DIRECT TITRATION OF VERY WEAK ACIDS(BASES)IN AQUEOUS SOLUTION WITH STRONG BASES(ACIDS)USING VISUAL END-POINT INDICATION WITHOUT INDICATOR

This paper reports a new method of titration for very weak acids and bases using the appearance of incisions on oscillopolarogram to indicate the end-point.This method has the advantages of rapidity,simplicity,no indicator needed as well as good precision.

QUANTITATIVE ANALYSIS OF VERY WEAK ACID AND BASE BY pH-FIXED TITRATION METHOD

pH-fixed titration method for the determination of weak acids and bases has been studied in this paper.It is not necessary to know the ionization constant of weak acid or base and the concentration of titrant. This method had been applied to determine phenol,4-aminoantipyrine and glycine,whose ionization constants range from 10^(-10)to 10^(-12).The results were satisfactory.

Numerical Method for Determination of Composition of Weak Acid Mixtures by Potentiometric Titration

An equation describing the state of weak acid mixtures was derived from the relationships between mole balance and charge balance. The equation was solved with numerical method and the compositions of the acid mixtures were determined. The advantages of this treatment were demonstrated by analyzing binary mixtures of chloroacetic, formic and acetic acids.

Response surface methodology for optimizing adsorption performance of gel-type weak acid resin for Eu(Ⅲ)

The conditions relating to enhanced adsorption procedure of earth element europium（Eu） onto gel-type weak acid resin（110-H） in aqueous solution were optimized by means of the response surface methodology（RSM）, which proved that 110-H owned satisfactory adsorption capacity（346.85 mg/g） in optimum conditions, belonging to one of the high adsorption capacity materials. Then, the adsorption and desorption behaviors were investigated by batch studies. The adsorption performance showed high agreement with the Lagergren-first-order model and Langmuir isotherm with thermodynamic adsorption parameters of ΔH= 36.1 k J/mol and ΔS=200 J/（mol·K）. Desorption study revealed that 110-H could be effectively eluted by a low concentration of HCl solution（0.1 mol/L） to regenerate and reuse. Finally, the 110-H and Eu（III） loaded 110-H were characterized by IR spectroscopy and scanning electron microscope（SEM） to analyze the mechanism of adsorption, which proved to be chemisorbed.

Study of Complexes of Lanthanum with Amino Acids by Titration Calorimeter

The stability constants and thermodynamic functions for complexes of lanthanum with eight kind of amino acids according to 1∶1 and 1∶2 in proportion have been determined by titration calorimeter at 298.15 K. The enthalpy change makes a predominant contribution to the stability of these complexes. The ring in amino acid associated with lanthanum ion helps to enhance the stability of complexes. Steric effects between rings in complexes leads to that the equilibrium constants of reaction of the complexes (1∶2) is much less than that of the complexes (1∶1).

Sorption of Pyruvic Acid with Weakly Basic Polymer Sorbents

Uptakes of pyruvic acid for two types of commercially available weakly basic polymer sorbents, D301G and D301R, have been measured over a wide pH range and at various salinities of MgSO4. The results show that the overloading adsorption of pyruvic acid occurs on both weakly basic polymer sorbents, and the overloading models can predict the experimental data of uptake very well. The overloading value for D301G is larger than that for D301R. The adsorption isotherm of pyruvic acid for both polymeric sorbents is greatly affected by the solution pH and MgSO4 concentration in the aqueous phase, and a high recovery efficiency of pyruvic acid from aqueous solution can be obtained at the solution pH around 2.

Removal of 5-Amino-2-chlorotoluene-4-sulfonic and Chlorhydric Acids from Wastewater by Weakly Basic Resin

This research deals with an investigation of the adsorption of two acids, namely, 5-amino- 2-chlorotoluene-4-sulfonic and chlorhydric acids from their solution onto weakly basic resin. The screening of res-ins, kinetics, and isotherm were studied. The results indicate that the D301R is more appropriate for the removal of acids from solution. The adsorption of acids obeys Langmuir isotherm and the first-order kinetics model. Sorptive affinity of the two acids on D301R was found to be in the order of 5-amino-2-chlorotoluene-4-sulfonic acid> chlorhydric acid. Thermodynamic parameters for the adsorption of acids were calculated and discussed. The maxi-mum removal of acids was observed around 97% and 76% at 25℃ for 5-amino-2-chlorotoluene-4-sulfonic acid and chlorhydric acid , respectively.

Adsorption of β-naphthalenesulfonic acid/sulfuric acid from their solution by weakly basic resin:equilibrium

Experiments for single and bisolute competitive adsorption were carried out to investigate the adsorption behavior of β-naphthalenesulfonic acid(NSA) and sulfuric acid (H_2SO_4) from their solution at 25℃ onto weakly basic resin D301R. Adsorption affinity of sulfuric acid on D301R was found to be much higher than that of NSA. The data of single-solute adsorption were fitted to the Langmuir model and the Freundlich adsorption model. The ideal adsorbed solution theory(IAST) coupled with the single-solute adsorption models were used to predict the bisolute competitive adsorption equilibria. The IAST coupled with the Langmuir and the Freundlich model for sulfuric acid and NSA, respectively, yields the favorable representation of the bisolute competitive adsorption behavior.

Adsorption of β-Naphthalenesulfonic Acid/Sulfuric Acid from Their Solution by Weakly Basic Resin

Experiments for single and bisolute competitive adsorption were carried out to investigate the adsorption behavior of /3-naphthalenesulfonic acid (NSA) and sulfuric acid from their solution at 25C onto weakly basic resin D301R. Adsorption affinity of sulfuric acid on D301R was found to be much higher than that of NSA. The data of single-solute adsorption were fitted to the Langmuir model and the Preundlich adsorption model. The ideal adsorbed solution theory (IAST) coupled with the single-solute adsorption models were used to predict the bisolute competitive adsorption equilibria. The IAST coupled with the Langmuir and the Freundlich model for sulfuric acid and NSA, respectively, yields the favorable representation of the bisolute competitive adsorption behavior.

Extraction Mechanism of Rare Earths with Sec-Octylphenoxy Acetic Acid by Two-Phase Titration Technique

The compositions of the extracted complexes of La, Gd, Er and Y with sec octyl phenoxy acetic acid in heptane and the related apparent extraction equilibrium constants K M were determined using two phase titration technique. The stoichiometric compounds for La, Gd, Er and Y should be LaA 3·2.5HA, GdA 3·3HA, ErA 3·3.1HA and YA 3·4.3HA respectively. And their p K M are 3.43, 3.46, 3.08 and 2.58 respectively.

Adsorption of Pb^(2+) on macroporous weak acid adsorbent resin from aqueous solutions: Batch and column studies

The adsorption properties of a novel macroporous weak acid resin （D152） for Pb^2＋ were investigated with chemical methods. The optimal adsorption condition of D152 resin for Pb^2＋ is at pH 6.00 in HAc-NaAc medium. The statically saturated adsorption capacity is 527 mg/g at 298 K. Pb^2＋ adsorbed on D152 resin can be eluted with 0.05 mol/L HCI quantitatively. The adsorption rate constants determined under various temperatures are k288 n=2.22×10-5 s^-1, k298 K=2.51 × 10^-5 s^-1, and k308 K= 2.95 × 10^-5 s^-1, respectively. The apparent activation energy, Ea is 10.5 kJ/mol, and the adsorption parameters of thermodynamics are ΔH^Θ=13.3 kJ/mol, ΔS^Θ=119 J/（mol·K）, and ΔG^Θ298 K =-22.2 kJ/mol, respectively. The adsorption behavior of D152 resin for Pb^2＋ follows Langmuir model.

THERMODYNAMIC STUDY ON ADSORPTION OF AROMATIC SULFONIC ACIDS ONTO MACROPOROUS WEAK BASE ANION EXCHANGER FROM AQUEOUS SOLUTIONS

The adsorption equilibrium isotherms of three aromatic sulfonic acid compounds, 2-naphthalenesulfonic acid, p-toluenesulfonic acid and p-chlorobenzenesulfonic acid, from aqueous solutions by macroporous weak base anion exchanger within the temperature range of 293 K-313 K were obtained. Several isotherm equations were correlated with the equilibrium data, and the experimental data was found to fit the three-parameter Redlich-Peterson equation best within the entire range of concentrations. The study showed that the hydrophobicity of solute has distinct influence on adsorption capacity of the anion exchanger for the aromatic sulfonic acid. Moreover, estimations of the isosteric enthalpy, free energy, and entropy change of adsorption were also reported. The positive isosteric enthalpy and entropy change for adsorption indicate an endothermic and entropy driven process in the present study.

Interaction of Ca^(2+) and soil humic acid characterized by a joint experimental platform of potentiometric titration, UV–visible spectroscopy, and fluorescence spectroscopy

Rocky desertification has become a major environmental issue in the karst region of southwestern China.Karst rocky desertification was more severe in regions of limestone soil than in adjacent regions of other soils,despite the relatively higher soil organic matter(SOM)content in limestone soil.The underlying mechanism remains ambiguous.We speculated that the geochemical characteristics of limestone soils in the karst region plays an essential role,especially the high calcium content of limestone soil.To test this hypothesis,we collected limestone soil samples from a limestone soil profile in the southwestern China karst region and extracted humic acid(HA)from these limestone soil samples.We investigated the interaction of Ca^(2+)and three HA samples on a joint experimental platform,which consists of an automatic potentiometric titrator,a UV–visible spectrometer,and a Fluorescence spectrometer.HA solutions were titrated by Ca^(2+)and optical spectra of the HA solutions were monitored during the titration experiments.The results indicated that:(1)the interaction of Ca^(2+)and HA is a combined process of adsorption and complexation.Adsorption dominated the overall distribution behavior of Ca^(2+),which could be fit by Langmuir and Freundlich isotherm models.Complexation was distinguished only when the concentration of Ca2+is low;(2)the changes of UV–visible spectroscopy and excitation–emission matrix fluorescencespectroscopy spectra of HA samples when they were binding with Ca^(2+)implied the apparent molecular size and structure of HA became larger and more complex;(3)the combination of Ca^(2+)and HA plays an important role in the SOM preservation of limestone soils but the stability of the Ca–HA association was relatively weak.The present study draws attention to maintaining the relatively higher Ca^(2+)concentration in limestone soils in ecologic restoration attempts in karst regions.

Determination of Formation Constants of Co￣(2+), Ni￣(2+),Cu￣(2+) and Zn￣(2+) Complexes with Humic and Fulvic Acidsby Potentiometric Titration Method

The formation constants of Co￣(2+), Ni￣(2+), Cu￣(2+) and Zn￣(2+) complexes with humic acid (HA) and fulvicacid (FA) in red soil were determined by the potentiometric titration method. The constants as a functionof composition of the complexation solutions were obtained by two graphical approaches respectively Theformation constants decreased with increasing concentration of metal in the solution. The results provideunambiguous evidence for the heterogeneity of the function groups of humic substances. The formationconstants of FA were much smaller than those of HA, and the formation constants of Cu￣(2+) were muchgreater than those of Co￣(2+) , Ni￣(2+) and Zn￣(2+) . The potentiometric titration method for determining formationconstants are also discussed in the article.

Determination of pKa values of alendronate sodium in aqueous solution by piecewise linear regression based on acid-base potentiometric titration

As a mono-sodium salt form of alendronic acid,alendronate sodium presents multi-level ionization for the dissociation of its four hydroxyl groups.The dissociation constants of alendronate sodium were determined in this work by studying the piecewise linear relationship between volume of titrant and p H value based on acidbase potentiometric titration reaction.The distribution curves of alendronate sodium were drawn according to the determined p Ka values.There were 4 dissociation constants(pKa_1=2.43,pKa_2=7.55,pKa_3=10.80,pKa_4=11.99,respectively) of alendronate sodium,and 12 existing forms,of which 4 could be ignored,existing in different p H environments.

Adsorption behavior of gel-type weak acid resin (110-H) for Pb^(2+)

The adsorption properties of a novel gel-type weak acid resin (110-H) for Pb2+ were investigated using chemical methods and IR spectrometry.The optimal adsorption condition of 110-H for Pb2+ is at pH=6.49 in HAc-NaAc medium and the statically saturated adsorption capacity is 485 mg/g at 298 K.Pb2+ adsorbed on 110-H resin can be eluted with 0.025 mol/L HCl quantificationally.The adsorption rate constants determined under the temperatures of 288,298,308 and 318 K are 2.46×10-5,3.82×10-5,4.46×10-5 and 5.71×10-5 s-1,respectively.The apparent activation energy,Ea,is 18.1 kJ/mol and the thermodynamic parameters of adsorption,ΔH=20.9 kJ/mol,ΔS=161 J/(mol.K) and ΔG298 K =-48.0 kJ/mol,respectively.The adsorption behavior of 110-H resin for Pb2+ accords with the Langmuir isotherm.Infrared spectra show that the oxygen atoms of the functional group of resin coordinate with Pb2+ to form the coordination bands.

Determination of Surface pKa of Pure Mercaptoacetic Acid and 2-Mercaptobenzothiazole Mixed Monolayers by Impedance Titration

Interfacial proton transfer reactions of pure mercaptoacetic acid (MA) and 2-mercaptobenzothiazole (Mbz) mixed self-assembled monolayers (SAMs) have been studied using a.c. impedance titration method. The charge-transfer resistance (Rct,) is measured with the monolayer composition and the ionic strength of pH solution. The surface pKa can be obtained by the plots of Rct and pH, the reasons of shifts of surface pKa are also explained.

Removal of 5-Amino-2-chlorotoluene-4-sulfonic and Chlorhydric Acids From Wastewater by Weakly Basic Resin: Equilibrium and Kinetics

Objective To study the adsorption of 5-Amino-2-chlorotoluene-4-sulfonic (CLT) and chlorhydric (HCl) acids from wastewater by weakly basic resin. Methods The kinetics and isotherm were studied. Thermodynamic parameters for the adsorption of acids were calculated and discussed. Results The adsorption of CLT and HCl acids followed Langmuir isotherm and the first-order kinetics model. Conclusion The adsorptive affinity of the two acids on D301R is in the order of CLT acid 〉 HCl acid. CLT and HCl acids can be separated.

The “Overlapping Equilibria” Effect in the Processes of the Electrolytic Dissociation of Weak Multibasic Organic Acids

The “overlapping equilibria” effect observed in the processes of electrolytic dissociation of many weak multibasic organic acids determines the character of these processes. In this communication, the degree of “overlapping equilibria” in case of weak dibasic organic acids is quantitatively characterized by the values of “partial” degree of dissociation for second step and ratio of the concentrations of dianion and monoanion. It has been shown that these dissociation parameters are directly connected with the values of the second dissociation constant. It has been also shown that the contribution of third dissociation step in the “overlapping equilibria” effect is especially appreciable in case of penta and hexabasic weak organic acids causing the double “overlapping” phenomenon.

New Method for the Determination of Ionization Constants of Polyprotic Weak Acid

A new method for the determination of ionization constants of polyprotic weak acids is presented. Based on dissociation equilibrium,mass balance and charge balance, the mathematic model is established and the non linear least squares Gauss Newton method is applied to numerically solve the model equations. In order to get the concentration of hydrogen ion, the Debye Hückel equation is used to calculate its activity coefficient. The ionization constants of H 2SO 3 and H 2C 2O 4 obtained by this method are in good agreement with the literature values.