东北草甸棕壤的零电荷点和界面酸-碱反应特征平衡常数

分别采用电势滴定(Potentiometric titration)法, 质量滴定(Mass titration)法和惰性电解质滴定(Inert electrolyte titration)法测定了荷结构负电荷的东北草甸棕壤的零净电荷点(PZNC), 研究表明荷结构负电荷的土壤依然存在与电解质浓度无关的零净电荷点, 三种方法的实验结果分别为2.9, 5.0和3.3. 相比较而言, 电势滴定法和惰性电解质滴定法的结果相近, 而质量滴定法的结果偏高. 对文献中推算表面质子活性位密度(N_s)的方法进行了改进, 得到东北草甸棕壤样品的N_s为2.5 mmol•g^－1. 根据实验测定的pH_PZNC, N_s和结构电荷密度(σ_st)值直接计算得出东北草甸棕壤样品的界面反应特征平衡常数即1-pK模型中的pK, 2-pK模型中pK_a1^int和pK_a2^int, 分别为3.37, 2.42和4.32, 与文献报道的沉积物和蒙脱土的值相吻合.     

Intrinsic Surface Reaction Constant in 1-pK Model of Mg-Fe Hydrotalcite-like Compounds

The relationship among intrinsic surface reaction constant (K) in 1-pK model, point of zero net charge (PZNC) and structural charge density (σst) for amphoteric solid with structural charges was established in order to investigate the effect of σst on pK. The theoretical analysis based on 1-pK model indicates that the independent PZNC of electrolyte concentration (c) exists for amphoteric solid with structural charges. A common intersection point (CIP) should appear on the acid-base titration curves at different c, and the pH at the CIP is pHPZNC. The pK can be expressed as pK=-pHPZNC log[(1 2αPZNC)/(1-2αPZNC)], where αPZNC≡σst/eNANs, in which e is the elementary charge, NA the Avogadro‘s constant and Ns the total density of surface sites. For solids without structural charges, pK=-pHPZNC. The pK values of hydrotalcite-like compounds (HTlc) with general formula of [Mg1-xFex(OH)2](Cl,OH)x were evaluated. With increasing x, the pK increases, which can be explained based on the affinity of metal cations for H^- or OH^- and the electrostatic interaction between charging surface and H^- or OH^-.     

TiO2和Mg-Fe型类水滑石特征电离/络合平衡常数研究

The intrinsic surface reaction constants, pKa1^int, pKa2^int, p^＊KC^int and p^＊KA^int , were evaluated by a modifieddouble extrapolation （MDE） for TiO2 without structural charge and Mg-Fe hydrotalcite-like compounds （HTlc） with structural charge, respectively. The results of intrinsic surface reaction constants for TiO2 were compared with those obtained by class double extrapolation （CDE） in literature. Furthermore, the values of intrinsic surface reaction constants obtained by MDE were used to simulate the charging behaviors of the materials. The following conclusions were obtained. For TiO2 without structural charge, the pKa1^int and pKa2^int evaluated by MDE are equal to those by CDE, however the p^＊KC^int and p^＊KA^int evaluated by MDE are much different from those by CDE. In principle, the results of the p^＊KC^int and p^＊KA^int evaluated by MDE are more accurate than those by CDE. The values of intrinsic surface reaction constants obtained by MDE can excellently simulate the charging curves for TiO2 with the triple layer model （TLM）. For HTlc with positive structural charge, the results of ^＊KC^int=0 and ^＊KA^int →∞ were obtained by MDE, which means the inert electrolyte chemical binding does not exist; the point of zero net charge （PZNC） of c-independence also exist as the same as solid without structural charge, and the PHPZNC obtained by the acid-base titration can excellently be simulated and the surface charging tendency can be simulated to a great extent using the pKa1^int and pKa2^int evaluated by MDE and the diffuse layer model （DLM）.     

Confusing Quantitative Descriptions of BrønstedLowry AcidBase Equilibria in Chemistry Textbooks – A Critical Review and Clarifications for Chemical Educators

In chemistry textbooks, the pK value of water in the solvent water at 25 °C is sometimes given as 14.0, sometimes as 15.7. This is confusing. The particular chemical reaction considered is the one in which water as Brønsted? Lowry acid reacts with water as Brønsted? Lowry base in water as solvent to yield equal concentrations of hydrated oxonium and hydroxide ions, H₃O⁺(aq) and HO^?(aq), respectively. This reaction is also known as the ‘self‐ionization’ of water for which the equilibrium constant is abbreviated as K_w with its known value of 10^?14.0 at 25 °C, i.e., pK_w(25 °C)=14.0. Identical values for pK and pK_w at a fixed temperature appear reasonable, since K and K_w refer to one and the same reaction. Therefore, reasons for the apparent disagreement between the ‘thermodynamically correct’ pK_a value for water (14.0 at 25 °C) and the value reported in most organic chemistry textbooks (15.7) should be discussed when teaching acid? base chemistry. There are good arguments for introducing, from the very beginning, the concepts of activity and thermodynamic standard states when teaching quantitative aspects of chemical equilibria. This also explains in a straightforward way why all thermodynamic equilibrium constants, including K_w, are dimensionless, and why pK(25 °C)=0.     

The first automated 470.59 MHz 19F NMR‐controlled titration: dissociation constants and ion‐specific chemical shifts of 2‐amino‐4‐fluoro 2‐methylpent‐4‐enoic acid

2‐Amino‐4‐fluoro‐2‐methylpent‐4‐enoic acid, obtained as a 1 : 1 salt with trifluoro‐acetic acid, was characterized by ¹H and ¹⁹F high‐resolution NMR spectroscopy. High‐precision potentiometry led to the dissociation constants pK = 1.879 and pK = 9.054. The first automated 470.59 MHz ¹⁹F NMR‐controlled titration yielded the dynamic chemical shift 〈δ_F〉 as a function of pcH or τ and the ion‐specific chemical shifts: δ_F(H₂L⁺) = ?94.81 ppm, δ_F(HL) = ?94.21 ppm, δ_F(L^?) = ?92.45 ppm. The deprotonation gradients were found to be Δ₁ = ?0.60 ppm and Δ₂ = ?1.76 ppm. Copyright © 2002 John Wiley & Sons, Ltd.     

Capillary zone electrophoresis of basic drugs in non-aqueous acetonitrile with buffers based on a conventional pH scale

Summary The pK _a ^* values of 10 nitrogen-containing basic drugs in non-aqueous acetonitrile were determined from the pH^* dependence of their electrophoretic mobilities. The pH^* scale in the organic solvent was established using background electrolytes with known conventional pK _a ^* values, making further calibration with reference pH electrodes unnecessary. In acetonitrile the pK _a ^* values of analytes (or their conjugated cation acids, BH⁺, respectively) were 5.2±8.9 pK units>those in water. The observed change in pK _a ^* values of cationic analytes was, however, much less than the known respective change for neutral acids type HA. From the pK _a ^* values and the actual mobilities, it is possible to predict pH^* conditions to enable separation of analytes, and this was demonstrated for two pairs of common drugs.     

pKa prediction for acidic phosphorus‐containing compounds using multiple linear regression with computational descriptors

Ninety‐six acidic phosphorus‐containing molecules with pK_a 1.88 to 6.26 were collected and divided into training and test sets by random sampling. Structural parameters were obtained by density functional theory calculation of the molecules. The relationship between the experimental pK_a values and structural parameters was obtained by multiple linear regression fitting for the training set, and tested with the test set; the R² values were 0.974 and 0.966 for the training and test sets, respectively. This regression equation, which quantitatively describes the influence of structural parameters on pK_a, and can be used to predict pK_a values of similar structures, is significant for the design of new acidic phosphorus‐containing extractants. © 2016 Wiley Periodicals, Inc.     

A Rational Approach to Selective Recognition of NH4+ over K+

An ion-selective electrode (ISE) based on receptor 1 is highly selective for binding NH₄⁺ over K⁺ (lg K=−2.6); the three imine nitrogen atoms in 1 are ideally positioned for hydrogen bonding with the tetrahedral NH₄⁺ ion. This selectivity is considerably greater than that found for commercial ISEs based on nonactin (lg K=−1.0).     

Study of Activation and Inhibition of Certain Metal Ions to Amylase Catalyzed Reaction by Microcalorimetry

IntroductionMostcomplicatedreactionshappenedinlivingcrea tures ,amongthemenzymecatalyzedreactionisanimpor tantclass .Itissignificantinboththeoryandpracticetoinvestigateenzymecatalyzedreaction .Therearemanyex perimentalmethodssuchasspectrophotometry ,titrimetry ,isotopemethod ,microcalorimetryandsoon ,inwhichmi crocalorimetryisanewoneduetoitshighsensitivityandaccuracy .Wecanstudythewholeprocessoftheheatef fectusingamicrocalorimeter .Sincetheabsorptionorpro ductionofheatisanintrinsicpropertyofe…     

The reaction of methyl p-nitrophenyl sulfate with hydrogen peroxide anion determination of pKa of hydrogen peroxide in methanol by a kinetic spectrophotometric procedure

A kinetic spectrophotometric investigation of the reaction of the hydrogen peroxide anion with methyl p-nitrophenyl sulfate in methanol solvent resulted in the evaluation of the pK_a of HOOH in methanol at 25°C as 15.8 ± 0.2. Since normal kinetic procedures for the determination of the equilibrium constant K for the process CH₃O^? + H₂O₂ ? CH₃OH + HO were found to be associated with high uncertainty, another procedure was devised to establish the magnitude of K. This method is based on an analysis of the changing slopes of plots of pseudo-first-order rate constants against the total base concentration as the stoichiometric amount of hydrogen peroxide is varied. The method is applicable to any system in which anionic nucleophiles generated in situ compete with solvent anions. Such a corroboration of kinetically determined equilibrium constants is believed essential. The kinetic data allow the specific rate constant k_HOO-for the reaction of methyl p-nitrophenyl sulfate with hydrogen peroxide anions to be evaluated and yield the rate constant ratio k/k = 8.8 ± 2.2. This confirms the existence of an α effect at saturated carbon in this system.     

Differential Pulse Polarography for a First‐Order EC Process and Its Diagnostic Parameters

Theoretical expressions for differential pulse polarography (DPP) for a reversible electron transfer coupled with an irreversible follow‐up first‐order chemical reaction (E_rC_i) is derived approximately. The peaks as given by the current expressions are analyzed in terms of several parameters such as a ratio of anodic‐to‐cathodic peak‐currents (i_p^a/i_p^c), a separation of peak‐potentials (E_p^c?E_p^a), and a ratio of anodic‐to‐cathodic half‐peak‐widths (W_1/2^a/W_1/2^c) in order to characterize the E_rC_i process and distinguish it from other types of electrode processes. The anodic peak is found to be more susceptible to the post kinetics than the cathodic peak. The new parameter of W_1/2^a/W_1/2^c ratio is much more sensitive to the post kinetics than the peak separation (E_p^c?E_p^a). The peak current ratio (i_p^a/i_p^c) and the peak‐width ratio (W_1/2^a/W_1/2^c) have comparable sensitivities to the kinetics. Hence, W_1/2^a/W_1/2^c ratio is a better diagnostic parameters than (E_p^c?E_p^a) which has a poor sensitivity. This phenomenon is different from cyclic voltammetry (CV) in which E_p^c?E_p^a is as sensitive as i_p^a/i_p^c. The new criteria for EC with DPV is tested and successfully applied to several Co(III) complex systems, including coenzyme B₁₂. The homogeneous rate constant (k) for the follow‐up step is estimated from the measurements of the experimental values of the parameters. The present treatment is valid quantitatively at lower values of k, yielding relatively larger errors for higher k values (k>10 s^?1).     

A Thermodynamic Analysis of Ion Adsorption in the Metal Oxide/Electrolyte Systems in which PZC and CIP do not Coincide

A theoretical-numerical analysis of two adsorption systems composed of the same kind of oxide- TiO₂, and of two different electrolytes, NaCl and CsCl is presented. For one kind of the electrolyte (NaCl), PZC and CIP coincide, whereas they are different for the other (CsCl) electrolyte. The analysis is carried out by applying the popular TLM model, and by drawing formal-mathematical consequences of CIP existence in both kinds of adsorption systems. The values of the adsorption parameters are found by fitting simultaneously the obtained theoretical expressions to both experimental titration isotherms, and to the individual isotherms of cation adsorption measured using radiometric methods. That theoretical-numerical analysis suggests, that the inequality PZC (pK ^int _a1 + pK ^int _a2) may be a general feature of the oxide/electrolyte systems including the systems in which PZC and CIP coincide.     

Determination of the surface properties of untreated and chemically treated kaolinites by inverse gas chromatography

Inverse gas chromatography is used to study the surface properties of the untreated and chemically treated kaolinite samples. Changes in the enthalpy of adsorption for a variety of probes and in the surface energy of clays are measured and the effect of modification of the natural clay after chemical treatment with Na₂CO₃ is determined. The surface energy of the natural clay increased by the modification due to an increase in the surface area. It can be concluded that the dispersive component of surface free energy, γ _s ^d , decreases with temperature in the 200–275°C temperature range for both samples. Temperature coefficients of γ _s ^d for untreated and modified kaolinites are −0.1185 and −0.3966 mJ/(m² °C) with the correlation coefficients (R ²) of 0.8479 and 0.965, respectively. From the retention data for polar probes at infinite dilution, information on the accessibility of surface sites to the probes and on the acid-base character of the surface is obtained. The specific free energy of adsorption, the specific enthalpy of adsorption (ΔH ^sp), and the specific entropy of adsorption of polar probes on initial and modified kaolinites are determined. The ΔH ^sp values correlated with the donor numbers and modified acceptor numbers of the probes to quantify the acidity (K _A) and basicity (K _D) parameters of clay surfaces. The values of K _A and K _D for initial and modified kaolinites are determined to be 0.1202 and 0.2803; 0.0130 and 0.0408 with the correlation coefficients of −0.9805 and −0.9782, respectively. The unmodified clay sample indicated a more acidic character, while the modified clay sample conferred a largely basic character. Consequently, the predominant surface basicity of the modified kaolinite agrees with expectation, bearing in mind the treatment with Na₂CO₃, taking into consideration that such a modification contributes to a decrease in the hydrophilicity of the surface and also results in the surface showing only weak Lewis acidity. The text was submitted by the authors in English.     

U(VI) sorption on kaolinite: effects of pH,U(VI) concentration and oxyanions

U(VI) sorption on kaolinite was studied as functions of contact time, pH, U(VI) concentration, solid-to-liquid ratio (m/V) by using a batch experimental method. The effects of sulfate and phosphate on U(VI) sorption were also investigated. It was found that the sorption kinetics of U(VI) can be described by a pseudo-second-order model. Potentiometric titrations at variable ionic strengths indicated that the titration curves of kaolinite were not sensitive to ionic strength, and that the pH of the zero net proton charge (pH_PZNPC) was at 6.9. The sorption of U(VI) on kaolinite increased with pH up to 6.5 and reached a plateau at pH >6.5. The presence of phosphate strongly increased U(VI) sorption especially at pH <5.5, which may be due to formation of ternary surface complexes involving phosphate. In contrast, the presence of sulfate did not cause any apparent effect on U(VI) sorption. A double layer model was used to interpret both results of potentiometric titrations and U(VI) sorption on kaolinite.     

Analysis of solvent‐accessible voids and proton‐coupled electron transfer of 2,6‐bis(1H‐imidazol‐2‐yl)pyridine and its hydrochloride

The crystal structures of the solid form of solvated 2,6‐bis(1H‐imidazol‐2‐yl)pyridine (H₂dimpy) trihydrate, C₁₁H₉N₅·3H₂O·[+solvent], I , and its hydrate hydrochloride salt 2‐[6‐(1H‐imidazol‐2‐yl)pyridin‐2‐yl]‐1H‐imidazol‐3‐ium chloride trihydrate, C₁₁H₁₀N₅⁺·Cl^?·3H₂O, II , are reported and analysed in detail, along with potentiometric and spectrophotometric titrations for evaluation of the acid–base equilibria and proton‐coupled electron‐transfer reactions. Compound I crystallizes in the high‐symmetry trigonal space group P3₂21 with an atypical formation of solvent‐accessible voids, as a consequence of the 3₂ screw axis in the crystallographic c‐axis direction, which are probably occupied by uncharacterized disordered solvent molecules. Additionally, the trihydrated chloride salt crystallizes in the conventional monoclinic space group P2₁/c without the formation of solvent‐accessible voids. The acid–base equilibria of H₂dimpy were studied by potentiometric and spectrophotometric titrations, and the results suggest the formation of H₃dimpy⁺ (pK_a1 = 5.40) and H₄dimpy²⁺ (pK_a2 = 3.98), with the electrochemical behaviour of these species showing two consecutive irreversible proton‐coupled electron‐transfer reactions. Density functional theory (DFT) calculations corroborate the interpretation of the experimental results and support the assignment of the electrochemical behaviour.     

Crystal structure,thermal properties and detonation characterization of bis(5‐amino‐1,2,4‐triazol‐4‐ium‐3‐yl)methane dichloride

Bis(5‐amino‐1,2,4‐triazol‐4‐ium‐3‐yl)methane dichloride (BATZM·Cl₂ or C₅H₁₀N₈²⁺·2Cl^?) was synthesized and crystallized, and the crystal structure was characterized by single‐crystal X‐ray diffraction; it belongs to the space group C2/c (monoclinic) with Z = 4. The structure of BATZM·Cl₂ can be described as a V‐shaped molecule with reasonable chemical geometry and no disorder, and its one‐dimensional structure can be described as a rhombic helix. The specific molar heat capacity (C_p,m) of BATZM·Cl₂ was determined using the continuous C_p mode of a microcalorimeter and theoretical calculations, and the C_p,m value is 276.18 J K^?1 mol^?1 at 298.15 K. The relative deviations between the theoretical and experimental values of C_p,m, H_T – H_298.15K and S_T – S_298.15K of BATZM·Cl₂ are almost equivalent at each temperature. The detonation velocity (D) and detonation pressure (P) of BATZM·Cl₂ were estimated using the nitrogen equivalent equation according to the experimental density; BATZM·Cl₂ has a higher detonation velocity (7143.60 ± 3.66 m s^?1) and detonation pressure (21.49 ± 0.03 GPa) than TNT. The above results for BATZM·Cl₂ are compared with those of bis(5‐amino‐1,2,4‐triazol‐3‐yl)methane (BATZM) and the effect of salt formation on them is discussed.     

Synthesis,Crystal Structure,Vibrational Spectroscopy and Thermal Behavior of the First Alkali Metal Hydrated Hexaborate： K2[B6O9（OH）2]

New hydrated potassium hexaborate K2[B6O9（OH）2] has been synthesized under mild solvothermal conditions. The structure was determined by single-crystal X-ray diffraction and further characterized by FT-IR, Rarnan spectra and DTA-TG. It crystallizes in the monoclinic system with space group P21/n, a=0.9036（2） nm, b=0.66052（18） nm, c=1.5997（4） nm, β=91.862（4）°, V=0.9543（4） nm^3 and Z=4. Its crystal structure consists of K-O polyhedra and 1-D stepped polyborate chains constructed by new [B6O9（OH）2]2- fundamental building blocks. 1-D polyborate chains contain 3,8-membered boron rings. Adjacent chains are further linked via H-bonding interactions into 2-D layers. The K^＋ cations reside not only between the layers but also in the 8-membered boron rings of the chains, compensating the negative charges of the borate chains and holding the layers together into the 3-D structure through bonding with oxygen atoms of the chains.     

Mimicking Tyrosine Phosphorylation in Human Cytochrome c by the Evolved tRNA Synthetase Technique

Phosphorylation of tyrosine 48 of cytochrome c is related to a wide range of human diseases due to the pleiotropic role of the heme‐protein in cell life and death. However, the structural conformation and physicochemical properties of phosphorylated cytochrome c are difficult to study as its yield from cell extracts is very low and its kinase remains unknown. Herein, we report a high‐yielding synthesis of a close mimic of phosphorylated cytochrome c, developed by optimization of the synthesis of the non‐canonical amino acid p‐carboxymethyl‐L ‐phenylalanine (pCMF) and its efficient site‐specific incorporation at position 48. It is noteworthy that the Y48pCMF mutation significantly destabilizes the Fe?Met bond in the ferric form of cytochrome c, thereby lowering the pK_a value for the alkaline transition of the heme‐protein. This finding reveals the differential ability of the phosphomimic protein to drive certain events. This modified cytochrome c might be an important tool to investigate the role of the natural protein following phosphorylation.     

Bridge‐Splitting Reactions of Platinum(II) Complexes with Parametalated Pyridine Spacer Groups: A Kinetic and Mechanistic Study

Substitution reactions of three dinuclear Pt(II) complexes connected by a pyridine‐bridging ligand of variable length, namely [ cis‐{PtOH₂(NH₃)₂}₂–μ–L]⁴⁺, where L = 4,4′‐bis(pyridine)sulfide ( Pt1 ), 4,4′‐bis(pyridine)disulfide ( Pt2 ), and 1,2‐bis(4‐pyridyl)ethane ( Pt3 ) with S‐donor nucleophiles (thiourea, 1,3‐dimethyl‐2‐thiourea, and 1,1,3,3‐tetramethyl‐2‐thiourea) and anionic nucleophiles (SCN^?, I^?, and Br^?) were investigated. The substitutions were followed under pseudo–first‐order conditions as a function of the nucleophile concentration and temperature, using stopped‐flow and UV–visible spectrophotometric methods. The observed pK_a values were, respectively, Pt1 (pK_a1: 4.86; pK_a2: 5.53), Pt2 (pK_a1: 5.19; pK_a2: 6.42), and Pt3 (pK_a1: 5.04; pK_a2: 5.45). The second‐order rate constants for the lability of aqua ligands in the first step decreased in the order Pt2 > Pt3 > Pt1 , whereas for the second step it is Pt1 > Pt2 > Pt3 . The obtained results indicate that introduction of a spacer atom(s) on the structure of the bridging ligand influences the substitution reactivity as well as acidity of the investigated dinuclear Pt(II) complexes. Also nonplanarity of the bridging ligand of Pt1 complex significantly slows down the rate of substitution due to steric hindrance, whereas release of the strain enhances the dissociation of the bridging ligand. The release of the bridging ligand in the second step was confirmed by the ¹H NMR of Pt1‐Cl with thiourea in DMF‐d₇. The temperature dependence of the second–order rate constants and the negative values of entropies of activation (ΔS^#) support an associative mode of the substitution mechanism.     

2–Butoxyethanol and benzyl alcohol reactions with the nitrate radical: Rate coefficients and gas‐phase products

The bimolecular rate coefficients k and k were measured using the relative rate technique at (297 ± 3) K and 1 atmosphere total pressure. Values of (2.7 ± 0.7) and (4.0 ± 1.0) × 10^?15 cm³ molecule^?1 s^?1 were observed for k and k, respectively. In addition, the products of 2‐butoxyethanol + NO₃^? and benzyl alcohol + NO₃^? gas‐phase reactions were investigated. Derivatizing agents O‐(2,3,4,5,6‐pentafluorobenzyl)hydroxylamine and N, O‐bis (trimethylsilyl)trifluoroacetamide and gas chromatography mass spectrometry (GC/MS) were used to identify the reaction products. For 2‐butoxyethanol + NO₃^? reaction: hydroxyacetaldehyde, 3‐hydroxypropanal, 4‐hydroxybutanal, butoxyacetaldehyde, and 4‐(2‐oxoethoxy)butan‐2‐yl nitrate were the derivatized products observed. For the benzyl alcohol + NO₃^? reaction: benzaldehyde ((C₆H₅)C(?O)H) was the only derivatized product observed. Negative chemical ionization was used to identify the following nitrate products: [(2‐butoxyethoxy)(oxido)amino]oxidanide and benzyl nitrate, for 2‐butoxyethanol + NO₃^? and benzyl alcohol + NO₃^?, respectively. The elucidation of these products was facilitated by mass spectrometry of the derivatized reaction products coupled with a plausible 2‐butoxyethanol or benzyl alcohol + NO₃^? reaction mechanisms based on previously published volatile organic compound + NO₃^? gas‐phase mechanisms. © 2012 Wiley Periodicals, Inc.

1 This article is a U.S. Government work and, as such, is in the public domain of the United States of America.

© 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 778–788, 2012