Conductance behaviour of a microporous membrane and the application of absolute reaction rate theory

The membrane conductance of a microporous membrane prepared by the hydrogen peroxide (5%) treatment of ion-exchange membranes of the ‘Neosepta’ family has been studied at different temperatures. The membranes were bathed in some common uni-univalent chloride solutions at different concentrations. In general, the membrane conductance, in the temperature range studied, shows values increasing more or less linearly with increases in concentration, but tends towards limiting values at higher concentrations. The magnitudes follow the order K⁺ > NH₄⁺ ≥ Na⁺ > Li⁺, which is the reverse order of the hydrated sizes of these ions. The temperature variations of the conductance have been utilised to calculate the activation parameters, E_a, ΔH3, ΔG3 and ΔS3, assuming the applicability of the theory of absolute reaction rate. The activation energies for conduction increase in the order K⁺ < NH₄⁺ ≤ Na⁺ < Li⁺, which is the reverse of the order of conductances but the same as the sequence of the hydrated sizes of the cations. For a particular electrolyte solution, the energy values decrease with increasing concentrations of the bathing electrolyte. The ΔS3 values are found to be mostly very small positive quantities, indicating that virtually neither any bond formation nor any loss of membrane structure takes place during the permeation process.     

Alkalikationen-Spezifität und Träger-Eigenschaften der Antibiotica Nigericin und Monensin

It is shown by means of IR. spectroscopic methods that nigericin and monensin have a cyclic conformation similar to that of their silver salts. Complex formation constants with sodium and potassium ions follow the selectivity order determined by EMF. measurements on liquid membranes: nigericin: K⁺ > Rb⁺ > Na⁺ > Cs⁺ > Li⁺; monensin: Na⁺ > K⁺ > Li⁺ > Rb⁺ > Cs⁺. Transport experiments show that nigericin and monensin facilitate the diffusion of potassiumions across model membranes, although in electrolytic transport experiments the permeability is not affected.     

Microcalorimetric determination of H 0 , G 0 and S 0 for the interaction of the carrier antibiotics nigericin and monensin with sodium and potassium ions

The thermodynamic parameters ΔH⁰, ΔG⁰ and ΔS⁰ – and thereby the equilibrium constants – for the complexation of the carrier antibiotics nigericin and monensin with sodium and potassium ions in methanol at 25°C have been determined by microcalorimetry. The results are discussed in terms of the nature of the interaction between ligands and cations.     

Collisionally activated dissociation of 2,4,6-triphenylpyridinium cations

Thresholds for the appearance of fragment ions allowed the estimation of threshold fragmentation energies (TFE) for the collisionally activated dissociation (CAD) in the gas phase of laser-desorbed pyridine-ring substituted N-benzylpyridinium cations to form pyridine and a carbocation. p-Methylbenzylpyridinium cation underwent an alternative CAD into pyridinium cation and the p-quinodimethane. The TFE are discussed in comparison with the energy differences (ΔΔH_f = ΔH_f(Py) + ΔH_f(R⁺) ? ΔH_f(Py ⁺R) calculated by the AM1 method to provide strong evidence for benzyl to tropylium cation rearrangement in an ion-molecule pair.     

Mechanistic Studies on Rhodium(III) Chelates Aquation of Cis-Dinitrobisbiguaniderhodium(III) Nitrate

Aquation of cis-dinitrobisbiguaniderhodium (III) nitrate was investigated conductometrically. Rates of the release of first and the second nitro groups were derived by a graphical method. For both the steps of aquation, the presence of electron accepting ‘nitro’ group, favours ‘bond formation’ by the incoming ligand in the transition stage and it occurs before the ‘bond rupture’ is complete. The loss of the second ‘nitro’ group most probably takes place along with a hydrogen ion from the ‘aquo’ ligand introduced in the first step of aquation with the resultant formation of the hydroxoaquobisbiguanide complex. Activation parameters were evaluated and are as follows: ΔH? are 18±1.2 and 18.6±1.1 k cals mole^?1 and ΔS? are ?15±2.7 and ?19±2.3 e. u. respectively for the first and the second steps of aquation.     

Ion cyclotron resonance studies of ambident nucleophiles. The reactions of the trimethylsilyl cation with alkenyl ethers and alkoxy ketones

Alkenyl ethers react through oxygen with Me₃Si⁺ to yield intermediates which undergo characteristic fragmentations. In the particular case of allyl ethers, the decomposing adduct undergoes several fragmentations through the allyl substituent via 6-membered transition states. The reaction between Me₃Si⁺ and alkoxy carbonyl derivatives yields both ‘ether’ and ‘keto’ adducts, characterized by their fragmentation patterns. The ‘ether’ adducts formed from Me₃Si⁺ and alkoxy acetones undergo the same basic eliminations as those observed for the allyl ether/Me₃Si⁺ systems.     

Komplexone VL. Reaktionsenthalpie und -entropie bei der Bildung der 1 : 1-Komplexe der Seltenen Erdionen mit 1,3-Diaminopropan-N,N, N′, N′-tetraacetat

The stability constants of the 1 :1 complexes of trimethylenediamine-N, N, N′ N′ tetraacetate ‘TMTA’ with rare earth trivalent cations have been checked. The heats involved in complex formation have been determined. The thermodynamic data show a similar trend as for those of the EDTA complexes, but the discontinuities in the plots ΔH vs. 1/r and ΔS vs. 1/r are displaced towards lower values of 1/r. A change of the coordination number and of the number of coordinated water molecules for the complexes along the series La³+ – Lu³⁺ is suggested. The simultaneous presence in solution of species differing only in the number of bonded H₂O for some members of the series has been confirmed by spectrophotometric measurements in the temperature range 2 to 70°. All facts support the conclusion that in dilute solution all SE^III aquo ions exhibit the same coordination number.     

Calorimetric determination of the standard enthalpy of the first ionization of aqueous sulfur dioxide or ‘sulfurous acid’ at 25°C

Previous investigations of the first ionization of aqueous sulfur dioxide or ‘sulfurous acid’ have led to ΔH ₁ ⁰ values ranging from ?15 to ?24.5 kJ-mol^?1. To help with selection of a ‘best’ value for this enthalpy of ionization we have made calorimetric measurements of enthalpies associated with adding dilute perchloric acid to dilute aqueous sulfur dioxide and sodium bisulfite. Results have led to ΔH ₁ ⁰ =?17.4₀ kJ-mol^?1, which we have combined with K₁=0.0139 and the related ΔG ₁ ⁰ =10.60 kJ-mol^?1 to obtain ΔS ₁ ⁰ =?93.₉ J-K^?1-mol^?1 for the first ionization, all referring to 25°C.     

A computational study of the suppression of ammonia volatility in aqueous systems using ionic additives

Controlling vapour pressure is necessary for the viability of aqueous ammonia solutions in commercial applications such as refrigeration. In this study, Gibbs ensemble Monte Carlo (GEMC) simulations were used to calculate the vapour–liquid equilibrium (VLE) of ammonia–water–MCl mixtures, M = Na or Cs, within the isobaric–isothermal- (NpT-) ensemble. The results indicate that in the presence of alkali metal additives, there is a non-negligible ‘salting-in’ effect for ammonia in the liquid phase. Experimental measurements of the liquid phase concentration of ammonia confirm the GEMC results i.e. the vapour loss rates in systems containing ionic additives is slightly lower. Gibbs ensemble Monte Carlo simulations also indicate that ammonia prefers to solvate aqueous cations as a result of electrostatic interactions. Ab-initio calculations show that the M⁺–ammonia complex is energetically more stable than the M⁺–water complex. The difference in the binding free energy Δ(ΔG _bind(M⁺–NH₃)?ΔG _bind(M⁺–H₂O)) depends on the size of the cation and is highest for the smallest tight cations (e.g. Li⁺) and lowest for the most polarisable cations (Cs⁺).     

Untersuchungen zur Thermochromie von Heterospiranen und Farbbildnern mit heterocyclischen Teilsystemen und O oder N als Ringschlussatom

Investigations on the Thermochromism of a Series of Spirocyclic Compounds and ‘Colourformers’ with Heterocyclic Parts and O or N as the ‘Key’ Atom . The thermochromism of a series of spirocyclic compounds with heterocyclic parts and O or N as the ‘key’ atom and of ‘colourformers’ was investigated in different solvents such as benzyl alcohol, dimethyl phthalate, decaline, toluence, or xylene. Thermodynamic data for the involed equilibria (ΔH°, ΔS°, and ΔG°_298k) and VIS-spectroscopic data were determined and discussed in relation to the ones known spiropyrances. Compounds with O as ‘key’ atom behave very similary to the known spiropyrances, compounds with N as ‘key’ atom mostly are unstable undergoing irreversible bleaching. The ‘colour formers’ usually show only small thermochromic effects and very small equilibrium concentration of the coloured form.     

Kinetic and thermodynamic parameters of volatilization of biodiesel from babassu, palm oil and mineral diesel by thermogravimetric analysis (TG)

The boiling point and volatility are important properties for fuels, as it is for quality control of the industry of petroleum diesel and biofuels. In addition, through the volatility is possible to predict properties, such as vapor pressure, density, latent heat, heat of vaporization, viscosity, and surface tension of biodiesel. From thermogravimetry analysis it is possible to find the kinetic parameters (activation energy, pre-exponential factor, and reaction order), of thermally simulated processes, like volatilization. With the kinetic parameters, it is possible to obtain the thermodynamic parameters by mathematical formula. For the kinetic parameters, the minor values of activation energy were found for mineral diesel (E = 49.38 kJ mol^?1), followed by babassu biodiesel (E = 76.37 kJ mol^?1), and palm biodiesel (E = 87.00 kJ mol^?1). Between the two biofuels studied, the babassu biodiesel has the higher minor value of activation energy. The thermodynamics parameters of babassu biodiesel are, ΔS = ?129.12 J mol^?1 K^?1, ΔH = +80.38 kJ mol^?1 and ΔG = +142.74 kJ mol^?1. For palm biodiesel ΔS = ?119.26 J mol^?1 K^?1, ΔH = + 90.53 kJ mol^?1 and ΔG = +141.21 kJ mol^?1, and for diesel ΔS = ?131.3 J mol^?1 K^?1, ΔH = +53.29 kJ mol^?1 and ΔG = +115.13 kJ mol^?1. The kinetic thermal analysis shows that all E, ΔH, and ΔG values are positive and ΔS values are negative, consequently, all thermodynamic parameters indicate non-spontaneous processes of volatilization for all the fuels studied.     

Mean amplitudes of vibration of the XF+4 interhalogen cations

Mean amplitudes of vibration for the cations ClF⁺₄, BrF⁺₄ and IF⁺₄ have been calculated using the ‘Method of the Characteristic Vibrations’ and recently revised spectroscopic data. The results are briefly discussed and some comparisons with isoelectronic molecules and other related species are made.     

Heavy Alkali Metal Manganate Complexes: Synthesis,Structures and Solvent-Induced Dissociation Effects

Rare examples of heavier alkali metal manganates [{(AM)Mn(CH₂SiMe₃)(N^‘Ar)₂}_∞] (AM=K, Rb, or Cs) [N^‘Ar=N(SiMe₃)(Dipp), where Dipp=2,6-iPr₂-C₆H₃] have been synthesised with the Rb and Cs examples crystallographically characterised. These heaviest manganates crystallise as polymeric zig-zag chains propagated by AM⋅⋅⋅π-arene interactions. Key to their preparation is to avoid Lewis base donor solvents. In contrast, using multidentate nitrogen donors encourages ligand scrambling leading to redistribution of these bimetallic manganate compounds into their corresponding homometallic species as witnessed for the complete Li - Cs series. Adding to the few known crystallographically characterised unsolvated and solvated rubidium and caesium s-block metal amides, six new derivatives ([{AM(N^‘Ar)}_∞], [{AM(N^‘Ar)⋅TMEDA}_∞], and [{AM(N^‘Ar)⋅PMDETA}_∞] where AM=Rb or Cs) have been structurally authenticated. Utilising monodentate diethyl ether as a donor, it was also possible to isolate and crystallographically characterise sodium manganate [(Et₂O)₂Na(ⁿBu)Mn[(N^‘Ar)₂], a monomeric, dinuclear structure prevented from aggregating by two blocking ether ligands bound to sodium.     

Calorimetric Investigation of the Complexation of Didodecylcalix[4]arene-crown-6 with Alkali Metal and Ammonium Cations in Acetonitrile

Abstract

The Cs⁺ selectivity of some calix-crown ligands makes them excellent candidates for use in separation systems such as liquid membranes. Separation performance can be understood and predicted from thermodynamic data for cation complexation. We have therefore determined the log K, ΔH and ΔS for the interaction of Na⁺, K⁺, Rb⁺, Cs⁺ and NH₄ ⁺ with didodecyl-calix[4]arene-crown-6 in acetonitrile at 25°C by titration calorimetry. The ligand is strongly selective for Cs⁺, and the selectivity trend results entirely from the enthalpy contribution, with entropy effects opposing the trend. These results are discussed in light of some corresponding data obtained by other researchers with similar ligands.     

Possible tests for the mechanisms of ligand exchange in solids: The deaquation-anation of [Cr(NH3)5(H2O)]X3 salts

The possibility of using correlations of ΔH⁺ and ΔH, and of ΔH⁺ and ΔS⁺ to gain insight into the mechanisms of ligand-exchange reactions in solids are discussed. These correlations are tested using literature values for the deaquation-anation reactions of [Cr(NH₃)₅(H₂O)]X₃, where X^? = Cl^?, Br^?, I^? or NO^?₃. The poor agreement in the activation parameters reported in the literature precluded a meaningful test of the ΔH?ΔH^* correlation. This poor agreement suggests that these activation parameters are strongly influenced by experimental factors that have not been controlled in studies to date. nevertheless, there is a linear correlation of ΔH² and ΔS² which gives an isokinetic temperature of 367 ± 11 K. This isokinetic behavior suggests that the same mechanism is operative throughout the series.     

NMR of Terminal Oxygen. Part 13. 17O-NMR spectra of C-nitroso compounds,thionitrites and NO+ Ion: Resonance effects in ON—X compounds and correlation with CD spectra

The ¹⁷O-NMR signals of four true C-nitroso compounds 1–4 appear at particularly low field (1550–1265 ppm), whereas the dimers (azodioxy type) resonate at ca. 400 ppm and the ‘isonitroso compounds’ ( ? quinone-oximes; 5 and 6 ) at ca. 250 ppm. S-Nitroso compounds ( ? thionitrites; 8 and 9 ) show shift values of ca. 1300 ppm, not far from C—NO; the NO⁺ ion is much stronger shielded (474 ppm). The results, together with those for higher-shielded nitroso compounds X—NO (X ? RO, R₂N, Cl, O^?) are discussed in terms of (a) resonance stabilization through n-donation from X(π-bond order, approximated by the known barriers of rotation around the X—N bond) and of (b) electronic excitation energies ΔE. The latter are approximated by long-wave (symmetry-forbidden) UV/VIS absorptions and confirmed, where available, by the maxima of the curves of circular dichroism (CD); the CD curve of thionitrite 9 has been measured. It is found that the δ(¹⁷O) values of X—NO depend both on bond order and on ΔE, which could not be separated. The higher shielding of NO⁺ compared with X—N?O is explained on the basis of anisotropy effects, which differ between sp and sp² systems.     

Cobaltchelate als Hydrierkatalysatoren. III. Die Hydridbildung des [Co(dpnH)]+-Komplexes in Gegenwart von Pyridin als axialer Base

Cobalt Chelates as Hydrogenation Catalysts. III. Hydride Formation of the [Co(dpnH)]⁺ Catalyst in the Presence of Pyridine as Axial Base The rate of the hydrogen uptake for [Co(dpnH)]⁺ is 2^nd order with respect to the complex concentration and depends on the amount of added pyridine, in accord with the assumption of a more active mono- and an inactive bis-pyridine adduct. The rate law, formulated on this basis agrees very well with the measured data. The ΔH^≠ - and Δ_RH°-values, calculated from the temperature dependence of the rate constants and equilibrium constants are in agreement with the suggested model, whereas the ΔS^≠ and Δ_RS° values do not correspond completely with these expectations.     

The Interaction of π-Orbitals in Barrelene

The photoelectron spectrum (PE. spectrum) of barrelene (bicyclo[2.2.2]octatriene, 4 ) is recorded and the first four bands are correlated with orbitals obtained with the MINDO/2-SCF procedure. The structural changes accompagnying the ionisation process 4 → 4 ⁺ are qualitatively derived from the features of the top-occupied a′₂ (π) MO of 4 , which shows complete σ-π separation. The vibrational pattern of the corresponding PE. band 1. as well as complete energy-minimisation of the geometries of 4 and 4 ⁺ support the conclusion that 4 is a rather strained molecule. The interaction of the three π? bonds in 4 are discussed in terms of ‘through-space’ and ‘through-bond’ interaction with lower lying σ-orbitals. It is found that the latter is far from being negligible.     

Studies on Heterocyclic Colouring Matters Part II: Δ2,2′ -Bi (2H-1, 4-benzothiazines)

A novel one-step ‘Inverse Indigo Synthesis’ of the Δ^2,2′-bi(3,4-dihydro-3-oxo-2H-1, 4-benzothiazine) chromophore is described. Structure, substitution reactions, mechanism of formation, colour and other relevant properties of this system have been investigated in relation to known thioindigos. A synthesis of the basic skeleton of one of the ‘Trichosiderins’, the colouring matters of human red hair, is reported.     

Primary-particle-beam-induced reduction of silver acetate in glycerol solutions to form a silver mirror

The liquid SIMS mass spectra of silver acetate dissolved in a glycerol matrix is discussed, with emphasis on the formation of a ‘silver mirror’ on the surface of the glycerol droplet owing to reduction of the silver acetate. Silver clusters containing up to three silver atoms have been observed from this mirrored surface; Ag₃⁺ cluster ions are not observed in the spectrum when conditions are such that the mirror is not formed. For example, use of a slightly oxidizing matrix (o-nitrophenyl octyl ether or m-nitrobenzylalcohol) prevents formation of the ‘mirror’; only Ag⁺ is sputtered from this surface.