17O-NMR. of Enriched Acetic Acid,Glycine, Glutamic Acid and Aspartic Acid in Aqueous Solution. I. Chemical Shift Studies

The ¹⁷O-NMR. chemical shifts of the enriched amino acids glycine, aspartic acid and glutamic acid were measured in aqueous solution as a function of pH. High magnetic fields are necessary to resolve the α, β- and α, γ-carboxyl resonances of aspartic acid and glutamic acid, respectively. The chemical shifts of acetic acid were measured for comparative reasons. Ionization constants and titration shifts were obtained by nonlinear least-squares fits to one-proton titration curves. The average excitation energy approximation is discussed in terms of the observed changes in ¹⁷O-shielding on deprotonation. No intramolecular association between the α-amino group and the α-carboxyl group in the zwitterionic form is required to explain the high-frequency shift of the carboxylate ion. Also no indication of an intramolecular association between the α-amino group and the side-chain carboxyl groups of aspartic acid or glutamic acid was found.     

ADSORPTION PROPERTIES OF THE STEARIC ACID-OCTADECANE PARTICLES IN AQUEOUS SOLUTIONS

The adsorption properties and surface charge creation for the stearic acid and octadecane/aqueous electrolyte solutions are considered. The hairy structure of surface charge for these systems was confirmed on the basis of potentiometric titration, ion adsorption and electrophoretic measurement data. For the system with stearic acid the reaction of ionization and complexation of carboxyl groups of stearic acid molecules from subsurface layer are responsible for the creation of surface charge and adsorption properties. The surface charge at octadecane particle is probably the results in adsorption and orientation of water molecules at the interface.     

Adsorption of polymers at the solution-solid interface. VI. Polyacids on nylon powder

The adsorption of some polyacids, principally poly(acrylic acid), on nylon powder has been studied. In aqueous solutions at low pH the adsorption behavior of poly(acrylic acid) is controlled by adsorbate coil dimensions rather than by electrostatic effects. Less adsorption takes place from methanol solutions but the process is much more rapid than from water. Above a critical value, increase of adsorbate molecular weight leads to a reduced adsorption, the effect being particularly evidenced by aqueous solutions. Model compounds (propionic and glutaric acids) are rapidly adsorbed from both methanol and water, but give low specific absorptions. Adsorption of poly(acrylic acids) and model compounds, is reduced, but not eliminated, by modification of the nylon adsorbent through acetylation or methoxymethylation. The adsorption of poly(acrylic acid) on nylon is not readily reversible; however, partial neutralization will release preadsorbed poly(acrylic acid) from nylon powder. The adsorption behavior of copolymers of acrylic acid with N-vinylpyrrolidone is reported, as are brief studies on some other homopolyacids. The results are generally interpreted on the basis of sorption of the macromolecules into a swollen, flexible adsorbent.     

Bilirubin acidity. Titrimetric and 13C NMR studies.

Acidimetric titration of bilirubin IX-alpha, dissolved in excess aqueous sodium hydroxide, showed that two protons are dissociated with pK values well below 7 and that one or several additional acidic groups titrate with pK around 12.9. Precipitation of the nearly insoluble acid precluded determination of the two lower pK values by titration in aqueous solution. In dimethyl sulfoxide solution, four acidic protons were demonstrated, titrating two by two without precipitation. 13C NMR spectra of bilirubin IX-alpha were recorded and complete assignments were made by comparison with the spectra of bilirubin XIII-alpha and mesobilirubin etc. Such spectra, recorded after addition of 2 and 4 mol of base per mol of bilirubin IX-alpha, showed that both carboxyl groups are titrated by the first 2 mol of base, and both lactams by the following 2 mol of base. Cotitrations of bilirubin IX-alpha with other acids, o- and m-hydroxybenzoic acid and 2-pyridone, were used to determine relative pK values in dimethyl sulfoxide solution, and pK values for the four acidic protons of bilirubin IX-alpha in aqueous solution were calculated from the Born equation. Both carboxyl groups exhibited pK = 4.4, and both lactams pK = 13.0, in good agreement with values expected from the chemical structure of the bilirubin molecule. The implications of these findings for understanding the mechanism of bilirubin neurotoxicity are discussed.     

Conformational transition of the copolymer of maleic acid and styrene in aqueous solution. II

The temperature dependence of the conformational transition from a compact to expanded-coil form of the alternating copolymer of maleic acid with styrene in aqueous 0.03M NaCl solution was studied at 15 to 40°C by pH titration, optical titration, and calorimetric measurements. The pH titration curve scarcely changed with temperature. The degree of dissociation of primary carboxyl groups in the copolymer at the midpoint of the conformational transition, determined by the optical titration, was almost independent of temperature. The standard enthalpy change of the transition at 25°C estimated from the calorimetric data was 0.36₃ kcal/mole, which may mean that the difference between the standard free energy changes of the transition at 20°C and 40°C does not exceed experimental error. The enthalpy change agrees well with the heat of transfer of benzene from the hydrophobic to the aqueous medium, and thus the compact form of the copolymer is considered to be stabilized by the hydrophobic interaction between the phenyl residues in the interior of the molecule.     

Micellar kinetics in aqueous acetonitrile. Part A. Sodium-hydrogen ion-exchange constant for 1-dodecanesulfonate surfactant. Part B. Substrate structural effects for micellar catalysis by perfluorooctanoic acid as reactive counterion surfactant

The sodium-hydrogen ion exchange constant for the system sodium 1-dodecanesulfonate-hydrochloric acid in aqueous acetonitrile has been determined from the pseudo-phase ion exchange model for surfactant catalytic effects. The results indicate that the micellar system behaves similarly for the aqueous and the aqueous acetonitrile (2.106 M) solvent systems. The influence of substrate molecular structure on micellar catalysis by perfluorooctanoic acid of the hydrolysis of hydroxamic acids (R—CO—NHOH) in aqueous acetonitrile has been explored. Data for substrate structures of fifteen compounds with R=alkyl, aralkyl, alicyclylalkyl, phenylalkyl, alkyl-substituted phenylalkyl, and with chain branching at the α, β, and γ positions are compared. Relative binding constant values indicate that substrates with aromatic groups are less well solubilized in the perfluoro micellar environment than are substrates with saturated groups. There is now evidence for specific micellar effects on the reaction rate as well as general micellar catalysis. © 1997 John Wiley & Sons, Inc.     

FAST METHOD OF TOTAL ACID GROUPS DETERMINATION IN FUNCTIONALIZED ACRYLIC DISPERSIONS

Acid functionalized acrylic dispersions are easily titrated in water phase by means of tetra-n-butylammonium hydroxide standardized aqueous solution. All acid groups react rapidly with the titer even in the case of crosslinked polymer latices. Results are in good agreement with the theoretical acid content and values obtained from back titration and organic solvent titration methods.     

Mathematical Modeling of Nylon 6/6,6 Copolymerization in Batch Reactor: Investigating Recipes without Water and with Cyclic Dimer

A model is used to simulate batch copolymerization of caprolactam with hexamethylene diamine (HMD) and adipic acid (ADA) to produce nylon 6/6,6. Four different recipes are considered: a recipe containing caprolactam and an aqueous solution of HMD and ADA, a recipe containing caprolactam and dry HMD/ADA salt, and two recipes with a portion of the caprolactam replaced by nylon 6 cyclic dimer (CD). Consuming CD would be advantageous because CD is an undesirable side product from nylon 6 production. Simulation results lead to three important findings: (i) operation using dry salt rather than aqueous salt solution leads to higher degree of polymerization, (ii) substantial quantities of CD can be consumed to produce nylon 6/6,6 copolymer, and (iii) including water in the recipe is beneficial for achieving improved consumption of CD. The results of this study will be helpful in designing experiments aimed at improving industrial nylon 6/6,6 copolymerization processes.     

Potentiometric study of reaction between periodate and iodide as their tetrabutylammonium salts in chloroform. Application to the determination of iodide and potentiometric detection of end points in acid-base titrations in chloroform

A potentiometric method for the titration of tetrabutylammonium iodide (TBAI) in chloroform using tetrabutylammonium periodate (TBAPI) as a strong and suitable oxidizing reagent is described. The potentiometric conditions were optimized and the equilibrium constants of the reactions occurring during the titration were determined. The method was used for the determination of iodide both in chloroform and aqueous solutions after extraction into chloroform as ion-association with tetraphenylarsonium. The reaction between TBAPI and TBAI was also used as acid indicator for the potentiometric detection of end points of acid-base titrations in chloroform.     

水溶性高分子链中磺酸盐基团含量的电导滴定测定法

研究了N ,N ,N 三甲基十六烷基溴化铵 (CTAB)与丙烯酰胺 (AM) 2 丙烯酰胺基 2 甲基丙磺酸钠盐(NaAMPS)二元共聚物P(AM co NaAMPS)的复合作用 .在复合作用过程中 ,由于不断释放出高导电性的无机盐小离子 ,故随着表面活性剂的加入 ,聚电解质水溶液的电导率不断增大 .当采用较低浓度 (0 0 0 1mol·L- 1 )且使二者的离子等摩尔量发生复合作用时 ,体系的电导率会发生明显的转折 .利用电导率的这一转折性变化 ,建立起了复合作用电导滴定法测定共聚物P(AM co NaAMPS)分子链中磺酸盐单体NaAMPS含量的新方法 .与元素分析进行比较的结果表明 ,上述复合作用电导滴定法可作为测定水溶性大分子链中磺酸盐单体含量的方便而又准确的方法 ,而且预计还可用作为测定水溶性大分子链中其它离子性基团含量的简捷方法     

New leading electrolyte for the direct determination of chloride and other anions in analytical isotachophoresis.

In a number of experiments it was shown that the dithionate ion possesses a higher effective mobility than the chloride ion in aqueous solution, thus enabling the direct and simultaneous isotachophoretic determination of chloride and other anions. Using an acid-base titration, we found only one pKa value for dithionic acid, which is in contrast to the two pKa values stated in the literature. Based on this pKa value, theoretical calculations and the experimentally observed effective mobility of the dithionate ion indicate a higher effective mobility compared to the chloride ion from pH 3. Taking into account the physico-chemical properties of the dithionate, its unrestricted use as isotachophoretic leading ion was confirmed. Based on the dithionate ion, new electrolyte systems for the determination of chloride were used. One system was optimised for the determination of chloride and other low-molecular-mass anions and applied to the analysis of waste water and drinking water. The water samples were analysed in parallel by ion chromatography and compared with the isotachophoretic results.     

Recovery and separation of Ce<Superscript>3+</Superscript> and Y<Superscript>3+</Superscript> ions from aqueous solutions by ion flotation

Experimental dependences of the distribution coefficients of cerium(III) and yttrium(III) dodecyl sulfates on the pH value of the equilibrium aqueous phase in the course of ion flotation are reported. Conditions for separation of cerium(III) and yttrium(III) are discussed. A value of the dissociation constant found from experimental results of potentiometric titration of dodecylsulfuric acid with sodium hydroxide is presented.     

Adsorption of valeric acid from aqueous solution onto activated carbons: role of surface basic sites

Adsorption of valeric acid was studied on two activated carbons of different origins, wood and bituminous coal. The effect of oxidation on the adsorption uptake was investigated. Both initial samples were oxidized with nitric acid, which caused the introduction of a significant number of oxygen-containing groups onto the carbon surface. Boehm titration, potentiometric titration, thermal analysis, and sorption of nitrogen were used for detailed surface characterization. Valeric acid adsorption from aqueous solution was measured at 333 K. The calculated isotherms showed a good fitting to the Freundlich equation. The capacity coefficients revealed a direct correlation with the number of basic groups present on the surface. The amount of valeric acid adsorbed at its low concentration is dependent on the number of basic groups, whereas at high concentration the amount adsorbed depends on the volume of micropores smaller than 10 A, where the adsorption potential is the strongest.     

Estimation of the surface sulfur content of cellulose nanocrystals prepared by sulfuric acid hydrolysis

The conditions required for the accurate measurement of the sulfur content of cellulose nanocrystals (CNCs) by conductometric titration are discussed. CNCs from sulfuric acid hydrolysis are electrostatically stabilized in aqueous suspension due to the introduction of charged sulfate ester groups onto the surface of the crystallites during reaction. The sulfur content thus largely reflects the surface charge of the crystals, and is crucial to the characterization and understanding of material properties. Conductometric titration is commonly used to quantify the sulfur content of CNCs, however, the exhaustive removal of free acid by dialysis and the necessity, type, quantity and duration of ion-exchange resin treatments are not always consistent. Here we explore the standard conditions of dialysis, ion-exchange, and the reproducibility of titration results. Extensive dialysis is found to be effective in the removal of free acid, but similar results are also achieved in shorter times and with less water using membrane ultrafiltration. It is also shown that the conditions of ion-exchange most commonly employed in the literature can lead to inaccurate sulfur contents. Finally, good agreement is obtained between the sulfur contents of different CNC batches prepared using the same hydrolysis conditions, and from titration and elemental analysis when thoroughly purified, well-dispersed samples, and appropriate resin conditions are used.     

Investigation of the drying conditions for amidosulfuric acid.

The drying conditions for primary standards of volumetric analysis have a significant effect on the titration results due to changes in the purity, stability and homogeneity. Amidosulfuric acid, a strong acid used as a reference material for volumetric analysis in Japan, was dried in a vacuum desiccator or heated at different temperatures, and then measured by Karl-Fischer titration, thermogravimetry/mass spectroscopy (TG-MS), ion chromatography and coulometric titration. The optimum drying conditions were at 50 degrees C for 24 h with crushing.     

Adsorption of cesium (I) from aqueous solution using oxidized multiwall carbon nanotubes

Multiwall carbon nanotubes (MWCNTs) were modified by nitric acid solution and then used to study the adsorption of cesium from aqueous solution using a batch technique under ambient conditions. As produced and oxidized MWCNTs were characterized by nitrogen adsorption/desorption, Boehm’s titration method and Fourier transform infrared spectroscopy. The physical properties of MWCNTs such as functional groups, total number of acid sites and specific surface area were greatly improved after oxidation, and these were responsible for more sorption of cesium from aqueous solution and made them more dispersible in water. The adsorption of cesium ions as a function of contact time, initial concentration of cesium, pH, ionic strength and oxidized MWCNT concentrations was also investigated. The results showed that cesium adsorption percentage strongly depended on the pH value, oxidized MWCNT content and on the solution ionic strength. Kinetic data indicated that the adsorption process achieved equilibrium within 80 min. Equilibrium data for as produced and oxidized MWCNTs was well described by both Freundlich and Langmuir isotherms. The dominant mechanism of cesium adsorption on oxidized MWCNTs may be mainly attributed to ion exchange. This study suggests that oxidized MWCNTs can be a promising candidate for the removal of cesium from nuclear waste solution.     

Copper and cobalt complexes of octadentate azamacrocycles: spectrophotometric titration, stopped-flow kinetics and crystallographic study

Details of complex formation kinetics are reported for tetrakis(2-hydroxyethyl) substituted cyclen (L(1)) and cyclam (L(2)) with Cu(II) and Co(II). Stopped-flow kinetics and spectroscopic titration methods were employed for the activation parameters and stability constants, respectively. X-ray studies revealed that the pendant 2-hydroxyethyl groups are not equivalent: two are folded over the macrocycle and maintained by intramolecular hydrogen bonds while the others are extended and pointed away from the macrocyclic cavity. Complex formation kinetics and spectroscopic titration were performed in aqueous acidic buffer solutions. Thermodynamic and kinetic parameters revealed that the ring size of the macrocycles plays an extremely important role for each metal ion studied. Stopped-flow kinetic measurements explained the mechanism of the complex formation process of both Cu(II) and Co(II) which proceed in outer-sphere interactions with ligands. There are two steps in the complex formation of the system studied. The initial step is a second order reaction between the metal ion and macrocycle with a second order rate constant.     

Determination of the composition and the stability constants of complexes of mercury (II) with amino acids

The execution of a titration rarely performed, or of one with a reagent of limited stability, may be facilitated by applying multiparametric curve-fitting to titration-curve data in such a way that the amount of the substance titrated and the concentration of the reagent are evaluated simultaneously; the necessity for prior standardization of the reagent is thereby eliminated. In the potentiometric titration of acetate ion, a very weak base, with unstandardized hydrochloric acid, the accuracy and precision of the concentration of acetate thus obtained are approximately five times better than those which can be secured by titration with standardized acid and location of the point of maximum slope. The accuracy and precision of the concentration of acid are comparable to those that can be secured in very careful standardizations against a primary standard that gives a titration curve of far more favorable shape.     

Modeling and Graphic Presentation of Acid–Base Titration Curves. Presentation of an Alternative Method

Titration curves for the acid—base–titration of polyvalent acids and bases and their mixtures can be created in a simple way and presented graphically. The method, an alternative to the existing procedures, shall be presented here for discussion. With the described method it is possible in an easy manner and for didactic purposes to show how the boundary conditions, such as concentrations, pK_a values, K_w values (temperature–dependent), and mixing ratios influence the shape of titration curves.The method comes from closed mathematical formulas, which can be developed in the form: titration degree, T = f(pH). An increase in the titration volume is, therefore, not considered. It can be neglected in practice by choice of suitable volumes and concentrations. The graphic presentation can be realized with the help of a customary mathematic program, such as MathCAD 7. The titration curves are derived in the familiar form of pH = f(T). During the derivation of the equations for the titration of polyvalent acids and bases, difficult expressions appear and approximations are suggested with only small deviations from the exact formulas, which nevertheless are both simple and manageable.The procedure is presented in a series of practical examples where computed and measured titration curves are compared. When using polyvalent acids, such as malonic acid or citric acid, the appropriate activity coefficients have to be considered. If the ionic strength is constant, which can be accomplished by addition of electrolytes like KCl, this is easily accomplished and is demonstrated by examples.     

Ion-selective electrode for the determination of dimethylbenzylammonium ions

A sensor is proposed for the direct potentiometric determination of dimethylbenzylammonium in acid and neutral aqueous solutions. The sensor membrane is made of a polymeric composition on the basis of polyvinylchloride containing an ion associate and a solvent as a plasticizer. Salts of the tetraphenylborate anion and its derivatives served as ionophores. Basic electroanalytical parameters of the developed potentiometric sensors are studied and the pH range of their possible application is determined. The developed sensor is used as a reference electrode in the potentiometric titration of dimethylbenzylammonium with tetraphenylborate anions.