HANSEN SOLUBILITY PARAMETERS IN CHROMATOGRAPHIC SCIENCES ADAM VOELKEL, K. ADAMSKA POZNAŃ UNIVERSITY OF TECHNOLOGY, POLAND
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1 HANSN SOLUBILITY PARAMTRS IN CHROMATOGRAPHIC SCINCS ADAM OLKL, K. ADAMSKA POZNAŃ UNIRSITY OF TCHNOLOGY, POLAND
2 SOLUBILITY PARAMTR THORY nergy f varzatn g l U ar U T d Chesve energy densty c c ch H w RT Slublty arameter unts : cal/cm 3 ) /, (J/m 3 ) /, (MPa) /
3 HANSN SOLUBILITY PARAMTRS (HSP) d h d h T d h
4 δ T = δ d + δ + δ a δ b ln γ h = RT δ d δ d + δ δ + δ a δ a δ b δ b ln K = RT δ T m δt S + δ d δ d S δ d m + δ δ S δ m + δ a δ b S δ b m + δ b δ a S δ a m R.Tssen H.A.H.Bllet, P.J.Schenmakers, Use f slublty arameters fr redctng selectvty and retentn n Chrmatgrahy, J.Chrmatgr., (976)
5 lsc = n A ad s + A + A ad = slvent; ad adsrbent; = slute Lqud sld chrmatgrahy s = δ δ d δ d δ δ δ n δ n δ a δ b δ a δ b A ad = δ d δ ad d + δ δ ad + δ ad n δ d + δ n δ ad d + δ a δ ad b + δ ad a δ b lsc = A ad A A A ad A, A mlecular area f and ; δ ttal slublty arameter; δ d - dsersn slublty arameter; δ - rentatn slublty arameter; δ n - nductn slublty arameter; δ a - rtn dnr slublty arameter; δ b - rtn akcetr slublty arameter B.L.Karger, L.Snyder, C. n, xanded Slublty Parameter Treatment fr Classfcatn and Use f Chrmatgrahc Slvents and Adsrbents, Analytcal Chemstry, 50 (978)
6 Lqud lqud chrmatgrahy k = slvent; k lqud statnary hase; = slute M = δ + δ δ d δ d δ n δ d δ n δ d δ a δ b δ a δ b S d d n d n d ab ab M k M S k S llc llc llc = δ k δ δ d δ d k δ d δ n δ d k δ d δ d δ n k δ n δ δ k δ B.L.Karger, L.Snyder, C. n, xanded Slublty Parameter Treatment fr Classfcatn and Use f Chrmatgrahc Slvents and Adsrbents, Analytcal Chemstry, 50 (978)
7 Retentn n gas-lqud chrmatgrahy δi = RI al RI δi retentn ndex dfference between a slute and hythetcal n-alkane al f the same mlar vlume as n statnary hase δi = 00 S CH δ al δ d δ d + δ n δ δ δ n δ d δ a δ b δ b δ a B.L.Karger, L.Snyder, C. n, xanded Slublty Parameter Treatment fr Classfcatn and Use f Chrmatgrahc Slvents and Adsrbents, Analytcal Chemstry, 50 (978)
8 Flry Huggns nteractn arameter SOLUBILITY PARAMTR IGC g ρ ρ B T R M R χ ln 73.5 ln and dentes the slute and examned materal, M -the mlecular weght f the slute, 0 -the saturated var ressure f the slute, B -the secnd vral ceffcent f the slute, 0 -the mlar vlume, -the densty, R -the gas cnstant ln g B T R R χ
9 GUILLT - DI PAOLA BARANYI APPROACH s RT s RT RT RT ()
10 HSP THROUGH IGC PROCDURS Cmbnatn f the exermental data f Flry-Huggns nteractn arameter wth cmnents f arameter fr test slute and examned materal RT slublty, d, d 0,, 5, h, h,5 0, where α,, R, T are a crrectve ceffcent, mlar vlume f the test slute, gas cnstant and temerature f measurement, resectvely. K. Adamska, R. Bellnghausen, A. elkel, New rcedure f the determnatn f Hansen Slublty Parameters by means f nverse gas chrmatgrahy, J. Chrmatgr. A, 95 (008)
11 BASIC RLATIONS N L K L K GL A GL K LS A LS g 3 t ' R F m w 73.5 T
12 Mdel f adsrtn descrbed by Snyder and Karger SOLUBILITY PARAMTR FOR SOLIDS cnst RT A g ln h h d d A
13 HSP FOR SOLIDS d h n nd n n n n nh * n n N N Nd N N N Nh N N Y X Y - the clumn vectr cntanng the N values f exermental measurements f the energy f adsrtn ( - N ) f N slutes, X - the exermental matrx, frmed f elements (X nk ), where, n s the mlar vlume f the n th slute and nk s ne f the Hansen Slublty Parameters f tye k (k = d,, r h) f the resectve test slute, Β - the vectr whch cntans the real values f HSPs f the adsrbent, ε the vectr whch crresnds t the exermental errrs, ε n.
14 Rle f Hansen slublty arameters n sld hase extractn HSPs and ttal slublty arameter fr srbents, eluents and analytes K. Belcka-Daszkewcza, A. elkel, M. Petrzyńska, K. Heberger, J. Chrmatgr. A, 7 (00)
15 Scre lts fr srbent-analyte, slvent-analyte, srbent-slvent systems : left ndcated stn f slvents rght - ndcated stn f srbents K. Belcka-Daszkewcza, A. elkel, M. Petrzyńska, K. Heberger, J. Chrmatgr. A, 7 (00)
16 I tuta tabelk z steru Squares f dfferences f srbent-analyte ars Squares f dfferences f srbent-slvent (eluent) ars 6
17 Takng nt accunt that the use f ethanl allwed t acheve better recvery, t can be cncluded that: ) the srbent fr whch the lwest (δ P δ A ) value s fund shuld be selected as a materal f fllng the needle devce; ) the value f (δ P -δ S ) des nt have t be as small as ssble, ) the nteractns between the analyte and the slvent are mre mrtant fr the extractn rcess than the nteractns between the lymer and slvent. Therefre, fr the selectn f a sutable extractn system shuld start frm fndng lwest value fr (δ P -δ A ). 7
18 THANK YOU FOR YOUR ATTNTION
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