Dr. SaMeH S. Ahmed

Civil and Environmental Engineering Department

pH


pH

          

In chemistrypH (Potential Hydrogen) is a measure of the acidity or basicity of an aqueous solution. Pure water is neutral, with a pH close to 7.0 at 25 °C (77 °F). Solutions with a pH less than 7 are said to be acidic and solutions with a pH greater than 7 are basic oralkaline. pH measurements are important in medicinebiologychemistryagricultureforestryfood scienceenvironmental science,oceanographycivil engineering and many other applications.

In a solution pH approximates but is not equal to p[H], the negative logarithm (base 10) of the molar concentration of dissolvedhydronium ions (H3O+); a low pH indicates a high concentration of hydronium ions, while a high pH indicates a low concentration. This negative of the logarithm matches the number of places behind the decimal point, so, for example, 0.1 molar hydrochloric acid should be near pH 1 and 0.0001 molar HCl should be near pH 4 (the base 10 logarithms of 0.1 and 0.0001 being −1, and −4, respectively). Pure (de-ionized) water is neutral, and can be considered either a very weak acid or a very weak base, giving it a pH of 7 (at 25 °C(77 °F)), or 0.0000001 M H+. The pH has no upper or lower limit and can be lower than 0 or higher than 14, although with water, it is limited by the acidity and basicity of water. For an aqueous solution to have a higher pH, a base must be dissolved in it, which binds away many of these rare hydrogen ions. Hydrogen ions in water can be written simply as H+ or as hydronium (H3O+) or higher species (e.g., H9O4+) to account for solvation, but all describe the same entity. Most of the Earth's freshwater bodies surface are slightly acidic due to the abundance and absorption of carbon dioxide. in fact, for millennia in the past, most fresh water bodies have had a slightly acidic pH.

However, pH is not precisely p[H], but takes into account an activity factor. This represents the tendency of hydrogen ions to interact with other components of the solution, which affects among other things the electrical potential read using a pH meter. As a result, pH can be affected by the ionic strength of a solution—for example, the pH of a 0.05 M potassium hydrogen phthalate solution can vary by as much as 0.5 pH units as a function of added potassium chloride, even though the added salt is neither acidic nor basic


pH

pH is defined as minus the decimal logarithm of the hydrogen ion activity, aH+, in a solution.[14]

mathrm{pH} = - log_{10}(a_{	extrm{H}^+}) = log_{10}left(frac{1}{a_{	extrm{H}^+}}
ight)

This definition was adopted because ion-selective electrodes, which are used to measure pH, respond to activity. Ideally, electrode potential, E, follows the Nernst equation, which, for the hydrogen ion can be written as

 E = E^0 + frac{RT}{F} ln(a_{	extrm{H}^+})=E^0 - frac{RT}{F} pH

where E is a measured potential, E0 is the standard electrode potential, R is the gas constantT is the temperature in kelvinsF is the Faraday constant. For H+ number of electrons transferred is one. It follows that electrode potential is proportional to pH when pH is defined in terms of activity. Precise measurement of pH is presented in International Standard ISO 31-8 as follows:[15] A galvanic cell is set up to measure the electromotive force (e.m.f.) between a reference electrode and an electrode sensitive to the hydrogen ion activity when they are both immersed in the same aqueous solution. The reference electrode may be a silver chloride electrode or a calomel electrode. The hydrogen-ion selective electrode is a standard hydrogen electrode.

Reference electrode | concentrated solution of KCl || test solution | H2 | Pt

Firstly, the cell is filled with a solution of known hydrogen ion activity and the emf, ES, is measured. Then the emf, EX, of the same cell containing the solution of unknown pH is measured.

 	ext{pH(X)} = 	ext{pH(S)}+frac{E_	ext{S} - E_	ext{X} }{z}

The difference between the two measured emf values is proportional to pH. This method of calibration avoids the need to know the standard electrode potential. The proportionality constant, 1/z is ideally equal to frac{1}{2.303RT/F}  the "Nerstian slope".

To apply this process in practice, a glass electrode is used rather than the cumbersome hydrogen electrode. A combined glass electrode has an in-built reference electrode. It is calibrated against buffer solutions of known hydrogen ion activity. IUPAC has proposed the use of a set of buffer solutions of known H+ activity.[14] Two or more buffer solutions are used in order to accommodate the fact that the "slope" may differ slightly from ideal. To implement this approach to calibration, the electrode is first immersed in a standard solution and the reading on a pH meter is adjusted to be equal to the standard buffer's value. The reading from a second standard buffer solution is then adjusted, using the "slope" control, to be equal to the pH for that solution. Further details, are given in the IUPAC recommendations.[14] When more than two buffer solutions are used the electrode is calibrated by fitting observed pH values to a straight line with respect to standard buffer values. Commercial standard buffer solutions usually come with information on the value at 25 °C and a correction factor to be applied for other temperatures. pH is an example of an acidity function. Hydrogen ion concentrations can be measured in non-aqueous solvents, but this leads, in effect, to a different acidity function, because the standard state for a non-aqueous solvent is different from the standard state for water. Superacids are a class of non-aqueous acids for which the Hammett acidity functionH0, has been developed.

pH in its usual meaning is a measure of acidity of (dilute) aqueous solutions only.[1] Recently the concept of "Unified pH scale"[16] has been developed on the basis of the absolute chemical potential of the proton. This concept proposes the "Unified pH" as a measure of acidity that is applicable to any medium: liquids, gases and even solids.


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