Complexes, measurement with electrodes

Table 2.5. ASSOCIATION CONSTANTS OF ATP AND ADP COMPLEXES MEASURED WITH lON-SELECnVE ELECTRODES AT 25 C AND ZERO IONIC STRENGTH...

Situation Suppose a (monovalent) ionic species is to be measured in an aqueous matrix containing modifiers direct calibration with pure solutions of the ion (say, as its chloride salt) are viewed with suspicion because modifier/ion complexation and modifier/electrode interactions are a definite possibility. The analyst therefore opts for a standard addition technique using an ion-selective electrode. He intends to run a simulation to get a feeling for the numbers and interactions to expect. The following assumptions are made ... 

The Department of the Environment UK [155] has described a number of alternative methods for the determination of total oxidised nitrogen (nitrate and nitrite) in aqueous solution, while specific methods for nitrate and nitrite are also included. Among the methods for total oxidised nitrogen, one is based on the use of Devarda s alloy for reduction of nitrate to ammonia, and another uses copperised cadmium wire for reducing nitrate to nitrite, which is determined spectrophotometrically. Nitrate may also be determined spectrophotometrically after complex formation with sulfosalicylic acid or following reduction to ammonia, the ammonia is eliminated by distillation and determined titrimetrically. Other methods include direct nitrate determination by ultraviolet spectrophotometry, measurements being made at 210 nm, and the use of a nitrate-selective electrode. Details of the scope, limits of detection, and preferred applications of the methods are given in each case. 

A sensitive assay for lipid hydroperoxides is afforded by prostaglandin endoperoxide synthase, that in the presence of hydroperoxides is activated to liberate O2, which is measured with an oxygen electrode . Although it may be of advantage in certain cases, the procedure seems too complex to become of widespread application in practical analysis. 

Lobacz et al. [52] have described partial adsorption ofTl+-cryptand (2,2,2) complex on mercury electrode. From voltocoulom-etry, cyclic voltammetry, and chrono-coulometry, it has been deduced that electroreduction of this complex proceeds via two parallel pathways from the solution and from the adsorbed states, which are energetically close. Also, Damaskin and coworkers [53] have studied adsorption of the complexes of alkali metal cations with cryptand (2,2,2) using differential capacity measurements and a stationary drop electrode. It has been found that these complexes exhibit strong adsorption properties. Novotny etal. [54] have studied interfacial activity and adsorptive accumulation of U02 " "-cupferron and UO2 - chloranilic acid complexes on mercury electrodes at various potentials in 0.1 M acetate buffer of pH 4.6 and 0.1 M NaCl04, respectively. 

Instruments are offered in the market for clinical determination of electrolytes in blood, plasma or serum. One of them, for example, carries out simultaneous determinations of Na, K, Ca, Mg, hematocrit and pH. The cations are of the free type (see Section m.A) and are measured with specific ion-selective electrodes. In complex matrices such as blood or its derived fractions the concentration of free Ca and Mg is affected by the pH of the solution, for example, a slight change of pH will produce or neutralize anionic sites in the proteins, binding or releasing these cations furthermore, the response of the Mg-selective electrode is also affected by the concentration of free Ca(II). The correction... 

An ion-selective electrode responds to the activity of free analyte, not complexed analyte. For example, when the Pb2+ in tap water at pH 8 was measured with a sensitive ion-selective electrode, the result was [Pb2+] = 2 X 10 10 M.25 When lead in the same tap water was measured by inductively coupled plasma-mass spectrometry (Section 21-6), the result was more than 10 times greater 3 X 10-9M. The discrepancy arose because the inductively coupled plasma measures all lead and the ion-selective electrode measures free Pb2+. In tap water at pH 8, much of the lead is complexed by CO -, OH, and other anions. When the pH of tap water was adjusted to 4, Pb2+ dissociated from its complexes and the concentration indicated by the ion-selective electrode was 3 X 10-9M—equal to that measured by inductively coupled plasma. 

The concentrations of HCO3" and CO32 may be obtained from acidimetric titrations. It is sometimes best to avoid this procedure, however, since the presence of hydroxo or carbonato complexes may cause serious difficulties. We conclude that determining Ksa is most convenient since Pco2 can be fixed and [H+] is available from measurements with a glass electrode. 

In the previous papers(12,13), we reported on the vessel access type, i.e. tubular type, glucose sensor. It consisted of a glucose electrode system with a GOX enzyme immobilized Nylon membrane and a glucose semipermeable membrane, and a reference oxygen electrode system. The sensor could directly measure up to 700 mg/dl of BGL in an arterial blood stream when it was placed into an external A-V shunt. This sensor, however, has some problems such as thrombus during in vivo testing without heparin and clinical complexity associated with implanting the sensor in a blood stream. 

In 1932, Jannik Bjerrums) started work on ammonia complexes of copper(l) and Cu(II). Some of the results were obtained with more direct techniques, such as measurement of the ammonia vapour pressure over the solution, or solubility of weakly soluble salts in various supernatant solutions. However, most of the work involved determination of the free concentration of ammonia [NH3 ] via measurements with a glass electrode of... 

It is worth comparing these locally obtained values with the effective conductivity creff of the same sample measured in a conventional setup. A measurement with macrosopic electrodes yields one semicircle in the complex impedance plane and an effective conductivity of 42 10 9 ft 1 cm-1. According to the brick layer model for... 

The nitrate ion activities in the aqueous phase were measured with a nitrate ion selective electrode taking into account the presence of high hydrogen ion concentration by calibration of the nitrate electrode with nitric acid. The nitrate ion concentration in the organic phase owing to the extraction of neodymium complexes by HDEHP was determined by back-extraction of the organic phase with 3M sulfuric acid, dilution, and analysis with a nitrate ion electrode calibrated for different nitrate and sulfate concentrations. The amount of the nitrate species extracted into the organic phase increases as the initial neodymium nitrate concentration increases. 

Potentiostats did not become commercially available until the late 1950s. Most earlier work was conducted either galvanostatically or potentiostatically, but with a two-electrode cell, in which one electrode served as both counter and reference electrode. Because of their complexity, potentiostats tend to have slower response times than galvanostats. It should be pointed out, though, that some of the limitations of potentiostats alluded to above are a matter of the past. With present day (1993) electronic components, it is possible to build home-made potentiostats, or to purchase commercial units, that make use of all the inherent advantages of potentiostatic measurements with little instrumental limitation, or none. 

Recently, Feldmann and Melroy [131] utilized a quartz microbalance technique to simultaneously determine the net current and the partial anodic and cathodic currents in a single complete electroless copper bath. The cathodic current is calculated by converting the deposition rate measured with the microbalance into the unit of current, while the anodic current is computed by subtracting the cathodic current from the net current measured directly on the microbalance electrode. Using this technique, Feldmann and Melroy showed that the potential at which the reduction of the Cu-EDTA complex begins at 70 °C shifts by as much as 0.3 V in positive direction upon addition of formaldehyde. It was also shown that at a given potential, the rate of copper deposition increases with increasing formaldehyde concentration (Fig. 23). The observed catalytic effect of formaldehyde is attributed to an interaction between formaldehyde and the Cu-EDTA complex, possibly to the formation of Cu(EDTA)/formaldehyde complex. However, the detailed mechanism of this catalytic effect has not been clarified. 

Figure 8.18. Measured redox potentials in a deep groundwater. Experimental values of the measured redox potentials (recalculated to the standard hydrogen electrode scale) versus (3pH + log[Fe ]). The concentration of [Fe J has been obtained from the analytical determinations by correction for the complex formation with carbonate. The notation refers to the different test sites. The full-drawn line has been calculated using the selected value of the standard potential E. The straight line has the theoretical Nemstian slope of +0.056 V, at the temperature of measurements. (Adapted from Grenthe et al., 1992.)...

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