UVvisible Spectroscopic Study on Nitrophenols Ionization Reactions to 225 o C


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1 P R E P R I N T ICPWS XV Berlin, September 8 11, 008 UVvisible Spectroscopic Study on Nitrophenols Ioniztion Rections to 5 o C Jn Ehlerov, Lilin Trevni b, Josef Sedlbuer, Krine BllertBusserolles c nd Peter R. Tremine b Deprtment of Chemistry, Technicl University of Liberec, Liberec, Czech Republic b Deprtment of Chemistry, University of Guelph, Guelph, Ontrio, Cnd N1G W1 c Lb. de Thermodyn. des Solutions et des Polymères, Université Blise Pscl, Aubière, Frnce Emil: The UVvisible spectr of queous o, m, nd pnitrophenol were mesured s function of ph t tempertures from 50 C to 5 C t pressure of 7 MP. These were used to determine equilibrium constnts for the cid ioniztion rection of ech isomer. The new erimentl results, long with dt from the literture, were used to develop thermodynmic model to describe the dependence of ioniztion properties on temperture nd pressure. The model yields predictions of the ioniztion constnts for o, m, nd p nitrophenol, log K, to t lest 50 C nd 0 MP with n estimted uncertinty in log K of less thn ± Therml decomposition studies, crried out by using the system s stoppedflow rector, showed tht the three isomers re significntly more stble in HCl cid solutions. At tempertures bove 5 o C nd lkline solutions, the residence time of the solution in the cell nd the preheter is so long tht significnt chnges in the spectr of the nitrophenolte species re observed in stoppedflow eriments s n indiction of therml decomposition rections. Introduction Nitrophenols re used s rw mterils in the chemicl, phrmceuticl, dyes nd herbicides industries, nd re lso produced in gsphse oxidtion of simple romtic hydrocrbons [1]. Their toxicity is high even t trce levels, prticulrly for green plnts nd for qutic orgnisms in surfce wters. Thermodynmic properties re needed for the design of effective remedition technologies, for instnce, stem oxidtion. Nitrophenols re wellknown colorimetric ph indictors, due to the differences in the UVvisible spectr of the protonted nd unprotonted species ( nm). However, only the ioniztion constnts for pnitrophenol hve been determined t tempertures bove 75 C by colorimetric methods []. The min objective of this work ws to supplement the existing erimentl informtion on queous nitrophenols (see for instnce references in [3]) by determining their cidbse ioniztion constnts over wide rnge of temperture. A second objective ws to develop thermodynmic model ble to describe these rections in form tht is suitble for developing predictive models, such s functionlgroup contribution models, for describing the properties of structurlly similr solutes in wter. Experimentl Methods Ioniztion constnts were mesured by UVvisible spectroscopy in high temperturehigh pressure pltinum flow cell with spphire windows. A schemtic digrm of the cell nd injection system is shown in Figure 1. Detils of the construction re described elsewhere [4]. Ammoni/mmonium buffer solutions were used to prepre nitrophenol solutions t fixed nd known ph, with different rtios of protonted to unprotonted species. To determine the spectr of the fully protonted nd fully unprotonted indictor, nitrophenol ws dissolved in solutions of dilute HCl(q), (the cid extreme ) nd NH 3 (q) or Figure 1: Schemtic of high temperturehigh pressure cell nd injection system.
2 NOH(q) (the bse extreme ). For o nd p nitrophenol t 5 o C nd NOH(q) (the bse extreme ) for mnitrophenol nd pnitrophenol t tempertures under 00 o C. Therml Stbility Experiments Stoppedflow eriments were conducted t 5± nd 5±C in order to study the therml stbility of nitrophenols in the queous mmoni/mmonium buffer solutions nd in the solutions of HCl(q), NOH(q) nd NH 3 (q) used to define the two extremes. In these eriments the flow ws stopped for 10 minutes nd the bsorbnce spectr between 50 nd 500 nm were mesured every 30 seconds. Significnt timedependnt chnges in bsorbnce were observed only for the o nd p nitrophenol solutions in queous NOH t 5 o C, but not for mnitrophenol. When NH 3 ws used insted of NOH, the chnges were smll nd comptible with the time scle of the eriments (collection times). Typicl results re shown in Figures nd 3. No ttempt ws mde to determine the decomposition mechnism in lkline medi or to identify the decomposition products. Although the uncertinty ssocited with eriments t 5 o C is somewht lrger thn tht t lower tempertures, the erimentl results t this temperture were included in the model presented below. Figure : Stoppedflow eriment for onitrophenol in lkline medi t 5 C nd 7 MP : () in NOH(q) nd (b) in queous NH 3 (q). Time between spectr, 30 seconds. Spectroscopic nlysis UVvisible spectr for the solutions of o, m nd pnitrophenol t constnt pressure, 7 MP, nd tempertures from 100 C to 5 C were collected t wvelength intervls of 0.5 nm from 00 nm to 800 nm nd scn rte of 100 nm.min 1. Representtive spectr for ll three isomers t 175 o C re shown in Figure 4. The temperture rnge ws determined by the useful ph rnge of the mmoni/ mmonium buffer solutions which defined the low temperture limit, nd the therml stbility of the indictor. At tempertures over 5 C, the results my include systemtic errors becuse of therml decomposition of the indictor. The deconvolution of the nitrophenol spectr in the buffer solutions ws crried out by liner combintion of the spectr of the cid nd the bse forms of the nitrophenol species (Beer s lw). From the deconvolution of the spectr obtined for ech buffer system, the concentrtion rtio of ionized nd unionized forms of the nitrophenol Figure 3: Stoppedflow eriments for mnitrophenol in NOH(q) bse extreme nd p nitrophenol in NH 3 (q) bse extreme t 5 C nd 7 MP. Time between spectr, 30 seconds.
3 (the indictor rtio ) could be determined t known ph. These rtios could then be used to clculte the ioniztion constnt. The resulting vlues of the fitted ioniztion constnts for ll the buffer solutions were verged to determine the erimentl pk vlue t ech temperture. The number of buffer solutions t ech temperture rnged from to 6. Results Averge pk vlues for the three nitrophenol isomers re tbulted elsewhere [3], long with their estimted uncertinties. The uncertinty estimtes re composed of the stndrd devition of the clculted pk s t given temperture plus the contribution of possible systemtic errors in solution preprtion. The two uncertinty contributions re usully comprble nd do not exceed 0.03 pk units ech, leding to totl uncertinties of up to 0.06 pk units. nd clculted vlues, respectively, nd σx is the estimted erimentl uncertinty. F = + + P j= 1 Q k= 1 O i= 1 pk pk σpk ΔH ΔH σδh ΔC p, ΔC σδc p, clc clc p, clc k j i R l= 1 ΔV ΔV σδv clc l Thermodynmic model Our erimentl vlues of pk cn be combined with other thermodynmic dt for nitrophenol ioniztion tken from the literture. These include stndrd prtil molr enthlpies ΔHΕ, volumes ΔVΕ, nd het cpcities ΔC p Εwhich re known ner 5 ΕC. Together with our results, there re enough erimentl results to develop model describing the chnges of K for ech nitrophenol with temperture nd pressure. Severl equtions of stte for the stndrd thermodynmic properties of hydrotherml solutions could be pplied for this purpose [e.g. 5, 6, 7]. The model proposed originlly by Mrshll nd Frnck [6] s correltion tool for the ioniztion constnt of wter ws chosen, becuse of its simplicity. For K the eqution tkes the form, ln K = pk.ln10 = b c d f g = e.ln ρ w T T T T T where ρ w is the density of wter, T is thermodynmic temperture, nd g re fitting prmeters. Other ioniztion properties re obtined by pproprite derivtions of this eqution. The ioniztion dt for ech nitrophenol were subjected to simultneous weighted fit with the objective function where nd clc stnd for erimentl 3
4 Figure 4 : Normlized spectr t t = 175 C, p = 7 MP for queous o, m, nd pnitrophenol. The rrows indicte the direction of incresing ph. The resulting fitted prmeters of the Mrshll Frnck model for the three nitrophenols re reported in [3]. Figure 5 provides grphicl comprison of erimentl K with predictions of Mrshll nd Frnck model long the sturtion line for wter. The fit of the model to the erimentl dt ws well within the estimted uncertinties of ll the dt used in the regression. The only erimentl vlues for comprison with our results re the ioniztion constnts of pnitrophenol reported by Shin et l. [] t tempertures up to 00 C. These were obtined by UVvisible spectroscopy using methods similr to ours in btch cells, rther thn flow cell. The results gree to within the combined estimted uncertinties, lthough Shin et l. s results for pk for p nitrophenol re systemticlly more positive with incresing temperture below 175 C. We regrd their mesurement t 00 C s suspect, becuse of the possibility of therml decomposition, which should be more pronounced in btch cell due to the much longer osure times. Possible resons for the systemtic difference between the two studies include the choice of ctivity coefficients, nd pproximtions used in dt tretment. Unfortuntely, it is not cler from the Shin et l. pper, how the solutions were prepred nd wht ws the trget ionic strength, so we could not reconstruct their tretment precisely. Solvtion Effects The effects of temperture nd pressure on solvtion re reflected in the stndrd stte thermodynmic properties derived from the model [6], see Fig.6. In our judgment, the dtbse from which the model prmeters were fitted is too limited to permit relistic estimtes of the uncertinties ssocited with these clculted derivtive functions by error propgtion nlysis. Insted, pproximte uncertinty limits were estimted from the reltive error of model predictions from erimentl pk dt, nd the mgnifiction of uncertinty upon derivtion, to determine the uncertinties in other properties [3]. This leds to estimted uncertinties in ΔH of kj mol 1 ; ΔS, 36 J K 1 mol 1 ; ΔC p,, J K 1 mol 1 ; nd ΔV, cm 3 mol 1 where the lower limits re for 5 C, the upper limits for 00 C. The lrge uncertinty in ΔV t elevted tempertures rises becuse with the exception of the volumetric dt t 5 C, the clculted vlues re entirely Figure 5: Ioniztion constnts of nitrophenols corrected to p st, plotted s pk vs. T. Fitted Mrshll nd Frnck model (full line). pk dt from this work corrected from p = 7 MP to p st (>); onitrophenol from Judson nd Kilptrick [8] ( ); mnitrophenol from Robinson nd Peiperl [9] ( ); pnitrophenol from Judson nd Kilptrick [8] ( ); pnitrophenol from Shin et l. [] ( ) temperture dependence, rther thn the pressure dependent on prmeters determined by fitting the dependence of pk. There re significnt differences in the properties of the three isomers t room temperture. These hve been ttributed to the electronwithdrwing effects of the nitro group, which stbilize the nitrophenolte nion, nd to solvtion effects tht mnifest themselves in the entropy, het cpcity nd volume of ioniztion. The electronwithdrwing effects re lrger for the o nd p isomers thn for mnitrophenol (See, for exmple, 4
5 Dewick [11]). Fernndez nd Hepler [1] hve noted tht mnitrophenol is weker cid thn o or pnitrophenol t room temperture becuse its entropy of ioniztion is significntly more negtive, nd not becuse of more endothermic enthlpy of ioniztion. Apprent molr volume nd het cpcity mesurements on p nd mnitrophenol nd their sodium slts [13, 14] suggest tht this effect rises primrily becuse of differences in solvtion for the unchrged species, with V (p NphOH) < V (mnphoh), nd C p (pnphoh) < C p (mnphoh). These observtions re ll consistent with solvtion effects in which wter is more tightly bound by the o nd p isomers thn by the m isomer t 5 C. Although the reltive positions of the Gibbs energies of ioniztion of the isomers do not chnge with incresing temperture, there re chnges in the contributions of the stndrd stte enthlpy nd entropy. While both ΔH nd ΔS become incresingly negtive with incresing temperture, the entropic term is the mjor contribution to the Gibbs energy of ioniztion bove bout 00 C, i.e. the bsolute vlues of T ΔS >>ΔH. This effect hs been observed for gret mny cids nd bses [15, 16]. It rises from longrnge polriztion of wter by the chrged nion nd hydrted proton, n effect which becomes much more importnt t elevted temperture s the dielectric constnt of wter decreses. While the reltive order of ΔH nd ΔS for the three isomers t tempertures bove 00 C is the sme s tht t room temperture, ΔS (mnphoh) < ΔS (pnphoh) ΔS (onphoh), the reltive position of the orthoisomer t intermedite temperture chnges significntly, so tht ΔS (mnphoh) < ΔS (o NphOH) < ΔS (pnphoh). This effect, which lies just outside the combined estimtes of estimted uncertinty, my reflect the competing effects of loclized hydrogen bonding bout the unchrged species nd solvent polriztion effects. Tempertures in the rnge t 100 C to t 50 C re typiclly considered trnsition region, in which wter behves like norml hydrogenbonded solvent, so tht both effects re often of similr mgnitude. Functions of the stndrd prtil molr het cpcity nd volume functions, ΔC p, nd ΔV, show tendencies tht re ssocited with solvent polriztion effects. There is the trnsition with incresing temperture from the distinctly different erimentl vlues for ech isomer t mbient tempertures, through mximum, towrds the lrge negtive vlues ssocited with solvent polriztion in the nercriticl region [15,16]. Becuse ΔC p, nd ΔV re derivtive functions, Figure 6: Stndrd prtil molr het cpcity, ΔC p,, nd stndrd Gibbs energy of ioniztion, ΔG, of nitrophenols s function of temperture t p st. Full line: onitrophenol; longdshed line: m nitrophenol; shortdshed line: pnitrophenol there is considerble uncertinty in the hightemperture vlues, so tht the results for the three isomers bove ~ 150 C gree to within the rther lrge combined error limits. Mesurements re under wy to determine the stndrd prtil molr het cpcity nd volume of ech isomer nd its conjugte bse, in order to confirm whether significnt differences do exist t elevted tempertures. Acknowledgement This work ws supported by the Interntionl Assocition for the Properties of Wter nd Stem (IAPWS Young Scientist Fellowship for J.E.); the Nturl Sciences nd Engineering Reserch Council of Cnd (NSERC); nd by the Reserch Centre of Advnced Remedil Technologies nd Processes t the University of Liberec. Literture 5
6 [1] J. Tremp, P. Mttrel, S. Fingler nd W. Giger: Phenol nd nitrophenol s tropospheric pollutnts: emissions from utomobile exhust nd phse trnsfer in the tmosphere. Wter Air Soil Pollut. 68, (1993) [] T.W. Shin, K. Kim nd I.J. Lee: Spectrophotometric determintion of the cid dissocition constnts for ccodylic cid nd p nitrophenol t elevted tempertures. J. Sol. Chem., 6, (1997) [3] J. Ehlerov, L. Trevni, J. Sedlbuer nd P.R. Tremine: Spectrophotometric determintion of the ioniztion constnts of queous nitrophenols t tempertures up to 5 ±C. J. Solution. Chem., 37, (008) [4] E. Bulemel, L. Trevni nd P.R. Tremine: Ioniztion constnts of queous glycolic cid t tempertures up to 50 ±C using hydrotherml ph indictors nd UVvisible spectroscopy. J. Sol. Chem., 34, (005) [5] J.C. Tnger nd H.C. Helgeson: Clcultion of the thermodynmic nd trnsport properties of queous species t high pressures nd tempertures: Revised equtions of stte for the stndrd prtil moll properties of ions nd electrolytes. Am. J. Sci. 88, (1988) [6] W.L. Mrshll nd E.U. Frnck: Ion product of wter substnce, C, 1 10,000 brs. New interntionl formultion nd its bckground. J. Phys. Chem. Ref. Dt, 10, (1981) [7] J. Sedlbuer, J.P. O Connell nd R.H. Wood: A new eqution of stte for correltion nd prediction of stndrd moll thermodynmic properties of queous species t high tempertures nd pressures. Chem. Geol. 163, (000) [8] C. M. Judson nd M. Kilptrick: The effects of substituents on the dissocition constnts of substituted phenols. I. Experimentl mesurements in queous solutions. J. Am. Chem. Soc. 71, (1949) [9] R. A. Robinson nd A. Peiper: The ioniztion constnt of mnitrophenol from 5 to 50 C. J. Phys. Chem. 67, (1963) [10] K.S. Pitzer: In: Pitzer, K.S. (ed.) Activity Coefficients in Electrolyte Solutions, nd edn. CRC Press, Boc Rton (1991) [11] P.M. Dewick: Essentils of Orgnic Chemistry. Wiley, New York (006). Chp. 4 [1] L.P. Fernndez nd L.G. Hepler: Hets nd entropies of ioniztion of phenol nd some substituted phenols. J. Am. Chem. Soc. 81, (1959) [13] H.P. Hopkins, W.C. Duer nd F.J. Millero: Het cpcity chnges for the ioniztion of queous phenols t 5 C. J. Solution Chem. 5, (1976) [14] C.L. Liott, A. Abidud nd H.P. Hopkins: Thermodynmics of cidbse equilibriums. IV. Influence of solvtion fctors on cidity. Volumes of ioniztion of the m nd pisomers of nitrophenol nd formylphenol in wter t 5 o C. J. Am. Chem. Soc. 94, 864 (197) [15] R.E. Mesmer, W.L. Mrshll, D.A. Plmer, J.M. Simonson nd H.F. Holmes: Thermodynmics of queous ssocition nd ioniztion rections t high tempertures nd pressures. J. Solution Chem. 17, (1988) [16] P.R. Tremine, P. Bénézeth, C. Xio nd K. Zhng, in: D.A. Plmer, R. FernndezPrini, A.H. Hrvey (eds.) Aqueous Systems t Elevted Tempertures nd Pressures: Physicl Chemistry in Wter, Stem nd Aqueous Solutions, Chpt. 13. Elsevier, Amsterdm (004) 6
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