Determinations of other ions

Discussion. The mercury is precipitated as mercury(I) chloride and the latter is reacted with standard potassium iodate solution  

To determine the purity of a sample of a mercury(II) salt, the following procedure in which the compound is reduced with phosphorous (phosphonic) acid may be used to assay a sample of a mercury(I) salt, the reduction with phosphorous acid is omitted. 

Procedure. Weigh out accurately about 2.5 g of finely powdered mercury(II) chloride, and dissolve it in 100 mL of water in a graduated flask. Shake well. Transfer 25.0 mL of the solution to a conical flask, add 25 mL water, 2mL 1M hydrochloric acid, and excess of 50 per cent phosphorous(III) acid solution. Stir thoroughly and allow to stand for 12 hours or more. Filter the precipitated mercury(I) chloride through a quantitative filter paper and wash the precipitate moderately with cold water. Transfer the precipitate with the filter paper quantitatively to a 250 mL reagent bottle, add 30 mL concentrated hydrochloric acid, 20 mL water, and 5 mL carbon tetrachloride or chloroform. Titrate the mixture with standard 0.025M potassium iodate in the usual manner (Section 11.127). 

Copper(II) compounds. Many other metallic ions which are capable of undergoing oxidation by potassium iodate can also be determined. Thus, for example, copper(II) compounds can be analysed by precipitation of copper)I) thiocyanate which is titrated with potassium iodate  

7IO 3 + 4CuSCN + 18H + + 7C1 = 7IC1 + 4Cu2 + + 4HSO + 4HCN + 5HzO 

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General kinetic scheme 501 6.2. Trace amount determination of other ions 508... 

In a related type of electrode the membrane is a pressed disc of Ag2S + AgX where X may be Cl , Br , I or SCN and the electrode responds to X . With such a membrane, it is a very low concentration of Ag" ions on both sides of the disc which determines the membrane potential and the selectivity is a function of the solubility product any anion which forms a silver salt with a solubility product lower than the ion being determined will be a serious interference. Hence the electrode responds strongly to Ag and S and for the determination of other ions their presence is catastrophic. Similarly I and Br is a serious interference to the Cl electrode and I to the Br electrode. A electrode (M = Cu, Pb, Cd) may be prepared by making a pellet from a mixture of Ag2S and MS. In these electrodes, the ion activity controls the S activity and thereby the Ag activity and hence the electrode response. The pellet is again positioned in an inert electrode body with epoxy resin. 

Studies using the flow analysis technique for the determination of acetate ions and acetic acid are not very common compared with the development of methodologies for the determination of other ions, such as phosphate and sulfate ions. Details regarding methods not previously mentioned carried out on the determination of acetic acid and acetate ions using FIA can be seen in Table 11.1. 

Especially sensitive and selective potassium and some other ion-selective electrodes employ special complexing agents in their membranes, termed ionophores (discussed in detail on page 445). These substances, which often have cyclic structures, bind alkali metal ions and some other cations in complexes with widely varying stability constants. The membrane of an ion-selective electrode contains the salt of the determined cation with a hydrophobic anion (usually tetraphenylborate) and excess ionophore, so that the cation is mostly bound in the complex in the membrane. It can readily be demonstrated that the membrane potential obeys Eq. (6.3.3). In the presence of interferents, the selectivity coefficient is given approximately by the ratio of the stability constants of the complexes of the two ions with the ionophore. For the determination of potassium ions in the presence of interfering sodium ions, where the ionophore is the cyclic depsipeptide, valinomycin, the selectivity coefficient is Na+ 10"4, so that this electrode can be used to determine potassium ions in the presence of a 104-fold excess of sodium ions. 

Retention of solutes in ion-exchange chromatography is determined by the nature of the sample, the type and concentration of other ions present in the mobile phase, the pH, temperature, and the presence of solvents. Because there are so many variables, it is often not easy to predict what will happen in an ion-exchange separation if we change the experimental conditions. There are some useful guidelines, and to see how they work we will look at the ion-exchange separation of two weak acids (see Fig. 3.3c). 

Several metal ions play a crucial role in biological processes, whereas some others are toxic. Alteration of the metal concentration in the body can often be correlated to disease states. The necessity for in vivo determination of metal ion concentration and distribution has prompted research to develop appropriate metal-responsive MRI contrast agents. 

The scope of CAR-CLS in analytical determinations has been expanded with one other type of CL reaction (luminol-based CL reactions are restricted to direct determinations of metal ions and some indirect ones). The so-called energy transfer CL is one interesting alternative, with a high analytical potential. As stated above, PO-CL systems based on the reaction between an oxalate ester and hydrogen peroxide in the presence of a suitable fluorophore (whether native or derivatized) and an alkaline catalyst are prominent examples of energy transfer CL. This technique has proved a powerful tool for the sensitive (and occasionally selective) determination of fluorophores its implementation via the CAR technique is discussed in detail later. 

The enhanced chemiluminescence associated with the autoxidation of luminol (5-amino-2,3-dihydro-1,4-phthalazinedione) in the presence of trace amounts of iron(II) is being used extensively for selective determination of Fe(II) under natural conditions (149-152). The specificity of the reaction is that iron(II) induces chemiluminescence with 02, but not with H202, which was utilized as an oxidizing agent in the determination of other trace metals. The oxidation of luminol by 02 is often referred to as an iron(II)-catalyzed process but it is not a catalytic reaction in reality because iron(II) is not involved in a redox cycle, rather it is oxidized to iron(III). In other words, the lower oxidation state metal ion should be regarded as a co-substrate in this system. Nevertheless, the reaction deserves attention because it is one of the few cases where a metal ion significantly affects the autoxidation kinetics of a substrate without actually forming a complex with it. 

The voltammetric determination of metal ions in the presence of particles are in principle able to differentiate without prefiltering the water sample between dissolved and labile species, i.e., the metal ions electrochemically available within the diffusion layer and (in addition to other non-labile complexes) those bound to particles and colloids (Gongalves et al., 1985, 1987). 

Molecular probe dyes for the determination of potassium, lithium, and sodium have been identified. Additionally, an NIR probe selective for potassium has been fabricated. The detection limits of this probe are in the ppm range. Lower detection limits may be achieved by varying the matrix which allows the entrapment of ions. Preliminary data for the detection of lead and cadmium demonstrate the potential capability of these probes for environmental applications. The development of OFMP for the detection of other ions of environmental interest such as Be2+, Hg2+, As3+, and Ni2+ is currently underway. 

Other electrodes of the liquid-membrane type can be used for the determination of the ions such as Cl , C104, N03, Cu, Pb " and BF4. ... 

The ISEs described in this section are useful primarily for determination of halide ions by direct potentiometry, where the silver halide in the membrane is identical with the determinand. As follows from the discussion on p. 48 an electrode made of a less soluble silver halide X can be used to determine other halide Y" if the condition... 

Analytical determinations with the fluoride ion-selective electrode These are based either on direct potentiometry of fluorides [37, 84, 85, 88, 430] or on titration determinations of either fluorides or of other ions and also on titrations with fluoride ions as indicator. The advantages of potentiometry with an ISE over other analytical methods for determining fluorides were pointed out by Crosby etai [67], Further comparison studies [42, 56, 191, 433] came to the same conclusions, confirmed also by a study of 16 methods [365]. Fluoride ions are titrated either with La (for concentrations greater than 1 mM) or Th (in the concentration range 0.2-1 mM F ) [13, 102, 103, 113,233, 234]. Titration with fluoride ions can be used for the determination of Al with formation of the AIF4 complex up to nanomolar concentrations, especially in ethanol-water mixtures [25] (see also [267,384]). Precipitation titrations can also be used to determine La, Th and UOJ [241, 384] as well as Li in... 

The effect of fluoride ions on the electrochemical behaviour of a metal zirconium electrode was studied by Pihlar and Cencic in order to develop a sensor for the determination of zirconium ion. Because elemental zirconium is always covered by an oxide layer, the anodic characteristics of a Zr/Zr02 electrode are closely related to the composition of the electrolyte in contact with it. These authors found the fluoride concentration and anodic current density to be proportional in hydrochloric and perchloric acid solutions only. In other electrolytes, the fluoride ion-induced dissolution of elemental zirconium led to an increase in the ZrOj film thickness and hindered mass transport of fluoride through the oxide layer as a result. The... 

Other electrode configurations, such as the radial arrangement consisting of four thin wires placed perpendicularly around the circumference of the separation capillary column, have found less application due to more complicated construction and restriction in space and diameter of the separation capillary [56]. Due to its low cost, robustness, minimal maintenance demands, possibility to be freely moved along the capillary [57], or combined with either UV-absorbance [58] or fluorescence [59] detection, the capacitively coupled contactless conductivity detector has recently gained wide acceptance not only for the determination of inorganic ions but also for biomolecules and organic ions, as it has been recently comprehensively reviewed by Kuban and Hauser [1]. 

The promise of luminescent methodology is based on many types of information that can be derived from mineralogical samples. These include RE from Ce to Yb, identities down to the ppb range, the valence states of the RE, the nature of the sites at which RE reside and the ways of compensating the charge, and features related to the presence of other ions (donors, activators). All this information can be used to determine the chemical, thermal, and deformational history of the material. 

An alternate explanation of the emission intensities of terbium in the presence of other ions was given by Peterson and Bridenbaugh (54), that for europium was given by Axe and Weller (52). These authors point out that resonance exchange is a major factor in determining the emission intensities in these cases. This work has shed some doubt on the necessity of phonon-assisted transfer for the terbium and europium ions in the cases considered by Van Uitert and Iida. 

The exchange of sodium and calcium on clay minerals is of special importance, because it largely determines the ionic form of the clay, which in turn affects the performance of surfactant and polymer floods and the distribution of other ions of interest. In concentrated NaCl environments, clay exists mainly in the sodium form however, at low ionic strength and moderate hardness, clay may be essentially in the calcium form. Measurements with the sodium, calcium, and mixed forms are therefore of interest. 

A wide variety of methods has been used in studies of oligomerization reactions. The most important quantitative method is potentiometric measurement of pH as a function of the total metal concentration and of the concentration of the analytical excess of acid or base. Other quantitative methods which are often used are potentiometric determination of metal ion concentration, calorimetry, spectrophotometry, and ion exchange. These, together with a number of other techniques, have recently been discussed thoroughly by Baes (22). 

Vanadium(II) reacted with SCN- and diphenylguanidine (L) to form a ternary complex with a V SCN L ratio of 1 2 2.176 Other ternary complexes like phenylguanidine iron(II) cyanide are being exploited in titrimetric determination of cyanide ions, for example. 

The glass electrode is so important that it deserves a special section in this book. However, there are other solid-state ISEs that have excellent performance, and one of them is the fluoride-selective electrode. There are only few analytical methods that allow simple and selective determination of fluoride ion. For this reason, the ion-selective electrode is one of the most important analytical tools. Although it was... 

Several metal ions are essential or beneficial to life while others, such as lead, cadmium or mercury, are highly detrimental. Many diseases have been associated in a way or another to altered metal ion concentrations in the body. Deficiencies can be as damaging as overloads. Copper deficiency has been associated to anemia while excess copper can lead to Wilson s disease (liver cirrhosis). Anemia may also be caused by a lack of iron and overload of this same metal ion is connected to thalassemia and siderosis [122]. In vivo determination of metal ion distribution is thus highly desirable and progresses have been made towards the design of MRI contrast agents sensitive to the concentration of metal ions. 

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