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A BRIEF DISCOURSE ON ERRORS IN pH MEASUREMENT Acid Base Error Because indicators are themselves acids or bases of differing strengths, when they are added to unbuffered or very weakly buffered solutions, they will effect the pH of the solution. That being said, however the quantity of indicator in a test strip is usually in the range of micrograms, thus the effect in even a 1-2ml volume is almost non-existent. If however, one is using a liquid system indicator, the effect may be pronounced enough to cause an erroneous reading by as much as one pH unit. The Salt Error When two different solutions containing inorganic material, having
equivalent pH values are tested with an indicator, we would expect the same pH
colour value to appear. However, if the two solutions contain different
concentrations of salts, the colour value may not be the same. It was
discovered that even a "Neutral Salt" will bring about a significant pH change.
Sorensen, Kolthoff, and Michaelis, all developed elaborate tables that provided
us with corrections for these salt errors, however under normal conditions,
where salt values are less that 0.2N we may expect pH values as being close to
accurate. "Protein" Effects The zwitterion characteristic exhibited by amino acids, and hence
carried through a protein chain may have a profound effect on our ability to
measure the pH of protein solutions with a degree of certainty. In some cases
it may be impossible to measure their pH at all, and in fact many of the
indicators are themselves used for accurate determinations of proteins. Temperature Effects Since temperature effects the ionisation constant for weak acids and
weak bases, then it must effect the concentration of hydrogen ion present in
solution as well. This of course will reflect upon the pH value obtained during
any given measurements. It is therefore wise to ensure that temperatures are
consistent when taking pH measurements. This is especially true when using pH
strips, since we can adjust pH meters for temperature differences. The Alcohol Error Differences in the composition of a solvent will effect its acid-base equilibrium. These same types of changes will occur with the indicator as well. This results the same colour reaction in an alcoholic solution and in an aqueous buffered solution may not yield identical pH values. Normally at room temperature (23"C) this effect may be between 0-0.5 pH unit. |
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