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.     

Phase titration with clarification end-point

An improved method of phase titration has been developed for the analysis of binary or pseudo-binary systems. A clarification end-point is used in place of the usual cloud end-point. Advantages are that end-points are equally sharp over a wide sample composition range, the titration volume is a very nearly linear function of composition so that often only one calibration point is needed, and the technique can be extended to cover the entire binary composition range.     

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.     

End-point construction and systematic titration error in linear titration curves-precipitation reactions

The systematic titration error which is introduced by the intersection of tangents to hyperbolic titration curves is discussed for precipitation reactions. A simple expression for the systematic titration error is derived, and S/C_x² is proposed as a measure of the sharpness of the titration curve. The effects of the conditional solubility product (S), the concentration of the unknown component (C_x), and the ranges used for the construction of the end-point, are considered. A graphical method is presented for the selection of pairs of ranges which result in small systematic titration errors. For equal values of S/C_x² and 1/KC_x, the optimum combinations of ranges are different for precipitation and complexation titrations. The differences are not large for values smaller than about 0.002. For titration curves with a reversed L-shape, the error is calculated when the end-point is constructed by the intersection of the tangent to the second branch of the curve with volume axis; in this case equal ranges result in the same titration error for equal values of S/C_x² and 1/KC_x. The systematic titration error is equal to -S/C_x² when the tangent to the curve is taken at f_a = 3.0.     

A new approach to flow-batch titration. A monosegmented flow titrator with coulometric reagent generation and potentiometric or biamperometric detection

Monosegmented flow analysis (MSFA) has been used as a flow-batch system to produce a simple, robust, and mechanized titrator that enables true titrations to be performed without the use of standards. This paper also introduces the use of coulometry with monosegmented titration by proposing a versatile flow cell. Coulometric generation of the titrand is attractive for titrations performed in monosegmented systems, because the reagent can be added without increasing the volume of sample injected. Also, biamperomeric and potentiometric detection of titration end-points can increase the versatility of the monosegmented titrator. The cell integrates coulometric generation of the titrand with detection of end-point by potentiometry or biamperometry. The resulting titrator is a flow-batch system in which the liquid monosegment, constrained by the interfaces of the gaseous carrier stream, plays the role of a sample of known volume to be titrated. The system has been used for determination of ascorbic acid, by coulometric generation of I₂ with biamperometric detection, and for determination of Fe(II), by coulometric generation of Ce(IV) with potentiometric detection of the end-point, both in feed supplements.     

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.     

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

A new numerical method of determining the position of the inflection point of a potentiometric titration curve is presented. It consists of describing the experimental data (emf, volume data-points) by means of a rational spline function. The co-ordinates of the titration end-point are determined by analysis of the first and second derivatives of the spline function formed. The method also allows analysis of distorted titration curves which cannot be interpreted by Gran's or other computational methods.     

滴定分析的终点误差随待测物浓度及反应平衡常数单调变化之商榷

为了获得滴定分析的终点误差随待测物浓度、反应平衡常数这两个因素变化的准确规律,推导了有别于林邦终点误差公式的终点误差计算式,根据该式可以判断每个因素对计算结果的影响,结合在配位滴定分析和酸碱滴定分析的具体应用,结果发现：这两个因素其大小的变化不会一定导致终点误差绝对值的单调变化。     

A novel titration technique for the analysis of streamed samples — the triangle-programmed titration technique : Part 3. Titrations with Electrically Generated Bromine

The triangle-programmed titration technique brings together the advantages of flow-through techniques and titration methods. Titrations with bromine prepared by current-programmed electrolysis are reported; suitable instrumentation is described for biamperometric end-point indication. The electrode processes and the effects of different parameters of the reagent addition program are discussed. The applicability of the method to organic and inorganic substances is described. The technique is applicable to flowing sample solutions of small volume, and the rate of analysis is similar to that achieved with other semi-automated analyzers.     

Photometric titration of iron with ethylenediaminedi(o-hydroxyphenylacetic acid)

Fractional mg quantities of ferric iron in 100 ml of solution can be titrated at PH 3.5 with a solution of ethylenediaminedi(o-hydroxyphenylacetic acid). The end-point is found photo- metrically. Errors are generally under 1%, and a number of metals do not interfere. By scaling down the volume of the solution and the titrant concentration, the titration can be extended to μg quantities of iron, and mg quantities are also accessible by changing to a wave length where the sensitivity is not so great. The titration may be useful in certain applications.     

Amperometric titration of copper with tetraethylenepentamine

Tetraethylenepentamine is a very selective titrant for the determination of copper in acidic medium. With amperometric end-point detection as little as 0.1 mg copper in a volume of 25 ml can, be determined with an accuracy of ± 1%. When the titration is performed in acetic acid/ ammonium acetate buffer of pH 4.1, only mercury causes significant interference.     

示波电导滴定

通常的电导滴定用电导仪测量滴定过程中溶液电导率的变化;以电导值对滴定剂体积作图,将两条直线外推,其交点为等当点。本文提出的示波电导滴定法,利用示波图的突然收缩或扩张指示滴定终点,简便快速,终点直观,适用于各类滴定反应。 1 原理 当交流电源输出电压为V=V_0sinωt,交流电频率较高,溶液浓度较稀时,“E～t”曲线与“i～t”曲线的相位差接近0°,电解池的阻抗接近纯电阻。若溶液电阻为R_L、外加电阻为R_0,则流     

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.     

Application of Polyaniline Incorporated Carbon Particles Coated Platinum Electrode in Coulometric Titration to Determination of Polyisoprene Alcohol

The feasibility of using electrodes modified with polyaniline incorporated carbon particles films for im-proving the precision of coulometric titration is demonstrated. The problem of large deviation produced dur-ing determining polyisoprene by coulometric titration with direct titration technique (double Pt electrodes indi-cating electrode) has been solved. In the titration process, polyisoprene alcohol, an electro-inactive species, is adsorbed on the surface of the bare Pt electrode, which inhibits the electrode reaction of Br- and Br2. Therefore, when the titration reaches the end-point, the detected current will slowly change with time, which can make the repeatability of end-point poor, The atomic force microscopic images show the morpholo-gy of the electrode surface of adsorbing polyisoprene alcohol. The application of the chemically modified elec-trode instead of the bare Pt electrode to indicating the end-point has been investigated. The results show that the Pt electrode coated with polyaniline incorporated carbon particles films is an excellent indicator electrode. This electrode has advantages that the indicating signals are sharp and repeatable at end-point. The precisionand the accuracy of the determination of polvisoprene alcohol are satisfactory.     

Use of a Tensammetric Wave for the End-Point Detection in Chelatometry

Abstract

A new method for the end-point detection in complexometric titration using a tensammetric wave of organic reagents such as oxine and alizarin complexone (ALC) was studied. The tensammetric wave of these reagents disappears by their chelate formation and reappears by the liberation of free indicator during the exchange reaction between indicator chelate and EDTA. This mechanism is utilized for the end-point detection in complexometric titration of metals. Since the sensitivity of tensammetric wave is extremely high, very sharp end-point can be obtained for the titration of metals even in the concentration of 10^?5M.     

交流示波极谱法中电流—电位曲线的研究——Ⅲ.电流-电位曲线示波极谱络合滴定法

利用交流示波极谱法中i_f-E曲线来指示滴定终点的容量分析方法,叫做i_f-E曲线示波极谱滴定法。本文研究i_f-E曲线示波极谱络合滴定法。     

液体推进剂偏二甲肼自动电位滴定分析方法的建立

设计了Metrohm809型自动电位滴定仪分析液体推进剂偏二甲肼的应用程序,解决了程序设计中滴定模式和终点确定方式选择、滴定速度确定等关键性技术问题,考察了环境温度对分析结果的影响,确定了最佳条件,实现了液体推进剂偏二甲肼的自动电位滴定分析。重复性试验和准确度试验表明,自动电位滴定法分析偏二甲肼具有准确度高、精密度好等优点,测量结果完全符合GJB753-89的要求：     

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.     

End-point evaluation in instrumental titrimetry-I Linear extrapolation of hyperbolic titration curves

A method is described for the estimation of a systematic titration error which is introduced by linear extrapolation of hyperbolic titration curves in amperometric, photometric, and other instrumental titrations. It is assumed that the titration is based upon a single-step ion-association reaction mA + nB right harpoon over left harpoon A(m)B(n) and that the measured physical property falls within known minimum and maximum values. The procedure is suitable for end-point determination, even when the titration curves have extensive curvature, and for predicting the choice of optimum experimental conditions for a given titration.     

A new and rapid titration of antimony(III) with potassium dichromate, with iron(II) as inductor

The optimum conditions for the titration of antimony(III) with dichromate, and diphenyl-aminesulphonic acid as indicator, have been established. No iodine catalyst is used; the analytical reaction is based on an induced reaction with iron(II) as inductor. The titration can be done as easily as an iron(II) titration and the end-point is equally sharp. Titrations are possible with 0.01N solutions.