Proton mobility in hydrates of inorganic acids and acid salts

Published data on the mechanisms of hydrogen ion transport in solids and aqueous solutions are described systematically, including defect formation, rotational mobility of proton-containing groups, proton hopping along a hydrogen bond, proton translational mobility, and proton conduction. Resorting to the authors" theoretical results and published data, the main criteria for the selection of systems possessing high proton mobility are formulated.     

Proton mobility in hydrated sulfonated polystyrene: NMR and impedance studies

Different ionomers were obtained by sulfonation of a commercial polystyrene (PS), using acetyl sulfate as reagent. The sulfonation was assessed by FTIR and XPS spectroscopies and the thermal and mechanical properties were deduced from DMA measurements. The acid form of the ionomers was characterized by means of ¹H and ¹³C MAS-NMR spectroscopies. Polymer hydration under controlled humidity atmosphere was analyzed by gravimetric, NMR and complex impedance techniques. In the hydrated state, two stages associated with formation of hydronium (H₃O⁺) species and proton hopping between adsorbed water molecules were deduced from NMR data. Both processes are responsible for important changes detected in mechanical properties and conductivity of sulfonated polymers during hydration processes.     

5-氯尿嘧啶质子转移异构化的密度泛函理论研究

采用密度泛函B3LYP/6-311+G**方法,对5-氯尿嘧啶分子内质子转移及水助催化质子转移引起的互变异构反应机理进行了计算研究,获得了互变异构过程的反应焓、活化能、活化吉布斯自由能和质子转移反应的速率常数等参数。计算结果表明,5-氯尿嘧啶无论是孤立分子还是一水合物,其双酮式CU1是最稳定异构体,由双酮式向烯醇式异构化找到3条通道(P1,P2,P3),各通道速控步骤的活化能分别为177.85、177.05和197.58kJ/mol。当水分子参与反应以双质子转移机理异构化时,活化能显著降低,各通道速控步骤的活化能依次降为66.24、69.36和77.85kJ/mol,有利于双酮式向烯醇式或酮醇式转变。计算结果还表明,氢键作用在增大5-氯尿嘧啶一水复合物稳定性、降低质子转移异构化反应活化能等方面起着重要作用。     

胞嘧啶一水复合物质子转移异构化反应机理的理论研究

采用密度泛函B3LYP方法,在6-311＋G＊＊基组水平上对胞嘧啶一水复合物质子转移引起的氨-酮式、氨-烯醇式与亚胺-酮式互变异构反应机理进行了计算研究,获得了互变异构过程的反应焓、活化能、活化吉布斯自由能和质子转移反应速率常数等参数。将Onsager反应场溶剂模型用于水相的计算,结果表明,胞嘧啶一水复合物无论在气相中...     

Thermal decomposition of lighter lanthanide selenate hydrates and their solid solutions

The thermal dehydration-decomposition of Ln₂(SeO₄)₃·nH₂O (wheren=12 forLn=Pr, Nd andn=8 forLn=Sm) and Pr_xLn_2−x(SeO₄)₃·nH₂O (wheren=12 forx=1.0 andLn=Nd;n=8 forx=0.2 and 1.0 in case ofLn=Sm) have been reported.

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Zusammenfassung Die thermische Dehydratation-Zersetzung von Ln₂(SeO₄)₃·nH₂O (mitn=12 fürLn=Pr, Nd undn=8 fürLn=Sm) und Pr_xLn_2−x(SeO₄)₃·nH₂O (mitn=12 fürx=1.0 undLn=Nd;n=8 fürx=0.2 und 1.0 in Falle vonLn=Sm) wurde beschrieben.

     

分子形貌所指示的羟基卡宾及其衍生物的质子转移反应

分子形貌(Molecular face, MF)定义分子的内禀电子转折边界面,同时在其上计算并描绘出前沿电子密度(MFED). MF不仅能显示分子的形状和大小,还能够指示分子的化学反应性.应用M06-2X/6-311++G(d,p)理论方法,对单线态和三线态羟基卡宾分子及其衍生物的质子化反应进行研究并计算了这些反应的活化能.结果表明,吸电性和供电性较强的取代基,均使单线态反应活化能增大,只有吸电性较强的─CN才能使三线态反应活化能增大.应用分子形貌理论研究了上述反应,不仅展示出分子的形貌变化、与反应位点的关联,以及有关物理量的变化倾向,而且还定量地显示出,单线态羟基卡宾及其衍生物分子边界面上前沿电子密度极大值与极小值的差值,与其质子转移反应的活化能之间存在线性相关.     

3-羟基对氧萘酮分子内激发态质子转移反应位能面和机理的研究

用MNDO和INDO-SCF-CI法研究了3-羟基对氧萘酮分子内激发态质子转移反应基态和激发态的位能面,求得相应能垒△E₁、△E₂和荧光移位,并对光化学反应机理进行了探讨.     

新型聚苯并咪唑树脂的微波合成及质子交换膜的性能

采用微波合成法, 调整己二酸和2,6-吡啶二甲酸2种二酸单体的配比, 使其与联苯四胺进行三元共聚, 制备出一系列新型含脂肪链结构的聚苯并咪唑(PBI)类质子交换膜, 并用红外光谱、 热重分析进行了表征, 对膜的吸水率、 溶胀率、 质子传导率、 机械强度及抗氧化性能等进行了测试. 当己二酸与2,6-吡啶二甲酸的摩尔比为3: 2时, 所制备的PBI-C₂膜掺杂磷酸后在160℃下的质子传导率可达30 mS/cm, 拉伸强度在常温下可达77.54 MPa, 断裂伸长率为39.25%, 最大储能模量为9.0623 MPa, 最大损耗模量为8.36 MPa, 玻璃化转变温度为360℃, 芬顿试验192 h后膜的降解率仅为0.21%, 表明PBI-C₂膜在高温质子交换膜燃料电池中具有较好的应用前景.     

Copolymerization of methacrylic acid alkali metal salts and polyether-containing monomers in solid polymer electrolytes

Copolymerization of methacrylic acid alkali metal salts (MAAM; M = Li, Na, K, Rb or Cs) and oligo(oxyethylene) methacrylate (MEO) was carried out in bulk or in poly(oligo(oxyethylene) methacrylate) (PMEO) at 60°C. The copolymers of MAAM and MEO which were obtained by bulk polymerization showed a cation conductivity of around 1 × 10^?7 S/cm at room temperature. On the other hand, the copolymers obtained by radical polymerization in PMEO, showed a higher cation conductivity (10^?6–10^?5 S/cm). Furthermore, higher cation conductivity was observed for the copolymer systems containing alkali metal cations with a larger ion radius. This tendency was explained by the strength of the bond between alkali metal cation and ether oxygens. The degree of dissociation had little effect on this difference in the conductivity. The effective dissociation of methacrylic salts was enhanced in the copolymer compared to the homopolymer because of the suppression of the adjacent dissociative carboxylic acid groups. Arrhenius plots for ionic conductivity show the migration of ions along with the segmental motion of the polymer matrix.     

Theoretical study of the N---H tautomerism in free base porphyrin

The N---H tautomerism of free base porphyrin is investigated at the semiempirical spin-unrestricted AM1 (UAM1) and ab initio RHF/3-21G levels. The UAM1 method provides delocalized geometries for all stationary structures without imposing any symmetry constraint. RHF/3-21G geometry optimizations have to be performed under symmetry restrictions to ensure that realistic delocalized structures are obtained. Both the semiempirical and the ab initio calculations predict that the interconversion between trans tautomers proceeds in an asynchronous two-step process via intermediate cis tautomers. The cis tautomers are characterized as minima in the potential energy surface and are 8–10 kcal mol⁻¹ higher in energy. The activation energy for the trans → cis interconversion is calculated to be approximately 23 kcal mol⁻¹ at the 3-21G level. The activation energy for the synchronous trans → trans interconversion is higher and has a value of 30.5 kcal mol⁻¹. The activation energies obtained at the semiempirical UAM1 level are twice as large as the ab initio values.     

Basicity and Proton Transfer in Proton Sponges and Related Compounds: An Ab Initio Study

Theoretical calculations at the B3LYP/6-31G* level were carried out on a family of 1,8-diR-naphthalenes, which include the proton sponge (1,8-bisdimethylaminonaphthalene, R = NMe₂) and other substituents (R = NH₂, R = OH, R = CH₃, R = F). Their basicity was compared with that of the corresponding monosubstituted benzenes. The dianion of 1,8-dihydroxynaphthalene should be a compound of extraordinary high basicity. The barriers to proton transfer, geometry, and density at the bond critical point of the hydrogen bond have been calculated and compared with experimental data when available.     

Evaluation of molten inorganic salt hydrates as reaction medium for the derivatization of cellulose

Molten inorganic salt hydrates are highly efficient solvents forcellulose. The carboxymethylation of the polymer dissolved in this new group ofcellulose solvents was investigated. The homogeneous carboxymethylation ofcellulose in molten LiClO₄3H₂O using sodiummonochloroacetate in the presence of NaOH is possible. The formation of CMC wasconfirmed by FT- Raman spectroscopy. Structure analysis by means of HPLC afterchain degradation showed the formation of CMC with a DS of 2 after a shortreaction time of 4 h. The derivatives exhibit a statisticaldistribution of substituents along the polymer chain if prepared in moltenLiClO₄3H₂O as solvent. A substituent distributioninthe order C-6 > C-2 C-3 for anhydroglucose units (AGU) was concludedfrom ¹H-NMR measurements. The synthesis of CMC in the swellingmediumLiClxH₂O (2 x 5) yields polymers with astatistical distribution of functional groups along the chain. The watercontentof the salt melts has a dramatic influence on the DS_CMC.     

氯离子对介孔氧化铝质子导电性的影响

掺杂氯盐使介孔氧化铝导电率提高近一个数量级,将掺杂的介孔氧化铝浸渍在水中24h后的导电率仍为纯介孔氧化铝的3～6倍。红外光谱结果显示,氯掺杂改变了表面酸碱活性中心,导致质子更易在介孔氧化铝中发生迁移,从而提高导电性。     

Proton and methanol transport behavior of SPEEK/TPA/MCM-41 composite membranes for fuel cell application

This paper reports proton and methanol transport behavior of composite membranes prepared for use in the direct methanol fuel cell (DMFC). The composite membranes were prepared by embedding various proportions (10–30 wt.%) of inorganic proton conducting material (tungstophosphoric acid (TPA)/MCM-41) into sulfonated poly(ether ether ketone) (SPEEK) polymer matrix. The results indicate that the proton conductivity of the membranes increases with increasing loading of solid proton conducting material. The highest conductivity value of 2.75 mS/cm was obtained for the SPEEK composite membrane containing 30 wt.% solid proton conducting material (50 wt.% TPA in MCM-41). The methanol permeability and crossover flux were also found to increase with increasing loading of the solid proton conducting material. Lowest permeability value of 5.7 × 10⁻⁹ cm² s⁻¹ was obtained for composite membrane with 10 wt.% of the solid proton conducting material (40 wt.% TPA in MCM-41). However, all the composite membranes showed higher selectivity (ratio between the proton conductivity and the methanol permeability) compared to the pure SPEEK membrane. In addition, the membranes are thermally stable up to 160 °C. Thus, these membranes have potential to be considered for use in direct methanol fuel cell.     

Analysis of trace inorganic anions in weak acid salts by single pump cycling‐column‐switching ion chromatography

The application of ion chromatography with the single pump cycling‐column‐switching technique was described for the analysis of trace inorganic anions in weak acid salts within a single run. Due to the hydrogen ions provided by an anion suppressor electrolyzing water, weak acid anions could be transformed into weak acids, existing as molecules, after passing through the suppressor. Therefore, an anion suppressor and ion‐exclusion column were adopted to achieve on‐line matrix elimination of weak acid anions with high concentration for the analysis of trace inorganic anions in weak acid salts. A series of standard solutions consisting of target anions of various concentrations from 0.005 to 10 mg/L were analyzed, with correlation coefficients r ≥ 0.9990. The limits of detection were in the range of 0.67 to 1.51 μg/L, based on the signal‐to‐noise ratio of 3 and a 25 μL injection volume. Relative standard deviations for retention time, peak area, and peak height were all less than 2.01%. A spiking study was performed with satisfactory recoveries between 90.3 and 104.4% for all anions. The chromatographic system was successfully applied to the analysis of trace inorganic anions in five weak acid salts.     

离子色谱法同时分析啤酒中的有机酸和无机阴离子

建立了以NaOH-甲醇混合淋洗液,离子交换色谱柱,电导检测器检测,分离啤酒中有机酸和无机阴离子的离子色谱法.结果表明：在20 min内分离出啤酒中的11种主要有机酸与无机阴离子,方法回收率和相对标准偏差分别为96.30%～104.8%和0.02%～4.0%.     

Hybrid Copolymerization via the Combination of Proton Transfer and Ring-opening Polymerization

Phosphazene base,t-BuP2,was employed to catalyze the proton transfer polymerization(PTP)of 2-hydroxyethyl acrylate(HEA),and PTP was further combined with ring-opening polymerization(ROP)to exploit a new type of hybrid copolymerization.The studies on homopolymerization showed that t-BuP2 was a particularly efficient catalyst for the polymerization of HEA at room temperature,giving an excellent monomer conversion.Throughout the polymerization,transesterification reactions were unavoidable,which increased the randomness in the structures of the resulting polymers.The studies on copolymerization showed that t-BuP2 could simultaneously catalyze the hybrid copolymerization via the combination of PTP and ROP at 25°C.During copolymerization,HEA not only provided hydroxyl groups to initiate the ROP ofε-caprolactone(CL)but also participated in the polymerization as a monomer for PTP.The copolymer composition was approximately equal to the feed ratio,demonstrating the possibility to adjust the polymeric structure by simply changing the monomer feed ratio.This copolymerization reaction provides a simple method for synthesizing degradable functional copolymers from commercially available materials.Hence,it is important not only in polymer chemistry but also in environmental and biomedical engineering.     

Proton dynamics in an extended array of hydrogen bonds: normal coordinates, proton transfer and macroscopic quantum entanglement in the ground state

After a brief introduction to neutron scattering techniques, illustrated with the scattering function for harmonic oscillators, some new aspects of proton dynamics in the KHCO₃ crystal are presented. The full scattering function for the proton modes measured on single crystals provides a graphic view of proton dynamics. Vibrational states are fully characterized with three quantum numbers. The effective oscillator mass of 1 amu confirms the decoupling of protons from the lattice. Combining infrared, Raman and inelastic neutron scattering techniques, the double minimum potential for the transfer of a single proton along hydrogen bonds is totally determined. Elastic neutron scattering techniques probe dynamics in the fully degenerate ground state. Quantum entanglement arising from normal coordinates gives rise to quantum interference. With diffraction techniques, the dynamical structure arising from large-scale quantum coherence is observed as ridges of intensity, well separated from Bragg's peaks. The vibrational wave function in the ground state must be regarded as a superposition of non-factorable macroscopic wave function.     

Crystal structures of hydrates of simple inorganic salts. II. Water‐rich calcium bromide and iodide hydrates: CaBr2·9H2O,CaI2·8H2O,CaI2·7H2O and CaI2·6.5H2O

Single crystals of calcium bromide enneahydrate, CaBr₂·9H₂O, calcium iodide octahydrate, CaI₂·8H₂O, calcium iodide heptahydrate, CaI₂·7H₂O, and calcium iodide 6.5‐hydrate, CaI₂·6.5H₂O, were grown from their aqueous solutions at and below room temperature according to the solid–liquid phase diagram. The crystal structure of CaI₂·6.5H₂O was redetermined. All four structures are built up from distorted Ca(H₂O)₈ antiprisms. The antiprisms of the iodide hydrate structures are connected either via trigonal‐plane‐sharing or edge‐sharing, forming dimeric units. The antiprisms in calcium bromide enneahydrate are monomeric.     

Influence of different inorganic salts on crystallization-driven morphological transformation of PCL-b-PEO micelles in aqueous solutions

Different inorganic salts, including NaSCN, NaCl, MgCl2 and Na2SO4, were added into the aqueous solution containing poly(ε-caprolactone)-b-poly(ethylene oxide)(PCL-b-PEO) semicrystalline micelles. The effects of inorganic salt on the micellar size and morphology were investigated with TEM and DLS. It is found that addition of NaSCN leads to increase of the micellar size, but the micelles remain to be spherical. By contrast, the other three inorganic salts can induce sphere-to-cylinder or sphere-to-lamella transformations of the PCL-b-PEO semicrystalline micelles. The alteration rate of the micellar size with the time after addition of the inorganic salts decreases in the following order: Na2SO4 NaCl ≈ MgCl2 NaSCN. These results were interpreted in terms of the "salting-out" ability of the cations and anions. The anions SO42- and Cl- have a stronger "salting-out" ability, driving the morphological transformations of the micelles and leading to a rapid change in micellar size. By contrast, SCN- has a weaker salting-out" ability. The cations Na+ and Mg2+ may associate with the PEO blocks, leading to a "salting-out" effect as well. However, the "salting-out" ability of cations is weaker than that of SO42- and Cl- anions, and the "salting-out" abilities of Na+ and Mg2+ are similar.