Hydrogen standard reduction potentials

If electron flow between the electrodes is toward the sample half-cell, reduction occurs spontaneously in the sample half-cell, and the reduction potential is said to be positive. If electron flow between the electrodes is away from the sample half-cell and toward the reference cell, the reduction potential is said to be negative because electron loss (oxidation) is occurring in the sample halfcell. Strictly speaking, the standard reduction potential, is the electromotive force generated at 25°C and pH 7.0 by a sample half-cell (containing 1 M concentrations of the oxidized and reduced species) with respect to a reference half-cell. (Note that the reduction potential of the hydrogen half-cell is pH-dependent. The standard reduction potential, 0.0 V, assumes 1 MH. The hydrogen half-cell measured at pH 7.0 has an of —0.421 V.)... 

Some typical half-cell reactions and their respective standard reduction potentials are listed in Table 21.1. Whenever reactions of this type are tabulated, they are uniformly written as reduction reactions, regardless of what occurs in the given half-cell. The sign of the standard reduction potential indicates which reaction really occurs when the given half-cell is combined with the reference hydrogen half-cell. Redox couples that have large positive reduction potentials... 

The oxidizing power of the halate ions in aqueous solution, as measured by their standard reduction potentials (p. 854), decreases in the sequence bromate > chlorate > iodate but the rates of reaction follow the sequence iodate > bromate > chlorate. In addition, both the thermodynamic oxidizing power and the rate of reaction depend markedly on the hydrogen-ion concentration of the solution, being substantially greater in acid than in alkaline conditions (p, 855). 

C19-0124. Using standard reduction potentials, determine -STeq for the decomposition reaction of hydrogen... 

The table of standard reduction potentials assists in the determination as to whether species can react with each other, or not. This can be substantiated by considering the reaction of hydrogen with two metals, copper and zinc. In order to determine whether or not a reaction takes place spontaneously under standard conditions, one calculates the standard potential using hydrogen ions and the metal as reactants. 

This technique is applied to mixtures of metal ions in an acidic solution for the purpose of electroseparation only the metal ions with a standard reduction potential above that of hydrogen are reduced to the free metal with deposition on the cathode, and the end of the reduction appears from the continued evolution of hydrogen as long as the solution remains acidic. Considering the choice of the cathode material and the nature of its surface, it must be realized that the method is disturbed if a hydrogen overpotential occurs in that event no hydrogen is evolved and as a consequence metal ions with a standard reduction potential below that of hydrogen will still be reduced a classic example is the electrodeposition of Zn at an Hg electrode in an acidic solution. 

The selectivity of RNH2 on M/A1203 and Raney catalysts decreased in the order Co Ni Ru>Rh>Pd>Pt. This order corresponds to the opposite sequence of reducibility of metal-oxides [8] and standard reduction potentials of metalions [9], The difference between Group VIII metals in selectivity to amines can probably been explained by the difference in the electronic properties of d-bands of metals [3], It is interacting to note that the formation of secondary amine, i.e. the nucleophilic addition of primary amine on the intermediate imine can also take place on the Group VIII metal itself. Therefore, the properties of the metal d-band could affect the reactivity of the imine and its interaction with the amine. One could expect that an electron enrichment of the metal d-band will decrease the electron donation from the unsaturated -C=NH system, and the nucleophilic attack at the C atom by the amine [3], Correlation between selectivity of metals in nitrile hydrogenation and their electronic properties will be published elsewhere. 

If the sign of the standard reduction potential, E°, of a half-reaction is positive, the half-reaction is the cathodic (reduction) reaction when connected to the standard hydrogen electrode (SHE). Half-reactions with more positive E° values have greater tendencies to occur in the forward direction. Hence, the magnitude of a halfcell potential measures the spontaneity of the forward reaction. 

In the discussion of the Daniell cell, we indicated that this cell produces a voltage of 1.10 V. This voltage is really the difference in potential between the two half-cells. The cell potential (really the half-cell potentials) is dependent upon concentration and temperature, but initially we ll simply look at the half-cell potentials at the standard state of 298 K (25°C) and all components in their standard states (1M concentration of all solutions, 1 atm pressure for any gases and pure solid electrodes). Half-cell potentials appear in tables as the reduction potentials, that is, the potentials associated with the reduction reaction. We define the hydrogen half-reaction (2H+(aq) + 2e - H2(g)) as the standard and has been given a value of exactly 0.00 V. We measure all the other half-reactions relative to it some are positive and some are negative. Find the table of standard reduction potentials in your textbook. 

You have learned that the standard hydrogen electrode has an assigned standard reduction potential of exactly 0 V, and is the reference for all half-cell standard reduction potentials. What would happen to cell potentials if a different reference were used You will address this question in the following ThoughtLah. 

In this section, you learned that you can calculate cell potentials by using tables of half-cell potentials. The half-cell potential for a reduction half-reaction is called a reduction potential. The half-cell potential for an oxidation half-reaction is called an oxidation potential. Standard half-cell potentials are written as reduction potentials. The values of standard reduction potentials for half-reactions are relative to the reduction potential of the standard hydrogen electrode. You used standard reduction potentials to calculate standard cell potentials for galvanic cells. You learned two methods of calculating standard cell potentials. One method is to subtract the standard reduction potential of the anode from the standard reduction potential of the cathode. The other method is to add the standard reduction potential of the cathode and the standard oxidation potential of the anode. In the next section, you will learn about a different type of cell, called an electrolytic cell. 

The standard reduction potentials used to calculate E ceii for the decomposition of water apply only to reactants and products in their standard states. However, in pure water at 25°C, the hydrogen ions and hydroxide ions each have concentrations of 1 x 10 mol/L. This is not the standard state value of 1 mol/L. The reduction potential values for the non-standard conditions in pure water are given below. The superscript zero is now omitted from the E symbol, because the values are no longer standard. 

It is possible to use the standard reduction potentials for the reduction of hydrogen ions and the reduction of water molecules to show that the dissociation of water molecules into hydrogen ions and hydroxide ions is non-spontaneous under standard conditions. Describe how you would do this. How is this result consistent with the observed concentrations of hydrogen ions and hydroxide ions in pure water ... 

Table 3.2 Standard reduction potential ( ) for some redox pairs relative to the standard hydrogen electrode potential 0...

To determine the E° of different cell arrangements, chemists use what are called standard reduction potentials for halfcells. A standard reduction potential is the electrical potential under standard conditions of a cell compared to the standard hydrogen electrode. The standard hydrogen electrode is a special half-cell that has been chosen as a reference to measure electrical potential. Just as sea level is a logical elevation for measuring gravitational potential,... 

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

Which one of the following metals does not react with water to produce hydrogen (Use Appendix D for standard reduction potentials)... 

Standard reduction potential The potential of a halfreaction under standard state conditions, as measured against the potential of the standard hydrogen electrode. 

On the hydrogen scale, the range of values for standard reduction potentials varies from about + 3 0 V to —3.0 V for solutions in which the activity of the hydrated hydrogen ion is 1. It is also conventional to quote values for standard reduction potentials in basic solutions with a unit activity of hydrated hydroxide ion, Typical values of range between about +2.0 V to —3.0 V. 

Many half-reactions of interest to biochemists involve protons. As in the definition of AG °, biochemists define the standard state for oxidation-reduction reactions as pH 7 and express reduction potential as E °, the standard reduction potential at pH 7. The standard reduction potentials given in Table 13-7 and used throughout this book are values for E ° and are therefore valid only for systems at neutral pH Each value represents the potential difference when the conjugate redox pair, at 1 m concentrations and pH 7, is connected with the standard (pH 0) hydrogen electrode. Notice in Table 13-7 that when the conjugate pair 2ET/H2 at pH 7 is connected with the standard hydrogen electrode (pH 0), electrons tend to flow from the pH 7 cell to the standard (pH 0) cell the measured E ° for the 2ET/H2 pair is -0.414 V... 

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+. 

By choosing E° = 0 V for the standard hydrogen electrode, we obtain standard reduction potentials that range from about +3 V to -3 V. 

The standard reduction potential for the a half-reaction is defined relative to an arbitrary value of 0 V for the standard hydrogen electrode (S.H.E.) ... 

Use standard reduction potentials to calculate the equilibrium constant at 25°C for disproportionation of hydrogen peroxide ... 

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