Applying the least squares method for the titrimetric determination of the concentration of VFA

The titrimetric method is used for on-site measurement of the concentration of volatile fatty acids (VFAs) in anaerobic treatment. In current practice, specific and interpolated pH-volume data points are used to obtain the concentration of VFA by solving simultaneous equations iteratively to convergence (denoted as SEq). Here, the least squares method (LSM) is introduced as an elegant alternative. Known concentrations of VFA (acetic acid and/or propionic acid) ranging from to 200 to 1,000 mg/L were determined using SEq and LSM. Using standard numbers of data points, SEq gave more accurate results compared with LSM. However, results favoured LSM when all data points in the range were included without any interpolation. For model refinement, unit monovalent activity coefficient (f(m) = 1) was found reasonable and arithmetic averages of dissociation constants and molecular weight of 80 mol% acetic acid were recommended in the model for VFA determination of mixtures. An accurate result was obtained with a mixture containing more VFA (butyric acid and valeric acid). In a typical VFA measurement of real anaerobic effluent, a satisfactory result with an error of 14% was achieved. LSM appears to be a promising mathematical model solver for determination of concentration of VFA in the titrimetric method. Validation of LSM in the presence of other electrolytes deserves further exploration.