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A half reaction is obtained by considering the change in oxidation states of individual substances involved in the redox reaction. Often, the concept of half reactions is used to describe what occurs in an electrochemical cell, such as a Galvanic cell battery. Half reactions can be written to describe both the metal undergoing oxidation (known ...
In electrochemistry, the Nernst equation is a chemical thermodynamical relationship that permits the calculation of the reduction potential of a reaction (half-cell or full cell reaction) from the standard electrode potential, absolute temperature, the number of electrons involved in the redox reaction, and activities (often approximated by concentrations) of the chemical species undergoing ...
At chemical equilibrium, the reaction quotient Q r of the product activity (a Red) by the reagent activity (a Ox) is equal to the equilibrium constant (K) of the half-reaction and in the absence of driving force (ΔG = 0) the potential (E red) also becomes nul. The numerically simplified form of the Nernst equation is expressed as:
In a chemical reaction, the half-life of a species is the time it takes for the concentration of that substance to fall to half of its initial value. In a first-order reaction the half-life of the reactant is ln(2)/λ, where λ (also denoted as k) is the reaction rate constant.
In other words, it assumes that the electrode mass transfer rate is much greater than the reaction rate, and that the reaction is dominated by the slower chemical reaction rate ". [7] [circular reference] Also, at a given electrode the Tafel equation assumes that the reverse half reaction rate is negligible compared to the forward reaction rate.
The reaction quotient (Q r) of the half-reaction is the ratio between the chemical activities (a) of the reduced form (the reductant, a red) and the oxidized form (the oxidant, a ox). = Considering the 2 H + / H 2 redox couple:
The rate of the overall reaction depends on the slowest step, so the overall reaction will be first order when the reaction of the energized reactant is slower than the collision step. The half-life is independent of the starting concentration and is given by t 1 / 2 = ln ( 2 ) k {\textstyle t_{1/2}={\frac {\ln {(2)}}{k}}} .
Using the Eyring equation, there is a straightforward relationship between ΔG ‡, first-order rate constants, and reaction half-life at a given temperature. At 298 K, a reaction with ΔG ‡ = 23 kcal/mol has a rate constant of k ≈ 8.4 × 10 −5 s −1 and a half life of t 1/2 ≈ 2.3 hours, figures that are often rounded to k ~ 10 −4 s ...