离子液体水溶液pH值测定及酸碱特性研究

在离子液体水溶液作为新一代优良吸收工质的工业应用研究和开发中,对该体系的物理化学性质（诸如离子液体在水中存在性状及其酸碱性问题等）的深入认识和掌握尤为重要. 本文采用pH酸度计和精密pH试纸两种方法,对水质量分数分别为0.04～0.95的1-乙基-3-甲基咪唑醋酸盐（[EMIM]Ac）和0.01～0.96的1-己基-3-甲基咪唑氯盐（[HMIM]Cl）离子液体水溶液的pH值进行测试和定量分析. 测试结果表明pH酸度计和精密pH试纸两种方法的测试结果有较大的差异,这种差异是由于离子液体-水混合体系中局部形态与整体特性不同造成的. 本文成功拟合了pH精密试纸测定值,计算获得的这两种离子液体水溶液的酸浓度与测定值基本符合,精密试纸测定的pH值可用于表征离子液体水溶液整体酸碱特性. 基于离子液体在水溶液中形成惰化聚合膜的假设,提出了分别表征聚合膜水溶解度和离子液体水溶液水活度系数的溶液理论模型,根据溶液相平衡理论建立了聚合膜中氢离子浓度与水溶液中氢离子浓度差别的计算方法,成功拟合了pH酸度计测定值. 研究结果为离子液体水溶液体系的pH值和酸碱度分析提供了实验依据和预测理论模型.     

酸碱体系pH统一公式及Mathematica精确求算

酸碱体系pH计算是大学分析化学理论课程学习的重点难点,教材涉及繁多的计算公式和近似条件,局限于常见的简单体系。采用酸离解常数（Ka）对酸、碱、两性物质的酸碱反应平衡进行统一描述,建立质子平衡方程,推导得到适用于所有酸碱体系的pH计算统一公式,并使用Mathematica数学软件,便捷地解决精确求解的问题。学习通法通式,并采用计算机精确计算pH,有助于学生整体掌握分析化学理论课程中pH计算的理论基础及解决复杂体系精确计算问题。     

索伦森与pH

1909年丹麦生物化学家索伦森提出的pH概念及其测试方法,保证了啤酒产业中产品质量和风味的统一。由于科学概念的简捷性和严密性,pH概念在国内外传播中产生了一些理解上的歧义;pH试纸在使用中出现了化学知识内涵不清的问题,通过回顾历史,恢复其本来面目,促进化学教学规范发展。     

Measurement of pH in subcritical and supercritical aqueous systems

The use of yttria-stabilized zirconia (YSZ) electrodes of the type Hg/HgO/ZrO₂(Y₂O₃)/H⁺, for measuring pH in aqueous solutions at high subcritical (150374°C) is reviewed. The construction and operation of the YSZ and reference electrodes employed in these studies are described and their application in measuring the pH of a variety of technologically-important aqueous system is discussed. We show that the YSZ electrode is thermodynamically viable at temperatures into the supercritical region, and that it is a primary pH sensor in that calibration is not necessary, provided that the activity of water is known. However, highly accurate pH measurements at high subcritical and supercritical temperatures will require the development of more accurate reference electrodes.Presented at the Second International Symposium on Chemistry in High Temperature Water, Provo, UT, August 1991.     

pH dependence of the composition of electrodeposited Co films in aqueous sulfate solutions

The electrodeposition of cobalt onto gold is studied as a function of the pH of the electrolyte. Electrochemical quartz crystal microgravimetry is used to identify the material deposited. Using a Co sulfate solution without additives, it is found that for pH <-3.2, Co metal deposits. For pH > 3.2 and at sufficiently negative applied potential, first Co hydroxide deposits and then Co metal. The addition of boric acid, H₃BO₃ to cobalt sulfate solutions leads to different results: measurements done up to pH 5.5 indicate that only Co metal deposits, showing that boric acid prevents the formation of cobalt hydroxide. Published in Russian in Elektrokhimiya, 2007, Vol. 43, No. 7, pp. 899–902. The text was submitted by the authors in English.     

浅论无机化学中弱酸碱和酸式盐溶液的pH近似计算问题

以一元弱酸碱溶液、多元弱酸碱溶液以及酸式盐溶液pH的计算为例,详细探讨分析了酸碱平衡理论中的近似计算及其具体的应用条件。     

pH荧光纳米传感器的研制及表征

利用溶胶-凝胶技术制得了单分散性很好的二氧化硅纳米微球,通过共价偶联方式引入对pH变化敏感的荧光素异硫氰酸酯（FITC）,这种FITC功能化二氧化硅纳米微球（FITC功能化硅微球）可作为pH荧光纳米传感器。当pH值从4.0变至7.5时,荧光强度增大约30倍。该传感器灵敏度高,响应速度快,容易制备,光稳定性好,可望用于单细胞的pH分析。     

The influence of pH on phosphatidylcholine monolayer at the air/aqueous solution interface

The measurements of the interfacial tension at the air/aqueous subphase interface as the function of pH were performed. The interfacial tension of the air–aqueous subphase interface was divided into contributions of individuals. A simple model of the influence of pH on the phosphatidylcholine monolayer at the air/hydrophobic chains of phosphatidylcholine is presented. The contributions of additive phosphatidylcholine forms (both interfacial tension values and molecular area values) depend on pH. The interfacial tension values and the molecular areas values for LH⁺, LOH⁻ forms of phosphatidylcholine were calculated. The assumed model was verified experimentally.     

茶园土壤水溶性氟与全氟和pH值的相关性研究

研究了遂昌茶园土壤水溶性氟与全氟和pH的相关关系。结果表明,茶园土壤水溶性氟和全氟均随土层深度的增大而减小,茶园土壤pH随土层深度的增大而增大;在同一土层深度,土壤全氟含量比土壤水溶性氟含量高得多,随着土层深度的增加,茶园土壤水溶性氟在全氟中所占比例增加;在0～20cm深土层中,土壤水溶性氟与全氟和pH之间存在显著的相关性;在20～40cm深土层中,土壤水溶性氟含量与pH之间存在相关性,而土壤水溶性氟与全氟含量无相关性;在40～60cm深土层中,土壤水溶性氟与全氟含量和pH均无相关性。     

On the use of alumina in HPLC with aqueous mobile phases at extreme pH

Summary The applicability of alumina as a stationary phase in liquid chromatography is considered. Despite the presence of hydroxyl groups on wetted alumina, chemical modification with silanes by analogy to silica is not successful. Although depolarisation can be achieved with hexamethyldisilazane, the product is not stable to hydrolysis in aqueous media. The use of alumina as an ion-exchanger is more promising, especially because alumina appears to be stable over a very broad pH range. As a result of its amphoteric character alumina can be used either as an anion-exchanger or as a cation-exchanger. The latter possibility is more profitable in alkaline solvents and allows the separation of strongly basic compounds at pH values as high as 12. Retention can be controlled by judicious choice of ionic strength, counter ion and pH.     

Monitoring the traceability of the pH of a primary tetraborate buffer: comparison of results from primary and secondary apparatus

This paper reports evaluation of the behaviour of different combined glass electrodes applied to measurement of the pH of a primary, 0.01 mol kg⁻¹, tetraborate buffer. Measurements were first performed by use of a primary Harned cell (at 15, 25, and 37 °C); these results were then compared with those obtained for the same solution by use of three combined glass electrodes (25 °C) with different membranes and liquid-junction designs, calibrated by use of commercial pH-metric buffers. The pH of the same solution was also measured in terms of the molal concentration of hydrogen ions, using acid–base titration to evaluate the formal potential difference K of each cell at fixed ionic strength, I, adjusted by addition of KCl or Et₄NI (tetraethylammonium iodide). The reference value from primary measurement, paH = 9.171, was slightly closer to the mean value obtained by determination of concentration, rather than that obtained by direct measurement of activity; the differences were smaller than the extended uncertainty characteristics of the secondary measurements. The importance of evaluation of the ionic strength of the solution under study is emphasised. We verified that for tetraborate buffer slight modification of the value of I used to calculate γ _i (the activity coefficient of a single ion) in the calculation of paH from the acidity function at zero molality of chloride can significantly affect the reference value of the calibrator tool. This is true, in general, for low values of the ionic strength, such as those considered in this work; an approximate value of I can then cause distortions along the pH traceability chain. Application of the concepts of thermodynamics to this traceability chain is discussed.     

Adsorption of organic probes on silica through Lewis interactions: a comparison of experimental results and quantum chemical calculations

The adsorption of organic probe molecules on a partly dehydroxylated silica (SiO(2)) surface has been studied in a non-aquatic and non-polar environment. These results were compared to, verified and explained by quantum chemical calculations on the same systems. Since the systems are water free and since the non-polar solvent cyclohexane is used in the experiments, the quantum chemical calculations are well comparable to the experimental results without any additional terms. The characterized surface was found to contain both Lewis acid and Lewis base sites and a good agreement between the experimentally determined and the calculated data was found.     

Structure of the aqueous electron: assessment of one-electron pseudopotential models in comparison to experimental data and time-dependent density functional theory

The prevailing structural paradigm for the aqueous electron is that of an s-like ground-state wave function that inhabits a quasi-spherical solvent cavity, a viewpoint that is supported by numerous atomistic simulations using various one-electron pseudopotential models. This conceptual picture has recently been challenged, however, on the basis of results obtained from a new electron-water pseudopotential model that predicts a more delocalized wave function and no well-defined solvent cavity. Here, we examine this new model in comparison to two alternative, cavity-forming pseudopotential models. We find that the cavity-forming models are far more consistent with the experimental data for the electron's radius of gyration, optical absorption spectrum, and vertical electron binding energy. Calculations of the absorption spectrum using time-dependent density functional theory are in quantitative or semiquantitative agreement with experiment when the solvent geometries are obtained from the cavity-forming pseudopotential models, but differ markedly from experiment when geometries that do not form a cavity are used.     

8-羟基喹啉-5-磺酸修饰电极pH传感器的制备及应用

制备了8-羟基喹啉-5-磺酸(HQS)修饰铂丝电极pH传感器,对其pH响应范围,斜率,线性相关系数,响应时间等进行了考察.将该电极用于表面修饰氨基纳米二氧化硅的测定,取得了满意结果.     

Effects of pH on dynamics and rheology during association and gelation via the Ugi reaction of aqueous alginate

Effects of solution pH on the physical properties of a semidilute aqueous alginate solution without cross-linker agent and during gelation via the Ugi multicomponent condensation reaction at a fixed cross-linker concentration have been investigated. Both rheology and turbidity results on the alginate solution without cross-linker revealed enhanced associations at low pH. In the course of the cross-linker reaction, the time of gelation is shortest at pH = 3.5 and at pH values above 3.8 no gel is formed but only a viscosification of the solution is observed. The turbidity during the cross-linking reaction rises as the pH increases from 3.5 to 5. Furthermore, the initial change of the turbidity in the course of the cross-linking process is more pronounced at higher pH. The dynamic light scattering (DLS) results of the reaction mixture at pH = 4.0 (ergodic features at this condition) show that the chain relaxation is slowed down as the reaction proceeds. The effect of pH on the kinetics of the Ugi reaction is discussed.     

Thermodynamic quantities relative to solution processes of Naproxen in aqueous media at pH 1.2 and 7.4

Based on van’t Hoff and Gibbs equations, the thermodynamic functions Gibbs free energy, enthalpy, and entropy of solution, mixing and solvation of naproxen (NAP) in water at pH 1.2 and 7.4, were evaluated from solubility values determined at several temperatures. The solubility at pH 7.4 and 25.0°C was almost 150 times higher with respect to pH 1.2. The enthalpies of solution were positive and greater for pH 1.2, while the entropies of solution were both negative, thereby implying a greater molecular organization at pH 7.4. The results were discussed in terms of solute–solvent interactions.     

A pH Scale for the Protic Ionic Liquid Ethylammonium Nitrate

To quantify the properties of protic ionic liquids (PILs) as acid–base reaction media, potentiometric titrations were carried out in a neat PIL, ethylammonium nitrate (EAN). A linear relationship was found between the 14 pK_a values of 12 compounds in EAN and in water. In other words, the pK_a value in EAN was found to be roughly one unit greater than that in water regardless of the charge and hydrophobicity of the compounds. It is possible that this could be explained by the stronger acidity of HNO₃ in EAN than that of H₃O⁺ in water and not by the difference in the solvation state of the ions. The pH value in EAN ranges from ?1 to 9 on the pH scale based on the pH value in water.     

Influence of buffer quality on pH measurement uncertainty: prediction and experimental evaluation

Dependence of the uncertainty of a pH measurement result on the quality of buffers (i.e. the uncertainty of their certified pH values) at different levels of instrumental uncertainty (pH-meter, etc.) was simulated using the Monte Carlo method and regression analysis. The contribution of the instrumental standard uncertainty (in the studied range from 0.1 to 1 mV) to the uncertainty of the pH measurement result is negligible, if the standard uncertainties of the pH buffers exceed 0.04 pH (e. g. for in-house buffers). It is shown how the choice of pH-meter and buffers should be correlated in order to meet the required uncertainty of a pH measurement result in a sample under analysis. The results of the simulation were compared with experimental data obtained from calibrations of a pH/ion-meter with a hydrogen working electrode (Radiometer PHM-240) and with a glass electrode (Metrohm 744). Buffers of different quality (National Institute for Standards and Technology standard reference materials, certified Radiometer buffers and Merck CertiPUR buffers) were used for the calibrations. The uncertainties of the experimental results are close to the predicted ones obtained by the simulation. Received: 16 June 2002 Accepted: 19 July 2002 Presented at the 14^th International Conference of the Israel Society for Quality, 18–21 November 2002, Jerusalem, Israel Correspondence to I. Kuselman     

A high-performance fluorosensor for pH measurements between 6 and 9

This study presents a high-performance ratiometric pH optode based on the fluorophore 6,8-dihydroxypyrene-1,3-disulfonic acid (DHPDS). The two pH-sensitive terminal hydroxy groups of DHPDS facilitated dual excitation/dual emission (F₁: λ_1,ex = 420 nm, λ_1,em = 462 nm; F₂: λ_2,ex = 470 nm, λ_2,em = 498 nm) properties for ratiometric (R_F1,F2 = F₁/F₂) normalization of sensor signal. The sensor demonstrated an exponentially decreasing ratiometric response with increasing pH, with a linear correlation (R² = 0.9936) between ¹⁰log(R_F1,F2) and pH within the pH interval 6-9. Precision determined as the IUPAC pooled standard deviation for the pH values 6.00, 7.01 and 9.01, was 0.0057 pH units for the fluorosensor and 0.0054 for a commercially available pH electrode used for comparison. Between the end-points of calibration at pH 7.01, the precision of the sensor was 0.0037 pH units. Effects from changes in ionic strength (I_tot, 10-700 mM) were more pronounced for the electrode, with a linear (R² = 0.9976) increase in response (δE/δpH) with increasing I_tot. The DHPDS-based fluorosensor, however, retained sensitivity (δ¹⁰log(R_F1,F2)/δpH = 0.8024 ± 0.0145), though with an overall increase in ratiometric signal with increasing I_tot. The preserved sensitivity despite changes in ionic strength was possibly a consequence from the dual photo-acidic properties of DHPDS. Analytical characteristics of immobilized DHPDS therefore not only facilitated high-performance measurements over a wide pH range, but also opened for straightforward simultaneous measurements of pH and ionic strength.