Calorimetric,X-ray and infra-red investigations on poly(hexamethylene adipamide)

Summary In dependence on crystallization conditions three ranges with different crystal structure and heat of fusion were found by DSC,WAXS,and IR for unoriented PA 6.6 samples of densities between 1.10 and 1.17gcm^–3: Range I:_I triclinic, _c ^I =1.225 gcm^–3,H _M ^I = 235 Jg^–1. Range II:_II triclinic, _c ^II =1.165 gcm^–3, H _M ^II =185 Jg^–1. Range III:Continuous variation from _c ^I ,H _M ^I to _c ^II , H _M ^II . _a=1.095 gcm^–3 is independent of crystallization. conditions. The transition between _I and _II is probably due to changes of the chain conformation.     

The role of soil pH in the dissolution of phosphate rock fertilizers

The influence of soil pH on the dissolution of phosphate rock fertilizers was investigated in laboratory experiments with reactive North Carolina phosphate rock (PR) in a lateritic soil adjusted to several pH values. Increased soil pH resulted in decreased dissolution as estimated by the increase in exchangeable calcium (Ca) method. The extent of PR dissolution was related to soil pH by an equation of the form Log Ca = a–b pH, and it increased with contact period and rate of PR application. Increased plant available P, as estimated by NaHCO₃ soluble-P (BicP) was about one third of the P dissolved from PR. BicP was related to soil pH by an equation of the form Log Bic P = c–d pH. Dissolution of PR in soil can be considered as a simple chemical reaction between apatite and hydrogen ions supplied by soil constituents.     

The effect of the level of phosphate rock application on its dissolution in soil and on bicarbonate-soluble phosphorus

The effect of the level of phosphate rock application on its dissolution in a lateritic podzolic soil was investigated in laboratory incubation studies. Dissolution of phosphate rock (PR) was estimated as the increase in soil exchangeable Ca ( Ca). Concomitant increases in bicarbonate-soluble P levels ( Bic P) were estimated with the Olsen extractant. Up to 19% of PR dissolved at 200µg P g^–1 soil level of PR application whereas a ten-fold increase in the level of application resulted in the percentage dissolution decreasing to 5%. The absolute amount of dissolution however increased with the level of PR application. The amount of PR dissolved was described by the equation P = A(1 – e^–CR) where P = P dissolved from PR (µg P g^–1 soil) calculated from Ca values, A = maximum dissolution asymptote, C = curvature coefficient and R = level of PR applied expressed asµg P g^–1 soil. Values of the A coefficient increased systematically from 28 to 93µg P g^–1 soil for incubation periods from 1 to 7 days. Corresponding values of the C coefficient ranged from 0.9 – 2.1 × 10^–3. Increases in Bic P arising from the dissolution of PR were also described by an exponential equation and the asymptote values ranged from 4 to about 18µ P g^–1 soil. For Bic P the curvature coefficient values increased with incubation period due to increased P retention with increasing contact period between PR and the soil.The form of the yield response curves of plants to PR was predicted on the basis of these data and compared with response curves reported in the literature. The response curves for PR differ in shape from the Mitscherlich response curve for superphosphate and indicate that in some situations PR is unable to support the same maximum yield as soluble P fertilizers due to inadequate dissolutiuon of PR at high rates of application.     

Pheromone biosynthesis in lepidoptera

Pheromone components for many lepidopteran species are produced by the use of unique chain-shortening and 9, 10, and 11 desaturase systems. Correlations in the Tortricidae indicate that the pheromone components derived from 9 and 01 desaturases are found in the more primitive species (those possessing morphological plesiomorphies). The precise blend ofZ andE acetates in a number of species is regulated in the final reduction sequence from acyl intermediates. Preliminary research has been conducted on the characterization of the various desaturase enzymes used and on the important blend regulating sequence. Initial purification work on the 11 desaturase enzyme found in the cabbage looper moth is reported.     

Thermodynamics of polymer systems

Summary Gas chromatography has been employed to determine partial molar free energies of sorption, C₁ ^s, as well as partial molar free energies of mixing, C₁ , of atactic poly(styrene) with linear and branched alkanes (C₆-C₉), alkenes (C₈), cyclohexane and alkylbenzenes (Ph-H to PhC₆H₁₃) within the temperature range from 403 to 463 K. The influence of nature and constitution of the solute molecule on sorption and mixing properties in poly(styrene) are discussed in terms of the competing group contributions of the components. Knowledge of this influence may be transduced to understand polymer-polymer compatibility. The cohesive energy density concept has been used to calculate the infinite dilution solubility parameter for the polymer, with the aid of G ₁ . From the high temperature range the HILDEBRAND parameter ₂ was extrapolated to 298 K. The value obtained, 9.14, indicates that gas chromatography is an promising alternative to the conventional methods for determination of the solubility parameter for polymers.Herrn Prof. Dr. R. C. Schulz zu seinem 65. Geburtstag herzlichst gewidmet     

Tissue-Specific Fatty Acid Composition of Glandular Trichomes of Mite-Resistant and -Susceptible Pelargonium xhortorum

Anacardic acids, alkyl phenolic acids excreted by tall glandular trichomes of the garden geranium, Pelargonium xhortorum, confer small-pest resistance. Up to 90% of the trichome exudate from mite-resistant P. xhortorum inbreds consists of an unusual anacardic acid with an unsaturated omega-5 (⁵) alkyl chain. As fatty acids are biochemical precursors to anacardic acids, we examined by GC the fatty acid composition of leaves, pedicels, petals, sepals, mature seeds, and glandular trichomes from pest-resistant and pest-susceptible Pelargonium inbred lines to determine the localization of ⁵-fatty acids within plant tissues. The fatty acid composition of lipid classes (galactolipids, phospholipids, and neutral lipids) extracted from glandular trichomes from mite-resistant pedicels were also examined. ⁵-Fatty acids (16:111 and 18:113) were found only in the glandular trichomes from pest-resistant geraniums (27.2% in trichomes of pedicels) and were localized predominantly in the phospho- and galactolipids (phosphatidylinositol, 25.9%; phosphatidylcholine, 18.2%; monogalactosyldiglyceride, 15.5%; and diglactosyldiglyceride, 14.0%).     

The temperature dependence of the electrochemistry of the lithium-sulphur dioxide system

Value for the activation energy, U ^act, and the entropy change, S, for the reaction 2Li + S₂O ₄ ^2– Li₂S₂O₄+2e in acetonitrile have been found to be 72 kJ mol^–11 and — 0.3 kJ mol^–1 K^–1, respectively, by a combination of impedance techniques and the use of a temperature-controlled environment on commercially manufactured cells which acted as constant volume containers.     

Infrared studies of the interaction of carbon monoxide and dinitrogen with ferrisilicate MFI-type zeolites

Fourier transform IR spectroscopy of CO and N₂, adsorbed at liquid nitrogen temperature, was used to characterize an MFI-type H-FeZSM-5 ferrisilicate which was synthesized with a Si/Fe ratio of 50. Thermal treatment of this material at 773 and 973 K was performed in order to follow formation of extraframework species. On samples fired at 773 K Brønsted acid sites were present which gave an O-H stretching band at 3630 cm^–1. These hydroxyl groups formed adducts with both probe molecules, which were monitored by the corresponding bathochromic shift, . Corresponding values for adsorbed CO and N₂ were = –270 and = – 100, respectively. Increasing the firing temperature up to 973 K led to complete removal of iron from the zeolite framework, and consequent disappearance of Brønsted acidity. In this process, extraframework iron oxide species were formed which were also characterized by IR spectroscopy of the adsorbed probe molecules. Both CO and N₂ gave Lewis-type adducts with coordinatively unsaturated Fe³⁺ ions present in the extraframework material. A comparison is made with results of a previous study on the H-GaZSM-5 isomorph.     

Enthalpy relaxation studies in isotactic polystyrene. Effects of crystallinity

Summary The enthalpy relaxation of the amorphus isotactic polystyrene is strongly affected from the crystalline phase induced by annealing at temperatures between Tg and Tm. All the parameters describing the relaxation process, H, T_max and T_ons depend also on the above T_g annealing conditions as the induced crystallinity alters the quantity and the quality (i.e.Tg, T_gons, T_g) of the remaining amorphous phase.     

Synthesis and characterization of soluble (porphyrinato)iron(II) polymers

The use of (tetrakis(4-hexylphenyl)porphyrinato)Fe(II) in polymerization reactions with bidentate ligands such as 9,10-diisocyanoanthracene and 1,4-diisocyanobenzene led to well-defined stacked polymers1 and2 which are still soluble in common organic solvents such as chloroform, dichloromethane, and tetrahydrofurane. They have been completely characterized by¹H-NMR and UV/vis spectropscopy in solution, even allowing end-group analysis for determination of the average degree of polymerization, yieldingn=10 andn=5 for1 and2, respectively. Mößbauer and IR spectroscopy further established the strong Fe-CN bonding reflected by very small isomer shifts and quadrupole splittings (E _Q0.2 mm s^–1) and a large decrease in the IR stretching frequency (v _CN60 cm^–1). The axially stacked polymers exhibit semiconducting properties only upon doping.Presented at the 5th International Symposium on Macromolecule-Metal Complexes (MMV), Summer 1993 in Bremen, Germany.     

On the possibility of estimating weak interactions of macromolecules in solutions from the experimental viscous flow activation energies data

Summary The initial viscosity and activation energy in viscous flow of the systems: water(W)-casein(C)-polysaccharide(PS) (gum arabic(G),de-xtran(D), extran sulfat (DS)) have been determined for various ionic strengths corresponding to total or limited thermodynamic compatibility of macrocomponents. Excess activation energy H ^E due to the protein-polysaccharide interactions has been calculated. It is positive for systems with total compatibility and negative for systems with limited compatibility. Moreover, it yields information on type of the protein-polysaccharide interactions. Negative H ^E means that repulsive forces are dominant, while positive H ^E means that attractive forces are dominant. Since the properties of the systems W-C-D and W-C-DS are similar, it is believed that C-D complexes can possibly be formed with an energy 2 kT(10 mJ/g).The authors express their sincere graditude to Konstantinov A.A., Kondratev V.P., Chernysh M.M. (Special Design Bureau of the Institute of Petroleum Chemical Synthesis, The USSR Academy of Sciences) and Dmitrienko A.P. (Institute of Organoelement compounds, The USSR Academy of Sciences) for their invaluable help.     

Generalized analytical expressions for Tafel slope,reaction order and a.c. impedance for the hydrogen evolution reaction (HER): mechanism of HER on platinum in alkaline media

Following the generally accepted mechanism of the HER involving the initial proton discharge step to form the adsorbed hydrogen intermediate, which is desorbed either chemically or electrochemically, generalized expressions for the Tafel slope, reaction order and the a.c. impedance for the hydrogen evolution reaction are derived using the steady-state approach, taking into account the forward and backward rates of the three constituent paths and the lateral interactions between the chemisorbed intermediates. Limiting relationships for the Tafel slope and the reaction order, previously published, are deduced from these general equations as special cases. These relationships, used to decipher the mechanistic aspects by examining the kinetic data for the HER on platinum in alkaline media, showed that the experimental observations can be consistently rationalized by the discharge-electrochemical desorption mechanism, the rate of the discharge step being retarded on inactive platinum compared to the same on active platinum.Nomenclature C _d double-layer capacity (µF cm^–2) - E _rev reversible electrode potential (V) - F Faraday number (96 487 C mol^–1 ) - R gas constant - T temperature (K) - Y _f Faradaic admittance (^–1 cm^–2) - Y _t Total admittance (^–1 cm^–2) - Z _f Faradaic impedance ( cm²) - i _f total current density (A cm^–2) - i _nf nonfaradaic current density (A cm^–2) - j - k ₀ ¹ rate constant of the steps described in Equations 1 to 3 (mol cm^–2 s^–1 ) - j - qmax saturation charge (µC cm^–2) - Laplace transformed expressions for i, and E - _{1 3} symmetry factors for the Equations 1 and 3 - saturation value of adsorbed intermediates (mol cm^–2) - overpotential - coverage by adsorbed intermediates - angular frequency This paper is dedicated to Professor Brian E. Conway on the occasion of his 65th birthday, and in recognition of his outstanding contribution to electrochemistry.     

On the mechanism of electroless plating. I. Oxidation of formaldehyde at different electrode surfaces

To elucidate the mechanism of electroless plating solutions with formaldehyde as the reductant, the anodic oxidation of formaldehyde in alkaline medium was studied. The influence of electrode material, pH and potential was investigated. The experimental results can be explained by a mechanism in which methylene glycol anion (CH₂OHO^–) is dehydrogenated at the electrode surface, yielding adsorbed hydrogen atoms. The atomic hydrogen can either be oxidized to water or be desorbed as a gas. Kinetic rate laws for these two reactions are given. Electroless copper, platinum and palladium solutions behave according to the mechanism.Nomenclature E applied potential - E _a activation energy of adsorption - E _d activation energy of desorption (=–H+E _a) - E _eq equilibrium potential of the reversible hydrogen reaction at a given pH - F Faraday's constant - –H heat of adsorption - i ⁰ apparent exchange current density for the reversible hydrogen reaction - i ₀ exchange current density for the reversible hydrogen reaction - k rate constant for the desorption of hydrogen - L _s heat of atomization - R gas constant - T absolute temperature - ₇ rate of oxidation of hydrogen atoms - ₈ rate of desorption of hydrogen - transfer coefficient (0.5) - overpotential (=E–E _eq) - fraction of the surface covered by hydrogen atoms - _M work function of metal M - potential of the outer Helmholtz layer relative to the bulk of the electrolyte     

The ratio of crystallinity and thermodynamical interactions of polycaprolactone with some aliphatic esters and aromatic solvents by inverse gas chromatography

Summary The retention diagrams of benzene, toluene, ethyl benzene, chloro benzene, n-propyl benzene, isopropyl benzene, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate and isoamyl acetate on the polycaprolactone were plotted at temperatures between 70 and 140^oC by inverse gas chromatography technique. Percent crystallinity of polycaprolactone were obtained at temperatures below melting point from the retention diagrams of benzene, toluene and ethyl benzene. It was concluded that the data obtained by inverse gas chromatography were comparable those of obtained by differential scanning calorimetry. Specific retention volume, V_g^o, Flory-Huggins polymer-solvent interaction parameters, ₁₂, the weight fraction activity coefficients of the solvents at infinite dilution, ₁, effective exchange energy parameters, X_eff were determined. Later, the partial molar heat of sorption, H_1,sorp and the partial molar heat of mixing, H₁ were obtained from the slope of the logarithm of specific retention volume, Ln V_g^o versus 1/T plot and from the slope of the logarithm of the weight fraction activity coefficients, ₁versus 1/T plot, respectively.     

Field application of the15N isotope dilution technique for the reliable quantification of plant-associated biological nitrogen fixation

To apply the isotope dilution (ID) technique, it is necessary to grow the N₂-fixing crop in a soil where the mineral N is labelled with¹⁵N. Normally the N₂-fixing crop and a suitable non-N₂-fixing control crop are grown in the same labelled soil and the¹⁵N enrichment of the control crop is assumed to be equal to the¹⁵N enrichment of the nitrogen (N) derived from the soil in the N₂-fixing crop. In this case the proportion of unlabelled N being derived from the air via biological N₂ fixation (BNF) in the N₂-fixing crop will be proportional to the dilution of the enrichment of the N derived from the labelled soil.To label the soil, the technique most often used is to add a single addition of¹⁵N-labelled N fertilizer shortly before, at, or shortly after, the planting of the crops. Data in the literature clearly show that this technique results in a rapid fall in the¹⁵N enrichment of soil mineral N with time. Under these conditions, if the control and the N₂-fixing crops have different patterns of N uptake from the soil they will inevitably obtain different¹⁵N enrichments in the soil-derived N. In this case the isotope dilution technique cannot be applied, or if it is, there will be an error introduced into, the estimate of the contribution of N derived from BNF.Several experiments are described which explore different strategies of application of the ID technique to attempt to attenuate the errors involved. The results suggest that it is wise to use slow-release forms of labelled N, or in some cases, multiple additions, to diminish temporal changes in the¹⁵N enrichment of soil mineral N. The use of several control crops produces a range of different estimates of the BNF contributions to the N₂-fixing crops, and the extent of this range gives a measure of the accuracy of the estimates. Likewise the use of more than one¹⁵N enrichment technique in the same experiment will also give a range of estimates which can be treated similarly. The potential of other techniques, such as sequential harvesting of both control and test crops, are also discussed.     

ΔCp, Δα and related quantities for epoxy-aromatic amine networks

Summary The parameters of glass transition in several epoxyamine polymer networks were obtained. The changes C_p (T_g) and (T_g) were proved to be correlated with the concentration of crosslinks in these systems. The difference in glass transition parameters for linear and densely crosslinked polymers was analysed in terms of Simha-Boyer (T_g) and Boyer (C_p·T_g) rules and Eyring's hole theory.     

Preparation of nanosize Pt clusters using ion exchange of Pt(NH3) 4 2+ inside mesoporous channel of MCM-41

Mesoporous molecular sieve MCM-41 with a Si/Al ratio of 35 was obtained by hydrothermal synthesis using a gel mixture with a molar composition of 6 SiO₂0.1 Al₂O₃1 hexadecyltrimethylammonium chloride 0.25 dodecyltrimethylammonium bromide 0.25 tetrapropylammonium bromide0.15 (NH₄)₂O1.5 Na₂O300 H₂O. The MCM-41 sample was calcined in O₂ flow at 813 K and subsequently ion exchanged with Ca²⁺. A small Pt cluster has been supported on the MCM-41 sample following a procedure using ion exchange of Pt(NH₃) ₄ ²⁺ . The Pt(NH₃) ₄ ²⁺ ion supported on MCM-41 has been activated in O₂ flow at 593 K and subsequently reduced with Fh flow at 573 K, in the same way used for the preparation of a Pt cluster entrapped inside the supercage of zeolite NaY. The resulting Pt cluster supported on the MCM-41 shows hydrogen chemisorption oftotal two H atoms per Pt at 296 K (based on the total amount of Pt) and high catalytic activity for hydrogenolysis of ethane. The chemical shift in¹²⁹Xe NMR spectroscopy of adsorbed xenon indicates that the Pt cluster is located inside the mesoporous molecular sieve.     

Impedance of a porous electrode with an axial gradient of concentration

When the impedance is measured on a battery, an inductive impedance is often observed in a high frequency range. This inductance is frequently related to the cell geometry and electrical leads. However, certain authors claimed that this inductance is due to the concentration distribution of reacting species through the pores of battery electrodes. Their argument is based on a paper in which a fundamental error was committed. Hence, the impedance is re-calculated on the basis of the same principle. The model shows that though the diffusion process plays an outstanding role, the overall reaction rate is never completely limited by this process. The faradaic impedance due to the concentration distribution is capacitive. Therefore, the inductive impedance observed on battery systems cannot be, by any means, attributed to the concentration distribution inside the pores. Little frequency distribution is found and the impedance is close to a semi-circle. Therefore depressed impedance diagrams in porous electrodes without forced convection cannot be ascribed to either a Warburg nor a Warburg-de Levie behaviour.Nomenclature A D¦C¦ (mole cm s^–1) - B j+K¦C¦ (mole cm s^–1) - b Tafel coefficient (V^–1) - C(x) Concentration ofS in a pore at depthx (mole cm^–3) - C ₀ Concentration ofS in the solution bulk (mole cm^–3) - C C(x) change under a voltage perturbation (mole cm^–3) - ¦C¦ Amplitude of C (mole cm^–3) - D Diffusion coefficient (cm² s^–1) - E Electrode potential (V) - E Small perturbation inE namely a sine-wave signal (V) - ¦E¦ Amplitude of E(V) - F Faraday constant (96500 A s mol^–1) - F(x) Space separate variable forC - f Frequency in Hz (s^–1) - g(x) KC(x)¦E¦(mole cm s^–1) - I Apparent current density (A cm^–2) - I _st Steady-state current per unit surface of pore aperture (A cm^–2) - j Imaginary unit [(–1)^1/2] - K Pseudo-homogeneous rate constant (s^–1) - K Potential derivative ofK, dK/dE (s^–1 V^–1) - K ^* Heterogeneous reaction rate constant (cm s^–1) - L Pore depth (cm) - n Reaction order - P Reaction product - p Parameter forF(x), see Equation 13 - q Parameter forF(x), see Equation 13 - R _e Electrolyte resistance (ohm cm) - R _p Polarization resistance per unit surface of pore aperture (ohm cm²) - R _t Charge transfer resistance per unit surface of pore aperture (ohm cm²) - S Reacting species - S _a Total surface of pore apertures (cm²) - S ₀ Geometrical surface area - S _p Developed surface area of porous electrode per unit volume (cm² cm^–3) - s Concentration gradient (mole cm^–3 cm^–1) - t Time - U Ohmic drop - x Distance from pore aperture (cm) - Z Faradaic impedance per unit surface of pore aperture (ohm cm²) - Z _x Local impedance per unit pore length (ohm cm³) - z Charge transfer number - Porosity - Thickness of Nernst diffusion layer - Penetration depth of reacting species (cm) - Penetration depth of a.c. signal determined by the potential distribution (cm) - Electrolyte (solution) resistivity (ohm cm) - ₀ Flow of S at the pore aperture (mole cm² s^–1) - Angular freqeuncy of a.c. signal, 2f(s^–1) - Integration constant     

Estimation of the contribution of biological N2 fixation to twoPhaseolus vulgaris genotypes using simulation of plant nitrogen uptake from15N-labelled soil

A technique for the application of the¹⁵N isotope dilution technique for the quantification of plant associated biological nitrogen fixation (BNF) was tested and applied to quantify the BNF contribution to two genotypes ofPhaseolus vulgaris. The technique makes use of sequential measurements of the¹⁵N enrichment of soil mineral N, and the uptake of labelled N by the N₂-fixing plant, to simulate its uptake of soil N (the soil to plant simulation technique). The test was made with two non-N₂-fixing crops (non-nodulating beans and wheat) and two bean genotypes (PR 923450 and Puebla 152), at two levels of N fertilizer addition (10 and 40 kg N ha^–1), to compare the actual N uptake with that simulated from the soil and crop¹⁵N data. The simulation of the soil N uptake by the non-nod bean crop using this soil to plant simulation technique underestimated by 20 to 30% the true N uptake, suggesting that the mineral N extracted from soil samples taken from the 0–15cm layer had a higher¹⁵N enrichment than that N sampled by the roots of this crop. In the case of the wheat crop the simulation resulted in a much greater underestimation of actual N uptake. In general the results using this technique suggested that BNF inputs to the bean cultivars was higher than would be expected from the nodulation and acetylene reduction data, except for the early PR beans in the 40 kg N ha^–1 treatment. In this case the total N and simulated soil N accumulation were well matched suggesting no BNF inputs. An allied technique (the plant to plant simulation technique) was proposed where the¹⁵N enrichrnent of soil mineral N was simulated from the data for total N and labelled N accumulation taken from sequential harvests of either of the non-N₂ -fixing control crops. This was then utilized in combination with the labelled N uptake data of the other crop to simulate its soil N uptake. However, the results using either technique indicated that the wheat and non-nod or nodulating beans exploited pools of N in the soil with completely different¹⁵N enrichments probably due to differences in exploitation of the soil N with depth.     

An investigation of some Schiff bases as corrosion inhibitors for austenitic chromium–nickel steel in H2SO4

The corrosion inhibition of austenitic chromium–nickel steel by two Schiff bases, N-(1-toluidine)salicylaldimine and N-(2-hydroxyphenyl)salicylaldimine, was investigated in sulphuric acid medium. The effect of concentration and temperature on inhibition properties was determined. It was found that when the concentrations of inhibitor were increased the inhibition efficiencies () and surface coverage () increased. Some thermodynamic parameters such as free energy of adsorption, G _ads, and enthalpy, H, were determined for the Schiff bases. Experimental results agree with the Temkin isotherm for N-(1-toluidine)salicylaldimine, but the Langmuir isotherm is more appropriate for N-(2-hydroxyphenyl)salicylaldimine.