Correction for axial dispersion in gel permeation chromatography with a detector of molecular masses

Abstract

Correction to axial dispersion of the results of analyses of polystyrene samples using a gel permeation chromatograph with an on-line viscometer was carried out by a procedure suggested in a preceding paper. Data obtained with each of the detectors of the apparatus were corrected separately, instead of correction of the molecular weight values calculated using data of both detectors. In this case there is no need to use procedures based on the solution of systems of linear equations: any method can be used which has originally been suggested only for correction of the concentration record, which in our case is the method of PIERCE and ARMONAS. Die Korrektur der yon einem Gelpermeationschromatographen mil on-line-gekoppeltem Viskosimeter erhaltenen MePwerte hinsichtlich der axialen DispersionDie Korrektur der an Polystyrenproben mittels eines Gelpermeationschromatographen mit on-line-Viskosimeter erhaltenen Analysenergebnisse wurde unter Verwendung eines Verfahrens dnrchgefiihrt, das in einer vorausgegangenen hrbeit beschrieben wurde. Die von den beiden Detektoren gelieferten Werte werden getrennt korrigiert, anstelle einer Korrektur der Molekulmassen unter Verwendung der Angaben beider Detektoren. Damit besteht keine Notwendigkeit, Systeme von linearen Gleichungen zu losen, man kann vielmehr jede Methode anwenden, die zur Korrektur der Konzentrationskurve geeignet ist. I n dieser Arbeit ist es die Methode von PIERCE und ARMONAS. Ilonpasica na ocesoe paccesnue aannbtx zem-nponuiEamzyeiL xpowamozpaguu c nocJceaymqe6 sucicoauwempueiLn o n p a m a H a oceBoe paccemme p e 3 y n b~a r o~ ~H~J I H~O B 0 6 p a s s o~ nonucTupona H a xpoMaTorpa4e AJIH r e a m p o m -KaIOKI(er0 aHaJIH3a (mx) C nPHC0eAHHeHHHM BHCKOBHMeTPOM 6una CAeJIaHa C HCnOJIb30BaHHeM MeTOAa, ripen-JIOXeHHOrO B IIpe,QIIIeCTBylO~e8 pa6ore. nOIIpaBKy H e BHOCHJIM B 3HaqeHHR MOJIeKyJIfIpHbIX MaCC, BbI'IHCJIeHHbIe H a OCHOBaHHH AaHHbIX o6onx AeTeKTOpOB annapaTypbI, K a K 3 T 0 0 6~9~0 AeJIaeTCH, a B AaHHbIe KaH(AOr0 H3 ABYX AeTeKTOpOB annapaTypbI B OTAeJIbHOCTH. B TaHOM CJIysae HeT HeO6XOAHMOCTH nOJIb30BaTbCH MeTOAaMH, OCHOBaHHbIMH H a PeIIIeHHH CHCTeM JIHHefiHbIX ypaBHeHH8 H K a K IIpaBHJIO He AaIoKI(HMH XOPOIIIHX pe3yJIbTaTOB, HO M O X H O IICIIOJIb-30BaTb ~110608 MeTOR, IIepBOHaqaJIbHO pa3pa60TaHHbIfi TOJIbKO AJIR BHeCeHHFi IIOnpaBKE B 3anECb KOHqeHTpaqEE, B HameM cnyqaa MeTOA nBPCA H APMOHACA. h k -lhk D k -l -D k ' h k + l = h k -D& 58 66 W 82 90 sif 98 V Pig. 2. Comparison between the calibration dependence (straight line) of the column the log d? vs y dependence determined from the data of the concentration and viscometric detectors of the GPC apparatus corrected for axial dispersion NETOPIL~K and SCHULZ: Correction for axial dispersion of data obtained by gel permeation chromatography 1220 1180 665 190 Acta Polymerica 35 (1984) Nr. 2 143 M , = 1.35 x 10' (LS) M , = 1.19 x l o 6 (LS) M , = 8.78 : 105 (LS) M , = 8.31 x 104 (0s) Table 1. Unfractionated samples. M , was calculated using K =0.039, a = 0.58 1 2 3 4 132 130 93 45 Table 2. Results of GPC ana...

Band Broadening in Size Exclusion Chromatography of Polymers. State of the Art and Some Novel Solutions

“…If now a real sample of molar mass distribution w(M) is injected into a chromatograph with a calibration M(V), the responses to each M add up to produce the following (noise-free) eluogram: [11,12] s k ðV Þ ¼ m If now a real sample of molar mass distribution w(M) is injected into a chromatograph with a calibration M(V), the responses to each M add up to produce the following (noise-free) eluogram: [11,12] s k ðV Þ ¼ m…”

Determination of the Band Broadening Function in Size Exclusion Chromatography With Light-Scattering Detection

“…Due to BB, a whole distribution of molar masses is present in the detection cells, even when linear homopolymers are analyzed. The following model has been proposed for describing the effect of BB on the LS and DR chromatograms: [19][20][21][22][23]…”

“…Most inversion algorithms assume a priori knowledge of the BBF. While some methods are restricted to Gaussian BBFs, [20,21,28,29] others admit asymmetric BBFs. [22,30,31] To avoid numerical inversions, it has been proposed to indirectly correct MMDs for BB through a counterclockwise rotation of logM(V).…”