar type, su.h as, s4aps and detergents
[91 As illustrated in Fig III-9e, the de.rease in surfa.e tensi4n n4w takes pla.e at ;ery l4w
.4n.entrati4ns s42eti2es sh4wing a p4int 4f abrupt .hange in sl4pe in a / C pl4t [92 The
surfa.e tensi4n be.42es essentially .4nstant bey4nd a .ertain .4n.entrati4n identified with
2i.elle f4r2ati4n (see Se.ti4n XIII-5` The lines in Fig III-9* are fits t4 Eq 111-5 The
auth4rs .42bined this analysis with the Gibbs equati4n (Se.ti4n III-5B` t4 4btain the surfa.e
ex.ess 4f surfa.tant and an al.4h4l .4surfa.tant
. %he Surface %ension of !olymeric Systems
In p4ly2er s4luti4ns and blends, it be.42es 4f interest t4 understand h4w the surfa.e
tensi4n depends 4n the 24le.ular weight (4r nu2ber 4f repeat units, ) 4f the
2a.r424le.ule and 4n the p4ly2er-s4l;ent intera.ti4ns thr4ugh the intera.ti4n para2eter, x-
In ter2s 4f a Fl4ry latti.e 24del, x is gi;en by the p4ly2er and s4l;ent intera.ti4ns thr4ugh

where , , and are the p4ly2er-s4l;ent, p4ly2er-p4ly2er, and s4l;ent-s4l;ent
intera.ti4n energies, respe.ti;ely Mu.h 4f the pi4neering w4rk in this area was d4ne by
Gaines and .4-w4rkers [94 Szleifer and Wid42 [95 de;el4ped a latti.e 24del 4f dilute
phase-separated p4ly2er s4luti4ns Their deri;ati4n per2its a si2ple expressi4n f4r the
surfa.e tensi4n


that requires kn4wledge 4f the .4existing phase .42p4siti4ns, <t> and (/, but n4t the
detailed .42p4siti4n pr4file thr4ugh the interfa.e The fun.ti4n h[<f>}



Fig III-9 Representati;e pl4ts 4f surfa.e tensi4n ;ersus .42p4siti4n, (a` Is44.tane-n-
d4de.ane at 30C: 1 linear, 2 ideal, with a - 486 Is44.tane-benzene at 30C: 3 ideal, with
a = 354, 4 ideal-like with e2piri.al a 4f 112, 5 unsy22etri.al, with o - 136 and o
2
- 45
Is44.tane-.y.l4hexane at 30C: 6 ideal, with a = 384, ideallike with e2piri.al a 4f
1093, (a ;alues in
2
/24le.ule` (fr42 Ref 93` (b) Surfa.e tensi4n is4ther2s at 350C
f4r the syste2s (Na-Rb` NO3 and (Na-Cs` NO3. D4tted lines sh4w the fit t4 E6. n-55
(fr42 Ref 83` (.` Water-ethan4l at 25C ( d ) Aque4us s4diu2 .hl4ride at 20C (e)
Interfa.ial tensi4ns between 4il and water in the presen.e 4f s4diu2 d4de.yl.hl4ride
(SDS` in the presen.e 4f hexan4l and 020 M s4diu2 .hl4ride In.reasing b4th the
surfa.tant and the al.4h4l .4n.entrati4n de.reases the interfa.ial tensi4n (fr42 Ref 92`
24 ffi THERMDYNAMICS F LIQUID
INTERFACES


represents the distan.e 4f the free energy fr42 its d4uble tangent (at the .4existing phase
.42p4siti4ns, <f> and [f>}. This requires the local intera.ti4n para2eter

A s.aling analysis [95-9 pr4;ides the te2perature and 24le.ular weight dependen.e

depending 4n the surfa.e tensi4n .riti.al exp4nent, (i = 126 Experi2ental studies ha;e
;erified the x -` 0 li2it with all 4f the a;ailable data falling within x < 1 [9 ne exa2ple 4f
this s.aling beha;i4r is f4r p4lystyrene in 2ethyl-.y.l4hexane [98, 99 where

The surfa.e tensi4n 4f p4ly2er 2elts .an be str4ngly influen.ed by the p4tential
surfa.e a.ti;ity 4f the .hain ends [100 While the density 4f a p4ly2er depends 4n its
24le.ular weight, the pri2ary effe.t 4n surfa.e tensi4n is n4t thr4ugh density ;ariati4n but
rather due t4 preferential ads4rpti4n 4r depleti4n 4f the ends at the surfa.e 4berstein and
.4-w4rkers [101 ha;e de24nstrated this effe.t with end-fun.ti4nalized
p4ly(di2ethylsil4xane` Their pendant dr4p studies (see Se.ti4n II-` 4f l4w-24le.ular-
weight p4ly2ers ha;ing amine-, hydroxyl- 4r 2ef/iyZ-ter2inal gr4ups sh4w surfa.e ten-
si4ns de.reasing, independent 4f, 4r in.reasing with 24le.ular weight due t4 the higher,
inter2ediate, 4r l4wer surfa.e energies, respe.ti;ely, 4f the end gr4ups The end gr4ups
als4 alter the interfa.ial tensi4n between i22is.ible p4ly2er blends [102 in a si2ilar
way The additi4n 4f bl4.k .4p4ly2ers t4 i22is.ible p4ly2er blends is anal4g4us t4
adding a surfa.e a.ti;e agent t4 i22is.ible liquids The interfa.ial tensi4n is redu.ed by
the ads4rpti4n 4f the bl4.k .4p4ly2er at the interfa.e until it is saturated [103

where f (x) is a s.aling fun.ti4n 4f the s.aling ;ariable x = 1\/A(1 - r/T
.
`,


III-5 THERMDYNAMICS F BINARY SYSTEMS 1
Finally, si2ilar effe.ts .an be seen in 2is.ible p4ly2er blends where the surfa.e tensi4n
.4rrelates with the enri.h2ent 4f the l4wer-energy .42p4nent at the surfa.e as 24nit4red by x-
ray ph4t4ele.tr4n spe.tr4s.4py [104


5. Thermodynamcs of Bnary Systems: The G--s E6uaton
We n4w .42e t4 a ;ery i2p4rtant t4pi., na2ely, the ther24dyna2i. treat2ent 4f the
;ariati4n 4f surfa.e tensi4n with .42p4siti4n The treat2ent is due t4 Gibbs [35 (see Ref 49
f4r an hist4ri.al sket.h` but has been a2plified in a 24re .4n;eniently readable way by
Guggenhei2 and Ada2 [105

A. Definition of Surface Excess
As in Se.ti4n III-2A, it is .4n;enient t4 supp4se the tw4 bulk phases, a and 0, t4 be unif4r2
up t4 an arbitrary di;iding plane 5, as illustrated in Fig Ill-10 We restri.t 4ursel;es t4 plane
surfa.es s4 that C and .
2
are zer4, and the .4nditi4n 4f equilibriu2 d4es n4t i2p4se any
parti.ular l4.ati4n f4r S. As bef4re, 4ne .42putes the ;ari4us extensi;e quantities 4n this basis
and .42pares the2 with the ;alues f4r the syste2 as a wh4le Any ex.ess 4r defi.ien.y is then
attributed t4 the surfa.e regi4n
Taking the se.ti4n sh4wn in Fig HI-10 t4 be 4f unit area in .r4ss se.ti4n, then, if the
phases were unif4r2 up t4 5, the a24unt 4f the ith .42p4nent present w4uld be

III THERMDYNAMICS F LIQUID
INTERFACES

26

Here, the distan.es x and a are relati;e t4 planes A and l4.ated far en4ugh fr42 the surfa.e
regi4n s4 that bulk phase pr4perties pre;ail The a.tual a24unt 4f .42p4nent i present in the
regi4n between A and will be

Where?Den4tes the surfa.e ex.ess per unit areat
F4r the .ase where the phase 8 is gase4us, 2ay be negle.ted, and quantities 111-65 and
111-66 be.42e


If 4ne n4w 2akes a se.4nd arbitrary .h4i.e f4r the di;iding plane, na2ely, 5 and distan.e x it
2ust f4ll4w that

(dr4pping the supers.ript a as unne.essary`, be.ause the sa2e t4tal a24unt 4f the its
.42p4nent 2ust be present between A and regardless 4f h4w the di;iding surfa.e is l4.ated
ne then has


s4 that

4r, in general,
The term sarface excess wll -e used as an alge-rac 6uantty. If post;e, an actual
excess of the component s present and, f negat;e, there s a surface defcency. An
alternat;e name that has -een used s saperf/c/a/ dens/t.


III-5 THERMDYNAMICS F BINARY SYSTEMS 3 where den4tes 24le
fra.ti4n, 4r

Sin.e S and S" are purely arbitrary in l4.ati4n, Eq 111-2 .an be true 4nly if ea.h side
separately equals a .4nstant






With the pre.eding intr4du.ti4n t4 the handling 4f surfa.e ex.ess quantities, we n4w pr4.eed
t4 the deri;ati4n 4f the third funda2ental equati4n 4f surfa.e .he2istry (the Lapla.e and el;in
equati4ns, Eqs II- and III-18, are the 4ther tw4`, kn4wn as the Gibbs equati4n
F4r a s2all, re;ersible .hange dE in the energy 4f a syste2, 4ne has

Sin.e

and si2ilarly f4r phase , it f4ll4ws that

If 4ne n4w all4ws the energy, entr4py, and a24unts t4 in.rease fr42 zer4 t4 s42e finite ;alue,
keeping % , A (area`, and the n .4nstant, Eq 111-6 be.42es

Equati4n 111- is generally ;alid and 2ay n4w be differentiated in the usual 2anner t4 gi;e
28 HI THERMDYNAMICS F LIQUID
INTERFACES

C42paris4n with Eq 111-6 gi;es




4r, per unit area
F4r a tw4-.42p4nent syste2 at .4nstant te2perature, Eq IJJ-80 redu.es t4
M4re4;er, sin.e and %
a
2
are defined relati;e t4 an arbitrarily .h4sen di;iding surfa.e, it is
p4ssible in prin.iple t4 pla.e that surfa.e s4 that % = 0 (this is dis.ussed in 24re detail
bel4w`, s4 that





or

where a is the a.ti;ity 4f the s4lute and the supers.ript 1 4n the V 2eans that the di;iding
surfa.e was .h4sen s4 that - 0 Thus if dy/ da is negati;e, as in Fig -9., is p4siti;e,
and there is an a.tual surfa.e ex.ess 4f s4lute If dy/ da is p4siti;e, as in Fig III-9J, there
is a surfa.e defi.ien.y 4f s4lute

C. %he Dividing Surface
A s.he2ati. pi.ture 4f h4w .4n.entrati4ns 2ight ;ary a.r4ss a liquid-;ap4r interfa.e is
gi;en in Fig III-l 1 The .4n;enti4n indi.ated by supers.ript 1, 2at is, the 0 is
illustrated The di;iding line is drawn s4 that the tw4 areas shaded in full str4kes are equal,
and the surfa.e ex.ess 4f the s4l;ent is thus zer4 The area shaded with dashed str4kes,
whi.h lies t4 the right 4f the di;iding





II1-5 THERMDYNAMICS F BINARY
SYSTEMS

29



surfa.e 2inus the s2aller si2ilarly shaded area t4 the left .4rresp4nds t4 the (in this .ase
p4siti;e` surfa.e ex.ess 4f s4lute The quantity %
l
2
2ay thus be defined as the (algebrai.`
ex.ess 4f .42p4nent 2 in a 1-.2
2
.r4ss se.ti4n 4f surfa.e regi4n 4;er the 24les that w4uld
be present in a bulk regi4n .4ntaining the same number of moles of solvent as does the
section of surface region.

b;i4usly, a sy22etri. definiti4n F
2
als4 exists Here %
2
= 0 and %
2
represents the
ex.ess 4f .42p4nent 1 in a 1-.2
2
.r4ss se.ti4n 4f surfa.e regi4n 4;er the 24les that w4uld
be present in a bulk regi4n .4ntaining the same number of moles of solvent as does the
section of surface region. An4ther way 4f l4.ating the di;iding surfa.e w4uld be su.h that
the algebrai. sum 4f the areas in Fig Ill-11 t4 the right 4f the di;iding line is equal t4 the
su2 4f the areas t4 the left The surfa.e ex.esses s4 defined are written If Si2ilarly, i f and
are the ex.ess 4f the ith .42p4nent in the surfa.e regi4n 4;er the 24les that w4uld be
present in a bulk regi4n 4f the same total mass or volume as the surface region.
We .an .4nstru.t a nu2eri.al illustrati4n with a 05 24l fra.ti4n s4luti4n 4f ethan4l in
water We take a sli.e 4f surfa.e regi4n deep en4ugh t4 in.lude s42e 4f the bulk s4luti4n
This is taken, let us say, fr42 a surfa.e regi4n 4f area A .2
2
, and .4ntains 10 24l 4f water
and 30 24l 4f ethan4l We 4btain T
2
by .42paring with a sa2ple 4f bulk s4luti4n
.4ntaining the sa2e 10 24l 4f water This sa2ple w4uld .4ntain 4nly 10 24l 4f ethan4l,
and %
2
is theref4re (30-10`//! = 20/A. %
2
w4uld be 4btained by .42paring with a bulk
sa2ple .4ntaining 30 24l 4f ethan4l and hen.e 30 24l 4f water; theref4re T
2
= (10-30`/A =
-20/A. We 4btain if and %
2
by .42paring with a bulk sa2ple ha;ing the sa2e t4tal 24les as
the surfa.e 4r 40 24l t4tal (20 ea.h 4f water and ethan4l` Thus if = (10-20`/A = -10/A and
1^ - (30-20`/A = 10/A
The surfa.e ex.esses 4bey the relati4nship

where ! is deter2ined by the spe.ifi. pr4perty in;4ked in de.iding h4w t4 .h44se the
di;iding surfa.e Thus f4r % f , ! is unity; f4r r f , !i is Mi , the 24le.ular weight; and f4r
r^ !i is V,, the 24lar ;4lu2e We .an su22arize the entire pi.ture as f4ll4ws:
30 III THERMDYNAMICS F LIQUID
INTERFACES

D. Other Surface %hermodynamic #elationships
The pre.eding 2aterial 4f this se.ti4n has f4.used 4n the 24st i2p4rtant
phen42en4l4gi.al equati4n that ther24dyna2i.s gi;es us f4r 2ulti.42p4nent syste2s-
the Gibbs equati4n Many 4ther, f4r2al ther24dyna2i. relati4nships ha;e been de;el4ped,
4f .4urse Many 4f these are su22arized in Ref 10 The t4pi. is treated further in Se.ti4n
XVII-13, but is w4rthwhile t4 gi;e here a few additi4nal relati4nships espe.ially appli.able
t4 s4luti4ns
Using the Gibbs .4n;enti4n f4r defining surfa.e quantities, we define

s4 that

4r, in .42binati4n with Eq 111-6,



Alternati;ely, f4r the whole syste2 (ie, in.luding the bulk phases`,
Thus
where M = M + 2M2 and V = i V +
2
V
2
. (N4te Pr4ble2 HI-1`
An appr4a.h de;el4ped by Guggenhei2 [106 a;4ids the s42ewhat artifi.ial .4n.ept
4f the Gibbs di;iding surfa.e by treating the surfa.e regi4n as a bulk phase wh4se upper
and l4wer li2its lie s42ewhere in the bulk phases n4t far fr42 the interfa.e


III-6 DETERMINATIN F SURFACE EXCESS QUANTITIES
Integrati4n 4f Eq 111-8 h4lding .4nstant the intensi;e quantities %, /*,, and gi;es

4r

where the extensi;e quantities are n4w 4n a per unit area basis G is the spe.ifi. surfa.e
ex.ess free energy, and, unlike the .ase f4r a pure liquid (Eq UI-2`, it is n4t in general equal
t4 . This last w4uld be true 4nly in the unlikely situati4n 4f n4 surfa.e ads4rpti4n, s4 that
the fs were zer4 (S42e auth4rs use the entirely per2issible definiti4n G = A - , in whi.h
.ase d4es n4t appear in the equati4n .4rresp4nding t4 Eq 111-92-see Ref 10`

6. Detennnaton of Surface Excess Quanttes
A. Experimental Methods
The 24st widely used experi2ental 2eth4d f4r deter2ining surfa.e ex.ess quantities at
the liquid-;ap4r interfa.e 2akes use 4f radi4a.ti;e tra.ers The s4lute t4 be studied is
labeled with a radi4is4t4pe that e2its weak beta radiati4n, su.h as
3
H,
14
C, 4r
35
S ne
pla.es a dete.t4r .l4se t4 the surfa.e 4f the s4luti4n and 2easures the intensity 4f beta
radiati4n Sin.e the penetrati4n range 4f su.h beta e2itters is s2all (ab4ut 30 2g/.2
2
f4r
14
C, with 24st 4f the ads4rpti4n 4..urring in the first tw4-tenths 4f the range`, the 2easured
radi4a.ti;ity .4rresp4nds t4 the surfa.e regi4n plus 4nly a thin layer 4f s4luti4n (ab4ut 006
22 f4r
l4
C and e;en less f4r
3
H`
As an exa2ple, Taji2a and .4-w4rkers [108 used
3
H labeling t4 4btain the ads4rpti4n 4f
s4diu2 d4de.yl sulfate at the s4luti4n-air interfa.e The results, illustrated in Fig Ill-12,
agreed ;ery well with the Gibbs equati4n in the f4r2

when .4rre.ted f4r a.ti;ity .4effi.ients The fa.t4r 4f 2 in the den42inat4r appears
be.ause 4f the a.ti;ity 4f an ele.tr4lyte, in this .ase (Na
+
, X"`, is gi;en by a
a+
ax- 4r by
C
2
if a.ti;ity .4effi.ients are negle.ted The quantity dp. in Eq 111-82 thus be.42es #%d
In C
2
4r 2#%dn C. If, h4we;er, lAf s4diu2 .hl4ride was present at a swa2ping
ele.tr4lyte, the experi2ental rj was twi.e
HI THERMDYNAMICS F LIQUID
INTERFACES

32
s4luti4ns (Fr42 Ref 108`


that in Eq 111-93 [109 as expe.ted sin.e is n4w .4nstant and du is just #%d n C
A 24re elab4rate treat2ent is gi;en by Hall et al [110
Results .an s42eti2es be unexpe.ted The first study 4f this type 2ade use 4f
35
S
labeled Aer4s4l TN [111, an ani4ni. surfa.tant, als4 kn4wn as di-n-4.tyls4diu2
sulf4su..inate The 2easured

was twi.e that in Eq 111-93 and it was realized that

hydr4lysis had 4..urred, that is, X
+
+ H
2
0 = HX + H", and that it was the undiss4.iated
a.id HX that was surfa.e-a.ti;e Sin.e pH was essentially .4nstant, the a.ti;ity 4f HX was
just pr4p4rti4nal t4 C A si2ilar beha;i4r was f4und f4r aque4us s4diu2 s tear ate [112
A quite different 2eans f4r the experi2ental deter2inati4n 4f surfa.e ex.ess quantities
is ellipsometry. The te.hnique is dis.ussed in Se.ti4n IV-3D, and it is suffi.ient t4 n4te
here that the 2eth4d all4ws the .al.ulati4n 4f the thi.kness 4f an ads4rbed fil2 fr42 the
ellipti.ity pr4du.ed in light refle.ted fr42 the fil2 .4;ered surfa.e If this thi.kness, , is
kn4wn, % 2ay be .al.ulated fr42 the relati4nship T = /V, where V is the 24le.ular
;4lu2e This last 2ay be esti2ated either fr42 24le.ular 24dels 4r fr42 the bulk liquid
density
S2ith [113 studied the ads4rpti4n 4f n-pentane 4n 2er.ury, deter2ining b4th the
surfa.e tensi4n .hange and the ellips42etri. fil2 thi.kness as a fun.ti4n 4f the equilibriu2
pentane pressure T .4uld then be .al.ulated fr42 the Gibbs equati4n in the f4r2 4f Eq
Ill-106, and fr42 The agree2ent was ex.ellent Ellips42etry has als4 been used t4
deter2ine the surfa.e .42p4siti4ns 4f s4luti4ns [114,115, as well p4ly2er ads4rpti4n at
the s4luti4n-air interfa.e [116
The a.tual stru.ture at a ;ap4r-liquid interfa.e .an be pr4bed with x-rays Ri.e and .4-
w4rkers [2,3,11 use x-ray refle.ti4n t4 deter2ine the .42p4siti4n perpendi.ular t4 the
surfa.e and grazing in.iden.e x-ray diffra.ti4n t4 study the trans;erse stru.ture 4f an
interfa.e In a study 4f bis2uth galliu2 2ixtures,
Fig Ill-12 Verifi.ati4n 4f the Gibbs equati4n by the radi4a.ti;e tra.e 2eth4d bser;ed
(4` and .al.ulated (line` ;alues f4r %
2
f4r aque4us s4diu2 d4de.yl sulfate


m-6 DETERMINATIN F SURFACE EXCESS QUANTITIES 9
they find a partial 24n4layer 4f bis2uth at the surfa.e with the stru.ture 4f a super.44led
liquid un2ixed with galliu2 [11,118

. istorical Footnote and Commentary
Alth4ugh Gibbs published his 24nu2ental treatise 4n heter4gene4us equilibriu2 in
185, his w4rk was n4t generally appre.iated until the turn 4f the .entury, and it was n4t
until 2any years later that the field 4f surfa.e .he2istry de;el4ped t4 the p4int that
experi2ental appli.ati4ns 4f the Gibbs equati4n be.a2e i2p4rtant
It was 4f interest t4 2any surfa.e .he2ists t4 ;erify the Gibbs equati4n experi2entally
ne 2eth4d, tried by se;eral in;estigat4rs, was t4 bubble a gas thr4ugh the s4luti4n and
.4lle.t the fr4th in a separate .4ntainer The s4luti4n resulting fr42 the .4llapsed fr4th
sh4uld differ fr42 the 4riginal a..4rding t4 the ;alue 4f the surfa.e ex.ess 4f the s4lute
Satisfa.t4ry results were n4t 4btained, h4we;er, perhaps be.ause 4f the diffi.ulty in
esti2ating the area 4f the bubbles Pr4bably the first su..essful experi2ental ;erifi.ati4n
4f the Gibbs equati4n is due t4 M.Bain and .4-w4rkers [119, 120 They ad4pted the ;ery
dire.t appr4a.h 4f a.tually ski22ing 4ff a thin layer 4f the surfa.e 4f a s4luti4n, using a
de;i.e .alled a microtome. A sli.e ab4ut 01 22 thi.k .4uld be taken fr42 ab4ut 1 2
2
4f
surfa.e, s4 that a few gra2s 4f s4luti4n were .4lle.ted, all4wing surfa.e ex.ess
deter2inati4ns f4r aque4us s4luti4ns 4f p-t4luidine, phen4l, and n-hexan4i. a.id (see
Pr4ble2s 111-24 and 111-25`
At this p4int a brief .422ent 4n the justifi.ati4n 4f testing the Gibbs 4r any 4ther
ther24dyna2i.ally deri;ed relati4nship is in 4rder First, it 2ight be said that su.h a.ti;ity
is f44lish be.ause it a24unts t4 an exhibiti4n 4f s.epti.is2 4f the ;alidity 4f the laws 4f
ther24dyna2i.s the2sel;es, and surely they are n4 l4nger in d4ubt! This is justifiable
.riti.is2 in s42e spe.ifi. instan.es but, in general, we feel it is n4t The laws 4f
ther24dyna2i.s are phen42en4l4gi.al laws ab4ut 4bser;able 4r 4perati4nally defined
quantities, and where 4ne 4f the 24re subtle dedu.ti4ns fr42 these laws is in;4l;ed it 2ay
n4t always be .lear just what the 4perati4nal definiti4n 4f a gi;en ;ariable really is This
questi4n .42es up in .4nne.ti4n with .4nta.t angles and the 2eaning 4f surfa.e tensi4ns
4f s4lid interfa.es (see Se.ti4n X-6` Se.4nd, ther24dyna2i. deri;ati4ns .an in;4l;e the
exer.ise 4f l4gi. at a ;ery rig4r4us le;el, and it is entirely p4ssible f4r n4nsequiturs t4
.reep in, whi.h es.ape attenti4n until an experi2ental disagree2ent f4r.es a
reexa2inati4n Finally, the testing 4f a ther24dyna2i. relati4nship 2ay re;eal
unsuspe.ted .42plexities in a syste2 Thus, referring t4 the pre.eding subse.ti4n, it t44k
experi2ent t4 deter2ine that the surfa.e a.ti;e spe.ies 4f Aer4s4l TN was HX rather
than (Na
+
, X~` and that, Eq 111-93 was the appr4priate f4r2 4f the Gibbs equati4n t4 use
The diffi.ulties in .4nfir2ing the el;in equati4n f4r the .ase 4f liquids in .apillaries ha;e
led pe4ple t4 .4nsider ;ari4us p4ssible .42plexities (see Se.ti4n III-1C`

C. %heoretical Calculation of Surface Excess Quantities
B4th the M4nte Carl4 and the 24le.ular dyna2i.s 2eth4ds (see Se.ti4n III-2B` ha;e
been used t4 4btain the4reti.al density-;ersus-depth pr4files f4r a hyp4theti.al liquid-
;ap4r interfa.e Ri.e and .4-w4rkers (see Refs 2 and 121` ha;e f4und that density al4ng
the n4r2al t4 the surfa.e tends t4 be a
III THERMDYNAMICS F LIQUID
INTERFACES

34
Fig 111-13 (a) Pl4ts 4f 24le.ular density ;ersus distan.e n4r2al t4 the interfa.e; a is
24le.ular dia2eter Upper pl4t: a diele.tri. liquid L4wer pl4t: as .al.ulated f4r liquid
2er.ury (Fr42 Ref 122` (b) Equilibriu2 density pr4files f4r at42s A and B in a rare-
gas-like 2ixture f4r whi.h CO.BBAO.AA = 04 and e4, AB is gi;en by Eq 111-56 At42s
A and B ha;e the sa2e a (4f Eq HI-46` and the sa2e 24le.ular weight 4f 50 g/24l; the
s4luti4n 24le fra.ti4n is *B = 004 N4te the str4ng ads4rpti4n 4f B at the interfa.e
[Reprinted with per2issi4n fr42 D J Lee, M M Tel4 de Ga2a, and E Gubbins, /
!hys. Chem., 89, 1514 (1985` (Ref 88` C4pyright 1985, A2eri.an Che2i.al S4.iety
24n4t4ni. fun.ti4n in the .ase 4f a diele.tri. liquid, while f4r a liquid 2etal su.h as Na 4r
Hg, the surfa.e regi4n is stratified as illustrated in Fig Ill-13a Su.h stratifi.ati4n .arries a
nu2ber 4f i2pli.ati4ns ab4ut the interpretati4n 4f surfa.e pr4perties 4f 2etals and all4ys
[123
It was n4ted in .4nne.ti4n with Eq 111-56 that 24le.ular dyna2i.s .al.ulati4ns .an
be 2ade f4r a liquid 2ixture 4f rare gas-like at42s t4 4btain surfa.e tensi4n ;ersus
.42p4siti4n The sa2e .al.ulati4n als4 gi;es the ;ariati4n 4f density f4r ea.h spe.ies
a.r4ss the interfa.e [88, as illustrated in Fig Ill-13ft The density pr4files all4w a
.al.ulati4n, 4f .4urse, 4f the surfa.e ex.ess quantities

7. Gibbs M4n4layers
If the surfa.e tensi4n 4f a liquid is l4wered by the additi4n 4f a s4lute, then, by the
Gibbs equati4n, the s4lute 2ust be ads4rbed at the interfa.e This ads4rpti4n 2ay a24unt
t4 en4ugh t4 .4rresp4nd t4 a 24n424le.ular layer 4f s4lute 4n the surfa.e F4r exa2ple,
the li2iting ;alue 4f in Fig Ill-12 gi;es an area per 24le.ule 4f 520

whi.h is ab4ut
that expe.ted f4r a .l4se-pa.ked
m- GIBBS MNLAYERS

35
layer 4f d4de.yl sulfate i4ns It is thus a physi.ally plausible .4n.ept t4 treat T
2
as gi;ing the
tw4-di2ensi4nal .4n.entrati4n 4f surfa.tant in a 24n424le.ular fil2
Su.h a 24n4layer 2ay be .4nsidered t4 exert a fil2 pressure T, su.h that

This fil2 pressure (4r "tw4-di2ensi4nal" pressure` has the units 4f dynes per .enti2eter and
.an be 2easured dire.tly As illustrated in Fig Ill-14, if 4ne has a tr4ugh di;ided by a thin
rubber 2e2brane int4 tw4 .42part2ents, 4ne filled with s4l;ent and the 4ther with s4luti4n,
then a f4r.e will be 4bser;ed t4 a.t 4n a fl4at atta.hed t4 the upper end 4f the 2e2brane In
the PLAWMf [124, 125, the rubber 2e2brane was ;ery thin, and the p4rti4n bel4w the
surfa.e was s4 highly .4n;4luted that it .4uld easily bu.kle s4 as t4 gi;e .42plete
equalizati4n 4f any hydr4stati. differen.es between the tw4 s4luti4ns The f4r.e 4bser;ed 4n
the fl4at was thus purely surfa.e tensi4nal in 4rigin and resulted fr42 the fa.t that a
displa.e2ent in the dire.ti4n 4f the surfa.e 4f higher surfa.e tensi4n w4uld result in a l4wer
4;erall surfa.e free energy f4r the syste2 This f4r.e .4uld be 2easured dire.tly by
deter2ining h4w 2u.h 4pp4sing f4r.e applied by a le;er atta.hed t4 a t4rsi4n wire was
needed t4 pre;ent the fl4at fr42 24;ing
In the pre.eding explanati4n ir arises as a differen.e between tw4 surfa.e tensi4ns, but
it appears physi.ally as a f4r.e per unit length 4n the barrier separating the tw4 surfa.es It
is a ;ery fruitful .4n.ept t4 regard the situati4n as in;4l;ing tw4 surfa.es that w4uld be
identi.al ex.ept that 4n 4ne 4f the2 there are 24le.ules 4f surfa.e-ads4rbed s4lute that
.an 24;e freely in the plane 4f the surfa.e but .ann4t pass the barrier The 24le.ules 4f
the ads4rbed fil2 p4ssess, then, tw4-di2ensi4nal translati4nal energy, and the fil2
pressure x .an be regarded as due t4 the b42bard2ent 4f the barrier by these 24le.ules
This is anal4g4us t4 ;iewing the pressure 4f a gas as due t4 the b42bard2ent 4f 24le.ules
against the walls 4f the .4ntainer This interpretati4n 4f ir all4ws

tPockels-Langmur-Adam-Wlson-McBan.
Fig ITI-14 Cr4ss se.ti4n 4f the PLAWM
(P4.kels-Lang2uir-Ada2-Wils4n-
M.Bain` tr4ugh
HI THERMDYNAMICS F LIQUID
INTERFACES

36
a nu2ber 4f ;ery pleasing and .4nstru.ti;e anal4gies t4 be 2ade with three-di2ensi4nal
syste2s, and the .4n.ept be.42es espe.ially plausible, physi.ally, when 4ne is dealing with
the quite ins4luble 24n4layers dis.ussed in the next .hapter
It is n4t the 4nly interpretati4n, h4we;er An4ther pi.ture, again parti.ularly useful in the
.ase 4f ins4luble 24n4layers where the rubber diaphrag2 4f the PLAWM tr4ugh is n4t
needed, is t4 regard the barrier as a se2iper2eable 2e2brane thr4ugh whi.h water .an pass
(ie, g4 ar4und a.tually` but n4t the surfa.e fil2 The surfa.e regi4n .an then be ;iewed as a
relati;ely .4n.entrated s4luti4n ha;ing an 4s24ti. pressure x
4s
, whi.h is exerted against the
2e2brane
It 2ust be kept in 2ind that b4th pi.tures are 24delisti. and in;4ke extrather-24dyna2i.
.4n.epts Ex.ept 2athe2ati.ally, there is n4 su.h thing as a "tw4-di2ensi4nal" gas, and the
"s4luti4n" wh4se 4s24ti. pressure is .al.ulated is n4t unif4r2 in .42p4siti4n, and its
a;erage .4n.entrati4n depends 4n the depth assu2ed f4r the surfa.e layer
A. %he %wo-Dimensional Ideal-Gas Law
F4r dilute s4luti4ns, s4lute-s4lute intera.ti4ns are uni2p4rtant (ie, Henrys law will
h4ld`, and the ;ariati4n 4f surfa.e tensi4n with .4n.entrati4n will be linear (at least f4r
n4nele.tr4lytes` Thus
where den4tes the surfa.e tensi4n 4f pure s4l;ent, 4r



Then, by the Gibbs equati4ns,

where a and A den4te area per 24le.ule and per 24le, respe.ti;ely Equati4n 111-99 is
anal4g4us t4 the ideal-gas law, and it is seen that in dilute s4luti4ns the fil2 4f ads4rbed
s4lute 4beys the equati4n 4f state 4f a tw4-di2ensi4nal



By Eq 111-95, -dy/ dC is equal t4 b, s4 that Eq 111-9 be.42es
4
III- GIBBS MNLAYERS

3
ideal gas Figure III-15a sh4ws that f4r a series 4f aque4us al.4h4l s4luti4ns T in.reases
linearly with C at l4w .4n.entrati4ns and, .4rresp4ndingly, Fig Ill-15. sh4ws that irA/#%
appr4a.hes unity as x appr4a.hes zer4

A sa2ple .al.ulati4n sh4ws h4w Fig Ill-15. is .42puted fr42 the data 4f Fig Ill-15a
Equati4n 111-9 2ay be put in the f4r2
. onideal %wo-Dimensional Gases
The de;iati4n 4f Gibbs 24n4layers fr42 the ideal tw4-di2ensi4nal gas law 2ay be
treated by pl4tting %A/#% ;ersus ir, as sh4wn in Fig Ill-15. Here, f4r a series 4f straight-
.hain al.4h4ls, 4ne finds de;iati4ns fr42 ideality in.reasing with in.reasing fil2 pressure;
at l4w ir ;alues, h4we;er, the li2iting ;alue 4f unity f4r %A/#% is appr4a.hed
This beha;i4r suggests the use 4f an equati4n e2pl4yed by A2agat f4r gases at high
pressure; the tw4-di2ensi4nal f4r2 is

This f4r2 is 4beyed fairly well ab4;e ir ;alues 4f 5-10 dyn/.2 in Fig Ill-15. Li2iting
areas 4r a
0
;alues 4f ab4ut 22

per 24le.ule result, nearly independent 4f .hain length, as

w4uld be expe.ted if the 24le.ules assu2e a final 4rientati4n that is perpendi.ular t4 the
surfa.e Larger A
0
;alues are f4und f4r l4nger-.hain surfa.tants, su.h as s4diu2 d4de.yl
sulfate, and this has been attributed t4 the hydr4.arb4n tails ha;ing a ;ariety 4f
.4nf4r2ati4ns [12
Vari4us 4ther n4n-ideal-gas-type tw4-di2ensi4nal equati4ns 4f state ha;e been
pr4p4sed, generally by anal4gy with gases V4l2er and Mahnert [128,


where A
0
has the aspe.t 4f an ex.luded area per 24le and 6 gi;es a 2easure 4f the
.4hesi;e f4r.es Rearrange2ent yields the linear f4r2
4r, at 25C and with a in angstr42 squared units, a
0
= 4116/[air/a
,
(ln C` F4r n-butyl
al.4h4l T is 154 dyn/.2 f4r C = 01020 and is 115 dyn/.2 f4r C = 0065 Taking the
sl4pe 4f the line between these tw4 p4ints, we find
This l4.ates a p4int at the appr4xi2ate x ;alue 4f (115 + 154`/2 4r 135 dyn/.2 Thus
%A/#%= ro/ k%= 141
38 HI THERMDYNAMICS F LIQUID
INTERFACES



III- GIBBS MNLAYERS

39

ne 2ay, 4f .4urse, use a tw4-di2ensi4nal 24difi.ati4n 4f the ;an der Waals equati4n:
Ads4rpti4n 2ay 4..ur fr42 the ;ap4r phase rather than fr42 the s4luti4n phase Thus
Fig Ill-16 sh4ws the surfa.e tensi4n l4wering when water was exp4sed f4r ;ari4us
hydr4.arb4n ;ap4rs; ! is the saturati4n pressure, that is, the ;ap4r pressure 4f the pure
liquid hydr4.arb4n The a.ti;ity 4f the hydr4.arb4n is gi;en by its ;ap4r pressure, and the
Gibbs equati4n takes the f4r2
129 added 4nly the .4;4lu2e .4rre.ti4n t4 the ideal-gas law:
(f4r si2pli.ity we ha;e written just % instead 4f the exa.t designati4n and 2ay thus
be .al.ulated fr42 the anal4gue 4f Eq Ill-100
Fig Ill-16 Surfa.e tensi4n l4wering 4f water at 15C due t4 ads4rpti4n 4f hydr4.arb4ns
#, rt-pentane; 2,2,4-tri2ethylpentane; O n-hexane; x, n-heptane; n-4.tane (Fr42
Ref 133`
40 III THERMDYNAMICS F LIQUID
INTERFACES


The data 2ay then be expressed in .4n;enti4nal x-;ersus-a 4r xa-;ersus pl4ts, as sh4wn
in Fig Ill-1 The beha;i4r 4f ads4rbed pentane fil2s was that 4f a n4nideal tw4-
di2ensi4nal gas, as .an be seen fr42 the figure
The data .4uld be expressed equally well in ter2s 4f T ;ersus !, 4r in the f4r2 4f the
.4n;enti4nal ads4rpti4n is4ther2 pl4t, as sh4wn in Fig Ill-18 The appearan.e 4f these
is4ther2s is dis.ussed in Se.ti4n X-6A The Gibbs equati4n thus pr4;ides a .4nne.ti4n
between ads4rpti4n is4ther2s and tw4-di2ensi4nal equati4ns 4f state F4r exa2ple, Eq
111-5 .4rresp4nds t4 the ads4rpti4n is4ther2

(where a and b are .4nstants`, whi.h is a f4r2 4f the Lang2uir ads4rpti4n equati4n (see
Se.ti4n XI-1 A` The re;erse situati4n, na2ely, the ads4rpti4n 4f water ;ap4r 4n ;ari4us
4rgani. liquids, has als4 been studied [136
C. %he Osmotic !ressure !oint of View
It was p4inted 4ut at the beginning 4f this se.ti4n that ir .4uld be ;iewed as arising
fr42 an 4s24ti. pressure differen.e between a surfa.e regi4n .42prising an ads4rbed fil2
and that 4f the pure s4l;ent It is instru.ti;e t4 de;el4p
Fig III-1 Ads4rpti4n 4f pentane 4n
III- GIBBS MNLAYERS

41











Fig D3-18 Ads4rpti4n is4ther2 f4r n-
pentane and n-4.tane at 15C The
d4tted .ur;e sh4ws the hyp4theti.al
is4ther2 ab4;e !/ !o = 1 and the
arr4ws 2ark the % ;alues .4rresp4nding
t4 a 24n4layer (Fr42 Refs 128, 129`

this p4int 4f ;iew s42ewhat further The treat2ent .an be 2ade al4ng the line 4f Eq 111-52,
but the f4ll4wing appr4a.h will be used instead
T4 re;iew briefly, the 4s24ti. pressure in a three-di2ensi4nal situati4n is that pressure
required t4 raise the ;ap4r pressure 4f s4l;ent in a s4luti4n t4 that 4f pure s4l;ent Thus,
re2e2bering Eq Ill-16,


where a den4tes the a.ti;ity 4f the s4l;ent; it is usually assu2ed that its .42pressibility .an
be negle.ted, s4 that the integral 2ay be repla.ed by ir
0S
Vi, where Vi is the 24lar ;4lu2e F4r
ideal s4luti4ns, the rati4 a j a is gi;en by i, the s4l;ent 24le fra.ti4n, and f4r dilute
s4luti4ns, - In is appr4xi2ated by A, whi.h in turn is appr4xi2ately 2/ n , the 24le
rati4 4f s4lute t4 s4l;ent Inserti4n 4f these appr4xi2ati4ns int4 Eq Ill-108 leads t4 the
li2iting f4r2

Let us n4w supp4se that the surfa.e regi4n .an be regarded as ha;ing a depth and an
area A and hen.e ;4lu2e V
s
. A ;4lu2e V
s
4f surfa.e regi4n, if 2ade up 4f pure s4l;ent,
will be


42 III THERMDYNAMICS F LIQUID
INTERFACES

and, if 2ade up 4f a 2ixture 4f s4l;ent and surfa.e ads4rbed s4lute, will be
assu2ing the 24lar ;4lu2es V and V
2
t4 be .4nstant The s4lute 24le fra.ti4n in this
surfa.e regi4n is then
using Eqs III-l 10 and III-l 11 t4 eli2inate nj There will be an 4s24ti. pressure gi;en
appr4xi2ately by
and if this is ;iewed as a.ting against a se2iper2eable barrier, the fil2 pressure will be
the 4s24ti. pressure ti2es the depth 4f the surfa.e regi4n in whi.h it is exerted, that is,
Equati4ns III-l 12 and III-l 13 2ay n4w be .42bined with III-l 14 t4 gi;e
N4w, n f V / % is just the surfa.e area A, and, 24re4;er, V / % and V
2
/ % ha;e the
di2ensi4ns 4f 24lar area If the surfa.e regi4n is .4nsidered t4 be just one 24le.ule thi.k,
V / % and V
2
/ % be.42es A? and A
2
, the a.tual 24lar areas, s4 that Eq III-l 15 takes 4n the
f4r2
4r, 4n rearranging and re2e2bering that

If further, A is negle.ted in .42paris4n with A
2
, then Eq III-l 1 be.42es the sa2e as the
n4nideal gas law, Eq Ill-103









HI- GIBBS MNLAYERS
This deri;ati4n has been 2ade in a f4r2 .al.ulated best t4 bring 4ut the ;ery .4nsiderable
and s42eti2es in.4nsistent appr4xi2ati4ns 2ade H4we;er, by treating the surfa.e regi4n as
a kind 4f s4luti4n, an a;enue is 4pened f4r e2pl4ying 4ur .4nsiderable kn4wledge 4f s4luti4n
physi.al .he2istry in esti2ating ass4.iati4n, interi4ni. attra.ti4n, and 4ther n4nideality
effe.ts An4ther ad;antage, fr42 the writers p4int 4f ;iew, is the e2phasis 4n the r4le 4f the
s4l;ent as part 4f the surfa.e regi4n, whi.h helps t4 .4rre.t the tenden.y, latent in the tw4-
di2ensi4nal equati4n 4f state treat2ent, t4 regard the substrate as 2erely pr4;iding an inert
plane surfa.e 4n whi.h 24le.ules 4f the ads4rbed spe.ies 2ay 24;e freely The appr4a.h is
n4t really any 24re e2piri.al than that using the tw4-di2ensi4nal n4nideal gas, and
.4nsiderable use has been 2ade 4f it by F4wkes [13
It has been p4inted 4ut [138 that algebrai.ally equi;alent expressi4ns .an be deri;ed
with4ut in;4king a surfa.e s4luti4n 24del Instead, surfa.e ex.ess as defined by the
pr4.edure 4f Gibbs is used, the di;iding surfa.e always being l4.ated s4 that the su2 4f the
surfa.e ex.ess quantities equals a gi;en .4nstant ;alue This last is .4n;eniently taken t4 be
the 2axi2u2 ;alue 4f T
2
A s42ewhat related treat2ent was 2ade by Handa and Mukerjee
f4r the surfa.e tensi4n 4f 2ixtures 4f flu4r4.arb4ns and hydr4.arb4ns [139
D. Surface Elasticity The elasticity (4r the surface
dilatational modulus) E is defined as

where A is the ge42etri. area 4f the surfa.e E is zer4 if the surfa.e tensi4n is in rapid
equilibriu2 with a large b4dy 4f bulk s4luti4n, but if there is n4 su.h 24le.ular traffi., A in
Eq III-l 18 2ay be repla.ed by A, the area per 24le 4f the surfa.e ex.ess spe.ies, and an
alternati;e f4r2 4f the equati4n is theref4re

The re.ipr4.al 4f E is .alled the compressibility.
It is n4t un.4224n f4r this situati4n t4 apply, that is, f4r a Gibbs 24n4layer t4 be in
4nly sl4w equilibriu2 with bulk liquid-see, f4r exa2ple, Figs 11-15 and 11-21 This
situati4n als4 h4lds, 4f .4urse, f4r spread 24n4layers 4f ins4luble substan.es, dis.ussed in
Chapter IV The experi2ental pr4.edure is illustrated in Fig Ill-19, whi.h sh4ws that a
p4rti4n 4f the surfa.e is b4unded by bars 4r fl4ats, an 4pp4sing pair 4f whi.h .an be
24;ed in and 4ut in an 4s.illat4ry 2anner The .4n.42itant .hange in surfa.e tensi4n is
f4ll4wed by 2eans 4f a Wilhel2y slide Thus f4r dilute aque4us s4luti4ns 4f a
2ethyl.ellu-
4
44 2 THERMDYNAMICS F LIQUID
INTERFACES

l4se p4ly2er, the equilibriu2 Gibbs 24n4layer was perfe.tly elasti. with E -95 dyn/.2
f4r a 24 10~
3
wt% s4luti4n [142 If the peri4d 4f 4s.illati4n in 9 is s2all .42pared t4
the bulk s4luti4n-surfa.e equilibrati4n ti2e, then E 2ay be deter2ined as a fun.ti4n 4f
surfa.e age. If the peri4d is .42parable t4 the equilibrati4n ti2e, E be.42es an is
whi.h depends 4n the peri4d This last was the situati4n f4r aque4us s4luti4ns 4f a series
4f surfa.tants 4f the type R[CH
2
CH
2
0,H [140, 141
Bian.4 and Mar2ur [143 ha;e de;el4ped a 2eans t4 2easure the surfa.e elasti.ity 4f
s4ap bubbles Their results are well 24deled by the ;4n Szyszk4wski equati4n (Eq 111-
5` and Eq Ill-118 They find that the elasti.ity in.reases with the size 4f the bubble f4r
s2all bubbles but that it 2ay g4 thr4ugh a 2axi2u2 f4r larger bubbles Li and Neu2ann
[144 ha;e sh4wn the effe.ts 4f surfa.e elasti.ity 4n wetting and .apillary rise phen42ena,
with i2p4rtant i2pli.ati4ns f4r 2easure2ent 4f surfa.e tensi4n
The dis.ussi4n 4f surfa.e ;is.4sity and 4ther aspe.ts 4f surfa.e rhe4l4gy is deferred t4
Se.ti4n IV-3C

E. %raubes #ule
The surfa.e tensi4ns f4r s4luti4ns 4f 4rgani. .42p4unds bel4nging t4 a h424l4g4us
series, f4r exa2ple, RCH`X, sh4w .ertain regularities R4ughly, Traube [145 f4und
that f4r ea.h additi4nal CH gr4up, the .4n.entrati4n required t4 gi;e a .ertain surfa.e
tensi4n was redu.ed by a fa.t4r 4f 3 This rule is 2anifest in Fig Ill-15ft; the su..essi;e
.ur;es are displa.ed by nearly equal inter;als 4f 05 4n the l4g C s.ale
Lang2uir [146 ga;e an instru.ti;e interpretati4n t4 this rule The w4rk W t4 transfer
4ne 24le 4f s4lute fr42 bulk s4luti4n t4 surfa.e s4luti4n sh4uld be
Fig HI-19 Tr4ugh f4r dyna2i. surfa.e 2easure2ents: A, stainless-steel dish; B, alu-
2inu2 2antle; C, inlet ther24statting water; D, l4wer PTFE bars; E, 4s.illating bars; F,
atta.h2ent l4wer bars; G, Wilhel2y plate (Fr42 Ref 140`
m-7 GIBBS MONOLAYERS

45
If the dependen.e 4n te2perature as well as 4n .42p4siti4n is kn4wn f4r a s4luti4n,
enthalpies and entr4pies 4f ads4rpti4n 2ay be .al.ulated fr42 the appr4priate ther24-
dyna2i. relati4nships [82 Nearn and Spaull [14 ha;e, f4r exa2ple, .al.ulated the
enthalpies 4f surfa.e ads4rpti4n f4r a series 4f straight-.hain al.4h4ls They find an
in.re2ent in enthalpy 4f ab4ut 196 kJ/24l per CH gr4up
Van ss and G44d [148 ha;e .42pared s4lubilities and interfa.ial tensi4ns f4r a series
4f al.4h4ls and their .4rresp4nding hydr4.arb4ns t4 deter2ine the free energy 4f
hydrati4n 4f the hydr4xyl gr4up; they find -14 kJ/24l per -H gr4up
F. Some Further Comments on Gibbs Monolayers
It is i2p4rtant t4 realize that there is, in prin.iple, n4 ne.essary differen.e between the
nature 4f the ads4rbed fil2s dis.ussed s4 far and th4se f4r2ed by spreading 24n4layers 4f
ins4luble substan.es 4n a liquid substrate 4r by ads4rpti4n fr42 either a gas 4r a liquid
phase 4nt4 a s4lid (4r a liquid` surfa.e The distin.ti4n that does exist has t4 d4 with the
nature 4f the a..essible experi2ental data In the .ase 4f Gibbs 24n4layers, 4ne is dealing
with fairly s4luble s4lutes, and the dire.t 2easure2ent 4f % is n4t easy t4 .arry 4ut
Instead, 4ne 2easures the .hanges in surfa.e tensi4n and 4btains % thr4ugh the use 4f the
Gibbs equati4n With spread 24n4layers, the s4lubility 4f the 2aterial is generally s4 l4w
that its .4n.entrati4n in s4luti4n is n4t easily 2easurable, but Y is kn4wn dire.tly, as the
a24unt per unit area that was spread 4nt4 the surfa.e, and the surfa.e tensi4n als4 .an be
2easured dire.tly In the .ase 4f ads4rpti4n, T is kn4wn fr42 the de.rease in
.4n.entrati4n (4r pressure` 4f the ads4rbate 2aterial, s4 that b4th % and the .4n.entrati4n
4r pressure (if it is gas ads4rpti4n` are kn4wn It is n4t generally p4ssible, h4we;er, t4
2easure the surfa.e tensi4n 4f a s4lid surfa.e Thus, it is usually p4ssible t4 2easure 4nly
tw4 4ut 4f the three quantities 7, I\ and C 4r !.
where C
5
is the surfa.e .4n.entrati4n and is gi;en by %/ r, where is the thi.kness 4f the
surfa.e regi4n F4r s4lutes 4f .hain length n and ( n - 1`, the differen.e in w4rk is then
By Traubes rule, if C,- / C, = 3, then y, = y
n
- I, and, as an appr4xi2ati4n, it is assu2ed
that the tw4 surfa.e .4n.entrati4ns are als4 the sa2e If s4, then
This ;alue 2ay be regarded as the w4rk t4 bring 4ne CH gr4up fr42 the b4dy 4f the
s4luti4n int4 the surfa.e regi4n Sin.e the ;alue per CH gr4up appears t4 be independent
4f .hain length, it is reas4nable t4 supp4se that all the CH gr4ups are si2ilarly situated
in the surfa.e, that is, that the .hains are lying flat


The su..eeding 2aterial is br4adly 4rganized a..4rding t4 the types 4f experi2ental
quantities 2easured be.ause 2u.h 4f the literature is s4 gr4uped In the next .hapter
spread 24n4layers are dis.ussed, and in later .hapters the t4pi.s 4f ads4rpti4n fr42
s4luti4n and 4f gas ads4rpti4n are .4nsidered Irrespe.ti;e 4f the experi2ental
.42part2entati4n, the .4n.lusi4ns as t4 the nature 4f 24bile ads4rbed fil2s, that is, their
stru.ture and equati4ns 4f state, will tend t4 be 4f a general ;alidity Thus, 4nly a li2ited
dis.ussi4n 4f Gibbs 24n4layers has been gi;en here, and n4ne 4f su.h related aspe.ts as
the .4nta.t p4tentials 4f s4luti4ns 4r 4f ads4rpti4n at liquid-liquid interfa.es, as it is 24re
effi.ient t4 treat these t4pi.s later

8 Pro-lems
1 Gi;en that dy/ d% is -0086 erg/.2
2
f4r ethan4l at 20C, .al.ulate E
s
and E
s
.
L44k up 4ther data 4n physi.al pr4perties, as needed
2 Referring t4 Pr4ble2 1, .al.ulate S
s
and S
s
f4r ethan4l at 20C D4 the sa2e f4r n-
4.tane and .42pare the results
3 Cal.ulate the ;ap4r pressure 4f water when present in a .apillary 4f 01 ju2 radius
(assu2e zer4 .4nta.t angle` Express y4ur result as per.ent .hange fr42 the n4r2al ;alue
at 25C Supp4se n4w that the effe.ti;e radius 4f the .apillary is redu.ed be.ause 4f the
presen.e 4f an ads4rbed fil2 4f water 100 thi.k Sh4w what the per.ent redu.ti4n in
;ap4r pressure sh4uld n4w be
4 Cal.ulate y
m
f4r s4diu2, using Eq Ill-12
5 Appli.ati4n 4f 150 MPa pressure in.reases the interfa.ial tensi4n f4r n-hex-ane-
water fr42 505 t4 530 2N/2 at 25C Cal.ulate AV
S
. What is AV
S
f4r that area
.4rresp4nding t4 a 24le.ular size (take a representati;e 24le.ular area t4 be 20

C4n;ert this t4 .2
3
/.2
2
24l
6 Illustrate the use 4f Eq 111-44 as f4ll4ws Appr4xi2ate g(r) by a step fun.ti4n,
g(r) - 0 f4r r < a and g(r) = 1 f4r r ^ a, assu2e that (r` is gi;en by Eq 111-46, and that
the 24le.ule is arg4nlike, with a = 34 and e4 = 124 where k is the B4ltz2ann
.4nstant Cal.ulate y fr42 this inf4r2ati4n and the density 4f liquid arg4n
Use Eq Ill-15 and related equati4ns t4 .al.ulate E
s
and the energy 4f ;ap4rizati4n
4f arg4n Take t4 be e4 4f Pr4ble2 6, and assu2e arg4n t4 ha;e a .l4se-pa.ked stru.ture
4f spheres 34 in dia2eter
8 Use Fig Ill-lb t4 esti2ate the surfa.e tensi4n 4f the arg4nlike liquid Pressure is
gi;en in units 4f eo/ a
3
, where e4 = 1198 and a - 34 int. re2e2ber Eq 111-40
9 The gradient 24del f4r interfa.ial tensi4n des.ribed in Eqs 111-42 and 111-43 is
li2ited t4 intera.ti4n p4tentials that de.ay 24re rapidly than r"
5
Thus it .an be applied t4
the Lennard-J4nes p4tential but n4t t4 a l4nger range intera.ti4n su.h as dip4le-dip4le
intera.ti4n Where d4es this li2itati4n .42e fr42, and what d4es it i2ply f4r interfa.ial
tensi4ns 4f ;ari4us liquids?
10 Pl4t the s.aling beha;i4r f4r the surfa.e tensi4n 4f p4lystyrene s4luti4ns using
Eq HI-64, f4r = 1,000 and % fr42 zer4 t4 %
c
. N4w pl4t the beha;i4r f4r % - 08/
.
f4r = 100-1000 C422ent 4n the influen.e 4f p4ly2ers 4n surfa.e tensi4n
III-8 PRBLEMS

4
11 Deri;e Eq DI-21 fr42 the first and se.4nd laws 4f ther24dyna2i.s and related
definiti4ns
12 Esti2ate, by 2eans 4f Eq 111-41, the surfa.e tensi4ns 4f CCU, CHCI3 and 4f
water at 20C L44k up the ne.essary data 4n ther2al expansi4n and .42pressibility
13 The f4ll4wing tw4 state2ents see2 2utually .4ntradi.t4ry and see2 t4 des.ribe a
parad4xi.al situati4n, (a` The .he2i.al p4tential 4f a spe.ies 2ust be e;erywhere the sa2e
f4r an equilibriu2 syste2 at .4nstant te2perature and pressure; theref4re, if we ha;e a
liquid in equilibriu2 with its ;ap4r (the interfa.e is planar`, the .he2i.al p4tential 4f the
spe.ies 2ust be the sa2e in the surfa.e regi4n as it is in the bulk liquid, and n4 w4rk is
required t4 24;e a 24le.ule fr42 the bulk regi4n t4 the surfa.e regi4n (b) It 2ust require
w4rk t4 24;e a 24le.ule fr42 the bulk regi4n t4 the surfa.e regi4n be.ause t4 d4 s4
2eans in.reasing the surfa.e area and hen.e the surfa.e free energy 4f the syste2
Dis.uss these state2ents and re.4n.ile the apparent .4ntradi.ti4n (N4te Ref 138`
14 Cal.ulate, using the data 4f Fig III-9a and Eq 111-53, the surfa.e tensi4n ;ersus
24le fra.ti4n pl4t f4r 2ixtures 4f .y.l4hexane and benzene
15 Deri;e an equati4n f4r the heat 4f ;ap4rizati4n 4f a liquid as a fun.ti4n 4f dr4p
radius r
16 Using Lang2uirs prin.iple 4f independent surfa.e a.ti4n, 2ake qualitati;e .al-
.ulati4ns and de.ide whether the p4lar 4r the n4np4lar end 4f ethan4l sh4uld be 4riented
t4ward the 2er.ury phase at the ethan4l-2er.ury interfa.e
1 C42plete the nu2eri.al illustrati4n pre.eding Eq 111-83 by .al.ulating %

)and
M
"
18 As Af
2
--0, Y )`k22i where k2 is a Henry law .4nstant, and, si2ilarly, Y]-
`k a s Wi - 0 Sh4w that r]- - k as
2
- 1 and that T
2
- - j f .
2
as -*0
N4te Eqs 111-83 and 111-84
19 A 15% by weight aque4us surfa.tant s4luti4n has a surfa.e tensi4n 4f 538 dyn/.2
(4r 2N/2` at 20C (a) Cal.ulate a, the area 4f surfa.e .4ntaining 4ne 24le.ule State
any assu2pti4ns that 2ust be 2ade t4 2ake the .al.ulati4n fr42 the pre.eding data, ( b )
The additi4nal inf4r2ati4n is n4w supplied that a 1% s4luti4n has a surfa.e tensi4n 4f
536 dyn/.2 If the surfa.e-ads4rbed fil2 4beys the equati4n 4f state ir(er - ) - k%,
.al.ulate fr42 the .42bined data a ;alue 4f , the a.tual area 4f a 24le.ule
20 There are three f4r2s 4f the Lang2uir-Szyszk4wski equati4n, Eq 111-5, Eq Ill-
10, and a third f4r2 that expresses ir as a fun.ti4n 4f %. (a) Deri;e Eq 111-5 fr42 Eq
Ill-10 and ( b ) deri;e the third f4r2
21 Taji2a and .4-w4rkers [108 deter2ined the surfa.e ex.ess 4f s4diu2 d4de-.yl
sulfate by 2eans 4f the radi4a.ti;ity 2eth4d, using tritiated surfa.tant 4f spe.ifi. a.ti;ity
916 Ci/24l The area 4f s4luti4n exp4sed t4 the dete.t4r was 350 .2 In a parti.ular
experi2ent, it was f4und that with 10 10
_2
Af surfa.tant the surfa.e .4unt rate was 10
10
3
.4unts per 2inute Separate .alibrati4n sh4wed that 4f this .4unt was 145 10
3

.a2e fr42 underlying s4luti4n, the rest being surfa.e ex.ess It was als4 deter2ined that
the .4unting effi.ien.y f4r surfa.e 2aterial was 11% Cal.ulate T f4r this s4luti4n
22 An ads4rpti4n is4ther2 kn4wn as the Te2kin equati4n [149 has the f4r2: ir -
<xr
2
/ r where a is a .4nstant and ' is the li2iting surfa.e ex.ess f4r a .l4se-pa.ked

48 III THERMDYNAMICS F LIQUID INTERFACES
24n4layer 4f surfa.tant Using the Gibbs equati4n find as a fun.ti4n 4f C and % as a fun.ti4n
4f C
23 An ads4rpti4n equati4n kn4wn as the Fru2kin is4ther2 has the f4r2

when Y Y
m
, %
m
is the li2iting ;alue 4f %. Sh4w what the .4rresp4nding tw4-di2ensi4nal
equati4n 4f state is, that is, sh4w what .4rresp4nding relati4nship is between and a.
(Suggested by W R Faw.ett`
24 M.Bain rep4rts the f4ll4wing 2i.r4t42e data f4r a phen4l s4luti4n A s4luti4n 4f 5 g 4f
phen4l in 1000 g 4f water was ski22ed; the area ski22ed was 310 .2
2
and a 32-g sa2ple was
4btained An interfer42eter 2easure2ent sh4wed a differen.e 4f 12 di;isi4ns between the bulk
and the s.44ped-up s4luti4n, where 4ne di;isi4n .4rresp4nded t4 21 x 10~
6
g phen4l per gra2
4f water .4n.entrati4n differen.e Als4, f4r 005, 012, and 0268AT s4luti4ns 4f phen4l at
20C, the respe.ti;e surfa.e tensi4ns were 6, 601, and 516 dyn/.2 Cal.ulate the surfa.e
ex.ess Y fr42 (a) the 2i.r4t42e data, ( b ) f4r the sa2e .4n.entrati4n but using the surfa.e
tensi4n data, and (.` f4r a h4riz4ntally 4riented 24n4layer 4f phen4l (2aking a reas4nable
assu2pti4n as t4 its .r4ss-se.ti4nal area`
25 The thi.kness 4f the equi;alent layer 4f pure water 4n the surfa.e 4f a 3M s4diu2
.hl4ride s4luti4n is ab4ut 1 Cal.ulate the surfa.e tensi4n 4f this s4luti4n assu2ing that the
surfa.e tensi4n 4f salt s4luti4ns ;aries linearly with .4n.entrati4n Negle.t a.ti;ity .4effi.ient
effe.ts
26 The surfa.e tensi4n 4f an aque4us s4luti4n ;aries with the .4n.entrati4n 4f s4lute
a..4rding t4 the equati4n 7 = 2 - 350C (pr4;ided that C is less than 005M` Cal.ulate the ;alue
4f the .4nstant k f4r the ;ariati4n 4f surfa.e ex.ess 4f s4lute with .4n.entrati4n, where k is
defined by the equati4n Y - kC. The te2perature is 25C
2 The data in Table ffl-2 ha;e been deter2ined f4r the surfa.e tensi4n 4f is44.tane-
benzene s4luti4ns at 30C Cal.ulate Y
2
, Y, Y

), and f4r ;ari4us .4n.entrati4ns and pl4t these

quantities ;ersus the 24le fra.ti4n 4f the s4luti4n Assu2e ideal s4luti4ns
28 The surfa.e tensi4n 4f water at 25C exp4sed t4 ;arying relati;e pressures 4f a



hydr4.arb4n ;ap4r .hanges as f4ll4ws:
!/ ! 010 020 030 040 050 060 00 080 090
7r(dyn/.2` 022 055 091 135 185 245 315 405 535
Cal.ulate and pl4t ir ;ersus a (in

per 24le.ule` and T ;ersus P/P D4es it appear that

this hydr4.arb4n wets water (n4te Ref [133`?
29 Deri;e the equati4n 4f state, that is, the relati4nship between ir and a, 4f the
ads4rbed fil2 f4r the .ase 4f a surfa.e a.ti;e ele.tr4lyte Assu2e that the a.ti;ity .4effi-
.ient f4r the ele.tr4lyte is unity, that the s4luti4n is dilute en4ugh s4 that surfa.e tensi4n is a
linear fun.ti4n 4f the .4n.entrati4n 4f the ele.tr4lyte, and that the ele.tr4lyte itself (and n4t
s42e hydr4lyzed f4r2` is the surfa.e-ads4rbed spe.ies D4 this f4r the .ase 4f a str4ng 1:1
ele.tr4lyte and a str4ng 1:3 ele.tr4lyte
30 S42e data 4btained by Ni.h4las et al [150 are gi;en in Table III-3, f4r the surfa.e
tensi4n 4f 2er.ury at 25C in .4nta.t with ;ari4us pressures 4f water ;ap4r Cal.ulate the
ads4rpti4n is4ther2 f4r water 4n 2er.ury, and pl4t it as % ;ersus !.
31 Esti2ate A
0
in Eq n-101 fr42 the data 4f Fig Ill-15 and then.e the 24le.ular area
in
2
/24le.ule
32 The surfa.e elasti.ity E is f4und t4 ;ary linearly with ir and with a sl4pe 4f 2
btain the .4rresp4nding equati4n 4f state f4r the surfa.e fil2, that is, the fun.ti4n relating
ir and a.
33 The f4ll4wing data ha;e been rep4rted f4r 2ethan4l-water 2ixtures at 20C
(andbook of Chemistry and !hysics, US Rubber C4`:
Wt% 2ethan4l 5 100 250 500 600 800 900 100 (dyn/.2` 6090
5904 4638 3531 3295 226 2536 2265
Make a the4reti.al pl4t 4f surfa.e tensi4n ;ersus .42p4siti4n a..4rding t4 Eq 111-53, and
.42pare with experi2ent (Cal.ulate the equi;alent spheri.al dia2eter f4r water and
2ethan4l 24le.ules and take a as the a;erage 4f these`