Thermodynamic characteristics of ion-exchange sorption of Co2+ cations on Na-vermiculite

The exchange of Na⁺ ions of vermiculite for Co²⁺ cations is measured by sorption-analytical and microcalorimetric methods. The previously revealed growth of the equilibrium constant with a rise in the degree of filling θ of vermiculite exchange sites with Co²⁺ cations is confirmed. This result is explained by the segregation of Co²⁺ and Na⁺ cations being exchanged in separate interlayer regions of vermiculite. The negative heats of exchange of Na⁺ cations for Co²⁺ cations are associated with the energy consumption for the rearrangement of the segregated interlayer regions in vermiculite. The positive entropy changes resulting from the exchange indicate the formation of a more disordered Co-Na-layered “cake” in comparison with the initial Na-form vermiculite. A decrease in the integral molal free-energy change ΔG _m of the mixed form of the mineral is determined by the entropy factor. It is shown that, as θ increases, the ΔG _m(θ) dependence passes from a positive to a negative range of values. This pattern of the curve may be interpreted as a gradual phase transition from the Na-form to the mixed Co-Na-segregated form. The first derivatives of the enthalpy and entropy changes with respect to the degree of filling θ exhibit distinct maxima at θ ～ 0.20 as a result of the transition from the ideal mixing of Co²⁺ and Na⁺ cations being exchanged to their segregation.     

Interaction between ozone and the chloride ion in sulfuric acid solutions up to 6-M concentration

The effect of sulfuric acid concentration on Cl₂ evolution in the reaction between O₃ and Cl^? has been investigated. The catalytic effects of metal ions in this reaction have been studied as a function of solution acidity. The chlorine evolution rate increases markedly with increasing acid concentration. At acid concentrations below 4 mol/l, the most effective catalyst is Co²⁺. The catalytic activities of Fe³⁺ and Cu²⁺ peak at $C_{H_2 SO_4 } $ = 4.8 mol/l. In passing to highly acidic solutions ( $C_{H_2 SO_4 } $ > 5 mol/l), the catalytic activity of the metal ions decreases, but the chlorine evolution rate remains high owing to the high acidity. Kinetics of VO²⁺ oxidation with ozone in acid media have been studied, and the ozone solubility in aqueous sulfuric acid has been measured.     

Influence of metal ions on the activity and stability of the glucose isomerase from Streptomyces atratus

The influence of a number of bivalent metals on the activity ofStreptomyces atratus glucose isomerase has been studied. Mg²⁺ ions are activators and Co²⁺ ions are stabilizers of the glucose isomerase activity. The effective kinetic parameters for the action of the enzyme have been determined.     

Liquid secondary ion mass spectrometry of several β-diketonates of cobalt(III) and chromium(III)

The positive, liquid secondary ion (LSI) mass spectra of six cobalt(III) and three chromium(III) (β-diketonates ligand = L^?) were examined in a 3-nitrobenzyl alcohol matrix. The complexes of both metals yield clean, matrix-free mass spectra, but there are important differences between them. The cobalt compounds show prominent peaks assignable to the molecular ion, CoL ₃ ⁺ , of the monomeric chelates, together with abundant dimeric ions, such as Co₂L ₄ ⁺ and Co₂L ₃ ⁺ ; in contrast, chromium complexes show protonated monomers, CrL₃H⁺, in addition to ionized monomers, CrL ₃ ⁺ , and only minor formation of dimeric ions. The collisionally-activated dissociation (CAD) mass spectrum of Co₂L ₄ ⁺ shows fragmentation to CoL ₂ ⁺ and Co₂L ₃ ⁺ . That of Co₂L ₃ ⁺ shows fragmentation only to dimeric ions, including Co₂L ₂ ⁺ and, for thienyl or phenyl substituted ligands, to Co₂L₂Ar⁺ or Co₂LAr⁺ (Ar = thienyl or phenyl). Neither Co₂L ₄ ⁺ nor Co₂L ₃ ⁺ dissociates to the CoL ₃ ⁺ ion. The LSI mass spectrum of a mixture of two different cobalt chelates shows dimeric ions containing both types of ligand, which can be explained by ion-molecule reactions in the selvedge region. The differing behaviors of the cobalt and chromium complexes is attributed to the relatively greater stability of the +2 oxidation state for cobalt than for chromium.     

The state of Cu2+ ions in concentrated aqueous ammonia solutions of copper nitrate

Stabilization of Cu²⁺ ions in concentrated aqueous ammonia solutions of copper nitrate in a wide range of ammonium ion concentrations has been studied by EPR and electronic absorption spectroscopy. Three types of Cu²⁺ associates with different types of orbital ordering have been identified. The ammonium ion concentration in a solution has a decisive effect on the type of orbital ordering of Cu²⁺ ions in associates. In all cases, Cu²⁺ ordering in associates is caused by the existence of bridging OH groups in the axial and equatorial positions of [Cu(NH₃) _n (H₂O)_{6 ? n} ]²⁺ complexes (n < 6). At a high concentration of ammonium ions, weakly bound associates of tetramminecopper with the $d_{x^2 - y^2 }$ ground state are formed. In solutions with low ammonium concentrations, bulky associates with the $d_{y^2 }$ and $d_{x^2 - z^2 }$ ground states and associates of Cu²⁺ ions with the $d_{x^2 - y^2 }$ ground state with hydroxyl groups in the equatorial plane and axial water molecules are formed.     

Effects of Ions on the OH Stretching Band of Water as Revealed by ATR-IR Spectroscopy

The effects of various cations (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Mn²⁺, Co²⁺, and Ni²⁺) and anions (Cl^?, Br^?, I^?, \( {\text{NO}}_{3}^{ - } \) , \( {\text{ClO}}_{4}^{ - } \) , \( {\text{HCO}}_{3}^{ - } \) , and \( {\text{CO}}_{3}^{2 - } \) ) on the molar absorptivity of water in the OH stretching band region (2,600–3,800 cm^?1) were ascertained from attenuated total reflection infrared spectra of aqueous electrolyte solutions (22 in all). The OH stretching band mainly changes linearly with ion concentrations up to 2 mol·L^?1, but several specific combinations of cations and anions (Cs₂SO₄, Li₂SO₄, and MgSO₄) present different trends. That deviation is attributed to ion pair formation and cooperativity in ion hydration, which indicates that the extent of the ion–water interaction reflected by the OH stretching band of water is beyond the first solvation shell of water molecules directly surrounding the ion. The obtained dataset was then correlated with several quantitative parameters representing structural and dynamic properties of water molecules around ions: ΔG _HB, the structural entropy (S _str), the viscosity B-coefficient (B _η ), and the ionic B-coefficient of NMR relaxation (B _NMR). Results show that modification of the OH stretching band of water caused by ions has quasi-linear relations with all of these parameters. Vibrational spectroscopy can be a useful means for evaluating ion–water interaction in aqueous solutions.     

Reactivity of positively charged cobalt cluster ions with CH4, N2, H2, C2H4, and C2H2

Reactivity of positively charged cobalt cluster ions (Co _n ⁺ ,n=2?22), produce by laser vaporization, with various gas samples (CH₄, N₂, H₂, C₂H₄, and C₂H₂) were systematically investigated by using a fast-flow reactor. The reactivity of Co _n ⁺ with the various gas samples is qualitatively consistent with the adsorption rate of the gas to cobalt metal surfaces. Co _n ⁺ highly reacts with C₂H₂ as characterized by the adsorption rate to metal surfaces, and it indicates no size dependence. In contrast, the reactions of Co _n ⁺ with the other gas samples indicate a similar cluster size dependence; atn=4, 5, and 10?15, Co _n ⁺ highly reacts. The difference can be explained by the amount of the activation energy for chemisorption reaction. Compared with neutral cobalt clusters, the size dependence is almost similar except for Co ₄ ⁺ and Co ₅ ⁺ . The reactivity enhancement of Co ₄ ⁺ and Co ₅ ⁺ indicates that the cobalt cluster ions are presumed to have an active site for chemisorption atn=4 and 5, induced by the influence of positive charge.     

Ordering of Cu(II) ions in supported copper-titanium oxide catalysts

Two types of ESR spectrum (A and B) of exchange-coupled Cu²⁺ ions have been found for Cu-Ti-O catalysts at 77 K and 300 K. In associates A and B, the Cu²⁺ ions form a system with orbital ordering. The difference between the spectra is due to the difference between the ground states of adjacent Cu²⁺ ions in the associates: the ground states are $d_{x^2 } $ and $d_{y^2 } $ for A type associates and $d_{x^2 - y^2 } $ and $d_{z^2 - x^2 } $ for B type associates. The copper associates lie on the surface of the TiO₂ (anatase) support microparticles.     

Analysis of optical absorption spectra of transition metal cluster ions by the spin-polarized DV-Xα method

Optical absorption spectra of cobalt cluster ions, Co _n ⁺ , and vanadium cluster ions, V _n ⁺ , were analyzed by a theoretical calculation based on the spin-polarized DV-Xα method, and their electronic and geometric structures were obtained. Relative absorption cross section associated with each electronic transition was calculated; the calculation enables a qualitative comparison of calculated spectrum with a measured one not only in its transition energy but also in its intensity profile. This analysis shows that Co ₄ ⁺ , Co ₃ ⁺ , and V ₄ ⁺ have, respectively, a tetrahedral structure with a bond distance of 2.00Å, an equilateral triangle with a bond distance of 2.30Å, and a distorted tetrahedral structure with five bonds having a distance of 2.34 Å and one of 2.89Å. The differences in the population between majority and minority spins (spin-difference) evaluated from the electronic structure thus obtained were 2.0, 1.7, and zero per atom in Co ₃ ⁺ , Co ₄ ⁺ , and V ₄ ⁺ , respectively. These spin differences indicate a ferromagnetic and an antiferromagnetic spin-coupling in the cobalt and vanadium cluster ions, respectively.     

Nickel and Cobalt Complexes of Non-protein L-Norvaline and Antioxidant Ferulic Acid: Potentiometric and Spectrophotometric Studies

Binary and mixed-ligand complexes of Ni²⁺ and Co²⁺ involving L-norvaline (Nva) and ferulic acid (FA) have been investigated in aqueous solutions by pH potentiometry and UV?Cvisible spectrophotometric techniques, at 298.15 K and fixed ionic strength (0.15?mol?dm^?3, NaNO₃). The overall stability constants of the Ni²⁺ and Co²⁺ complexes with the ligands studied were obtained by the HYPERQUAD2008 program from the pH-potentiometric data. As a result of the numerical treatment, a model composed of seven species NiNva⁺, NiNva₂, NiNvaH_?1, $\mathrm{NiNva}_{ - 2}^{ -}$ , NiFA, $\mathrm{NiFAH}_{ - 1}^{ -}$ and NiNvaFA^? was obtained for the Ni²⁺+Nva+FA system, whereas for the Co²⁺+Nva+FA system the complexes CoNva⁺, CoNva₂, CoNvaH_?1, $\mathrm{CoNvaH}_{ - 2}^{ -}$ , CoFA, $\mathrm{CoFAH}_{ - 1}^{ -}$ , and CoNvaFA^? were obtained. The complex species distributions in certain pH ranges were calculated by the HySS2009 simulation program. Spectroscopic UV?Cvisible measurements were carried out to give qualitative information about the complexes formed in these solutions.     

Fragmentation of doubly charged ammonia cations NH 3 ++ studied by the photoion-photoion coincidence (PIPICO) method

Doubly charged NH ₃ ⁺⁺ cations were produced by double photoionization of neutral ammonia molecules by using the synchrotron radiation from ACO as a photon source of variable energy in the 35–49 eV energy range. The fragmentation of NH ₃ ⁺⁺ was studied by the photoion-photoion coincidence (PIPICO) method. NH ₃ ⁺⁺ cations were produced in the \(\tilde X^1 \) A ₁ and \(\tilde B^1 \) electronic states of which the onset energies were measured at, respectively, 35.4±0.5 eV and 44.5±0.5 eV. It was shown that the NH ₃ ⁺⁺ ions, initially produced in their \(\tilde X^1 \) A ₁ state, rapidly dissociate (in less than 50 ns), into NH ₂ ⁺ + H⁺. Furthermore, the comparison with results obtained by other methods indicates that NH ₃ ⁺⁺ ions can either be long-lived (τ>10 µs) or slowly dissociating (1 µs<τ<10 µs) or rapidly dissociating (τ<50 ns), depending on their geometry and/or internal energy in their \(\tilde X^1 \) E A ₁ electronic state.     

Synergistic extraction of some divalent metal cations into nitrobenzene by using strontium dicarbollylcobaltate and electroneutral macrocyclic lactam receptor

From extraction experiments and $ \gamma $ -activity measurements, the exchange extraction constants corresponding to the general equilibrium M²⁺(aq) + 1·Sr²⁺(nb) $ \Leftrightarrow $ 1·M²⁺(nb) + Sr²⁺(aq) taking place in the two-phase water–nitrobenzene system (M²⁺ = Mg²⁺, Ca²⁺, Ba²⁺, Pb²⁺, Cu²⁺, Zn²⁺, Cd²⁺, $ {\hbox{UO}}_{2}^{2 + } $ , Mn²⁺, Co²⁺, Ni²⁺; 1 = macrocyclic lactam receptor–see Scheme 1; aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Moreover, the stability constants of the 1·M²⁺ complexes in nitrobenzene saturated with water were calculated; they were found to increase in the following cation order: Mg²⁺ < Co²⁺ < Cu²⁺, Mn²⁺, Ni²⁺ < Cd²⁺ < Ca²⁺ < Ba²⁺, Zn²⁺ < Pb²⁺ <  $ {\hbox{UO}}_{2}^{2 + } $ .

The thermodynamic parameters of oxygen nonstoichiometry defects in lanthanum cobaltite doped with acceptor impurities (Sr and Ni)

The oxygen nonstoichiometry δ of lanthanum cobaltite doped with acceptor impurities (Sr and Ni), La_{1 ? x} Sr_xCo_0.9Ni_0.1O_{3 ? δ} (x = 0.1, 0.3), was studied by high-temperature thermogravimetry over the temperature and pressure ranges 723 K ≤ T ≤ 1373 K and 10^?3 atm ≤ $p_{O_2 } $ ≤ 1 atm. The partial replacement of cobalt with nickel and lanthanum with strontium increased the oxygen nonstoichiometry δ. The partial molar enthalpies $\Delta \bar H^\circ _O $ and entropies $\Delta \bar S^\circ _O $ of solution of oxygen in the solid phase were calculated. Models of point defect formation were suggested and analyzed. The equilibrium constants of formation and concentrations of predominant point defects, ionized oxygen vacancies V _o ^.. , holes Me _Co ^. (Co _Co ^. and Ni _Co ^. ), and electrons Me _Co ^′ (Co _Co ^′ and Ni _Co ^′ ) localized on 3d transition metals, were determined by nonlinear regression from the experimental and theoretical logp $p_{O_2 } $ ?δ dependences.     

A thermodynamic study of complexation of 18-crown-6 with Zn2+, Tl+, Hg2+ and {\text{UO}}^{{{\text{2 + }}}}_{{\text{2}}} cations in acetonitrile-dimethylformamide binary media and study the effect of anion on the stability constant of (18C6-Na+) complex in methanol solutions

The equilibrium constants and thermodynamic parameters for complex formation of 18-crown-6(18C6) with Zn²⁺, Tl⁺, Hg²⁺ and $ {\text{UO}}^{{{\text{2 + }}}}_{{\text{2}}} $ cations have been determined by conductivity measurements in acetonitrile(AN)-dimethylformamide(DMF) binary solutions. 18-crown-6 forms 1:1 complexes [M:L] with Zn²⁺, Hg²⁺ and $ {\text{UO}}^{{{\text{2 + }}}}_{{\text{2}}} $ cations, but in the case of Tl⁺ cation, a 1:2 [M:L₂] complex is formed in most binary solutions. The thermodynamic parameters ( $ \Delta {\text{H}}^{ \circ }_{{\text{c}}} $ and $ \Delta {\text{S}}^{ \circ }_{{\text{c}}} $ ) which were obtained from temperature dependence of the equilibrium constants show that in most cases, the complexes are enthalpy destabilized but entropy stabilized and a non-monotonic behaviour is observed for variations of standard enthalpy and entropy changes versus the composition of AN/DMF binary mixed solvents. The obtained results show that the order of selectivity of 18C6 ligand for these cations changes with the composition of the mixed solvent. A non-linear relationship was observed between the stability constants (logK_f) of these complexes with the composition of AN/DMF binary solutions. The influence of the $ {\text{ClO}}^{ - }_{{\text{4}}} $ , $ {\text{NO}}^{ - }_{{\text{3}}} $ and $ {\text{Cl}}^{ - } $ anions on the stability constant of (18C6-Na⁺) complex in methanol (MeOH) solutions was also studied by potentiometry method. The results show that the stability of (18C6-Na⁺) complex in the presence of the anions increases in order: $ {\text{ClO}}^{ - }_{{\text{4}}} $  >  $ {\text{NO}}^{ - }_{{\text{3}}} $  >  $ {\text{Cl}}^{ - } $ .     

Exploiting thermodynamic data to optimize the enantioseparation of underivatized amino acids in ligand exchange capillary electrophoresis

Stereoselective amino acid analysis has increasingly moved into the scope of interest of the scientific community. In this work, we report a study on the chiral separation of underivatized d,l-His by ligand exchange capillary electrophoresis (LECE), utilizing accurate ex ante calculations. This has been obtained by the addition to the background electrolytes (BGE) of NaClO₄ which renders the separations “all in solution processes”, allowing to accurately calculate in advance the concentrations of the species present in solution and to optimize the system performances. To this aim, the formation of ternary complexes of Cu²⁺ ion and l-lysine (l-Lys) or l-ornithine (l-Orn) with l- and d-histidine (His), and histamine (Hm) have been studied by potentiometry and calorimetry at 25 °C and with 0.1 mol dm^?3 (KNO₃) in aqueous solution. The ternary species [Cu(L)(l-His)H]⁺ and [Cu(L)(d-His)H]⁺ (where L?=?l-Lys or l-Orn) show a slight but still detectable stereoselectivity, and the determination of ΔH° and ΔS° values allowed the understanding of the factors which determine this phenomenon. The stereoselectivity showed by the protonated ternary species has been exploited to chirally separate d,l-His in LECE, by using the binary complexes of copper(II) with l-Lys or l-Orn as background electrolytes added with the appropriate amounts of NaClO₄.

Two-Temperature Chemical-Nonequilibrium Modelling of a High-Velocity Argon Plasma Flow in a Low-Power Arcjet Thruster

A numerical simulation has been performed of a high-velocity argon plasma arc flow in a low power arcjet including a finite-rate chemical kinetic model. Electrons, ions, molecular ions ( $ {\text{Ar}}_{2}^{ + } $ ), neutral atoms including the ground and excited argon atoms (Ar^*) are treated as separate species in the plasma mixture. The chemical reactions considered are excitation, de-excitation, ionization and recombination processes, in which reactions involving excited argon atoms (Ar^*) and molecular ions ( $ {\text{Ar}}_{2}^{ + } $ ) are taken into account. The relative importance of different production and loss processes in determining the densities of excited argon atoms and ions is calculated inside the constrictor and expansion portion of the nozzle. The roles of the excited argon atoms and molecular ions are investigated. It is found that excited argon atoms play an important role in the ionization of argon atoms in the core of plasma arc, while the molecular ions have a significant effect on the recombination process at the arc fringes inside the constrictor and in the arc attachment zone of the anode.     

On the role of dissociative ionization in the formation of argon dimer ions

The formation of Ar ₂ ⁺ ions has been investigated by means of the threshold photoelectron photoion coincidence (TPEPICO) technique. Two pathways for the formation of Ar ₂ ⁺ ions are important. One is a direct path via excitation of Rydberg states of Ar₂ with consecutive autoionization. The other path is dissociative ionization of larger argon clusters, in this case argon trimers. These two pathways lead to Ar ₂ ⁺ ions with different internal energy. The pathways are easily distinguished in the TPEPICO-TOF spectra by the kinetic energy released (KER) in the dissociative ionization. The KER for the reaction Ar ₃ ⁺ → Ar ₂ ⁺ + Ar was measured as a function of the photon energy and compared to the KER expected from statistical theory. The agreement is satisfying and confirms that Ar ₃ ⁺ ions do indeed dissociate at the thermochemical threshold. At higher photon energy the excited²Π(3/2)g state of Ar ₃ ⁺ is also detected from a second component in the KER. By applying a kinetic energy discrimination it is possible to measure cluster ion spectra in the presence of larger clusters but essentially without interference from the latter.     

Heat capacity and density of solutions of calcium and cadmium nitrates in N-methylpyrrolidone at 298.15 K

The heat capacity and density of solutions of calcium and cadmium nitrates in N-methylpyrrolidone (MP) at 298.15 K are studied by calorimetry and densimetry. The obtained data are discussed in relation to certain features of solvation and complex formation in solutions of these salts. The standard partial molar heat capacities and volumes ( $\overline {C_{p^2 }^0 }$ and $\overline {V_2^0 }$ ) of the electrolytes in MP are calculated. The standard heat capacities $\overline {C_{p^i }^0 }$ and volumes $\overline {V_i^0 }$ of Ca²⁺ and Cd²⁺ ions in MP at 298.15 K were determined, along with the contribution from specific interactions to the values of $\overline {C_{p^i }^0 }$ and $\overline {V_i^0 }$ of Cd²⁺ ions in MP solution.     

Charge Transfer Dissociation (CTD) Mass Spectrometry of Peptide Cations Using Kiloelectronvolt Helium Cations

A kiloelectronvolt beam of helium ions is used to ionize and fragment precursor peptide ions starting in the 1+ charge state. The electron affinity of helium cations (24.6 eV) exceeds the ionization potential of protonated peptides and can therefore be used to abstract an electron from—or charge exchange with—the isolated precursor ions. Kiloelectronvolt energies are used, (1) to overcome the Coulombic repulsion barrier between the cationic reactants, (2) to overcome ion-defocussing effects in the ion trap, and (3) to provide additional activation energy. Charge transfer dissociation (CTD) of the [M+H]⁺ precursor of Substance P gives product ions such as [M+H]^2+? and a dominant series of a ions in both the 1+ and 2+ charge states. These observations, along with the less-abundant a + 1 ions, are consistent with ultraviolet photodissociation (UVPD) results of others and indicate that C–C_α cleavages are possible through charge exchange with helium ions. Although the efficiencies and timescale of CTD are not yet suitable for on-line chromatography, this new approach to ion activation provides an additional potential tool for the interrogation of gas phase ions. Graphical Abstract

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Solvent extraction of strontium and barium into nitrobenzene by using hydrogen dicarbollylcobaltate in the presence of dicyclohexano-24-crown-8

Extraction of microamounts of strontium and barium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H⁺B^?) in the presence of dicyclohexano-24-crown-8 (DCH24C8, L) has been investigated. The equilibrium data have been explained assuming that the complexes HL⁺, $ {\text{HL}}_{2}^{ + }, $ ML²⁺ and $ {\text{ML}}_{ 2}^{2 + } $ (M²⁺ = Sr²⁺, Ba²⁺) are extracted into the organic phase. The values of extraction and stability constants of the species in nitrobenzene saturated with water have been determined. It was found that in water–saturated nitrobenzene, the stability constants of the complexes BaL²⁺ and $ {\text{BaL}}_{ 2}{^{2 + }}, $ where L = DCH24C8, are somewhat higher than those of the corresponding species SrL²⁺ and $ {\text{SrL}}_{ 2}{^{2 + }} $ with the same ligand L.