Ionic strength adjusting

Another approach to matrix matching, which does not rely on knowing the exact composition of the sample s matrix, is to add a high concentration of inert electrolyte to all samples and standards. If the concentration of added electrolyte is sufficient, any difference between the sample s matrix and that of the standards becomes trivial, and the activity coefficient remains essentially constant. The solution of inert electrolyte added to the sample and standards is called a total ionic strength adjustment buffer (TISAB). 

The total ionic strength adjustment buffer serves several purposes in this procedure. Identify these purposes. 

Fig. 8. Protease washing performance in a U.S. liquid detergent. Grass soiling in a 10 min wash at 30°C with one enzyme dosage, (a) pH profile of commercial proteases A and B. (b) Effect of increasing ionic strength, adjusted with Na2S04, of commercial protease B at (—°—) pH 8 and (- pH 11.

Total Ionic Strength Adjustment Buffer (TISAB). Dissolve 57 mL acetic acid, 58 g sodium chloride and 4g cyclohexane diaminotetra-acetic acid (CDTA) in 500 mL of de-ionised water contained in a large beaker. Stand the beaker inside a water bath fitted with a constant-level device, and place a rubber tube connected to the cold water tap inside the bath. Allow water to flow slowly into the bath and discharge through the constant level this will ensure that in the... 

Ionic strength adjuster buffer 565, 570 Ionisation constants of indicators, 262, (T) 265 of acids and bases, (T) 832, 833, 834 see also Dissociation constants Ionisation suppressant 793 Iron(II), D. of by cerium(IV) ion, (cm) 546 by cerium(IV) sulphate, (ti) 382 by potassium dichromate, (ti) 376 by potassium permanganate, (ti) 368 see also under Iron... 

At 25 °C, and with the ionic strength adjusted to 1.5 M with potassium nitrate, the values of and K2 are 3.76x10 sec and 22.4 l.mole , respectively. At higher concentrations of Cr(VI) an analogous mechanism applies, HCr04 being replaced by Cr207 . No evidence is cited for the formation of As(IV) it seems likely that As(V) and Cr(IV) are formed in the slow step. 

In fact, any type of titration can be carried out potentiometrically provided that an indicator electrode is applied whose potential changes markedly at the equivalence point. As the potential is a selective property of both reactants (titrand and titrant), notwithstanding an appreciable influence by the titration medium [aqueous or non-aqueous, with or without an ISA (ionic strength adjuster) or pH buffer, etc.] on that property, potentiometric titration is far more important than conductometric titration. Moreover, the potentiometric method has greater applicability because it is used not only for acid-base, precipitation, complex-formation and displacement titrations, but also for redox titrations. 

Like nitrate, sulfate is also a constituent of textile processing wastewaters. Sulfate is generally added to the dye baths for ionic strength adjustment or it may be formed by the oxidation of sulfur species used in dyeing processes, such as sulfide, hydrosulfide, and dithionite [37]. 

As with pH measurements, a specific amount of water or ionic strength adjusting solution is added to soil, mixed, and allowed to stand. For some analyses, the resulting solution is filtered to separate the soil from the liquid. 

Total ionic strength adjustment buffers TISABs) are used to equalize Ionic activity n different solutions. 

It is often more convenient to relate the potentiometer reading directly to concentration by adjusting the ionic strength and hence the activity of both the standards and samples to the same value with a large excess of an electrolyte solution which is inert as far as the electrode in use is concerned. Under these conditions the electrode potential is proportional to the concentration of the test ions. The use of such solutions, which are known as TISABs (total ionic strength adjustment buffers), also allows the control of pH and their composition has to be designed for each particular assay and the proportion of buffer to sample must be constant. 

To leam that the change of y with ionic strength is a major cause of error in electroanalytical measurements, and so it is advisable to buffer the ionic strength (preferably at a high value), e.g. with a total ionic strength adjustment buffer (TISAB). 

Solutions of known ionic strength are now available commercially, as are tablets of inert electrolyte, where the latter are dissolved in a known volume of water to produce a solution of predetermined I - this is merely a volumetric procedure. Such tablets are much like buffer tablets, and are called ionic strength adjusters. 

Often, the potentiometric determination of concentration requires a preferred pH range. If pH is also important, then the ionic strength adjuster can conveniently function additionally as a pH buffer. Such tablets are called total ionic strength adjustment buffers (or TISABs). ... 

Incidentally, ionic strength adjusters and TISABs also decrease all junction potentials (see Section 3.6.5). 

The fluoride content of a sample of toothpaste is unknown. Accordingly, a sample of the toothpaste was digested in acid solution, filtered to remove the white gritlike solid and then buffered with a total ionic strength adjustment buffer (TISAB) to pH 6. A fluoride electrode is immersed in the clear solution and the emf recorded when the reading was steady. 

From the discussions above, we will be aware that the concentration ([F ]) determined will in fact be an activity, i.e. a(F ). It will also be apparent that adding an acid to digest the sample of toothpaste will introduce errors into the calculation since two electrolytes are involved, thereby increasing the ionic strength / (see SAQs 3.10 and 3.11). Since the preferred pH range of the fluoride electrode is 5-6, the ionic strength adjuster (TISAB) can also conveniently function as a pH buffer. 

Not very accurate as the selectivity coefficient can vary with ionic strength. Ions in the ionic strength adjuster can in fact make the problem worse... 

While this relationship is simple, it introduces more errors because the activity coefficient (or more normally, the mean ionic activity coefficient y ) is wholly unknown. While y can sometimes be calculated (e.g. via the Debye-Huckel relationships described in Section 3.4), such calculated values often differ quite significantly from experimental values, particularly when working at higher ionic strengths. In addition, ionic strength adjusters and TISABs are recommended in conjunction with calibration curves. 

The activity a and concentration c are related by a = (c/c ) x y (equation (3.12)), where y is the mean ionic activity coefficient, itself a function of the ionic strength /. Approximate values of y can be calculated for solution-phase analytes by using the Debye-Huckel relationships (equations (3.14) and (3.15)). The change of y with ionic strength can be a major cause of error in electroanalytical measurements, so it is advisable to buffer the ionic strength (preferably at a high value), e.g. with a total ionic strength adjustment buffer (TISAB). 

TISAB total ionic strength adjustment buffer... 

Frant and Ross [108] recommended sample adjustment using TISAB buffer ( Total Ionic Strength Adjustment Buffer ), obtained by dissolving 57ml glacial acetic acid, 58 g NaCl and 4g 1,2-cyclohexanediaminetetraacetic acid (CDTA), adjustment of the solution pH with sodium hydroxide to 5 to 5.5 and dilution to 1 litre, all to maintain a constant ionic strength and pH between 5 and 5.5 and to complex ions such as Al or Fe that interfere in the determination. A detailed... 

For dilute solutions, the Debeye-Huckel law (log 7 = —0.5zf/°5) indicates that 7 will be a constant for a given ionic strength /. Therefore, the same quantity of inert electrolyte, called the support electrolyte, must be added to the sample and to the series of standards to increase the concentration of external ions and stabilise the ionic strength. This addition of ISAB (Ionic Strength Adjustment Buffer) is intended to limit variation in 7. Under these conditions, the measured difference in potential only depends on the concentration of the ion to be analysed and is given by equation (18.3). 

There are many methods that allow the determination of the concentration q of an ionic species i in a sample. In the presence of an ionic strength adjuster (ISA) or a buffering solution that can fix the pH (TISAB, Total Ionic Strength Adjustment Buffer) all of these methods are based on application of equation (18.3). 

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