Appendix B General pH Information
B.1 pH Measurement Theory
pH is the negative logarithm of the hydrogen ion activity and a measure of the acidity or alkalinity of a solution.
pH =
pH is normally measured using a glass electrode and a reference electrode.
The glass electrode acts as a transducer, converting chemical energy (the hydrogen ion activity) into an electrical energy (measured in millivolts). The reaction is balanced and the electrical circuit is completed by the flow of ions from the reference solution to the solution under test.
The electrode and reference solution together develop a voltage (emf) whose magnitude depends on the type of reference electrode, the internal construction of the glass electrode, the pH of the solution and the temperature of the solution. This voltage is expressed by the Nernst Equation:
E = Eo – (2.3 RT/F) x log A[H+]
E = Eo – (slope) x log A[H+]
where:
E = the emf of the cell
Eo = the zero potential (isopotential) of the system. It depends on the internal construction of the glass and reference electrodes.
R = gas constant
T = temperature in Kelvin
A[H+] = activity of the hydrogen ion (assumed to be equivalent to the concentration of hydrogen ions)
F = Faraday constant
For every unit change in pH (or decade change in ion concentration) the emf of the electrode pair changes by 59.16 mV at 25 °C. This value is known as the Nernstian Slope of the electrode.
The pH electrode pair is calibrated using solutions of known and constant hydrogen ion concentration, called buffer solutions. The buffer solutions are used to calibrate both the electrode isopotential and slope.
47