Surface area of papermaking woodpulps used by the British paper industry

The surface area was determined for various papermaking woodpulps: bleached eucalyptus globulus sulphate pulp; bleached eucalyptus grandis sulphate pulp; bleached betula verrucosa sulphate pulp; bleached pine/spruce sulphate pulp; bleached pine/spruce sulphate pulp fines. The method of negative adsorption was used which gives an effective wet surface area. By looking at negative adsorption data more closely, some inference can be made about the morphology of the substrate.Glossary of symbols B (e²/2kT)^1/2 - ¯C concentration of fibre per unit volume of pulp - 1 - ¯¯c - h angle between pore and the axis of the bed in a permeable material - K permeability coefficient - k Boltzmann constant - k ₀ shape factor for pores in a permeable material - n _i concentration of co-ion in the bulk solution - n _i experimentally observed increase in concentration of co-ion in the bulk solution - S surface area - S _t wS - S ₀ surface area per unit volume of permeable material - V _t total volume of solution - V excluded volume - V _s excluded volume accessible to water but not to ions - V _obs experimentally observed excluded volume - w weight of dry fibre - ¯ effective volume of fibres in a permeable pad - surface potential at outer Helmholtz plane     

Diastereoselective addition of organomanganese compounds to chiral polyalkoxyaldehydes

Organomanganese compounds RMnI (R=Me, Pr, Bu, Hex, Ph, BuCC) prepared from RLi and MnI₂ in Et₂O react with 3-O-benzyl-1,2-O-isopropylidene--D-xylo-pentodialdo-1, 4-furanose, 1,23,4-di-O-isopropylidene--D-galacto-hexodialdo-1,5-pyranose, andR-2,3-dibenzyloxypropanal to afford 4,5-threo-, 5,6-threo-, and 2,3-threo-isomeric products, respectively, with high diastereoselectivity.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1122–1126, June, 1993.     

Hydrogenation of CO2 on carbon-supported nickel and cobalt

The hydrogenation of CO₂ has been studied at atmospheric pressure on Co/C and Ni/C catalysts and the results are compared with those obtained on unsupported Co and Ni. Specific activites in the form of turnover frequencies for CO₂ hydrogenation decrease with increasing metal dispersity. Carbon supported Co and Ni present a smaller selectivity for methane than bulk metals. Higher specific activities and smaller activation energies are obtained on Co catalysts, compared with those determined for Ni catalysts.

---

CO₂ Co/ Ni/ Co Ni . CO₂ . Co Ni , . .

     

Comparison of DSC and optical transmission measurements of polymorphic transitions

Using optical measurements on single crystals, the speed of first order transitions (K₂Cr207, KNO₃, AgNO₃) was determined and compared with the strongly smeared DSC signals. Such optical measurements are proposed to select materials which are suitable for the determination of the DSC apparatus function.

---

Zusammenfassung Mit Hilfe von optischen Messungen wird die Geschwindigkeit von polymorphen Phasenumwandlungen 1. Ordnung (K₂Cr₂O₇, KNO₃, AgNO₃) bestimmt und mit entsprechenden stark verschmierten DSC-Signalen verglichen. Derartige optische Messungen erscheinen geeignet, um Substanzen zu suchen, welche für die Bestimmung der DSC-Apparatefunktion geeignet sind.

---

K₂Cr₂O₇, KNO₃ AgNO₃ $ , $ . , $ .

     

Cyclodextrin-accelerated oxidation of iodide by oxygen in aqueous solutions containing HClO4

The oxidation of iodide to I ₃ ^– by oxygen dissolved in water containing HClO₄ has been found to be accelerated by -cyclodextrin (-CD). Among -, -, and -CDs, -CD is the most effective mediator for the oxidation reaction of iodide by oxygen. The oxidation rate of iodide is first order in the concentrations of -CD and HClO₄, whereas it is second order in the KI concentration.Part of this work was carried out at Department of Physics, Miyazaki Medical College, Miyazaki 889-16, Japan.     

Organotitanium chemistry 12. Synthesis of some new chiral cyclopentadienyl titanium and zirconium complex. The crystal structure of (S-cyclo-C4H7OCH2Cp)2TiCl2

Summary New chiral cyclopentadienyl-titanium and-zirconium complexes Cp₂TiCl₂, CpCpTiCl₂ and Cp₂ZrCl₂ (Cp=⁵ -cyclopentadienyl and Cp=substituted cyclopentadienyl), have been synthesized. The (S,S)-3 complex, which forms red plate crystals, has been studied by x-ray analysis. It belongs to the monoclinic space groupC2, witha 23.963(3),b 6.6470(6),c 12.6618(9) Å, 103.089(7)°, V=1964.4(3) ų and Z=4. The structure was relined to an R factor of 0.048 for 868 observed reflections.     

Mixed Micelles in the Presence of Macrocyclic Additives: A Host–Guest Conductometric Study

The conductances of sodium dodecylsulphate (SDS) + sodium decylsulfate (SDeS) and decyltrimethylammonium bromide (DeTAB) + tetradecyltrimethylammonium bromide (TTAB) over the entire mole fraction range of SDS (_SDS) or DeTAB (_DeTAB) were measured in water, 18-crown-6 ether + water (CR + W) and -cyclodextrin + water (CYC + W) mixtures at fixed 4 mM and 8 mM of CR or CYC in their respective binary mixtures at 30 °C. The conductivity plots for SDS + SDeS mixtures show a single break whereas two breaks are observed at most of the _DeTAB for DeTAB + TTAB mixtures. From the break in the conductivity data, the mixed critical micellar concentration (cmc) and degree of counter-ion association () were computed. The first break corresponds to the classical cmc of TTAB is termed as the first cmc (C₁) and the second break which is observed at concentrations about 4 times the first one, corresponding to the classical cmc of DeTAB and is considered to be the second cmc (C₂). The non-ideality in SDS + SDeS mixtures has been evaluated by using the regular solution theory and it has been observed that the mixture is close to ideal in the absence and presence of additives. The variation in C₁, C₂ and ₁, ₂ for DeTAB + TTAB has been discussed in terms of the mixed micelle formation which are predominantly rich in the TTAB and DeTAB monomers respectively.     

The investigation of thermally treated glasses of controlled porosity by means of differential thermal analysis

Some of the materials used as chromatography packings, adsorbents or catalyst supports are glasses of controlled porosity (CPGs). The chemical structure of these materials can easily be changed by heating the porous glass. Such thermal modification leads to the enrichment of the CPG surface in boron atoms. The long exposure of CPGs to thermal treatment can even cause the formation of borate crystals in the pores of the glasses. This paper considers the application of thermal analysis to the investigation of porous glasses heated for different periods of time.

---

Zusammenfassung Einige der als chromatographische Säulenpackungen, Adsorbenten oder Katalysatorträger verwendeten Materialien sind Gläser mit definierter Porosität (CPGs). Die chemische Struktur dieser Materialien kann leicht durch Erhitzen verändert werden. Eine solche thermische Modifizierung führt zu einer Anreicherung von Bor in der Oberflächenschicht. Eine langdauernde Erhitzung der CPGs kann sogar zur Bildung von Boratkristallen in den Poren der Gläser führen. Im vorliegenden Artikel wird die Anwendung der thermischen Analyse zur Untersuchung von porösen Gläsern in Abhängigkeit von der Erhitzungsdauer behandelt.

---

, , , . . . . , .

     

ESR investigation of vanadium-molybdenum oxide catalysts

Upon calcination of vanadium-molybdenum catalysts in air at 500°C two ESR signals are observed. They are attributed to a solid solution of MoO₃ in V₂O₅ (a) and to the incorporation of VO²⁺ into the compound V₂MoO₈ (b).

---

500°C - - , MoO₃ V₂O₅, - VO⁺² V₂ MoO₅.

     

Preparation of cobalt doped γ-Fe2O3 and Mn-Zn ferrites by the thermal decomposition of the hydrazine precursors

Fine particle cobalt doped-Fe₂O₃ and Mn-Zn ferrites have been prepared by the thermal decomposition of N₂H₅Co _x Fe_1–x (N₂H₃COO)₃.H₂O wherex=1–10 atom% and (N₂H₅)₃Mn_xZn_1–x Fe₂(N₂H₃COO)₉· 3H₂O wherex=0.2–0.8, respectively. Formation of these oxide materials has been confirmed by thermogravimetry and X-ray powder diffraction patterns. The fine particle nature of these oxide materials is evident from particle size analysis and surface area measurements.

---

Zusammenfassung Mit fein verteiltem Kobalt versetztes-Fe₂O₃ sowie Mn-Zn Ferrite wurden durch thermische Zersetzung von N₂H₅Co _x Fe_1–x (N₂H₃COO)₃·H₂O mit jc=1–10 Atomprozent bzw. (N₂H₅)₃Mn _x Zn_1–x Fe₂(N₂H₃COO)₉·3H₂O mitx=0,2–0,8 hergestellt. Die Bildung dieser Oxidstoffe wurde durch Thermogravimetrie und Pulverdiffraktionsmethoden bekräftigt. Die Feinkornstruktur dieser Oxidstoffe wird durch Korngrößenverteilungs- und Oberflächenmessungen augenscheinlich.

---

N₂H₅Co _x Fe_1–x (N₂H₃COO)₃·H₂O, x-1–10 %, (N₂H₅)₃Mn _x Zn_1–x Fe₂(N₂H₃COO)₉ · 3H₂O, x=0,2–0,8, , , -Fe₂O₃ Mn-Zn . . .

     

A rapid method for catalyst activity measurements by combination of pulse reactor, mass spectrometer and process computer

The combination of a pulse reactor attached directly (without a separation column) to a mass spectrometer/process computer system is described. To obtain a conversion/temperature diagram for the dehydration and dehydrogenation of 2-butanol less than one hour is required. Therefore, the method can be used for rapid characterization or comparison of the activities of various samples.

---

, ( ) - . / 2- . .

     

The electronic structure of molecules by a many-body approach

The vertical valence ionization potentials of cyclopropane, ethylene oxide and ethylene imine are calculated by a many-body Green's function method. For C₃H₆ the ordering of the ionization potentials is 2e(), 1e(), 2a₁(), 1a₂(), 1e(). The assignment of the 2a₁ and the 1a₂ ionization potentials which has been controversial is thus clarified. The ordering is in agreement with the result obtained via Koopmans' theorem. For ethylene oxide and ethylene imine Koopmans' theorem fails in predicting the correct order of ionic states. For C₂H₄O the ordering of the ionization potentials is 2b ₁(), 4a ₁, 1a ₂(), 2b ₂,3a ₁, 1b ₁(), 1b ₂, 2a ₁ and for C₂H₅N 6a, 5a, 3a, 2a, 4a, 3a, 1a, 2a. The agreement of the computed ionization potentials with the experimental values is very satisfactory.     

Cobalt(II) and nickel(II) chloride complexes with some 2-(4′-Methyl-2′-pyridyl and 2′- or 8′-quinolyl)benz-X-azoles

Summary Complexes of general formula ML_mCl₂ · nH₂O, where M=cobalt(II) or nickel(II); L=2-(4-methyl, 2-pyridyl)-benzimidazole (mpbi), 2-(4-methyl, 2-pyridyl)benzothiazole (mpbt), 2-(4-methyl, 2-pyridyl)benzoxazole (mpbo), 2-(4-methyl, 2-quinolyl)benzoxazole (mqbo), or 2-(4-methyl, 8-quinolyl)benzoxazole (mqbo); m=1,2; n=0–3, were prepared and characterized by t.g.a., conductance and magnetic measurements, i.r. and diffuse-reflectance electronic spectra.All the ligands behave as bidentate and coordinate through the pyridine- and isoxazole-nitrogen atoms.The nickel complexes have distorted octahedral or fivecoordinate structures. The cobalt complexes arepseudo-tet- rahedral except Co(mpbo)₂Cl₂·2H₂O where the metal is six-coordinate.     

Sensitivity of the solution of kinetic differential equation systems to the variations in the initial state exemplified by liquid-phase chain oxidation of hydrocarbons

The influence of the initial states on the solution of the system of differential equations for the chain mechanism of liquid phase hydrocarbon oxidation has been studied.

---

, .

     

Unicyclic Graphs with Minimal Energy

If G is a graph and ₁,₂,..., _n are its eigenvalues, then the energy of G is defined as E(G)=|₁|+|₂|++| _n |. Let S _n ³ be the graph obtained from the star graph with n vertices by adding an edge. In this paper we prove that S _n ³ is the unique minimal energy graph among all unicyclic graphs with n vertices (n6).     

Transformed steroids

The approaches to the synthesis of various 16,17-disubstituted pregna-4,9-dien-3,20-diones from the corresponding 9-derivatives with labile epoxide, dioxolane, and oxathiolane ringsD have been studied. The transformation has been found to proceed efficiently when the 9-sulfinic esters are used at the intermediate stage and then elimination of sulfinic acid by TsOH/SiO₂ is carried out.For part 193, see ref. 7.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 983–986, May, 1993.     

Kinetics and mechanism of the hydrolysis of sodium carboxymethylcellulose (Na-CMC) by a cellulase complex

TheSomogyi-Nelson colorimetric method is applied in a new manner more suitable for evaluating the kinetics of the enzyme hydrolysis of sodium carboxymethylcellulose (Na-CMC) catalyzed by the cellulase complex. By means of selective inhibition of a chosen enzyme from the cellulase complex it became possible to trace the effect of the other enzymes included in its composition.

---

Kinetik und Mechanismus der Hydrolyse von Natriumcarboxymethylcellulose (Na-CMC) durch einen Cellulase-Komplex

Zusammenfassung Die kolorimetrische Methode nachSomogyi undNelson wird nach einem neuen Verfahren zur Verfolgung der Kinetik der hydrolytischen Spaltung von Natriumcarboxymethylcellulose (Na-CMC), katalysiert durch den Cellulase-Komplex, angewandt. Durch selektive Inhibierung eines bestimmten Enzyms des Cellulase-Komplexes kann man die Wirkung der anderen zu seiner gesamten Zusammensetzung gehörenden Enzyme verfolgen.

---

Symbols Used E enzyme (E—cellulase;E—exo-cellobiohydrolase;E—-glucosidase) - [E] _w weight concentration of enzymeE - S substrate (Na-CMC—sodium carboxymethylcellulose) - [S]₀ weight concentration of substrateS - I inhibitor (I—lactose;I—calcium chloride;I—condurrite-B-epoxide) - P product (P—oligosaccharides;P—cellobiose;P—D-glucose) - P end product (K , K , K ) - DP degree of polymerization - DS degree of substitution - ES enzyme-substrate complex (E S, E S, E S) - EP enzyme-product complex (E P, E P) - EI enzyme-inhibitor complex (E I, E I, E I) - M _s molecular mass of substrateS - K _s substrate constant (K _s , K _s , K _s ) - K _I inhibitor constant (K _I , K _I , K _I ) - K _m Michaelis-Menten constant - k ₊₁,k ₊₂ (k ₊₂ ,k ₊₂ ,k ₊₂ ) forward rate constants - k _–1 reverse rate constant - ₀ initial rate of reaction - V maximal reaction rate - A change in absorbance - molar absorption coefficient - wavelength Herrn Prof. Dr.Hans Tuppy zum 60. Geburtstag herzlichst gewidmet.