A pH indicator is a halochromic chemical compound added in small amounts to a solution so the pH (acidity or basicity) of the solution can be determined visually or spectroscopically by changes in absorption and/or emission properties. Hence, a pH indicator is a chemical detector for hydronium ions (H3O+) or hydrogen ions (H+) in the Arrhenius model. Normally, the indicator causes the color of the solution to change depending on the pH. Indicators can also show change in other physical properties; for example, olfactory indicators show change in their odor. The pH value of a neutral solution is 7.0 at 25 °C (standard laboratory conditions). Solutions with a pH value below 7.0 are considered acidic and solutions with pH value above 7.0 are basic. Since most naturally occurring organic compounds are weak electrolytes, such as carboxylic acids and amines, pH indicators find many applications in biology and analytical chemistry. Moreover, pH indicators form one of the three main types of indicator compounds used in chemical analysis. For the quantitative analysis of metal cations, the use of complexometric indicators is preferred, whereas the third compound class, the redox indicators, are used in redox titrations (titrations involving one or more redox reactions as the basis of chemical analysis).
Theory In and of themselves, pH indicators are usually weak acids or weak bases. The general reaction scheme of acidic pH indicators in aqueous solutions can be formulated as:
HInd(aq) + H2O(l) ⇌ H3O+(aq) + Ind−(aq) where, "HInd" is the acidic form and "Ind−" is the conjugate base of the indicator. Vice versa for basic pH indicators in aqueous solutions:
IndOH(aq) + H2O(l) ⇌ H2O(l) + Ind+(aq) + OH−(aq) where "IndOH" stands for the basic form and "Ind+" for the conjugate acid of the indicator. The ratio of concentration of conjugate acid/base to concentration of the acidic/basic indicator determines the pH (or pOH) of the solution and connects the color to the pH (or pOH) value. For pH indicators that are weak electrolytes, the Henderson–Hasselbalch equation can be written as:
pH = pKa + log10 [Ind−]/ [HInd]
pOH = pKb + log10 [Ind+]/ [IndOH] The equations, derived from the acidity constant and basicity constant, states that when pH equals the pKa or pKb value of the indicator, both species are present in a 1:1 ratio. If pH is above the pKa or pKb value, the concentration of the conjugate base is greater than the concentration of the acid, and the color associated with the conjugate base dominates. If pH is below the pKa or pKb value, the converse is true. Usually, the color change is not instantaneous at the pKa or pKb value, but a pH range exists where a mixture of colors is present. This pH range varies between indicators, but as a rule of thumb, it falls between the pKa or pKb value plus or minus one. This assumes that solutions retain their color as long as at least 10% of the other species persists. 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 pKa + 1 or pKb + 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 pKa − 1 or pKb − 1. For optimal accuracy, the color difference between the two species should be as clear as possible, and the narrower the pH range of the color change the better. In some indicators, such as phenolphthalein, one of the species is colorless, whereas in other indicators, such as methyl red, both species confer a color. While pH indicators work efficiently at their designated pH range, they are usually destroyed at the extreme ends of the pH scale due to undesired side reactions.
Application
pH indicators are frequently employed in titrations in analytical chemistry and biology to determine the extent of a chemical reaction. Because of the subjective choice (determination) of color, pH indicators are susceptible to imprecise readings. For applications requiring precise measurement of pH, a pH meter or litmus paper is frequently used. Sometimes, a blend of different indicators is used to achieve several smooth color changes over a wide range of pH values. These commercial indicators (e.g., universal indicator and Hydrion papers) are used when only rough knowledge of pH is necessary. For a titration, the difference between the true endpoint and the indicated endpoint is called the indicator error. Tabulated below are several common laboratory pH indicators. Indicators usually exhibit intermediate colors at pH values inside the listed transition range. For example, phenol red exhibits an orange color between pH 6.8 and pH 8.4. The transition range may shift slightly depending on the concentration of the indicator in the solution and on the temperature at which it is used. The figure on the right shows indicators with their operation range and color changes.
Universal Indicator
Precise pH measurement
An indicator may be used to obtain quite precise measurements of pH by measuring absorbance quantitatively at two or more wavelengths. The principle can be illustrated by taking the indicator to be a simple acid, HA, which dissociates into H+ and A−.
HA ⇌ H+ + A− The value of the acid dissociation constant, pKa, must be known. The molar absorbances, εHA and εA− of the two species HA and A− at wavelengths λx and λy must also have been determined by previous experiment. Assuming Beer's law to be obeyed, the measured absorbances Ax and Ay at the two wavelengths are simply the sum of the absorbances due to each species.
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