Variable‐temperature IR spectroscopic studies of CO adsorbed on Na‐ZSM‐5 and Na‐Y zeolites

CO interacts with extraframework alkali metal cations (M⁺=) of zeolites to form both M⁺CO and M⁺OC species. By using variabletemperature FTIR spectroscopy, these Cbonded and Obonded species were found to be in a temperaturedependent equilibrium. For the same cation, the difference in interaction energy depends upon the zeolite framework. Thus, for the equilibrium process ZNa⁺=CO ZNa⁺OC, where Z represents the zeolite framework, H ⁰ was found to take the values 3.8 and 2.4 kJ mol^– for CO/NaZSM5 and CO/NaY, respectively. The Cbonded species show always the highest cation–CO interaction energy.     

Note of the estimation of the Θ temperature and Ψ parameter from the critical temperature data

Summary Critical values of the polymer volume fraction _2,c and the interaction parameter _c have been computed for the case that the equation for the chemical potential of solvent contains terms _{c 2} ³ and _{c 2} ⁴ in addition to ₂ ² . For 0 _c 1/3, the limits for infinite chain length are _2,c = 0 and _c = 0.5. Quite different results are obtained for _c > 1/3, _2,c being finite and _c lower than 1/2. Conclusions for the estimation of the temperature and the entropy-of-dilution parameter are discussed.     

Weak Gel Behaviour of Poly(vinyl alcohol)-Borax Aqueous Solutions

Thermal transition of PVA-borax aqueous gels with a PVA concentration of 60 g/L and a borax concentration of 0.28 M was investigated at temperatures ranging from 15 to 60C using static light scattering (SLS), dynamic light scattering (DLS), and dynamic viscoelasticity measurements. Three relaxation modes, i.e. two fast and one slow relaxation modes, were observed from DLS measurements. Two fast relaxation modes located around 10^–310¹ sec, with one fast mode (_f1) being scattering vector q-dependent and the other fast mode (_f2, with _f2>_f1) being q-independent. The _f1 mode was attributed to the gel mode whilst the _f2 mode could be due to the hydrodynamics of intra-molecular hydrophobic domains formed by uncharged segments of polymer backbones. The slow relaxation mode with relaxation time located around 10¹10³ sec in DLS data was due to the motion of aggregated clusters and was observed only at temperatures above 40C. The amplitude and relaxation time of slow mode decrease as temperature is increased from 40 to 60C. At temperatures below 40C, no slow relaxation mode was observed. The SLS measurements showed PVA-borax-water system had fractal dimensions D _f2.4 and D _f2.0 as temperature was below and above 40C, respectively. The simple tilting test indicated gel behaviour for the PVA-borax aqueous system at temperatures below 40C with a creep flow after a long time exposure in the gravity field. But the dynamic viscoelasticity measurements demonstrated a solution behaviour for PVA/borax/water at temperatures below 40C, the critical gel point behaviour for G() and G() was not observed in this system as those reported for chemical crosslinked gels. These results suggest that the PVA-borax aqueous system is a thermoreversible weak gel.     

Studies concerning charged nickel hydroxide electrodes I. Measurement of reversible potentials

Reversible potentials (E _R) have been measured for nickel hydroxide/oxyhydroxide couples over a range of KOH concentrations from 0·01–10 M. It is shown that the couples derived from the parent- and-Ni(OH)₂ systems can be distinguished by the relative change in KOH level on oxidation and reduction. In the case of couples derived from the-class of materials a dependence of 0·470 moles of KOH per 2e change is found compared with 0·102 moles of KOH per 2e change for the-class of materials. Couples derived from the- and-Ni(OH)₂ systems can be encountered in a series of activated and de-activated forms having a range of formal potentialsE ₀ . Activated. and de-activated-Ni(OH)₂/-NiOOH couples are found to lie in the range 0·443–0·470 V whilst-Ni(OH)₂/-NiOOH couples lie in the range 0·392–0·440 V w.r.t. Hg/HgO/KOH. It is demonstrated for de-activated,-Ni(OH)₂/-NiOOH couples thatE _R is independent of the degree of oxidation of the nickel cation between states of charge of 25% and 70%. SimilarlyE _R is constant for states of charge between 12% and 60% for activated-Ni(OH)₂/-NiOOH couples. The constant potential regions are considered to be derived from heterogeneous equilibria between pairs of co-existing phases both containing nickel in upper and lower states of oxidation. Differences inE ₀ between the activated and de-activated couples are considered to be related to the degree of order/disorder in the crystal lattice.     

Ethynylene-disilanylene copolymers

Polymers of structure (SiR₂SiR₂-C C-SiR₂SiR₂-C C) _n , in which ethynylene units alternate with disilylene units, have been prepared by two routes: (a) condensation of dichlorodisilanes with dilithium derivatives of 1,2-diethynyldisilanes and (b) ring-opening polymerization of strained cyclic disilanylene-acetylnes, (SiR₂SiR₂C C)₂. The polymers display UV absorption near 240 nm indicative of – conjugation between the Si₂ and the C C moieties. Polymers with R=R=n-Bu or R=n-Bu, R=Ph, undergo solid-state transitions to form liquid crystalline mesophases resembling those observed for many poly(silylenes). Single crystals were obtained for the polymer with R=R=CH₃, by precipitation from dilute cyclohexane solution. The solid-state properties and structures of this family of polymers are discussed.This paper was presented at the Second International Topical Workshop, Advances in Silicon-Based Polymer Science.     

Leaf surface chemicals fromNicotiana affecting germination ofPeronospora tabacina (adam) sporangia

A bioassay was used to evaluate the effects of cuticular leaf components, isolated fromN. tabacum, N. glutinosa (accessions 24 and 24a), and 23other Nicotiana species, on germinationof P. tabacina (blue mold). The leaf surface compounds included- and-4,8,13,-duvatriene-l,3-diols (DVT-diols), (13-E)-labda-13-ene-8-,15-diol (labdenediol), (12-Z)-labda-12,14-diene-8-ol (cis-abienol), (13-R)-labda-8,14-diene-13-ol (manool), 2-hydroxymanool, a mixture of (13-R)-labda-14-ene-8,13-diol (sclareol), and (13-S)-labda-14-ene-8,13-diol (episclareol), and various glucose and/or sucrose ester isolates. The above in acetone were applied onto leaf disks of the blue moldsusceptibleN. tabacum cv. TI 1406, which was then inoculated with blue mold sporangia. Estimated IC₅₀ values (inhibitory concentration) were 3.0g/cm² for-DVT-diol, 2.9/cm² for-DVT-diol, 0.4g/cm² for labdenediol and 4.7g/cm² for the sclareol mixture. Manool, 2-hydroxymanool, andcis-abienol at application rates up to 30g/cm² had little or no effect on sporangium germination. Glucose and/or sucrose ester isolates from the cuticular leaf extracts of 23Nicotiana species and three different fractions fromN. bigelovii were also evaluated for antimicrobial activity at a concentration of 30g/cm². Germination was inhibited by >20% when exposed to sugar esters isolated fromN. acuminata, N. benthamiana, N. attenuata, N. clevelandii, andN. miersii, and accessions 10 and 12 ofN. bigelovii. These results imply that a number of compounds may influence resistance to blue mold in tobacco.     

Chemistry of Combustion Waves in Substances with a Complicated Structure of Reagent Molecules. 1. Structure of the Front of Rich Isopentane Flame

Results on the structure of the lowtemperature relaxation zone of the front of a laminar Bunsen flame of isoC₅H₁₂ (2methylbutane) under atmospheric pressure are presented. The flame of a premixed mixture isoC₅H₁₂ + O₂ + Ar with a fueltoair equivalence ratio of 1.7 is examined. The mass fluxes, total rates of reactions of matter consumption and expenditure, balance of substances, and profiles of bulk heatrelease rates are calculated on the basis of the experimental concentration and temperature profiles. The results obtained indicate that there is a vast region of lowtemperature conversion of isopentane in the flame front. It is found that only part of the products sampled by the microprobe from different points of the flame front results from transformations in the lowtemperature region, namely, oxygen, isopentane, water, carbon monoxide, propane, methane, and methanol. Ethylene, propylene, hydrogen dioxide, and formaldehyde are present in the lowtemperature zone in insignificant amounts; they are secondary products of conversion of methyl and propyl radicals. It is assumed that the observed feature is a result of the competing interaction of two mechanisms of fuelmixture conversion: selfcatalysis and thermal selfacceleration. Based on the previously suggested mechanism of oxidation pyrolysis by the scheme of intramolecular quadratic destruction, experimentally observed fragmentation of the isopentane molecule is demonstrated. In contrast to npentane, formation of methyl alcohol has been found in isopentane convection products.     

Molybdenum nitride for the direct decomposition of NO

The physico-chemical properties of passivated -Mo₂N have been investigated. The material showed high activities for NO direct decomposition: nearly 100% NO conversion and 95% N₂ selectivity were achieved at 450C. The amount of O₂ taken up by -Mo₂N increased with temperature rise and reached 3133.9 molg^–1 at 450C; we conclude that there formation of Mo₂O_xN_y occurred. This oxygen-saturated -Mo₂N material was catalytically active: NO conversion and N₂ selectivity were 89 and 92% at 450C. We found that by means of H₂ reduction at 450C, Mo₂O_xN_y could be reduced back to -Mo₂N and the oxidation/reduction cycle is repeatable; such a behaviour and the high oxygen capacity (3133.9 molg^–1) of -Mo₂N suggest that -Mo₂N is a promising catalytic material for automobile exhaust purification.     

Mechanisms of Iron Activation on Fe-Containing Zeolites and the Charge of α-Oxygen

According to previous Mössbauer data [1] -sites formation at the activation of Fe-containing zeolites is accompanied by irreversible self-reduction of the iron, proceeding without participation of an external reducing agent. Reduced Fe²⁺ ions are inert to O₂ but are reversibly oxidized to Fe³⁺ by N₂O, generating the -oxygen species, O, which provide selective oxidation of hydrocarbons.In this work, the mechanism of -sites formation was studied via quantitative measurement of the dioxygen amount desorbed into the gas phase at the step of self-reduction. A prominent role of the zeolite matrix chemical composition has been revealed. For example, with zeolites of Al–Si composition (FeZSM-5 and Fe-), heating to 900 °C in a closed vacuum space leads to irreversible evolution of O₂, which is accompanied by the immediate formation of -sites. Similar heating of B–Si and Ti–Si zeolites also leads to dioxygen evolution; however, this evolution is reversible and is not accompanied by formation of -sites. Activation of these zeolites occurs only in the presence of water vapor. Stoichiometric measurements showed that in terms of charge one regular O^2- ion, removed at the activation, is equivalent to two -oxygen atoms. So, -oxygen is identified as an ion-radical species O ^-., whose unique oxidation properties still distinguish it from the generally observed O^-. radicals.The mechanism of -sites formation is proposed, in which the process of strong chemical stabilization of reduced Fe²⁺ atoms in the zeolite structure is a key step, making impossible the reoxidation of the iron with O₂.     

Electrochemical behaviour of viologen-cyclodextrin inclusion complexes. The case of non-alkyl group substituted viologen

The electrochemical behavior of non-alkyl substituted viologen, 4,4-dibenzyl bipyridinium (BzV), 4,4-dicyanophenyl bipyridinium (CyV) and -,-,-cyclodextrin (, , -CD) was studied using cyclic voltammetry and a spectroelectrochemical method. It was found that BzV and Fe(CN) ₆ ^4– formed a charge-transfer (CT) complex with a ratio of 21 and the colour of the solution faded with the addition of an electrolyte. This behaviour is the same as in then-heptyl viologen and ferrocyanide system [1]. BzV, -CD and -CD formed an inclusion complex only in the reduced state, whilst BzV and -CD formed an inclusion complex in both the oxidized and the reduced state. An EC scheme in which a chemical reaction follows an electrochemical reaction was considered to predominate in the BzV and -, -CD systems, while a CE scheme in which a chemical reaction preceded an electrochemical reaction predominated in the BzV and -CD system. On the other hand, CyV was found to form an inclusion complex with -, -, -CD in both the oxidized and the reduced states. therefore a CE scheme was considered to predominate in the CyV--, -, -CD systems.     

Durability and thermal cycling of Ni/YSZ cermet anodes for solid oxide fuel cells

The long-term properties of Ni/yttria stabilized zirconia (YSZ) cermet anodes for solid oxide fuel cells were evaluated experimentally. A total of 13 anodes of three types based on two commercial NiO powders were examined. The durability was evaluated at temperatures of 850 C, 1000 C and 1050 C over 1300 to 2000h at an anodic d.c. load of 300mA cm^–2 in hydrogen with 1 to 3% water. The anode-related polarization resistance, R _P, was measured by impedance spectroscopy and found to be in the range of 0.05 to 0.7 cm². After an initial stabilization period of up to 300h, R _P varied linearly with time within the experimental uncertainty. At 1050 C no degradation was observed. At 1000 C a degradation rate of 10 m cm² per 1000 h was found. The degradation rate was possibly higher at 850 C. A single anode was exposed to nine thermal cycles from 1000 to below 100 C at 100 C h^–1. An increase in R _P of about 30m cm² was observed over the first two cycles. For the following thermal cycles R _P was stable within the experimental uncertainty.     

Isolation,characterization and activity of phytotoxic compounds from quackgrass [Agropyron repens (L.)Beauv.]

Previous experiments showed that legumes grown in the presence of living or herbicidally treated quackgrass residues or extracts exhibited reduced seedling root and shoot growth and decreased nodulation and nitrogen fixation. Aqueous extracts of quackgrass shoots were most inhibitory to plant growth. Upon sequential partitioning of an aqueous extract of quackgrass shoots, the ether extract possessed the most activity and caused 50% reductions in radicle elongation of eight crop and weed species at concentrations of less than 240 g/ml (small-seeded species) and 1000 g/ml (large-seeded species). Snapbeans (Phaseolus vulgaris L. Bush Blue Lake) grown aseptically in agar containing an ether extract at 100 and 200 g/ml exhibited severe root browning, lack of root hair formation, and a two- to three-fold reduction in root and shoot dry weights. The ether extract of quackgrass shoots had no inhibitory effect on the growth of fourRhizobium species in Petri dishes or two species in broth culture. Inhibitors present in the ether extract may influence the legumeRhizobium symbiosis indirectly by reducing legume root growth and root hair formation. The ether extract of quackgrass shoots was separated using high-pressure liquid, thin-layer, and liquid column chromatography in an attempt to isolate and identify the inhibitors responsible for the inhibition of seedling growth. Two closely related flavonoid inhibitors were isolated from the ether extract. One was identified as 5,7,4-trihydroxy-3,5-dimethoxyflavone (tricin). Both flavonoids caused 50% inhibition of radicle elongation in cress (Lepidium sativum L. Burpee curly) seeds at concentrations of less than 125 g/ml. Both flavonoids were found in ether extracts of quackgrass shoots and rhizomes, but the largest amounts of both compounds occurred in quackgrass shoots collected from the field.Journal article No. 11887 of the Michigan Agricultural Experiment Station.     

On the NiMoO4 oxidative dehydrogenation of propane to propene: some physical correlations with the catalytic activity

The - and -phases of NiMoO₄ have been investigated with different techniques (X-ray diffraction, electrical conductivity, IR spectroscopy) in order to tentatively rationalise the different catalytic activities observed in the oxidative dehydrogenation of propane to propene. XRD analyses have shown that at 595 ° C, the -phase is already present but a temperature of 700 ° C is required to obtain a full conversion into a pure -phase. Electrical conductivity showed the presence of anionic vacancies. It is proposed that propene is formed by the reaction of propane with surface O^2- anions. The -phase is almost twice more selective in propene formation than the -phase for comparable conversion at identical temperatures. This could derive from different oxygen environments on the active catalytic site.     

Calculation of Temperature Dependences of the Viscosity and Volume Relaxation Time for Oxide Glass-Forming Melts from Chemical Composition and Dilatometric Glass Transition Temperature

The relaxation parameter K _sthat is equal to the ratio of the viscosity to the Kohlrausch volume relaxation time _s is analyzed. It is shown that this parameter can be evaluated from the temperature T ₁₃(corresponding to a viscosity of 10¹³P) and the glass transition temperature T ₈ ⁺determined from the dilatometric heating curve. The maximum error of the estimate with due regard for experimental errors is equal to ±(0.4–0.5)logK _sfor strong glasses and ±(0.6–0.8)logK _sfor fragile glasses, which, in both cases, corresponds to a change in the relaxation times with a change in the temperature by ±(8–10) K. It is revealed that the viscosity, the Kohlrausch volume relaxation time _s , and the shear modulus Gof glass-forming materials in silicate, borate, and germanate systems satisfy the relationship log( _s G/) 1. The procedure for calculating the temperature dependences of the viscosity and the relaxation times in the glass transition range from the chemical composition and the T ₈ ⁺temperature for glass-forming melts in the above systems is proposed. The root-mean-square deviations between the calculated and experimental temperatures T ₁₁and T ₁₃are equal to ±(6–8) K for all the studied (silicate, borate, germanate, and mixed) oxide glass-forming systems. The proposed relationships can be useful for evaluating the boundaries of the annealing range and changes in the properties and their temperature coefficients upon cooling of glass-forming melts.     

Properties ofSrMO 3-δ(M=Fe,Co) as oxygen electrodes in alkaline solution

Strontium ferrates and cobaltates with compositions SrFeO_3- (0.060.40) and SrCoO_3- (0.040.30) were synthesized. The dependence of the oxygen electrode properties on the value was examined in 1 mol dm^–3 KOH solution. In the SrFeO_3- series, the samples with 0.24<<0.29, showed the highest activity in both oxygen evolution and reduction reactions. In contrast, no strong dependence on the value was observed in SrCoO_3-, which also showed a high catalytic activity for oxygen evolution.     

Fertilizer requirements for specified yield targets. I. Theoretical derivation of mathematical models for the computation of soil and fertilizer nutrient efficiencies

The conventional deduction procedure of computation of soil () and fertilizer () nutrient efficiencies for the amount of fertilizer required for specified yield targets does not make provision of the amount of soil nutrient derived by crops from the available pool of soil nutrients not accounted for in the amount extracted by a soil test procedure. The derivation of two mathematical models, viz., Tamil Nadu Agricultural University Model I [TNAU Model I] and Model II [TNAU Model II] is reported in this paper which aim at computing the soil () and fertilizer () nutrient efficiencies not accounted for by the conventional method.In the case of TNAU Model I, the relationship between the nutrient uptake (U) and the soil (S) and the fertilizer (F) nutrients was established by assuming a functional relationship of the type U =S +F such that 0 1 and 0 1. In TNAU Model II the same relationship was established as U =S +F + such that 0 1, 0 1 and > 0. The term in the latter model is a measure of the amount of soil nutrient the crop absorbs from a slowly available pool of nutrients not accounted for in the amounts extracted by the soil test procedure employed or applied through fertilizer.The field verification of these models is reported elsewhere.     

Sex pheromone of aPlanotortrix excessana sibling species and reinvestigation of related species

The sex pheromone of aPlanotortrix excessana sibling species was investigated. Females were found to produce eight potential pheromone components: dodecyl acetate, tetradecyl acetate (14OAc). (Z)-5-tetradecenyl acetate (Z5-14OAc), (Z)-7-tetradecenyl acetate (Z7-14OAc), (Z)-9-tetradecenyl acetate, hexadecyl acetate, (Z)-7-hexadecenyl acetate, and (Z)-9-hexadecenyl acetate. When these compounds were bioassayed using field-trapping and wind-tunnel techniques, only 14OAc,Z5-14OAc, andZ7-14OAc were found to be behaviorally active. The sex pheromone glands of females of other species including,Planotortrix MBS,Planotortrix M,P. notophaea, Ctenopseustis servana, and aC. obliquana sibling species, were also found to containZ5-14OAc orZ7-14OAc, singly or in combination. In the case ofPlanotortrix M, the addition ofZ7-14OAc to the previously identified sex pheromone blend ofZ5-14OAc and 14OAc was found to increase trap captures of male moths of this species. Thus in these New Zealand species (and in some Australian species),Z5-14OAc andZ7-14OAc appear to be utilized in combination in pheromonal communication just as (Z)-11-tetradecenyl acetate and (E)-11-tetradecenyl acetate are used by many species of Holarctic Tortricidae in the tribe Archipini.Lepidoptera: Tortricidae: Tortricinae.     

New polyisobutylene based model ionomers

Three-arm star polyisobutylene ionomers (¯M_n=8800) with terminal SO₃ M (M=K or Ca²) groups were synthesized and their mechanical properties investigated. Compression molded films displayed high elongations, i.e., -1000% for Ca² ionomers with lower values for the K counterions. Strain induced crystallinity was observed at higher elongations. Mechanical properties in general compared favorably with conventional covalently linked rubbery networks and were comparable and in some cases superior to EPDM-based ionomers carrying randomly distributed SO₃ M groups.For the first two parts see Proceedings, 28th IUPAC Macromolecular Symposium, Amherst, MA, July 11–16, 1982, p. 905 and 906     

Influence of tobacco leaf surface chemicals on germination ofPeronospora tabacina adam sporangia

Chromatographic procedures were utilized to isolate and purify components of tobacco cuticular extracts and leaf surface chemicals.In vitro microbial bioassays determined the influence of these leaf surface compounds on germination and germ tube morphology ofP. tabacina sporangia, the tobacco blue mold pathogen, and to a lesser extentAlternaria alternata, the tobacco brown spot pathogen. Exposure to 10 g/cm² of - and -duvatrienemonols, sucrose esters, or hydrocarbons did not inhibit germination, whereas germination was significantly decreased bycis-abienol.cis-Abienol did not inhibit sporangial germination when combined with sucrose esters or hydrocarbons at a combined 10 g/cm². Germination of sporangia was completely inhibited by - and -duvatrienediols. In contrast to a previous report, -DVT-diol was more inhibitory than the isomer. Toxic effects of the DVT-diols were not altered by pH. Diluting the DVT-diols to less than 0.1 g/cm² resulted in a small but significant stimulation of germination. Previously, the DVT-diols had been identified only as inhibitory toP. tabacina. None of the leaf surface chemicals affected germination ofA. alternata conidia.Present Address: Department of Forestry, Biltmore Hall, North Carolina State University, P.O. Box 8002, Raleigh, North Carolina 27695-8002.     

Flow-through and flow-by porous electrodes of nickel foam Part III: theoretical electrode potential distribution in the flow-by configuration

This paper deals with the theoretical potential distribution within a flow-by parallelepipedic porous electrode operating in limiting current conditions in a two-compartment electrolytic cell. The model takes into account the influence of the counter-electrode polarization and of the separator ohmic resistance. The results show that the design of the porous electrode requires the knowledge of the solution potential distribution within the whole cell volume.Nomenclature a _c specific surface area per unit volume of electrode - C ₀ entrance concentration (y=0) - C _s exit concentration (y=y ₀) - E electrode potential (= _M – _S ) - E _o equilibrium electrode potential - F Faraday number - i current density - mean mass transfer coefficient - K parameter [a _ea zFi _oa/(_a RT)]^1/2 - L porous electrode thickness - n number of terms in Fourier serials - P specific productivity - Q volumetric flow-rate - mean flow velocity based on empty channel - V constant potential - V _R electrode volume - x thickness variable - X conversion - y length variable - y ₀ porous electrode length - z number of electrons in the electrochemical reaction Greek symbols parameter - parameter - ionic electrolyte conductivity in pores - _S solution potential - _M matrix potential ( _M = constant) - parameter [=n/y ₀ - parameter [=+K] - overpotential Suffices a anodic - c cathodic - eq equilibrium - s separator - S solution