Thermodynamic stabilities of NiTeO3 and Ni3TeO6 by solid oxide electrolyte e.m.f. method

The e.m.f. of the galvanic cells Pt,C,Te(l),NiTeO₃,NiO/15 YSZ/O₂ (P_o2 = 0.21 atm),Pt and Pt,C,NiTeO₃,Ni₃TeO₆,NiO/15 YSZ/O₂ (P_o2 = 0.21 atm),Pt (where 15 YSZ=15 mass% yttria-stabilized zirconia) was measured over the ranges 833–1104 K and 624–964 K respectively, and could be represented by the least-squares expressions E₍₁₎±1.48 (mV) = 888.72 − 0.504277 (K) and E_(II) ±4.21 (mV) = 895.26 − 0.81543T (K).

After correcting for the standard state of oxygen in the air reference electrode, and by combining with the standard Gibbs energies of formation of NiO and TeO₂ from the literature, the following expressions could be derived for the ΔG^°_f of NiTeO₃ and Ni₃TeO₆: ΔG_f^°(NiTeO₃) ± 2.03 (kJ mol⁻¹) = −577.30 + 0.26692T (K) and ΔG^°_f(Ni₃TeO₆)±2.54 (kJ mol⁻¹) = −1218.66 + 0.58837T (K).     

Saturation molalities and standard molar enthalpies of solution of cytidine(cr), hypoxanthine(cr), thymidine(cr), thymine(cr), uridine(cr), and xanthine(cr) in H2O(l)

Saturation molalities m(sat) in H₂O(l) have been measured for the substances cytidine(cr), hypoxanthine(cr), thymidine(cr), thymine(cr), uridine(cr), and xanthine(cr) by using h.p.l.c. The states of hydration were established by performing Karl-Fischer analyses on samples of these substances, which had been allowed to equilibrate with their respective aqueous saturated solutions for several days at T≈298 K and then dried with air at T≈296 K for ≈24 h. The crystalline forms of the substances were identified by comparison of the results of X-ray diffraction measurements with results from the literature. Also, molar enthalpies of solution Δ_solH_m(cal) for these substances were measured by using an isoperibol solution calorimeter. A self-association (stacking) model was used to estimate values of the activity coefficients γ and relative apparent molar enthalpies L_φ for these substances. These γ and L_φ values were used to adjust the measured values of m(sat) and Δ_solH_m(cal) to the standard state and thus obtain values of the standard molar Gibbs free energy Δ_solG^∘_m and enthalpy changes Δ_solH_m^∘ for the dissolution reactions of these substances. The values of the pKs and of the standard molar enthalpies of the ionization reactions were also used to account for speciation of the substances in the calculations of Δ_solG_m^∘ and Δ_solH_m^∘. Values of standard molar enthalpies of formation Δ_fH_m^∘, standard molar Gibbs free energies of formation Δ_fG_m^∘, and standard partial molar entropies S_2,m^∘ for the aqueous species of hypoxanthine and xanthine were calculated. A detailed summary and comparison of thermodynamic results from the literature for these substances is presented.     

高效液相色谱-电感耦合等离子体质谱法测定土壤和沉积物中Cr(Ⅲ)与Cr(Ⅵ)EI北大核心CSCD

Cr(III) and Cr(VI) were separated by high performance liquid chromatography by using EDTA-Naj as mobile phase. Oxygen was added to reduce the interference of40Ar12C on+52Cr in mass spectrometry. The results showed that the linear relationships of Cr(HI) and Cr(VI) were good in the concentration range of 0.5-100 μXg/L, and the correlation coefficients were 0.9997 and 0.9998, respectively. The method detection limits of Cr(TH) and Cr(VI) both were 0.1 μxg/L. The method was applied to determine standard substances of NSI Lab Solutions with three kinds of chromium speciation, and the results were agreement with the certified values. The recoveries were 91.9%-116.7% at three spiked concentrations. The method is suitable for the determination of water-soluble chromium in soil and sediment samples. © 2023, Youke Publishing Co.,Ltd. All rights reserved.     

The standard molar Gibbs free energy of formation of NiO from high-temperature e.m.f. measurements

The standard molar Gibbs free energy of formation of NiO was determined in the temperature range 760 to 1275 K from measurements on reversible galvanic cells of the form: $\text{Pt}\text{Ni}\text{+}\text{NiO}\text{ZrO}{}_2\text{+}\text{CaO}\text{O}{}_2\text{(air)/Pt}$. The results can be represented by the equation: Δ_fG_m^o(NiO) = {?232450+83.435(T/K)} J·mol^?1, in excellent agreement with those previously reported.     

Thermodynamic stability and reactivity of silylated bis(oxy)iminium ions

Silylation of various nitronates with trialkylsilyl triflates was investigated by applying NMR techniques. In several cases, a flexible nitronate-bis(oxy)iminium ion (as an ion pair with triflate as counterion) equlibrium was found, and its thermodynamic parameters were determined. Elevation of temperature or dilution shifts this equilibrium toward the reactants. Activation parameters for the C,C-coupling reaction of silylated bis(oxy)iminium ions with a series of reference nucleophiles were determined. Estimated electrophilicity of bis(oxy)iminium ions allows one to count on C,C-coupling when partner nucleophilicity is N > 4.     

Thermodynamic stability and acidic properties of platinum(II) and palladium(II) bromide complexes

The instability constants of the platinum(II) and palladium(II) bromide complexes have been determined by potentiometry. The thermodynamic stability has been found to depend on the geometric structure of the complex and the nature of the central atom. The acid dissociation constants of the aqua complexes have been determined from pH measurements of the equilibrated solutions.     

RNA表观遗传修饰——N~6-甲基腺嘌呤与植物的生长发育

RNA表观遗传修饰N~6-甲基腺嘌呤(m~6A)是真核生物信使RNA(mRNA)上存在的最为广泛的中间化学修饰。它在哺乳动物中存在较为广泛,证实m~6A为mRNA上的动态可逆化修饰,它由甲基转移酶复合物(编码器)催化形成,同时可以被去甲基酶(消码器)氧化去甲基;m~6A可以被结合蛋白(读码器)识别,进而调控mRNA的剪接、稳定性、翻译、出核等。相较之下,m~6A在植物中的研究较少。本文将简要回顾目前m~6A的研究进展,重点综述m~6A在植物中的研究结果,展望m~6A在植物生长发育和应对外界刺激时的潜在重要功能。     

Determination of the standard Gibbs free energies of formation of the silicates of cobalt,magnesium, and strontium by e.m.f. measurements

Standard Gibbs free energies of formation of the silicates in the quasi-binaries: CoO and SiO₂, MgO and SiO₂, and SrO and SiO₂ were determined with the help of solid-state galvanic cells in the temperature ranges 1273 to 1673 K, 1373 to 1573 K, and 1323 to 1473 K, respectively. Stabilized ZrO₂ was used as an electrolyte for the CoO and SiO₂ system. For the MgO and SiO₂ system MgF₂, and for the SrO and SiO₂ system SrF₂, was used as an electrolyte embedded in a silicate-matrix phase.     

Standard Gibbs free energy of formation of SnO2 from high-temperature e.m.f. measurements

The thermodynamic equilibrium Sn(l) + O₂(g) = SnO₂(s) has been studied between 773 and 1380 K by e.m.f. measurements on cells involving a solid electrolyte, of the type:

$\text{Pt∥Ni(s), NiO(s)∥ZrO}{}_2\text{+ Y}{}_2\text{O}{}_3\text{∥Sn(1), SnO}{}_2\text{(s)∥Pt}$

     

Thermodynamic Properties of Nanosized Cobaltite (Nickelite) Cuprate Manganites LaMgCoCuMnO6 and LaMgNiCuMnO6

Russian Journal of Physical Chemistry A - The temperature dependences of the specific heat capacities of nanosized samples of lanthanum magnesium cobaltite cuprate manganite LaMgCoCuMnO6 and...     

Gas-phase stability of cluster ions SF m + (SF6) n with m = 0–5 and n = 1–3

The gas-phase stabilities of cluster ions SF⁺_m (SF₆)_n with m = 0−5 were determined by using a high pressure mass spectrometer. The bond energies of SF⁺_m (SF₆)₁ were found to be less than 10 kcal/mol and to decrease with m = 0 → 5. There appear to be rather large gaps in the bond energies between n = 1 and 2 for the clusters SF⁺_m (SF₆)_n with m = 0−4. The structures of SF⁺₅, SF⁺ (SF₆)₁, SF⁺₃ (SF₆)₁, and SF⁺₅ (SF₆)₁ were investigated by ab initio molecular orbital calculations. For SF⁺₅, the D_3h geometry is found to be most stable andC_4v is a transition state of the Berry pseudorotation. For the ion-molecule complexes, the “on-top hat” models were found to be the most stable structures.     

Thermodynamic stability constants of beryllium(II) and p-substituted N-phenyl benzohydroxamic acid complexes

The thermodynamic stability constants of beryllium(II) complexes of p-substituted N-phenylbenzohydroxamic acids have been determined in 50% v v aqueous dioxan at 35 degrees. The effect of methoxy, methyl, chloro, bromo, and nitro groups as substituents is discussed. There is a linear relationship between log K(1) and pK(a) and the Hammett equation is applicable. The beryllium complexes have been compared with those of Cu, Zn, Ni and Mn.     

First-principles study of electronic and magnetic properties of Co(n)Mn(m) and Co(n)V(m) (m + n < or = 6) clusters

The electronic and magnetic properties of small Co(n)Mn(m) and Co(n)V(m) (m + n < or = 6) clusters are systematically studied using density functional theory. The results show that Co and V atoms prefer to aggregate in Co-Mn and Co-V clusters, respectively. Significant magnetic moment enhancement in Co-Mn clusters with Mn doping and reduction in Co-V clusters with V doping are found, consistent with experiment results for larger clusters [Phys. Rev. Lett. 2007, 98, 113401]. The results are discussed by analyzing the magnetic coupling type and local magnetic moment on each atoms. Density of states and vertical ionization potentials are calculated and show cluster size dependent behavior.     

Lifetime of the He2(e), He2(d) and He2(f) states

Starting from the He₂(a) state absorption and induced fluorescence experiments were performed using a narrow band dye laser. The saturation intensity for the He₂(e)←He₂(a) transition yields a radiative lifetime of τ=(67±10) ns. Time resolved measurements of the laser induced fluorescence yield the radiative lifetimes for the states He₂(e): (57±10) ns, He₂(d): (25±5) ns and He₂(f): (19±5) ns. From the time integrated fluorescence data the collisional quenching rates between the above states were determined.     

Thermodynamic stability of Ni(II) and Cu(II) chelates with biladiene-a,c in DMF

The equilibria of the reactions of complex formation between alkyl-substituted biladiene-a,c and Ni(II) and Cu(II) acetates in DMF were studied by the electronic spectroscopy. Porphyrin-like complexes (1:1) were shown to form in the systems under study. Concentration constants of complex formation were calculated and extrapolated to infinite dilution in order to obtain standard thermodynamic quantities. The role of the nature of a metal cation on thermodynamic parameters of complex formation processes was discussed.     

Aminotroponiminatogermaacid halides with a ge(e)x moiety (e = s, se; x = f, cl)

Fluorination of aminotroponiminate (ATI) ligand-stabilized germylene monochloride [(t-Bu)(2)ATI]GeCl (1) with CsF gave the aminotroponiminatogermylene monofluoride [(t-Bu)(2)ATI]GeF (2). Oxidative addition reaction of compound 2 with elemental sulfur and selenium led to isolation of the corresponding germathioacid fluoride [(t-Bu)(2)ATI]Ge(S)F (3) and germaselenoacid fluoride [(t-Bu)(2)ATI]Ge(Se)F (4), respectively. Similarly, reaction of aminotroponiminatogermylene monochloride [(i-Bu)(2)ATI]GeCl (9) with elemental sulfur and selenium gave the aminotroponiminatogermathioacid chloride [(i-Bu)(2)ATI]Ge(S)Cl (11) and aminotroponiminatogermaselenoacid chloride [(i-Bu)(2)ATI]Ge(Se)Cl (12), respectively. Compound 9 has been prepared through a multistep synthetic route starting from 2-(tosyloxy)tropone 5. All compounds (2-4 and 6-12) were characterized through the multinuclear NMR spectroscopy, and single-crystal X-ray diffraction studies were performed on compounds 2, 4, and 8-12. The germaselenoacid halide complexes 4 and 12 showed doublet (-142.37 ppm) and singlet (-213.13 ppm) resonances in their (77)Se NMR spectra, respectively. Germylene monohalide complexes 2 and 9 have a germanium center in distorted trigonal pyramidal geometry, whereas a distorted tetrahedral geometry is seen around the germanium center in germaacid halide complexes 4, 11, and 12. The length of the Ge═E bond in germathioacid chloride (11) and germaselenoacid halide (4 and 12) complexes is 2.065(1) and 2.194(av) ?, respectively. Theoretical studies (based on the DFT methods) on complexes 4, 11, and 12 reveal the nature of the Ge═E multiple bond in these germaacid halide complexes with computed Wiberg bond indices (WBI) being 1.480, 1.508, and 1.541, respectively.