INTERMOLECULAR AND SURFACE FORCES. Sicono Eomow Jacoa N. Iastacivi Depanment of Chemical & Nuclear Engineering od Materals Department Calflora USA @ ACADEMIC PRESS sect ar oar, ties sraney "Foxe Toroih © 100 Contents ‘The Forces Between Atoms and Molecules: Principles and Concepts (Chapter 1 Hints Pempectve (Chapter 2 Some Thermodynamic Aypectsof nermoleclar (Chapter 3 srongttermotecalr Forces: Covaletand CoulombChapter 4 Chapter S Chaper 6 date ein eretaes Bly on Ste sos aaa Intcatons tvaving Polar Molecaler tenes mestons erate errs: hated one ‘Sohn floret stra oc, haan Fores ‘in dae rcs ere ipl sn arge-enragd pot Aneraions Invaving the Polarization of Molecules The palo ste an lle ‘he Pama of por mows Tans ttre ore and unccped moc Sioteautseenenace Sever ae es van er Waal Forces ‘rig athe san de Wl depen force beween ‘Scere: te London squaton Seg ps anv ate an Sar Se Wash equatan of ate Chapter 8 Chapter 9 ‘69° Fomter aspects of van der Waals forces” aniottepy, non ‘atvay rd radon eect epulive Forces Total ntrmolecla Pair Fotentiat find gid Stocture 3 fat eye ne nay Donde soe 25) Katee ce owe Special teractions: Hydrogen Bonding Hydrophobic ad Hydrophi neractons i ee Seg Seta ma 5 The ero ect : Eee a 2 ccc PART TWO ‘The Forces Between Particles and Surfaces ‘Some Untying Concepts intermolecular and Imerparcle FercerChapter tt Chapter 12 Contrasts Benen intermolecular, Inerparice and Interface Freee ‘lec itraction te of to pres Ue Langer it ap dls cmp etn ‘vam der Wale Forces Between Surtaces ‘Sar eran der Wal ces ewer ode septs ofthe Libhez theory to interactions a ane a ew ‘Sire rr Wan orcs near sone Sas Sac tronic Forces Between Surfaces in Liga Chapter 13 Caper 146 ‘RoR Saban eeqaton “Sheehan cron cece octane yt 3 tr wen de tice in wate he Lone ol earns ch ton apes ee es Seach optic poncee ermal ‘te bye ere “oratopeterland encom om 3Riped sce ie deter ee en en ee ae at cng pe Eur esate dey VO Solvation, Structural and Hydration Forces ‘Sotieuret td popes ten res ean, ‘Sivan farce utes epuve yat Scivation forces in aqua aysteratractve ‘hyo eet Sec and Faction Forcer Pom aces eaeChaper 15 Chapter 16 143 apn st oF ntfs beeen pre 14a forerunner kg pte mat 145th tanepmere "noe cp’ ces MS Tooele eon ea Adhesion 152 Since rmpesoamal cer ani cusedstaces 133 Gone ges a wei fee 134 Heese contac aeand asn mesures 183 Mionsheventldpnes heer 186 BETS pay cto nator Micelles, Bilayers and Biological Membranes ‘emote Pine of ami 28) EEE we tty 1 SS aiaaa acre See « Eaten See Se acees i Beers 8 RESET en 3 SPEER Fluid-Like Structures and Self-Assembling Systems: (Chaper 17 (Chapter 18 Aggregation of Amphipiic Molecles ino Micelles, Slayers Vesicles and Baloge! Membranes osc: agian conideratns a amphi Spal heey oe (Ceo pking corsets ‘Seon rete Serer dren cn Fir sting cng ra one scr anther, inate eyo ayes snd ember Sota rarer Nerbrane pe brane prt an avane stirs Petia dao ope ‘Thelnteractons between pi Bilayer and Boogie Membrane efor nly oe rea he dation mode rope ce Rede arrae armentane etrencer trdenUST OF TABLES Ties Tate gs Tate Tle 1 Tie na Ten ong points and ate! heats (Trowtons rs) 36 ‘Seng of covalent onde 2 Dis coat of oie ad ius i Delco rls oir gous} Molly polaratites rom moteur and bale “a Van der Waals dispersion imeraction between non-polar 87 ‘Vander Wale persion interaction betwen alane 9 Vie dr Wasi ieeaction between polar molar 9 Molecular ai ded! fo dice atode a Efncsoftygrocatonchinunsatesionend ranching 16 Rate stent of diperson, dipolar ané Hetooding 128 Hamaker conta scree & edn, ‘Sere ners enone om LAs isory 204 ‘Strns corps of meal experimental as ‘Strns ener of meal clad) ie ‘Sere pontine nr aifoont dectrae sons 238 ‘Common polymer 0 Tora enerpes (nso) us “Table 162i miele onceotraions ‘Table 112, Common amphphie sructres as mm atPREFACE TO SECOND EDITION ‘Size 1988 when the fs ton ofthis book apened see has been much perineal and thor progestin his ulidacpiary sj. The tate of some ld frer have ben aed wine orcs bane bee (Sood Te vbjet he mated iin grou dcp ands wang See hy, pes and oldman wert oh ‘more praca sd, many ins and conical engieting proses ae ow binning tote understood ad control a the uncumenta vet I. [uh these developert ia mid, topier with he eedbackT reeed From aumerous claps tat the cond elon was prepared "Fhe ssondedion We basely an updated teratoma the it, bat 3 ‘contain moe than 10 pres Mt appear othe sod of ac chp, bittome appear as worked examples in the tex. Thee problems ould hance he oy of hebook sean advanced undergrasteor graduate ‘Exbook The protic have ben deve to state mid; many are sed on gene resuchprblens, oes tek}, some are extensos ‘ihe text ito more advanced ata, and few ate operended to te The: reading dicson and even speclaton, “The tet lll has teen expanded to include recent develops in te tent of rae ore mestureent, solvation and srr! forces, [ydrton snd pdropbobicforrsomcoreltion orc, thermal aruton ‘ed psd soe sont a i Poe am tf to many colleagues who commented o he ret ition, ad se se th upgestons a wig the second. tn pre, my hans 9 fo Hans Ljklonm Hakan Wenner, cob Kl to Fisea Ve thd Jost Inetcbl fo pag the manus to Dove MeLarea for ‘rowing many of the gues 6 my wile Kana who tportd me roughowt, aad fal (0 my stents who haves trough my etre ‘td bythe ques have uawitngy contd the met PREFACE TO FIRST EDITION fewonverty cures Jove {Stra wih theamofprestngscompeeheae tune mrodction {oimermalcr and suas foes denrbig th lei determing he ‘oper of tinpe tee ich 2 ges hus and so bt eel Pore mle and mare imerene. seme The are nitersple igus or so but ater 8 mya of dled ote moles, oles saaepien or macroscopic eating iu or apo ister ch ene tn lly Gms e eh td Proper ofeerdy tangy st lian hen pitti aes ecm any chloe! roses tego, miss eget fleas and membrans and we ouncvr-for each ft one it Wlcotodal sem compoed of abot 755 water as are mon ink fs et therfore foushes on 4 very broad area of penomens in psc chemi, chemi! engcsing and ilgy im whch thre have srngein hep Sears Teese vance can be wed ach dap or wits a roser mutiny approach ir adope nhs Dok, wre That ed {Sprnnta pew ew of merle and sce ores wit ramen ‘tf nuioe and on somingy parte phenomena whic hey ly Sole Tecnu of the wide ang ftp covered and the dierent sips to bic the book added hve presumed oly = Bac Keowiedge of {hint sla puts (cemerry coset of nergy th oe ‘Sraenchomty (ase sermodyeumicr and quantum mans) Std 'mathemasr (abn and Coney aku) The. mathemateal ‘Std eostal developmenty In parc, have Seen hep at = sine Stlophsictd level troughs "Vesors ae ome opt Mx ‘Geton se dene rom fx pai alowed by eam of how they ‘Bp topes santos Mote complcated equation ze ated bate 2 chy expand snd Secttna book sch a his of modest ie yet covering such 3 wide spectra ‘nas So poe to tat sch tpi exhautvely or Horus ad lasumay dhl pari ubet Seed somewhat superialy se edn hoe parts, he st dealing with the nections eres i mole ie cco wth the nations bee ee a 22 ce ob te thd ah soe molar agentes ee doch as mine apretesof seat molecules} and lop ion eco id aod pts) Whi the fdamentl (ees ae een each fhe exer they Mane Dense Fee scat ways that es they ae best eta ce Pa Fern a ie bok to prone a horou eounding i te Scop ofinrmolcua fore otha he ede wl be able Teas ahh forces ae emporst m whatvet sytem e o she ‘eee to opi these theses corey to specie problems ang wi? here) ebook need for Bra yar wndergrase a raat stent nd nn-specas earch Work "em Spy arte ote fllowsg people who have rea the fx ad re ee eens rman epesetaton: Dee Ca, Dav cas a sale Roger Horn. sgepan Masel Job Mitchel, akan eee ae at Lae White My thnks ao end to Daa Wace or Hance and to Ton Sakis fo hs carta ring of sk ane parte a amined omy wie Kai without whose SieBot hs bok would aot have been WOES UNITS AND SYMBOLS Mach oft pu eat and gute on itera sure (Se te Cn otf okt Sate Inco (3) wd, te see he ngomme {Ggvfrmas the wae rg these (0) a, ee {ir sempre the Spee (A ste quan td theme {monn onue Stall ts ch agrme tg 10° ‘Shtmete (tom = 10" mhngiromt menage {Senet commonly ooh ha tent pa fe Spe ‘TS ths may vate oer be CS oo a when res ‘re Tar ps fre ce es Na eee ‘icc tec aos hm nme comniey Sonn Smbt Fort Norton ‘ Power Wa ¥ ee carge—— Coukmib e in pcaial Vo Yo Bheteses Hs i Vetere veeeee ita’ Seville 2 MAA ete Geog SSRIS Seat ‘Convtison 0M COS 10 St Th aprog = 107 = 10" om =O pm = 107 ital = 40844) mol PEP gs tot eg = 4014 10°23 at HK (28°C) fos Sto! eng = 4048 10-2 J aL OK (=20°C) Ler per molecule = O82 Kekmal"1= 247K mal“ a 296K TeV Stop x 10 erg = 1608» 1077) {EY pet mole = 2206 eal ma = 96481) mal 1m ravenna eit fenegy) = 1886 10"? 5 Ses Leen ta heomt = LN mt = i nif tension) VGjpeam-?= 1 Paden) {Nines Tors x 10¢ dyes cme? = 1013 bar~ 1013 «108 Pa Nn?) {ier mm lig ste 10 atm = 1883 PaN@ O'e = HRN (ie ott of wate) Tou 3316 x OC tatoesis) DeeiD) 336% 10." C man clemirediplemament) Cones kom S110 COS Tam 210-7 m= 0A = 10am TIT Toterg = 250cal= 6242 10!%ev Soe Tol cme! = 9088 = 10 Ladino! = 0259 eal ml IN = dine [Bre tNme? 94725 10 Phare 0m Pa stu quaves a0 HUAONS nary equvelet mo of oe ami an wt 0) — 1492 «103 Mean volme oecpied pet moe = (MW) > deny) Mave any som or mou = (MW) {L601 10") Sundar voleme ofa! gs = 224140? mal"! (Leal) Wien kYF= 2809 mv at 290% VG scars pe O16." (1642) 1! (Dege length) = 0504//Mnm for 1:1 etait a 298, where 1M = mol m= 622 108" molec perm as ofthe cath = 5978 10" eg Deny ofeh(ean) = 5518 10? kgm? alos of gvitatonlsclertion ‘Equator (9.80 m1), nathan South poles 9.8525", ‘New Yor! (9801 ms} London 9812") Common secs F_ Haar constant aaa (mh Helo fe ea 4, Mamilr mle rd Redo ares Se Boneradis (0083 am). ¢ Tetrion constant (4) aqueous lt conceovation in mae fraction ait eld 9/583)annge e 2 papprtay © Distance ema mo sacs) Dom to occ weight tame as MW) hs stent (V Fore) Entaips Toman ptetl Se nn pi cms firemen tomemeg) eet, axa fe eh ri (esha ps Sh ee oer eee ee wh neon eon a See egnnt oem in pe Pe ean) onic Se san tin teats oe eter areata Ste eet tO OIggyeauwwye Surface sion (Nm), suc energy (S82, {ano 7) = tate 108} 298K Imecaia ney Tm) Stace coverage (abet perm) Stem yer hss (0). Redatie permit, wate iets constant Energy ord me) ‘Ange (deg or rad theta tompratute of when (K) Inverse Dee eth im) (Characters exponent dey nth wavelength) {Colton length (Ghemizal potentia Frequency ("or Heh onatoneueney (eet) ‘amber dns fn) or mae deny tka”) Sic che density (Cm?) nandard deviation ‘Chiral elation ie (3 ‘Ange (de Fe) Elssniate trace pil (V) ‘wo dimensional are prsure(N on") Approsimataly egal 9, roughly Equiaent 0 Proportional vo Cpe or ieence in Sto en of Worked sampPART ONE ‘THE FORCES BETWEEN ATOMS ‘AND MOLECULES: PRINCIPLES AND CONCEPTSCuurne HISTORICAL PERSPECTIVE “U1 We ou rorcs oF nave {eis now well abs tha tere are our din free naar. Two Ctose ae the svong and wat rats that ae Retwen nesons, Protos eto an wer cmenty parler Toot two forces hae 2 ‘ery sort rage acon ss thas 10” aman Selon tothe domain of Iie ad hgh ener phys The ter two fore arth ltromape| ‘rbatuen elementary parks) Tesoro ones much get ‘ange of itancn, fom sobiomie prey inf distances and te ‘eeguenly the forer that gover the behuoour of svt) tags (Fie ih. For example eictromapntc frcesthe source tl Inermoieleinacions determine the properties of sol ue and tues the Behniour of parle slain, chmical reasons nd the ‘Stpnization of toga! stature. Gravitational free account fra ‘motionand many colo phere, abd when acting together mt ‘rela fores, determine Suh petnen the Height hts ga ‘sl aes sal apa an the asi ie that oa oct Si stain Thompeen "This book saa) concerned wih iemolecuar fore Let ws enter the ubjesiy bly reining Natori elope rm he ae {Grets othe preset ay 12 Ga m0 meDevA NonoNS OF RoTIMORICHA YoREES “The Gress ound tha they needed ony two fandamental Fore to account {oral natural phenomena! One ma Lave the ste wat Hate The Bt ‘oaght hing gether whe hewn aed champs The ea Wat=~ = ® SCS Cian and nemo oes tg ger ater fast proposed by Empstoces around 450 BC, was much “inprosed” by ‘inland ormed the arr of emi her foe 300 yee “Theuniens pper to have ten pricy sed by tah mysterious foros, or infunees, tha smatines appated ewe various forms of Inne (ce that ne mould now abel te apa or tone They tere imtgued by Uhescuonata-dstnce’ pope ahplaea by tee [ears av well a by gravitational orcs and were moved to ee upon ther hte What they laced in copcete experimental fs they moe {fee Protlem 11) Thay. magnet forse could ete dass though they Sit sh cae hy an ney Magnets il ed and they wee elie a love potions fo eng the casi ‘omen Unoranstey come mgnesc rosa lon hr powers rbbed ‘Dt pie (ot they tray recovered when tested with goats Hood) eee phenomena, were endowed ith atibuts no ls Specacat Imaniesing thomsen ae vike sparks io addon to ® mos) of ‘teeeve rep nuens tht appeted when flret bodies were rubbed gether All thee wondrous pass and meh be, ere oye your oebears tl wal ito the sevetenth 113. any Somstc Paso: CONTRASTS WN CRAMTATORAL FORCES nthe scyententh century our sujet etre fist phase of scien ‘Soutny. Nowion omidered how the fret betwen moles could be kod to the pial oper fate and itr numberof heat, ‘rntury yovachers invented the phenomenon a the expaay toe of Au gies toen In 908 Clirat seared ta expat could be ‘ipl the aration betwee thegud and gas mols was dle from he ateacton of he gd molcls for thease tt ao sed fat he hight sea gid cola dos not depend onthe capillary ‘llth whic df the contusion that tee frees mst eo ery hort rage (ori the language of the ie extended oer “ies? ‘rane ‘Daring the nite century was bleed tht one seus foros (or to Newtons aw forthe pavistonl fee) would ‘tently be ound to sncount fr litera tacons. Th ob ‘Tomb of interaction ponte were propos that arly contin the mas of the mae, testing to the bee at the te tat hee fore ar ltd to pein fren Ths, pi nerecton Ptethe force t F) bse then by FU) aide emmy oy here msm te he molecule mas thr separation, C x onsan an ‘some ins bevel tote 4 or 5 bch me) be compas sang nt forthe gravitational intescton “ hI 12) eis srt tse ow the power inden was 0 chown. are ‘roman apprecton othe fc hai cman brea over lrg distance, the valve of «most fe pee sn 3 Wis oe ‘a benoit a follow uppon te uracine plea e ‘0 moles o partes tobe a the onl larm noe at tn ites, Now comer 3 rgion of spe where the umber Sey ef shee moles sp This elon ean bet sli slid oe ec ‘exon in outer space etending ver sronomial dane oa a {he ltracton terse of one parca leu witha other ly inthe sate The mumber of mean fon of yas eee ea (4dr ancy will te par ar ne tr dr'b the rolane et oe She of ris 7 and hikes dete, of aes Sqr and tekoee {alteration energy of one motes ial he ther malas ‘sem wil there be pen by soley = [welt tcp 7] 5 wer i the diameter ofthe molecules snd Liste ste a he system (cx, hedimensoar fs soldorthetas tthe boc contnnee Sou Wn ss tha sine @ ist be sulle than L (hes a/f Ih aps na ‘Sinebutons to the neracion wil appeat cay fr values om eee thin 3h. form 45,6.) Bat form sa than the eed a aj (13) wl be eer and the comtbton fom more saa pee vl dominate over tha f nearby molecule tn sch ces soe a Prem mest bean acount arose fo he rion eet nd were data planes, sary, nd even sais at tl strongly ‘ering wit ach ether se Problem 12) nate ches we sale ht thesia derivations intrmokclar for pots do nde pre tat haaye eels Sapa, and itis forth reason that te bul peop of el has ol ae oot epend te vole of mater oon the ake Se este (ens ths ar extrerey smal Dut ony onthe vcs betncra See {nce proximiy to each other Imposten ngrans ate ae tho eat eps betwece matsp pers sonaen Cae Reming 10 the later par af the sotecoth century, hopes fo an altenbracng ore la dine a became teal spe aan ‘uta canste would be Tocoming i gle he seo oy oo @ 1.13 pera ct panphenome. Hower, y ths ie the modern concep of race tension [Brrr firmly etapa ewes he reonguton te the orc ar the ‘ne at thowe tat hl! moe together sn sos Bi, and {Body cae hy ares fom intercon acting over vey abst tans Than, kw chown hw thn ery sbortange surface eso ores ‘So secur or seh phenomena a plan. he shape of macoseope Iiuiddroplton sees the contac snglebetween cones oap tubes, fin he ep of ae water nto spel Jeoes (Fig 12) Tous {ft eased tat tery snortrange fret cam Had to er logan (ie, maroon) ene bu fabs dencopent mer tobe otha fom gut lent savers: oon work om porate hen gue In an attempt o spain why ral pate dot obey the idea gs ta (nV seers Pit the presi, tema ome the as constant. tnd Tbe temperature the Dutch phat Dan der Wal considered the efece oe uaractveforss betwee sels at «tine whee the er ‘steno awe Eno her ony war oi being oly debated) Tn BTS heaved at hs famous equation of wate forge and igs, (rai —by= Rr 0s) in which he brated the tr b from th ole to acount forthe ite ‘lof mola and added the term a/¥ tothe rere to account Sor the atcnctvelnemolesar oes now bow a sander Was fore ‘bythe eary tent cetary wa recon tat intermolcl fores sug oto spl tread the part foe si oc a ae Se) {o'r lee ambos sear foe seme expresso tat suid wzoun {oe weste phenomena Inthe ven ein 1903, proposed an imeraction pir potent of oe fom, male + Bie 06) ich fo theft ine iced repive tr aswel a an ata {em Thiwar the Sr oa sumbe of sar ws ses acount fers wide ange of pbevmena and tm tl sed today a8 the va det ‘Waailequaono tater we thallae how the pram in poteti Sich as he Ni pot sun te eaed ote constant sed bn the an (er Waals equation of sine Lament wes son found that any “iat potenti with a wide range of (adjustable) parameters would Satstetoriysscount or bem enpermen dt sah a hela A olds or te PCV“ tehaoor of une This while such min ‘saton; were cul se ate and cr ofthe foes themes ema a © WorkeD EXAMPLE @ Question: The Lemar-Jones pot wd aie 4 et an Isa special atthe Mi potenti (161 thi poeta the attri nog) constuton ibe van de Walston penal wick ‘ine wih the inverse sth power the dstance (Chapter) Make asitch how the eoorgy (0) nd force FC") vary wth r- What dour the {Camano pote pret forthe pation = rhe he nergy Se nn ol ae, a) eo my Ft) the rato afr deited by wr] = and (the ati of, 0 ‘Sather ethesepiaton beret ade oceans Fo? or the intercon between wo toms the rales fA a Ba own tote ont tad Ba 10°) mi” Whats aor theneacton| {hunt of HT at 38K, and what i the maximum adhesion fore Fon ‘wean the wo oma? I foe measurable ith sentinels dong: 2° Flite 13 shows shematie pl of wr and Fe {wr} iasmum when dw dr =O. The oor = r= (28/4) $Subutating so Eq (1.2) pee wr) on = = #8/4B = 4/2 anf) er) (ABCA) =f Sine (7 0 a roy (8/4 obtain lrg 2° = 112 ‘Th oe shen by P= sd Poy ota at dm) = ie Wen r= r= 268/74)" Tha rte (8/7 = 136 faba aS ey 85 10H /A1 10" 061K Fagen ide A020) at y= (268/74) © 03958 am TR ra ina ab 20 = M188 1 + Sonatina pron oats aan canna downs hot