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Assumption 2. The self-ionization of water can be ignored. This assumption is not, strictly speaking, valid with pH values close to 7, half the value of pK w, the constant for self-ionization of water. In this case the mass-balance equation for hydrogen should be extended to take account of the self-ionization of water.
Figure 2 gives an example; in this example, the two x-intercepts differ by about 0.2 mL but this is a small discrepancy, given the large equivalence volume (0.5% error). Similar equations can be written for the titration of a weak base by strong acid (Gran, 1952; Harris, 1998).
Between the two buffer regions there is an end-point, or equivalence point, at about pH 3. This end-point is not sharp and is typical of a diprotic acid whose buffer regions overlap by a small amount: pK a2 − pK a1 is about three in this example. (If the difference in pK values were about two or less, the end-point would not be noticeable ...
This procedure is illustrated in an ICE table which can also be used to calculate the pH when some additional (strong) acid or alkaline has been added to the system, that is, when C A ≠ C H. For example, what is the pH of a 0.01 M solution of benzoic acid, pK a = 4.19? Step 1: = =
V eq is the volume of titrant (ml) consumed by the crude oil sample and 1 ml of spiking solution at the equivalent point, b eq is the volume of titrant (ml) consumed by 1 ml of spiking solution at the equivalent point, 56.1 g/mol is the molecular weight of KOH, W oil is the mass of the sample in grams. The normality (N) of titrant is calculated as:
The concentration of water, [H 2 O], is omitted by convention, which means that the value of K w differs from the value of K eq that would be computed using that concentration. The value of K w varies with temperature, as shown in the table below. This variation must be taken into account when making precise measurements of quantities such as pH.
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To illustrate the processes, consider the case of dissolving a weak acid, HA, in water. The pH can be calculated using an ICE table. Note that in this example, we are assuming that the acid is not very weak, and that the concentration is not very dilute, so that the concentration of [OH −] ions can be neglected. This is equivalent to the ...