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REPORT DOCUMENTATION PAGE ARRL-SR-AR-TH-O 0093 _ asec taer eee omy Piste op nor feruih Your Pom Tansy 2008 OAL, 1 Disember 1999~31 Junsry 2004 ws fe-aR ROE ——————— Sis n Busived Cova loc Ligue 0061 PAA LENNY MEE nergy, Rober A. a ‘Depanneetof Chemie REPORT NUDE ‘Nor Carta tle Datong en Raleigh, NC 227635-800¢ a HRSTRRTTGRF OA RENT RARER PND ARETE 6 OSES AEB ‘ATOSR ‘As Force Otne of eae ReveneNt, S15 Viton Bid ee 71 br-samsennmrars RR —] ‘Adlagea, VA 22031855 woes bsemsarene —“rominentrsmt 0040224 072 DISTRIBUTION STATEMENT A, nie Cadet! impli ebore- wna glondn. This wa complete ate tls under erg ndinveled aes af buteing cfs atau The balk of far weil lectern shes oobi ionic igcids, ily |-buy-}-nedginisnaien eraPuorepbooptat= ANA cl susion prota Weer ets at spect enol ih rll lacie was ound and explo and rc-on peo ved oot of poypyle Figen he arbennig were care, Te igus vrting evoke; eon pole __REEreEORE-—— TEER Te eR alicia aie ec u c 2 9199-$15-6970 Soe as oe inal Repout an Grant No-F49620-00-1-0061 Studies in Buffered Chlorusluminste Ionic Liquids This activity was limded feow: December 1, 1999 through January 37, 2004 for $308,421, In addition, a suppleroent of $30,545 was added from August £, 2002 through Jaomary 31 2004, This ws added as a separate ereut with the samc tt, ‘The Principal Investigator hus bun funded eontinunusly since 1971, by AFOSR. Lic haa been forlumets to have had ‘ncredibly capable Progeam Managers ~ Deno Elliol, Jolnn Wilkes, ugh De Long. andl Pal Trulove — wha have allowed hin: 9 perform this work, He's also boon forunsie ty have hut euperb students and pos-oce lover the years, without whorn none of the vark carried oat would have been done. Twa of his graduste sindenls were Air Farve officers sent to do Ph.D. work inthe molten sale arca. Appenilix A lists publications, which asknowledgc AFOSR suppor since support ‘was initiated ia 1971, Duting the period of suppor, the PU has ressivel several uovards, ‘which are Fisted ia Appendix C. All are in purl the result ofthe AFOSR yupport Tor the past sever moni, pst ot the eAfort has bosn dovored to witding down all, aboratoxy work and cleaning up a laboratory that has ad over 30 years of AFORR, support fo amass cemiaals aud equipment. With the PIs reticement, the luhoratory goes to oer researchers SFOM STAYEMENT A AgpiGved ior Public Retoase Uistibution Unamited SUMMARY OF WORK, 1 December; 1999~ 31 January, 2004 ‘Completed Wark 1. Work Curried Out Under Previous Grant Several manusesps ltd as “in press” o "suite inthe inal Report cn Canin 749620.96-1-0007, “Shidies of Talent Acidity and Nenval Buffered Chlorcshuminate Tonic Liguids,” have been published. ‘hese include: Robert A, Osleryoung. *Butlered Chioroaluminate Melts and Latent Acidity.” Proceedings af the Twelfth insernattonal Syupostin on Molten Rats, P-C. Trulove, HC. De Loug, G. R, Sifftee, and 8. Dele, Fas Proceedings Volunic 99-41, pp. 12-19, The Elecinichemical Society Penninatan, NI (2006). Diffusion Cosfficionts of Ferrocene in Composite Materials Concaining ‘Atubient Temperature Tonle Liquids, Mavele Kosmlski, Robert A Osteryoung, ‘ant Malgorvata Cisrkavske, J Blecrrechert Sor. 147, [454-1458 (2000). Use of the Ag/AgCUCT Electrode to Estimate $0 "Temperature Tonie Liquids, Peter Korourios and Rober! A: Osteryoung, Electrochem, Sue, 147, 3414-19 (2000). TL. Work Completed under Present Grunt ‘Most of the work varvled out under ais presout conte has heen published, o- in press Titles und Abstracts ofthe wouk follow. A, Halonluminate Fonie Liquids Buffering of 1-Rthy1-3-Methylimidazoliom Chtoride/Aluminum Chloride “Melt Using Alkali Mein] Beoraides and Hilides, Peter Ko-ouaivs aud Robert ‘A. Osteryoung, J Electrochem Soe., 148, B482.488 (2001). ‘The buffering of -cthy1-3-mcthy’ imidavotiure chloride (EMC) — oun tichlorido (AlCl) ragm-teemperature ionic liquids (celts) using alkalé metal bromides and ioeides cs suuied. ‘Ihe bromide of iocide salts wafer the mets, but she bromide of iodide ions donot replace the chloride iors in the melts ‘sy to depastt the alkali metas, and thus it may'be possible to wio those buffsred mets in peer souers, Tn melts buttered with aimixture of Tibia chloride and iodide itis ‘possible to both: doposit and slrp Hidhium metal. As as beau sec with mls ‘ruffered with a'kali mactal chlorides, the buifered melts appaur to be rane acidic than would bs expecled rot: the low concentration of the aside Aly Rober! A. Viens, Hugh C. De Tag, Robert A. Osteryoung. and Paul C. Tealave, “Studiex af Cativn Transport ia Multen Salts and Mollen Sult-Polymer Gels by Pulse-Fietd Gradient Spin-Kcho NMI," iroveedings of the Twelfk Internarional Ssmposiuon on Moltor Sais, B.C. Taulove, H.C. De Long, @. 8. Stafford, and 8, Deki, Eds. Proveestings Veluxac 99-41, pp. 269-176, the Eloctrocheroical Society, Penningloe, NT (2000), Abbstrac Pulsed fiekd-pradient spin-echo NMR as been e:el to detsrnrine the oafticients of te cation species in a series of chloroaluminate noom- lempecutuve molten salts as well as that of 1,2-dimethyl-3-peogslimilzoliata tetcafluroborate and a molten salt polymer gel. Based oa the diffusion coefficients, the activation ensrgy for diffusion of the meft cetious has been caleulsted, In eddition, rhe bydeodynaoie adie of the melt cation has been, etormined using the Stakes-Linstetn selaian B, Studies in Nou-Hulosluminate Tonie Liquids lectrocheraieal Properties of Alkali Metals in 1-ButyL3-Methylimidazoliumn Hexalluorophosphates, Deborea L. Boxall and Robsrt A, Ostcryoung, J Hlectrochens, Soc. 149, 2185-188 (2002). Abstract: Foetal potentials end diffusion coofficicuts ofthe alkali mesa! couples of Hehiuma, sedium und pulassium hexafluoraphoxphate salts dissolved im t-buty3- S-methsl-imidavofium keeaffnorphosphate wwese detecminod using a hanging ‘mercury drop elactrade as the working slesueds, Chroneampatomctry was used to decermine the diffusion cosffcients. which ranged fiom 1.4 x 10" to 4.5.x 10" ews far the Na and K cetions, respectively, Formal redustion potcnticls of ~2.96 £ 0.006 V and 335 + 0.003 V vs. the fermtene'ferocenium souple were obtains! Tor sndiure and potassium using nozmal pulse voltammetry. The presence of adsogprion maxima in the lihion noraal poise voltmamogeans eaditacd the use of chrmopotentiometry We celermtine # Huhium formal potential of -2.45 40.025 V. Apparent Anomaly During Rotating Disk Voltemonetry in Tonie Liquids, Daboral: L, Hossll, Tol I. O'Dea. and Robert A. Ostecsoung, J. Heotrucken: Soe. 149, FASB-FATI (2002), Allatrael: Aa apparent asaimaly is deseibed in whigh maxima on romaine disk ‘yan magrams for ferrocene oni¢aticu in an ion fiquid were found. The fonie liquid, 1-bcty}-3-methy] itnidazolinn hexellaorophosphate, boalmPy, is a enteric solvent of eureut interest. The muteima.ore shywn th be due lu the very high viscosity of thu wolvent, 3.26 poise, Which yields a unusuaily hiph Schmidt shumber of 3.5.x 10", compared a a value of shot £0" faraquenus solutions. This estimated that ovr 100 revultions af Ge dish are cxedad lo avhieve the Levich limiting current (oliowicg, application ofa voltage step t the disk, The current ‘Wansieat resutiirg ftom application ofa voltage stop ta tho matting disk is found to bei agreement with previowsly developed theory. even fr these highl ‘viscous systims, Analysis of the ransien! permits u determination of the Schuridt amumbers withon! measurement of the viscosity and devsily of the solvent, ar AdigTasion eoetTicient of the reacting species. Switching potentials and conductivity of polypyrrole films prepared in the ionic liquid 1-buty]-3-orcthylimidacofium hexalluarephusphate, Deborah E Boxall and Robert A. Osterysiung, Jf Rleerrache: Soe, 151, FAl-45 (2004). Abstract; Polypyrrole (ppy) and poly(N-anerylpyrnole) (pmpy) films we Prepared gelvanostatically af the ving of «rotating ring-disk electrode from the comesponding monomers disenlved in ionie Fu bul _methylimidazoliom hexaluorephuspha'e QheimPT 2). Rotating rings ‘voltammetry was used ‘o determine switching potentials and conductivity of the films while immerse in brniPF,. Switching potentials of 0.63 = 0.04 ¥ and 1,07-401.03 V vs, the cobaltoceniumycobaltocene couple, [CoCpa}, were determined for the pry ard prpy films, respectively, rom negative potential sean ‘voltammograms, Pevitive potential scan votamoetey was used to obtain the potential dependent conductivity ofthe films as the fas switched froma thelr insulating (at potentils morc negsl've than yeiching ptersiel) (a quasi-mclllic slate. ‘Two different computational models (son-Finear vs. Hneur conslustence agradiouts) and tw dierent redox peobes ([GoCps."? aad ecsmmethyHermcenium‘decarethyHenraosne} were uscd in the calculation of film eondustivity. ‘Ihe conductivity ofthe ppy films wus found to ineresso by an ordsr off magnimude for every 72:4 & mV change in the applied potential. At potentials Jess than the ssitching potential, he voadyctivigy of the pmpy films increased tenfold (or every 110°| 15 m¥ change inhe applicd potenrial. At poteutials treater han the switching potontal, the pmgy films required n 200 mV change to induce the sans degrce of change in film conductivity. OL, Personael Senior Rewarch Personnel De. Doterah Boxall Dr.John O'Dea Dy, Peter Kiranios AFOSR-11-19S5: | Jan. 1971 +28 Feb, 1975 10 APPENDIX A, Publications--Grant Reluied Activity - sinoe AFOSR smpport initiated, Janet Oste-young and R. 8. Ostaryoung, "The Advactage of Charge ‘Measurements for Delerinining Kinele Purartster,” Plectrachinsicn Acta, 16, 525 (1971). A.A. Osteryeung, "Intrsinotion to the On-Line Use of Compurers in bblostrochemistry,” Vol. 1, "Application of Compntsrs to Chemical Instrumentation,” Fa. by Mattson, Mark ard MacDonsl, Marco] Dekker (1973). LG, Boxall, HT. Jones and R. A. Oxteryoung, "Solvent Tgailitvia fn (AICI-NaCl Melis,” I. lecteochern, Soe, 1208), 223 (1973) LL Lloyd Jones, 1. Ct, Boxall and R, A, Osteryoung, "Organic Elsctrade Reactions in Fsed AICIy Containing Solven's,” I. Flocioanal, Chem. 38, 476 (1972). 1... Boxall, ML. Jones and &. A. Osteryoung, “blccttoaiemical Studies on As, Fe and Cu Species ir, AIC}4-NaC Melis” I. Fleetrosral. Chem. 121,212 (1974, lectinde Reactions af Ammare Amines 1 Blecteonaal. Chem. 49, 281 (1978), H, Hoye Tones and R. A. Osterynung in Solvents Comtsining Fused AICL3 RI. Gale and R. A. Osterycung, "Tuvest’gulior of Suhvalent Tan Tifeots During ‘ATuminun Aundization in Molten NaCI-AICl; Salveats,” J, Electtoctiem. Soe 121, 9831979) V.R, Kook J.T. Miler and 8 A. Ostrgoung, "Reductive Defunctonaivation of T-sctlituled Adamantanes in Moltsr Sodium Yotrachloroaluninsts,” J. Ore. Chem, 39, 2816 11974), H, Lloyd Jones ond R. A. Osteryounp, "O-ganic Renetiors in Molen ‘Telzachloroaluminate Sotvents." Advances in Molten Salt Chewmistry, Vol. 3, Eaited by J. Brawnstein, G-P, Seif and @, Mamantv, Plenum Publishing 1975). RI. Gale ard @. A. Osceryoung, “Dissociative Cliorination of Kittogen Oxides and Osyanions ia Molten Sodinm Chiloride- Aluminum Chloride Solvent,” Inorg, Chom, 14, 1232-1979), HL, Chm, V,R Koh, LT. Miller an R. A. Osteryoung, "An. Hlecl-ochemical Secutiny of Organomerallc Ion Conuptexes and Hexamethylocrzius ir a Room Tempcrature Molten Salt,” J. Aa. Chem. Soe, 97, 3264 (1975). 12. DE, Bartak and R, A, Osteryoung, "The Pleetochemicul Oxidation of A NIN\N'-Teuamethylbemidine in Molten Sodiun Tetrachlorealuminate.” J 1Hlccwochem, Soc, 122, 600 (1975). 13. I.Phillips, J. Galo. R,G, Wier end R, A, Ostorvoung, "Glassy Carbon Rotating Ring-Dise Electrodes for Motten Sull Stulies,” Anal Chem, 48, 1266 (1976) 14. D.T Basta aad RA, Osteryoug, "Ihe Redox Behavior of Tetzchloro- p-Bexzoqninons-Terachlorobylroquinons Systems in Mollen Aluminpm, Chloride-Sodium Chlride Solvents,” J, Electwanal. Chem. 74, 69 (1976), 31 Mav 197: 15. W.R-Koob. LL, Miller and 8. A. Osteryoung, “Hlectroniliaed Priedel-Crafts “Trausetkylations in a Rooen Temperature Moen Salt Med'a”"J. Atm. Chem. Sne., 98, 5377 (1976). 16. K.A.Paulson and R. A. Oergcung, "Pletroclesnital Studien ov Sulfur and Sulfies in AIC}g-NaC Melis" J. Am. Chem, Soc., 98, 6866 (1476) 1}, RA. Outeryoung, "Chemistry end Btectrochemistry in Alumiiaom Chloride “Motien Salt Systems,” Proceedings of the Syraposiur an Mule Salts, edited by 1B, Paisley J. Braunstein, K. Nobe, D.R. Morris, np. 240-282, The Electrochemical Society, Penuinguoa, NI (1976). AEOSR 765-2978; 1 April 1976 «30 June, 1979 18. L.Phillips aud K, A. Osterycung, "Molyblenuin Chemistey in NeClAICTs Melis al 175°C," J. Blesteockem. Soe. 124. 1405 (1977). J9. A, Robinson, B, Gilsext and R. A. Ontaryomng, "The Acid-Base Chemistry af ‘Oxide and Chalengenides iu Sodimn Yetachforosiuninate Metts at 173°C," Inorg. Chem., 16, 3080 (1977) 20, Helena Li Clumn, T. Ruhackui, J Philips aul R.A. Osteryunung, “Ligand Oxidation in Tron Diiraine Coraplexes, MM, Blcctrochemical Oxidation of triv-(alyoxalbis(ine¢hyliming))Iron(IQ” Inorg, Chem, 16, 1812 (1977) Helena Li Chow, ). Koran and R. A. Osexyoung, “Ihe Mleet-ochemical Behavior of Met Carbonglsin a Mixnue of s Room Temperature Molen Salt acd Thenzece,” J. Oxganometallic Chem., 140, 349 (1977), B 30. 34 }SR FADG20-79-L-0142: 1 June 1979 - 30 Spt Helena J. Chum, D. Koran and R. A Osteryoung, "Photochemistry a! Tron(iitrine Camplexes ina Roora Venipetature Molten Sal" 1. Aro, Chem Sac. 109, 181978) 4. Robinson and X. A. Osoryoung "Eeerocbemicl Studies of Scloninn and Selenium Compounds in Meten Sou Teteacloreatursnste Mel". Blostroohere. Soc, 25, 1454 97), ‘B. Cithert and R.A. Osteryoung, "Elecuochemica! Siucics on Nickel Electrodes in Motten Socun Teusebloroaliminstes,” J, Ara, Chena Sos., 100, 2725 (1978). Glob Mamantov and R, A. Osteryoung, “Acid-Dute Dependent Redox Cheraistry in Motien Chlorvolurninstes,” in "Charecterization Or Solutes ‘a Non-Aqueo.s Soluuions,” pe 225-250, G. Mercantov, Ea, Plonumn Publisting Co. (197). RJ, Gale, B. Gilbert and R. A. Outeryoung, "Ruman Spectma of Molten ‘Aluminum Chloride: I Butylpptidinium Chloride Systems at Ambient Temperature,” Trg, Chese., 17, 2728 -978) J.Robinson and. &. Oxleryaung, "The Llecteochemical Bebavior of Te} ie Radium Tettochloreatuminstes,”" f klectractsera, Soe, 125, 1784 11978) J, Robinson and R.A. Osteryoung, "The Electrochemical and Speccroscopic, Tiehavior of Some Aromatic Hydrecerbans in the Rocea Temperaurre Molten Salt System AlCl -Butylpyridinium Chloride,” J. Am. Chem. Soc., 301, 321 (1978) J. Robinson, R. C. Bug's, 11. L. Chum, D. Koran and R.A. Ostcryoung, 1H and 13¢ Nuclear Magnetic Resonance Specttoscopy Studies of unin Hetide-Alky! Pyridin've Llalide Molten Sais and Their Benzene Solutions," ‘Am. Chem. Soe, 101, 3776 (297%). RJ Gale und R. A. Osteryonng, "Porentiomenie Investigation of Dialurninu Hepraebloride Fonation in Aluminum Chloride: 1.butylpyridin‘um Chloride Mixtures,” Lueis. Chee, 18, 1603 (19). 1. Roblagon and R. A, Osteryoung, "The Tlestrochemical Bekavior of Abuminum inthe Lowy Temperature Molten Sate Systema a-Butel Pyridinivm Chloride; ‘Aluminum Chloride and Mixtuces of tis Moloen Salt with Benzene,” Bleewuchem, See, 127, 122 (1980). J. Robinson and LL A, Osteryoong, "An Tnvestigatin into the Electrochemical (Oxidation of Some Aronnati Aruised in the Roors Temperature Moltcn Salt, 33, 34 System AlCl2N-Butylpysidinium Clcride,” J, am. Chem. Sac. 102, 4415 £980), RJ. Gale and BR, A Osteryoung, “Hlectochemisal Reductin af Pyridininus loas in lenie Afuminnun Chloride-Alky pyridinium Ha‘ ide Atnbient Temperature Liquids," ), Blootwachom Soo, 127, 2167 (1980) RJ. Gale and R. A. Ostervoung, "Uleetsical Double Tayer al Meroury in Room ‘Temperature Aluminum Chloride. Burylpyridinien Chloride lonie Liquids,” IMeoteoebemica Acta, 25, 1527 (1980) RJ. Gale and R. A Osteryoung, "Iuftarod Speewal Investigations of Aribient Motion Aluminum Chlotide:-|-Butylpyridiniom Chloride Systems,” Inorg Chem. 19.2246 (1980), Taget Osteryoung and Emilia Nirowa-bisner, "Reverse Pulse Palesvgraphy,” ‘An, Chem. $2, 62-66 (1980). Roivhi Aoki, R. A. Osteryoung and Janet Osteryoung, “Ditlerential Nonnal Hulse Voltsmemetry," J. leectrosmal. Chem. 110, 1-18 (180), 81-0007, 1 October, 1990-31 August, 1984 39. 40. al, 43 +48 8, |, Welch and R, A. Osteryoung, “Elotrochemicd Studios in Low lemperature ‘Malien Sull Systems Containing Atominam Chlorides.” I. Hlestrounal. Chem, 138, 435-456 (1981), Z. Swilek, H. Lingaand R. A. Osteryoune, * Petermivation of Oxide in Baslo n-tsuy- pyri (Chloride Melts." J. Electronnal, Chom, 19, 365 “Viration Procedure le the jm Chlaride: Aten 0 (1981) Tl Linga, Z. Sijek and R. A. Osteryoung, “Electrochemistey of Titanium(™M in Basic n-B.ty pyridinium Chloride and Alumnara Chloride in Presence of Oxide," J, Amn, Chem. Soe, 103, 3754 (1981). Helena Li Chum, D. Korea aa¢ A. Osteryoune, "Subsinwent Teel in Tro, Dilmine Complexes: Conclsrions vith Thermodynamic Properias ina Room ‘Temperate Molten Sal,” Inorg. Chem. 20, 3304-3307 (1981). T_R. Beumleve, Joha I, ODea, Robert Oataryocug and Joust Ostsryoung, "Diftrer tal Normal Paks Voliommetr inthe Allereale Palse Made Reversible lestode Reactions” Anal Chem, 53, 702 (1980) T.R. Beumleve and Janet Osteryoung, "Iheory of Diffesential Normat Pulse Voltammetry in the Altemating Pulss Mode for Totally Ineversible Electrace Resotioms,” Ana’. Chem, $3, 988.991 (1980) 444. TLR Brumbeve, RA. Osteryoung and Junet Oslecyoung, "Differential Narmal Pulse Vottaamery for the Anodic Oxidatim of em(l Asal, Chem, 782-787 (1982), 245. TR. Brumave and Janet Ost in Reverse Pulse Voltaramtry, jung, "Spherical Piffosion and Shicldiag INeets J. Phys. Chet, 86, 1794-186 (1992), 46, G.T.Cheok and R. A. Ostryoung, "Plesirchemieal and Spectroscopic States 6 9,10-Anireypinone na Renn Temporsine Molton Sel" J. Elestchem Suse, 129, 248 (1982) 47. C.Neajundiah, K. Shimizu and R.A. Osteryoung, "Flevtrochemtcal Stadiss of o(U} and ¥e() in an Aluminua Chloride-Hurylpyriciniura Chloride Torie Liquid,” J, Electrochem, Soc,, £29, 2474 (1982), 48. G.T. Cheek and R. A. Osteryoung, "Preperatim and Characterization of a Substinted Alkvipyridinium Chlorosfuninate Mfoleen Salt System.” Inorg Chem, 21, A581 (198), 49, G,T.Cheek and R.A. Osteryoung, "An Tlectrachemical and Infrared Study of | Cioran in a-8-xylpytidininen Chloride: unin Chloride Tomie Liquid,” I. Hlectrachem. S00, 129. 2739 (1982). 50, Chenniah Nanjundiah wat R. A. Ostexyouny, "Flecirvshomical Shidies of Ca() and CulMD in wn Aluroimun Clioside-N4n-Dulylpyridisium) Chloride Fonie Tiguid,* J Blectastiom, Soe. 130, 13:2 (1983) $1, Snose Sahni ard R. A. Osteryouny, "Votur-mcric Determination of Waicr in ‘an Alumina Chlotiée-N-n-Butylpyidinina Chloride lonie Liquid,” Anal Chem, 55, 1970 (1983), Work related o pulse methodology development but aot supportel by AT.OSR. 52, Z, Kaxpinski and. A. Osteryoung, "Tlectrochsmical Shudies of Todine in an ‘Alunizon Chleride-Butylayeidinium Chloride lonie [utd I, Acidie Solvent ‘Compostian,” J, lectsoaual. Chem, 164, 281 (1984), D. A. Habbonsh and R. A. Osteryoung, "F ectrochemicsl Stadics of Sb) and ShCW) io Molten Mixtures of Alusuinun Chloride aud Butylpysidinium Caleride,” Trang. Cher, 23, 1726 (1984), R.A. Osteryoung, R. J. Gale {. Robinaon, R. Bugle und R, Gilbert, "Blesitou'erival Studies io Room Temperature Mallen Salts,” in "Proceedings of the Second International Symposium or. Molten Salts" J, Breuustein and R. Salman, es, 7g. 214-219, The Pleetrachemical Soviety, Pesninglon, NF (1981),