Potential measurement error

Another consideration of the logarithmic function of pH is the pH or percent concentration error resulting from a potential measurement error. The previously stated equation (11) represents the potential measured by a pair of electrodes. The difference between two measurements can be represented as... 

The relative measurement error in concentration, therefore, is determined by the magnitude of the error in measuring the cell s potential and by the charge of the analyte. Representative values are shown in Table 11.7 for ions with charges of+1 and +2, at a temperature of 25 °C. Accuracies of 1-5% for monovalent ions and 2-10% for divalent ions are typical. Although equation 11.22 was developed for membrane electrodes, it also applies to metallic electrodes of the first and second kind when z is replaced by n. 

Relationship Between Measurement Error in Potential and Relative Error in Concentration... 

It should be noted also that the intercept is difficult to determine accurately because of large potential experimental error in observing the time of the start of filtration and the time-volume correspondence during the first moments when the filtration rate is high. The value of / calculated from the intercept may vaiy appreciably from test to test, and will almost always be different from the value measured with clean medium in a permeability test. 

Reference electrodes are used in the measurement of potential [see the explanation to Eq. (2-1)]. A reference electrode is usually a metal/metal ion electrode. The electrolyte surrounding it is in electrolytically conducting contact via a diaphragm with the medium in which the object to be measured is situated. In most cases concentrated or saturated salt solutions are present in reference electrodes so that ions diffuse through the diaphragm into the medium. As a consequence, a diffusion potential arises at the diaphragm that is not taken into account in Eq. (2-1) and represents an error in the potential measurement. It is important that diffusion potentials be as small as possible or the same in the comparison of potential values. Table 3-1 provides information on reference electrodes. 

CU-CUSO4 electrodes with saturated CUSO4 solution are recommended for potential measurements in soil. Their potential constancy is about 5 mV. Larger errors can be traced to chemical changes in the CUSO4 solution. These electrodes have been developed for long-life applications in potential-controlled rectifiers and built-... 

Application of this method or Eq. (3-25 ) in the presence of stray currents is conceivable but would be very prone to error. It is particularly valid for good coating. Potential measurement is then only significant if stray currents are absent for a period, e.g., when the source of the stray current is not operating. In other cases only local direct measurements with the help of probes or test measurements at critical points can be considered. The potential test probes described in Section 3.3.3.2 have proved true in this respect. 

The switching-off method for 7/ -free potential measurement is, according to the data in Fig. 3-5, subject to error with lead-sheathed cables. For a rough survey, measurements of potential can be used to set up and control the cathodic protection. This means that no information can be gathered on the complete corrosion protection, but only on the protection current entry and the elimination of cell activity from contacts with foreign cathodic structures. The reverse switching method in Section 3.3.1 can be used to obtain an accurate potential measurement. Rest and protection potentials for buried cables are listed in Table 13-1 as an appendix to Section 2.4. The protection potential region lies within U[[Pg.326]

Figure 19-7 shows off potential measurements as an example, in which the 100-mV criterion, No. 3 in Table 3-3, as well as the potential criterion t/ ff < is fulfilled. It has to be remembered with off potential measurements that according to the data in Fig. 3-6, depolarization is slower with age, so that the 100 mV criterion must lead to errors with a measuring time of 4 hours. Off potential measurements should be carried out after commissioning at 1-, 2-, 6- and 12-month intervals and then annually. 

Depolarization times greater than 48 hours should be allowed when applying the 100-mV criterion. Comparison of measured potentials is only possible where conditions of temperature and moisture are similar. Figure 19-8 shows the dependence on season and temperature which can probably be ascribed to different aeration. In repair work, potential probes should be provided at different places on the object to reduce IR errors in off potential measurements arising from equalizing currents. 

Since usually the reference electrode is not equipped with a capillary probe (see Fig. 2-3), there is an error in the potential measurement given by Eq. (2-34) in this connection see the data in Section 3.3.1 on IR-free potential measurement. The switching method described there can also be applied in a modified form to potential-controlled protection current devices. Interrupter potentiostats are used that periodically switch off the protection current for short intervals [5]. The switch-off phase is for a few tens of microseconds and the switch-on phase lasts several hundred microseconds. 

The proof of protection is more difficult to establish in this case for two reasons. First, the object is to restore passivity to the rebar and not to render it virtually immune to corrosion. Second, it is difficult to measure the true electrode potential of rebars under these conditions. This is because the cathodic-protection current flowing through the concrete produces a voltage error in the measurements made (see below). For this reason it has been found convenient to use a potential decay technique to assess protection rather than a direct potential measurement. Thus a 100 mV decay of polarisation in 4 h once current has been interrupted has been adopted as the criterion for adequate protection. It will be seen that this proposal does not differ substantially from the decay criterion included in Table 10.3 and recommended by NACE for assessing the full protection of steel in other environments. Of course, in this case the cathodic polarisation is intended to inhibit pit growth and restore passivity, not to establish effective immunity. 

Fig. 10.9 Diagram illustrating the source of the IR error in potential measurements on a cathodically protected structure. BA is the absolute electrode potential of the structure CD is the absolute electrode potential of the anode and CB is the field gradient in the environment due to cathodic protection current flux. A reference electrode placed at E will produce an IR error of EFin the potential measurement of the structure potential. If placed at G the error will be reduced to GH. At B there would be no error, but the point is too close to the structure to permit insertion of a reference electrode. If the current is interrupted the field immediately becomes as shown by the dotted line, and no IR is included...

In an impressed-current cathodic protection system the power source has a substantial capacity to deliver current and it is possible to change the state of polarisation of the structure by altering that current. Thus effective control of the system depends on credible potential measurements. Since the current output from any given anode is substantial, the possibility of an IR error which may reach many hundreds of millivolts in any potential measurements made is high. Thus the instant-off technique (or some other means of avoiding IR error) is essential to effective system management. 

Voltmeters and potentiometers The instruments described here are generally referred to as corrosion voltmeters. As mentioned previously, the current flowing through any potential-measurement circuit must be small to avoid errors due to polarisation. Moreover, if the current flow is too large, errors will be introduced owing to the voltage drop caused by the contact resistance between the reference electrode and the electrolyte. It is thus clear that the prime requirement of a potential measurement circuit is high resistance. 

An exact potential measurement is difficult - particularly in organic electrochemistry - and probably requires very sophisticated techniques to avoid a variety of possible errors (e.g. [75]). Fortunately, for practical applications in electroorganic synthesis, it will usually be sufficient to get reproducible potentials for the current density-potential curves (see Fig. 1) as well as for the synthesis cell. A constant deviation in both measurements may be acceptable, even though the accurate value may be unknown. Some aspects will be discussed here, a more detailed overview is given, for example, in [3a]. 

The relative uncertainties of the potential measuring devices are assumed to be correct that is, the sensors considered to measure the measurands included in the mathematical models are assumed to work according to the accuracy specified by the manufacturer of the instrument. Systematic errors associated with the sensors are neglected. 

Metal Predicted potential Measured potential Percent error... 

Both the air sample matrix C and the matrix of the potential source profiles A were perturbed by measurement error. In Set I only 9 sources were active, among which there was an unreported source. 

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