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The hydrophobi c effect forms the basi s for many impor tant chemi cal phenomena. Enthalpy and entropy are often l eft with l I ttl e choi ce but to explain the hydrophobic effect.
The hydrophobi c effect forms the basi s for many impor tant chemi cal phenomena. Enthalpy and entropy are often l eft with l I ttl e choi ce but to explain the hydrophobic effect.
The hydrophobi c effect forms the basi s for many impor tant chemi cal phenomena. Enthalpy and entropy are often l eft with l I ttl e choi ce but to explain the hydrophobic effect.
116 Journal of Chemical Education Vol. 75 No. 1 January 1998 JChemEd.chem.wisc.edu
The Real Reason Why Oil and Water Dont Mix Todd P. Silverstein* Chemistry Department, Willamette University, Salem, OR 97301 Background Most i ntroductory chemi stry textbooks i ncl ude i n thei r di scussi on of sol ubi l i ty and mi sci bi l i ty the famous rul e of thumb, l i ke di ssol ves l i ke. The converse of thi s rul e, that nonpol ar sol utes are i nsol ubl e i n pol ar sol vents, i s often re- ferred to as the hydrophobi c effect. Thi s effect forms the basi s for many i mpor tant chemi cal phenomena: the cl eani ng acti on of soaps and detergents, the i nfl uence of surfactants on surface tensi on, the formati on of bi ol ogi cal membranes, and the stabi l i zati on of protei n structure are al l based i n l arge part on the hydrophobi ci ty of nonpol ar groups. I n thei r expl anati on of the hydrophobi c effect, i ntroductory chemi stry textbooks often rel y pri mari l y on the concepts of enthal py and i ntermol ecul ar forces. Because the sol uti on process i s gen- eral l y di scussed after enthal py, but before entropy or free energy, authors are l eft wi th l i ttl e choi ce but to emphasi ze enthal py over entropy when expl ai ni ng the thermodynami c basi s of l i ke di ssol ves l i ke and the hydrophobi c effect. For exampl e, one text states that octane and carbon tet- rachl ori de are mi sci bl e because the nonpol ar mol ecul es are both hel d together i n the l i qui d phase by weak di spersi on forces and thus are attracted to one another. However, for the very reason that both mol ecul es experi ence si mi l ar i ntermol ecul ar forces, H of mi xi ng shoul d be cl ose to zero. These mol ecul es are thus not attracted to one another i n the normal enthal pi c sense of the word, but rather i n an en- tr opi c sense. Spontaneous mi xi ng of the two phases i s dri ven not by enthal py, but by entropy. Regardi ng the i mmi sci bi l i ty of octane and water, an- other text states that the val ue of the over al l enthal py change, H sol uti on , i s l i kel y to be posi ti ve, refl ecti ng an endo- thermi c process. I n l arge part, i t i s for thi s reason that pol ar and nonpol ar l i qui ds do not mi x wel l . I n the l egend of an accompanyi ng fi gure, thi s text offers the most common (i n- correct) expl anati on as to why oi l and water dont mi x: The weak i nter mol ecul ar i nter acti ons between the nonpol ar mol ecul es and water cannot overcome the very strong forces between water mol ecul es and al l ow them to be mi sci bl e wi th water. Another versi on of thi s expl anati on appeared i n a recent overhead projector demonstrati on i n thi s J ournal, enti tl ed Why Dont Water and Oi l Mi x? The authors stated the argument thi s way: The water mol ecul es are attracted to each other through hydrogen bondi ngresul ti ng i n the expul si on of the nonpol ar oi l mol ecul es i nto a separ ate l ayer. They go on to descri be an overhead projector dem- onstrati on usi ng magneti c sti r bars to si mul ate the water water attracti on and marbl es to si mul ate nonpol ar sol utes. Once agai n, the probl em here i s the stress these authors pl ace on enthal py and hydr ogen bondi ng, whi l e omi tti ng any reference to the i mportance of entropi c effects. Thi s i ssue has i n fact sur faced i n the pages of thi s J ournal i n the past. I n a bri ef note publ i shed i n 1994, Al ger (2) poi nted out that many organi c chemi stry textbooks offer the same i ncorrect expl anati on for the i mmi sci bi l i ty of water and organi c l i qui ds. Huque (3), wri ti ng i n thi s J ournal i n 1989, pr ovi ded a detai l ed ther modynami c, stati sti cal - mechani cal anal ysi s of the hydrophobi c effect. Somehow the i deas stressed i n these papers and many others have been l argel y overl ooked i n i ntroductory and organi c chemi stry textbooks. 1 I n thi s paper I wi l l descr i be the scope of the probl em, present thermodynami c data al ong wi th a generall y accepted model that expl ai ns the hydrophobi c effect, and r ecommend how textbook author s shoul d appr oach the probl em. Discussion Fi rst consi der the di scussi on of the i mmi sci bi l i ty of oc- tane and water quoted above. The choi ce of octane as sol ute i s fortui tous because di ssol vi ng octane i n water i s, as these authors propose, sl i ghtl y endothermi c. However, thi s i s not the mai n r eason why octane does not spontaneousl y di s- sol ve i n water. I n fact, di ssol vi ng smal l er hydrocarbons such as ethane, propane, butane, and pentane i n water i s actu- al l y an exothermic process (see Tabl e 1). Even for hexane, benzene, tol uene, and xyl ene, H sol uti on i s cl ose to zero. What then i s the correct expl anati on for the hydrophobi c effect? Consi der hexane and water: they are i mmi sci bl e, yet H sol uti on i s about zero (see Tabl e 1). The reason for the i m- mi sci bi l i ty must ther efor e be entr opi c and not enthal pi c. Sei del l s thermodynami c data (4) showi ng the enthal py of sol uti on for most organi c l i qui ds i n water to be negati ve 2 were al ready avai l abl e i n 1941. I n the 1940s, Butl er (5) and Frank and Evans (6) were the fi rst to poi nt out the i mpor- tance of i ncreased order i n the aqueous phase i n expl ai ni ng the hydr ophobi c effect. Later, Kl otz (7), Kauzmann (8), Nemethy and Scher aga (9), and Tanfor d (10) devel oped fur ther Frank and Evanss entropi c model . Tanford i n par- ti cul ar performed a seri es of experi ments i n whi ch he mea- sured changes i n enthal py, entropy, and free energy upon transferri ng nonpol ar sol utes from organi c to aqueous sol vent phases. The data col l ected i n Tabl e 1 cl earl y show that the thermodynami c barri er to the sol uti on process i s entropi c rather than enthal pi c. How can we expl ai n thi s? How i s i t that H sol uti on i s zero for di ssol vi ng hexane i n water (Tabl e 1)? I s i t not true that i n order to i ntroduce a hexane mol ecul e i nto bul k sol vent, waterwater hydrogen bonds must fi rst be broken to create a cavi ty (11), after whi ch the sol ute mol ecul e may be i n- serted and al l owed to i nteract wi th surroundi ng sol vent? For thi s si mpl e seri es of steps the entropy shoul d be posi - ti ve (due to phase mi xi ng) and the enthal py shoul d al so be posi ti ve (because the br oken hydr ogen bonds ar e much stronger than the newl y formed di pol e-i nduced di pol e i n- teracti ons). However, the process does not stop there. What happens after the nonpol ar sol ute i s pl aced i n the aqueous sol vent cavi ty i s cl earl y expl ai ned i n most modern bi ochemi stry textbooks, especi al l y those devoted to bi ol ogi - cal membranes (1218). I f H i s zero for di ssol vi ng hexane i n water, then after the sol vent cavi ty forms, strong attracti ve i nteracti ons must be created to counterbal ance the posi ti ve enthal py of waterwater hydrogen bond breaki ng. Further- more, i f the process i s endergoni c and H i s zero, then S must be negati ve. Both of these facts may be expl ai ned i f one consi ders the change i n structure that takes pl ace i n the water cage sur r oundi ng the sol ute mol ecul e. Water *Email: TSilvers@Willamette.edu; fax: 503/375-5425. Information Textbooks Media Resources JChemEd.chem.wisc.edu Vol. 75 No. 1 January 1998 Journal of Chemical Education 117 mol ecul es at the surface of the aqueous cavi ty may compen- sate for thei r broken hydrogen bonds by maki ng extra hy- drogen bonds wi th nearest nei ghbors. The resul ti ng struc- ture i s often vi sual i zed as an i cel i ke cl athrate hydrate i n whi ch water provi des a hydrogen-bonded framework that contai ns hol esoccupi ed by sol ute mol ecul es. The frame- work resembl es i ce i n the sense that every water mol ecul e i s hydr ogen-bonded to four other water mol ecul es, but thegeometry of i ce i s somewhat di storted[whi ch] gi ves ri se to the types of cavi ty structures (3, but see di scussi on bel ow for al ternati ve model ). From thi s descri pti on i t i s easy to see that the newl y made hydrogen bonds i n the i cel i ke cl athrate structure com- pensate for the H-bonds that were broken i ni ti al l y to make the cavi ty; hence H coul d be zero or even negati ve. Fur- thermore, because of the i ncrease i n order and ri gi di ty upon formati on of the i cel i ke cl athrate hydrate, S for the pro- cess coul d easi l y be negati ve. Hi l debrand (19) has provi ded data that have been used to support thi s model , showi ng that at 25 C, methanes di ffusi on coeffi ci ent i n water i s 40% l ess than i t i s i n carbon tetrachl ori de (D H 2 O =1.72 10 5 cm 2 /s vs. D CCl 4 = 2.89 10 5 cm 2 /s). Presumabl y the l oose cl athrate water cages serve to i nhi bi t free di ffusi on of the nonpol ar sol ute. Fr om these data i t seems that both the nonpol ar sol ute (i n thi s case, methane) and the aqueous sol vent ex- peri ence a decrease i n entropy upon di ssol v- i ng i n water. Hi l debrands data have been i nterpreted as supporti ng the cl athrate cage model , but he hi msel f di d not accept thi s model as a l ogi cal expl anati on for the hydr ophobi c ef- fect. He stressed that i f cl athrate cages as such real l y exi sted, then methanes di ffusi on coeffi ci ent woul d be much l ess i n water, per- haps by one or two orders of magni tude, than i t i s i n CCl 4 . Al though the cl athr ate cage model has been wi del y accepted by most physi cal chemi sts and bi ochemi sts (1218, 28), i n fact, experi mental evi dence for the i n- ducti on of i cel i ke structure by the addi ti on of nonpol ar sol utes to water i s equi vocal (20, 21), and some r esear cher s have pr esented data that ar gue agai nst the exi stence of hi ghl y ordered cl athrate structures (11, 19 21). Several authors have devel oped an al ter- nati ve stati sti cal mechani cal approach cal l ed the scal ed parti cl e cavi ty theory (22). Si mu- l ati ons usi ng thi s theor y suggest that the hydr ophobi c effect stems mostl y fr om the smal l si ze of the water mol ecul e, rather than from hydrogen-bonded cl athrate structures (2327). Accor di ng to these r esul ts, the probabi l i ty of fi ndi ng an appropri ate voi d i n the fl ui d that wi l l accommodate a sol ute i s l ow because water i s such a smal l mol ecul e, not because of i ts hydrogen-bondi ng capac- i ty. Entropy l oss stems from the excl usi on of water from these rel ati vel y l arge sol ute cavi - ti es, decreasi ng rotati onal and transl ati onal freedom (2527) of the sol vent (and sol ute). I t i s i mportant to poi nt out that both the cav- i ty-based model and the cl athr ate cage model rest upon the fact that the hydropho- bi c effect i s entr opy, not enthal py dr i ven. The model s di ffer onl y i n how they expl ai n the source of the entropy l oss. Fi nal l y, r ecent news r epor ts featur i ng fl ami ng i ce retri eved from the ocean depths meri t a menti on here. The arguments di scussed above ex- pl ai n why oi l and water dont mi x at standard temperature and pressure. But they al so expl ai n why oi l and water do mi x bel ow the surface of the ocean or the arcti c permafrost. I n these regi ons of the earth, temperature i s l ow (often si g- ni fi cantl y l ess than 0 C), and pressure i s qui te hi gh. Both of these condi ti ons mi ti gate i n favor of the aqueous sol ubi l - i ty of nonpol ar sol utes. Recal l that for most nonpol ar sol utes, both S and H are negati ve; therefore as T decreases, sol u- bi l i ty i ncreases. And because the average densi ty of the two unmi xed phases i s si gni fi cantl y l ess than the densi ty of the aqueous sol uti on, as pressure i ncreases, sol ubi l i ty i ncreases. Fi nal l y, when these sol uti ons freeze under hi gh pressure, the hydrocarbon sol utes remai n stabl y trapped i n ti ght pock- ets i n the frozen hydrate. A recent report (29) stated that fro- zen cl athrate hydrates trapped beneath oceans and arcti c permafrost may contai n up to 53% of the worl ds organi c carbon reserves. Methane i s the most common gas found i n frozen hydrates, and the amount of methane i n these frozen reserves i n the U.S. al one may exceed [by more than 30-fol d] the esti mated total remai ni ng conventi onal methane resources i n the enti re worl d. I f effecti vel y mi ned, these enor mous r eser voi r s of fr ozen gas hydr ates coul d easi l y transform our energy economy from one based on oi l to one based on gas. Al l thi s from cl athrate hydrates! t a s e t u l o S r a l o p n o N g n i r r e f s n a r T r o f s n o i t c n u F c i m a n y d o m r e h T . 1 e l b a T 5 2 r e t a W o t t n e v l o S c i n a g r O m o r f C e t u l o S t n e v l o S H TS G a G b f e r H C 4 l C C 4 5 . 0 1 6 . 2 2 + 1 . 2 1 + 8 2 H C 4 C 6 H 6 7 . 1 1 6 . 2 2 + 9 . 0 1 + 8 2 H C 4 r e h t e 0 . 0 1 7 . 3 2 + 8 . 3 1 + 3 H C 4 e n a x e h o l c y c 0 . 0 1 6 . 7 1 + 6 . 7 + 3 H C 4 e n a x o i d - 4 , 1 9 . 1 1 9 . 7 1 + 0 . 6 + 3 H C 4 H C 3 H O 0 . 8 7 . 4 1 + 7 . 6 + 3 H C 4 C 2 H 5 H O 2 . 8 9 . 4 1 + 7 . 6 + 3 C 2 H 6 l C C 4 5 . 7 7 . 3 2 + 2 . 6 1 + 9 . 5 1 + 6 1 C 2 H 6 l C C 4 1 . 7 4 . 2 2 + 3 . 5 1 + 5 . 5 1 + 3 C 2 H 6 C 6 H 6 2 . 9 9 . 4 2 + 7 . 5 1 + 1 . 5 1 + 6 1 C 2 H 6 C 2 H 6 5 . 0 1 2 . 6 2 + 7 . 5 1 + 3 . 6 1 + 6 1 C 2 H 4 C 6 H 6 7 . 6 8 . 8 1 + 1 . 2 1 + 8 2 C 2 H 2 C 6 H 6 8 . 0 8 . 8 + 0 . 8 + 8 2 C 3 H 8 C 3 H 8 1 . 7 4 . 7 2 + 3 . 0 2 + 5 . 0 2 + 6 1 C 3 H 8 C 3 H 8 5 . 7 7 . 8 2 + 2 . 1 2 + 3 C 4 H 0 1 C 4 H 0 1 3 . 3 7 . 8 2 + 3 . 5 2 + 7 . 4 2 + 6 1 C 4 H 0 1 C 4 H 0 1 2 . 4 7 . 8 2 + 5 . 4 2 + 3 C 5 H 2 1 C 5 H 2 1 1 . 2 2 . 1 3 + 1 . 9 2 + 7 . 8 2 + 6 1 C 6 H 4 1 C 6 H 4 1 0 . 0 4 . 8 2 + 4 . 8 2 + 4 . 8 2 + 6 1 C 6 H 6 C 6 H 6 1 . 2 + 5 . 7 1 + 6 . 9 1 + 3 . 9 1 + 6 1 C 6 H 6 C 6 H 6 0 . 0 2 . 7 1 + 2 . 7 1 + 8 2 C 6 H 6 C 6 H 6 0 . 0 0 . 7 1 + 0 . 7 1 + 3 C 6 H 5 H C 3 C 6 H 5 H C 3 7 . 1 + 2 . 1 2 + 9 . 2 2 + 6 . 2 2 + 6 1 C 6 H 5 H C 3 C 6 H 5 H C 3 0 . 0 0 . 0 2 + 0 . 0 2 + 8 2 C 6 H 5 H C 3 C 6 H 5 H C 3 0 . 0 5 . 9 1 + 5 . 9 1 + 3 C 6 H 5 C 2 H 5 C 6 H 5 C 2 H 5 0 . 2 + 7 . 3 2 + 7 . 5 2 + 9 . 5 2 + 6 1 C 6 H 5 C 2 H 5 C 6 H 5 C 2 H 5 0 . 0 1 . 3 2 + 1 . 3 2 + 3 C 6 H 5 C 3 H 7 C 6 H 5 C 3 H 7 3 . 2 + 2 . 6 2 + 5 . 8 2 + 9 . 8 2 + 6 1 m r o - p e n e l y x - e n e l y x 0 . 0 3 . 4 2 + 3 . 4 2 + 3 Note: All thermodynamic data are in units of kJ/mol. a Calculated from experimental values of H and S. b Measured experimentally. Information Textbooks Media Resources 118 Journal of Chemical Education Vol. 75 No. 1 January 1998 JChemEd.chem.wisc.edu Conclusion Al though data and theory have been avai l abl e for more than hal f a century to expl ai n correctl y why oi l and water dont mi x, thi s knowl edge has not yet found i ts way i nto many i ntroductory and organi c chemi stry textbooks i n the Uni ted States. I t seems curi ous that after such a l ong peri od of ti me thi s error remai ns uncorrected i n i ntroductory texts; apparentl y, the si mpl i ci ty of the hydrogen-bondi ng expl a- nati on makes i t a powerful and attracti ve model . I nterest- i ngl y enough, some of the bl ame for the wi despread accep- tance of thi s expl anati on may l i e wi th pi oneeri ng membrane bi ochemists who, even as they developed a robust new entropi c model , confusi ngl y hel d onto aspects of the ol d enthal pi c expl anati on. Several exampl es of thi s are evi dent i n the l i t- eraturefor i nstance, i n hi s i ntroducti on, Tanford (16, p 3) refers to the domi nant rol e of water sel f-attracti on i n the hydrocarbon-water system and states that the cause of the [i mmi sci bi l i ty] effect must l i e sol el y i n a l ack of affi ni ty be- tween hydrocarbon and water. By usi ng terms l i ke water sel f-attracti on and l ack of affi ni ty, Tanford seems to retai n vesti ges of the ver y enthal pi c model that he pr oceeds to demol i sh several pages l ater. The fi nal questi on that must be addressed here i s what type of physi cal expl anati on for the hydrophobi c effect i s appropri ate at the begi nni ng undergraduate l evel . Shoul d textbook authors conti nue to offer the age-ol d si mpl e, fami l - i ar, but i ncorrect enthal pi c/hydrogen-bondi ng expl anati on? Most emphati cal l y not. Shoul d authors offer i n i ts pl ace de- tai l s of the correct entropi c expl anati on? Perhaps not. Thi s expl anati on may l i e beyond the scope of ei ther fi rst-year intr oductor y chemi str y or second-year or gani c chemi str y. There may not be any need for these students to know about cl athrate hydrate cages or scal ed parti cl e cavi ty theory. A di scussi on of the i mpor tance of sol vati on entr opy effects coul d fi t ni cel y i n the secti on on the hydrophobi c effect, but onl y i f the format of the text al l ows such a di scussi on (i .e., i f entropy and enthal py have both al ready been i ntroduced). Otherwi se, the si mpl e rul e l i ke di ssol ves l i ke, i n the con- text of a di scussi on of di ffer ent types of i nter mol ecul ar forces, seems qui te suffi ci ent. Acknowledgments I wi sh to acknowl edge here hel pful di scussi ons wi th my col l eagues Fr ances Chappl e, Nor m Hudak, Joyce Whi te- head, and Anders Ni l sson. Notes 1. Interestingly, my brief and anecdotal survey of European (British, French, German, and Swedish) introductory chemistry texts showed that these authors do stress the importance of en- tropy in explaining the hydrophobic effect. Perhaps this is because European introductory chemistry courses generally introduce the concepts of enthalpy, entropy, and free energy all together, in advance of their discussion of solubility. 2. Seidells monograph tabulated solubilities of organic liquids in water at various temperatures. From the decrease in solubility with temperature it was clear that the solution process was exo- thermic. By plotting lnK eq vs. 1/T it was possible to determine H solution from these data. Literature Cited 1. Pr avi a, K.; Maynar d, D. F. J . Chem. Educ. 1996, 73, 497. 2. Al ger, D. B. J . Chem. Educ. 1994, 71, 281. 3. Huque, E. M. J . Chem. Educ. 1989, 66, 581-585. 4. Sei del l , A. 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