STRUCTURE OF WATER NEAR SOLID INTERFACES

Evidence is presented for the existence of ordered elements of !ter str"ct"re ne!r
cert!in !#"eo"s$solid interf!ces% This evidence is &!sed on v!rio"s pieces of
experiment!l o&serv!tions &' m!n' !"thors( &"t p!rtic"l!r import!nce is !tt!ched to the
existence of therm!l !nom!lies in the properties of vicin!l !ter% A three)l!'er model
for the str"ct"re of !ter ne!r cert!in !ter$solid interf!ces is disc"ssed in some det!il*
in this model ! l!'er of ordered +str"ct"red, !ter is expected to exist ne!r the solid
s"rf!ce( the orderin- extendin- into the &"l. li#"id !nd decre!sin- !s ! f"nction of
dist!nce from the interf!ce% As the de-ree of str"ct"redness is decre!sed( the loc!l
disorder is incre!sed% At s"fficientl' l!r-e dist!nces from the s"rf!ce( &"l. !ter
str"ct"re exists% /ec!"se of 0l!ttice misfit0 &eteen the +"n.non, str"ct"re of the &"l.
!ter +possessin- loc!l order, !nd the differentl' str"ct"red !ter ne!r the interf!ce !
re-ion of enh!nced disorder m!' occ"r( !.in to the disordered str"ct"re post"l!ted in the
Fr!n.)Wen model of h'dr!tion% Indic!tions !re th!t the vicin!l !ter is -ener!ll' not
Ice)I)li.e% The ordered str"ct"res ne!r some t'pes of interf!ces m!' &e cl!thr!te c!-e)
li.e +in p!rtic"l!r( in the presence of cl!thr!te)formin- sol"tes, or resem&le hi-h
press"re ice pol'morphs% The prim!r' distin-"ishin- fe!t"res !re pro&!&l' not the
specific -eometric !spects per se( &"t r!ther the expected lifetimes of the +possi&l'
r!ther illdefined, str"ct"res% The properties of !ter in interf!ci!l s'stems often exhi&it
not!&le therm!l !nom!lies !nd these !nom!lies !re interpreted !s m!nifest!tions of
str"ct"r!l tr!nsitions% This is consistent ith the s"--estions th!t the str"ct"res
responsi&le for the !nom!lies possess elldefined therm!l st!&ilit' limits% The'
constit"te evidence for hi-her)order ph!se tr!nsitions( effected thro"-h cooper!tive
!ction ithin the str"ct"red "nits% The proposed model h!s sever!l !dv!nt!-es1 +!, it
m!' expl!in h' idel' differin- v!l"es !re fre#"entl' o&s t!ined for &oth
thermod'n!mic !nd tr!nsport propertie of interf!ci!l s'stems in different st"dies on
s"pposedl' simil!r m!teri!ls* +&, &' invo.in- cl!thr!te c!-e form!tion +or the cre!tion
of some other str"ct"r!l entit' possessin- voids or 0sites0, !s the predomin!nt fe!t"re of
the str"ct"red vicin!l !ter( the predeliction of some nonpol!r sol"tes for m!n'(
otherise rel!tivel' inert( s"rf!ces m!' &ecome re!dil' "nderst!nd!&le% The 2!"lin-
model for !nesthesi! is consistent ith the notion of vicin!l cl!thr!te form!tion% The
!nom!lo"s !ter descri&ed &' Der'!-in m!' possi&l' represent ! ne t'pe of &ondin-
in !ter( !s recentl' proposed &' Lippincott et at. If Lippincott is correct( the role of the
#"!rt3 s"rf!ce is pro&!&l' to f!cilit!te the reh'&ridi3!tion of the !ter molec"le to !llo
for ! completel' ne t'pe of O42 compo"nd% Ret"rnin- to the more -ener!l c!se(
str"ct"red !ter ne!r !n interf!ce m!' represent st!&ili3ed !ter +ith ! str"ct"re
different from Ice)Ih,* it m!'( for inst!nce( &e its on cl!thr!te h'dr!te +possi&l' ith
the m!5orit' of the interstiti!l positions filled ith !ter molec"les,% The !ter ne!r !n
interf!ce ind"cin- s"ch ! str"ct"re ill not serve !s n"clei for Ice)I% The n"cle!tin-
efficienc' of cert!in m!teri!ls +s"ch !s silver iodide, m!' inste!d &e d"e to f!cilit!ted
n"cle!tion in the disordered !ter &eteen the vicin!l !ter !nd the &"l. str"ct"re% The
o&vio"s diffic"lt' ith models of the t'pe disc"ssed here is ho to m!.e them
#"!ntit!tive% v6ith !s m!n' different 0ph!ses0 +ph!ses in the sense of t'pes of str"ct"res
of !ter, !s !re involved here( it is o&vio"s th!t ! l!r-e n"m&er of !d5"st!&le p!r!meters
m"st &e invo.ed% 4ence( #"!ntit!tive +or semi#"!ntit!tive, !-reement &eteen
c!lc"l!ted +estim!ted, !nd o&served v!l"es is not li.el' to &e s"fficient proof of the
model if tested onl' on ! sm!ll n"m&er of phenomen!% For this re!son( evidence for the
correctness of the model m"st &e so"-ht in terms of the l!r-est possi&le n"m&er 7,f
#"!lit!tive fe!t"res hich c!n &e correctl' expl!ined%
I. INTRODUCTION
A. Interfacial Water The properties of !ter h!ve &een s'stem!tic!ll' st"died for
more th!n 89 'e!rs% Unfort"n!tel'( these st"dies h!ve res"lted in onl' ! modest incre!se
in o"r "nderst!ndin- of !ter str"ct"re% Even less is .non !&o"t the str"ct"re of !ter
ne!r !n interf!ce( !ltho"-h not for !nt of experiment!l inform!tion% One p"rpose of
this !rticle is to s"--est th!t( in some respects( !dv!nces m!' &e m!de more r!pidl' in
the st"d' of interf!ci!l !ter th!n in &"l. !ter% To of the most n!t"r!l #"estions to
!s. re-!rdin- !ter ne!r !n interf!ce !re1 +:, 4o is the !ter str"ct"re ne!r ! solid
interf!ce different +if it is different !t !ll, from &"l. !ter; +<, If the str"ct"re of vicin!l
!ter is( indeed( different( ho f!r from the interf!ce does the !ltered str"ct"re penetr!te
into the &"l. re-ion; In this p!per( ! &rief revie of some d!t! is presented hich
s"--ests th!t the str"ct"re of !ter ne!r interf!ces is different from &"l. !ter !nd !
fe comments !re m!de on the thic.ness +the depth, of the ch!n-ed l!'er +or l!'ers,% A
specific model is proposed +&!sed on !n e!rlier s"--estion &' the present !"thor, hich
invo.es ! 0three)l!'er model0 for the str"ct"re of !ter ne!r cert!in interf!ces% This
model is concept"!ll' simil!r to the h'dr!tion model for ions in +&"l., electrol'te
sol"tion s"--ested &' Fr!n. !nd Wen +=>,% The p"rpose of the present p!per is not
prim!ril' to present ! -ener!l revie of the str"ct"re of !ter ne!r ! solid s"rf!ce%
Inste!d( the p!per is intended to develop some possi&le concept"!l models of vicin!l
!ter% To develop s"ch models( it is "sef"l to revie ! p!rt of the liter!t"re( !nd in m!n'
respects the present p!per is !n extensivel' !nnot!ted +!ltho"-h f!r from complete,
s"mm!r' +r!ther th!n ! critic!l revie, of the !v!il!&le evidence for lon-)r!n-e
orderin- of !ter ne!r v!rio"s interf!ces% S"ch ! present!tion is 5"stified &' the c"rrent
need to c!ll !ttention to the l!r-e n"m&er of m"ltif!ceted t'pes of s"rf!ce chemic!l
st"dies hich contri&"te f!irl' s"&st!nti!l evidence for the existence of lon-)r!n-e
orderin- ne!r interf!ces% Tho"-h not specific!ll' st!ted in e!ch c!se( the re!der is
!l!'s !dmonished to scr"tini3e c!ref"ll' for himself e!ch of the ex!mples mentioned%
Also( it sho"ld &e .ept in mind th!t hile some of the ex!mples ?#"oted m!' not( &'
themselves( &e ver' stron- contri&"tions( one sho"ld see. to see the over!ll pict"re(
r!ther th!n see. o"t the fl!s in the min"ti!e% It is m' firm opinion th!t hen !ll of the
evidence is seen !s ! hole( there is -ood re!son to &elieve th!t extensive orderin- c!n(
indeed( occ"r ne!r interf!ces% One f!cet of this st"d'( hoever( is presented ith no
!polo-ies or hesit!tion% I !m #"ite firml' convinced!nd hope th!t the evidence ill
s"pport this contentionth!t therm!l !nom!lies fre#"entl' occ"r in the properties of !ter
ne!r interf!ces !nd th!t this m!' &e t!.en !s evidence for the existence of str"ct"red
"nits of !ter ne!r interf!ces% As the therm!l !nom!lies !re not prono"nced !nd h!ve
not &een firml' demonstr!ted in the properties of &"l. !ter( &"t seem re!dil'
discerni&le in the properties of vicin!l !ter( it is re!son!&le to infer th!t the interf!ce is
!&le to ind"ce or st!&ili3e str"ct"res% In other ords( st!&le str"ct"res ith ! definite
therm!l st!&ilit' limit m!' &e ind"ced &' the proximit' to ! s"rf!ce% It is reco-ni3ed( on
the other h!nd( th!t o"r .noled-e of the depth of s"ch s"rf!ce)ind"ced str"ct"res
rem!ins ver' "ncert!in% The !"thor merel' c!lls !ttention to v!rio"s possi&le estim!tes
r!ther th!n !ttempt to provide firm limits for the r!n-e of the 0deep s"rf!ce orient!tion
l!'ers%0
B. Previous Studies The older liter!t"re re-!rdin- orient!tion ne!r interf!ces !s
revieed &' 4enni.er +@>, in !n !rticle entitled 0The Depth of the S"rf!ce Aone of !
Li#"id%0 Th!t !rticle h!s)for &etter or orse)&ecome ! cl!ssic in the field% While
4enni.erBs !rticle is concerned ith h!t he referred to !s 0deep s"rf!ce orient!tion(0 in
-ener!l( the present !rticle de!ls onl' ith some of the !v!il!&le evidence for s"ch
s"rf!ce orient!tion in !#"eo"s s'stems% It is prim!ril' intended to &e ! s"mm!r' of
some of the experiment!l o&serv!tions pertinent to this #"estion !nd ! contempl!tive
disc"ssion of v!rio"s ide!s hich m!' ell s"--est the existence of ordered str"ct"res
ne!r !#"eo"s interf!ces% Introd"ced !lso is the notion th!t ! sep!r!te 3one of disorder
m!' exist &ec!"se of 0l!ttice misfit0 &eteen one of the possi&le +0lon-)r!n-e0, ordered(
vicin!l !ter str"ct"res !nd the differentl' str"ct"red +&"t onl' 0short)r!n-e0 ordered,
&"l. !ter% The older liter!t"re( on hich the cl!im h!s &een &!sed th!t there exists !t
m!n' !ter$solid interf!ces( lon-)r!n-e orderin-( !s revieed in the !rticle &'
4enni.er% S"&se#"entl'( !r-"ments for !nd !-!inst orderin- !t interf!ces +especi!ll'
cl!' s"rf!ces, h!ve &een presented &' m!n' !"thors( not!&l' &' Lo)see( for inst!nce
+8<,)!nd &' C!rtin +88,% Core recentl'( the possi&ilit' of si-nific!nt str"ct"r!l ch!n-es
in !ter ne!r ! p!rtic"l!r interf!ce +#"!rt3, h!s &een &ro"-ht to c"lmin!tion &' the
si-n!l contri&"tion of Der5!-"in +<@, in R"ssi!% Der5!-"inBs no ell).non reports on
hi-hl' !nom!lo"s !ter in n!rro #"!rt3 c!pill!ries +sometimes referred to !s 0ortho
!ter(0 0!nom!lo"s !ter(0 0s"per !ter(0 0!ter II(0 or 0pol'!ter0, !ppe!r to &e
evidence th!t !ter m!' exist in 0st!tes0 other th!n those cl!ssic!ll' reco-ni3ed%
C. Evidence for Structure Based on Theral Anoalies The !r-"ments in the
present p!per !re &!sed on ! different !ppro!ch from th!t p"rs"ed &' previo"s !"thors%
At its fo"nd!tion is the o&serv!tion th!t therm!l !nom!lies exist in the properties of
!ter !nd some !#"eD"s sol"tions !nd th!t these !nom!lies !re indic!tive of str"ct"r!l
tr!nsitions% It is f"rther noted th!t the therm!l !nom!lies !re f!r more re!dil' o&served
!nd more prono"nced in the properties of !ter ne!r interf!ces)e%-%( the !ter$!ir
interf!ce% If therm!l !nom!lies exist in the properties of vicin!l !ter( the' !re most
li.el' d"e to str"ct"r!l tr!nsitions( !.in to hi-herorder ph!se tr!nsitions% The tr!nsitions
th"s !nno"nce the existence of st!&ili3ed str"ct"res ne!r the interf!ce( e!ch str"ct"re
possessin- specified therm!l st!&ilit' limits% The possi&le existence of therm!l
!nom!lies in !#"eo"s s'stems h!s &een !mpl' disc"ssed elsehere EDrost)4!nsen +FG)
F=( F8,H% A point to &e stressed is th!t the str"ct"re of &"l. !ter pro&!&l' does not
cont!in Ice)lh)Ii.e elements( &"t some other t'pe of str"ct"res)perh!ps cl!thr!teli.e*
perh!ps some t'pe of cl"sters( or possi&l' hi-hpress"re ice pol'morphs% This implies
th!t the model for +&"l., !ter str"ct"re most li.el' to prove correct is ! 0mixt"re
model0 in hich e#"ili&ri"m exists &eteen monomers !nd some str"ct"red "nits( &e
the' cl"sters( ice pol'morphs( or cl!thr!te c!-e)li.e str"ct"res% Witho"t det!iled
doc"ment!tion( it is proposed !t this time +&"t consistent ith e!rlier propos!ls &' the
present !"thor, th!t !ter ne!r cert!in interf!ces m!' possess ! re-ion of enh!nced
disorder &eteen the to ordered 3ones)respectivel'( the 3one !d5!cent to the solid on
the one h!nd !nd the +loc!ll' ordere~l) &"l. str"ct"re on the other h!nd% Some of the
evidence for the existence of enh!nced disorder +ne!r cert!in solid s"rf!ces, is presented
l!ter in the p!per%
D. Pro!le of Cla"s The properties of !#"eo"s cl!' s'stems !re mentioned onl' in
p!ssin-% An impressive vol"me of liter!t"re exists concernin- the pro&lem of !ter$cl!'
inter!ctions( !nd the re!der is referred to the ritin-s of 2rofessor 2hilip Lo !nd his
!ssoci!tes +ho -ener!ll' f!vor the ide! of lon-)r!n-e orderin- ne!r interf!ces, !nd Dr%
v!n Olphen !nd Dr% Torrence C!rtin +&oth of hom h!ve( ith e#"!l elo#"ence( !r-"ed
!-!inst the notion th!t lon-)r!n-e orderin- occ"rs !t cl!')miner!l s"rf!ces) or( !t le!st(
!r-"ed th!t it is not necess!r' to invo.e s"ch lon-)r!n-e order to expl!in the rheolo-ic!l
properties of !#"eo"s cl!' s'stems,% Cl!'s !nd cl!' s"spensions h!ve !ttr!cted m"ch
!ttention &ec!"se of their pr!ctic!l import!nce)r!n-in- from pro&lems in soil
mech!nics( !nd the petrole"m ind"str'( to !tmospheric n"cle!tion pro&lems% Even more
intri-"in- !re the rem!r.!&le properties hich s"ch s'stems possess% 4oever( the
present !"thor h!s l!r-el' !voided disc"ssin- the !ter$cl!' s'stems in connection ith
the possi&le existence of ind"ced !ter str"ct"res ne!r interf!ces1 It is diffic"lt to
sep!r!te str"ct"r!l phenomen! from the -eometric effects &ec!"se of the p!c.in- of the
cl!' pl!telets or the effects of the !dsor&ed +exch!n-e!&le, ions on the !ter str"ct"re%
+Iener!ll'( the concentr!tion of ions ne!r the cl!' s"rf!ce is hi-h% This res"lts in r!ther
concentr!ted 0loc!l0 sol"tions !nd s"ch !re theoretic!ll' f!r more diffic"lt to tre!t th!n
!ter itself or !ter in dil"te sol"tions%, F"rthermore( the cl!'s in !#"eo"s s"spensions
!re o&vio"sl' never in ! tr"e e#"ili&ri"m st!te% Th"s( their properties ill contin"e to
v!r' ith time( &ec!"se of s"ch f!ctors !s the contin"ed h'drol'sis of !l"min"m !nd
other de-r!d!tions d"e to !ter$cl!' inter!ctions% An !ddition!l diffic"lt'( of co"rse(
ith !ter in cl!' s'stems( is the interl!mell!r sorption res"ltin- in l!ttice exp!nsion%
This p!rtic"l!r effect m!' &e monitored ith precision &' J)r!' diffr!ction% 4oever(
this !ter m"st &e so hi-hl' infl"enced &' the confinin- s"rf!ces th!t it &ecomes !
m!tter of sem!ntics if one ishes to refer to this !s !ter or simpl' !s !n extension of !
h'dr!te str"ct"re of ! ver' complex chemic!l form% An excellent &rief s"rve' of the
colloid!l !nd s"rf!ce properties of cl!'s c!n &e fo"nd in !n !rticle &' Ch!m&ers +:@,%
This !rticle !lso s"mm!ri3es ! fe of the c"rrent ritin-s re-!rdin- !ter str"ct"res
ne!r cl!' s"rf!ces%
II. T#ER$A% ANO$A%IES
A. Anoalies in Surface Tension of Water As o"tlined in the Introd"ction( p!rt
of the evidence for the existence of ordered str"ct"res ne!r interf!ces is &"ilt !ro"nd the
occ"rrence of therm!l !nom!lies in the properties of !ter% It h!s &een s"--ested th!t
these !nom!lies !re evidence of hi-her)order ph!se tr!nsitions)s"ch tr!nsitions(
o&vio"sl'( onl' occ"rrin- in p!rti!ll' ordered( str"ct"red "nits of ! cert!in minim"m
si3e% F"rthermore( the !nom!lies !re more fre#"entl' tD"nd in the properties of
interf!ci!l s'stems th!n in &"l. s'stems( !ltho"-h v!rio"s sol"tions !ppe!r !lso to
reve!l therm!l !nom!lies +the therm!l !nom!lies !re often referred to !s 0.in.s0,% As !n
ex!mple of ! therm!l !nom!l'( Fi-"re : shos the s"rf!ce tension of !ter !s
determined &' Timmerm!ns !nd /odson (134). This ex!mple( to-ether ith ! l!r-e
n"m&er of other interf!ci!l phenomen!( h!s &een disc"ssed in det!il in !n !rticle &' the
present !"thor EDrost)4!nsen (34)]. In Fi-"re : the s"rf!ce tension of !ter !ppe!rs to
possess !n inflection point in the vicinit' of :< to := K C% The d!t! ere o&t!ined &'
sever!l independent methods( !ll 'ieldin- the s!me #"!ntit!tive res"lts% It sho"ld &e
noted th!t other investi-!tors h!ve me!s"red the s"rf!ce tension of !ter over this +!nd
extended, r!n-e of temper!t"re itho"t findin- corro&or!tin- evidence for the !nom!l'%
ESee( hoever( the cl!ssic st"d' &' Fr!n.s !nd Ives +=8, on the interf!ci!l tension
&eteen hex!ne !nd !ter% See !lso Note Added in 2roof%H
B. Infrared Evidence for Theral Anoalies Some of the more spect!c"l!r
demonstr!tions of therm!l !nom!lies h!ve come from Iorin- !nd coor.ers% Elsehere
in this p!per e disc"ss the o&serv!tions m!de &' R!mi!h !nd Iorin- (112) on !ter
ne!r cell"lose s"rf!ces !nd the viscosit' st"d' &' Ihn!t +>=,( or.in- in Iorin-Bs
l!&or!tor'% For the present( e foc"s !ttention on the spectroscopic o&serv!tions m!de
&' S!l!m! !nd Iorin- +::8,% These !"thors me!s"red the intensit' of infr!red
!&sorption of !ter !t <:99 cm)1 !nd -!ve their res"lts in terms of per cent ch!n-e in
!&sorption !s ! f"nction of temper!t"re% Their -r!ph shos ! not!&le inflection point in
the vicinit' of F9KC%( !nd th!t fe!t"re !s stressed &' the !"thors% A c!ref"l inspection
of the d!t! s"--ests !lso the possi&le existence of ! simil!r( &"t less prono"nced(
!nom!l' in the vicinit' of =@KC% S!l!m! !nd Iorin- !pplied ! 0movin- #"!dr!tics0
c"rve)fittin- method of !n!l'sis% The res"lt of this !n!l'sis to the infr!red !&sorption
d!t! is shon in Fi-"re <% The ver' prono"nced minim"m !t 30 C% is one of the most
convincin- ex!mples of ! therm!l !nom!l' th!t h!s &een reported in this temper!t"re
r!n-e% 4oever( it is "nfort"n!te th!t in this otherise impressive ex!mple( one m"st
exert some c!"tion in interpret!tion% The me!s"rements ere m!de "sin- ! hi-h)
resol"tion Unic!m 6!c""m Ir!din- Spectrophotometer( c!lci"m fl"oride indos
&ein- "sed% 4oever( the tot!l cell thic.ness !s onl' :<:B)% If one !ss"mes th!t
str"ct"res m!' exist ne!r interf!ces hich conceiv!&l' co"ld extend to ! not!&le depth(
it rem!ins possi&le +!ltho"-h not hi-hl' pro&!&le, th!t the o&served !&sorption ch!n-es
m!' &e c!"sed( in p!rt( &' the !ter !d5!cent to the indos% Th"s( the o&served effect
m!' not &e directl' !pplic!&le to &"l. !ter% Another possi&ilit' is th!t the o&served
!nom!l' is rel!ted to the !ter !ssoci!ted ith the h'dr!tion of dissolved ions +C!< L(
F), either in sol"tion or in the indo m!teri!l% Fin!ll'( &ec!"se the me!s"rements ere
m!de !t ! fixed fre#"enc'( ! movement in &!nd pe!.s ith temper!t"re co"ld res"lt in
v!rio"s de-rees of s"perposition of different &!nds ith r!ther different temper!t"re
coefficients% 4ence( !nom!lo"s ch!n-es !re conceiv!&l' possi&le &ec!"se of this shift
!lone% On the other h!nd( the !&r"ptness of the tr!nsition !ppe!rs to !r-"e !-!inst this
possi&ilit'( !s does the coincidence of the temper!t"re !t hich the ch!n-e is o&served
ith the temper!t"re !t hich !nom!lies in ! v!riet' of other !#"eo"s properties occ"r%
The fore-oin- to ex!mples ill"str!te #"ite t'pic!ll' the notion of more or less !&r"pt
ch!n-es over ! rel!) tivel' n!rro temper!t"re interv!l% As disc"ssed &efore &' the
present !"thor( the occ"rrence of s"ch n!rro tr!nsition re-ions !ppe!rs #"ite
fre#"entl'% In f!ct( ! l!r-e n"m&er of s"ch inst!nces h!ve &een fo"nd !nd descri&ed
!ltho"-h the existence of the tr!nsitions h!s &een vi-oro"sl' denied &' other !"thors% A
someh!t concili!tor' notion( hich m!' expl!in in p!rt the diver-ence of opinion( h!s
&een proposed recentl' EDrost4!nsen (38)].
III. E&IDENCE O' SUR'ACE STRUCTURES (Anoalous Te)erature
De)endencies in &arious Pro)erties*
A. Disjoining Pressures C"ch of the evidence for lon-)r!n-e order ne!r interf!ces
presented in the e!rl' 'e!rs +especi!ll' &' Der5!-"in !nd coor.ers, !s critici3ed
&ec!"se of the possi&le sp"rio"s infl"ences of s"ch f!ctors !s d"st( s"rf!ce sellin-( qr
electrovisco"s effects +in viscosit' or.,% Recentl'( 2eschel !nd Aldfin-er +:9@,)see
!lso 2eschel +:9=,)h!ve determined the dis5oinin- press"re of !ter &eteen #"!rt3
s"rf!ces% These !"thors me!s"red the force &eteen to #"!rt3 pl!tes in !ter +one
pl!n!r pl!te( the other sli-htl' c"rved* r!di"s of c"rv!t"re !&o"t :99 cm,% At const!nt
temper!t"re( the press"re dependence on the sep!r!tion c!n &e represented &' !n
e#"!tion in the form (1) here Pd is the dis5oinin- press"re( d is the sep!r!tion( !nd C
!nd n !re p!r!meters% The !"thors st"died the dis5oinin- press"re for sep!r!tion &eteen
the to #"!rt3 s"rf!ces of ! fe tho"s!nd A or less% The p!r!meters C !nd n !re
temper!t"re dependent( !nd Fi-"re F shos the o&served temper!t"re dependence of the
dis5oinin- press"re !nd of the p!r!meters C !nd n. The res"lts !re seen to &e hi-hl'
"nexpected !nd complex% 2eschel !nd Aldfin-er s"--est th!t the extrem! o&served ne!r
:@ !nd F<KC%( !s ell !s the !nom!l' sli-htl' !&ove >9KC%( m!' &e rel!ted to the
!nom!lies disc"ssed &' the present !"thor% Core recentl'( Aldfin-er +person!l
comm"nic!tion( :M>8, h!s o&t!ined !ddition!l me!s"rements of dis5oinin- press"res
!nd these !re shon in Fi-"re =% A-!in( one o&serves the persistent !ppe!r!nce of
m"ltiple( rel!tive m!xim! in the dis5oinin- press"re !s ! f"nction of temper!t"re% This
ex!mple is of consider!&le interest &ec!"se hile e!rlier res"lts "sed to demonstr!te the
existence of s"rf!ce)ind"ced str"ct"res in the !ter mi-ht h!ve &een infl"enced &'
sp"rio"s effects( there is no re!son to s"spect th!t !n' 0mech!nic!l0 dist"r&!nce +for
inst!nce( the presence of d"st or 0sollen s"rf!ce l!'ers0, sho"ld -ive rise to s"ch
not!&le temper!t"re) dependent v!ri!tions% In p!rtic"l!r( one does not expect( &' p"re
ch!nce !lone( th!t !n' v!ri!tions in the temper!t"re dependenc' o"ld correl!te ith
the !nom!lo"s temper!t"res( proposed independentl' on !n entirel' different &!sis%
Th"s( it seems re!son!&le to t!.e the experiments &' 2eschel !nd Aldfin-er !s
"ne#"ivoc!l evidence for the re!lit' of ordered str"ct"res( possi&l' of consider!&le
r!n-e( "nder-oin- tr!nsitions !t the v!rio"s temper!t"res proposed &' the present
!"thor%
B. NMR Studies of Colloidal Suspensions 2ethic!( Clifford( !nd coor.ers Esee
Nohnson et al. +GG,H h!ve m!de ! comprehensive st"d' of colloid st!&ilit' !nd the role of
!ter str"ct"re in the interpret!tion of s"ch st!&ilit'% While the -ener!l topic of colloid
st!&ilit' is someh!t peripher!l to the m!in s"&5ect p"rs"ed in the present p!per( e
stress here the f!ct th!t str"ct"red !ter h!s &een proposed to exist s"rro"ndin- micron)
si3ed colloid!l p!rticles of pol'vin'l !cet!te +26 A, !nd pol'vin'l tol"ene +26T,%
2ethic! !nd coor.ers prep!red sols of these pol'mers !nd st"died them &' v!rio"s
techni#"es% Fi-"re @ shos the r!te of flocc"l!tion of pol'vin'l tol"ene p!rticles vs.
reciproc!l( !&sol"te temper!t"re% An !&r"pt !nom!l' is indic!ted in these d!t! !t
!pproxim!tel' =<K or 43C. Fi-"re > shos the spin)spin rel!x!tion time (T2) !s !
f"nction of the !&sol"te temper!t"re for ! s"spension of 9%8C 2OA p!rticles% It is seen
th!t !&r"pt ch!n-es occ"r ne!r FKC% !nd ne!r F:KC% 2ethic!( Clifford( !nd coor.ers
disc"ss the s"--estion th!t there is ! str"ct"r!l &re!.don in the !ter &eteen F9K !nd
F<KC% This( indeed( is the temper!t"re !t hich e h!ve cl!imed the existence of !
not!&le !nom!l')in p!rtic"l!r( in !#"eo"s s"rf!ce phenomen!% 2ethic! !nd coor.ers
concl"ded th!t 0the evidence presented +here, -ener!ll' s"pports the vies of Der5!-"in
on the lon-r!n-e str"ct"rin- of &o"nd!r' l!'ers of !ter%0 v6e ret"rn to the p!pers &'
Der5!-"in !nd &' 2ethic!( Clifford et at. in the disc"ssions in Sections 6III)D !ndJ%
C. Dielectric Constant of Water as a Solute In connection ith the colloid
st"dies disc"ssed !&ove( it is of interest to note th!t dielectric const!nt me!s"rements
h!ve shon r!ther !&r"pt !nom!lo"s ch!n-es in dielectric properties of !ter)s!t"r!ted
+!nd p!rti!ll' s!t"r!ted, h'droc!r&ons !t discrete temper!t"res% Fi-"res G !nd 8 sho
some of the res"lts o&t!ined &' the present !"thor +"np"&lished d!t!, here the
c!p!cit!nce of the dielectric cell is plotted !s ! f"nction of temper!t"re !t ver' closel'
sp!ced interv!ls over the r!n-e from 20C. +Fi-"re G, to @@KC% +Fi-"re 8,% It is !pp!rent
th!t not!&le ch!n-es in the dielectric properties occ"r !t !pproxim!tel' =@KC% In f!ct(
f"rther me!s"rements of this t'pe on p!rtl' !ter)s!t"r!ted sol"tions +!ter in &en3ene(
c'clohex!ne( !nd c!r&on tetr!chloride, reve!led !nom!lies !t or !&o"t !ll fo"r
temper!t"res here !nom!lies h!ve &een cl!imed to exist in p"rel' !#"eo"s s'stems% It
is possi&le th!t the o&served effects !re d"e 0onl'0 to !ter !dsor&ed from the sol"tions
onto the !lls of the c!p!cit!nce cells% If this is the c!se( the res"lts impl' the existence
of ordered !ter str"ct"res &eteen ! 0et0 h'droc!r&on ph!se !nd ! -l!ss s"rf!ce% If
the o&served effects( hoever( !re not d"e to s"ch !dsor&ed !ter( the res"lts s"--est
inste!d th!t !t le!st some of the !ter in the or-!nic li#"ids is present in !n !ssoci!ted
+pol'meric, str"ct"red form% In either c!se( it is noteorth' th!t therm!l !nom!lies !re
o&served in the !&sence of ! &"l. ph!se of !ter( !nd this point is essenti!l to cert!in
!spects of the disc"ssion hich follos%
D. Micelle Sizes Otteill( Storer( !nd W!l.er (107) h!ve st"died the micell!r ei-ht of
! nonionic s"rf!ct!nt +dodec'l)hex!ox'eth'lene) -l'col monoether, in D<9% The res"lts
shoed ! rem!r.!&le const!nc' in molec"l!r ei-ht +ne!r !pproxim!tel' @9(999, in the
r!n-e from @K to :@Ke% folloed &' ! ver' !&r"pt incre!se in micelle si3e to
!pproxim!tel' 8=9(999 !t F@Ke% +Fi-"re M,% The method emplo'ed !s the Archi&old
sediment!tion e#"ili&ri"m proced"re( !nd the res"lts ere essenti!ll' simil!r +!t
temper!t"res !&ove :@Ke%, to the res"lts o&t!ined &' /!lm&r! &' ! li-ht sc!tterin-
method% Otteill !nd coor.ers concl"de th!t !&ove :@KC% +!nd "p to F@K e%, spheric!l
micelles !re !--re-!tin- to form l!r-er "nits% The #"estion of h' the si3e rem!ins
const!nt !t the loer temper!t"re is not el"cid!ted% 4oever( it o"ld !-!in &e
re!son!&le to s"ppose th!t !n expl!n!tion m!' &e invo.ed in terms of differences in
!ter str"ct"re% Th"s( &elo :@ Ke%( ! !ter str"ct"re is st!&le hich is cond"cive to
st!&ili3in- ! cert!in .ind of micelle( &"t !s the temper!t"re is incre!sed !&ove this point(
the st!&ilit' is more or less !&r"ptl' diminished !nd the micelles( !s ! res"lt( find it
ener-etic!ll' more f!vor!&le to re!rr!n-e into the l!r-er "nits( consistent ith th!t
vicin!l !ter str"ct"re hich is st!&le in the re-ion !&ove :@ C%
E. Water and Hdrocar!on Dispersions The !&sence of ! sh!rp free3in- point for
s"percooled !ter in intim!te cont!ct ith v!rio"s hi-hl' poro"s m!teri!ls is ! s"&5ect
of !ctive disc"ssion% Th"s( C'sels (98) felt th!t the ph!se r"le o"ld dem!nd ! sh!rp
meltin- point for Der5!-"inBs !ter in n!rro #"!rt3 c!pill!ries +see the disc"ssion in
Section J)/,( here!s the !ct"!l free3in- !ppe!rs to &e reversi&l' spre!d o"t over the
re-ion from ):@K to )F9KC% Fo.es +=@, commented on this phenomenon !nd reported
me!s"rements on !ter)s!t"r!ted h'droc!r&ons( hich ere st"died &' ! li-ht)
sc!tterin- method% On coolin-( !ter droplets !ppe!red to occ"r +!pp!rentl' f!irl'
!&r"ptl', in these !ter)s!t"r!ted !nd ell)stirred h'droc!r&ons( !t !&o"t L:@Ke% The
sc!tterin- from these droplets !s folloed( "pon coolin-( to ) 89KC% !nd !-!in d"rin-
rehe!tin- to L<99 e% Fo.es points o"t th!t 0 %%% ! sh!rp incre!se in sc!tterin- occ"rred
!t )<9 to )F:Ke% +dependin- on h'droc!r&on present,( &"t no f"rther ch!n-e !s seen in
coolin- to ) SOKC%0 Fo.es s"--ests th!t these res"lts co"ld &e interpreted !s
m!nifest!tions of 0specific !ter0 hich fro3e !nd melted in the r!n-e from ) <9 to ) F:
C%( &"t never free3in- !t OKC%
'. Water on Silver Iodide The pro&lem of the st!te of !ter on ! silver iodide s"rf!ce
h!s !ttr!cted consider!&le !ttention &ec!"se of the import!nce of silver iodide !s !
n"cle!tin- !-ent in clo"d)seedin- experiments% L'.lem! +8@, h!s me!s"red the s"rf!ce
ch!r-e +!nd th"s the differenti!l c!p!cit!nce, on ! silver iodide s"rf!ce% One of the
interestin- res"lts o&t!ined &' L'.lem! is ! not!&le decre!se in the s"rf!ce ch!r-e ith
!n incre!se in temper!t"re% Specific!ll'( ! definite inflection point is fo"nd in the
vicinit' of @9 to @@ K C% for the differenti!l c!p!cit!nce !s ! f"nction of temper!t"re%
L'.lem! correctl' infers th!t this implies ! f!irl' s"dden 0meltin-0 +!t !&o"t @9KC%,%
Th!t this 0meltin-0 is rel!tivel' s"dden is f"rther s"pported &' some differenti!l therm!l
!n!l'sis experiments performed &' v!n der 2l!s !nd reported &' L'.lem!% These
experiments shoed ! ph!se tr!nsition !t !&o"t @9KC%( ith ! et silver iodide% No s"ch
tr!nsition !s o&served ith dr' silver iodide* hence( the effect m"st &e !scri&ed to !
propert' of the !ter !d5!cent to the silver iodide s"rf!ce% F"rther evidence for the
!&r"pt ch!n-e comes in experiments here flocc"l!tion concentr!tions for the silver
iodide !re determined !s ! f"nction of temper!t"re shoin- the dis!ppe!r!nce of
specific ion effects !&ove >9K or >@KC% Unfort"n!tel'( here( !s in so m!n' other
inst!nces( me!s"rements ere m!de onl' !t rel!tivel' idel' sp!ced temper!t"re
interv!ls !nd f!r more det!ils mi-ht h+lve &een reve!led h!d me!s"rements &een m!de
over temper!t"re interv!ls of onl' ! fe de-rees% L'.lem! concl"ded th!t the silver
iodide s"rf!ce( !t le!st pr!-m!tic!ll'( m!' &e descri&ed !s 0h'dropho&ic%0 Romo +::@,
in#"ired if the o&served ph!se tr!nsitions reported &' L'.lem! mi-ht not &e d"e to !
s"dden ch!n-e in the st!te of h'dr!tion of the lithi"m or r"&idi"m ions emplo'ed in this
st"d'% In repl'( L'.lem! st!ted th!t the ch!n-e of !&o"t <9P in therm!l ener-' (kT)
co"ld h!rdl' &e s"fficient to c!"se ! deh'dr!tion of the !l.!li ions( more or less !&r"ptl'
!nd completel'( ne!r @9KC% 4e !lso points o"t th!t the DTA experiment !s performed
in the !&sence of s!lt !nd in the !&sence of ! &"l. !#"eo"s ph!se% 4ence( the
phenomenon is !pp!rentl' !n effect of the !ter !t the !ter$ silver iodide interf!ce !nd
not of the &"l. sol"tion% It sho"ld &e noted in this connection th!t m!n' ion properties
do seem to -o thro"-h not!&le ch!n-es in the vicinit' of @9KC%( s"ch !s the m!xim"m in
the B-coefficient for electrol'tes Esee( for inst!nce( Cillero( Drost)4!nsen( !nd Qorson
+M=,H% We postpone f"rther disc"ssion of the #"estion of !ter ne!r silver iodide
p!rticles to ! s"&se#"ent note on n"cle!tion phenomen! !s rel!ted to !ter str"ct"re
models ne!r interf!ces%
+. &oluetric Data for Water,Cellulose S"stes R!mi!h !nd Iorin- +::<, h!ve
de!lt ith !ter $ cell"lose inter!ction in ! ver' interestin- p!per% These !"thors
me!s"red dil!tometric!ll' the therm!l exp!nsion of v!rio"s ood constit"ents !nd
discovered l!r-e( !nom!lo"s ch!n-es in the exp!nsion of !ter)sollen m!teri!ls
+cell"lose( hemicell"lose( !nd li-nin,% The' !scri&ed the ch!n-es to pert"r&!tions in the
!ter str"ct"re c!"sed &' the h'drophilic s"rf!ces of the ood' m!cromolec"les%
R!mi!h !nd Iorin- o&served ! series of tr!nsition temper!t"res( &oth for the 0dried0
compressed ood constit"ents( !s ell !s for those in cont!ct ith !ter% The
me!s"rements &' R!mi!h !nd Iorin- ere s"fficientl' precise th!t( not onl' !s it
possi&le to differenti!te the vol"me ch!n-es ith respect to temper!t"re +to o&t!in plots
of deriv!tives vs. temper!t"re,( &"t the d!t! co"ld( in f!ct( profit!&l' &e differenti!ted
tice to prod"ce -r!phs hich still shoed rem!r.!&l' little sc!tter% In the c!se of the
0dr'0 s!mples( the tr!nsition temper!t"res sometimes extended over sever!l de-rees%
R!mi!h !nd Iorin-( to !id the !n!l'sis of the d!t!( "sed ! 0movin- #"!dr!tics0 method(
hich s"&se#"entl' S!l!m! !nd Iorin- +::8, "sed to -re!t !dv!nt!-e to st"d' the
intensit' of infr!red !&sorption !t <:99 !ve n"m&ers for p"re !ter (vide infra).
BWhen !tersollen s!mples ere "sed( simil!r +&"t more prono"nced, !nom!lies ere
o&served% Altho"-h R!mi!h !nd Iorin- h!d some re!son!&le s"--estions for the
possi&le ori-in of the tr!nsitions in the dried st!te of the cell"losic m!teri!ls( it is
possi&le those !nom!lies ere !lso c!"sed &' resid"!l !ter% In spite of the vi-oro"s
dr'in- efforts exercised &' the !"thors( it seems possi&le th!t the l!st tr!ces of !ter
m!' not h!ve &een removed% +In -ener!l( the s!mples ere de-!ssed in ! v!c""m( :) to
@)::) press"re( !t rel!tivel' hi-h temper!t"res%, On the other h!nd( there is little do"&t
th!t the !nom!lo"s tr!nsitions in the !ter)sollen cell"losic components !re d"e to
str"ct"r!l ch!n-es in the !ter !ssoci!ted ith the cell"lose s"rf!ces% ESee !lso lRBote
Added in 2roof%H R!mi!h !nd Iorin- proposed ! model for s"ch !ter( !s shon in
Fi-"re :9% This model is essenti!ll' identic!l to the one !dvoc!ted e!rlier &' the present
!"thor !nd el!&or!ted "pon in this p!per% The model is ! three)l!'er model in hich the
str"ct"re of the vicin!l !ter is pert"r&ed &' inter!ction ith the pol!r -ro"ps on the
s"rf!ce of the solid% S"fficientl' f!r removed from the s"rf!ce is the "npert"r&ed !ter
str"ct"re hile in)&eteen exists ! re-ion hich h!s elements of &oth "n&onded !nd
&onded !ter% In o"r interpret!tion( this intermedi!te l!'er o"ld &e the more dis
ordered( &ro.en)don str"ct"re( not conformin- to either of the differentl' ordered
str"ct"res of the vicin!l !ter or the &"l. !ter%
#. #eat of Trans)ort and Other Phenoena across Cellulosic $e!ranes
In connection ith the st"dies &' Iorin- !nd coor.ers( mention sho"ld &e m!de !lso
of the !nom!lo"s res"lts o&t!ined &' 4!!se !nd Steinert +@F, in ! st"d' of the he!t of
tr!nsport !cross ! cell"losic mem&r!ne% In ! s"&se#"ent p!per( 4!!se !nd deIreiff +@<,
noted th!t the !nom!lies reported e!rlier co"ld not &e reprod"ced% Recent or. in the
present !"thorBs l!&or!tor' +"np"&lished, on the mem&r!ne properties of Cillipore
filters impre-n!ted ith tol"ene E0Il!ni Cem&r!nes0 +>@)>8,H h!s shon th!t therm!l
!nom!lies !re sometimes enco"ntered in v!rio"s properties of these mem&r!nes( &"t !re
!&sent !t other times% The properties in hich the therm!l !nom!lies h!ve fre#"entl'(
&"t not inv!ri!&l'( &een o&served incl"de concentr!tion potenti!ls( &i)ionic potenti!ls(
!nd mem&r!ne cond"ct!nces% Re!sons for the l!c. of reprod"ci&ilit' !re not c"rrentl'
.non ith cert!int'( &"t m!' &e rel!ted to the penetr!tion of !ter into the poro"s
m!trix +Cr!tin !nd Drost)4!nsen( :M>M( "np"&lished,%
I. Therod"naic Pro)erties of Adsor!ed Water on Cellulose Some
interestin- thermod'n!mic properties of !dsor&ed !ter on cell"lose h!ve &een reported
&' Corrison !nd D3ieci"ch +M>,% These !"thors fo"nd evidence for ! tr!nsition from !n
immo&ile to ! mo&ile film or the !ppe!r!nce of ! ne mo&ile film( !&ove the immo&ile
one( !nd ! disorderin- effect( ith incre!sin- !mo"nts of !dsor&ed !ter% These !"thors(
incident!ll'( !lso disc"ssed the o&serv!tion th!t there seems to &e ! ch!n-e in the
cell"lose$!ter s'stem !t !&o"t =9K to SOKC% The' #"ote Collins !s h!vin- fo"nd 0!
p!r!llel &re!. in the c"rves of the cross)section!l !re! ch!n-es !nd the re-!in hen
plotted !-!inst temper!t"re( ith ! complete ch!n-e in direction occ"rrin- in the r!n-e
of =9K to SOKC%0 The' !lso #"ote W!h&! !nd N!shed( ho fo"nd the isosteric he!t of
!dsorption to decre!se m!r.edl' !&ove !n optim"m temper!t"re of from =9K tf, SOKc(
for 0"nst!&ili3ed0 cell"lose% We ret"rn to st"dies of !ter on cell"lose s"rf!ces l!ter in
this p!per +Sections 6II)E !nd JI)C,%
". #eat of Iersion of Cla"s Another ex!mple of prono"nced therm!l !nom!lies
!s disc"ssed previo"sl' &' the present !"thor +F8,n!mel'( the res"lts o&t!ined &'
Sl!&!"-h from he!t of immersion me!s"rements on homo)ionic cl!'s% In the st"d' &'
Sl!&!"-h +:<8,( ! ver' s"dden incre!se in he!t of immersion occ"rred in prehe!ted
c!lci"m &entonite( !ro"nd <MK to F9KC% In spite of the ver' sm!ll !mo"nt of !ter
ret!ined on the cl!' !fter the pretre!tment( this findin- m!' perh!ps &e interpreted in
terms of ! s"dden ch!n-e in str"ct"re of the +rem!inin-, !ter str"ct"res on the
prehe!ted c!lci"m cl!'s( prior to immersion%
-. Rates of Wettin. of 'att" Acids An interestin- experiment ith f!tt' !cids in
cont!ct ith !ter h!s &een m!de &' Oi!nnos +:=@,( ho st"died the orient!tion of f!tt'
!cids on !ter s"rf!ces% Oi!nnos determined the r!te of !ppro!ch to e#"ili&ri"m of the
cont!ct !n-le !s ! f"nction of temper!t"re !nd concl"ded th!t to of his res"lts +!t F9K
!nd FSoC%, ere o"t of line ith the rem!inin- points !nd s"--ested th!t this co"ld
possi&l' &e expi!ined in terms of ! tr!nsition t!.in- pl!ce !t the s"rf!ce% Oi!nnos
spec"l!ted th!t this mi-ht &e rel!ted to ! to)dimension!l l!ttice st!&ilit' for f!tt' !cids
on ! s"rf!ce Esee !lso Section 6II)/H% It seems re!son!&le to s"--est th!t the res"lts !re
!nother m!nifest!tion of the different !ter re-imes !t the interf!ce( le!din- to different
.inetic !nd e#"ili&ri"m properties of !ter ne!r interl!ces%
%. Rates of Cr"stal +ro/th fro A0ueous Solution Sip'!-in +:<G, h!s st"died
the r!te of -roth of different cr'st!l f!ces of to !l.!li chlor!tes !s ! f"nction of
temper!t"re !t const!nt s"pers!t"r!tion% 4is res"lts s"--est th!t !nom!lo"s -roth r!tes
occ"r for &oth sodi"m chlor!te !nd pot!ssi"m chlor!te in to temS%er!t"re r!n-es% The
r!n-es depend someh!t on the p!rtic"l!r cr'st!l f!ce st"died( &"t in -ener!l( f!ll in
th~ vicinit' of : K to :FKC% !nd F: K to =<KC% The !"thor concl"ded th!t these
!nom!lies !ppe!r to reflect ch!n-es in the str"ct"re of the !ter ne!r the -roin-
cr'st!l f!ces% O&vio"sl' e !re de!lin- here ith !ter in r!ther concentr!ted sol"tions%
It o"ld &e expected th!t the str"ct"re of the !ter o"ld &e consider!&l' infl"enced &'
the force fields of the ions !nd( !s ! res"lt( not sho !n' evidence of those t'pes of
discrete stnBct"res hich o"ld &e expected in p"re !ter or in dil"te sol"tions of
electrol'tes% The present !"thor h!s COl%lmen ted on this pro&lem on !n e!rlier occ!sion
+F<,% Another st"d' of cr'st!lli3!tion fr"m s"pers!t"r!ted sol"tions of stron-
electrol'tes h!s &een m!de &' Celi! !nd Coffitt +M9,% These !"thors determined the
n"m&er of n"clei prod"ced in fresh !nd !-ed sol"tions of s"pers!t"r!ted !mmoni"m
&romide% Their d!t!( for the n"m&er of cr'st!llites formed( distinctl' sho the
occ"rrence of therm!l !nom!lies ne!r :@K !nd F9KC% A-!in( it is rem!r.!&le th!t
str"ct"r!l effects sho"ld &ecome m!nifested in s"ch concentr!ted electrol'te sol"tions%
M. #$er%al Ano%alies as E&idence of Surface Structures The ex!mples disc"ssed in
this section !re intended to conve' some of the evidence for more or less !&r"pt ch!n-es
in m!n' !#"eo"s interf!ci!l s'stems !t discrete temper!t"res% Other ex!mples !re
mentioned in ! recent Note &' the present !"thor +FF,% The ex!mples &' 2eschel !nd
Aldfin-er !nd the st"d' &' 2ethic! !nd coor.ers cle!rl' demonstr!ted the existence of
therm!l !nom!lies in the properties of !ter ne!r solid interf!ces% The d!t! on the
dielectric properties of !ter dissolved in or-!nic solvents +or !dsor&ed from s"ch
or-!nic solvents, s"--est th!t the !nom!lies !re fo"nd even for ver' lo concentr!tions
of !ter% The st"d' &' Otteill !nd coor.ers s"--ests th!t the !nom!lies m!' occ"r
for !ter in interf!ci!l s'stems here the 0s"&str!te0 is hi-hl' dispersed +micelles,(
hile the res"lts &' Fo.es s"--est the existence of lo temper!t"re !nom!lies
+someh!t simil!r in n!t"re to the dielectric st"dies &' the present !"thor,% The res"lts
&' L'.lem! on silver iodide !nd &' Iorin- !nd coor.ers on the !ter$cell"lose
interf!ce( !s ell !s the res"lts &' 4!!se !nd Steinert on cell"lose( !ll s"--est th!t !ter
is str"ct"red !t the interf!ces st"died !nd is c!p!&le of "nder-oin- str"ct"r!l tr!nsitions
!t discrete temper!t"res% The ex!mple &' Sl!&!"-h of the he!t of immersion of cl!'s !s
! f"nction of temper!t"re shos definite effects of the temper!t"re of pretre!tment( &"t
the res"lts !re pro&!&l' too diffic"lt to interpret in str"ct"r!l terms &ec!"se of the
extremel' lo concentr!tion of resid"!l !ter% Simil!rl'( it is !lso diffic"lt to interpret
the res"lts &' Oi!nnos on the r!te of ettin- of f!tt' !cids% A f"rther complic!tion is
introd"ced in the st"dies &' Sip'!-in !nd &' Celi! !nd Coffitt( !ltho"-h( !-!in( there
!ppe!rs to &e little do"&t &"t th!t !nom!lies do occ"r !nd it seems re!son!&le to propose
th!t the' !re !lso rel!ted to !ter str"ct"re%
I&. DIE%ECTRIC AND N$R RESU%TS
A. Dielectric Studies Dielectric !nd n"cle!r m!-netic reson!nce me!s"rements h!ve
fre#"entl' &een "sed for st"dies of str"ct"res ne!r interf!ces% v6e h!ve !lre!d'
mentioned the st"dies &' 2ethic!( Clifford( !nd coor.ers( &' Otteill !nd coor.ers(
!nd &' the present !"thor% These st"dies ere concerned ith temper!t"re effects on the
r!te processes* e no t"rn o"r !ttention to f"rther dielectric !nd n"cle!r m!-netic
reson!nce st"dies in -ener!l% FIrst( e revie &riefl' some of the !v!il!&le evidence
o&t!ined &' dielectric me!s"rements% One of the most interestin- of these st"dies is one
m!de &' 2!lmer !nd coor.ers (102) ho me!s"red the dielectric properties of !ter
&eteen sheets of mic!% In this st"d'( ver' lo v!l"es for the dielectric const!nt of
!ter ere o&t!ined( indic!tin- oriented !ter !d5!cent to the mic! s"rf!ces% The
experiments &' 2!lmer( C"nliffe( !nd 4o"-h on mic! !re !mon- the most convincin-
ex!mples of evidence for lon-)r!n-e order in !ter ne!r s"it!&le interf!ces% As ! res"lt
of me!s"rement !t fre#"encies !t to !nd three m43( these !"thors ere !&le to st!te1
0It !s fo"nd th!t the dielectric const!nt of the !ter decre!sed ith the thinness of the
film from more th!n <9 for films !&o"t Sj.L in thic.ness to less th!n :9 for films !&o"t
2M in thic.ness +thic.ness c!lc"l!ted !ss"min- no !&sorption,% Even ith ver' et(
composite dielectrics( the dielectric const!nt of the !ter did not exceed >9%0 The' !lso
concl"ded th!t 0The !ter film is tendin- to !ct not !s BsolidB !ter( &"t r!ther !s Bli#"id
iceB%0 % In this connection( the' o&serve th!t hile the distinction m!' &e s"&tle( it m!'
&e import!nt in connection ith !ttempts to -!in ! &etter "nderst!ndin- of the !&norm!l
mech!nic!l properties of li#"id films( !nd this is pro&!&l' ! p!rtic"l!rl' v!l"!&le point
in connection ith !ter in &iolo-ic s'stems% Core recentl'( Af!n!sBev !nd Cesti. +<,
h!ve contri&"ted ver' si-nific!ntl' &' their dielectric st"dies on !ter ne!r mic!
s"rf!ces% These !"thors !lso interpret their d!t! in terms of orderin- of the !ter &' the
s"&str!te% C!n' of the res"lts o&t!ined from dielectric st"dies( especi!ll' sBc"dies of
!ter on h'dr!ted !l"min"m oxide !nd simil!r !dsor&ents( h!ve s"--ested the existence
of ver' firml' &o"nd !ter !t interf!ces% Tr!nsition l!'ers !ppe!r to exist !nd these m!'
extend for ! cert!in depth !!' from the solid s"rf!ce% This li#"id resem&les
s"percooled li#"id !t s"fficientl' lo temper!t"res) here the li#"id m!' -o into !n
!morpho"s -l!ss over ! p!rtic"l!r r!n-e of temper!t"res% In connection ith the
#"estion of dielectric properties( see !lso the st"dies &' Windle !nd Sh! +:=:, on the
h'dr!tion of ool( st"died !t ver' hi-h fre#"encies +<> .ilome-! 43,% 6!rio"s t'pes of
!dsor&ed( &o"nd( mo&ile( !nd intermedi!te !ter !re considered &' these !"thors% Also
of interest is the st"d' of the 4!ll effect &' Ch!i !nd 6o-elh"t +:=,% These !"thors
st"died the str"ct"re of &o"nd !ter on cr'st!lline hemo-lo&in &' ! micro!ve
techni#"e !t M%F> .ilo me-! 43% It !s o&served th!t ! h'dr!tion of 9%:F - of !ter per
-r!m of dr' hemo-lo&in !ppe!red to &e ! critic!l n"m&er +to &e comp!red ith ! v!l"e
of 9%<= - per -r!m of hemo-lo&in( o&t!ined &' Rosen,% The !"thors concl"de th!t the
!n-le of rot!tion of the initi!ll' !dsor&ed !ter &e-ins to incre!se !&ove the critic!l
h'dr!tion level !nd t!.e this to indic!te the form!tion of h'dr!tion l!'ers( d"e to
h'dro-en &onded cl"sters of !ter( on the s"rf!ce of the hemo-lo&in molec"le%
B. Ad&antages and 'ntrinsic Difficulties of Dielectric Studies Unfort"n!tel'( one of
the pro&lems in the interpret!tion of dielectric me!s"rements on mixed s'stems is the
n!t"re of the m!them!tic!l models re#"ired% It is diffic"lt to sep!r!te the individ"!l
+dielectric, properties of the &"l. ph!ses from those effects hich !re derived from the
p!rtic"l!r !nd "ni#"e !spects of the interf!ci!l re-ions% Th"s( De&'e dipol!r rel!x!tion
!nd C!xell)W!-ner cond"ctivit' !&sorption ill contri&"te to the over!ll dielectric
&eh!vior of hetero-eneo"s s!mples% As ! res"lt( complex c"rves !re "s"!ll' o&t!ined for
EB !nd E0 in( s!'( cl!' s"spensions( !s ! f"nction of fre#"enc'% Amon- the !"thors ho
h!ve contri&"ted not!&l' to this field !re E&ert( Frisch !nd Wood( Ste!rt( 2!lmer(
C"ir( Windle !nd Sh!% Essenti!ll'( the di!-nostic "sef"lness of dielectric
me!s"rements lies in the f!ct th!t &"l. !ter h!s ! dielectric dispersion of !&o"t :9:9
43 hile( for ice +dependin- on the temper!t"re,( the dispersion occ"rs &eteen :99
!nd :9(999 43% As pointed o"t)for inst!nce( &' N!co&son +>M,)m!n' m!cromolec"l!r
sol"tions of molec"les( for hich one m!' !ss"me !n ordered !ter l!ttice +0Iceli.e0, !s
the h'dr!tion shell( h!ve dispersions of !&o"t : 9@ to : 9G 43% ESee !lso the !rticle &'
Windle !nd Sh! +:=:,H%
C. Water on C$ondroitin()(Sulfate An ex!mple of "nexpected temper!t"re
dependencies for !ter comes from ! recent st"d' &' L"&e3.' et al. (84). These
!"thors st"died the dielectric properties of !ter !dsor&ed on chondroitin)=)s"lf!te%
Amon- the interestin- res"lts o&served in this micro!ve st"d' !s the persistent
occ"rrence of pe!.s in the loss t!n-ent of !ter !dsor&ed on the pol'mer in the vicinit'
of F@KC% +or sli-htl' &elo, !nd the not!&le drop in !&sorption !&ove !pproxim!tel' >9K
to >:KC% +Fi-"re ::,% The !"thors reco-ni3ed th!t the phenomenon o&served c!nnot &e
expl!ined in terms of c!pill!r' condens!tion in the convention!l sense% Inste!d( !n
expl!n!tion !s !ttempted in terms of specific h'dro-en &ondin- to sli-htl' different
sites for &indin- +hich ere pres"med ener-etic!ll' close to e!ch other, on the
h'drophilic s"rf!ce of the s"&str!te% The present !"thor( hoever( prefers to interpret the
res"lts in terms of specific therm!l st!&ilit' limits for different( discrete !ter str"ct"res
!dsor&ed onto the solid s"rf!ce% If this is the c!se( it m!' o&vio"sl' &e of -re!t
import!nce in connection ith the st!tes of !ter in connective tiss"es% Chondroitin)=)
s"lf!te is !pp!rentl'( to ! l!r-e extent( responsi&le for the !ter retention in the
connective tiss"es of !nim!ls +see Section 6 re !ter in &iolo-ic!l s'stems,%
D. *t$er Dielectric Studies Another interestin- dielectric st"d' is reported &' Nohnson
!nd Ne!l +G<,% These !"thors concl"ded from ! st"d' of the dielectric properties of
!l"min!( fi&ers( !nd c!r&or"nd"m +in !#"eo"s s'stems, th!t !n orientin- effect li.el'
existed( c!"sed &' the solid s"rf!ce% This orient!tion extended into the li#"id to !
consider!&le dist!nce from the s"rf!ce% The' !lso c!lled !ttention to some dielectric
st"dies on pol'electrol'te sol"tions hich tend to s"pport s"ch ! model% The !"thors(
hoever( did not propose !n' specific depths of orient!tion of the !ter !d5!cent to the
solids%
E. Water Adsor!ed on Alu%ina S"&se#"ent to the import!nt st"dies &' 2!lmer !nd
coor.ers Esee 2!lmer (102) !nd Conie !nd 2!lmer +<F,H( E&ert !nd L!n-h!mmer
+FM, h!ve p"rs"ed the pro&lem of the dielectric properties of !ter !dsor&ed on v!rio"s
solids !nd( in p!rtic"l!r( de!lt ith !ter !dsor&ed on !l"min"m oxide% While it is not
possi&le here to s"mm!ri3e !ll the si-nific!nt findin-s of E&ert !nd coor.ers( e c!ll
p!rtic"l!r !ttention to one fe!t"re% E&ert !nd L!n-h!mmer o&served rem!r.!&le pe!.s in
the temper!t"re deriv!tive of the dielectric const!nt of their s'stems !t ! discrete
temper!t"ren!mel'( in the vicinit' of )F9KC% +ithin( s!'( TF to @ de-rees,% The
occ"rrence of !nom!lo"s r!te phenomen! in poro"s m!trices !t lo temper!t"res is !lso
mentioned in connection ith Antonio"Bs (5) st"d' of !ter on 6'cor +see &elo,%
A-!in( s"ch phenomen! li.el' reflect "n"s"!l properties of rel!tivel' thic. str"ct"red
l!'ers of !ter( st!&ili3ed &' the proximit' to the solid% Another interestin- findin- &'
E&ert !nd L!n-h!mmer is the not!&le m!xim! in the loss t!n-ent for !ter !dsor&ed
on (,()!l"min! +me!s"red !t :99 .43, hen plotted !s ! f"nction of the !mo"nt of !ter
!dsor&ed% The position of the m!xim! (i.e., m!xim"m for loss t!n-ent vs. !mo"nt of
!ter per -r!m !l"min!, shifts to loer concentr!tions !t hi-her temper!t"res% As !n
ex!mple( !t ):9KC%( the m!xim"m !ppe!rs !t !pproxim!tel' @> m- 4 29$- !l"min!
hile !t L<9KC%( the m!xim"m occ"rs !t !pproxim!tel' F9 m- 4 29$- !l"min!% This
s"--ests the therm!l &re!.don( !t hi-her temper!t"res( of the thic.ness of ! str"ct"red
l!'er% CcIntosh +8G, h!s disc"ssed E&ert !nd L!n-h!mmerBs experiments in det!il( !nd
s"--ests th!t "It is re!son!&le to s"ppose th!t the first !mo"nts !dsor&ed !re firml'
&o"nd !nd h!ve little orient!tion!l freedom% As !mo"nt of !dsor&!te is incre!sed(
s"ccessive !dditions h!ve -re!ter !nd -re!ter freedom of movement !nd the' !lso
infl"ence the condition of the first #"!ntities !dsor&ed%0
f. Nuclear Magnetic Resonance Studies Resin- +::=, h!s recentl' presented ! c!ref"l
revie of the present st!te of n"cle!r m!-netic reson!nce rel!x!tion !s ! tool for the
st"d' of the st!te of !dsor&ed molec"les on s"rf!ces% Amon- sever!l other !spects(
Resin- disc"sses the molec"l!r motion of !dsor&ed !ter on v!rio"s specific
!dsor&!nts%
+. Water on Silica The #"estion of !ter ne!r silic! s"rf!ces !nd ne!r !l"min! s"rf!ces
h!s &een st"died &' n"cle!r m!-netic reson!nce techni#"es !nd reported on in det!il &'
Cichel +MF, !nd &' Re&!ll !nd Win.ler +::F,% The st"d' &' Cichel s"--ests th!t for
!ter !dsor&ed on silic! -el( to t'pes of !ter exist in s!mples ith onl' ! F$=
st!tistic!l monol!'er% The !ter str"ct"res !re pres"med to &e or-!ni3ed into cl"sters
+cont!inin- !s m"ch !s M@P of the !dsor&ed molec"les, ith ! correl!tion time of <%G J
:9):9 sec +!t OKC1, !nd individ"!ll' !dsor&ed molec"les( ith ! correl!tion time of
l!r-er th!n <%F J :9)8 sec%
H. Water and Cclo$e,ane on Hig$ Surface Area Silica An interestin- NCR st"d'
!s m!de &' 2ic.ett !nd Ro-ers (107). These !"thors ere p!rtic"l!rl' concerned ith
the n!t"re of !dsorption of li#"ids on p'ro-enic silic! !s ell !s on other silic!
prep!r!tions% Fi-"re :< shos ! -r!ph of the o&served line)idth vs. the +c!lc"l!ted,
n"m&er of s"rf!ce l!'ers for !ter !nd c'clohex!ne !dsor&ed on C!&)O)Sil C)@% The'
proposed th!t the n!rro line)idth of the reson!nce lines o&served on C!&)O)Sil C)@
for lo s"rf!ce cover!-es m!' &est &e expl!ined &' s"--estin- hi-hl' mo&ile molec"les
on the s"rf!ce% For the hi-her s"rf!ce cover!-es +<9 to @= l!'ers,( the si-n!l &ro!denin-
m!' &e rel!ted to pol!ri3!tion !nd orient!tion of the first fe l!'ers !nd these( in t"rn(
c!"sin- f"rther l!'ers to &ecome &"ilt "p ith l!ttice)li.e order% The !"thors concl"de1
0A&ove !&o"t @9 l!'ers( the ordered str"ct"re !pp!rentl' &re!.s don !nd ! more
mo&ile( -el)li.e str"ct"re m!' &e formed%0 Res"lts o&t!ined ith c'clohex!ne !nd !ter
ere simil!r% The simil!rit' &eteen the NCR res"lts o&t!ined ith !ter !nd ith
c'clohex!ne on C!&)O)Sil indic!te th!t hile !#"eo"s s'stems li.el' do possess
!nom!lo"s properties specific!ll' rel!ted to the n!t"re of the !ter molec"le( -ener!l
s"rf!ce effects +s"ch !s those d"e to v!n der W!!l !nd London disperson forces, ill(
o&vio"sl'( &e fo"nd in !n' interf!ci!l s'stem% Usin- NCR( Q!r!-o"nis et al. +G=,( for
inst!nce( h!ve shon ! loerin- of the meltin- points of v!rio"s or-!nic compo"nds
+s"ch !s M)eth'l!nthr!cene, !dsor&ed on silver% In this connection( rec!ll th!t 4enni.er(
!s ell !s Der5!-"in( h!ve lon- !dvoc!ted lon-)r!n-e order for &oth !ter !nd or-!nic
li#"ids +incl"din- oils, on ! n"m&er of solid s"rf!ces% See !lso the Note &' A% D%
/!n-h!m !nd D% R% /!n-h!m +8,%
'. Water on -arious Clas W" (144) h!s st"died the cl!')!ter &ondin- &' ! n"cle!r
m!-netic reson!nce techni#"e% Spin)spin !nd spin)l!ttice rel!x!tion times ere
determined ith !ter !nd de"teri"m oxide !dsor&ed on .!olinite( -r"ndite( !nd
montomorillonite% W" concl"ded from this st"d' th!t &elo OKC%( the !ter !d5!cent to
the cl!' s"rf!ce h!s ! str"ct"re different from th!t of ice% Rel!tin- the inverse of the
rel!x!tion time to the viscosit'( W" finds !pp!rent viscosit' v!l"es for !ter ne!r
sodi"m montmorillonite +!t ! !ter content of :99P, of ::9 2% At ! !ter content of
=9P( !n !pp!rent viscosit' of FF9 2 is o&t!ined% These v!l"es !re in re!son!&le
!-reement ith the v!l"es estim!ted &' Oster !nd Lo (100) &!sed on !n ener-' of
!ctiv!tion of !&o"t 8 .c!l$-mol for ion movement in &entonite ith to molec"l!r
l!'ers of !ter% If e !ss"me the ener-' of !ctiv!tion for visco"s flo is close to the
v!l"e for ionic cond"ction( the res"lt o"ld correspond to ! viscosit' of these !ter
l!'ers of G99 times th!t of ordin!r' !ter% W" comp!red his me!s"rements !lso ith
e!rlier me!s"rements &' Rosen#vist (117). It m"st &e concl"ded th!t the v!rio"s
estim!tes for viscosit' of !ter ne!r cl!' s"rf!ces sho ver' l!r-e sc!tter( !nd the
concept of l!min!r 2oise"ille flo for !ter l!'ers( onl' to molec"l!r l!'ers thic.(
seems hi-hl' in!ppropri!te +the cl!ssic!l diffic"lt' ith the !pplic!tion of contin""m
mech!nics to molec"l!r( discrete h!ppenin-s,% At the s!me time( it !ppe!rs definitel' !s
if !nom!lo"s !nd( indeed( extremel' hi-h v!l"es of !pp!rent viscosit' !re o&t!ined in
st"dies of !ter ne!r cl!' s"rf!ces%
". .urt$er Studies of Water on Silica +el Aimmerm!n !nd coor.ers (147) h!ve
st"died the n!t"re of !ter on silic! -el &' n"cle!r m!-netic reson!nce spectrometr'%
These contri&"tions !re !mon- the most !"thorit!tive st"dies of their .ind% In
connection ith the present p!per( p!rtic"l!r interest !tt!ches to the st"dies &' Woessner
!nd Aimmerm!n (143). These !"thors( !mon- m!n' other o&serv!tions( noted !
tr!nsition in the vicinit' of :@KC% for the !pp!rent proton lon-it"din!l rel!x!tion time !s
! f"nction of temper!t"re for !ter !dsor&ed on silic! -el !t ver' lo s"rf!ce cover!-es%
/. 0tilit of Dielectric and NMR Data In this section e h!ve disc"ssed &oth
dielectric !nd n"cle!r m!-netic reson!nce st"dies of !#"eo"s interf!ci!l phenomen!%
The diffic"lties enco"ntered here !re the tr!dition!l diffic"lties of interpretin- r!te
processes in -ener!l !nd( p!rtic"l!rl'( "nder circ"mst!nces here no specific models !re
!v!il!&le for the #"!ntit!tive tre!tment of the d!t!% Th"s( !ll dielectric d!t! s"ffer from
the possi&ilit' of sp"rio"s infl"ences of v!rio"s pol!ri3!tion mech!nisms hile the
NCR res"lts !re complic!ted &' the "nderl'in- ph'sic!l processes !nd their
#"!ntit!tive descriptions% 4oever( hile none of the st"dies per se m!' prove
concl"sivel' the existence of ordered !#"eo"s str"ct"res ne!r interf!ces( some of the
d!t! do stron-l' tend to s"--est the possi&ilit'% 2erh!ps this( in p!rtic"l!r( -oes for the
dielectric st"dies &' 2!lmer !nd coor.ers !s ell !s &' E&ert% Undo"&tedl'( the most
sophistic!ted st"dies !re those &' Aimmerm!n !nd coor.ers( Resin-( Cichel( !nd
Re&!ll !nd Win.ler% 4oever( it is here th!t the diffic"lties of interpret!tion &ecome the
-re!test%
&. BIOC#E$ICA% AND BIOP#1SICA% STUDIES A. NMR Studies of #M- In
no field is the pro&lem of !ter ne!r interf!ces more pertinent !nd cr"ci!l th!n in the
-ener!l field of &iolo-'% /iolo-ic!l s'stems per se f!ll entirel' o"tside the scope of the
present !rticle* hoever( e &riefl' descri&e ! ver' sm!ll fr!ction of the evidence for
the existence of ordered !ter str"ct"res in &iolo-ic s'stems( !s s"--ested &'
&iochemic!l !nd &ioph'sic!l st"dies% Even tho"-h rel!tivel' simple &iolo-ic!l s'stems
in vitro m!' &e complex &e'ond description comp!red to( s!'( the !ir$!ter interf!ce or
! solid$!ter interf!ce( &iolo-ic s'stems m"st event"!ll' &e interpreted in terms of the
ph'sics !nd chemistr' of the "nderl'in- molec"l!r processes% As !n ex!mple of s'stems
of &iolo-ic interest hich h!ve &een st"died in det!il !re sol"tions of to&!cco mos!ic
vir"s% The res"lts from these st"dies !mpl' demonstr!te the contr!dictor' res"lts hich
h!ve &een o&t!ined so f!r% In p!rtic"l!r( ver' different res"lts h!ve &een o&t!ined( !nd
!ntithetic!l concl"sions h!ve &een dr!n from self)diff"sion coefficient me!s"rements
+for !ter, in s"ch sol"tions% l!rdets.' !nd l!rdets.' (70) concl"ded on the &!sis of
their NCR st"dies th!t !s m"ch !s <9P of the !ter in ! :%MP to&!cco mos!ic vir"s
sol"tion exists in !n ordered +0ice)li.e0, str"ct"re% 4oever( Do"-l!ss et at. +<M,
concl"ded from selfdiff"sion me!s"rements th!t the diff"sion coefficient of !ter in
s"ch sol"tions is ver' close to the diff"sion coefficient of !ter in p"re !ter% In f!ct( it
!s estim!ted th!t no more th!n FP of the !ter +in ! =P to&!cco mos!ic vir"s
sol"tion, is in !n ordered st!te +comp!re Section IJ,% Other st"dies of simil!r n!t"re
h!ve &een m!de &' /!l!3s( /othner)/'( !nd Ier-el' +G,% These !"thors st"died
sol"tions of DNA( h'!l"ronic !cid( coll!-en( -el!tin( !nd m'osin% In none of these
sol"tions !s evidence o&t!ined for the existence of ordered +0iceli.e0, dom!ins%
4oever( ! &ro!denin- of the proton si-n!l !s o&served in the DNA sol"tions% Simil!r
&ro!denin- !s o&served in the presence of -r!phite p!rticles hile the presence of
sodi"m chloride h!d no effect on the &ro!denin-% L!ter( 4echter( Wittstr"c.( CcNiven(
!nd Lester +@@, st"died !ter in !-!r -els &' hi-h resol"tion NCR methods% These
!"thors concl"ded th!t 0The NCR d!t! c!n &est &e expl!ined !t present on the &!sis th!t
!ter in !n !-!r -el is in ! modified st!te ith properties of str"ct"r!l ri-idit' !nd
mo&ilit' intermedi!te &eteen BfreeB !ter !nd ice%0 Collison !nd CcDon!ld +:8,
st"died the &ro!denin- of the !ter proton line in the NCR spectr! of st!rch -els !nd
concl"ded th!t the idth of the !ter line in st!rch -els !nd s"spensions depended "pon
the h'dr!tion of the st!rch( s"--estin- ! more hi-hl' ordered l!ttice th!n exists in p"re
!ter +hile p!rt of the line idth !s determined &' the mo&ilit' of se-ments of the
m!cromolec"les, %
B. N$R in Nerve 'i!ers Other evidence for the orient!tion of !ter molec"les &'
proximit' to ! &iolo-ic!ll' import!nt interf!ce h!s come from proton m!-netic
reson!nce st"dies &' Ch!pm!n !nd CcL!"-hlin +:>, on the sci!tic nerve of r!&&its%
These !"thors me!s"red the proton m!-netic reson!nce spectr! of ! =)mm)lon-
c'lindric!l s!mple of nerve( the orient!tion of hich co"ld &e v!ried ith respect to the
!pplied m!-netic field% The res"lts of the experiment s"--ested th!t the 0&"l.0 !ter
inside the nerve is in ! p!rti!ll' ordered st!te% F"rthermore( other spectr!l pe!.s shoed
orient!tion)dependent shifts hich ere l!r-er th!n co"ld &e !cco"nted for oin- to
s"scepti&ilit' shifts% A-!in( this !s interpreted !s indic!tin- p!rti!ll' oriented !ter%
The !"thors considered fo"r possi&ilities for s"ch orderin-1 +A, The !ter mi-ht simpl'
&e constr!ined &' v!n der \,y !!ls forces to move in !nn"li of ! pproxim! te molec"l!r
dimensions +#"oted to &e !&o"t :9 A). +/, The orient!tion co"ld &e prod"ced !s !
second!r' effect c!"sed &' the orient!tion of the protein molec"les( hich &'
themselves( o"ld &e !li-ned in the pores of the nerve% +C, Orient!tion effects ere
s"--ested c!"sed &' electrost!tic inter!ctions ne!r the fi&er str"ct"re% 4oever(
c!lc"l!tions !pp!rentl' s"--ested th!t s"ch field stren-ths o"ld &e too e!. to expl!in
the o&served effects% +D, It !s s"--ested th!t the !ter co"ld &e !rr!n-ed in ! ch!in
str"ct"re !s post"l!ted for the coll!-en s'stem% The !"thors dismiss this l!tter possi&ilit'
!s h!vin- no 5"stific!tion( cl!imin- the de-ree of orient!tion o&served to &e explic!&le
completel' in terms of norm!l !ter% The' concl"ded1 0In vie of the norm!ll'
!ccepted pore si3es in nerves hich !re m"ch too l!r-e to c!"se orient!tion( it is
s"rprisin- th!t most of the !ter is not in its norm!l st!te%0 In vie of the l!r-e n"m&er
of ex!mples disc"ssed in the present p!per( it m!' not &e too s"rprisin- !t !ll to discover
th!t ! l!r-e fr!ction of the !ter is in !n 0!&norm!l0 st!te%
C. Studies of $uscles /r!tton( 4op.ins( !nd v6ein&er- +:F, me!s"red the ch!n-e in
the tr!nsverse rel!x!tion time for protons in the !ter of ! livin- s.elet!l m"scle +from !
fro-,% These !"thors fo"nd th!t 0A fr!ction of the intr!cell"l!r !ter molec"les h!ve
restricted rot!tion!l freedom !nd this fr!ction decre!ses hen contr!ction occ"rs%0 The'
concl"de th!t the !v!il!&le evidence points to the existence of +!t le!st, ! to)ph!se
s'stem of free !nd &o"nd !ter in this s'stem%
D. Evidence for E2tensive 3Ice4%i5e3 Restructurin. Cope +<G, "sed the NCR
spectr"m of sodi"m ions to st"d' the sol"&ilit' of sodi"m in the interstiti!l !ter of
!ctom'osin -el% The sol"&ilit' of sodi"m in this +-elled, !ter is consider!&l' loer
th!n the sol"&ilit' in &"l. !ter( s"--estin- th!t the !ter in the -el is or-!ni3ed
+str"ct"red, into !n 0ice)li.e0 st!te !s ! res"lt of the !ctom'osin molec"le$!ter
interf!ce inter!ctions% Cope concl"ded1 "If ! m!5or fr!ction of intr!cell"l!r sodi"m ions
exists in ! complex st!te( then m!5or revisions in most theoretic!l tre!tments of
e#"ili&ri!( diff"sion( !nd tr!nsport of cell"l!r sodi"m ions h!ve &ecome !ppropri!te%0
Core recentl'( Cope +GM, extended his NCR st"dies &' the "se of de"t"r!ted !ter
+!dministered to the live !nim!ls for sever!l d!'s prior to isol!tion of the &r!in !nd
m"scle tiss"e st"died,% Cope !s !&le to demonstr!te #"!ntit!tivel' th!t the res"lts
o&t!ined ere not !rtif!cts c!"sed &' p!r!m!-netic ions( !nd he concl"ded( on the &!sis
of !ll the !v!il!&le evidence( th!t his d!t! co"ld onl' &e expl!ined &' !ss"min-
extensive str"ct"r!l orderin- of the !ter in tiss"es% The to !rticles &' Cope !re li.el'
to &ecome cl!ssic ex!mples of the !ttempts to demonstr!te evidence for ordered !ter
str"ct"res in livin- s'stems% The res"lts cle!rl' !re consistent ith the over!ll pict"re
hich h!s &een developed over the p!st sever!l 'e!rs &' the present !"thor re-!rdin-
the !&ilit' of interf!ces to ind"ce prono"nced str"ct"r!l ch!n-es in vicin!l !ter)
ch!n-es hich m!' extend over consider!&le dist!nces( !nd hich co"ld( in f!ct(
0restr"ct"re0 the !ter contents of the entire cell%
E. &ariolus Biolo.icall" I)ortant E2a)les6 Biolo.ic A..re.ation
Phenoena Re-!rdin- the implic!tions for &iolo-' of str"ct"red !ter( !ttention is
c!lled to the r!ther inspired sm!ll &oo. &' S3ent)I'i11ir-'i +:<M, !nd the S'mposi"m
2roceedin-s on 0W!ter in /iolo-ic!l S'stems0 edited &' Q!'"shin +GG,% See !lso the
2roceedin-s from the Conference on 0Forms of W!ter in /iolo-ic S'stems0 Esee Ne
Oor. Ac!dem' of Sciences +MM, N% Re-!rdin- !ter ithin mem&r!nes( !ttention is
c!lled to recent !rticles &' Coldm!n !nd Iood +:G, !nd &' Sche"plein +:<:,( the st"d'
&' Thorh!"- !nd Drost)4!nsen +:FF, on temper!t"re)ind"ced( !nom!lo"s ch!n-es in
mem&r!ne properties% F"rther reference is m!de to the mono-r!ph &' We&& (140), the
!rticles &' Cope +:M( 20), !nd to the recent st"d' &' F"ller !nd /re' +=M,% The l!tter
!rticle ill &e disc"ssed in some det!il in the section on Str"ct"r!l Interpret!tions !nd
Some S"pportin- Evidence +Section JI)I,% S"ffice it here to note th!t these !"thors
o&served -re!ter freedom of motion of protons in the second!r' !ter l!'er th!n in the
0solid(0 initi!ll' !dsor&ed !ter !nd ! m"ch less re-"l!r str"ct"re% The' f"rther disc"ss
the occ"rrence of ! 0.ind of second order ph!se tr!nsition in hich incre!sin-
temper!t"re disorders the !rr!n-ement of the li#"id &ond &' the protein%0 6er' lo
ener-ies of !ctiv!tion !re c!lc"l!ted for the NCR !&sorption line idth +!&o"t : to <
.c!l$ mol for ordin!r' !ter, !t hi-h temper!t"res% This le!ds the !"thors to propose
th!t the correl!tion time is determined &' tr!nsfers &eteen the prim!r' !nd second!r'
ph!ses of !ter( r!ther th!n &' either of the ph!ses !lone% F"ller !nd /re' !lso o&served
! tr!nsition &elo <9KC%( in hich ! f!irl' !&r"pt decre!se !s noted in line idth ith
incre!sin- !mo"nts of !ter% Comp!re this findin- ith the t'pes of ph!se tr!nsitions
disc"ssed in the present p!per% It is( indeed( this t'pe of temper!t"re effect hich is
emplo'ed in the present !rticle !s !n import!nt p!rt of the evidence for the existence of
str"ct"res( ne!r interf!ces( hich !re different from &"l. !ter !nd hich h!ve definite
orderin-)i%e%( str"ct"res hich !re c!p!&le of "nder-oin- specific( therm!l tr!nsitions%
We ret"rn to the st"d' &' F"ller !nd /re' in the !&ovementioned section% An interestin-
st"d' of the effect of !ter str"ct"re in ! &iolo-ic s'stem !s reported &' A&d"ll! +:,%
This !"thor st"died the !--re-!tion of pl!telets of h"m!n &lood* specific!ll'( he
me!s"red the effect on r!te of !--re-!tion of pl!telets d"e to the presence of ver' dil"te
sol"tions of pent!nol( hex!nol( oct!nol( !nd dec!nol% The hi-her the n"m&er of c!r&on
!toms in the !lcohol +!ll !t ver' lo concentr!tions1 @ m-$:99)ml sol"tion,( the l!r-er
the effect% A&d"ll! s"--ests th!t the h'drox'l -ro"ps of the !lcohols tend to disr"pt the
0ice)l!ttice0 s"rro"ndin- e!ch pl!telet hile the nonpol!r( h'droc!r&on p!rt enh!nced
the str"ct"red ness of the vicin!l !ter% A&d"ll! !lso me!s"red the effects of !r-on !nd
xenon on the pl!telet !--re-!tion !nd !-!in o&served not!&le effects% As the res"lt(
A&d"ll! s"--ests th!t 0Ordered !ter !cts !s !n entropic tri--er th!t trips the &!l!nce
!nd c!rries the s'stem +pl!telets, over ! sm!ll potenti!l ener-' &!rrier( so th!t the
intern!l ener-' of the s'stem c!n drop !nd its entrop' c!n incre!se%0 Th"s( the effect of
the inert -!ses( in this c!se( is to enh!nce the !ter str"ct"re s"rro"ndin- the pl!telet%
.. Cell Ad$esion in +eneral In connection ith the pro&lems of cell !dhesion( !n
e!rlier contri&"tion &' 2ethic! (106) is !lso of interest% In o"tlinin- the f!ctors hich
ill !ffect !dhesion !nd rep"lsion &eteen cell s"rf!ces( 2ethic! lists specific!ll' the
rep"lsion &eteen cell mem&r!nes hich m!' &e d"e to 0hindr!nce to !ttr!ction d"e to
steric &!rriers( s"ch !s inert c!ps"les !nd solv!ted l!'ers%0 Incident!ll'( 2ethic! pointed
o"t( 0This hindr!nce is not ! BforceB of rep"lsion( except th!t the entrop' effect d"e to the
m"t"!l disorderin- of !dsor&ed l!'ers !s the s"rf!ces !ppro!ch mi-ht &e re-!rded !s !
force% The effect of !dsor&ed inert l!'ers m!' more "s"!ll' &e to incre!se the r!n-e
&eteen otherise !ctive -ro"ps( !nd to !tten"!te the !ttr!ctions &eteen the s"rf!ces to
the point here reversi&le collisions c!n t!.e pl!ce%0 Indeed( if the three)l!'er model
disc"ssed elsehere in this p!per is correct( there m!' &e 0steric interferences(0
determinin- the minim"m dist!nce of !ppro!ch &eteen !--re-!tin- cells +or other
t'pes of !--re-!tin-( colloid!l p!rticles,( here the minim"m dist!nce of !ppro!ch
&eteen cells corresponds to the m!xim"m excl"sion of the disordered l!'er &eteen
!d5!cent p!rticles% The effects of str"ct"r!l ch!n-es of !ter in !nd ne!r &iolo-ic!ll'
interestin- interf!ces h!ve &een disc"ssed in some det!il &' the present !"thor +FF, !nd
&' Thorh!"- !nd the present !"thor +FF, !nd &' Thorh!"- +:F<,%
+. Structural #ransitions Affecting DNA In ! recent revie (30), some pertinent
rem!r.s ere m!de re-!rdin- temper!t"re effects on &iolo-ic!ll' import!nt s'stems%
Th"s( it !s o&served th!t interf!ci!l pol!ri3!tion effects( d"e to !cc"m"l!ted ions
!ssoci!ted ith the s"rf!ces of DNA( m!' expl!in lo fre#"enc' dispersion phenomen!
+for fre#"encies sm!ller th!n : .43,% The !"thors( hoever( note th!t 0On the other
h!nd( it is diffic"lt to "nderst!nd vlh this nonline!rit' of ionic ori-in dis!ppe!rs !t
!&o"t >9KC%0 In ! n"m&er of experiments( o&t!ined over ide fre#"enc' r!n-es( the
c!p!cit' of DNA s!mples +ith =9P !ter content, is shon in Fi-"re :F( p!rt /%
Do"3o" !nd S!dron (30) s"--est th!t the ch!n-es in slope !t the temper!t"res indic!ted
!re d"e to some 0str"ct"r!l tr!nsition0 !ffectin- the DNA molec"le% Amon- the possi&le
expl!n!tions hich the' offer for this phenomenon is the dis!ppe!r!nce of 0&o"nd0
!ter +or str"ct"r!l !ter, of the DNA% This s"--estion is eminentl' comp!ti&le ith
the !"thorBs notions hich s"--est the occ"rrence of therm!l !nom!lies in !ter ne!r
=@K !nd >9KC%
#. Inter)retin. Biolo.ical Pro)erties As is to &e expected( &iochemic!l(
&ioph'sic!l( !nd p!rtic"l!rl' &iolo-ic!l s'stems often sho ver' complex properties(
incl"din- "nexpected responses to ch!n-es in temper!t"re% The possi&ilit' cert!inl'
exists of interpretin- so!e of these "nexpected res"lts in terms of vicin!l !ter str"ct"re
ch!n-es +!ltho"-h !dmittedl'( some of the evidence is m"t"!ll' contr!dictor'* comp!re
especi!ll' the NCR st"dies on to&!cco mos!ic vir"s( DNA( h'!l"ronic !cid( coll!-en(
-el!tin( !nd m'osin,%
&I. SUR'ACE CONDUCTANCE STUDIES A. Thic5 %a"ers in 'ree Drainin.
'ils The evidence for the existence of lon-)r!n-e orderin- ne!r interf!ces h!s often
&een critici3ed on the -ro"nds of s"ch possi&le sp"rio"s effects !s s"rf!ce ro"-hness
+s"rf!ce 0r"-osit'0,( s"rf!ce sellin-( d"st( or electrovisco"s effects% 4oever( m!n' of
these o&5ections c!nnot &e leveled !-!inst the res"lts o&t!ined from s"rf!ce cond"ctivit'
st"dies% Th"s( "ndo"&tedl' of ! complex n!t"re( the s"rf!ce cond"ct!nce me!s"rements
&' Tsch!pe. !nd N!t!le (138) m!' &e hi-hl' si-nific!nt% These !"thors h!ve s"--ested
the existence of thic. l!'ers of !ter in free dr!inin- films +in ! s!t"r!ted !tmosphere,%
The thic.nesses of these films !mo"nt to !s m"ch !s F999 to =999 A !fter <=)hr
dr!in!-e% The me!s"rements m!' &e less critic!ll' dependent "pon the dist"r&in-
infl"ences mentioned !&ove% 4oever( even tho"-h the method m!' &e sin-"l!rl' free
of some of the o&5ections disc"ssed !&ove( Tsch!pe. !nd N!t!le do point to some
diffic"lties hich !re inherent in !n' s"ch st"dies( s"ch !s colloid!l imp"rities
B. Ener." of Activation Studies6 $easureents on &"cor In Sections JI !nd
JII the h'pothetic!l( concept"!l models for !ter ne!r interf!ces ill &e disc"ssed% A
distinction ill &e m!de &eteen !ter !d5!cent to predomin!ntl' nonpol!r( pol!r( !nd
ionic s"rf!ces% In !ll c!ses( ordered str"ct"res of !ter !re li.el' to &e ind"ced in the
immedi!te proximit' to the s"rf!ce( hile in one( or possi&l' to( of these c!ses the
str"ct"res m!' &e prop!-!ted over consider!&le dist!nces% While the disc"ssion of the
concept"!l models !pplies to the !ter ne!r !n 0infinitel' l!r-e( fl!t0 s"rf!ce( these
models m"st +if the' represent re!lit' !t !ll, in the c!se of c'lindric!l pores le!d to the
cre!tion of concentric !nn"li ith different properties% Th"s( it is to &e expected(
h!tever the n!t"re of the s"&str!te( th!t not!&le ch!n-es ill occ"r in the !ver!-e
over!ll properties of the !ter cont!ined ithin the pore !s the pore si3e decre!ses%
Initi!ll'( the decre!se in pore si3e m!' res"lt in the elimin!tion of &"l. !ter%
Dependin- on the n!t"re of the s"&str!te( ! f"rther decre!se in pore di!meter m!' res"lt
in overl!ppin- of str"ct"r!l re-ions or -r!d"!l red"ction in ! core of disordered
str"ct"res% /ec!"se it !ppe!rs "nli.el' th!t s"ch #"!ntities !s the !pp!rent ener-ies of
!ctiv!tion for cond"ction( diff"sion( or visco"s flo o"ld &e identic!l to the v!l"es
o&served in &"l. sol"tion( temper!t"re st"dies of the tr!nsport properties in the s'stems
considered m!' prove ! discrimin!tin- tool for el"cid!tin- the str"ct"re of the !ter in
the pores in ! #"!lit!tive f!shion% 4oever( even if s"&st!nti!ll' correct tr!nsport
theories ere !v!il!&le for li#"ids in -ener!l !nd for !ter in p!rtic"l!r( composites of
s"ch m"ltiple str"ct"r!l properties ill( no do"&t( res"lt in ! ver' complex over!ll
temper!t"re)dependent &eh!vior% 4oever( it is this t'pe of !ppro!ch hich !s
"ndert!.en &' the present !"thor e!rlier +F>( FG, !nd &' Sch"fle !nd coor.ers*
me!s"rements h!ve &een m!de of temper!t"re effects on the cond"ction in n!rro pores
!lon- the lines descri&ed !&ove% We t"rn to ! disc"ssion of these res"lts in Sections 6I)
D !nd 6I)E% 4"&er !nd Flood +><, me!s"red the cond"ctivit' of 0.1 " sol"tions of
sodi"m !nd pot!ssi"m chloride cont!ined ithin the pores of le!ched poro"s 6'cor
-l!ss% Altho"-h the !"thors o&t!ined h!t !ppe!rs to &e v!stl' incre!sed temper!t"re
coefficients for cond"ction +especi!ll' &elo !pproxim!tel' L@KC% for sodi"m chloride
!nd )@KC% for pot!ssi"m chloride,( the' did not p!rtic"l!rl' p"rs"e the notion th!t these
incre!sed temper!t"re coefficients reflected incre!sed ener-ies of !ctiv!tion for ionic
cond"ction% 4"&er !nd Flood did mention th!t the temper!t"re coefficient for the
viscosit' of s"rf!ce !ter is someh!t -re!ter th!n th!t of &"l. !ter( &"t the !"thors
!ppe!r not to h!ve exploited this findin-% As indic!ted !&ove( it is interestin- to
spec"l!te on the temper!t"re effects (i.e., the ener-' of !ctiv!tion, on s"ch p!r!meters
!s visco"s flo( ionic diff"sion( !nd ionic cond"ctivit' in ver' n!rro pores #i.e., for
pore s'stems here rel!tivel' simil!r tot!l vol"mes of li#"id m!' &e cont!ined in
c'lindric!l shells +!nn"li, ith d&ltinctl' different propertiesH%
C. Surface Conduction on +lass Q!!s!.i( Q!no"( !nd Se.it! +G>, h!ve
me!s"red the s"rf!ce cond"ction of -l!ss pl!tes !t v!rio"s rel!tive h"midities% From the
d!t! o&t!ined( the' estim!ted the n"m&er of !dsor&ed l!'ers !nd shoed th!t the s"rf!ce
cond"ctivit' incre!ses !pproxim!tel' line!rl' ith the n"m&er of !dsor&ed l!'ers !&ove
! cert!in minim"m n"m&er of l!'ers +of the order of six l!'ers,% The' interpreted this !s
evidence for immo&ili3!tion of the inner l!'ers "nder the infl"ence of the stron- field of
!ttr!ction of the -l!ss s"rf!ce( hile the l!'ers f"rther removed !ppe!red mo&ile% The
cond"ction c"rrent +the p!r!meter me!s"red, incre!ses m!teri!ll' onl' hen s"fficient
!ter is present to provide the mo&ile +more li#"id)li.e, l!'ers( cond"cive to
cond"ction% Comp!re in this connection the cl!ims for the existence of discrete l!'ers of
!ter !dsor&ed on -l!ss s"rf!ces( m!de &' Der5!-"in !nd Aorin +<8, !ndi*&' Aorin !nd
Ch"r!ev +:=8,( !nd see !lso the disc"ssion ofthe st"dies &' Id! !nd Nishim"r! +>F, in
Section JI)E%
D. Conduction in Narro/ Ca)illaries Sch"fle !nd O" +:<=, h!ve me!s"red the
ener-' of !ctiv!tion for ionic cond"ction of dil"te !cids in v!rio"s c!pill!ries% The
res"lts indic!te th!t the ener-' of !ctiv!tion for ionic cond"ction incre!ses ith
decre!sin- concentr!tion of electrol'tes% In the initi!l st"d'( Sch"fle chose to me!s"re
the cond"ctivit' of dil"te !cids* one m"st therefore &e concerned !&o"t the disr"ptive
infl"ence of the h'dro-en ions on !n' !ter str"ct"re( &e it in &"l. or ne!r the
interf!ces% Nonetheless( it seems re!son!&le to t!.e the res"lts &' Sch"fle !nd
coor.ers !s evidence for the possi&ilit' of lon-)r!n-e ordered str"ct"res ne!r the
c!pill!r' !lls1 Str"ct"res ind"ced &' the proximit' to the c!pill!r' !ll !ppe!r to
impede the motion of the ions% 4oever( it rem!ins to &e determined ho to sep!r!te
specific s"rf!ce cond"ct!nce effects from the effects of the ch!n-e in the !#"eo"s
environment d"e to the lon-)r!n-e orderin-% Recentl'( Sch"fle !nd coor.ers +person!l
comm"nic!tion( :M>M, h!ve extended the me!s"rements to incl"de pot!ssi"m chloride
sol"tions% The incre!ses in the ener-' of !ctiv!tion ith decre!sin- c!pill!r' r!dii !re
not so l!r-e !s those o&served ith the dil"te !cids% Oet( the v!l"es for the ener-' of
!ctiv!tion do !ppe!r to incre!se ith decre!sin- c!pill!r' r!di"s( consistent ith the
res"lts o&t!ined from the st"d' on the !cid%
E. Conduction in Co)acted 7uart8 Beds Independentl'( the present !"thor +F>(
FG, me!s"red the cond"ctivit' of dil"te sol"tions of sodi"m chloride s!t"r!tin- close)
p!c.ed( compressed s!mples of podered #"!rt3 +irre-"l!rl' sh!ped #"!rt3 p!rticles(
o&t!ined &' -rindin-* the !ver!-e p!rticle si3e !s ! fe microns,% /ec!"se of the
"ncert!int' in 0!ver!-e pore openin-0 in s"ch ! s!mple of comp!cted cr"shed #"!rt3(
!nd in vie of the possi&ilit' of sli-ht re!rr!n-ements of the p!rticles d"rin- !n
experiment( the res"lts !re not p!rtic"l!rl' reli!&le% 4oever( it !ppe!red th!t for QCI
concentr!tions of :9)2 !nd 10-3", the incre!se in the ener-' of !ctiv!tion for ionic
cond"ction !s( respectivel'( @9 !nd :@9 c!l$-moll!r-er th!n the correspondin- v!l"es
for &"l. cond"ction% While these n"m&ers !re +&!rel', o"tside the experiment!l error
!nd pres"m!&l' me!nin-f"l( the' !re not re!dil' interpreted theoretic!ll'% 4oever( it
!s proposed( on the &!sis of th!t st"d'( th!t ! to)l!'er model co"ld &e constr"cted for
the cond"ction in n!rro c!pill!r' sp!ces( in hich ! l!'er of oriented !ter is cre!ted
ne!r the #"!rt3 s"rf!ces here the motion of the ions is impeded &' the enh!nced
ri-idit' of ! st!&ili3ed !ter str"ct"re( ith ! re-ion ne!r the 0center0 of the pore sp!ce(
hich ret!ined more or less "nch!n-ed( &"l. properties% /!sed on some !ddition!l
!ss"mptions( estim!tes ere m!de of the thic.ness of the oriented !ter l!'er ne!r the
interf!ces !nd 'ielded res"lts &eteen 0.2J.i, !nd 0.3J.i,.
'. %iitations on Surface Conductance Studies The s"rf!ce cond"ct!nce
st"dies disc"ssed in this section !re perh!ps the le!st convincin- evidence on hich to
cl!im the existence of lon-)r!n-e orderin- ne!r !#"eo"s interf!ces% 4oever( the res"lts
cert!inl' do not tend to disprove the thesis th!t s"ch orderin- m!' exist( &"t ! -re!ter
de-ree of sophistic!tion is "ndo"&tedl' needed in f"t"re st"dies to m!.e this ! "sef"l
tool for the intended p"rpose%
&II. &ISCOSIT1 STUDIES
A. Rheolo.ical $easureents and Interferin. Effects Rheolo-ic!l
me!s"rements h!ve &een m!de fre#"entl' on !#"eo"s colloid!l s"spensions% Sometimes
the inform!tion from these st"dies h!ve &een "sed in !ttempts to deline!te str"ct"r!l
properties of the !ter in s"ch s'stems% The interpret!tions !re -ener!ll' open to serio"s
#"estionin-% Simil!rl'( st"dies of visco"s flo of !ter !nd !#"eo"s sol"tion in poro"s
m!trices h!ve &een performed in the hope of o&t!inin- inform!tion re-!rdin- the
str"ct"re of vicin!l !ter in these s'stems% A-!in( m!n' o&5ections c!n &e r!ised to the
interpret!tions &ec!"se of s"ch dist"r&in- f!ctors !s d"st( s"rf!ce sellin-(
electrovisco"s !nd viscoelectric effects% ESee( for inst!nce( the thoro"-h st"dies of
electrovisco"s effects &' Elton +=G,H% Nonetheless( hoever limited the evidence m!' &e
hich is o&t!ined from s"ch !nd rel!ted st"dies +s"ch !s diff"sion coefficient
me!s"rements for sm!ll sol"tes in n!rro c!pill!ries,( it seems li.el' th!t the !pp!rent
ener-ies of !ctiv!tion for v!rio"s tr!nsport properties m!' &e rel!tivel' "n!ffected &'
some of the f!ctors hich !ffect direct r!te me!s"rements% Cert!inl'( there is no re!son
to s"spect th!t !n' tr!nsport phenomenon or thermod'n!mic propert' sho"ld reve!l
!&r"pt ch!n-es over n!rro temper!t"re in terv!ls% Oet( s"ch !nom!lies !re( indeed(
o&served( !nd it is this f!cet of the !v!il!&le d!t! hich is of "tilit' in cert!in st"dies%
B. Surface &iscosit" of Dodec"l Sulfate Tr!pe3ni.ov !nd Do.".in! +:FG, h!ve
me!s"red the temper!t"re dependence of the s"rf!ce viscosit' of sodi"m dodec'l s"lf!te
in the presence of !dded dodec!nol% These me!s"rements sho !n !&r"pt decre!se in
!pp!rent viscosit' +!&ove !pproxim!tel' F: K to F<K9%,% The ch!n-e in viscosit' is
rem!r.!&le in th!t it extends over fo"r orders of m!-nit"de% E!rlier( Tr!pe3ni.ov +:F>,
o&served ver' interestin- temper!t"re dependencies for some s"rf!ce phenomen!% The
present !"thor +F=, h!s referred to these o&serv!tions &' Tr!pe3ni.ov on !ter
inter!ctin- ith p!lmitic !cid cr'st!ls( shoin- h!t Tr!pe3ni.ov interpreted !s "n"s"!l
ph!se tr!nsitions of !ter)p!lmitic !cid complexes% It !s proposed &' the present
!"thor th!t this phenomenon m!' &e d"e to specific !ter str"ct"re ch!n-es of the
vicin!l !ter +ne!r these temper!t"res,% EIn ! recent letter( 2rofessor Tr!pe3ni.ov h!s
indic!ted th!t he still feels th!t the !pp!rent 0cr'st!l tr!nsition0 phenomen! !re d"e to
the s"&str!te( r!ther th!n to specific effects of !ter str"ct"re +person!l
comm"nic!tion,% See( hoever( the r!te of ettin- st"dies &' Oi!nnos (745) referred to
in Section III)Q%H
C. &i!ratin. 3#air)in &iscoeter3 Another interestin- ex!mple of visco"s
!nom!lies is reported &' Forslind +==, ho st"died the visco"s d!mpin- d"e to !ter
cont!ined in ! n!rro c!pill!r' vi&r!tin- 0h!irpin viscometer%0 Forslind o&served th!t
the d!mpin- of ! vi&r!tin- !ter)filled c!pill!r' decre!sed si-nific!ntl' hen the
temper!t"re of the !ter in the c!pill!r' !s &eteen <@K !nd F@KC%( ith !n !pp!rent
sh!rp pe!. ne!r F9KC% +Fi-"re :=,% Res"lts hich !re ro"-hl' simil!r to ForslindBs h!ve
&een o&t!ined recentl' in the !"thorBs l!&or!tor' +Qerr !nd Drost4!nsen( :M>8(
"np"&lished,% It is interestin- to spec"l!te on this temper!t"re dependence in connection
ith the -ener!l notion of st!&ilit' of !#"eo"s interf!ci!l str"ct"res% Th"s( if the re-ion
&elo F9KC( is ch!r!cteristic of ! st!&le !ter str"ct"re +perh!ps s"ch !s st!&ili3ed(
cl!thr!te)li.e c!-es( or hi-h)press"re ice pol'morphs,( hile other( different +!nd
pro&!&l' sm!ller, str"ct"r!l "nits !re st!&le somehere !&ove this temper!t"re( !
tr!nsition re-ion m!' ell exist in hich there is enh!nced disorder d"e to ! l!tent
inst!&ilit' of either of the st!&ili3ed str"ct"res( !nd th"s &e ch!r!cteri3ed &' !n
incre!sed concentr!tion of rel!tivel' "nstr"ct"red "nits +"n&onded( 0monomeric)li.e0
!ter,% In this temper!t"re r!n-e( the less str"ct"red "nits ill red"ce the mech!nic!l
co"plin- to the confinin- c!pill!r' !lls !nd le!d to decre!sed d!mpin- !s indeed
o&served experiment!ll'% S"ch !n interpret!tion o"ld &e entirel' consistent ith the
entropies of s"rf!ce form!tion reported &' the present !"thor +F=, in ! st"d' of this
#"!ntit'( for p"re !ter( !s ! f"nction of temper!t"re% In th!t p!rtic"l!r st"d'( it !s
shon th!t the entrop' of s"rf!ce form!tion o&t!ined from closel' sp!ced
me!s"rements &' three different sets of !"thors( independentl'( shoed not!&le
incre!ses in s"rf!ce entrop' !t( or !&o"t F9KC% R)Rlor. is "nder !' in the !"thorBs
l!&or!tor' to tr' to s"&st!nti!te !nd exp!nd these me!s"rements% ESee Note Added in
2roof%H
D. Anoalies in Ener." of Activation for &iscous 'lo/ Elsehere( the present
!"thor !nd his !ssoci!tes h!ve disc"ssed extremel' precise me!s"rements on the
viscosit' of p"re &"l. !ter !t closel' sp!ced temper!t"re interv!ls +G8,% These
me!s"rements ere o&t!ined ith ! viscometer hich !s desi-ned( !s f!r !s possi&le(
to elimin!te interferences d"e to s"rf!ce effects% Th"s( ! re!son!&l' l!r-e c!pill!r'
di!meter !s emplo'ed +!pproxim!tel' <@9)("di!meter, !nd( &' "sin- ! s"spended
menisc"s method( the need for s"rf!ce tension corrections !s minimi3ed% The
me!s"rements ere m!de !t : K interv!ls &eteen 90 !nd G9KC% The res"lt !s ! set of
d!t! for the ener-' of !ctiv!tion for visco"s flo of !ter !s ! f"nction of temper!t"re(
hich( hen plotted( -!ve ! c"rve hich !s exceedin-l' smooth% Th"s( no evidence
!s o&t!ined for the existence of therm!l !nom!lies in the visco"s flo of !ter "nder
conditions here s"rf!ce effects h!d &een minimi3ed !s f!r !s possi&le% Contr!r' to the
res"lts disc"ssed !&ove !nd someh!t e!rlier( Ihn!t +>=, me!s"red the viscosit' of
!ter &' ! sli-htl' different techni#"e% The res"lts +the viscosit' d!t! themselves( r!ther
th!n their temper!t"re coefficient- i.e., the ener-' of !ctiv!tion( !s emplo'ed &' the
present !"thor !nd coor.ers, ere !n!l'3ed &' ! mov) % in- #"!dr!tics method% /!sed
on this !n!l'sis( Ihn!t proposed tent!tivel' th!t !nom!lo"s tr!nsitions occ"r ne!r :F%GK(
33.$, !nd =GKC% These temper!t"res !re in re!son!&le !-reement ith those proposed
e!rlier &' the present !"thor)n!mel'( ne!r 1%, 30&, 4%, +!nd >9KC%,% Ihn!t !lso
o&served !n !nom!lo"s ch!n-e ne!r <<%=KC%( hich h!s not &een o&served &' the
present !"thor% ESee( hoever( the !nom!lo"s temper!t"re dependence of the resist!nce
of ! &imolec"l!r( &l!c. lipid film( st"died &' Thompson (137).]
E. $echanical Da)in. and &olue Anoalies in Cellulosic $aterials
Antonio" (5) h!s st"died the st!te of !ter !dsor&ed on poro"s -l!ss +see the disc"ssion
in Section I6)E,% Not!&le !nom!lies ere o&served !t ! n"m&er of temper!t"res &elo
the norm!l free3in- temper!t"re of &"l. !ter !nd some interestin- !n!lo-ies c!n
perh!ps &e dr!n &eteen this st"d' !nd some st"dies m!de &' Q"&!t !nd 2!tt'r!nie
(80). These !"thors investi-!ted the mech!nic!l d!mpin- of cell"lose s!mples !s !
f"nction of temper!t"re !nd mention the existence of ! d!mpin- component !ssoci!ted
ith the presence of !ter% Some !"thors h!ve reported critic!l d!mpin- to occ"r ne!r
20 !nd <@0C%( hile( &' the method "sed &' Q"&!t !nd 2!tt'r!nie( the d!mpin-
!ppe!red to occ"r ne!r F@KC% Another re-ion of enh!nced d!mpin- !ppe!rs to occ"r !t
!&o"t )F9KC% Addition!l independent evidence for the existence of ! tr!nsitlOn !t )F9KC%
!s o&t!ined &' ! dil!tometric techni#"e% The res"lts seem to s"--est ! ver' re!l( !&r"pt
!nom!l' ne!r +or sli-htl' &elo, )F9KC% The !"thors ere "n!&le to propose !n'
specific ph'sic!l expl!n!tion for the phenomenon% The' did notice th!t the presence of
-l'cerol seemed to elimin!te the phenomenon !nd spec"l!ted &riefl' th!t this m!' &e
indic!tive of inter!ction &eteen the -l'cerol +!t lo temper!t"re, !nd the !ter
str"ct"re ne!r the interf!ces +! point hich s"rel' m"st &e of import!nce to those
interested in cr'o&iolo-',% ESee !lso Note Added in 2roof%H
'. 'lo/ of #"drocar!ons Throu.h &"cor De&'e &ec!me interested in the flo of
li#"ids thro"-h finel' pored m!teri!ls% De&'e !nd Clel!nd +<=, me!s"red the flo
ofli#"id h'droc!r&ons +n)pent!ne thro"-h n)dec!ne, thro"-h poro"s le!ched 6'cor% In
the !n!l'sis s"--ested &' De&'e !nd Clel!nd( to different flo re-imes ere
post"l!ted% One is the norm!l 2oise"ille t'pe +!ltho"-h of d"&io"s !pplic!&ilit' &ec!"se
of the sm!ll r!tio of 0!ver!-e pore di!meter0 to !ver!-e si3e of molec'le- i.e., the
diffic"lties in !ppl'in- contin""m mech!nics to !lmost individ"!l( molec"l!r
h!ppenin-s,( !nd the other is ! re-ion of flo !d5!cent to the !ll of the c!pill!r' pores
in the 6'cor% In the l!tter re-ion( !dsorption !s !ss"med to &e effective in orientin- !
l!'er of molec"les hich ere( hoever( movin- ith ! cert!in velocit' thro"-h the
c!pill!r' +"nder the !pplied press"re -r!dient, &ec!"se of slipp!-e% A sli-htl' different
!ppro!ch to the visco"s flo of li#"id +!#"eo"s sol"tions, in n!rro c!pill!ries !s
developed independentl' &' the present !"thor (36,37). +The model hich !s
developed !s !lso !pplied to ionic cond"ction in c!pill!ries%, It !s !ss"med th!t +A,
the !dsor&ed( oriented l!'er !s not slippin-( &"t st!tion!r' !t the confinin- !ll( !nd
+/, th!t the thic.ness of this l!'er !s consider!&l' l!r-er th!n ! sin-le molec"l!r l!'er%
+. &iscous 'lo/ Phenoena in Ca)illaries In ! &rief revie !rticle( Der5!-"in
+<>, h!s disc"ssed the o&serv!tion &' Fed'!.in +=<,( indic!tin- ! depressed v!l"e of
c!pill!r' press"re in n!rro c!pill!ries +!&o"t 200( in r!di"s,% Notithst!ndin- this
depression( the c!pill!r' s"ction occ"rred !t ! r!te sever!l times th!t c!lc"l!ted from
W!sh&"rnBs form"l! !ss"min- th!t 2oise"illeBs e#"!tion held% The discrep!nc' !s
tent!tivel' !scri&ed to slipp!-e !lon- the c!pill!r' !ll +comp!re De&'e !nd Clel!nd,
!nd some s"pportin- evidence for this !s the me!s"rements &' Tolsto' (735) on the
flo of merc"r' in -l!ss c!pill!ries of :9)(" r!di"s% It is proposed here th!t perh!ps !n
e#"!ll' re!son!&le expl!n!tion for Fed'!.inBs res"lts m!' &e in terms of incre!sed flo
in ! 3one of disordered !ter +see the disc"ssion in Sections JI !nd JII,% The !ter(
pres"m!&l' !.in to the disordered !ter 3one in the h'dr!tion model of Fr!n. !nd 66en
+=>,( mi-ht ell &e expected to h!ve loer viscosit' th!n th!t of either &"l. !ter or the
+pro&!&l' hi-hl' str"ct"red !nd therefore hi-hl' visco"s, !ter ne!r the -l!ss c!pill!r'
!ll% A-!in( some of the o&5ections +s"ch !s electrovisco"s effects, hich h!ve &een
r!ised to other flo me!s"rements !re still !s !pplic!&le !s &efore% 4oever( it seems
diffic"lt to !scri&e !n incre!se in c!pill!r' s"ction to s"ch sp"rio"s effects%
&III. ASPECTS O' SUR'ACE ORDERIN+ AND BOUND WATER A. &arious
Surface Studies A s"rve' of &o"nd !ter !s p"&lished &' 4i-!si +@G, ho
specific!ll' !ddressed himself to the role of &o"nd !ter in ph'siolo-ic!l s'stems(
&!sed on !ttempts to "nderst!nd the properties !nd str"ct"re of s"ch vicin!l !ter in
terms of ph'sic!l chemistr' +in p!rtic"l!r( thro"-h dielectric st"dies,% 2riv!lov +G9M, h!s
!lso spec"l!ted on the possi&le existence of str"ct"r!ll' ch!n-ed l!'ers !d5!cent to
&iolo-ic!ll' import!nt s"rf!ces% One of 2riv!lovBs interestin- s"--estions is th!t
&iolo-ic!l s'stems sho"ld &e considered !s "nits of ordered str"ct"res 0since it h!s &een
shon th!t the !ter is in !n ordered st!te0 !nd f"rthermore( th!t 0 %%% effects c!n &e
tr!nsmitted to ! dist!nce &' proton tr!nsfer% An' dist"r&!nce is tr!nsmitted !s ! !ve of
str"ct"r!l disor-!ni3!tion%0 Altered !ter str"ct"re ne!r s"rf!ces h!ve !lso &een
disc"ssed &' 4orne !nd coor.er(S +>:, hile Fr!n.s +=G, h!s presented ! &rief s"rve'
of !ter str"ct"re in disperse s'stems% See !lso Q!v!n!"Bs mono-r!ph +G@,%
B. &a)or Pressure %o/erin. in Ca)illaries One of the cl!ssic st"dies hich h!s
&een "sed to s"pport the contention th!t lon-)r!n-e order exists ne!r interf!ces is the
li#"id)v!por e#"ili&ri"m me!s"rements in microscopic c!pill!ries &' Shereshefs.' !nd
coor.ers% Ce!s"rements on !ter in n!rro c!pill!ries ere reported &' Shereshefs.'
!nd C!rter +:<>,% Definite loerin- of v!por press"re !s o&served f!r &e'ond h!t
co"ld &e expl!ined &' the Qelvin e#"!tion% Shereshefs.' !nd coor.ers interpreted this
o&serv!tion in terms of the e!rlier s"--estion m!de &' Der5!-"in( th!t c!pill!r')held
!ter &eh!ves !s if it ere solid)li.e( someh!t resem&lin- ice% To the &est of this
!"thorBs .noled-e( the experiments of Shereshefs.' !nd coor.ers h!ve rem!ined
"nch!llen-ed !s first)r!te experiment!l evidence for the existence of ch!n-ed !ter
str"ct"res ne!r interf!ces !nd the li.el' existence of lon-)r!n-e order%
C. Te)erature of $a2iu Densit" in Ca)illaries (Schufle* Sch"fle !nd
6en"-op!l!n +:<F, h!ve me!s"red the specific vol"me of !ter over !n extended r!n-e
of temper!t"res in n!rro c!pill!ries% The res"lt of this interestin- experiment!l st"d'
!s the independent discover' th!t the m!xim"m densit' for !ter in n!rro c!pill!ries
is shifted to temper!t"res loer th!n = DC% These me!s"rements !re in r!ther -ood
!-reement ith some of the me!s"rements &' Der5!-"in !nd more recent me!s"rements
&' S!vits.i +G<9,% In Sch"fle !nd 6en"-op!l!nBs c!pill!r' of 4-.u di!meter( the vol"me
minim"m !ppe!rs to &e closer to OKC% th!n to =KC%
D. N$R Results on Dis)ersion In Section '''(B e h!ve !lre!d' disc"ssed the
me!s"rements &' 2ethic! !nd coor.ers +G:, on the rel!tion &eteen !ter str"ct"re
!nd colloid st!&ilit'% Fi-"re :@ shos !nother ill"str!tion from their p!per)n!mel'( the
spin)l!ttice rel!x!tion r!te +:$ T 1) !s ! f"nction of the inter p!rticle dist!nce for ! 26 A
dispersion +p!rticle r!di"s( O.8.u). Fi-"re :> shos the spin)spin rel!x!tion r! te +:$ T
<, !s ! f"nction of p!rticle sep!r! tion for sm!ller 26 A p!rticles +p!rticle r!di"s(
O.13.u). In &oth Fi-"res :@ !nd :>( me!s"rements !re reported !t different
temper!t"res +see le-ends,* it is rem!r.!&le ho r!pidl' the rel!x!tion r!te decre!ses
ith incre!sin- temper!t"re for sm!ller sep!r!tions &eteen p!rticles% In Fi-"re :@( the
tr!nsverse rel!x! tion time is !lso seen to incre!se ver' r!pidl' ith incre!sin-
concentr!tioni. e., ith decre!sin- p!rticle sep!r!tion% 2ethic! !nd coor.ers disc"ssed
the possi&le ori-ins of !ter str"ct"rin- !t the dist!nces involved here !nd concl"ded
th!t str"ct"rin- o"ld res"lt either from overl!p of electric!l do"&le l!'ers( or from
London6!n der W!!ls dispersion force inter!ctions% From me!s"rements in the presence
of 10-3M sodi"m chloride( it !s concl"ded th!t overl!ppin- do"&le l!'ers ere not the
c!"se of the !ter str"ct"rin-% From this it co"ld &e concl"ded th!t the spin)spin
rel!x!tion r!te sho"ld incre!se ith p!rticle r!di"s( &ein- c!"sed &' dispersion forces(
!nd this !s indeed o&served% The !"thors concl"ded 0 %%% th!t the hole phenomenon of
!ter str"ct"rin- is one of -ener!l import!nce in "nderst!ndin- colloid st!&ilit' %%%% 0
F"rthermore( the !"thors concl"de th!t the0 %%% evidence presented here -ener!ll'
s"pport the vies of Der5!-"in on the lon-r!n-e str"ct"rin- of &o"nd!r' l!'ers of
!ter%0
E. Possi!le Effects on Classical Diffusion $easureents Considerin- the
li.el' existence of ch!n-ed !ter str"ct"res ne!r s"ch !ter$solid interf!ces !s the
!ter$ -l!ss !nd !ter$#"!rt3 interf!ces( e s"spect th!t 0cl!ssic!l0 diff"sion
experiments( "sin- sin-le c!pill!ries or poro"s fritted dis.s( m!' &e !ffected &' the
presence of ch!n-ed s"rf!ce l!'ers% CcC!ll !nd Do"-l!ss +8>, h!ve noted th!t( in spite
of the l!r-e n"m&er of st"dies hich h!ve &een m!de to determine the selfdiff"sion
coefficient for !ter( the over!ll !cc"r!c' on this #"!ntit' is onl' !&o"t U:11:9P +!t
<@KC( )o * <%F J :9)5 cm2$sec,% The !"thors c!ll !ttention to the f!ct th!t this pro&lem
deserves f"rther st"d'%
'. $echaniss of Anesthetics (Paulin.* In p!ssin-( e note th!t !n interpret!tion
of vicin!l !ter str"ct"re( possessin- cl!thr!te)li.e ch!r!cteristics( is consistent ith the
s"--estion &' 2!"lin- (103) th!t !nesthetic !ction m!' &e loc!ted !t ne"ron interf!ces
&ec!"se of cl!thr!te form!tion &eteen the !nesthetic !-ent !nd the vicin!l !ter
str"ct"re%
+. Discrete %a"ers at the +lass,Water,Air Interface In experiments &'
Der5!-"in !nd Aorin +<8,( li#"id films ere condensed on -l!ss pl!tes from sli-htl'
s"&s!t"r!ted !tmospheres% It !s o&served th!t ith ! polished -l!ss pl!te( !
0h'dropho&ic0 &eh!vior !s fo"nd( res"ltin- in the form!tion of limitin- l!'ers of !ter
hich ere onl' :G A thic.% Norm!ll'( the -l!ss is( of co"rse( !ss"med to &e completel'
h'drophilici. e., !ter is considered to form ! 3ero !n-le of cont!ct% For this re!son( it
o"ld &e expected th!t no definite( fixed film thic.ness sho"ld !tt!in% 4oever( !
findin- s"ch !s th!t of Der5!-"in !nd Aorin is ex!ctl' h!t o"ld &e expected did !ter
form ! t'pe of st!&le cl!thr!te c!-e str"ct"re ith onl' one or( !t the most( ! fe t'pes
of st!&le pol'hedr!% It o"ld &e interestin- to cond"ct st"dies of this t'pe in the
presence or !&sence of v!rio"s cl!thr!te h'dr!te +-!s, formers% Comp!re the e!rlier
res"lts &' /!n-h!m +8, here s"rf!ces ere m!de !"topholic &' expos"re to the v!por
onl' of ! norm!ll' ettin- li#"id%
#. Shoc5 Tu!e E2)erients9 Wetta!ilit" Phenoena. Nucleation
Phenoena In connection ith the st"d' &' Der5!-"in !nd Aorin( rec!ll !lso the
interestin- o&serv!tions m!de &' Ioldstein (51) in shoc. t"&e experiments% These
experiments ere m!de "nder conditions hich !lloed for the st"d' of the initi!l
condens!tion of !ter% Cle!n h'drophilic -l!ss s"rf!ces &eh!ved pr!ctic!ll'
0h'dropho&ic!ll'(0 in th!t the initi!l !dsorption too. pl!ce in the form of sm!ll( discrete
droplets% On the other h!nd( pretre!ted h'dropho&ic s"rf!ces -!ve the initi!l
condens!tion of thin contin"o"s films% After -roth of these films to thic.nesses of
!&o"t : ooA, the' &e-!n to sho droplet form!tion +0&e!din-0, !s o"ld norm!ll' &e
expected for ! 0-re!s'0 s"rf!ce% The interpret!tion hich is temptin- here is the
st!&ili3!tion of cl!thr!teli.e l!'ers of !ter str"ct"re( st!&ili3ed +&' h'dropho&ic
&ondin-, on the co!ted s"rf!ces% EComp!re n"cle!tion phenomen! o&served ith 0ver'
p"re0 vs. 0imp"re0 silver iodide s"rf!ces* for inst!nce( disc"ssions &' Corrin !nd Nelson
+<<,%H For ! disc"ssion of !ter ne!r interf!ces in -ener!l !nd disc"ssions of n"cle!tion
pro&lems in p!rtic"l!r( see the st"dies &' Aettlemo'er !nd coor.ers +G=>,* !lso
Tche"re.&5!in et al. (130). Rec!ll( in this connection !lso( the st"dies &' L'.lem!
disc"ssed in the present p!per +Section III)F,% Aorin !nd Ch"r!ev +:=8, contin"ed the
st"dies &' Der5!-"in !nd Aorin( "sin- optic!l techni#"es( of the n!t"re of !ter !d5!cent
to #"!rt3 s"rf!ces% Usin- !n in-enio"s device( Aorin !nd Ch"r!ev demonstr!ted the
existence of steepl' stepped s"rf!ces of !ter &eteen !n !ir &"&&le !nd ! #"!rt3
s"rf!ce% The 0e#"ili&ri"m0 thic.ness of the m"ltimolec"l!r !dsorption film !s of the
order of :99A thic.% A second( discrete l!'er existed !lon- the peripher' of the !ir
&"&&le pressed !-!inst the #"!rt3 s"rf!ce% The thic.ness of this film !s !pproxim!tel'
=ooA% While it is li.el' th!t no tr"e e#"ili&ri"m films ere o&served( the !"thors noted
th!t the stepped film did not ch!n-e its !ppe!r!nce over sever!l ho"rs% The' !lso c!lled
!ttention to the coexistence of films of different thic.nesses of &en3ene on ! merc"r'
s"rf!ce !nd( in the c!se of free films( of !#"eo"s sol"tions of deter-ents% The !"thors
disc"ssed the phenomenon in terms of Der5!-"inBs to)&r!nch !ter !dsorption
isotherm% The' ded"ced from the mode of form!tion !nd the -ener!l p1roperties of the
film th!t the centr!l circ"l!r film &elon-ed to the !)&r!nch hile the thic.er( !nn"l!r
film &elon-s to the 7F)&r!nch of the dis5oinin-)press"re isotherm% 0It follos from the
coexistence of films of to different thic.nesses( th!t "nder cert!in conditions( the
st!&ilities of the a- !nd 7F)films m!' &e e#"!l%0 For ! disc"ssion of the !dsorption
isotherms of interest here( see the e!rlier p!pers &' Der5!-"in !nd Aorin( the recent
revie of Ad!mson( the !rticle &' Shel"d.o +G<@,( !nd the older extensive ritin-s &'
/!n-h!m !nd coor.ers +8,%
I. Diension and #eat Ca)acit" Chan.es in &"cor. Rates of Dendritic Ice
+ro/th Antonio" +@, st"died the !dsorption of !ter v!por on poro"s 6'cor -l!ss ith
ver' hi-h s"rf!ce !re! in the r!n-e from )=9 to L<KC% Antonio" me!s"red &oth the
specific he!t ch!n-es( !s ell !s the len-th ch!n-es( !ssoci!ted ith the !dsorption of
!ter% 4e concl"ded th!t !t )=9KC%( !n !mo"nt of !ter rem!ined "nfro3en( !mo"ntin-
to !&o"t three monol!'ers% F"rthermore( his res"lts s"--ested th!t even in the middle of
the c!pill!ries +ith !n !ver!-e c!pill!r' r!di"s of !&o"t F9A, the !ter rem!ined in !
different st!te from th!t of &"l. !ter% Fi-"res :G !nd :8 sho( respectivel'( the
o&served len-th ch!n-es !nd the 0!pp!rent he!t c!p!cit'0 of the !dsor&ed !ter% The
0!pp!rent he!t c!p!cit'0 is the c!lc"l!ted excess he!t c!p!cit' over the he!t c!p!cit' of
the poro"s -l!ss s!mple itself( de-!ssed !t room temper!t"re( !t :9)= mm prBess"re% This
l!tter press"re( !t room temper!t"re( is pro&!&l' not s"fficientl' lo to remove ne!rl'
!ll tr!ces of !dsor&ed !ter% In connection ith these -r!phs( it sho"ld &e noted th!t !n
!nom!l' seems to exist in the properties of s"percooled !ter ne!r ):: or ):<K9% Recent
experiments &' 2r"pp!cher (110) h!ve !lso s"--ested th!t !nom!lo"s ch!n-es m!'
occ"r !t this temper!t"re in the str"ct"re of !ter)ch!n-es hich m!' ell &e
!ssoci!ted prim!ril' ith !ter ne!r interf!ces% Fi-"re :M shos the -roth velocit' for
ice dendrites in p"re !ter !s ! f"nction of the s"percoolin-%
". Other Studies on &"cor Another interestin- tr!nsition in !ter !dsor&ed on
poro"s 6'cor -l!ss h!s &een identified &' 4od-son !nd CcIntosh +@8,% These !"thors
fo"nd from ! st"d'( monitorin- dimension!l ch!n-es of le!ched poro"s 6'cor( th!t the
!dsor&ed !ter !ppe!red to "nder-o ! ph!se tr!nsition in the vicinit' of )<<K9% This
st"d' !s folloed &' ! more det!iled st"d' of &oth !ter !nd &en3ene in 6'cor +@M,%
-. +eneral Evidence for Surface4Induced Structures To s"m "p( e h!ve
revieed some of the evidence for the existence of ind"ced str"ct"res of !ter ne!r !
v!riet' of interf!ces% The evidence( !dmittedl'( is often indirect( !t times ten"o"s( &"t
cert!inl' !&"nd!nt% Some experiments( especi!ll' those not cond"cted on cl!' s'stems(
!ppe!r !t le!st occ!sion!ll' to 'ield "n!m&i-"o"s res"lts% If e "se the concept of
therm!l !nom!lies in m!n' properties of !#"eo"s interf!ci!l s'stems !s evidence for the
existence of ind"ced( st!&ili3ed str"ct"res ne!r interf!ces seems 5"stified( !nd
constit"tes ! stron-( #"!lit!tive !r-"ment for the re!lit' of the phenomenon of
str"ct"red !ter ne!r interf!ces% The contri&"tions &' Der5!-"in !nd coor.ers h!ve
f"rther stron-l' s"--ested s"ch existence of st!&ili3ed str"ct"res of !ter ne!r
interf!ces% The evidence for ! three)l!'er model of !ter ne!r cert!in interf!ces +r!ther
th!n merel' ! tr!nsition from !n ordered( str"ct"red 3one to the more disordered( &"l.
3one, is mostl' indirect !nd &!sed !s m"ch on simple ph'sic!l int"ition !s on !v!il!&le
experiment!l inform!tion% F"rthermore( the three) !'er model m!' !ppl' onl'( or
predomin!ntl'( to ! str"ct"r!l model for !ter ne!r ! pol!r s"rf!ce( !&le to ind"ce !
l!'er of dipoles !t the interf!ce% 4oever( it seems th!t the s"--estion &' Fr!n. !nd
Wen !s to the existence of ! disordered 3one !ro"nd ions in sol"tion o"-ht to !ppl'
e#"!ll' ell to colloid!l s'stems% O&vio"sl'( the introd"ction of one !ddition!l de-ree
of freedom in o"r model +n!mel'( the disordered 3one, le!ds to incre!sed flexi&ilit' in
interpret!tion( &"t( !t the s!me time( re#"ires 5"stific!tion &ec!"se of o"r -ener!l
!dherences to ! principle of m!xim"m concept"!l econom' +0Simplex Si-ill"m 6eri0,%
4oever( pr!-m!tic!ll'( one m!' c!ll for the introd"ction of s"ch !n !ddition!l de-ree
of freedom in vie of the hi-hl' conflictin- experiment!l inform!tion hich is
!v!il!&le !nd the "ns"ccessf"l !ttempts hich h!ve &een m!de in the p!st tr'in- to
expl!in this e!lth of diver-ent d!t! in terms of simpler models (i.e., in terms of ! to)
l!'er model or( in p!rtic"l!r( in terms of complete ne-lect of the role pl!'ed &'
interf!ci!l str"ct"res,%
I:. OT#ER #1DRATION P#ENO$ENA IN $ACRO$O%ECU%AR AND
CO%%OID S1STE$SA. %on.4Ran.e Order in A0ueous Solutions Th!t
str"ct"red elements m!' &e ind"ced in !ter &' the presence of cert!in sol"tes)!s ell
!s &' the presence of ! solid( li#"id( or -!s interf!ce)seems est!&lished r!ther firml'%
Th"s( !s !n ex!mple( elsehere in this p!per +Sections '''(B !nd 6III)D,( e h!ve
disc"ssed the st"dies &' 2ethic! !nd coor.ers on n"cle!r rel!x!tion times !s ! f"nction
of concentr!tion (i.e., p!rticle sep!r!tion, of 2OA !nd 26T l!tex p!rticles% The res"lts
s"--ested str"ct"r!l effects th!t !ppe!r to &e prop!-!ted over dist!nces of sever!l
tho"s!nd !n-stroms% Other evidence for p!rtic"l!rl' lon-)r!n-e str"ct"r!l st!&ili3!tion
in the &"l. !#"eo"s ph!se m!' li.el' &e in) ferred from the rheolo-ic!l properties of !n
!#"eo"s sol"tion of the copper s!lt of cet'l phen'l ether s"lfonic !cid hich ret!ins
el!stic properties +!t ! temper!t"re of M9KC%, in ! 9%99<P sol"tion% ESee Qr"'t +GM,%H It
!ppe!rs th!t in this s'stem( lon-)r!n-e orderin- of !ter m"st &e invo.ed( !s the
sol"tion cont!ins onl' !pproxim!tel' <%:9)6 -mol$l% sol"te 0p!rticles0 or ro"-hl' one
sol"te molec"le per <9 million !ter molec"les% 2hr!sed sli-htl' differentl'( the
!pproxim!te line!r sep!r!tion &eteen sol"te molec"les is of the order of <@9 !ter
molec"les% Li.eise( the existence of lon-)r!n-e str"ct"rin- effects !ppe!rs li.el' from
rheolo-ic!l d!t! on ver' dil"te !#"eo"s pol'eth'lene oxide sol"tions% If these
orient!tion!l effects !re re!l( it is little onder th!t the' m!' not &e p!rtic"l!rl' st!&le
to!rd mech!nic!l dist"r&!nces +!s little !s the' c!n &e p!rtic"l!rl' st!&le ith respect
to therm!l fl"ct"!tions)i%e%( the' !re li.el' to &e hi-hl' temper!t"re sensitive,% We ret"rn
to the pro&lem of mech!nic!l st!&ilit' l!ter in this section%
B. E2a)les of Coo)erative Chan.e in A0ueous Solutions of
$acroolecules We m!' mention in p!ssin- th!t !pp!rentl' m!n' other pol'meric
sol"tes c!n si-nific!ntl' infl"ence the str"ct"re of !ter in !#"eo"s sol"tion !nd the
effects &e interpreted in terms of h'dr!tion str"ct"res of consider!&le si3e% Th"s(
4!mmes !nd Schimmel (54) h!ve shon from !n "ltr!sonic st"d' of pol'eth'lene
-l'col in !#"eo"s sol"tion th!t the rel!x!tion process m!' &e !ttri&"ted to ! cooper!tive
ch!n-e in the 0loc!l !ter0 !nd h'dropho&ic str"ct"res !ssoci!ted ith the pol'mer%
Consider!&le !mo"nts of !ter !ppe!r to &e involved in the h'dr!tion of the pol'mer% It
is of interest th!t in ! prelimin!r' st"d' of the ener-' of !ctiv!tion for visco"s flo of
dil"te sol"tions +9%<P, of 2ol'ox +pol'eth'lene oxide, +F<,( st"died in ! simple
c!pill!r' viscometer (i.e., itho"t re-!rd for the nonNetoni!n &eh!vior,( the o&served
ener-ies of !ctiv!tion for visco"s flo of s"ch sol"tions ere !pproxim!tel' const!nt !t
@=99 T F99 c!l$-mol over the r!n-e from :9 to @@KC% The rem!r.!&le f!ct is th!t(
!ltho"-h the sol"tion is MM%8P !ter( the ener-' of !ctiv!tion for visco"s flo rem!ins
const!nt over the temper!t"re r!n-e st"died( hile over the s!me r!n-e the ener-' of
!ctiv!tion for visco"s flo of p"re !ter decre!ses from !pproxim!tel' =@99 to FF99
c!l$-mol%
C. $echanical Effects on Rheolo.ical Pro)erties Tr!pe3ni.ov !nd Do.".in!
+:FG, +see Section 6II)/, h!ve st"died the effect of temper!t"re !nd vi&r!tion on the
viscosit' of s"rf!ce films !nd s"rf!ce l!'ers of sol"tions of sodi"m dodec'l s"lf!te
cont!inin- dodec!nol% The !"thors o&served( in !ddition to the rem!r.!&l' sh!rp drop in
the viscosit' of s"rf!ce films !nd s"rf!ce l!'ers ne!r F9K to FFKC%( ! m!r.ed sensitivit'
to e!. vi&r!tions% Sli-ht mech!nic!l vi&r!tions +c!"sed &' !n electric f!n in the
instr"ment!tion "sed &' these !"thors, not!&l' loered the viscosities of &oth film !nd
s"rf!ce l!'ers of the sol"tions st"died% 4ence( hile sever!l non!#"eo"s s'stems !re
.non to exhi&it m!r.ed she!r r!te dependent rheolo-ic!l properties( it !ppe!rs
possi&le( !nd in f!ct( li.el' th!t speci!l mech!nisms m!' !t le!st sometimes h!ve to &e
invo.ed for the expl!n!tion of non)Netoni!n &eh!vior in !#"eo"s s'stems( !nd these
mech!nisms involve the mech!nic!l &re!.don of l!r-e ind"ced !ter str"ct"res% ESee
!lso the disc"ssion of mech!nic!l effects of sol)-el !ter tr!nsform!tions presented &'
2% 4% 4erm!ns in Qr"'tBs tre!tise on Colloid Chemistr'( lac. cit. Comp!re !lso the
st"dies &' Lo +8<( 8F,* see &eloH%
D. $echanical Brea5do/n of Water in Cla" S"stes A set of experiments
hich m!' confirm the !&ilit' of mech!nic!l !-it!tion to &re!. don !ter str"ct"res in
!#"eo"s s'stems +ith l!r-e !mo"nts of vicin!l !teri. e., hi-h s"rf!ce)to)vol"me
r!tios, !s p"&lished &' Lo et al. +8F,% These !"thors st"died +A, the r!te of
-ermin!tion +of lett"ce seeds,( +/, the he!t evolved in the -roth of ! &!cteri"m
(+treptococc's faecalis) ( !nd +C, the r!te of <<N! "pt!.e &' corn seedlin-s% The res"lts
of this st"d' indic!ted th!t &iolo-ic!l !ctivit' in !ll three c!ses !s -re!ter in s'stems
th!t h!d &een dist"r&ed mech!nic!ll' th!n in "ndist"r&ed( control s'stems%
E. &iscosit" Anoalies in Dilute -aolinite Sus)ensions Another st"d' hich
m!' reflect lon-)r!n-e orderin- of !ter in ! cl!' s'stem +.!olinite, !s m!de &'
2lot3e et al. (10,). These !"thors o&served th!t the !pp!rent viscosit' +!s o&t!ined ith
!n Ost!ld c!pill!r' viscometer, of dil"te s"spensions of .!olinite !s ! f"nction of
concentr!tion shoed discrete pe!.s of hi-h rel!tive +!s ell !s !&sol"te, viscosities%
The m!xim! !re extremel' sh!rp)i%e%( extended over ! concentr!tion r!n-e of onl' :9)=
-$cmF sol"tion( !nd the m!-nit"de of the m!xim! exceeded the -ener!l sc!tter in the
experiments &' !&o"t to orders of m!-nit"de% The s"spension of .!olinite p!rticles
h!d !n !ver!-e p!rticle si3e of 1.%,'- in the loest concentr!tion r!n-e( the first sh!rp
m!xim"m in viscosit' occ"rred !t ! concentr!tion of !&o"t 9%99@ -$cmF( correspondin-
to !n !ver!-e dist!nce &eteen nei-h&orin- pl!telets of !pproxim!tel' ,,'. The !"thors
spec"l!ted th!t the effect mi-ht &e rel!ted to the overl!p of discrete h'dr!tion str"ct"res
of the individ"!l p!rticles !nd( !s sever!l rel!tive m!xim! ere o&served( possi&l'
reflect different t'pes of !ter str"ct"re s"rro"ndin- the p!rticles% It is "nfort"n!te th!t
rel!tivel' "nsophistic!ted instr"ment!tion !s "sed in this st"d' (i.e., ! fixed)he!d
c!pill!r' viscometer( inste!d of ! v!ri!&le she!r r!te device% 4oever( it is import!nt to
note th!t the viscosit' of .!olinite s"spensions is not stron-l' she!r)r!te dependent,%
.. Nucleation Studies on Clas 1Anderson2 Anderson h!s m!de some interestin-
o&serv!tions on !ter? ne!r miner!l s"rf!ces thro"-h ! st"d' of ice n"cle!tion &' cl!'s%
Th"s( Anderson !nd 4oe.str! +=, st"died &' me!ns of J)r!' diffr!ction the st!te of
!ter in fro3en cl!')!ter p!stes% The import!nt findin- of this st"d' is th!t the ice
cr'st!ls formed h!ve their c)!xis oriented perpendic'lar to the c)!xis of the cl!' l!ttice%
This( then( s"--ests th!t the ice !s not formed initi!ll' &' direct epit!x' on the solid
s"&str!te% Anderson !nd 4oe.str! considered to !ltern!tive methods &' hich the
.non n"cle!tin- !&ilit' of cl!'s mi-ht &e expl!ined% The first of these expl!n!tions is
centered !ro"nd the possi&le n"cle!tion on ! 0f!vor!&le site0 on the cl!'Bs s"rf!ce% The
ice n"cle"s th"s formed co"ld -ro p!r!llel ith the cl!')pl!telet s"rf!ce +except for
points of occ!sion!l !tt!chment,( &"t o"ld l!r-el' &e sep!r!ted from the cl!' s"rf!ce
&' ! film of 0"nfro3en str"ct"red !ter cont!inin- the exch!n-e!&le ions( h'dr!ted
oxides( !nd !n' electrol'te present%0 An !ltern!tive expl!n!tion proposed &' these
!"thors is th!t the n"cle!tion occ"rs !t ! dist!nce from the s"rf!ce +for one re!son or
!nother,( &"t ith the ice cr'st!l "n!&le to m!.e direct cont!ct ith the cl!' pl!telets
&ec!"se of the excl"sion of the electrol'te from the -roin- ice hich ill tend to
concentr!te the s!lts in the l!'er &eteen the cl!' pl!telet !nd the ice cr'st!lthe re-ion
ne!r ! cl!' s"rf!ce hich( !s mentioned &efore( m"st cont!in ! f!irl' hi-h concentr!tion
of ions% Anderson !nd 4oe.str! -o on to disc"ss the possi&ilit' th!t lon-)r!n-e orderin-
of the vicin!l !ter m!' extend to dist!nces l!r-er th!n soA from the cl!' s"rf!ces% On
this &!sis( the' s"--est th!t 0Epit!x' in this inst!nce is controlled not &' the !tomic
confi-"r!tion of the cl!' s"rf!ce( &"t &' lon-)r!n-e cl!')!ter inter!ction%0 In !
s"&se#"ent p!per( Anderson +F, reported on f"rther st"dies of the ice n"cle!tin- !&ilities
of cl!' s"rf!ces% Usin- ! differenti!l therm!l method of !n!l'sis( he o&served
exothermic pe!.s for lo !ter contents on .!olinite s"rf!ces( in the vicinit' of )=9KC%
Someh!t simil!r res"lts ere o&t!ined ith sodi"m montmorillonite% This is of interest in
connection ith the disc"ssion of )=9KC% !s !n "n"s"!l temper!t"re in meteorolo-'% ESee the
!rticle &' the present !"thor on the n! t"re of the !ter$ice interf!ce (37).J As s"--ested in the
p!per ith 4oe.str!( Anderson in the second p!per !-!in stresses the possi&ilit' th!t the
0form!tion !nd -roth of em&r'os !ct"!ll' occ"r !t ! loc!tion sever!l( perh!ps m!n'( molec"l!r
#i!meters dist!nt from the s"&str!te%0 As implied in the present p!per( it seems possi&le th!t the
se!t of n"cle!tion is in ! disordered 3one &eteen the vicin!l( ordered !ter !nd the differentl'
str"ct"red +loc!ll' str"ct"red( &"t onl' short)r!n-e ordered, &"l. !ter( hich is li.el' not Ice)
Ih)li.e% Th"s( the e!se of n"cle!tion of this !ter is simpl' ! m!nifest!tion of the l!c. of ! more
ordered str"ct"re hich o"ld &e re#"ired to &e &ro.en don to &ecome re!rr!n-ed into the
hex!-on!l Ice)Ih)form% The possi&ilit' th!t others of the more ell).non n"cle!tin- !-ents
+s"ch !s silver iodide !nd cert!in or-!nic m!teri!ls, !ct in ! li.e m!nner ill &e disc"ssed in !
forthcomin- p!per%
+. Diffusi&ities in Pol%eric +el Sste%s An interestin- disc"ssion of order$disorder !t
interf!ces derives from ! st"d' of diff"sivities in pol'meric -el s'stems% Admittedl'( it is !-!in
necess!r' here to extend the notion of !n interf!ce to incl"de the re-ion &eteen( s!'( ! -el)
formin- m!teri!l +s"ch !s C!r&opole or c!r&ox')meth'Icell"lose( CCC, !nd the !ter str"ct"re%
Ast!rit! +>, determined the diff"sivit' of CO2 !nd C24 4 in !#"eo"s sol"tions !nd v!rio"s
s"spensions* the s'stems ere nOh)Netoni!n% Altho"-h the !pp!rent viscosities of some of the
li#"id +for inst!nce( 9%: to 9%<P C!r&opole or 9%@ to <%9P CCC in !ter, ere m"ch hi-her
th!n the viscosit' of !ter( the me!s"red diff"sivities of the -!seo"s molec"les ere of the
s!me order of m!-nit"de !s in p"re !ter% In f!ct( the diff"sivities !ppe!red to incre!se
si-nific!ntl' ith incre!se in concentr!tion of the pol'merV This o"ld !-ree ell ith !n
interpret!tion of excl"sion of &"l. str"ct"red !ter !s the pol'molec"l!r m!cromolec"les
&ecome s"fficientl' concentr!ted to excl"de the &"l. +loc!ll' ordered, !ter str"ct"re !nd th"s
enh!nce the effects of ! disordered 3one% Ast!rit! !lso shoed the s!me to hold for c!r&on
dioxide diff"sion in &entonite s"spension here the diff"sivit' incre!sed from :%M: to <%=9 :9)@
cm<$sec on -oin- from ! F%89P &entonite to ! @%:9P &entonite s"spension% Interestin-l'
eno"-h( the !"thor concl"ded th!t hile his reported diff"sivities !ppe!r s"&st!nti!ll' correct(
he h!d no expl!n!tion to offer for the f!ct th!t the' !re "nexpectedl' hi-h% The s"--estion
proposed in the present p!per o"ld seem?! n!t"r!l expl!n!tion for the phenomenon% D"inn !nd
/l!ir +GGG, c!lled !ttention to the controvers' &eteen res"lts &' Cet3ner +M<, !nd &' Ast!rit!
+>,( on the one h!nd( ho &oth !ppe!r to find incre!sed diff"sion coefficients for sm!ll sol"tes
in -el !nd sol"tions of pol'mers( !nd their on res"lts( here( itho"t exception( diff"sion
coefficients r!tios of one or less ere o&served% While the res"lts &' D"inn !nd /l!ir seem
convincin-( ! possi&le expl!n!tion for the discrep!nc' m!' lie in the !forementioned possi&ilit'
th!t the o&served 0!ver!-e0 diff"sion coefficient m!' &e the !ver!-e of three distinct diff"sion
coefficients)n!mel'( the coefficient for the diff"sion in the str"ct"red( ordered l!'er( vicin!l to
the solid s"rf!ce* the diff"sion coefficient in the disordered str"ct"re* !nd the diff"sion
coefficient in the +loc!ll' str"ct"red, &"l. !ter ph!se% Th"s( the 0!ver!-e0 diff"sion coefficient
ill depend critic!ll' on the concentr!tion of the pol'meric molec"les( res"ltin- in v!rio"s
de-rees of excl"sion of the &"l. !ter +!nd the disordered 3one,% A c!ref"l st"d' !lon- the lines
s"--ested experiment!ll' &' Ivlet3ner( Ast!rit!( !nd D"inn !nd /l!ir( ith p!rtic"l!r !ttention
p!id to the concentr!tion dependencies( mi-ht indeed thro li-ht on the proposed three)l!'er
model%
H. Diffusion in *t$er +el Sste%s Other st"dies of orderin- ne!r cl!')!ter interf!ces h!ve
&een c!rried o"t &' I!st (50). Iener!ll'( I!st feels th!t the decre!sed diff"sion of s"lf!te ion
comp!red to chloride ion m!' lend #"!lit!tive s"pport for the ide! of incre!sed viscosit' of
!ter ne!r cl!' s"rf!ces( &"t !s "n!&le to m!.e ! fin!l 5"d-ement &ec!"se of the other f!ctors
hich h!ve fre#"entl' &een mentioned( s"ch !s electrost!tic effects !nd tort"osit'% I!st does
mention th!t L!i !nd Cortl!nd h!ve fo"nd th!t the ener-ies of !ctiv!tion for diff"sion decre!sed
ith incre!sin- cl!' concentr!tion !nd concl"ded( therefore( th!t visco~ity did not !ppe!r to
&e the controllin- f!ctor for ion diff"sion +! t cl!' concen tr! tions !s hi-h !s :@ to <8P,% The
decre!se in ener-' of !ctiv!tion for diff"sion in these s'stems co"ld ell &e !n other
m!nifest!tion of the decre!se in order( oin- to the elimin!tion of the 0&"l. ph!se0 of !ter !nd
the rel!tive incre!se of the role of the disordered l!'ers( !d5!cent to the more stron-l' &o"nd
ordered !ter str"ct"re +immedi!tel' !d5!cent to the solid s"rf!ce,% A-!in( the evidence is
circ"mst!nti!l( &"t !ppe!rs !t le!st to &e consistent%
'. Water Near Mica The existence of str"ct"red !ter ne!r !n interf!ce h!s !lso &een s"--ested
&' Cesti. !nd Aid!nod! +M:,% These !"thors me!s"red the he!t cond"ctivit' of !ter &eteen
consec"tive l!'ers of mic! !nd !ter% The' o&served th!t the therm!l cond"ctivit' of the !ter
&eteen the mic! sheets !s more th!n !n order of m!-nit"de hi-her th!n the therm!l
cond"ctivit' of &"l. !ter% +The !ter films ere !&o"t O%lC thic.i. e., F99 !ter molec"l!r
l!'ers deep%, For comp!rison( the therm!l cond"ctivit' of the ice is onl' F%@ times th!t for &"l.
!ter% This st"d' !ppe!rs therefore to demonstr!te #"ite cle!rl' str"ct"r!l ch!n-es in !ter ne!r
! mic! s"rf!ce%
:. ANO$A%OUS WATER
A. Derjaguin Sc$ool of Surface C$e%istr3 4Blo5(*ff4 E,peri%ents Fe persons h!ve
contri&"ted !s m"ch to the "nderst!ndin- of !ter ne!r interf!ces !s /oris 6% Der5!-"in !nd the
school of s"rf!ce chemists from his l!&or!tor'% For m!n' 'e!rs( Der5!-"in h!d !dvoc!ted the
existence of lon-)r!n-e orderin-( extendin- from v!rio"s interf!ces into the &"l. of some
li#"ids( incl"din-( !nd in p!rtic"l!r( !ter% Reference is m!de !t v!rio"s pl!ces ::: this p!per to
the m!n' contri&"tions &' the R"ssi!n school% As !n ex!mple of the st"dies &' Der5!-"in !nd
coor.ers( e mention here the 0&lo)off0 experiments in hich the thic.ness !s me!s"red of
l!'ers of li#"id !d5!cent to ! solid s"rf!ce( hile s"&5ect to ! const!nt she!r stress( cre!ted &'
&loin- over the s"rf!ce Esee Der5!-"in !nd Q!r!ssev +<G,H% Nonvol!tile( nonpol!r li#"ids
ret!ined their &"l. viscosit' re-!rdless of ho thin the l!'er hich rem!ined on the solid% On
the other h!nd( pol!r li#"ids !nd sol"tions of pol!r s"&st!nces -!ve incre!sin- viscosities !s the
films thinned% The thic.ness of the l!'ers ith not!&l' incre!sed viscosit' r!n-ed from !&o"t
:99 to :999A% Recentl'( Sin-leterr' !nd /!scom +person!l comm"nic!tion( :M>M, h!ve repe!ted
this t'pe of me!s"rement !nd concl"ded th!t sp"rio"s effects m!' h!ve -iven rise to the
!pp!rent hi-h viscosit' v!l"es o&t!ined &' Der5!-"in !nd coor.ers% The controvers' implied
here is interestin- from m!n' points of vie% First of !ll( it !mpl' demonstr!tes the diffic"lties
!ssoci!ted ith s"rf!ce chemic!l st"dies% Altho"-h 0simple)minded(0 the ver' ide! of
deline!tin- str"ct"r!l ch!r!cteristics on the molec"l!r level &'( liter!ll'( &loin- !!' the
molec"les is in-enio"s( &"t it is pro&!&l' little onder th!t concord!nt res"lts m!' not &e
o&t!ined &' the "se of s"ch methodolo-' in the h!nds of different rese!rchers% 4oever(
hether ! third independent st"d' of this p!rtic"l!r experiment ill find on the &!l!nce in f!vor
of Der5!-"in !nd coor.ers or Sin-leterr' !nd /!scom( there is little do"&t th!t the pro&lem of
orderin- ne!r interf!ces h!s ch!llen-ed the most c!ref"l !nd competent scientists for m!n'
'e!rs%
B. Preparation and Properties of Ano%alous WaterPossi!le E,planation v6e proceed no
to s"mm!ri3e the essenti!l o&serv!tions m!de &' Der5!-"in !nd coor.ers on the properties of
!ter condensed in #"!rt3 c!pill!ries% This( in t"rn( le!ds to ! disc"ssion of !nom!lo"s !ter +!s
noted previo"sl'( v!rio"sl' referred to !s ortho)!ter( s"per!ter( pol'!ter( or !ter II,% The
essence of the disc"ssion hich follos is !n !ttempt to decide hether the !nom!lo"s !ter
represents ! 0ne s"&st!nce0 or merel' represents the "ltim!te in lon-)r!n-e orderin- ne!r
interf!ces% The -ross difference &eteen the to possi&ilities is essenti!ll' one of ener-etics1
either ne t'pes of &ondin- +s"ch !s si-nific!nt reh'&ridi3!tion of the !ter molec"le, occ"r or
merel' sli-ht ch!n-es in ener-' levels &' the form!tion of ne +or simpl' "nreco-ni3ed,
different str"ct"r!l orderin-s of the molec"les% We &e-in &' descri&in- &riefl' the experiment!l
set"p "sed ori-in!ll' &' Der5!-"in Ein p!rtic"l!r +<>,H% Freshl' dr!n #"!rt3 c!pill!ries ere
pl!ced in !n ev!c"!ted -l!ss ch!m&er% 66!ter v!por !s !dmitted to the ch!m&er from !
comm"nic!tin- reservoir% /' m!int!inin- ! sm!ll temper!t"re difference &eteen the !ter
reservoir !nd the m!in vessel cont!inin- the #"!rt3 c!pill!r'( rel!tive !ter !ctivities &eteen
9%M9 !nd 9%MG co"ld &e !chieved +9%M9 W 2c!p$2s!t W 9%MG,% The c!pill!ries initi!ll' r!n-ed from
: to 30,' in di!meter &"t consider!&l' l!r-er c!pill!ries h!ve &een emplo'ed l!ter% Contr!r' to
expect!tion( !ter col"mns ere seen to form &' condens!tion from the s"&s!t"r!ted v!por
ph!se into the c!pill!r' t"&es% It is the !ter th"s prod"ced hich possesses hi-hl' !nom!lo"s
properties% The re!der is referred to the ritin-s &' Der5!-"in !nd coor.ers for det!ils( !s ell
!s to the reports &' l!ter investi-!tors% The essenti!l !nd hi-hl' !nom!lo"s properties of the
c!pill!r')condensed !ter !re1 +:, A densit' !ppro!chin- :%=9 -$cm3 +<, A coefficient of
therm!l exp!nsion ne!r room temper!t"re !&o"t @9P l!r-er th!n th!t for ordin!r' !ter +F,
/oilin- point li.el' -re!ter th!n <99KC% +=, A&sence of ! definite free3in- point +&"t !&le to
"nder-o ! noncr'st!lline tr!nsition !t !&o"t ) @9KC%* ith h'steresis, +@, 6iscosit' 8 to :@ times
th!t of ordin!r' !ter +>, App!rent densit' of the #"!sisolid !&o"t @P less th!n the li#"id +G,
Index of refr!ction of :%=8 C"ch of the ori-in!l or. !s initi!ted &' Fed'!.in( &"t the
phenomenon did not !ttr!ct -ener!l !ttention +or possi&l' !s not even t!.en serio"sl', "ntil the
present!tion &' Der5!-"in !t the disc"ssion of the F!r!d!' Societ' on 0Colloid St!&ilit' in
A#"eo"s !nd Non!#"eo"s Cedi!0 held !t the Universit' of Nottin-h!m to!rd the end of
Septem&er :M>>% Since th!t time( ! l!r-e n"m&er of investi-!tors h!ve tried( ith v!r'in-
de-rees of s"ccess( to prod"ce the !nom!lo"s !ter( determine its properties( !nd identif' its
str"ct"re% Amon- the noteorth' contri&"tions !re those of 2ethic! !nd coor.ers* see Willis et
al. +:=<,( /el!m' !nd coor.ers +M):G,* !nd Lippincott !nd coor.ers +8G,% Other p!pers h!ve
!ppe!red( mostl' cont!inin- spec"l!tions itho"t p!rtic"l!r reference to experiment!l or.%
Recentl'( Cr!tin !nd the present !"thor h!ve !n!l'3ed the !v!il!&le thermod'n!mic d!t! +from
Der5!-"inBs or., !nd considered the folloin- possi&le !ltern!tives1 +:, Anom!lo"s !ter m!'
&e the "ltim!te m!nifest!tion of lon-)r!n-e order( ori-in!tin- from the s"rf!ce% +<, Anom!lo"s
!ter m!' represent ! 0ne s"&st!nce0 (i.e., h'dro-en !nd ox'-en in ! com&in!tion not !.in to
ordin!r' !ter)! s"--estion m!de &' Der5!-"in !nd -iven consider!&le credence &' LippincottBs
or.,% +F, Anom!lo"s !ter m!' &e ! sol"tion of s"ch ! nonvol!tile modific!tion of !ter in
&"l. !ter +or in ordered !ter ne!r ! #"!rt3 s"rf!ce,% +=, Anom!lo"s !ter m!' &e !n !rtif!ct
d"e to s"ch sp"rio"s effects !s dissol"tion of -l!ss( #"!rt3( or other "ninterestin- cont!min!nts%
C. Distinction !et/een Anoalous Water and Surface $odified Water
(%i))incott;s Studies* As indic!ted in this section( it no !ppe!rs th!t !ter condensed from
"ns!t"r!ted v!pors in #"!rt3 c!pill!ries li.el' possesses properties hich !re v!stl' different
from the properties of !ter in &"l.% The res"lts &' Der5!-"in !nd coor.ers on this s"&5ect ill
li.el' ithst!nd close scr"tin' &' l!ter or.ers% 4oever( !ter !d5!cent to ! #"!rt3 s"rf!ce
+!nd( indeed( in #"!rt3 c!pill!ries, m!' !lso sho !nom!lo"s properties hich !re li.el' not
rel!ted to the properties of the Der5!-"in !nom!lo"s !ter% Rec!ll( for ex!mple( the v!por
press"re me!s"rements &' Shereshefs.' !nd coor.ers* the ener-' of !ctiv!tion me!s"rements
&' Sch"fle !nd coor.ers !nd &' the present !"thor* the d!mpin- of !ter)filled #"!rt3
c!pill!ries &' Forslind +recentl' confirmed &' Qerr !nd Drost)4!nsen,* the dis5oinin- press"re
me!s"rements &' 2eschel !nd Aldfin-er* some dielectric !nd n"cle!r m!-netic reson!nce d!t!*
the cond"ctivit' me!s"rements &' 4"&er !nd Flood* !nd the mech!nic!l ch!n-es in poro"s
#"!rt3 m!trices st"died &' Antonio"% The st"dies &' Der5!-"in( !s ell !s the l!ter st"dies &'
/el!m' !nd in p!rtic"l!r( &' Lippincott !nd coor.ers( stron-l' tend to s"--est th!t the
!nom!lo"s !ter condensed from !n "ns!t"r!ted !ter !tmosphere into +freshl' dr!n, #"!rt3
c!pill!ries constit"te ! ne 0compo"nd0 of h'dro-en !nd ox'-en% This compo"nd m!' ell
h!ve consider!&le st!&ilit' !nd possi&l' &e st!&le in the presence of ordin!r' +or str"ct"r!ll'
modified( vicin!l, !ter% Li.el'( the !nom!lo"s !ter h!s !t le!st li!ited st!&ilit' ith respect
to ordin!r' !ter% It m!' &e ! di"t"rn!l s'stem% The #"estion !rises then if !nom!lo"s !ter c!n
&e cre!ted from( or in the presence of( ordin!r' &"l. !ter% Accordin- to Lippincott !nd
coor.ers( the ener-' of form!tion of !nom!lo"s !ter m!' &e somehere &eteen >9 !nd :99
.c!l$-mol !ter +in the str"ct"r!l "nits,% Considerin- the mode of cre!tion of !nom!lo"s !ter
!nd the f!ct th!t all !ter on e!rth h!s not &een converted to s"ch +st!&le;, modific!tion( it c!n
pro&!&l' &e !scert!ined th!t !nom!lo"s !ter is never cre!ted in ordin!r' !ter Enor in !ter
ne!r !n interf!ce( !ss"min- th!t s"ch +0ordin!r' vicin!l0, !ter possesses the t'pes of str"ct"res
disc"ssed in this p!per)s"ch !s( cl!thr!te h'dr!te)li.e c!-es or hi-h)press"re ice pol'morphsN%
In other ords( once ordin!r' !ter is present( it !ppe!rs ver' "nli.el' th!t !n' 0c!t!l'tic
s"rf!ce0 sho"ld &e !&le to ind"ce !nom!lo"s !ter% This m!' &e the expl!n!) tion for the
o&serv!tion th!t !nom!lo"s !ter is !pp!rentl' formed most re!dil' +!nd possi&l' onl', on
freshl' dr!n #"!rt3 +or 2'rex, s"rf!ces% The effects of the freshl' dr!n s"rf!ce is pres"m!&l'
to !ct !s the necess!r' c!t!l'st for ! complete reh'&ridi3!tion of the !ter molec"le in the v!por
ph!se% Once formed( hoever( the !nom!lo"s !ter m!' in t"rn reh'&ridi3e !ddition!l
+monomeric, !ter molec"les !rrivin- via the v!por ph!se( &"t possi&l' not the molec"les in !
0&"l.0 ph!se% /' the s!me to.en( !nom!lo"s !ter m!' not pl!' !n' role in ordin!r' interf!ci!l
phenomen!( r!n-in- from !tmospheric condens!tion processes +possi&l' exceptin- phenomen!
in the "pper str!tosphere here extremel' lo p!rti!l press"res of !ter m!' exist, to ordin!r'
!#"eo"s to)ph!se s'stems* it cert!inl' !ppe!rs "nli.el' th!t the !nom!lo"s !ter ill pl!' !
role in &iolo-ic s'stems% On the other h!nd( the m!in theme of the present p!per is th!t lon-)
r!n-e orderin- of !ter ne!r !n interf!ce does occ"r !nd th!t this orderin- is most li.el' d"e to
+minor, str"ct"r!l reor-!ni3!tion of the &"l. str"ct"re !nd m!' li.el' !cco"nt for m!n'
!nom!lo"s properties of hetero-eneo"s( !#"eo"s s'stems%
D. Possi!le Connection !et/een Anoalous Water and Surface Structures If
Der5!-"inBs !nom!lo"s !ter is( indeed( ! ne t'pe of compo"nd( effected thro"-h
reh'&ridi3!tion of the !ter molec"les( the pro&lem is of limited interest onl' in connection
ith the m!in s"&5ect of this p!pern!mel'( the n!t"re of !ter ne!r interf!ces in -ener!l !nd the
possi&ilit' of lon-)r!n-e order of 0ordin!r'0 vicin!l !ter% S"ffice it to s!' th!t the evidence
seems to point to the sep!r!te existence of !n !nom!lo"s t'pe of ox'-en$h'dro-en)cont!inin-
compo"nd% The thermod'n!mic st!&ilit' of s"ch !nom!lo"s !ter ill &e disc"ssed in !
forthcomin- p!per &' Cr!tin !nd the present !"thor% 4oever( one sho"ld consider !n' possi&le
0&rid-e0 &eteen !nom!lo"s !ter !nd lon-r!n-e ordered str"ct"res% At the present time( onl'
one or to s"ch connectin- lin.s !ppe!r to exist% Densit' me!s"rements &' Sch"fle !nd
coor.ers( disc"ssed in Section 6III)C( h!ve indic!ted ! displ!cement to loer temper!t"res of
the temper!t"re of m!xim"m densit' !s ! f"nction of +decre!sin-, c!pill!r' di!meter% Simil!r
&eh!vior is o&served ith Der5!-"inBs !nom!lo"s !ter% 4oever( it !s reported recentl' th!t
direct densit' me!s"rements h!ve f!iled to sho !nom!lo"sl' hi-h densit' for the !ter for
hich Sch"fle +:<<, o&served the displ!ced temper!t"re of m!xim"m densit' +me!s"rements &'
R!&ide!" et at. !t Los Al!mos,% Th"s( !t present( it !ppe!rs someh!t "nli.el' th!t !nom!lo"s
!ter in the Der5!-"in sense is involved in the !ter in Sch"fleBs c!pill!ries !nd the experiments
&' Sch"fle !nd coor.ers pro&!&l' reflect merel' the t'pe of str"ct"r!l re!rr!n-ements hich
h!ve &een considered ne!r !n interf!ce in the present p!per% 2ossi&le densit' !nom!lies in the
t'pe of vicin!l !ter li.el' enco"ntered in Sch"fleBs c!pill!ries !re disc"ssed in the section on
models of !ter ne!r interf!ces% I t h!s &een con5ect"red recentl' +in v!rio"s reports in tr!de
5o"rn!ls, th!t the !ter ne!r ! cl!' s"rf!ce m!' &e of the s!me t'pe !s Der5!-"inBs !nom!lo"s
!ter% F!r more experiment!l or. m"st &e done &efore s"ch ! s"--estion c!n &e !ccepted%
4oever( sho"ld the s"--estion prove correct( it immedi!tel' indic!tes th!t !nom!lo"s !ter(
hile f!irl' re!dil' cre!ted( is not the thermod'n!mic!ll' f!vored species or !ll n!t"r!ll'
occ"rrin- !ter o"ld h!ve &een converted to !nom!lo"s !ter%
:I. STRUCTURA% INTERPRETATIONS AND SO$E SUPPORTIN+ E&IDENCE A.
As)ects of the Three4%a"er $odel If sep!r!te l!'ers of ordered +or disordered, str"ct"res
exist !d5!cent to ! s"rf!ce( the #"estion &ecomes import!nt !s to the n!t"re of the 0tr!nsition
re-ion0 over hich one str"ct"re 0dec!'s0 into !nother% This pro&lem !s reco-ni3ed e!rl' &'
s"ch !"thors !s Lo !nd 4enni.er)n!mel'( th!t if there existed ! lon-r!n-e ordered str"ct"re
ne!r cert!in solid s"rf!ces +s"ch !s #"!rt3,( hich extended into the &"l. li#"id for !
consider!&le dist!nce +s!'( "p to ! tenth of ! micron,( this ordered str"ct"re o"ld necess!ril'
h!ve to dis!ppe!r +li.el' exponenti!ll', ith dist!nce from the s"rf!ce &ec!"se of the effects of
therm!l motion in r!ndomi3in- the str"ct"re% Within the fr!meor. of the three)l!'er model(
proposed for the str"ct"re of !ter ne!r cert!in +pro&!&l' mostl' pol!r, s"rf!ces in the present
p!per( e m!' no in#"ire !s to ho !&r"pt !re the ch!n-es !t the to &o"nd!ries &eteen the
three str"ct"red ele!ents-i.e., &eteen the ordered str"ct"re ne!r the interf!ce( the disordered
3one( !nd the &"l. ph!se% If( indeed( the ordered re-ion ne!r the solid s"rf!ce is ch!r!cteri3ed &'
cl!thr!te c!-e)li.e str"ct"res Ecomp!re the :G A thic.ness of !dsor&ed l!'er on ! -l!ss s"rf!ce
descri&ed &' Der5!-"in !nd Aorin +<8,H( it is proposed th!t the &o"nd!r' &eteen the ordered
str"ct"re !nd disordered str"ct"re m!' &e #"ite sh!rp% Even in the presence of ! &"l. ph!se(
Der5!-"in !nd Q!r!ssev +<G, stressed the possi&le !&r"ptness of str"ct"r!l ch!n-es !nd
discreteness of the !dsor&ed !ter in their comments on this pro&lem1 "It is commonl' tho"-ht
th!t the orient!tion of the molec"les of ! li#"id sho"ld dis!ppe!r -r!d"!ll' in p!ssin- from the
s"rf!ce to the &"l.% This -ro"ndless !ss"mption( hoever( does not t!.e into !cco"nt the
pec"li!rities of condensed ph!ses( ch!r!cteri3ed &' intensive inter!ction &eteen nei-h&orin-
molec"les !nd contr!dicts the &eh!vior of li#"id cr'st!ls( hose molec"les !c#"ire or ch!n-e
the orient!tion !l!'s 5"mpise%0 F"rther1 0The ide! of molec"l!r orient!tion in pol'molec"l!r
&o"nd!r' l!'ers en!&les expl!n!tion of ! -re!t n"m&er of other effects( p!rtic"l!rl' the
depressed dielectric perme!&ilit' of pol'molec"l!r !dsorption l!'ers%0 Undo"&tedl'( one m"st
distin-"ish &eteen the pro&lem of the str"ct"re of ! fe molec"l!r l!'ers in ! solidi !ter$!ir
interf!ci!l s'stem !nd the str"ct"re of !ter ne!r ! -ener!l solid$!ter interf!ce% In the
folloin- sections e disc"ss these pro&lems in more det!il( dr!in- &oth on the precedin-
sections !s ell !s on !ddition!l experiment!l evidence% B. E2a)les9 #eat of Wettin. of
-eratin An import!nt st"d' !s m!de &' Corrison !nd 4!nl!n +MG, on the he!ts of ettin- of
ool).er!tin &' !ter% These !"thors me!s"red the differenti!l he!ts !nd entropies of ettin-
!nd s"--ested th!t 0!ter molec"les !re cl"sterin- on the ool s"rf!ce inste!d of formin- !
contin"o"s film !s in the c!se of sil. !nd cell"lose%0 F"rthermore( the' fo"nd the differenti!l
entrop' to -o thro"-h ! prono"nced m!xim"m for rel!tivel' lo s"rf!ce cover!-es% Fi-"re <9
shos the d!t! o&t!ined &' Corrison !nd 4!nl!n hile Fi-"re <:( !lso t!.en from the !rticle &'
these !"thors( shos the d!t! &' D"nford !nd Corrison% The hi-h entropies o&served in &oth
c!ses +for intermedi!te !mo"nts of !ter !dsor&ed, !re stri.in-% This is !n interestin-
o&serv!tion !s it is the t'pe of entrop' c"rve hich e mi-ht predict on the &!sis of ! three)
l!'er model% The present !"thor does not necess!ril' !-ree ith the !"thorsB !cco"ntin- of !ll
the different det!ils of the d!t! +in terms of the deposition of the v!rio"s l!'ers,% 4oever( it is
interestin- to #"ote Corrison !nd 4!nl!n re-!rdin- the !pp!rent complexit' of the !dsorption
phenomenon1 0Concernin- the -roth of the sor&ed l!'er( the present res"lts confirm h!t h!s
!lre!d' &een fo"nd for sil. fi&roin( other proteins( !nd even s"ch ! complex m!teri!l !s rice%
Th"s( in the c!se of .er!tin( !ter "p to n U 9%< mol enters the intermolec"l!r ch!ins to sep!r!te
them +in ! sense( to "nloc. them, !nd "p to 7. U 9%=@ or 9%@9( the first molec"l!r l!'er is
completed%0 Corrison !nd 4!nl!n !lso point o"t th!t Windle fo"nd it necess!r' to post"l!te !
third( intermedi!te species of sor&ed !ter to expl!in his micro!ve dielectric d!t! on the ool)
!ter s'stem% C. Adsor)tion of !t"# $!%o# o& #"dro)hilic Pol"ers C!s"3!! !nd
Sterlin- +8M, h!ve st"died the !dsorption of !ter v!por on fo"r different +h'drophilic,
pol'mers)n!mel'( !-!r( c!r&ox'meth'l cell"lose +CCC,( -el!tin( !nd m!i3e st!rch% One of the
interestin- res"lts !s th!t for !-!r !nd CCC( the initi!l v!l"es of the st!nd!rd differenti!l
entrop' of !dsorption &e-!n !t rel!tivel' lo v!l"es +!t !&o"t <9 e%"%,( rose to ! m!xim"m v!l"e
!nd decre!sed to!rd the &"l. v!l"e +F9 e%"%,% On the other h!nd( for -el!tin !nd st!rch( the
st!nd!rd differenti!l entrop' of !dsorption &e-!n !t ! hi-her level th!n for the &"l.( &"t !ll
s"&str!tes exhi&ited ! m!xim"m for !n intermedi!te v!l"e of !ter v!por !dsor&ed% In terms of
the three)l!'er model disc"ssed in the present p!per( the m!xim"m in the entrop' c"rve is
ex!ctl' h!t o"ld &e expected if ! disordered 3one exists !t some dist!nce from the immedi!te
s"rf!ce% D. Three4%a"er $odel for the Water,Cla" S"stes In connection ith the
proposed three)l!'er model( it is interestin- th!t ! simil!r ide! !s disc"ssed independentl' &'
Rosen#vist% We h!ve !lre!d' referred to h!t is essenti!ll' ! three)l!'er model( proposed &'
R!mi!h !nd Iorin- for !ter !d5!cent to v!rio"s ool constit"ents% Rosen#vistBs +::>, model
!s presented in connection ith ! disc"ssion of !ter !d5!cent to cl!' s"rf!ces% While the
disc"ssion( in -ener!l( -ives !n excellent pict"re of the st!te of conf"sion re-!rdin- the n!t"re of
!ter ne!r interf!ces( some of the rem!r.s &' Rosen#vist !re p!rtic"l!rl' pertinent% Fi-"re <<
shos( hi-hl' schem!ti3ed( the ide! proposed &' Rosen#vist% For ! dist!nce of onl' ! ver' sm!ll
n"m&er of !dsor&ed !ter l!'ers( ! cert!in ener-' of !ctiv!tion for some tr!nsport process +for
inst!nce( diff"sion, prev!ils( determined &' the ri-idit' of the oriented str"ct"re ne!r the
interf!ce% At s"fficientl' l!r-e dist!nces from the s"rf!ce( &"l. str"ct"re prev!ils( &"t 0in
&eteen(0 ! f!r -re!ter temper!t"re coefficient is expected)i%e%( hi-her !pp!rent ener-' of
!ctiv!tion% In his disc"ssion( Rosen#vist !s p!rtic"l!rl' concerned ith diff"sion of ions
+!nd$or !ter,( &"t ! simil!r -r!ph o"ld( "ndo"&tedl'( !ppl' to the ener-' of !ctiv!tion for
ionic cond"ction% The present !"thor feels th!t Rosen#vistBs -r!phic!l pict"re cont!ins some
import!nt elements of tr"th* hoever( the -r!ph m!' li.el' need to &e 0inverted(0 in the sense
th!t the disordered 3one m!' &e p!rtic"l!rl' cond"cive to the movement of !ter molec"les !nd
ions% In either c!se( it is li.el' th!t Rosen#vist h!d essenti!ll' the correct ide! hen he
s"--ested th!t 0s"ch ! meltin- of( s!'( the third( fo"rth( !nd fifth molec"l!r l!'ers from the
s"rf!ce of the miner!l m!' expl!in most of the r!ther conf"sin- diff"sion d!t!%0 A-!in( it is
"ndo"&tedl' d!n-ero"s to -ener!li3e on st"dies &!sed on cl!'s( here so m!n' other dist"r&in-
effects m!' t!.e pl!ce% E. Dielectric Evidence for Discrete Order4Disorder
Phenoena. Let "s !ss"me th!t !n incre!se in the n"m&er of !dsor&ed l!'ers of !ter on !
solid s"rf!ce le!ds to different str"ct"r!l re-imes% For inst!nce( 0ti-ht0 &ondin- !nd hi-h de-ree
of order for lo cover!-e +s!' ! fe molec"l!r l!'ers,( enh!nced disorder "pon f"rther
deposition !nd fin!ll'( more &"l.)li.e l!'ers for m"ltil!'er !dsorption% It sho"ld then &e
possi&le to demonstr!te s"ch &"ild)"p &' contin"o"s me!s"rements +!s ! f"nction of time, of
v!rio"s p!r!meters rel!ted to the s"rf!ce properties d"rin- the process of deposition of !ter
molec"les on the s"rf!ce% Id! !nd Nishim"r! +>F, h!ve performed ex!ctl' s"ch experiments%
These !"thors monitored the c!p!cit!nce ch!n-es d"rin- the !dsorption of moist"re onto ! 0dr'0
sod! lime +0soft0, -l!ss pl!te hen the pl!te !s s"ddenl' exposed to ! MFP rel!tive h"midit'
environment% A not!&le m!xim"m in the c!p!cit!nce !s o&served !fter ! fe min"tes of
expos"re( folloed &' ! minim"m !nd ! s"&se#"ent rise( hich event"!ll' led to ! 0pse"do)
e#"ili&ri"m0 v!l"e% D"!ntit!tivel'( the effect-i.e., the development of !n initi!l m!xim"m(
folloed &' ! minim"m !nd ! s"&se#"ent rise)decre!sed ith decre!sin- temper!t"res% In other
ords( !t loer temper!t"res the !dsor&ed molec"les in the disordered l!'er !ppe!red more
ri-idl' &o"nd% Someh!t simil!r res"lts ere o&t!ined ith pl!tes of ! di!tom!ceo"s e!rth% In
this c!se( the phenomenon !s st"died &oth d"rin- !dsorption !nd desorption of moist"re*
!-!in( rel!tive m!xim! !nd minim! ere seen% '. Water in <eolites Corris (95) h!s st"died
the he!ts !nd entropies of !dsorption of !ter on Linde =)A !nd @)A 3eolites% C!n' of the
res"lts o&served ere re!dil' expl!in!&le in terms of the expected &eh!vior for !ter in the
str"ct"r!l c!vities of the 3eolites% 4oever( some res"lts ere s"rprisin-( p!rtic"l!rl' the
incre!se in the resid"!l entrop' of the !dsor&ed !ter +on ! =)A 3eolite, for !ter contents
!&ove !pproxim!tel' << molec"les per "nit% While Corris s"--ests th!t this phenomenon m!'
&e d"e to none#"ili&ri"m conditions prev!ilin- d"rin- the experiment( the !ltern!tive possi&ilit'
sho"ld &e considered)n!mel'( th!t ! disordered str"ct"re &e-ins to form !s implied in the three)
l!'er model% +. Water on Seru Al!uin9 Evidence of &arious De.rees of Orderin.
F"ller !nd /re' +=M, st"died !ter !dsor&ed on ser"m !l&"min &' NCR techni#"es% Amon-
their res"lts is ! set of d!t! for the ener-' of !ctiv!tion for tr!nsverse n"cle!r m!-netic
rel!x!tion of the !ter protons% The sh!pe of this c"rve resem&les the sh!pe hich o"ld &e
predicted from the three)l!'er model disc"ssed in the present p!per% Fi-"re <F( t!.en from the
p!per &' F"ller !nd /re'( shos this v!ri!tion of the !pp!rent ener-' of !ctiv!tion +for the
tr!nsverse m!-netic rel!x!tion of the protons of !ter on solid ser"m !l&"min, !s ! f"nction of
the !mo"nt of !ter present% The !pp!rent ener-' of !ctiv!tion +!t lo temper!t"re, drops from
! v!l"e of !pproxim!tel' 8 .c!l5-mol for ver' lo !ter contents to F .c!l5-mol !s the !ter
content incre!ses from =@ m- 4 29$- protein to :99 m- 4 29$- protein% A&ove this v!l"e !nd "p
to 1%0 m- 4 29$- protein( the ener-' of !ctiv!tion !-!in incre!ses to ! v!l"e of !&o"t =%@
.c!l5-mol( hile f"rther !ddition of !ter merel' res"lts in ! ver' sli-ht decre!se +"p to !&o"t
F@9 m- 4 29$- protein,% The !"thors estim!te ! n"m&er of pol!r -ro"ps in the protein s"fficient
to &ind G> m- 4 29$- protein in ! one)to)one r!tio +!ter molec"les per pol!r -ro"p,% The
dependence +!t lo temper!t"re, of the !pp!rent ener-' of !ctiv!tion th"s p!r!llels ex!ctl' the
predictions from o"r modeL The 0innermost0 !ter is ti-htl' &o"nd !nd str"ct"red( folloed &'
! mo&ile disordered 3one !s !n intermedi!te( !nd fin!ll'( ! more or less "n!ffected( 0&"l.)li.e0
!ter str"ct"re% Another interestin- res"lt of the st"d' &' F"ller !nd /re' is the o&serv!tion th!t
!t :G> m- 4 29$- protein +correspondin- to ! cover!-e hich co"ld h!ve extended &e'ond the
ordered str"ct"red r!n-e( into the disordered 3one,( ! not!&le &re!. occ"rs ne!r F@KC% The
!"thors( in one of their ill"str!tions( cle!rl' sho this &' the intercept of to str!i-ht)line
se-ments% For ! concentr!tion of :<8 m- 4 29$- protein( no s"ch !nom!l' !s o&served(
here!s in the presence of l!r-e !mo"nts of !ter +correspondin- to cover!-e incl"din- !ter
of the more &"l.)li.e properties,( ! definite anomal is indic!ted in the vicinit' of )<9KC% +In
this l!tter c!se( it m!' &e noteorth' th!t the point o&served !t F@KC% is still si-nific!ntl' !&ove
the str!i-ht)line se-ment coverin- the hi-her temper!t"re re-ion%, #. Distri!ution of Water
on Availa!le Sites on a Surface A serio"s so"rce of concern in !ll !dsorption st"dies
Econfer( hoever( p!pers s"ch !s th!t &' Corrison !nd 4!nl!n +MG, H is the pro&lem of the
distri&"tion of the !dsor&!te% For pol!r m!teri!ls( it is norm!ll' !ss"med th!t the initi!l &indin-
t!.es pl!ce &' specific !dsorption on r!ndoml' distri&"ted pol!r sites% Onl' r!rel' is the
!ltern!tive possi&ilit' disc"ssed)th!t ! sm!ller n"m&er of s"ch sites m!' form the initi!l
0isl!nds0 of deposition ith the next +m!n', !ter molec"les &ein- !ssoci!ted directl' ith the
initi!ll' deposited !ter molec"les r!ther th!n on other !v!il!&le sites% All sites !re li.el' not
e#"iv!lent* if the' ere( one o"ld expect th!t the res"lts &' F"ller !nd /re' +=M, o"ld reve!l
! hi-h const!nt ener-' of !ctiv!tion +for the tr!nsverse n"cle!r m!-netic rel!x!tion of the !ter
protons !dsor&ed on the solid ser"m !l&"min, !s ! f"nction of !pp!rent cover!-e% 4oever( the
o&serv!tions !re #"ite to the contr!r'* the ener-' of !ctiv!tion drops exceedin-l' sh!rpl' from
!&o"t 8 .c!l$-mol +!t !pproxim!tel' =G m- 4 <9$- protein( correspondin- to 9%>< !ter
molec"le per pol!r -ro"p, to = .c!l5-mol for 7' m- 4 29$- protein +correspondin- to 9%MF
!ter molec"le per pol!r -ro"p of the protein,% Another distressin- f!ct !&o"t most st"dies of
the properties of !ter ne!r solid s"rf!ces is the -re!t v!ri!&ilit' of the s"rf!ces st"died% 6er'
fre#"entl'( me!s"rements h!ve &een m!de "nder conditions hich !re f!r from comp!r!&le%
Th"s( st"dies of !ter !dsor&ed on ! nonpol!r solid h!ve often &een exemplified &' st"dies of
!ter !dsor&ed on -r!phite here the effective pore di!meter is li.el' of the order of onl' :@ A%
On the other h!nd( st"dies on !l"min!( hich is o&vio"sl' pol!r( represent !ter in &oth micro
pores +ith r!dii( s!'( less th!n @9 A) !nd in m!cropores +ith r!dii of more th!n !n order of
m!-ni t"de l!r-er,% As !nother ex!mple( st"dies of !ter in 3eolites impl' the st"d' of !ter in
exceedin-l' sm!ll c!vities +for inst!nce( > A di!meter,% 6er' fe st"dies h!ve &een m!de on
ener-etic!ll' homo-eneo"s s"rf!ces* most of the solids "sed for the st"d' of !ter$solid
inter!ctions h!ve( in f!ct( ver' &ro!d distri&"tions of l!ttice ener-ies ith v!r'in- n"m&ers of
hi-h ener-' sites% O&vio"sl'( f"rther complic!tions !re introd"ced in the st"d' of solids ith
hi-h s"rf!ce ch!r-e deficits or excesses)s"ch !s ion)exch!n-e m!teri!ls or proteins ith l!r-e
n"m&ers of pol!r !nd ioni3!&le -ro"ps% :II. $O%ECU%AR ASPECTS O' &ICINA%
WATER STRUCTURE A. Structure of Water Evidence is overhelmin- for !nom!lo"s
properties of !ter +!nd !#"eo"s sol"tions, ne!r m!n' interf!ces* hence( str"ct"r!l differences
m"st "ndo"&tedl' exist &eteen &"l. !ter !nd vicin!l !ter% Unfort"n!tel'( the !mo"nt of
incontroversi!l inform!tion !v!il!&le re-!rdin- the /'l0 str"ct"re of !ter is extremel' limited%
ESee( for inst!nce( W!lr!fen !nd Irish +:FM,H% If e t!.e for -r!nted str"ct"r!l differences
&eteen &"l. !nd vicin!l !ter( it o"ld &e hi-hl' "sef"l to .no h!t t'pes of str"ct"red
elements c!n exist in &"l. !ter% We c"rrentl' do not h!ve s"ch inform!tion ith !n' de-ree of
cert!int'* in f!ct( it rem!ins to &e seen if the -ross str"ct"re of !ter on the molec"l!r level is
&est represented &' ! contin""m +nonstr"ct"recont!inin-, model or ! mixt"re model +in Fr!n.Bs
sense of the ord,% The present st"d' !s not intended to thro li-ht on the #"estion of the &"l.
str"ct"re of !ter% If one notes( hoever( the m!n' ex!mples hich s"--est the possi&le
existence of discrete interf!ci!l str"ct"res( it m!' &e !r-"ed th!t either &"l. !ter !lre!d'
cont!ins str"ct"red elements)!nd it is these str"ct"res hich &ecome st!&ili3ed &' the
interf!cesor( in the !ltern!tive( th!t s"ch str"ct"res !re l!tentl' present or !t le!st re!dil' ind"ced
!nd st!&ili3ed &' the presence of !n interf!ce% B. $eanin. of the Word 3Structure3 in
%i0uid Water and Near Surfaces The present !"thor &elieves th!t the model for the
str"ct"re of !ter hich is most li.el' to prove correct is one involvin- the existence of discrete
str"ct"r!l elements% Cost li.el' c!ndid!tes !s str"ct"r!l "nits !re those !ssoci!ted ith !
mixt"re model cont!inin- str"ct"red cl"sters s"ch !s cl!thr!te c!-es or hi-hpress"re ice
pol'morphs in e#"ili&ri"m ith monomeric molec"les% 4ere( !s !l!'s( the re!der is !rned
!-!inst the d!n-er of -ener!li3in- the notion of str"ct"r!l entities to me!n 0discrete( perm!nent(
microcr'st!lline ch"n.s0 of one form of l!ttice or other% Recentl'( Eisen&er- !nd Q!"3m!nn
+=9, -!ve ! -ood disc"ssion of the ver' me!nin- of the term 0str"ct"re0 !s it !pplies to li#"id
!ter% S"ffice it here to s!' th!t on -ener!l -ro"nds( !s ell !s in vie of the str"ct"r!l
implic!tions of this p!per( e sh!ll !dopt ! concept"!l model of !ter involvin- str"ct"red
elements !nd disc"ss the li.el' occ"rrence of specific str"ct"red entities !d5!cent to v!rio"s
interf!ces% Th"s( notithst!ndin- the recent criticism of the "tilit' of the concept of !ter
str"ct"re in -ener!l +>9, the "se of str"ct"r!l models !ppe!rs hi-hl' pr!ctic!l for the disc"ssion
!t h!nd% A-!in( it m"st &e emph!si3ed th!t the str"ct"r!l entities envisioned !re not 0st!&le(
perm!nent microcr'st!lline ch"n.s0* r!ther( the' !re distorted !ppe!r!nces of elements ith
identifi!&le s'mmetries or other str"ct"r!l fe!t"res possessin- the ch!r!cteristics of flic.erin-
cl"sters% In other ords( the' m!' s"ffer fre#"ent disr"ptions d"e to therm!l motions( &"t hen
recre!ted elsehere in the li#"id vol"me "nder consider!tion( !-!in present ! preponder!nce of
one str"ct"r!ll' ch!r!cteris) => I ( ) * S + , I A - A() E(. I (EE , I ( . / 0EM 1S+ ,
1 tic element or !nother)for inst!nce( the occ"rrence of pent!-on!l rin-s or simil!r -eometric
identifi!&le fe!t"res% Undo"&tedl'( the essenti!l point in this disc"ssion is the tempor!l st!&ilit'
of s"ch identifi!&le ch!r!cteristics% When disc"ssin- str"ct"re ne!r !n interf!ce( the implic!tion
is onl' th!t the str"ct"re "nder consider!tion m!' h!ve ! lifetime hich is not!&l' lon-er th!n
the correspondin- lifetime of the str"ct"red entit' in the &"l. of the li#"id% It rem!ins to &e
determined hether this me!ns !n incre!se in the rel!x!tion time &' !n order of m!-nit"de +s!'(
from :9):: to :9):9 sec,( or !n incre!se correspondin- to the incre!se in +dielectric, rel!x!tion
time on -oin- from !ter to ice% Undo"&tedl'( f"t"re refinements of dielectric !nd NCR st"dies
ill thro consider!&le li-ht on this #"estion% C. #i.h Pressure Ice Pol"or)hs and
Clathrates Re-!rdin- the str"ct"re of &"l. !ter( the folloin- is noted in p!ssin-% The
present !"thor &elieves th!t &"l. !ter does not possess elements of Ice)Ih li.eness Efor !
disc"ssion of this pro&lem +FG( F@,H% 4oever( m!n' other str"ct"r!l possi&ilities exist hich
m!' expl!in &oth the str"ct"re of !ter in -ener!l( !s ell !s the str"ct"re of !ter ne!r !n
interf!ce% Th"s( !t le!st nine hi-h)press"re ice pol'morphs !re .non +s"ch !s Ice II !nd Ice
III,* for ! l"cid description of these( see the !rticle &' Q!m& (73) or the recent mono-r!ph &'
Eisen&er- !nd Q!"3m!nn +=9,% F"rthermore( m!n' t'pes of cl!thr!te)c!-e h'dr!te str"ct"res !re
.non% Th"s( there is no l!c. of 0str"ct"red forms0 of !ter ith hich to constr"ct concept"!l
models% D. Solid,Water and Solid,Water,Air Interfacial S"stes In connection ith
m!n' st"dies of !ter ne!r interf!ces( incl"din- sever!l of those s'stems disc"ssed in the
present p!per( ! cle!r distinction m"st &e m!de &eteen the folloin- to t'pes1 ! solid$!ter
interf!ce)here the thic.ness of the !#"eo"s ph!se is consider!&le( s!'( more th!n :9(999
molec"l!r di!meters)!nd the solidi !ter$!ir +or v!por, t'pe of s'stem)in other ords( ! three)
ph!se s'stem% This distinction( hile o&vio"s( is often not emph!si3ed in disc"ssions of the
#"estion of orderin- ne!r interf!ces% Cle!rl'( the three)ph!se s'stem possesses to opposin-
!#"eo"s interf!ces% In vie of the li.el' str"ct"rin- of !ter ne!r the !ter$!ir interf!ce(
consider!&l' different res"lts m!' &e o&t!ined re-!rdin- the str"ct"re of vicin!l !ter from
st"dies of the to t'pes of s'stems% EFor evidence of str"ct"rin- of !ter !t the !ter$!ir
interf!ce see( in p!rtic"l!r( Drost)4!nsen +F=,H% E. Possi!le Structures of &icinal Water In
the folloin- sections( e descri&e to possi&le !ltern!tive !'s of loo.in- !t str"ct"res of
vicin!l !ter% The first is concerned solel' ith the de-ree of orderin- of the !ter molec"les(
hich m!' &e expected ne!r three t'pes +cl!sses, of s"rf!ces !nd some most tent!tive -"esses !t
dist!nces over hich str"ct"rin- m!' occ"r% In the folloin- section( specific molec"l!r models
!re disc"ssed &riefl'% We sh!ll consider the three folloin- t'pes of !ter$ solid interf!ces (i.!.,
the interf!ce &eteen to semiinfinite vol"mes in cont!ct,% The first is ! completel' nonpol!r
s"rf!ce +s!'( the s"rf!ce of ! solid h'droc!r&on, * the second is ! stron-l' pol!r s"rf!ce +s"ch !s
#"!rt3,* the third is the s"rf!ce of ! completel' ionic solid +of lo sol"&ilit',% It sho"ld &e
re!li3ed from the &e-innin- th!t the c!ses considered !re &oth extremes !nd h'pothetic!l !nd do
not !llo for s"ch items !s s"rf!ce irre-"l!rities !nd !dsor&ed ions% The "s"!l +!nd li.el' hi-hl'
"nre!listic, !ss"mption is m!de th!t the s"rf!ce c!n &e represented &' !n 0infinite smooth
pl!ne%0 Ad5!cent to the nonpol!r s"rf!ce( !ter m!' &ecome str"ct"red &' h'dropho&ic
inter!ction% Th"s( !ctin- !s ! moment"m sin. for therm!l fl"ct"!tions( the solid m!' st!&ili3e
str"ct"r!l "nits !lre!d' present in the &"l. or ind"ce +l!tentl' existin-, str"ct"res in the !ter%
Considerin- the st!&ilit' of cl!thr!te h'dr!tes !nd the li.el' occ"rrence of str"ct"red entities
even !t !n !ir $ !ter interf!ce( the dist!nce over hich si-nific!nt str"ct"rin- m!' occ"r
&ec!"se of s"ch st!&ili3!tion is -"essed !t somehere &eteen tens !nd h"ndreds +or more, of
molec"l!r di!meters% The ind"ced( st!&ili3ed str"ct"res ill dec!' ith dist!nce from the
s"rf!ce% If the str"ct"re of &"l. !ter proves to &e( for inst!nce( ! mixt"re of monomers !nd
hi-h press"re ice pol'morphs E!ccordin- to Q!m&( possi&l' incl"din- Ice)Ih +GF,H( ! 3one of
disorder m!' exist &eteen the vicin!l !ter +if it is( indeed( cl!thr!te c!-e)li.e, !nd the &"l.%
This possi&ilit' is s"--ested &' the dotted c"rves in Fi-"re 24a. In this connection( if the vicin!l
!ter str"ct"re ne!r ! nonpol!r s"rf!ce is( indeed( cl!thr!te c!-e)li.e)i%e%( if the str"ct"re
provides discrete sites +voids, for sm!ll molec"les)it is then to &e expected th!t s"ch vicin!l
!ter m!' le!d to si-nific!nt !dsorption of cert!in sol"tes% +See Fi-"re <>%, This ide! is the
essence of the theor' of !nesthesi! proposed independentl' &' 2!"lin- !nd &' Ciller% If the
str"ct"red entities vicin!l to the solid prove to &e one or more of the hi-h)press"re ice
pol'morphs( &"t the str"ct"re of &"l. !ter is discovered to &e &est descri&ed &' ! cl"ster model
or cl!thr!te h'dr!te model( ! 3one of disorder mi-ht still exist% Fi-"re 24/ shos the possi&le
de-ree of orient!tion of !ter molec"les ne!r ! pol!r s"rf!ce% The so"rce of orient!tion !t the
interf!ce( dependin- on the chemic!l n!t"re of the solid( co"ld &e either h'dro-en &ondin- or
dipole)dipole inter!ctions% It seems re!son!&le to !ss"me th!t the orderin- o"ld decre!se
consider!&l' more r!pidl' ith dist!nce from the s"rf!ce th!n in the c!se of ! nonpol!r s"rf!ce%
Dependin- on the dissimil!rit' &eteen the ordered +s!'( dipole)dipole,( ind"ced str"ct"re ne!r
the interf!ce !nd the &"l. str"ct"re( v!rio"s thic.nesses of the ordered l!'ers !re possi&le%
Fin!ll'( e consider !n ionic s"rf!ce( Fi-"re 24c. In this c!se( stron- ion)dipole inter!ctions
m!' occ"r( -ivin- rise to ti-htl' &onded !ter !d5!cent to the interf!ce% The n!t"re !nd de-ree
of str"ct"rin- ill( "ndo"&tedl'( depend on the n!t"re of the solid !nd !lso on the diff"se do"&le
l!'er% ~eglecting for the time &ein- electric!l do"&le l!'er effects( one mi-ht expect th!t the
ordered str"ct"res in the c!se of !ter ne!r !n ionic solid !re the ones le!st comp!ti&le ith the
str"ct"re of &"l. !ter !nd( hence( dec!' most r!pidl'% If this is the c!se( then)&ec!"se of the
ver' dissimil!rit'the disordered 3one mi-ht( in this c!se( &e most prono"nced% 4oever( the
#"estion no !rises hether ordered str"ct"res c!n &e ind"ced &' the innermost dipole)oriented
l!'ers% The !nser to this #"estion seems to &e 0'es%0 C!n' c!ses of therm!l !nom!lies !re
noted in the properties of vicin!l !ter ne!r &oth pol!r !nd ionic s"rf!ces +see( for inst!nce(
Fi-"res =( ::( :F( !nd :=,% This s"--ests( then( th!t s"ch str"ct"rin- does indeed occ"r even ne!r
ionic s"rf!ces( &"t this is not necess!ril' in dis!-reement ith ! re!son!&le extension of the
Fr!n.)Wen model% /l!nd!mer !nd S'mons +:<, c!ll !ttention to the stron- inter!ctions le!din-
to 0str"ct"rin-0 in the second +or more dist!nt, l!'ers of !ter of h'dr!tion% The !ter
molec"les ne!rest the ion find themselves in ! stron- centro)s'mmetric field% 4oever(
nei-h&orin- l!'ers ill &e oriented onl' in p!rt &' the centros'mmetric field* dipole)dipole
inter!ctions ill !lso pl!' !n import!nt role% This( then( m!' le!d to the st!&ili3!tion of specific
!ter str"ct"res% This modific!tion or extension of the Fr!n.)Wen model !s disc"ssed &'
Drost4!nsen +FG,% Colec"les f!rther !!' from the ion m!' not even &e !ffected notice!&l'%
Indeed( recent ne"tron inel!stic sc!tterin- d!t! &' S!fford et al. +person!l comm"nic!tion( :M>M,
s"--est th!t in rel!tivel' concentr!ted sol"tions( s!' &elo 1.%", elements of !ter str"ct"re
rem!in in spite of the closeness of !ppro!ch of ions in s"ch sol"tions% ESee !lso Drost4!nsen
+FG,%N 4ence( ordered str"ct"res m!' occ"r !d5!cent to !n ionic solid +this possi&ilit'( hoever(
h!s not &een shon in Fi-"re 24c). To s"m "p1 The n!t"re !nd extent of the orderin- of the
!ter molec"les immedi!tel' !d5!cent to the interf!ce ill( to ! l!r-e extent( determine hether
! disordered 3one ill exist* in other ords( ! disordered 3one ill depend on the str"ct"r!l
dissimil!rit' &eteen the vicin!l !ter !nd the &"l. !ter% .. Molecular Models for -icinal
Water We fin!ll' !ttempt ! 0molec"l!r0 interpret!tion in terms of some conceiv!&le vicin!l
str"ct"res% Fi-"re <@ shos ! possi&le interf!ci!l str"ct"re for !ter ne!r ! pol!r s"rf!ce% The
!ter molec"les ne!r the solid !re oriented &' dipole)dipole inter!ctions% These inter!ctions !re
not li.el' to prop!-!te over ver' m!n' molec"l!r di!meters% S"fficientl' f!r removed from the
s"rf!ce !re the str"ct"res in &"l. !ter% In Fi-"re <@ these !re indic!ted &' pent!-on!l circ"its
!nd p!rti!l pent!-on!l o"tlines% These o"tlines !re intended to conve' onl the presence of
-eometric!ll' identifi!&le str"ct"r!l entities +&"t not necess!ril' str"ct"res rel!ted to pent!-on!l
dodec!hedr! or other cl!thr!te)li.e "nits, &e the' cl"sters( cl!thr!te c!-e)li.e or hi-h)press"re
ice pol'morphs% It is s"--ested th!t the str"ct"red entities !re in e#"ili&ri"m ith monomeric
!ter molec"les +indic!ted &' !rros, !nd possi&l' present voids or 0sites0 hich m!'or m!'
not &e occ"pied &' individ"!l !ter molec"les +the 2!"lin- !nd the Fr!n.D"ist model for
!ter,% The intermedi!te 3one is the disordered tr!nsition &eteen the ordered vicin!l !ter
str"ct"re !nd the differentl' str"ct"red &"l.% Simil!r concept"!l models c!n e!sil' &e
constr"cted for the other c!ses disc"ssed in the precedin- p!r!-r!phs* one s"ch c!se is shon in
Fi-"re <>% Onl' limited pro-ress c!n &e expected re-!rdin- det!ils of vicin!l !ter str"ct"re
"ntil ! -ener!l theor' of &"l. !ter str"ct"re h!s &een re!ched% 4oever( cert!in fe!t"res of
!ter ne!r interf!ces m!' still &ecome !pp!rent &efore ! more complete "nderst!ndin- of &"l.
!ter is !chieved% +. Densit" of &icinal Water 6icin!l !ter ith ! densit' l!r-er th!n th!t
of &"l. !ter li.el' exists% Incre!sed densit' c!n &e prod"ced in ! l!ttice in hich interstiti!l
sites +in the fr!meor., !re occ"pied &' monomeric !ter molec"les% S!moilov +GGM, !nd
Forslind +=F,( for inst!nce( h!ve disc"ssed the fillin- of the voids in !n Ice)Ih l!ttice &'
monomers* !nother possi&ilit' comes from the tre!tment &' 2!"lin- !nd &' Fr!n. !nd D"ist1 the
densit' of +&"l., !ter c!n &e !cco"nted for &' v!rio"s de-rees of fillin- of the interstiti!l sites
in cl!thr!te c!-e)li.e str"ct"res% Simil!r effects sho"ld( "ndo"&tedl'( &e considered !lso for
!ter ne!r interf!ces% 4oever( in !ddition( incre!sed densit' for vicin!l !ter m!' !lso res"lt
from the presence of ! disordered 3one ith closer p!c.in- of the !ter molec"les +see Note
Added in 2roof,% #. Possi!le De)th of Surface Orientation The models presented !&ove
!re o&vio"sl' hi-hl' h'pothetic!l( &"t not necess!ril' ph'sic!ll' "nre!son!&le% In !pplic!tions
to 0re!l0 s'stems( !cco"nt m"st &e t!.en of the effects of ch!r-es !t the s"rf!ce +s"ch !s those
d"e to !dsor&ed ions( ch!r-e defects or excesses in the solid( !nd p!rti!l "nshieldin- of ch!r-es,(
!s ell !s of the specific effects of ionic sol"tes on the !ter str"ct"re% 4oever( &ec!"se of its
ten"o"s n!t"re !nd the complexit' of the proposed models( it h!rdl' seems orthhile !t this
time to spec"l!te in det!il !s to the effects of( s!'( specific ion)!dsorption% The depth of the
v!rio"s l!'ers involved h!ve not &een disc"ssed in !n' -re!t det!il% These depths !re o&vio"sl'
even more "ncert!in th!n the possi&le str"ct"res themselves% Th"s( the l!r-est m!r-in of error
m"st &e !ss"med% The r!n-e of the st!&ili3ed str"ct"res( ne!r ! nonpol!r s"rf!ce( referred to here
!s 0lon-)r!n-e ordered str"ct"re(0 m!' li.el' &e !t le!st three or fo"r di!meters of pent!-on!l
dodec!hedr! !nd possi&l' f!r more +of the order of h"ndreds to tho"s!nds molec"l!r di!meters,%
The disordered re-ion( in p!rtic"l!r !t some dist!nce from ! pol!r or ionic s"rf!ce m!'( in t"rn(
extend over onl' ! fe molec"l!r di!meters of !ter molec"les( or perh!ps( !s m!n' !s :9
di!meters% The thic.ness of the l!'ers of oriented dipoles +effected &' dipole)dipole inter!ctions
&eteen consec"tive l!'ers,( sho"ld s"ch dipole orient!tion !ct"!ll' occ"r( ill most li.el'
dec!' over ! dist!nce of( s!'( :9 molec"le di!meters or less)pro&!&l' less% 4oever( the
disordered 3one in this c!se m!' prove consider!&l' l!r-er% I. O))osin. &ie/s of Water
Near Interfaces As mentioned elsehere in this p!per( Torrence C!rtin h!s( for some time(
!dvoc!ted the existence of incre!sed disorder of !ter ne!r cl!' s"rf!ces% The concl"sion(
re!ched from ! c!ref"l st"d' of entropies of !dsorption( !s th!t the v!l"es for the entropies
!l!'s exceed the entrop' of norm!l( li#"id !ter% C!rtin +88, s"--ested specific!ll' th!t 0the
folloin- is presented !s ! possi&le !ltern!tive h'pothesis for the sor&ed ph!se in hich inste!d
of &"ildin- the sor&ed ph!se o"t!rd from the solid s"rf!ce to li#"id !ter( one &"ilds in!rd
from the li#"id !ter to the solid s"rf!ce%0 This concept is !n !d!pt!tion to the cl!')!ter
s'stem of c"rrent theories for the !ter str"ct"re in electrol'te sol"tions EFr!n. !nd Wen +=>, N%
The difference &eteen the model proposed &' C!rtin !nd the one proposed &' the present
!"thor is &est seen &' the 5"xt!position of the concl"sions &' C!rtin +in the p!per cited, !nd the
ide!s s"--ested &' the present !"thor% CARTIN% "It is proposed th!t the sor&ed ph!se( the
interf!ci!l re-ion &eteen solid !nd norm!l li#"id( consists not of !n ordered str"ct"re &"t of !
!ter str"ct"re more disordered th!n th!t fo"nd in li#"id !ter% The disordered str"ct"re
-r!d"!ll' &ecomes more ordered "ntil !t some dist!nce from the cl!' s"rf!ce( !ter str"ct"re is
!-!in th!t of norm!l li#"id !ter%0 2RESENT AUT4OR% W!ter ne!r cert!in( !nd possi&l' most(
s"rf!ces is ordered% The de-ree of orderin- decre!ses ith the dist!nce from the solid% The
n!t"re !nd extent of the orderin- ill depend critic!ll' on the n!t"re of the solid% For !t le!st
cert!in t'pes of s"rf!ces( perh!ps p!rtic"l!rl' pol!r s"rf!ces( ! possi&le model consists of !
l!'er of ordered +str"ct"red, !ter ne!r the solid s"rf!ce* the orderin- extends into the &"l.
li#"id !nd( !s deline!ted !&ove( decre!ses !s ! f"nction of dist!nce from the interf!ce% As the
de-ree of str"ct"redness is decre!sed( the loc!l disorder is incre!sed% At s"fficientl' l!r-e
dist!nces from the s"rf!ce( &"l. !ter str"ct"re exists% /eteen the +"n.non, str"ct"re of the
&"l. !ter +possessin- loc!l order, !nd the ordered !ter ne!r the interf!ce( there m!' &e !
re-ion of enh!nced disorder +!.in to the disordered str"ct"re post"l!ted in Fr!n.)Wen model of
h'dr!tion, in those c!ses here the vicin!l !ter str"ct"re differs si-nific!ntl' from the &"l.
str"ct"re% :III. SU$$AR1 The experiment!l o&serv!tions disc"ssed in the present p!per seem
s"fficient to !rr!nt !t le!st to concl"sions ith some de-ree of cert!int' !nd perh!ps to
someh!t more tent!tive concl"sions% The first concl"sion is th!t the str"ct"re of !ter ne!r !
!ter$solid interf!ce fre#"entl' !ppe!rs si-nific!ntl' different from the str"ct"re of !ter in
&"l.% The second concl"sion is th!t the vicin!l !ter str"ct"res m!' !pp!rentl' &e prop!-!ted
over consider!&le dist!nces from the s"rf!ce into the &"l. li#"id% The !v!il!&le evidence( on
hich these to concl"sions rest( consists essenti!ll' of to sep!r!te t'pes of !r-"ments1 it !s
first !sserted th!t( &ec!"se therm!l !nom!lies !ppe!r to exist in the properties of !ter ne!r
interf!ces( &"t do not seem overtl' m!nifested in &"l. properties +of p"re !ter,( it c!n &e
concl"ded th!t str"ct"red elements exist ne!r +!t le!st some, !ter$solid interf!ces% The second
t'pe of evidence for str"ct"r!l orderin- of !ter ne!r ! s"rf!ce consists of the !r-"ments
tr!dition!ll' presented( &!sed on st"dies of thermod'n!mic +e#"ili&ri"m, properties( !s ell !s
on st"dies of v!rio"s tr!nsport phenomen! E!s ex!mples( e #"ote s"ch me!s"rements !s the
v!por press"re me!s"rements &' Shereshefs.' !nd coor.ers( the therm!l exp!nsion coefficient
me!s"rements of !ter in n!rro #"!rt3 c!pill!ries( !nd some +&"t not !ll, of the dielectric(
n"cle!r m!-netic reson!nce( !nd viscosit' st"dies reported &' v!rio"s !"thorsH% Fin!ll'( the third
concl"sion hich one m!' possi&l' dr! from the !v!il!&le d!t! is th!t not onl' m!' vicin!l
!ter &e str"ct"red differentl' from th!t of &"l. !ter +!nd extend over consider!&le r!n-es(
s!'( tens to tho"s!nds of molec"l!r di!meters,( &"t th!t ! third 0st!te0 of disordered !ter m!'
exist( !t le!st in some c!ses( &eteen the vicin!l !ter !nd the differentl' str"ct"red &"l. +the
0three)l!'er model0,% Fin!ll'( it !ppe!rs th!t ! completel' different t'pe of !ter m!' &e cre!ted
ne!r some s"rf!ces* this !nom!lo"s !ter m!' possess consider!&le st!&ilit'% Note Added in
Proof 2hilip F% Lo !nd N% L% White +Cl!'s !nd Cl!' Ciner!ls( 6ol% :8( :M>M( in press* priv!te
comm"nic!tion, h!ve s"--ested th!t !nom!lo"s res"lts o&t!ined for the densit' of !ter
!d5!cent to cl!' s"rf!ces m!' &e rel!ted to the Der5!-in !nom!lo"s !ter% The' present nine
different( sep!r!te !r-"ments p"rportin- to s"pport this vie% Densities of !ter ne!r v!rio"s
solids h!ve &een determined &' I% E. 6!n Iils (.. Colloid 2nterface +ci., 6ol% F9( p <G<(:M>M,(
"sin- ! dil!tometric techni#"e +!ter ne!r n'lon( d!cron( -l!ss fi&ers !nd -l!ss poder,% 46 I(
) * S + , I A LA( )E( .I( E E , I ( . / 0EM 1S+ , 1 The !pp!rent densities o&t!ined
in this m!nner r!n-ed from :%:= to <%@@ -$cmFX I% N% Iittens (.. Colloid 2nterface +ci., 6ol% F9(
p =9>( :M>M, h!s reme!s"red the s"rf!ce tension of !ter !t closel' sp!ced temper!t"re interv!ls
itho"t findin- !n' firm evidence for the therm!l !nom!lies% 4oever( Iittens notes th!t 0this
s"&5ect is not 'et closed(0 !s the !nom!lies m!' &e sensitive to "n.non( sp"rio"s infl"ences(
s"ch !s cont!min!tion of extremel' lo concentr!tions% Cini !nd coor.ers +R% Cini( I% Lo-lio(
!nd A% Fic!l&i( 3at're, 6ol% <<F( p ::=8( :M>M, h!ve shon evidence for therm!l !nom!lies in
the s"rf!ce tension of !ter !nd in the interf!ci!l tension &eteen !ter !nd hex!ne !nd dec!ne%
F"rthermore( some d!t! !re presented s"--estin- !nom!lies in the m!-netic s"scepti&ilit' of
!ter in silic! -el dispersions% This is t!.en !s evidence for the re!lit' of the therm!l !nom!lies
!s m!nifest!tions of s"rf!ce phenomen!% Independentl'( S% N!rmell +priv!te comm"nic!tion, h!s
!lso me!s"red the s"rf!ce tension of !ter "sin- !n !"tom!tic recordin- &!l!nce !nd o&t!ined
not!&le !nom!lies in the vicinit' of the temper!t"res of the .in.s reported &' the present !"thor%
Christer Soerem!r. !nd Sver.er C!rtin)Loef +person!l comm"nic!tion, h!ve !lso o&served the
existence of therm!l !nom!lies in the properties of !#"eo"s cell"lose s'stems +"sin- !
dil!tometric techni#"e* comp!re st"dies &' Iorin- !nd R!mi!h( Section III)I,% 4!3elood(
Nichols( !nd Ch!m&erl!in +C% F% 4!3elood( /% L% Nichols( !nd N% F% Ch!m&erl!in( 3at're, 6ol%
<<<( p G=G( :M>M, h!ve o&t!ined evidence for !t le!st to +str"ct"r!ll' ordered, !#"eo"s ph!ses
in m"scle &' NCR spectroscop'% The !"thors spec"l!te1 +:, 0The !ter molec"les of the m!5or
ph!se experience ! si-nific!nt loss of tr!nsl!tion!l motion !nd possi&l' some loss of rot!tion!l
motion* !nd +<, the !ter molec"les ithin the minor ph!se experience !n even -re!ter
restriction in tr!nsl!tion!l motion !nd ! si-nific!nt loss of some rot! tion!l motion%0
AC-NOW%ED+$ ENT The !"thor expresses his sincere -r!tit"de to 2rofessor 4enr' S%
Fr!n. for his .ind !dvice !nd repe!ted !dmonitions to s!fe-"!rd !-!inst dr!in- inferences
from those p!rts of the !v!il!&le experiment!l evidence hich m!' &e "ncert!in or not
!men!&le to simple interpret!tions% Wh!tever orthhile m!' &e fo"nd in this p!per oes( in
no sm!ll p!rt( its existence !nd presence to the helpf"l s"--estions of 2rofessor Fr!n.% An'
fl!s in present!tion( lo-ic or concl"sions( !re d"e entirel' to the !"thor% The !"thor !lso th!n.s
the editors of the No"rn!l for their incredi&le p!tience !nd contin"ed cooper!tion% Fin!ll'( the
fin!nci!l !ssist!nce of &oth the Office of S!line W!ter !nd the Office of ~aval Rese!rch is
-r!tef"ll' !c.noled-ed%
RE.4ERENCES
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Der5!-"in( Ed% +:M>>,% Cons"lt!nts /"re!"( N%O% B
+F, Anderson( D% C%( 3at're, <:>( @>F +:M>G,%
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+:9, /ell!m'( L% N%( !nd Oen( A% N%( +pectrochi!. (cta, <@A( F:M +:M>M&,%
+::, /ell!m'( L% N%( !nd 2rice( R% N%( i/id., <@A( F<M +:M>Mc,%
+:<, /l!nd!mir( C% N%( !nd S'mons( C% C% R%( .. Phs. Chern., >G( :F9= +:M>F,%
+:F, /r!tton( C% D%( 4op.ins( A% L%( !nd Wein&er-( N% W%( +cience, :=G(GF8 +:M>@,%
+:=, Ch!i( S% O%( !nd 6o-elh"t( 2%O%( .. (ppl. Phs., F8( >:F +:M>G,%
+:@, Ch!m&ers( I% 2% C%( Chern. 2nd. (5ondon), :M>G(M8<%
+:>, Ch!pm!n( I%( !nd CcL!"-hlin( Q% (., 3at're, <:@( FM: +:M>G,%
+:G, Cold m!n( C% F%( !nd Iood( W%( Bioche!. Biophs. (cta, :@9( :M= +:M>8,*i/id., :@9( <9>
+:M>8,%
+:8, Collison( R%( !nd CcDon!ld( C% 2%( 3at're, :8>( @=8 +:M>9,%
+:M, Cope( F% W%( Biophs. .., M( F9F +:M>M,%
+<9, C-pe( F% W%( B'll. "athe!atical Biophs., <M( @8F +:M>G!,%
+<:, Cope( F% W%( .. 6en. Phsiol., @9( :F@F +:M>G&,%
+<<, Corrin( C% L%( !nd Nelson( N% (., .. Phs. Chern., G<( >=F +:M>8,%
+<F, Conie( (., !nd 2!lmer( L% S%( Proc. Phs. +oc., / >@( <M@ +:M@<,%
+<=, De&'e( 2% N%( !nd Clel!nd( R% L%( .. (ppl. Phs., F9( 8=F +:M@M,%
+<@, Der5!-"in( /% 6%( )isc'ssions 7arada +oc., =<( :9M +:M>>,%
+<>, Der5!-"in( /% 6%( 0The St!te !nd Covement of W!ter in Livin- Or-!nisms(0S'mp% Soc% for
Experiment!l /ioI% :M( Ac!demic 2ress( Ne Oor.( N% O%( 2 @@ +:M>@,%
+<G, Der5!-"in( /% 61V !nd Q!r!ssev( 6% 6%( Proc. +econd laternational Coni. +'rlace (ctivit, F(
@F: (18%9).
+<8, Der5!-"in( /% 6%( !nd Aorin( A% C%( i/id., <( p :=@ +:M@G,%
+<M, Do"-l!ss( D% C%( Frisch( 4% L%( !nd Anderson( E% 9%( B:;ocht!. Biophs. (cta,==(=9: +:M>9,%
+F9, Do"3o"( 2%( !nd S!dron( C%( (dvan. Chern. Phs., G( FFM +:M>=,%
+F:, Drost)4!nsen( W%( (dvan. in Chern. +er., >G(G9):<9( ACS( 2"&% in 0E#"ili&ri"mConcepts
in N!t"r!l W!ter S'stems(0 +:M>G&,%
+F<, Drost)4!nsen( W%( (nn. 3. <. (cad. +ci., :<@(=G: +:M>@!,%
+FF, Drost)4!nsen( W%( Chern. Phs. 5etters, +Dec :M>8!,%
+F=, Drost)4!nsen( W%( 2!rt I( IND% ENI% C4EC%( @G +F,( F8* 2!rt ::(@G +=,(:8 +:M>@&,%
+F@, Drost)4!nsen( =., ..Colloidinterlac.+ci., <@( :F: +:M>Gc,%
+F>, Drost)4!nsen( W%( 2!n Americ!n 2etrole"m Corp% Rese!rch Dept% Report No% F@M)I)>(
0Litholo-ic!l Effects on Resistivit'(0 "np"&lished +:M@M&,%
+FG, Drost)4!nsen( W%( 2!n Americ!n 2etrole"m Corp% Rese!rch Dept% Report N"m&er FSM)I)
< 0+2" Resistivit' of /rines in C!pill!ries(0 "np"&lished +:M@M!,%
+F8, Drost)4!nsen( W%( Proc. 7irst 2ntern. +!p. on =ater )esai., Oct% +:M>@,* 6oVB :( pp F8<)
=9>( U% S% Iovt% 2rintin- Office( Sprin- +:M>G!,%
+FM, E&ert( I%( !nd L!n-h!mmer( E%( >olloid ?., :G=(@ +:M>:,%
+=9, Eisen&er-( D%( !nd Q!"3m!nn( (., 0The Str"ct"re !nd 2roperties oZ W!ter(0 Oxford
Universit' 2ress( Ne Oor.( N% O%( :M>M%
+=I, Elton( I%A% 4%( 4oa2+ociet,+eries(,184, <@M +:M=8,%
+=<, Fed'!.in( N% N%( .. Phs. Chern. (4'ssian), F>( :=@9 +:M><,%
+=F, ForsIind( E%( llA Theor' of W!ter(0 4!ndlin-!r( Svens.! Fors.nin-sinstit"ttet
for Cement och /eton- vid Q"n-V% Te.nis.! 4o-s.ol!n( Stoc.holm :>(:M@<%
+==, Forslind( E%( +vens0 3at'rvetens0ap, :M>>( M%
(4%) 7o@0es, F% C%( )isc'@;ons 7arada +oc., =<( :=9 +:M>>,%
+=>, Fr!n.( 4% S%( !nd Wen( W% O%( i/id., <=( :FF +:M@G,%
+=G, Fr!n.s( 7.,Che!.2nd. +London,( :M>8( @>9%
+=8, Fr!n.s( F%( !nd Ives( D% N% I%( .. Chern. +oc. +London,( :M>9( G=:%
+=M, F"ller( C% E% II( !nd /re'( W% /% Nr%( .. Bioi. Chern., <=F( +<, <G= +:M>8,%
+@9, I!st( R% I%( 2ntern. Cla Coni., 2!rt :(<@: +:M>F,%
+@:, Ioldstein( R%( .. Chern. Phs., =9( <GMF +:M>=,% %
+@<, 4!!se( R%( !nd deIreiff( 4% N%( ?. Phsi0. Chern. +Fr!n.f"rt,( ==( F9: +:M>@,%
+@F, 4!!se( R%( !nd Steinert( C%( i/id., <:( <G9 +:M@M,%
+@=, 4!mmes( I%( !nd Schimmel( 2% R%( .. (!er. Chern. +oc., 8M(==< +:M>G,%
+@@, 4echter( 9%( Wittstr"c.( T%( CcNiven( N%( !nd Lester( I%( Proc. 3at. (cad. 1f +ci., =G( G8F
+:M>9,%
+@>, 4enni.er( N% C%( 4ev. "od. Phs., <:( F<< +:M=M,%
+@G, 4i-!si( Q%( Cono-r!ph Series of the Rese!rch of Applied Electricit'( No%@( p M( 4o..!ido
Universit'( S!pporo( N!p!n +:M@@,%
+@8, 4od-son( C%( !nd CcIntosh( R%( Can. .. Chern., FG( :<G8 +:M@M,%
+@M, 4od-son( C%( !nd CcIntosh( R%( i/id., F8( M@8 +:P9,%
+>9, 4olt3er( A%( !nd Emerson( C% F%( .. Phs. Chern., GF( <> +:M>M,%
+>:, 4orne( R% A%( D!'( A% F%( Oo"n-( R% 2%( !nd O"( N% T%( Aleclroche!. (cta, :F(FMG +:M>8,%
+><, 4"&er( C%( !nd Flood( E% (., Can. .. Chern., F=( :=MG +:M@>,%
+>F, Id!( C%( !nd Nishim"r!( T%( .. Phs. +oc. .ap., <=(::G= +:M>8,%
+>=, Ihn!t( C%( Thesis( CcIill Universit'( D"e&ec( C!n!d!( "np"&lished +:M>>,
+>@, II!ni( (., Bioche!. Biophs. (cta, M=(=9@ +:M>@!,%
+>>, 4!ni( A%( i/id., M=( =:@ +:M>@&,%
+>G, II!ni( (., Biophs. .., >( +F,(F<M +:M>>,%
+>8, II!ni( (., .. 6en. Phsiol., =>( 8FM +:M>F,%
+>M, N!co&son( /%( .. (!. Chern. +oc., GG( <M:M +:M@@,%
+G9, N!rdets.'( C% D%( !nd N!rdets.'( 9%( Bioche!. Biophs. (cta, <>( >>8 +:M@G,%
+G:, Nohnson( I% A., Lecchini( S% C% A., Smith( E% I%( Clifford( N%( !nd 2ethic!( /% A%(
)isc'ssions 7arada +oc., =<( :<9 +:M>>,%
+G<, Nohnson( I% A% N%( !nd Ne!l( S% N%( >olloid ?.-?. Pol!., :8@( :F9 +:M><,%
+GF, Q!m&( /%( 0Str"ct"re of Chemistr' !nd Colec"l!r /iolo-'(0 Rich( D!vidson( Freem!n !nd
Co%( S!n Fr!ncisco !nd London( p @9G +:M>8,%
+G=, Q!r!-o"nis( I%( 2!p!'!nni.is( E%( !nd St!ssinopo"los( C% I%( 3at're, 221, >@@ +:M>M,%
+G@, Q!v!n!"( N% L%( 0W!ter !nd Sol"te)W!ter Inter!ctions(0 4!iden)D!'( Inc%( S!n Fr!ncisco(
+:M>=,%
+G>, Q!!s!.i( Q%( Q!no"( Q%( !nd Se.it!( O%( .. Phs. +oc. (.ap.), <( <<< +:M@8,%
+GG, Q!'"shin( L% 2%( Ed%( 0W!ter in /iolo-ic!l S'stems(0 Cons"lt!nts /"re!" (~rans. from
R"ssi!n,( Ne Oor.( N% O%( :M>M%
+G8, Qorson( L%( Drost)4!nsen( W%( !nd Cillero( F% N%( .. Phs. Chern., GF F= +:M>M,% B
+GM, Qr"'t( 4% R%( 0Colloid Science(0 6ol% <( !rticle &' /ooi5( 4% L%( p >8:( Elsevier +:M=M,%
+89, Q"&!t( N%( !nd 2!tt'r!nie( C%( 3at're, <:@( FM9 +:M>G,%
+8:, Lippincott( E% R%( Strom&er-( R% R%( Ir!nt( 06% 4%( !nd Cess!c( I% L%( +cience, :>=( :=8<
+:M>M,%
+8<, Lo( 2% F%( (dvan. (Bron., :F(<>M +:M>:,%
+8F, Lo( 2% F%( D!ve'( /% T%( Lee( 3. W%( !nd /!.er( D% E%( +elen&, :>:( 8MG +:M>8,%
+8=, L"&e3.'( Q%( /ettelheim( F% A%( !nd Folm!n( C%( Crans. 7arada +oc.- $3, :GM= +:M>G,%
+8@, L'.lem!( N%( )isc'ssions 7arada +oc., =<( 8: +:M>>,%
+8>, CcC!ll( D% W%( !nd Do"-l!ss( D% C%( .. Phs. Ch,!., >M( <99: +:M>@,%
+8G, CcIntosh( R% L%( 0Dielectric /eh!vior of 2h'sic!l Adsor&ed I!sses(0 C!rcel )e00er, 3e@
Oor. +:M>>,%
+88, C!rtin( R% T%( 2!per presented !t 8th N!tion!l Cl!' Conference !t Norm!n( O.l!%( p F
+:M@M,%
+8M, C!s"3!!( C%( !nd Sterlin-( C%( .. (ppl. Pol!. +ci., :<( <9<F +:M>8,%
+M9, Celi!( T% 2%( !nd Coffitt( W% 2%( .. Call. +ci., :M(=FF +:M>=,%
+M:, Cesti.( N% S%( !nd Aid!nod!( O% S%( 0Rese!rch in S"rf!ce W!ters(0 Der %%5!-"in( Ed%( 6ol% <(
p :>M +:M>>,%
+M<, Cet3ner( A% /%( 3at're, <98( <>G +:M>@,%
+MF, Cichel( D%( ?. 3at'rlorsch., <<A( :G@: +:M>G,%
+M=, Cillero( F%( Drost)4!nsen( W%( !nd Qorson( L%( J. Phs. Chern., G<( <<@:+:M>8,%
+M@, Corris( /%( .. Colloid 2nter lac. +ci., <8( :=M +:M>8,%
+M>, Corrison( N% L%( !nd D3ieci"ch( C% (., Can. .. Chern., FG( :FGM +:M@M,%
+MG, Corrison( N% L%( !nd 4!nl!n( N% F%( Proc. +econd. 2ntern. ConBo +'rface (ctivit (5ondon) <(
F<< +:M@G,%
+M8, C'sels( Q% N%( )isc'ssions 7arada +oc., =<( :F8 +:M>>,%
+MM, Ne Oor. Ac!dem' of Sciences( 0Forms of W!ter in /iolo-ic +ste!s& (nn. 3. <. (cad.
+ci., :<@(<=M( Article < +:M>@,% B
+:99, Oster( N% D%( !nd Lo( 2% F%( Proc. +oil +ci. (!er., <G(F>M +:M>F,%
+:9I, Otteill( R% A%( Storer( C% C%( !nd W!l.er( T%( Crans. 7arada +oc., >F(<GM> +:M>G,%
+:9<, 2!lmer( L% S%( C"nliffe( (., !nd 4o"-h( N% C%( 3at're, :G9(GM> +:M@<,%
+:9F, 2!"lin-( L%( +cience, :F=( :@ +:M>M,%
+:9=, 2eSChel( I%( ?. Phs. Chern. +Fr!n.f"rt, @M( <GB +:M>8,%
+:9@, 2eschel( I%( !nd Aldfin-er( Q% 4%( 3at'r@issenschalten, @=( >:= +:M>G,%
+:9>, 2ethic!( /% (., ADp. Cell 4es., +'ppl. 8( :<F +:M>I,%
+:9G, 2ic.ett( N% 4%( !nd Ro-ers( L% /%( (nal. Chern., FM(:8M< +:M>G,%
+:98, 2Wt3e( E%( 4"c.crt( I%( !nd 2Wt3e( R%( 3at'r@issenschalten, =@( F> +:M@8,%
+:9M, 2riv!lov( 2% L%( Biophsics, F(>M: +:M@8,%
+::9, 2r"pp!cher( 4% R%( .. Chern. Phs., =G( :89G +:M>G,%
+::I, D"inn( N% (., !nd /l!ir( L% C%( 3at're, <:=( M9G +:PG,%
+::<, R!mi!h( C% /%( !nd Iorin-( D% A% I%( .. Pol!. +ci. 22, Part C( <G +:M>@,%
+::F, Re&!ll( S%( !nd Win.ler( 4%( ?. 3at'rlo!h. :MA( 8>: +:M>=,%
+::=, Resin-( 4% (., (dvan. "olec'lar 4elaDation, :(:9M +:M>8,%
+::@, Romo( L% A%( )isc'ssions 7arada +oc., =<( MM +:M>>,%
+::>, Rosen#vist( :% Th%( Intern% Cl!' Conf%( p"&lished in 2ntern. +er. "onoBraphs Aarth +ci. <:(
2!rt <( F=9( 2er-!mon 2ress +:M>@,%
+::G, Rosen#"ist* I% Th%( .. +oil "echanics, 8@( F: +SC<, +:M@M,%
+::8, S!l!m!( C%( !nd Iorin-( D% A% I%( .. Phs. Chern., G9( F8F8 +:M>>,%
+::M, S!moilov( O% O!%( 0Str"ct"re of A#"eo"s Electrol'te Sol"tions !nd the 4'dr!tion of Ions(0
tr!ns% &' Ives( Cons"lt!nts /"re!"( Ne Oor. +:M>@,%
+:<9, S!vits.i( A% N%( Colloid .., F9( M9 +:M>8,% %
+:<:, Sche"plein( R% N%( Biophs. E., >( : +:M>>,%
+:<<, Sch"lle( N% A., Div% Colloid !nd S"rf!ce Chemistr'( :@Gth N!tion!l ACS Ceetin-(
Cinne!polis( Cinn%( +April :M>M,%
+:<F, Sch"lle( N% A%( !nd 6en"-op!l!n( C%( 6eophs. 4es., G<( F<G: +:M>G,%
+:<=, Sch"lle( N% A%( !nd O"( N%( .. Colloid 2nter lac. +ci., <>( FM@ +:M>8,%
+:<@, Shel"d.o( (., (dvan. Colloid 2nterlae. +ci., :( FM: +:M>G,%
+:<>, Shereshefs.'( N% L%( !nd C!rter( C% 2%( .. (!er. Chern. +oc., G<( F>8< +:M@9,* Shereshefs.'(
N% L%( !nd Folm!n( C%( .. Phs. Chern., @M( >9G +:M@@,%
+:<G, Sip'!-in( 6% 2%( +oviet Phs. Crst. (AnB. Cransl.), :<( @M9 +:M>8,%
+:<8, Sl!&!"-h( W% 4%( .. Phs. Chern., >F( :FFF +:M@M,%
+:<M, S3ent %% I'or-'i( A%( 0/ioener-etics(0 Ac!demic 2ress( Ne Oor.( +:M@G,%
+:F9, Tche"re.&5!in( N%( Aettlemo'er( A% C%( !nd Chessic.( N% N%( .. Phs. Che! >8(GGF +:M>=,%
+:F:, Thompson( T% E%( 4Cell"l!r Cem&r!nes in Development0 Loc.e( Ed%(%Ac!demic 2ress(
3e@ Oor. +:M>=,%
+:F<, Thorh!"-( A%( Thesis( "np"&lished +:M>M,( Univ% of Ci!mi%
+:FF, Thorh!"-( A%( !nd Drost)4!nsen( W%( 3at're, <:@( @9> +:M>G,%
+:F=, Timmerm!ns( N%( !nd /odson( 4%( Co!pt. 4end., <9=( :89= +:MFG,%
+:F@, Tolsto'( D% C%( )o0la, (0ad. 3a'0., +++4, 8@(:98M +:M@<,%
+:F>, Tr!pe3ni.ov( A% A%( +econd. 2ntern. ConBo +'rface (ctivit, :( 2 :9M( Ac!demic 2ress(
3e@ Oor. +:M@G,%
+:FG, Tr!pe3ni.ov( A% (., %!nd Do.".in!( E% S%( 4'ssian .. Phs. Chern., =9 888 +:M>>,% % B
+:F8, Tsch!pe.( C%( !nd N!t!le( I%( >olloid-?.-?. Pol!., <::( => +:M>>,%
+:FM, W!lr!fen( I% E%( Irish( D% E%( !nd Oo"n-( T% F%( +!p., 0Str"ct"res of W!ter !nd A#"eo"s
Sol"tions(0 "np"&lished( +:M>M,%
+:=9, We&&( S% :%( 0/o"nd W!ter in /iolo-ic!l Inte-rit'(0 ! C Thom!s Sprin-% field( Ill%
+:M>@,%
+:=I, Windle( N% N%( !nd Sh!( T% C%( .. Chern. Phs., <@( =F@ +:M@>,%
+:=<, Willis( E%( Rennie( I% Q%( Sm!rt( C%( !nd 2ethic!( /% (., 3at're, <<<( :@M +:M>M,%
+:=F, Woessner( 6% E%( !nd Aimmerm!n( N% R%( .. Phs. Chern., >G( :@M9 +:M>F,%
+:==, W"( Th%( .. 6eophs. 4es., >M( :98F +:M>=,%
+:=@, Oi!nnos( 2% N%( .. Colloid +ci., :G( FF= +:M><,%
+:=>, Aettlemo'er( A% C%( .. Colloid 2nterlac. +ci., <8(F=F +:M>8,%
+:=G, Aimmerm!n( N% R%( etal., ...;.hs. Chern., >9( ::@G +:M@>,* i/id., >:( :F<8 (18%7)-
i/id., ><(::@G +:M%:8,* , i/id., >G( :@M9 +:M>F,%
+:=8, Aorin( A% C%( !nd Ch"r!ev( N% 6%( Colloid .., F++4, AnB. Crans., F9( <GM +:M>8,%