Potentiometric back-titration of sulfate ion using a tetraphenylborate derivative as a titrant and a titrant-sensitive plasticized poly(vinyl chloride) membrane electrode

A potentiometric back-titration method for the determination of sulfate ions using a plasticized poly(vinyl chloride) membrane electrode without added ion-exchanger is described. A solution of a derivative of tetraphenylborate is used as titrant. The method is based on the ion association between an excess of 2-aminoperimidinium added to the sulfate containing sample and the tetraphenylborate derivative in the titrant. The titration end-point is detected as a sharp potential change due to an increase in the concentration of the free tetraphenylborate derivative at the equivalence point. The sharpness of the titration curve at the end-point is compared for two tetraphenylborate derivatives. Good results are obtained with a solution of sodium tetrakis (4-fluorophenyl) borate.     

End-point detection of the potentiometric titration of anionic polyelectrolytes using an anionic surfactant-selective plasticized poly (vinyl chloride) membrane electrode and an anionic surfactant as a marker ion

A plasticized poly (vinyl chloride) (PVC) membrane electrode sensitive to dodecylbenzenesulfonate (DBS) ion is applied to the determination of anionic polyelectrolytes such as potassium poly (vinyl sulfate) (PVSK) by potentiometric titration, using a poly (diallyldimethylammonium chloride) (Cat-floc) solution as a titrant. The end-point of the titration is detected as the potential jump of the plasticized PVC membrane electrode caused by decrease in the concentration of DBS ion added to the sample solution as a marker ion, due to the ion association reaction between the DBS ion and Cat-floc. The effects of the concentration of DBS ion, coexisting surfactants and electrolytes in the sample solution and pH of the sample on the degree of the potential jump at the end-point were examined. A linear relationship between the concentration of anionic polyelectrolyte and the end-point volume of the titrant exists in the concentration range from 2 × 10^–5 to 4 × 10^–4 N for PVSK, alginate, and carrageenan. Received: 30 April 1998 / Revised: 6 July 1998 / Accepted: 11 August 1998     

Determination of sulfate ion by potentiometric back-titration using sodium tetrakis (4-fluorophenyl) borate as a titrant and a titrant-sensitive electrode

A potentiometric back-titration method for the determination of sulfate ions using a plasticized poly(vinyl chloride) membrane electrode sensitive to a titrant is described. The method is based on ion association between the excess of 2-aminoperimidinium added to the sulfate ion in the sample and sodium tetrakis (4-fluorophenyl) borate (FPB) in the titrant. The titration end-point was detected as a sharp potential change due to an increase in the concentration of the free FPB at the equivalence point. The end-point was detected even in the presence of a 20-fold excess of common cations and anions relative to the concentration of the sulfate ion within approximately 2% of titration error. A linear relationship between the concentration of the sulfate ion and the end-point volume of the titrant exists in the sulfate ion concentration range from 2x10(-4) to 3x10(-3) mol l(-1) using 10(-2) mol l(-1) FPB solutions as the titrant. The present method could be applied to determine sulfate ions in sea water.     

Stalagmometric titrations

End-point detection in some precipitation titrations is achieved by measurement of the surface tension between mercury and the solution ("stalagmometric" titration). The drop-time of a polarographic dropping mercury electrode in open circuit is plotted against volume of surface-active titrant added, and shows a break or a peak at the end-point. The stalagmometric titration of sodium tetraphenylborate with Zephiramine (tetradecyldimethylbenzylammonium chloride) was satisfactory and made possible the determination of potassium by back-titration. Potassium was also titrated directly with tetraphenylborate and with calcium dipicrylaminate. Sodium dodecylbenzenesulphonate was titrated directly with Zephiramine and the results were compared with those obtained by the p-toluidine method and Epton's method.     

Potentiometric titration of anionic polyelectrolytes using a cationic surfactant solution as a titrant and a titrant-sensitive plasticized poly(vinyl chloride) membrane electrode

A potentiometric titration method for the direct determination of anionic polyelectrolytes using a plasticized poly(vinyl chloride) membrane electrode is described. A cationic surfactant solution is used as titrant. The method is based on ion association between the anionic polyelectrolyte in the sample and the cationic surfactant in the titrant. The end-point is detected as a sharp potential change due to an increase in the concentration of the free cationic surfactant at the equivalence point. The sharpness of the titration curve at the end-point is compared for several cationic surfactants; a solution of stearyltrimethylammonium ion has been found to be superior. Received: 8 October 1996 / Revised: 17 December 1996 / Accepted: 18 December 1996     

Potentiometric titration of anionic polyelectrolytes using a cationic surfactant solution as a titrant and a titrant-sensitive plasticized poly(vinyl chloride) membrane electrode

A potentiometric titration method for the direct determination of anionic polyelectrolytes using a plasticized poly(vinyl chloride) membrane electrode is described. A cationic surfactant solution is used as titrant. The method is based on ion association between the anionic polyelectrolyte in the sample and the cationic surfactant in the titrant. The end-point is detected as a sharp potential change due to an increase in the concentration of the free cationic surfactant at the equivalence point. The sharpness of the titration curve at the end-point is compared for several cationic surfactants; a solution of stearyltrimethylammonium ion has been found to be superior. Received: 8 October 1996 / Revised: 17 December 1996 / Accepted: 18 December 1996     

End-point detection of the potentiometric titration of anionic polyelectrolytes using an anionic surfactant-selective plasticized poly (vinyl chloride) membrane electrode and an anionic surfactant as a marker ion

A plasticized poly (vinyl chloride) (PVC) membrane electrode sensitive to dodecylbenzenesulfonate (DBS) ion is applied to the determination of anionic polyelectrolytes such as potassium poly (vinyl sulfate) (PVSK) by potentiometric titration, using a poly (diallyldimethylammonium chloride) (Cat-floc) solution as a titrant. The end-point of the titration is detected as the potential jump of the plasticized PVC membrane electrode caused by decrease in the concentration of DBS ion added to the sample solution as a marker ion, due to the ion association reaction between the DBS ion and Cat-floc. The effects of the concentration of DBS ion, coexisting surfactants and electrolytes in the sample solution and pH of the sample on the degree of the potential jump at the end-point were examined. A linear relationship between the concentration of anionic polyelectrolyte and the end-point volume of the titrant exists in the concentration range from 2 × 10^–5 to 4 × 10^–4 N for PVSK, alginate, and carrageenan.     

Simple instrument for titrimetry without visual indicators. gasometric titrations: Cerimetry,chlorometry, nitrate,nitrite, hydroxide and carbonate determination

It was shown in previous papers, that many titrimetric problems can be solved by observing the pressure change of a closed system above the solution titrated at the equivalence point. This principle was made the basis of a gasometric titration method in which the end-point is found graphically. The titrant is added to the sample solution in measured increments at fixed intervals of time and the corresponding gas pressure or volume of the system is recorded and then plotted against the volume of added titrant. Half a dozen readings are sufficient to establish the end-point of a titration, which is found at the intersection of two straight lines. This graphical method was applied to cerimetry and chlorometry, as well as to some other analytical reactions (determination of nitrite, nitrate, hydroxide and carbonate) already described in previous papers on the gas pressure end-point technique. The results are comparable in precision and accuracy to the values obtained by the conventional visual end-point titrations. A gasometric titration takes about 10 minutes. The presence of other substances in the sample capable of reacting with the titrant does not necessarily cause interference.     

Simple instrument for titrimetry without visual indicators. Gasometric titrations: Dichromatometry

Even ions which do not release gases with a certain titrant can be determined by direct gasometric titration. To achive this end, a substance which liberates a gas with the titrant, must be added to the sample solution. The end-point of the main reaction can be read from the gasometric titration curve of this indicator substance.This principle is applied in the present paper to the titration of ferrous and stannous ions by potassium dichromate. Hydrazine sulfate serves as indicator. The results are comparable in precision and accuracy to the values obtained by the conventional visual end-point titrations.     

Effect of hydrophobicity of marker anions on the sensitivity of end-point detection for potentiometric titrations of anionic polyelectrolytes

A potentiometric titration method is described for the determination of anionic polyelectrolytes using a marker anion and a plasticized poly (vinyl chloride) membrane electrode sensitive to this marker anion. A solution of an anionic polyelectrolyte, such as potassium poly (vinyl sulfate) (PVSK) added the marker ion has been titrated with a solution of poly (diallyldimethylammonium chloride) (Cat-floc). The end-point has been detected as a sharp potential change due to the rapid decrease in the concentration of the marker ion caused by its association with the titrant, Cat-floc. The sharpness of the endpoint of the titration curve has been compared for several marker ions and the dodecylbenzenesulfonate ion was found to be the best among the marker anions studied.     

Determination of cationic polyelectrolytes using a photometric titration with crystal violet as a color indicator

The reaction of the cationic dye, crystal violet (CV) with the anionic polyelectrolytes such as potassium poly (vinyl sulfate) (PVSK) results in a decrease of the absorbance of CV at the maximum absorption wavelength (590 nm). This change of the absorption spectra of the CV has been already applied to the determination of anionic polyelectrolytes using flow injection analysis method. In this paper, CV was applied to the indicator for the determination of cationic polyelectrolytes such as poly (diallyldimethylammonium chloride) (Cat-floc) by photometric titration, using a PVSK solution as a titrant. The end-point of the titration is detected as the break point of the titration curve. A linear relationship between the concentration of cationic polyelectrolyte and the end-point volume of the titrant exists in the concentration range from 0 to 5×10⁻⁵ eq. mol dm⁻³ for Cat-floc, glycol chitosan and methylglycol chitosan. The effects of the concentration of CV and coexisting electrolytes in the sample solution and the effect of pH of the sample solution on the degree of the change of absorbance at the end-point were also examined.     

Use of marker ion and cationic surfactant plastic membrane electrode for potentiometric titration of cationic polyelectrolytes

A plasticized poly (vinyl chloride) (PVC) membrane electrode sensitive to stearyltrimethylammonium (STA) ion is applied to the determination of cationic polyelectrolytes such as poly (diallyldimethylammonium chloride) (Cat-floc) by potentiometric titration, using a potassium poly (vinyl sulfate) (PVSK) solution as a titrant. The end-point of the titration is detected as the potential change of the plasticized PVC membrane electrode caused by decrease in the concentration of STA ion added to the sample solution as a marker ion due to the ion association reaction between the STA ion and PVSK. The effects of the concentration of STA ion, coexisting electrolytes in the sample solution and pH of the sample on the degree of the potential change at the end-point were examined. A linear relationship between the concentration of cationic polyelectrolyte and the end-point volume of the titrant exists in the concentration range from 2×10⁻⁵ to 4×10⁻⁴ N for Cat-floc, glycol chitosan, and methylglycol chitosan.     

Determination of cationic surfactants in pharmaceutical disinfectants using a new sensitive potentiometric sensor

A new sensitive potentiometric surfactant sensor was prepared based on a highly lipophilic 1,3-didecyl-2-methyl-imidazolium cation and a tetraphenylborate antagonist ion. This sensor was used as a sensing material and incorporated into the plasticized PVC-membrane. The sensor responded fast and showed a Nernstian response for investigated surfactant cations: cetylpyridinium chloride (CPC), hexadecyltrimethylammonium bromide (CTAB) and Hyamine with slope 59.8, 58.6 and 56.8 mV/decade, respectively. The sensor served as an end-point detector in ion-pair surfactant potentiometric titrations using sodium tetraphenylborate as titrant. Several technical grade cationic surfactants and a few commercial disinfectant products were also titrated, and the results were compared with those obtained from a two-phase standard titration method. The sensor showed satisfactory analytical performances within a pH range of 2-11, and exhibited excellent selectivity performance for CPC compared to all of the organic and inorganic cations investigated. The influence of the nonionic surfactants on the shape of titration curves was negligible if the mass ratio of ethoxylated nonionic surfactants and cationic surfactants (EONS:CS) was not greater than 5.     

A numerical method of finding potentiometric titration end-points by use of approximative spline functions

A new numerical method of determining potentiometric titration end-points is presented. It consists in calculating the coefficients of approximative spline functions describing the experimental data (e.m.f., volume of titrant added). The end-point (the inflection point of the curve) is determined by calculating zero points of the second derivative of the approximative spline function. This spline function, unlike rational spline functions, is free from oscillations and its course is largely independent of random errors in e.m.f. measurements. The proposed method is useful for direct analysis of titration data and especially as a basis for construction of microcomputer-controlled automatic titrators.     

Potentiometric titration of polyhexamethylene biguanide hydrochloride with potassium poly(vinyl sulfate) solution using a cationic surfactant-selective electrode.

A potentiometric titration method using a cationic surfactant as an indicator cation and a plasticized poly(vinyl chloride) membrane electrode sensitive to the cationic surfactant is proposed for the determination of polyhexamethylene biguanide hydrochloride (PHMB-HCl), which is a cationic polyelectrolyte. A sample solution of PHMB-HCl containing an indicator cation (hexadecyltrimethylammonium ion, HTA) was titrated with a standard solution of an anionic polyelectrolyte, potassium poly(vinyl sulfate) (PVSK). The end-point was detected as a sharp potential change due to an abrupt decrease in the concentration of the indicator cation, HTA, which is caused by its association with PVSK. The effects of the concentrations of HTA ion and coexisting electrolytes in the sample solution on the degree of the potential change at the end-point were examined. A linear relationship between the concentration of PHMB-HCl and the end-point volume of the titrant exists in the concentration range from 2.0 x 10(-5) to 4.0 x 10(-4) M in the case that the concentration of HTA is 1.0 x 10(-5) M, and that from 1.0 x 10(-6) to 1.2 x 10(-5) M in the case that the concentration of HTA is 5.0 x 10(-6) M, respectively. The proposed method was applied to the determination of PHMB-HCl in some contact-lens detergents.     

A conductometric method for colloid titrations

A negative or positive colloid sample solution can be directly titrated, respectively, with a polycationic (poly-N, N-diallyldimethylammonium chloride) or polyanionic (potassium polyvinylsulfate) titrant to a conductometric end-point. With the conventional toluidine blue indicator method a positive colloid solution is titrated directly with a polyanionic titrant, but a negative colloid solution must be treated with an excess of a polycationic titrant, which is back-titrated with the polyanionic titrant. For positive colloid solutions, both indicator and conductometric methods are suitable; for negative colloids the conductometric method is preferable because of its constant titration vlues over a range of pH values.     

Ein einfaches verfahren zum bestimmen von hydrosulfit

When titrating hydrosulphite with a neutral solution of ferric chloride, using a mixture of thiocyanate and ferrocyanide as indicator, a deep red coloration of ferric thiocyanate is observed near the end-point of the titration. At the final end-point the solution rapidly turns blue. By this means it is possible to titrate very rapidly and a slight excess of titrant is easily estimated. A preliminary titration gives the approximate quantity of iron to add in the final solution to which the solid hydrosulphite is to be added; as in the final titration there remain only minimal quantities of hydrosulphite, the error due to aerial oxidation is thus completely eliminated. Without the protection of an inert gas and without back-titration it is possible to obtain results with an error less than 0.1 %.     

A new automatic recording titrator and its applications

A new type of automatic recording titrator has been developed. The titrant is added intermittently and the titration curve is recorded stepwise, potential changes being registered in the intervals between deliveries of titrant. The increments of titrant and the intervals can be pre-set, but give the best results if controlled automatically during the titration. The end-point and the volume of titrant consumed are read from the recorded titration curve.     

Mechanism and reaction rate of the karl fischer titration reaction: Part V. Analytical Implications

The Karl Fischer titration procedure for the determination of water has been studied. In view of the results of previous investigations, a methanolic sodium acetate—sulfur dioxide solution is recommended as solvent and an iodine solution in methanol as titrant. The advantages of this procedure over a conventional Karl Fischer titration are: a much more rapidly reacting reagent, the possibility of a visual end-point detection, a titrant of constant titre over a long period of time, and the absence of the disagreeable odour of pyridine.     

浊度滴定法

报道了一种实用的浊度传感器及浊度滴定仪，以及一种利用此仪器检测溶液的浑浊程度（溶液中散射光相对强度）来判断沉淀反应滴定终点的方法。将一束光线通入溶液，在溶液中与其垂直的方向上，利用内置浊度传感器检测散射光相对强度；随着滴定剂的加入，溶液将渐变得浑浊，散射光相对强度逐渐增强。如果沉淀反应完全且溶解度足够小，散射光相对强度将在化学计量点处达最大值，由此可判断滴定终点。以AgNO3溶液滴定NaCl溶液为例俊证了浊度滴定法，结果表明：浊度滴定法样化学指示剂法适用于更低的浓度；在适当的条件下浊度滴定法的精密度和准确度均可＜0.2%。