Document nmaYZM38Dzkj6QEr94xObrRXa

AR226-3355 PHYSICOCHEMICAL PROPERTIES Or FLUOROTELOMER ALCOHOLS M ary A Kaiser ttryi P Cabranchi,3 Chien-Ping Chai K a o / Pan! J. KrtiSic.1Alexander A. Marchiane, ' Robert L. Wateriond * and Robert C. Back 3 Ptegisf'h, ssfavi fcg&grh rvyi &$vf&gUR0r($', Abstract Physicochemical properties such as vapor pressure and water 1 solubility a r e necessary to d eterm ine environmental transp ort potential and environmental f a t e O fte n th e s e p rop erties are estim ated from models based an properties o f chem ically similar i materials. Fluorinated compounds, however, are especially d iffic u lt to model since th e properties o f fluorinated compounds j are quite d iffe re n t from their hydrocarbon analogues. Fluorotelom er Alcohols a r e also d iffic u lt to obtain in pure fo rm sin ce t h e y a re 'p rod u cts by p rocess' which a r e a m ixture o f several compounds each d iffe rin g by two carbon u nits and d iffic u lt to measure since many a r e solids a t room tem perature. Introduction The environmental f a t e o f perfiu onnated chemicals, such as fluorotelom er-based substances is o f growing interest.1-4 Fluorotelomer Alcohols, including 8 -2 Telomer B alcohol, C F s C C F ^ H a C K -O H , used in th e manufacture o f fluorinated surfactants and fluorinated polymers. These substances provide unique s u rfa c e modification properties in a wide variety o f consumer products. Fluorotelomer Alcohols are o f particular interest since they are expected to b e amor# th e possible compounds into which fluorotelom er-based su rfa cta n ts and polymers may potentially transform in th e environment. VWiln- <jtili,bili1y of8 -3 Tedj t t R Alcohol C JrtrC H ^ yM T<4rx<<w I I . SiotvibtHJ tin *. Hgritd.'3 1 * * 1 B? i tF Vapor P ressu re Three techniques were used to measure th e vapor pressure. VP Method 1 (refO 'Sh ee 8) - based on a dynamic measurement procedure developed by Sco tt - equilibrium temperature measured at a controlled pressure. - temperature varied from 80 to 200 C. - approximately 30 g o f th e 8 -2 Telomer B alcohol were placed in a boiler. The pressure was held constant to 0.01% {0.01 kPa) and measured to an accuracy o f 0.01 %. - Apparatus Mensor PCS400 presstre controller (San Marcos, TX) Parascientlfie 740 pressire transducer (Redmond. WA) Hart Scientific stack base unit for temperature measurement (Americm Fork, UT). VP M ethod Z (reference 9) - based on th e EPA OPPTS gas saturation m ethod (used to obtain the vapor p ressu re o f 8 -2 Telomer 0 Alcohol a t room temperature) - quantity o f a sub stance transported by a known volume o f a carrier gas is determined. - alcohol placed in a gloss therm os ta te d tube. G asc hromatogrephic grad e helium (99.999%) flow ed over t h e solid 8-2 Telomer B alcohol. - flow controller from a H ew lett Packard (now A gilent. Little Falls, DE) model 58 90 gas chromatograph - Due to th e adsorptive properties o f th e alcohol, th e vapor pressure was calculated from w eight loss r a th er than fro m th e weight o f trapped material downstream - vapor pressure is calculated from th e vapor density, W /V. by means o f th e equation P /Pa = W /V RTZtA,. where P is th e vapor pressure in Pa. W is th e mass o f transp orted substance in gram s, V is t h e volume o f satu rated g a s in cubic m eters, R is th e universal molar gas constant, T is th e tem perature In K, and M r is th e relative molecular mass - vapor p ressu re a t 21 C was 3 Pa VP Method 3 (r e fe r e n c e s 10J l ) gas phase nuclear magnetic resonance method measures the vapor density a t various temperatures relative to th at o f a much more volatile internal mass standard present in much smaller molar amounts o f die order o f 1 mol % vapor density is converted to vapor pressure using the ideal gas law or another appropriate equation o f stote. Solubility methods 1 and 2 GC/ECti and GC/MSD determination o f analyte in a closed, sealed, shaken container in the presence of excess sample Proton and Fluorine 6 a s rPhase N M R S p e c tra , o f 8 -2 T e lo m e r B Alcohol a t D if f e r e n t Tem peratures s CPtiCFaiaCejCMjCHjOH '-I Comparison o f Literature Vapor Pressures of H ex a f iuorobenzene with Vapor Pressures Obtained by Gas-Phase NM R with Least-Squares F its Based on the x Lefts Gaj-PHaceNM# Ampule Attached to VacuumSystembefore Sealingwith Tard % Center: Sealedampuleattached vfct Teflon* sleeve to Matching5 mmOD Slats Stub xHoldingTube. Tuberests firmly In aMaceA ceramicheadthatsealsthe heated X- compartment of commercial high-T NMRprobe X Right: Ampule Assembly loweredInto the magnet usinga string and not spun Vapor Pressure o f 8 - 2 Telomer 8 alcohol by th e Boiler Method with Le a s t Squares f i t using Antoine Equation. Also shovwi. Vapor Pressure a t 21 " C by Gas Saturation Method Vapor Pressure o f Se le ct Telomer Alcohols b y Sas-Phase NM R Spectroscopy Comparison with o th er methods Koa vs poL fo r Perfluoroalkylated Substances Ab-initio Calculation of AEibond T A (unbound) H-bond new fkml/moll : Conclusions: 1. The cyclic structure b has 0 weak H-bond. 2. There would be no significant change Inthe vaporpressure of the fluorotelomer alcohols dueto bonding o f type (b). Results & Discussions Vapor P ressure. T h e vapor pressure o f th e 8 -2 Telom er 8 Alcohol varies fr o m 3 Pa a t 21 C to 101 kPa a t 201 C . - a least-squares f i t o f the data, including th e low temperature measurement by th e gas saturation method, was obtained using th e Antoine equation log,o (P/kRa) = a - b/(c + 1/ C) (Figure 2) with th e parameters a = 6.457, b = 1623, and c = 163.3 - boiling point o f 20L3 C was extracted (vepor p ressire at IOL325kPa) - excluding th e gas saturation value from th e d a ta to be fitted has no e f fe c t on th e resulting Antoine parameters (as might be expected since it is several orders o f magnitude smaller than the boiler data a t substantially higher temperatures). W a ter Solubility. The solubility in w ater a t 12 C is 134 ppb ( 29 ppb)(134 g/L); 137 ppb ( 53 ppb) a t 25 C: 318 ppb ( 176 ppb) at 37 C . and 225 ppb ( 51 ppb) a t 60 C. Varying pH from 3 to 11 hod little or m impact on the solubility measurement. x 1Htkiter FlorisMxLem*.Remi W. ?.M.' deVoogt,Pirn. 1iokmefBuinmenralCoiilamtimmd : ToxM w (2003). 179 99-121. $i 2. ScWR,McIm o Ml. Smiskt, DoughsF.: ReW,JenniferK.EmromurrtalEngietrtogScieta . (2003). 20(5), 467-501. 3. tXmitrov.S: tonetsko, V- Wolher. 3. d: Winlie.W;%#y. RJlands,M.: Melwyai O.. SAOari QSASinmimnntrrtallciarch (2004). 15(1). 69-62) X 4. Stock hhornlL. Lou RomtU BUS.DavidA; Marlin,JonathanW; Miir, OerekC.&: Motury, Scott A. BiWwoenfalScienceanSTecImbgr (2004). 38(4), 991-996. 5. K,sso.. nxhratcdStrfccnntsaKtKpeBtnK. Moral fetter. Inu Net.for*, 2091.P 37. f: 6. Cotton.F. A: WiOdmon.G. AdvertedImytruc Chmusiry, Int*rsciencePii>Isl*i*:NewYork. 1966 v. 7. Barin, (l Ej Sirart, 0.Ej Tatto*. J.C.,Eds. OrgarctUnmcOimieny. PrkKtplesardOxmcrcid $ App/teolbns PlenistiProseNewVarV.1994. $: S.Scsn.UOetenitartonof ActivityCoefficient* byAatretcMesuremcntaf ftolingAwrt Diognini FluidReje Egiibfia 1966.26,149*163. 9. UsrtedStatesSwurncnm) ProtectionAgency,Cilice,at Prawntion.f'esnci* andT>c SiOslwices(7101),CPFTS830.7950, VaporPressure.Aujust 1996.p 13.Get Satiratbn MeIhod X 10. to w . A. 8x Krutlc. p.J,,- Snort,B. ExOefWer.W.ft.Jr. ftmoleeularKnetlcStudiai wfthKghTeimercturc6<a-Fhasel9FtWlt CycleoddtianfteocliensofFluoroolefin*. J. Amdiem.Sot A 2031,123.9956-9962. i- I l inalo.P.J. ftoe.D.________ _ 6m4>haseNMA. tUnettcMoaureraami, V t falser,Mary A.. CobrancfV.OayfP., tej.Oaen-Prw uri Brnk.Robert C,Riyjleoehemlcd [Gertieof Engr Dato,inprejt. X 13.Moiri L Steak,DavidA. 01tt.LifaOefceb*d!.Dn-d<C6. Mor.uri Scott A.Matut. V Prmsureaof IheRuonnatedTcSonurAlcriiols-Unutatieniof EotsnationMuhods Emiron. Set TechnoL 2004: Jg6)pp1693-1699