Standard voltage electrode potential

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 potentials of the metals in their 1 mol U salt solution are all related to the standard or normal hydrogen electrode (NHE). For the measurement, the hydrogen half-cell is combined with another half-cell to form a galvanic cell. The measured voltage is called the normal potential or standard electrode potential, E° of the metal. If the metals are ranked according to their normal potentials, the resulting order is called the electrochemi-... 

The pressure dependency of the cell voltage (and correspondingly the electrode potential) can also be derived using standard thermodynamic equations... 

The titration is represented in Fig. 2.22 by plotting the Pt electrode potential versus the titration parameter k. BB is the voltage curve for titration of Fe2+ with Ce4+ and B B that for titration of Ce4+ with Fe2+ they correspond exactly to the pH curves BB and B B in Fig. 2.18, with the exception that the initial point in Fig. 2.22 would theoretically have an infinitely negative and an infinitely positive potential, respectively. In practice this is impossible, because even in the absence of any other type of redox potential there will be always a trace of Fe3+ in addition to Fe2+ and of Ce3+ in addition to Ce4+ present. Further, half way through the oxidation or reduction the voltage corresponds to the standard reduction potentials of the respective redox couples it also follows that the equivalence point is represented by the mean value of both standard potentials ... 

QB For this cell because the electrodes are identical, the standard electrode potentials are numerically equal and subtracting one from the other leads to the value c°dl = 0.000 V. However, because the ion concentrations differ, there is a potential difference between the two half cells (non-zero nonstandard voltage for the cell). [Pb2+] = 0.100 M in the cathode compartment. The anode compartment contains a saturated solution of Pbl2. We use the Nemst equation (with n = 2) to determine [Pb2+] in the saturated solution. 

We have seen already that an absolute potential at an electrode cannot be known, so, in accord with all other electrochemistry, it is the potential difference between two electrodes which we measure. However, if the potential of the electrode of interest is cited with respect to that of a second electrode having a known, fixed potential, then we can know its voltage via the concept of the standard hydrogen electrode (SHE) scale (see Section 3.1). We see that a reliable value of overpotential requires a circuit containing a reference electrode. 

Electrode potential, E The energy, expressed as a voltage, of a redox couple at equilibrium. E is the potential of the electrode when measured relative to a standard (ultimately the SHE). E depends on temperature, activity and solvent. By convention, the half cell must first be written as a reduction, and the potential is then designated as positive if the reaction proceeds spontaneously with respect to the SHE. Otherwise, E is negative. 

The of this standard cell is +0.76 V. By international convention, the half-cell potential of the hydrogen reduction is assigned a value of exactly OV. Thus, the half-cell potential of the zinc oxidation is equal to K.n (i.e., +0.76 V). This voltage is called the standard half-cell potential and is represented by the symbol 1, to indicate that it was determined against a standard hydrogen electrode. 

We have seen in Section 5.2 that one can determine the relative electrode potential by measuring cell voltage. To form a series of relative electrode potentials, one has to select a reference electrode and standard conditions of components of an electrode/ electrolyte interphase. 

The standard cell voltage 5-° can in turn be calculated from the standard electrode potentials EP for the partial reactions using the expression... 

Near the middle of the list, you will see 0 volts arbitrarily assigned to the standard hydrogen electrode all other potentials are relative to the hydrogen half-reaction. The voltages are given signs appropriate for a reduction reaction. For oxidation, the sign is reversed thus, the oxidation half-reaction,... 

Problem 38 Considering only the elements in the chart of standard electrode potentials (Table 12-2), which pair can make a battery with the greatest voltage What would the voltage be ... 

Consulting the standard electrode potentials (see Table 12-2), what is the voltage for a cell using this reaction ... 

V°rev = 1.229V is the standard state reversible potential for the water splitting reaction and Vaoc is the anode potential at open circuit conditions. Term Vmeas-Vaoc arises from the fact that Voc represents the contribution of light towards the minimum voltage needed for water splitting potential (1.229V) and that the potential of the anode measured with respect to the reference electrode Vmeas has contributions from the open circuit potential and the bias potential applied by the potentiostat (i.e. Vmeas= Vapp+Vaoc). The term Vmeas-Vaoc makes relation (3.6.16) independent of the electrolyte pH and the type of reference electrode used. Thus the use of V°rev in relation (3.6.16) instead of VV or V°hz as in the case of relation (3.6.15) is justified. 

Standard Reduction Potential the voltage measured for a half-cell under standard conditions when in reference to the standard hydrogen electrode... 

The voltage we measure is characteristic of the metals we use. As an additional example, unit activity solutions of CuCE and AgCl with copper and silver electrodes, respectively, give a potential difference of about 0.45 V. We could continue with this type of measurement for aU the different anode-cathode combinations, but the number of galvanic cells needed would be very large. Fortunately, the half-reactions for most metals have been calculated relative to a standard reference electrode, which is arbitrarily selected as the reduction of hydrogen ... 

Passage of 1.0 mol of electrons (one faraday, 96,485 A s) will produce 1.0 mol of oxidation or reduction—in this case, 1.0 mol of Cl- converted to 0.5 mol of Cl2, and 1.0 mol of water reduced to 1.0 mol of OH- plus 0.5 mol of H2. Thermodynamically, the electrical potential required to do this is given by the difference in standard electrode potentials (Chapter 15 and Appendix D) for the anode and cathode processes, but there is also an additional voltage or overpotential that originates in kinetic barriers within these multistep gas-evolving electrode processes. The overpotential can be minimized by catalyzing the electrode reactions in the case of chlorine evolution, this can be done by coating the anode with ruthenium dioxide. 

The standard reduction potential would be observed if the half-cell of interest (with unit activities) were connected to a standard hydrogen electrode, as it is in Figure 14-7. It is nearly impossible to construct such a cell, because we have no way to adjust concentrations and ionic strength to give unit activities. In reality, activities less than unity are used in each half-cell, and the Nemst equation is employed to extract the value of E° from the cell voltage.12 In the hydrogen electrode, standard buffers with known pH (Table 15-3) are used to obtain known activities of H+. 

When you calibrate an electrode with standard buffers, you measure a voltage with the electrode in each buffer. The pH of buffer SI is pHs, and the measured electrode potential in this buffer is Es>- The pH of buffer S2 is pHS2 and the measured electrode potential is s2-The equation of the line through the two standard points is... 

D Dj Do, DR E Ea E° Ea Ec Em, Eoui m-3) diffusion coefficient (m2 s 1) diffusion coefficient of species (m2 s-1) diffusion coefficient of species O and R (m2 s-1) electrode potential (vs. some reference electrode) (V) null or equilibrium potential (V) standard potential (V) interelectrode potential (V) voltage input and output of a circuit (V)... 

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