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1.
Kaiser's “abt” concept rests on the experimental establishment of a linear relation between band width at half height, b0.5, and capacity ratio, k, according to His column specification quantity, hreal, is dependent on the square of the slope a, obtained from a linear regression analysis based on this relation. It is shown in the present paper that an improvement of the experimental conditions leading to a lower extra-column contribution to band broadening, b, introduces a tendency towards a negative curvature in the plot at low k values. The mean slope increases, and an uncritical linear regression would yield an hreal-value which is higher than before and which would be in the opposite direction to the requirements of a reliable column specification. Generally the linear regression analysis has to be moved to higher k regions in cases of curvature, especially as it is also shown that hreal is an estimation of the traditional HETP value, H∞, that would be obtained when k approaches infinity. This theoretically expected relation is a strong motivation for the use of hreal as a column specification, since the b0.5-value associated with H∞ is expected to be practically independent of b.  相似文献   

2.
The CO2 absorption properties and the microstructure of (Ba,Ca)(Fe,Mg)O3 - have been studied by TGA, XRD, and Mössbauer spectrometry. Paramagnetic doublets of FeIV and FeIII appeared in the Mössbauer spectra of cubic (Ba0.5Ca0.5)(Fe0.5Mg0.5)O3 - heated in CO2 up to 600 °C, and a pair of sextets of tetrahedral FeIII (Hin = 43 T) and octahedral FeIII (Hin = 51 T) were produced above 800 °C, and an additional sextet characteristic of FeIII in a spinel structure (Hin = 48 T) was observed at 1000 °C. On the other hand, a pair of sextets of tetrahedral and octahedral FeIII of the orthorhombic (Ca0.95Ba0.05)(Fe0.5Mg0.5)O3 - showed hardly any change after absorption of CO2. It is concluded that only a small portion of Mg entered the orthorhombic phase of (Ca0.95Ba0.05)(Fe,Mg)O3 - and Mg preferred the octahedral B site of the perovskite lattice. The excess Mg formed separate CaO-MgO mixed oxide, and the primary mechanism of CO2-trapping is the formation of CaMg(CO3)2.  相似文献   

3.
A block copolymer (PS-b-poly(l-Glu)) composed of polystyrene and poly(l-glutamic acid) was used as a stabilizer for dispersion polymerization of styrene. When dispersion polymerization of styrene was conducted at 70 °C in 80% dimethylformamide-water with 0.5 wt% PS-b-poly(l-Glu), spherical polystyrene particles with Dn = 0.72 μm and narrow size distribution were obtained. Whereas AIBN concentration did not have any effects on particle size, molecular weight of the polystyrene particles was strongly dependent on the initiator concentration. As concentration of the PS-b-poly(l-Glu) increased from 0.2 to 1.0 wt%, particle size decreased from Dn = 0.91 to 0.69 μm with keeping surface area occupied by one poly(l-glutamic acid) chain about = 50 nm2. On the other hand, an increase in initial concentration of styrene from 2 to 20 wt% caused an increase in particle size from Dn = 0.48 to 1.36 μm and a decrease in surface area per poly(l-glutamic acid) block from = 91 to 45 nm2. Colloidal stability of the polystyrene particles in aqueous solution was responsive to pH due to the surface-grafted poly(l-glutamic acid). For dispersion polymerization of styrene, the PS-b-poly(l-Glu) functions as both a stabilizer and a surface modifier.  相似文献   

4.
Zusammenfassung Die Wärmekapazitätc V des 100% kristallinen Polyäthylens nach einer neueren, vonWunderlich zusammengestellten Tabelle (4) verläuft unterhalb 10 °K proportional zuT 3. Zwischen 10 °K und 50 °K genügt sie der Gleichungc V=a3T3+anTn [A] mit einem Exponentenn, der mit steigender Temperatur von 3 nach 3/2 abfällt. Zwischen 100 °K und 200 °K ist sie durch cV=a1T+a1/2T1/2 [B] darstellbar. Dieser Verlauf läßt sich qualitativ sehr gut mit Hilfe desStockmayer-Hecht-Modells verstehen.Einen wesentlichen Unterschied zwischen Polymer-Kristallen und vergleichbaren niedermolekularen Kristallen (etwa Äthylen-Kristallen) erzeugt die Biegesteifigkeit der Polymer-Ketten. Sie bewirkt, daß sich die transversalen akustischen Phononen in bezug auf ihre Energie-Impuls-Relation und ihre Geschwindigkeit zum Teil wie mit Masse belegte freie Teilchen verhalten. Die longitudinalen akustischen Phononen bleiben dagegen — wie die akustischen Phononen in niedermolekularen Kristallen allgemein — mit den masselosen Photonen im Vakuum vergleichbar. Sowohl die Beschränkung der Gültigkeit desDebyeschen T 3-Gesetzes auf sehr tiefe Temperaturen, als auch das zusätzliche Glied zum-Debyeschen T 3-Gesetz in [A] und das zusätzliche Glied zumTarasovschen T-Gesetz in [B] sind auf die Besonderheit der transversalen Phononen zurückzuführen.Die Verwendbarkeit desStockmayer-Hecht-Modells zu quantitativen Aussagen wird unter anderem dadurch eingeschränkt, daß die Zahl der Freiheitsgrade im Falle der linearen Kette im Verhältnis 21, im Falle der ebenen Zickzack-Kette dagegen im Verhältnis 11 auf die trägen und trägheitslosen Phononen verteilt wird.
Summary According to a table recently compiled byWunderlich (4) the heat capacitycV of 100% crystalline poly-ethylene is proportional to T3 below 10 °K. Between 10 °K and 50 °K it suffices the equation cV=a3T3+anTn [A] with an exponentn which decreases from 3 to 3/2 with increasing temperature. Between 100 °K and 200 °K it fits to the equation cV=a1T+a1/2T1/2. [B] This behaviour is easy to understand qualitatively by means of theStockmayer-Hecht-model.A fundamental difference between polymeric crystals and comparable nonpolymeric crystals (such as ethylene crystals) is due to the stiffness of the polymer chains. This stiffness provokes the transverse acoustical phonons to behave like free particles charged with mass, as far as their energy-momentum-relation and their velocity are concerned. On the contrary the Iongitudinal acoustical phonons, like the acoustical phonons in nonpolymeric crystals in general, remain comparable to the massless photons in the vacuum.The limitation of theDebye T3-law to very low temperatures as well as the additional term to theDebye T3-law in [A] and the additional term to theTarasov T-law in [B] can be attributed to the peculiarity of the transverse phonons.The availability of theStockmayer-Hecht-model for quantitative statements is limited, among others, by the fact that the number of the degrees of freedom is distributed to the inert and the inertialess phonons in the proportion of 21 in case of linear chains and of 11 in case of planar zig-zag chains.


Vorgetragen auf der Frühjahrstagung des Regionalverbandes Hessen-Mittelrhein-Saar der Deutschen Physikalischen Gesellschaft in Darmstadt am 12. März 1970.  相似文献   

5.
Summary A simple and sensitive method for the determination of iron(III) is described. It is based on the extraction of the yellow-coloured complex of iron with quinaldic acid-N-oxide in chloroform. The absorption maximum is at 380 nm with molar absorptivity 380=1.03 · 104. Beer's Law is obeyed over the range 0.6–6 ppm iron with relative standard deviation of +-0.3% (Sandell sensitivity 0.005 g/ml/cm2). The absorbance of the reagent blank is however high with consequent occasional disturbances, which are avoided when measured at 395 nm; molar absorptivity 395=7.4 · 103; effective concentration range 3–8 ppm iron with relative standard deviation +-0.5% (Sandell sensitivity 0.008g/ml/cm2). A fairly large number of common ions do not interfere. Job's method of continuous variations and Asmus method indicate a iron-reagent ratio of 13. Heterogeneous formation constant is K D =2 · 108.
Extraktionsphotometrische Bestimmung von Eisen(III) mit Chinaldinsäure-N-oxid
Zusammenfassung Die einfache und empfindliche Bestimmung beruht auf der Extraktion des gelben Komplexes von Eisen(III) mit Chinaldinsäure-N-oxid in Chloroform. Das Absorptionsmaximum liegt bei 380 nm mit dem molaren Extinktionskoeffizient 380=1.03 · 104. Das Beersche Gesetz gilt im Bereich 0,6–6 ppm Eisen. Die relative Standardabweichung beträgt+-0,3% (Sandell-Empfindlichkeit 0,005g/ml/cm2). Die Absorption der Blindprobe ist jedoch hoch und verursacht manchmal Störungen, die beim Messen bei 395 nm vermieden werden; molarer Extinktionskoeffizient 395= 7,4 · 103; im Konzentrationsbereich 3–8 ppm Eisen beträgt die relative Standardabweichung+-0,5% (Sandell-Empfindlichkeit 0,008g/ml/cm2). Eine ziemlich große Zahl von Fremdionen bewirkt keine Störung. Methoden nach Job und Asmus liefern ein Verhältnis Eisen/Reagens wie 13. Die heterogene Bildungskonstante beträgt K D =2 · 108.
  相似文献   

6.
The linearity of the relationship between σT,t2 and (1 + k)2 is studied with the view of using it for the evaluation of GC equipment. Based on appropriate analytical expressions it is concluded that in general this relationship is not linear and that practical procedures for column evaluation should be developed that take this non-linearity into account.  相似文献   

7.
A new metal–formate framework, poly[1H‐imidazol‐3‐ium [tri‐μ2‐formato‐manganese(II)]], {(C3H5N2)[Mn(HCOO)3]}n, was synthesized and its structural phase transition was studied by thermal analysis and variable‐temperature X‐ray diffraction analysis. The transition temperature is around 435 K. The high‐temperature phase is tetragonal and the low‐temperature phase is monoclinic, with a β angle close to 90°. The relationship of the unit cells between the two phases can be described as: aHT = 0.5aLT + 0.5bLT; bHT = −0.5aLT + 0.5bLT; cHT = 0.5cLT. In the high‐temperature phase, both the framework and the guest 1H‐imidazol‐3‐ium (HIm) cations are disordered; the HIm cations are located about 2mm sites and were modelled as fourfold disordered. The Mn and a formate C atom are located on fourfold rotary inversion axes, while another formate C atom is on a mirror plane. The low‐temperature structure is ordered and consists of two crystallographically independent HIm cations and two crystallographically independent Mn2+ ions. The phase transition is attributable to the order–disorder transition of the HIm cations.  相似文献   

8.
Generalised n×n eigenvalue equation B| i = i S b | i (i=1,...,n) where B and S b are n×n Hermitian matrices while S b is in addition positive definite is considered. This equation is augmented to a generalised (n+1)(n+1) eigenvalue equation H| k = k S| k (k=1,...,n+1) where Hermitian matrices H and S represent matrices B and S b , respectively, augmented by one additional row and one additional column. It is shown how the eigenvalues k and the eigenvectors | k of the augmented eigenvalue equation can be expressed in terms of the eigenvalues i and the eigenvectors | i of the original eigenvalue equation. Operation count to obtain by this method all augmented eigenvalues and eigenvectors is of the order O(n 2). Unless matrices involved are of some special kind such as sparse matrices or alike, this operation count is one order of magnitude smaller than operation count required by other presently known methods. In many practical cases operation count to obtain a single selected eigenvalue and/or eigenvector by this method is of the order O(n). In the case of the generalised eigenvalue equation, all other methods usually require again O(n 3) operations, even if only a single eigenvalue and/or eigenvector is required. Thus in many cases of interest operation count to obtain a selected eigenvalue and/or eigenvector by this method is two orders of magnitude smaller than operation count required by other methods.  相似文献   

9.
Crystals of [97N(35)]uBr2 (IV) and [97N(35)][u2Br3] (V) were prepared by ac electrochemical synthesis from uBr2, N-allylquinolinium bromide, on copper electrodes in the ethanol–benzene medium. X-ray diffraction study has shown that crystals IV and V are monoclinic: space group A21/a, a = 13.776(3) Å, b = 14.304(3) Å, c = 13.147(2) Å, = 107.90(1) Å, V = 2465(2) Å3, Z = 8 for IV and space group P21/n, a = 13.881(2) Å, b = 15.446(2) Å, c = 7.111(1) Å, = 104.64(1)°, V = 1475.0(8) Å3, Z = 4 for V. Structures IV and V are built of the N-allylquinolinium cations and different anions i.e., (CuBr2) n- n forming infinite chains in IV and peculiar {[CuI 4Br6]2–} n arranged in polymeric chains in V. In the latter case, two independent metal atoms have trigonal–pyramidal and trigonal–planar environments. In the structures of both compounds, the C=C bond of the allyl group is not involved in coordination with the Cu(I) atom.  相似文献   

10.
The solubility of CaSO3·1/2H2O(c) was studied under alkaline conditions (pH>8.2), in deaerated and deoxygenated Na2SO3 solutions ranging in concentration from 0.0002 to 0.4M and in CaCl2 solutions ranging in concentration from 0.0002 to 0.01M, for equilibration periods ranging from 1 to 7 days. Equilibrium was approached from both the over- and the under-saturation directions. In all cases, equilibrium was reached in <1 days. The aqueous Ca2+–SO 3 2– ion interactions can be satisfactorily modeled using either ion-association or ion-interaction aqueous thermodynamic models. In the ion-association model, the log K°=2.62±0.07 for Ca2++SO 3 2– CaSO 3 0 . In the Pitzer ion-interaction model, the binary parameters (0) and (1) for Ca2+–SO 4 2– were used, and the value of (2) was determined from the experimental data. As expected given the strong association constant, the value of (0) was quite small (about –134). We feel a combination of the two models is most useful. The logarithm of the thermodynamic equilibrium constant (K°) of the CaSO3·1/2H2O(c) solubility reaction (CaSO3·1/2H2O(c)Ca2++SO 3 2+ +0.5H2O) was found to be –6.64±0.07.  相似文献   

11.
Using Brion, Moser and Yamazaki's SCF LCAO MO the spin orbit splitting of the X 2 state of NO has been calculated using various potentials. Experimentally W (2 3/2) –W (2 1/2) is known to be 122 cm–1. Using an unscreened nuclear field we find a value of 328 cm–1. Inclusion of screening due to electronic repulsions reduces this value to 283 cm–1. Agreement with the experimental value may be obtained by reducing the orbital exponents in the 2 molecular orbital by 30% over the value given by Slater's rules.
Zusammenfassung Die Spin-Bahn-Aufspaltung des X 2 -Zustandes von NO wurde mit verschiedenen Potentialen unter Verwendung der SCF LCAO MOs von Brion, Moser und Yamazaki berechnet. Der experimentelle Wert für W (2 3/2) –W (2 1/2) beträgt 122 cm–1. Die Rechnung mittels eines reinen Kernfeldes liefert den Wert 328 cm–1 und unter Einschluß der Abschirmung durch die Elektronen 283 cm–1. Übereinstimmung mit dem experimentellen Wert läßt sich erzielen, wenn man den Exponenten des 2-Zustandes 30% kleiner als nach den Slater Regeln macht.

Résumé Avec les orbitals moléculaires SCF LCAO de Brion, Moses et Yamazaki, nous avons calculé le dédoublement spin-orbitale de l'état X 2 de NO. La valeur expérimentale W (2 3/2) –W (2 1/2) est 122 cm–1. Dans un champ nucléaire «sans écran» on trouve 328 cm–1. L'inclu-sion de l'effet d'écran dû aux répulsions interélectroniques réduit cette valeur à 283 cm–1. La valeur expérimentale s'obtient, si l'on réduit de 30% les exposants d'après Slater dans l'orbi-tale moléculaire 2.
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12.
Short-wavelength nSe * and long-wavelength nSe * bands are observed in the UV spectra of saturated trialkylarsine selenides in the near-UV region. The nx * band in going from arsine selenides to arsine sulfide and then to arsine oxides is shifted hypsochromically, as in the corresponding phosphorus compounds. The nx * band is only slightly sensitive to the chalcogen. Saturated trialkylarsines, in contrast to alkylphosphines, absorb in the near UV region (the nAs * band is at 208 nm).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 940–942, April, 1990.  相似文献   

13.
It is shown that substituting activities of individual ions for their concentrations in the equation for the ionic strength of solution substantially extends application of the first approximation of the Debye–Hückel theory for electrolytes of different valence. The obtained relationship predicts a changeover from the square root law in the charge region where the average distance between ions lis smaller than the ionic-atmosphere thickness 1/, to the cube root law, at l> 1/. The increasing deviation from experimental data upon going from LaCl3solutions to La2(SO4)3is attributed to the formation of ionic pairs LaSO4 +.  相似文献   

14.
Summary Quantitative structure-activity relationships were performed on a set of 5-nitrofuran derivatives. The correlation parameters used were hydrophobicity and connectivity. The former was measured by means of the capacity factor (log k o ) obtained by HPLC and the latter through the molecular valence connectivity index1 v obtained by computational methods. The biological activity data considered were growth inhibition percentages ofT. cruzi (GI % (48 h)) and half-maximal inhibitory concentration of Glutathione Reductase (I0.5 (max)). Good adjustment, r=0.98, was obtained if a logarithmic model is used for I0.5 (max) correlations. When GI% is considered, correlations were poorer and the consideration of both structural parameters was necessary for their improvement, r=0.94.  相似文献   

15.
Summary Induced peaks observed in indirect detection of nonelectrolytes in high-performance liquid chromatography are simulated. The equation representing the signal intensity of the induced peaks is derived, and it is verified by the experimental results. The peak area is proportional to (K b +1) k a /| a —k b |, where k a ad k b are the capacity factors of the visualization agent and the analyte, respectively.  相似文献   

16.
The reliability of the two-layer own N-layered integrated molecular orbital and molecular mechanics (ONIOM) method was examined for the SN2 reaction CH(4–n)Cln+OH. In the ONIOM calculation, only the methyl chloride and OHwere treated at a high level and the effect of polychlorination was taken into account only at a low level. The ONIOM results were compared with the target CCSD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ results obtained by Borisov etal. [(2001) J. Phys. Chem. A 105:7724]. The ONIOM[MP2/aug-cc-pVDZ:B3LYP/6-31+G(d)] was found to reproduce well the target geometry and energy at the MP2/aug-cc-pVDZ level. The single-point improved energetics at the ONIOM[CCSD(T)/aug-cc-pVDZ:MP2/6-31+G(d)] is found to give results nearly as accurate as the target CCSD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ results. The substantially reduced cost, 20% for optimization and 5% for single-point improved energy of the target cost for n=4, as well as small errors suggest that ONIOM is a powerful tool for accurate potential-energy surfaces of the reaction of large polyhalohydrocarbons.  相似文献   

17.
In this work, the syntheses of poly(butyl methacrylate-b-methyl methacrylate-b-butyl methacrylate) triblock copolymer and poly(methyl methacrylate-b-butyl methacrylate-b-methyl methacrylate-b-butyl methacrylate-b-methyl methacrylate) pentablock copolymers using copper mediated living radical polymerisation are reported. Living radical polymerisations were performed using the system CuIBr/N-(n-propyl)-2-pyridylmethanimine as catalyst in conjunction with a difunctional initiator, the 1,4-(2-bromo-2-methylpropionoto)benzene (1). The syntheses of poly(MMA), poly(BMA-b-MMA-b-BMA) and poly(MMA-b-BMA-b-MMA-b-BMA-b-MMA) are described in detail using 1H NMR spectroscopy and size exclusion chromatography. The living behaviour and the blocking efficiency of these polymerisations were investigated in each case. Difunctional initiator, 1, based on hydroquinone was synthesised and fully characterised and subsequently used to give difunctional poly(methyl methacrylate) macroinitiators with molecular weights up to 54,000 g mol−1 and polydispersity between 1.07 and 1.32; molecular weights were close to the theoretical values. The difunctional macroinitiators were used to reinitiate butyl methacrylate to give triblock copolymers of Mn between 17,500 and 45,700 g mol−1. Polydispersities remained narrow below 25,000 g mol−1 but broadened at higher masses. The difunctional triblock macroinitiators were subsequently used to reinitiate methyl methacrylate to give ABABA pentablock copolymers with Mn up to 37,000 g mol−1 with polydispersity=1.13. Under certain conditions radical-radical reaction led to a broadening of polydispersity index.  相似文献   

18.
The two-photon fluorescence excitation spectrum of pyrene in n-hexane and n-heptane matrices has been measured at 10 K in the region of the first electronic transition (26800–30200 cm?1). The spectrum consists of a rich number of sharp bands, being in general better resolved in n-hexane than in n-heptane matrix. Shpol'skii multiplets have been observed for the most intense bands. A strong two-photon band dominates the spectrum = 1495 cm?1 from the 0—0 line and was assigned to B1u × b1u = Ag symmetry. Other weaker vibronic origins occur in the spectrum which were correlated to vibrational modes of b1u, b2u, b3u and au symmetry. Intense vibronic bands are observed close to the origin of the second electronic transition and were interpreted as combination bands of B1u × b1u × b3g symmetry. A two-photon vibronic theory to account for their intensity is proposed where the electronic moment is linearly expanded in powers of the nuclear displacements.  相似文献   

19.
The electrodeposition of uranium and trace quantities of239Pu,234Th,144Ce on a stainless steel disk has been investigated from 0.5–2.0M NaOH and the two-phase system: extract of actinides in TBP-aqueous solution of NaOH. The electrodeposition yield of the above elements reaches 98–100% in 40 min of electrolysis with current density 0.4–0.5 A/cm2. The presence of 0.5M Na2CO3, 2.0M NaNO3, 2.0M NaNO2, 0.2M NaF in alkaline solutions does not decrease the electrodeposition yield. The electrodeposited films meet all the requirements of -spectrometry. The uranium oxidation states (V) and (IV) have been determined in the electrodeposited films.  相似文献   

20.
The elucidation of the structure-function relation of reconstituted ion channel proteins into artificial planar bilayers is expected to be greatly influenced by the physical properties of these bilayers. The dependence of the gating mode of a voltage- and calcium-dependent small chloride channel (SCl channel) on the bilayer properties, as deduced from the specific bilayer capacitance, Cb, was investigated. In bilayers having a Cb value of 0.42 μF/cm2 the SCl channel was in the “burst mode”. At a Cb value of 0.28 μF/cm2 the “burst mode” gave way to a “flickering mode”. At Cb values between 0.24 and 0.28 μF/cm2 channel bursts were often infrequent and brief. No ion channel activities were observed at Cb values lower than 0.24 μF/cm2. These results suggest that changes in bilayer thickness, mediated via n-decane, contribute to changes in channel gating mode, i.e. “gear shift”. Standardizing Cb and its time-independence are important in comparative and detailed investigations of ion channel characteristics.  相似文献   

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