Precipitation titration, conductance

We now turn our attention to details of precipitation titrations as an illustration of principles that underlie all titrations. We first study how concentrations of analyte and titrant vary during a titration and then derive equations that can be used to predict titration curves. One reason to calculate titration curves is to understand the chemistry that occurs during titrations. A second reason is to learn how experimental control can be exerted to influence the quality of an analytical titration. For example, certain titrations conducted at the wrong pH could give no discernible end point. In precipitation titrations, the concentrations of analyte and titrant and the size of Ksp influence the sharpness of the end point. For acid-base titrations (Chapter 11) and oxidation-reduction titrations (Chapter 16). the theoretical titration curve enables us to choose an appropriate indicator. 

The use of ISEs with ion-selective membranes based on plasticized PVC, as well as glass pH electrodes, is limited to the analysis of aqueous solutions. On the other hand, sensors based on conducting polymer membranes are usually insoluble in organic solvents, which extends the range of possible applications. Electrosynthesized polypyrrole doped with calcion works as a Ca2+ sensor that can be applied as indicator electrode in the titration of Ca2+ with NaF in mixed solvents, such as water-methanol (1 1) and water-ethanol (1 1) [52], Another example is the use of polyaniline as indicator electrode in order to follow the acid-base precipitation titration of trimeprazine base with tartaric acid in isopropanol solution (see Procedure 5). 

Salts are the products of the acid-base neutralisation reaction. The salts used most in textile wet processes are common salt (NaCl, sodium chloride) and Glauber s salt (Na SO, sodium sulphate). The content analysis of salts is usually conducted by using a precipitation titration method which may be followed by fdtering and weighing procedures to obtain the final results. 

Industrial grade NaCl has a content of 92-98%. The precipitation titration can be conducted using 0.1 N AgNO, as the titrant and 5% K,Ci<) as the indicator (the Mohr method). The sample chloride solution should be buffered with calcium carbonate to a pH between 6.3 and 7.2 in order to avoid any interference from other... 

A second method which is now probably the most widely used method in the Pediatric Laboratory is to use amperometric titration. In this connection, a constant current flows through the solution. The silver dissolves and reacts stolchlometrlcally with chloride, precipitating silver chloride. When all of the chloride has reacted, there is a sharp increase in conductivity which is read as an end point. This instrument, therefore, measures the amount of time a current flows. Instruments are now available for which 5 microliters can be used routinely, rapidly, titration being of the order of about 20 seconds. 

In principle, any type of titration can be carried out conductometrically provided that during the titration a substantial change in conductance takes place before and/or after the equivalence point. This condition can be easily fulfilled in acid-base, precipitation and complex-formation titrations and also the corresponding displacement titrations, e.g., a salt of a weak acid reacting with a strong acid or a metal in a fairly stable complex reacting with an anion to yield a very stable complex. However, for redox titrations such a condition is rarely met. 

Conductometric titrations. Van Meurs and Dahmen25-30,31 showed that these titrations are theoretically of great value in understanding the ionics in non-aqueous solutions (see pp. 250-251) in practice they are of limited application compared with the more selective potentiometric titrations, as a consequence of the low mobilities and the mutually less different equivalent conductivities of the ions in the media concerned. The latter statement is illustrated by Table 4.7108, giving the equivalent conductivities at infinite dilution at 25° C of the H ion and of the other ions (see also Table 2.2 for aqueous solutions). However, in practice conductometric titrations can still be useful, e.g., (i) when a Lewis acid-base titration does not foresee a well defined potential jump at an indicator electrode, or (ii) when precipitations on the indicator electrode hamper its potentiometric functioning. 

A prerequisite for a precise and accurate titration is the reproducible identification of an end point which either coincides with the stoichiometric point of the reaction or bears a fixed and measurable relation to it. An end point may be located either by monitoring a property of the titrand which is removed when the stoichiometric point is passed, or a property which can be readily observed when a small excess of the titrant has been added. The most common processes observed in end-point detection are change of colour change of electrical cell potential change of electrical conductivity precipitation or flocculation. (Electrochemical methods are discussed in Chapter 6 precipitation indicators find only limited use.)... 

The electrical conductance of a solution is a measure of its current-carrying capacity and is therefore determined by the total ionic strength. It is a nonspecific property and for this reason direct conductance measurements are of little use unless the solution contains only the electrolyte to be determined or the concentrations of other ionic species in the solution are known. Conductometric titrations, in which the species of interest are converted to non-ionic forms by neutralization, precipitation, etc. are of more value. The equivalence point may be located graphically by plotting the change in conductance as a function of the volume of titrant added. 

Conveniently, the TDS content of public water supplies parallels the total electrolyte concentration, so that both the TDS and total electrolyte concentrations can be gauged, at least approximately, by measuring the conductivity of the water 1.00 fj,S cm-1 corresponds to 0.65 ppm TDS.2 Calcium and magnesium contents were traditionally determined by titration with EDTA4- at pH 10, at which both Ca2+ and Mg2+ are complexed, and then in a fresh sample at pH 12-13, at which Mg(OH)2 precipitates... 

Issa et al. [9] used various metal ions for the volumetric determination of mefenamic acid. Mefenamic acid was precipitated from its neutral alcoholic solution by a standard solution of either silver nitrate, mercurous acetate, or potassium aluminum sulfate. In the argentimetric procedure, residual Ag(I) was titrated with standard NH4SCN. With Hg(OAc)2 or potash alum, the residual metal was determined by adding EDTA and conducting back titration of excess of EDTA with standard Pb(N03)2 using xylenol orange indicator. The applied methods were used for the determination in bulk drug substance, and in its formulations. 

Casciola et al. " also used a solution chemistry technique to produce LiTi r2 c(P04)3 compounds. First, amorphous precipitates of nominal composition, LiTi Zr2 (P04)3 H20, were formed by adding an aqueous solution of ZrOCl2 and TiCl4 to phosphoric acid. The precipitates were dried and placed in a vacuum oven at 150°C to remove HCl fumes. Titration with 1 M LiOH was used to obtain the lithium salts. The samples were crystallized at 9(X)°C in air for various times. For all of the compositions studied, the 300°C conductivity was within the range of 4 x 10 to 3 x 10 " S/cm and no discemable dependence of the conductivity on composition was observed. 

Fig. 12 illustrates the titration of sodium chloride with silver nitrate. After all chloride is precipitated, the addition of excess silver nitrate causes a rapid increase in conductivity. The slope of the initial portion of the curve may be either downward or upward, depending on the relative conductance of the ion being determined and the ion of like charge in the reagent that replaces it. Slow reactions and coprecipitation are sources of difficulty with precipitation and complex-formation titrations. 

The redox titration is carried out using permanganate and oxalic acid. First, a known excess amount of KMnO is added into the sample HCOOH solution, which is adjusted to alkaline pH using Na,CO. prior to the addition of permanganate warm the solution to facilitate the redox reaction then add a known excess amount of oxalic acid solution and a small amount of H,SO, to the mixture to dissolve the precipitated MnO. Excess oxalic acid is back titrated with KMnO. A blank titration should be conducted to determine the background values of the reagents and the water used. 

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