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Pourbaix diagram of iron. [1] The Y axis corresponds to voltage potential. In electrochemistry, and more generally in solution chemistry, a Pourbaix diagram, also known as a potential/pH diagram, E H –pH diagram or a pE/pH diagram, is a plot of possible thermodynamically stable phases (i.e., at chemical equilibrium) of an aqueous electrochemical system.
The pH range is commonly given as zero to 14, but a pH value can be less than 0 for very concentrated strong acids or greater than 14 for very concentrated strong bases. [ 2 ] The pH scale is traceable to a set of standard solutions whose pH is established by international agreement. [ 3 ]
The values below are standard apparent reduction potentials (E°') for electro-biochemical half-reactions measured at 25 °C, 1 atmosphere and a pH of 7 in aqueous solution. [1] [2] The actual physiological potential depends on the ratio of the reduced (Red) and oxidized (Ox) forms according to the Nernst equation and the thermal voltage.
To use potentiometric (e.m.f.) measurements in monitoring the + concentration in place of readings, one can trivially set [+] = and apply the same equations as above, where is the offset correction /, and is a slope correction / (1/59.2 pH units/mV at 25°C), such that replaces .
Buffer capacity falls to 33% of the maximum value at pH = pK a ± 1, to 10% at pH = pK a ± 1.5 and to 1% at pH = pK a ± 2. For this reason the most useful range is approximately pK a ± 1. When choosing a buffer for use at a specific pH, it should have a pK a value as close as possible to that pH. [2]
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For example, if the concentration of the conjugate base is 10 times greater than the concentration of the acid, their ratio is 10:1, and consequently the pH is pK a + 1 or pK b + 1. Conversely, if a 10-fold excess of the acid occurs with respect to the base, the ratio is 1:10 and the pH is pK a − 1 or pK b − 1.
A typical titration curve of a diprotic acid, oxalic acid, titrated with a strong base, sodium hydroxide.Both equivalence points are visible. Titrations are often recorded on graphs called titration curves, which generally contain the volume of the titrant as the independent variable and the pH of the solution as the dependent variable (because it changes depending on the composition of the ...