The Open Circuit

There are three reasons for the importance of the investigation of the iron/acid interface under open-circuit conditions. First, it is of practical significance because the main corrosion processes encountered in real life involve free corrosion. Second, it supplies diagnostic criteria for elucidating the reaction mechanism such as the steady-state corrosion potential and corrosion current as a function of time, pH, anions, hydrodynamics, and metal surface characteristics. In this section, special attention will be given to the kinetic quantities A log / VA pH and A Ef /A pH, where the superscript cor and the subscript s refer to steady-state open-circuit conditions. Finally, a number of experiments, especially recent ones, carried out under well-controlled conditions have revealed the influence of the waiting time on both open-circuit and polarization kinetic quantities. 

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Under both short-circuit and open-circuit conditions, a solar cell produces no electric power, the power is consumed internally in the cell and is dissipated as heat. When a resistive load is connected to a cell in sunlight, a photogenerated voltage, F, is induced across the load and a current flows through it. The existence of requites that the flow of majority carriers be reduced from that in the open-circuit condition there must be a higher battier potential than in the open-circuit case (Fig. 2d). This higher barrier potential (V6 — ) indicates a smaller reduction from Since the photogenerated... 

Fig. 1. The energy cycle of a thermal electric generating station having two alternative cooling systems (—) the open-circuit or once-through system and (-------------------------------------) a representative closed-cycle, cooling-tower system. Reproduced by permission (3).

Fig. 6. Discharge behavior of a battery where is the open circuit voltage (a) current—potential or power curve showing M activation, ohmic, and M concentration polarization regions where the double headed arrow represents polarization loss and (b) voltage—time profile.

To calculate the open circuit voltage of the lead—acid battery, an accurate value for the standard cell potential, which is consistent with the activity coefficients of sulfuric acid, must also be known. The standard cell potential for the double sulfate reaction is 2.048 V at 25 °C. This value is calculated from the standard electrode potentials for the (Pt)H2 H2S04(yw) PbS04 Pb02(Pt) electrode 1.690 V (14), for the Pb(Hg) PbS04 H2S04(yw) H2(Pt) electrode 0.3526 V (19), and for the Pb Pb2+ Pb(Hg) 0.0057 V (21). 

The temperature dependence of the open circuit voltage has been accurately determined (22) from heat capacity measurements (23). The temperature coefficients are given in Table 2. The accuracy of these temperature coefficients does not depend on the accuracy of the open circuit voltages at 25°C shown in Table 1. Using the data in Tables 1 and 2, the open circuit voltage can be calculated from 0 to 60°C at concentrations of sulfuric acid from 0.1 to 13.877 m. 

C, the corrosion current density, /, at the open-circuit corrosion potential, E. See also discussion in text. 

Thus, because the standard cell potential for reaction 15 is positive, the reaction proceeds spontaneously as written. Consequendy, to produce chlorine and hydrogen gas, a potential must be appHed to the cell that is greater than the open-circuit value. This then becomes an example of an electrolytic process. 

Typical polarization curves for SOFds are shown in Fig. 27-67. As discussed earlier, the open-circuit potential of SOFds is less than 1 because of the high temperature, but the reaction overpotentials are... 

Usually, a gas turbine plant operates on open circuit , with internal combustion (Fig. 1.3). Air and fuel pass across the single control surface into the compressor and combustion chamber, respectively, and the combustion products leave the control surface after expansion through the turbine. The open circuit plant cannot be said to operate on a thermodynamic cycle however, its performance is often assessed by treating it as equivalent to a closed cyclic power plant, but care must be taken in such an approach. 

For the open circuit gas turbine of Fig. 1. .3, if the reactants (air and fuel My) enter at temperature T,), and the exhaust products (M. - - My) leave at temperature T4. then the steady-flow energy equation yields... 

Essentially, the analytical approach outlined above for the open circuit gas turbine plants is that used in modem computer codes. However, gas properties, taken from tables such as those of Keenan and Kaye [6], may be stored as data and then used directly in a cycle calculation. Enthalpy changes are then determined directly, rather than by mean specific heats over temperature ranges (and the estimation of n and n ), as outlined above. 

We first consider how the simple analysis of Section 7.3, for the combined doubly cyclic series plant, is modified for the open circuit/closed cycle plant. The work output from the gas-turbine plant of Fig. 7.3 is... 

But if combustion is adiabatic, then the steady flow energy equation for the open-circuit gas turbine (with exhaust of enthalpy (//p)s leaving the HRSG and entering the exhaust stack with a temperature Ts greater than that of the atmosphere. To) is... 

The electrode process at -500 mV on this potential scale is correlated to the growth of 250 20 pm high islands. They grow immediately upon a potential step from the open circuit potential to -500 mV (arrow in Figure 6.2-13). 

Secondary Voltage of Wound-Rotor Motors. The secondary voltage of wound-rotor motors is the open-circuit voltage at standstill, measured across the slip rings, with rated voltage applied on the primary winding. 

The open-circuit potential of most metals in sea water is not a constant and varies with the oxygen content, water velocity, temperature and metallurgical and surface condition of the metal. 

Duncan and Frankenthal report on the effect of pH on the corrosion rate of gold in sulphate solutions in terms of the polarization curves. It was found that the rate of anodic dissolution is independent of pH in such solutions and that the rate controlling mechanism for anodic film formation and oxygen evolution are the same. For the open circuit behaviour of ferric oxide films on a gold substrate in sodium chloride solutions containing low iron concentration it is found that the film oxide is readily transformed to a lower oxidation state with a Fe /Fe ratio corresponding to that of magnetite . 

Electrochemical aspects of the stress-corrosion behaviour have been investigated, mainly in neutral solutions. The open-circuit potential of Ti-8Al-lMo-l V is —800mV (v5. S.C.E.). The crack initiation load reaches... 

The operating potential of an anode material is its potential when coupled to a structure (i.e. the closed-circuit potential). Since all commercial anode materials are formulated to suffer only slight polarisation under most conditions of exposure, the operating potential approximates to the open-circuit potential. Indeed, any substantial difference (>50mV) between these two potentials will call into question the suitability of the anode in the particular environment. 

The simplest procedure in studying galvanic corrosion is a measurement of the open-circuit potential difference between the metals in a couple in the environment under consideration. This will at least indicate the probable direction of any galvanic effect although no information is provided on the rate. A better procedure is to make similar open-circuit potential measurements between the individual metals and some appropriate reference electrode, which will yield the same information and will also permit obser-... 

Fig. 19.16 Schematic E — I diagrams of local cell action on stainless steel in CUSO4 + H2SO4 solution showing the effect of metallic copper on corrosion rate. C and A are the open-circuit potentials of the local cathodic and anodic areas and / is the corrosion current. The electrode potentials of a platinised-platinum electrode and metallic copper immersed in the same solution as the stainless steel are indicated by arrows, (a) represents the corrosion of stainless steel in CUSO4 -I- H2 SO4, (b) the rate when copper is introduced into the acid, but is not in contact with the steel, and (c) the rate when copper is in contact with the stainless steel...

In an Evans diagram 89> the mixed potential can easily be found and also be verified by measuring the open circuit potential of a zinc-amalgam electrode in a Cu2+-ion solution. Even the complication by the simultaneous presence of another reducible species, e.g., Pbz+ can be graphically demonstrated for different limiting conditions... 

There is experimental consensus on the most important parameters of singlelayer polymer photovoltaic devices, the short circuit current / , the open circuit voltage V c, and the filling factor FF. From these parameters the efficiencies of PPV based devices were typically calculated to be around 0.1% under monochromatic low light intensities. Efforts to extend the classical semiconductor picture of... 

MIM or SIM [82-84] diodes to the PPV/A1 interface provides a good qualitative understanding of the device operation in terms of Schottky diodes for high impurity densities (typically 2> 1017 cm-3) and rigid band diodes for low impurity densities (typically<1017 cm-3). Figure 15-14a and b schematically show the two models for the different impurity concentrations. However, these models do not allow a quantitative description of the open circuit voltage or the spectral resolved photocurrent spectrum. The transport properties of single-layer polymer diodes with asymmetric metal electrodes are well described by the double-carrier current flow equation (Eq. (15.4)) where the holes show a field dependent mobility and the electrons of the holes show a temperature-dependent trap distribution. 

Friend et at. studied the influence of electrodes with different work-functions on the performance of PPV photodiodes 143). For ITO/PPV/Mg devices the fully saturated open circuit voltage was 1.2 V and 1.7 V for an ITO/PPV/Ca device. These values for the V c are almost equal to the difference in the work-function of Mg and Ca with respect to 1TO. The open circuit voltage of the ITO/PPV/A1 device observed at 1.2 V, however, is considerably higher than the difference of the work-function between ITO and Al. The Cambridge group references its PPV with a very low dark carrier concentration and consequently the formation of Schottky barriers at the PPV/Al interface is not expected. The mobility of the holes was measured at KT4 cm2 V-1 s l [62] and that for the electrons is expected to be clearly lower. 

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