water near solid interfaces.doc

8/11/2019 WATER NEAR SOLID INTERFACES.doc

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STRUCTURE OF WATER NEAR SOLID INTERFACES

Evidence is presented for the existence of ordered elements of !ter str"ct"re ne!rcert!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 modelfor 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 ons"pposedl' simil!r m!teri!ls* +&, &' invo.incl!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' iththe 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%


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I. INTRODUCTION

A. Interfacial Water The properties of !ter h!ve &een s'stem!tic!ll' st"died formore 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 ofthis !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; +,% 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( onthe 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 !srevieed &' 4enni.er +@>, in !n !rticle entitled 0The Depth of the S"rf!ce one of !

Li#"id%0 Th!t !rticle h!s)for &etter or orse)&ecome ! cl!ssic in the field% While4enni.erBs !rticle is concerned ith h!t he referred to !s 0deep s"rf!ce orient!tion(0 in


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-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


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!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 thecl!' pl!telets or the effects of the !dsor&ed +exch!n-e!&le, ions on the !ter str"ct"re%

+ener!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%IESA. Anoalies in Surface Tension of Water As o"tlined in the Introd"ction( p!rtof 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-en"m&er of other interf!ci!l phenomen!( h!s &een disc"ssed in det!il in !n !rticle &' the

present !"thor Drost)4!nsen (34)]. In Fi-"re : the s"rf!ce tension of !ter !ppe!rs topossess !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 +!ndextended, r!n-e of temper!t"re itho"t findin- corro&or!tin- evidence for the !nom!l'%

See( 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!rdemonstr!tions of therm!l !nom!lies h!ve come from orin- !nd coor.ers% Elsehere

in this p!per e disc"ss the o&serv!tions m!de &' R!mi!h !nd orin- (112) on !terne!r cell"lose s"rf!ces !nd the viscosit' st"d' &' Ihn!t +>=,( or.inin orin-Bs

l!&or!tor'% For the present( e foc"s !ttention on the spectroscopic o&serv!tions m!de

&' S!l!m! !nd orin- +::8,% These !"thors me!s"red the intensit' of infr!red

!&sorption of !ter !t


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the vicinit' of 9KC%( !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 orin- !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 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


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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"rech!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 see

ohnson 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( estress 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' =


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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


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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


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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!ranesIn connection ith the st"dies &' orin- !nd coor.ers( mention sho"ld &e m!de !lso

of the !nom!lo"s res"lts o&t!ined &' 4!!se !nd Steinert +@, 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 dereiff +@@)>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"sm!trix +Cr!tin !nd Drost)4!nsen( :M>M( "np"&lished,%

I. Therod"naic Pro)erties of Adsor!ed Water on Cellulose Someinterestin- thermod'n!mic properties of !dsor&ed !ter on cell"lose h!ve &een reported

&' orrison !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 +8,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 +:


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!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 +:


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!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


12/43

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( &' !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% See !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 @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 theres"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!timport!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 &' ohnson

!nd Ne!l +G


13/43

s"--ests the therm!l &re!.don( !t hi-her temper!t"res( of the thic.ness of ! str"ct"red

l!'er% cIntosh +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 &'

ichel +M, !nd &' Re&!ll !nd Win.ler +::,% The st"d' &' ichel s"--ests th!t for

!ter !dsor&ed on silic! -el( to t'pes of !ter exist in s!mples ith onl' ! $=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


14/43

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 9 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 thev!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"sestim!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 immerm!n !nd coor.ers (147) h!vest"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 immerm!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

NR 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 &' immerm!n !nd coor.ers( Resin-( ichel( !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- Inno 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'stemsper 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!icvir"s% The res"lts from these st"dies !mpl' demonstr!te the contr!dictor' res"lts hich


15/43


16/43

C. Studies of $uscles /r!tton( 4op.ins( !nd v6ein&er- +:, me!s"red the ch!n-e inthe 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 +


17/43

disc"ssed in the present p!per% It is( indeed( this t'pe of temper!t"re effect hich isemplo'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 ofthe 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 hichill !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 +, !nd

&' Thorh!"- !nd the present !"thor +, !nd &' Thorh!"- +:


18/43

the !"thorBs notions hich s"--est the occ"rrence of therm!l !nom!lies in !ter ne!r

=@K !nd >9KC%

#. Inter)retin Bioloical 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 NR 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"--estedthe 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 999 to =999 A !fter


19/43

D !nd 6I)E% 4"&er !nd Flood +>


20/43

"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 ioniccond"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 tocl!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 STUDIESA. Rheoloical $easureents and Interferin Effects Rheolo-ic!lme!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% See( 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% et( 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! +:G, h!veme!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' : K to


21/43

!"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,% In ! 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 &' i!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


22/43

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


23/43

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 &eenr!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. &ariousSurface Studies A s"rve' of &o"nd !ter !s p"&lished &' 4i-!si +@G, hospecific!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 &eenshon 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% e!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 !nd6en"-op!l!n +:


24/43

O.13.u). In &oth Fi-"res :@ !nd :>( me!s"rements !re reported !t differenttemper!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"dedth!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 thec!"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 $easureents Considerin- theli.el' existence of ch!n-ed !ter str"ct"res ne!r s"ch !ter$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% cC!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 :11:9P +!t


25/43

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' &eexpected 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% Comp!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

+


26/43

!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 onporo"s 6'cor -l!ss h!s &een identified &' 4od-son !nd cIntosh +@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 )


27/43

sol"tion cont!ins onl' !pproxim!tel'


28/43

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' hichm!' 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)=

-$cm 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@ -$cm( 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!trel!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 orientedperpendic'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-ionne!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% Onthis &!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 +, 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-'% See the

!rticle &' the present !"thor on the n! t"re of the !ter$ice interf!ce (37).J As s"--ested in thep!per ith 4oe.str!( Anderson in the second p!per !-!in stresses the possi&ilit' th!t the0form!tion !nd -roth of em&r'os !ct"!ll' occ"r !t ! loc!tion sever!l( perh!ps m!n'( molec"l!r


29/43

#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( CC, !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"ss"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%


30/43

'. Water Near Mica The existence of str"ct"red !ter ne!r !n interf!ce h!s !lso &een s"--ested

&' esti. !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%l thic.i. e., 99 !ter molec"l!r

l!'ers deep%, For comp!rison( the therm!l cond"ctivit' of the ice is onl' %@ 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$A%OUS WATERA. Derjaguin Sc$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 ofl!'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 see Der5!-"in !nd Q!r!ssev +


31/43

!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 +, App!rent densit' of the #"!sisolid !&o"t @P less th!n the li#"id +G,

Index of refr!ction of :%=8 "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 edi!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. +:=


32/43

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 IfDer5!-"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 +:


33/43

discreteness of the !dsor&ed !ter in their comments on this pro&lem1 "It is commonl' tho"-htth!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 &' orrison !nd 4!nl!n +MG, on the he!ts of ettin- ofool).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


34/43

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 Order4DisorderPhenoena. 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 &epossi&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! +>, 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 ! MP 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% "!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


35/43

this l!tter c!se( it m!' &e noteorth' th!t the point o&served !t @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 Wateron Availa!le Sites on a Surface A serio"s so"rce of concern in !ll !dsorption st"diesconfer( hoever( p!pers s"ch !s th!t &' orrison !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 < !ter

molec"le per pol!r -ro"p, to = .c!l5-mol for 7' m- 4 29$- protein +correspondin- to 9%M!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 ofm!-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"sproperties 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 /'l str"ct"re of !ter is extremel' limited%

See( for inst!nce( W!lr!fen !nd Irish +:M,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&leexistence 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 &' theinterf!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 thestr"ct"re of !ter hich is most li.el' to prove correct is one involvin- the existence of discrete

str"ct"r!l elements% ost 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


36/43

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+ tic element or !nother)for inst!nce( the occ"rrence of pent!-on!l rin-s or simil!r -eometricidentifi!&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 &edetermined 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 NR st"dies

ill thro consider!&le li-ht on this #"estion% C. #ih Pressure Ice Pol"or)hs and

Clathrates Re-!rdin- the str"ct"re of &"l. !ter( the folloin- is noted in p!ssin-% Thepresent !"thor &elieves th!t &"l. !ter does not possess elements of Ice)Ih li.eness for !disc"ssion of this pro&lem +G( @,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 ithm!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% For evidence of str"ct"rin- of !ter !t the !ter$!ir

interf!ce see( in p!rtic"l!r( Drost)4!nsen +=,H% E. Possi!le Structures of &icinal Water Inthe 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!rs"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


37/43

hi-h press"re ice pol'morphs !ccordin- to Q!m&( possi&l' incl"din- Ice)Ih +G,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 &' iller% If thestr"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-reeof 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 theordered 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 thever' 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 !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 =( ::( :( !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 +:M,

s"--est th!t in rel!tivel' concentr!ted sol"tions( s!' &elo .%", elements of !ter str"ct"re

rem!in in spite of the closeness of !ppro!ch of ions in s"ch sol"tions% See !lso Drost4!nsen

+G,% 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!ldissimil!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


38/43

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!tof &"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 +=,( 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 "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 WaterNear Interfaces As mentioned elsehere in this p!per( Torrence !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% !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 Fr!n. !nd Wen +=>, %

The difference &eteen the model proposed &' !rtin !nd the one proposed &' the present

!"thor is &est seen &' the 5"xt!position of the concl"sions &' !rtin +in the p!per cited, !nd theide!s s"--ested &' the present !"thor% ARTIN% "It is proposed th!t the sor&ed ph!se( theinterf!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 !


39/43

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 seems"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! !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 thirdconcl"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 % L% White +Cl!'s !nd Cl!' iner!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 &' % E. 6!n ils (. Colloid nterface +ci., 6ol% 9( p


40/43


41/43

+=9, Eisen&er-( D%( !nd Q!"3m!nn(., 0The Str"ct"re !nd 2roperties oZ W!ter(0 Oxford

Universit' 2ress( Ne or.( N% %( :M>M%

+=I, Elton( %A% 4%(oa+ociet,+eries,184, >( M%

(4%) o@es, F% %(isc'@;ons arada +oc., =>,%

+=>, Fr!n.( 4% S%( !nd Wen( W% %( i/id., 8( @>9%

+=8, Fr!n.s( F%( !nd Ives( D% % %(. Chern. +oc. +London,( :M>9( G=:%

+=M, F"ller( % E% II( !nd /re'( W% /% r%(. Bioi. Chern., 9,%

+@>, 4enni.er( % C%(ev. "od. Phs., M,%

+>:, 4orne( R% A%( D!'( A% F%( o"n-( R% 2%( !nd "( N% T%(Aleclroche!. cta, :(MG +:M>8,%

+>=, Ihn!t( %( Thesis( cill Universit'( "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. ., >( +,(>,%

+>8, II!ni(., . 6en. Phsiol., =>( 8M +:M>,%

+>M, !co&son( /%(. !. Chern. +oc., GG( >8 +:M@G,%

+G:, ohnson( %A., Lecchini( S% %A., Smith( E% %( Clifford( %( !nd 2ethic!( /% A%(isc'ssions arada +oc., =,%

+Golloid ?.-?. Pol!., :8@( :9 +:M>8,%

+G=, Q!r!-o"nis( %( 2!p!'!nni.is( E%( !nd St!ssinopo"los( C% I%(at're, 221, >@@ +:M>M,%

+G@, Q!v!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!( %(. Phs. +oc. (ap.), =( :=8M,%

+8:,%

+8, Lo( 2% F%( D!ve'( /% T%( Lee( . W%( !nd /!.er( D% E%( +elen&, :>:( 8MG +:M>8,%+8=, L"&e3.'( Q%( /ettelheim( F% A%( !nd Folm!n( %( rans. arada +oc. $3, :GM= +:M>G,%

+8@, L'.lem!( %(isc'ssions arada +oc., =>,%


42/43

+8>, cC!ll( D% W%( !nd Do"-l!ss( D% C%(. Phs. Ch,!., >M( @,%

+8G, cIntosh( R% L%( 0Dielectric /eh!vior of 2h'sic!l Adsor&ed !sses(0 !rceleer, e@

or. +:M>>,%

+88, !rtin( R% T%( 2!per presented !t 8th N!tion!l Cl!' Conference !t Norm!n( O.l!%( p

+:M@M,%

+8M, !s"3!!( %( !nd Sterlin-( C%(. ppl. Pol!. +ci., :>,%

+MM,%

+:9=, 2eSChel( %(?. Phs. Chern. +Fr!n.f"rt, @M( 8,%

+:9@, 2eschel( %( !nd Aldfin-er( Q% 4%(at'r@issenschalten, @=( >:= +:M>G,%

+:9>, 2ethic!( /%., ADp. Cell es., +'ppl. 8( :I,%

+:9G, 2ic.ett( % 4%( !nd Ro-ers( L% /%(nal. Chern., M(:8M< +:M>G,%

+:98, 2Wt3e( E%( 4"c.crt( %( !nd 2Wt3e( R%(at'r@issenschalten, =@( > +:M@8,%

+:9M, 2riv!lov( 2% L%(Biophsics, (>M: +:M@8,%

+::9, 2r"pp!cher( 4% R%(. Chern. Phs., =G( :89G +:M>G,%+::I, "inn( %., !nd /l!ir( L% %(at're, 8,%

+::@, Romo( L% A%(isc'ssions arada +oc., =>,%

+::>, Rosen#vist( :% Th%( Intern% Cl!' Conf%( p"&lished inntern. +er. "onoraphs Aarth +ci. ,%

+::M, S!moilov( O% !%( 0Str"ct"re of A#"eo"

water near solid interfaces.doc

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