Cation exchange membranes as solid solutions

The ion exchange equilibrium between KCl and SrCl₂ solutions and the cation selective membrane CR61 AZL386 has been examined. Equilibrium isotherms are measured for membrane—electrolyte equilibria for two total concentrations of Cl^?in the electrolyte solution and at three different temperatures. The results show that Sr²⁺ is strongly preferred to K⁺ in the membrane. Selectivity increases with temperature in the range 10°C to 40°C. It decreases with increasing total concentration from 0.01 N to 0.03 N. Electrolyte absorption in the membrane was not detected for the experimental conditions used. Contents of water in the membrane is constant for external salt concentrations between 3 x 10^?8N and 3 x 10^?2N. The difference in water content between the pure K form and the pure Sr form is approximately 5%.A thermodynamic treatment of ion exchange is presented. The thermodynamic equilibrium constant for the exchange reaction 2 KR + SrCl₂ = SrR₂+ 2 KCl has been determined by two different integration procedures, R being an ion exchange site in the membrane. The variations of the thermodynamic functions ΔG_mix, ΔH_mix and ΔS_mix are calculated from experimental data for an assumed mixing process of membranes in the pure forms.Activity coefficients for the membrane components are calculated from experimental data. Results are compared to two lattice models. A model with a random distribution of K⁺, Sr²⁺ and a vacant site seems preferred at low concentration of Sr²⁺. At high concentrations, Sr²⁺ and the vacant site associate.     

Thermodynamics of metal cyanide coordination : Part IX. Log K, ΔH, and ΔS values for the Ni-, Zn-, Cd-, and Hg- CN systems at 10, 25, and 40 °C

Log K, ΔH⁰, and ΔS⁰ values valid at zero ionic strength are reported or summarized from previous studies for cyanide ion interaction with bivalent nickel, zinc, cadmium, and mercury at 10, 25, and 40 °C. From the values of ΔH⁰ as a function of temperature, average ΔC_p⁰ values are calculated.     

The 1B1u ← 1A1g 0—0 transition in crystal benzene

The transition linewidth ΔE in crystal C₆H₆, C₆D₆ and sym-C₆H₃D₃ has been measured as a function of temperature T from 4.2 to 135°K, and it extrapolates to a common value of ΔE_o = 50 cm^? at O°K. In C₆H₆ ΔE = (50 + 7T^{$\text{1}\text{2}$}) cm^?1, indicative of strong exciton—phonon coupling, and there is a line shift of +40 cm^?1 per substituent deuteron. Fluorescence excitation spectral data are used to separate the ¹B_1u(= S₂) decay rate k_H = 9.4 × 10¹² sec^?1, derived from ΔE₀, into S₂S₁ internal conversion (rate ≈ 6.6 × 10¹² sec^?1) and S₂S_x (channel 3) internal conversion (rate ≈ 2.8 × 10¹² sec^?1. A similar value of k_H = 9.9 × 10¹² sec^?1 is obtained from the S₂S_o fluorescence quantum yield of liquid benzene.     

The thermodynamic effect of fluorine as a substituent: Vinylic CF2 and CFH and allylic CF2C

I₂-catalyzed isomerizations of 3-fluoropropene and 3,3 - difluoropropene, and a Cope rearrangement of 1,1 - difluoro - 1,5 - hexadiene provide thermodynamic data which allow the determination of a number of important group values for contributions to ΔH^o_f which when combined with those determined in the preceding paper allow the calculations of ΔH^o_f's of most simple F-substituted hydrocarbons: [C_d(F)(H)] = ? 38.4, [C_d(F)₂] = ? 88.0, [C(F)₂(C)(C_d)] = ? 103.9, [C(F)₂(C)₂] = ? 104.9 kcal/mole. A kinetic study of the conversion of 1,1 - difluoro- to 3,3 - difluoro - 1,5 - hexadiene provided activation parameters for the process: Log A = 10.8, E_a = 33.0 kcal/mole and ΔS^≠ = ? 12.2 e.u. Incremental geminal stabilizations of F and other substituents are discussed and contrasted.     

Zur koordination mehrfunktioneller thioether in cyclopentadienyleisen-komplexen

[C₅H₅Fe(CO)₂thf]⁺ reacts with the ligands LL and LLL to give the cations [C₅H₅Fe(CO)₂LL]⁺ (LL = RS(CH₂)_nSR, 1,4-dithiane) and [C₅H₅Fe(CO)₂LLL]⁺ (LLL = 1,3,5-trithiane, tris(methylmercapto)methane) containing monodentate coordinated sulfur ligands. In a similar way, sulfur ligand bridged dinuclear dications [(C₅H₅Fe(CO)₂)₂(μ-LL)]²⁺ and [(C₅H₅Fe(CO)₂(μ-LLL)]²⁺ and tri-nuclear trications [(C₅H₅Fe(CO)₂)₃(μ-LLL)]³⁺ are formed. Irradiation of the mononuclear cations gives the chelate complexes [C₅H₅Fe(CO)(η²-LL)]⁺.     

Reduction of copper (II) chloride by molybdenum and rhenium biscyclopentadienyl hydrides. Investigation of the crystal and molecular structure of [(η5-C5H5)2Re]+[CuCl2]−

The reduction of copper (II) chloride by molybdenum and rhenium biscyclopentadienyl hydrides upon their interaction in donor-type solvents has been studied by NMR, X-ray diffraction, and magnetic methods. It is established that the ionic complex [(η⁵-C₅H₅)₂Re]⁺[CuCl₂]^? forms ortho rhombic crystals with a - 13.696(2) Å, b = 7.317(1) Å, c = 5.969(1) Å, space group Pm2₁n, Z = 2. The cyclopentadienyl rings make a bent-sandwich with an angle between the ring centres and Re atom of 150.1°; the ClCuCl angle being 174.8° and the ReCu minimum distance 4.346(29) Å. The solution of [(η⁵-C⁵H₅)²Re]⁺ [CuCl₂]^? seems to activate the CH bond of the C₅H₅ rings, which results in the addition of the [(C₅H₅)(C₅H₄)ReH]⁺ hydride ion.     

The synthesis of a novel trimetallic complex containing three redox centres and an assessment of inductive effect transmission through an iron atom

The novel trimetallic complex [Fe{η⁵-C₅H₄SMo(NO)LCl}₂]; in which L = tris(3,5-dimethylpyrazolyl)hydroborate, and its bimetallic analogue [{(Mo(NO)LCl)}₂(m-S₂C₆H₄)] have been synthesised; electrochemical studies of these compounds indicate that the inductive effects of the molybdenum-containing substituent are transmitted to equal extents through the CFeC and CCC bridging atom chains.     

Preparation and properties of new ferrocenyl heterobimetallic complexes with counterion dependent NLO responses

New ferrocenyl-based bimetallic cationic compounds of the type of (E)-[CpFe(η⁵-C₅H₄)(CHCH)(C₆H₄)CNRuCp(PPh₃)₂]X (X=PF₆, BF₄) and of (E)-[CpFe(η⁵-C₅H₄)(CHCH)(C₆H₄)CNFeCp(CO)₂]PF₆ have been obtained and characterized. The crystal structure of (E)-[CpFe(η⁵-C₅H₄)(CHCH)(C₆H₄)CNRuCp(PPh₃)₂]BF₄ has been established by means of X-ray diffractometry. The NLO responses of the compounds have been studied by the hyper-Rayleigh scattering technique and the hyperpolarizability is found to be dependent on the nature of the counterion.     

Conformational analysis—XXI : H NMR Conformational Study of Alkyl-Substituted 2-Oxo-1,3,2-Dioxathianes

2-Oxo-1,3,2-dioxathiane and all methyl- and several alkyl-substituted 2-oxo-1,3,2-dioxathianes were prepared for a ¹H NMR conformational study. The conformational energy of the axial SO group in CCl₄, - ΔG^θ_SO = 14.8±0.3kJ mol^?1, was determined by chemical equilibration of the epimeric cis-4,6-dimethyl derivatives and it was found to decrease with the increasing solvent polarity. The conformational equilibria of alkyl-substituted derivatives were solved and the proportions of the conformers estimated using ¹H NMR chemical shifts, vicinal coupling constants and in three cases also dipole moments. The configurational interactions in the C₄C₅C₆ moiety are close to the corresponding values of 1,3-dioxanes.     

The structure of the dithionite ion

The Raman spectra of aqueous and solid sodium dithionite have been recorded. Differences in the location, intensity, and number of observed bands are attributed to conformational changes in the dithionite ion. The structure of the aqueous ion is non-planar with a C_2h symmetry with an SS bond distance estimated to be 0.220–0.226 nm, as opposed to the dithionite structure in the Na₂S₂O₄·2H₂O salt which is known to have C_2ν structure with a bond distance of 0.2389 nm. The Raman spectra of aqueous dithionite are assigned to A_g (SO) = 997 cm^?1; B_g (SO) at 912 cm^?1, B_g SO₂ twist at 324 cm^?1. The remaining bands are a strong A_g, the SO₂ wag, the SO₂ scissor, and the SS stretch at 584, 461, and 232 cm^?1, respectively, but due to coupling all three motions are expected to exhibit substantial SS character. The variation of the spectra of the solid and aqueous sodium dithionite indicate strong environmental effect on the structure of the anion.     

Löslichkeiten und Aktivitätskoeffizienten von H2S in Elektrolytmischungen

From solubility measurements on hydrogen sulfide in aqueous solutions of the composition [H⁺] = HM, [Na⁺] = (I — H) M = A M, [Cl^?] = I M at 25°C, the molar and molal activity coefficients of H₂S have been calculated. The activity coefficients of H₂S in the electrolyte mixtures have been found to be additive functions of the activity coefficients in the individual electrolyte solutions at the same ionic strength. This result is predicted by the internal pressure theory of salt effects on non-electrolyte activity coefficients, provided that the volume change upon mixing two electrolyte solutions of the same ionic strength is zero.     

Mixed-pole terms in the anisotrophy of the long-range interaction coefficients for H2He and H2H2

It is shown that mixed-pole terms can make significant, and even dominant, contributions to the anisotropy of the long-range interaction C₈ coefficients for H₂He and H₂H₂.     

The heat of dehydration of concentrated sodium chloride and potassium chloride solutions

The molar heats of dehydration, ΔH¯_dehyd., of concentrated sodium chloride and potassium chloride solutions were measured with a differential scanning calorimeter in the scanning and isothermal modes. The overall ΔH¯_dehyd. was found to be 44.5 and 44.3 kJ mole^?1 H₂O for NaCl and KCl solutions respectively. There is an astonishing difference between concentrated NaCl and KCl solutions in the way water is lost. The number of fractions of heat dehydration were 2 for NaCl and 3 for KCl. The excess ΔH¯_dehyd. was about 10 kJ mole^?1 H₂O for fraction II of NaCl, and 17 and 55 kJ mole^?1 H₂O for fractions II and III, respectively, of KCl.     

Electron-gas interaction potentials for collisions of CaCl(X 2Σ+) and KCl(X 1Σ+) with Ar

Interaction potentials for CaCl(X ²Σ⁺)-Ar and KCl(X ¹Σ⁺)-Ar have been determined. They include a Gordon-Kim electron-gas repulsive part smoothly joined to the long-range van der Waals potential. The van der waals potential for KClAr was taken from Meyer and Toennies. For CaClAr, the necessary molecular parameter were estimated from the Rittner model, which predicts both the dipole and quadrupole moments fairly accurately. The CaClAr interaction potential is quite different from that of KClAr. Due to the outer 4s electron on the Ca⁺ ion. the CaClAr potential exhibits a deep minimum in the odd-order Legendre terms which is expected to have a large effect on the cross sections for collisional rotational excitation. The KClAr potential determined here also shows significant differences in the repulsive and well regions from that predicted by Meyer and Toennies using a site-site model for the repulsive contribution.     

Enthalpic characteristics of solution of amino acids and aliphatic dipeptides in aqueous solutions of KCl

The integral enthalpies of dissolution Δ_sol H ^m of L-α-serine and L-α-asparagine in mixtures of water with KCl were measured in electrolyte concentrations of up to 4 mol/kg at 298.15 K. The standard enthalpies of dissolution (Δ_sol H ^o) and transfer (Δ_tr H ^o) of amino acids from water to aqueous solutions of KCl were calculated. The enthalpic pair interaction coefficients h _xy of biomolecules with KCl were estimated within the McMillan-Mayer theory. The changing nature of the interaction between the components of the solution (depending on the structure of the dissolved biosubstance side substituents) is shown on the basis of data we obtained earlier for amino acids and dipeptides series. Estimates of the contributions from the electrostatic and other interactions of dipolar ions of amino acids and dipeptides with ions of electrolyte KCl in the enthalpic pair interaction coefficients h _xy are obtained using the Kirkwood approach.     

On the possibility of a carbenium ion structure for the complexes [Os3H3(CO)9CCR2]+. Further application of the 187Os nucleus

In the ¹H NMR spectrum of the complex [Os₃H₃(CO)₉C$\text{C(CH}{}_2\text{C}$H₂]⁺ at 30°C, under conditions of rapid exchange, the single hydride resonance has two sets of satellites of equal intensity (separated by 32.0 and 28.8 Hz) caused by ¹⁸⁷Os¹H spin—spin coupling. The spectral data rule out the upright carbenium ion structure for the complex, and are consistent with the fluxional process involving hydrocarbon ligand rotation about the C$\text{C(CH}{}_2\text{)}{}_2\text{C}$H₂ axis in a tilted structure, with concomitant rotation of the Os₃H₃(CO)₉ moiety.     

Strength of the PtCS2 bond in Pt(PPh3)2(CS2)

The enthalpy of the reaction: Pt(PPh₃)₂(CH₂CH₂)(cryst.) + CS₂(g) → Pt(PPh₃)₂(CS₂)(cryst.) + CH₂CH₂(g) has been determined as ΔH = ? 4.40 ± 2.2 kJ mol^?1 from solution calorimetry, and the bond dissociation energy D(PtCS₂) shown to be slightly greater than D(PtC₂H₄).     

Displacement of dienes from planar complexes Reaction of (1,2-bisdiphenylphosphinoethane)(3a,4,7,7a-tetrahydro-exo-6-methoxy-endo-4,7-methanoindene-endo-5τ,2π)-palladium(II) and -platinum(II) cations with acids

A kinetic study of the reaction of [M(C₁₀H₁₂ · OCH₃)(P)]⁺ complexes (M = Pd, Pt; PP = 1,2-bisdiphenylphosphinoethane; C₁₀H₁₂ = endo-dicyclopentadiene) with hydrogen halides, HX (X = Cl, Br) in aqueous methanol at 35° C is described. The proposed mechanism involves slow formation of the solvato species [M(C₁₀H₁₂)(solv.)(P)]²⁺ followed by fast reaction with X^- to give M(PP)X₂.     

1,1-Dimethyl-1-silaethylene : Heat of formation,ionization potential and the energy of the siliconcarbon π-bond

The thermodynamic cycle consisting of thermal decomposition and dissociative ionization processes for 1,1-dimethyl-1-silacyclobutane is calculated. The heat of formation and the ionization potential (IP) for 1,1-dimethyl-1-sila-ethylene (DMSE) have been obtained: ΔH^o_f(DMSE) = 15.5 ± 5 kcal/mol; IP(DMSE) = 7.5 ± 0.3 eV. The siliconcarbon π-bond energy in DMSE is estimated: D_π(SiC)  28 ± 8 kcal/mol.     

Electrokinetic studies on testosterone/aqueous electrolyte interface : Part 1. Electro-osmosis,electrophoresis, streaming potential and streaming current

The electrical properties of testosterone interfaces were investigated. For this purpose, measurements of electro-osmosis, hydrodynamic permeation, streaming potential and streaming currents of metabolically important solutions of the electrolytes NaCl, KCl and MgCl₂ (in the concentration range 10^?4?10^?3 mol/l) across a testosterone plug were carried out. Electrophoretic mobility of testosterone particles suspended in these electrolyte solutions was also studied. The data were analysed from the viewpoint of nonequilibrium thermodynamics. Phenomenological coefficients were evaluated from the linear transport equations and Saxen's relationship was verified. Dependence of phenomenological coefficients on electrolyte concentration was examined. Electro-osmotic and electrophoretic transport coefficients were found to vary linearly with concentration, whereas hydrodynamic permeation and membrane conductance coefficients show non-linear variation. The results are explained on the basis of structural modifications occurring during the passage of the permeating species through the membrane. The nature of the electrical double layer formed at the testosterone/solution interface was ascertained on the basis of the direction of electro-osmotic permeation and electrophoretic migration of testosterone particles.Zeta potentials were estimated in order to obtain a plausible picture of the electrical double layer at the testosterone/solution interfaces. Dependence of zeta potentials on concentration was examined and membrane parameters calculated. The double layer thickness was estimated, which reveals that the diffuse double layer is more compact in the case of MgCl₂ than in that of KCl.