The long-term in-situ accurate measurement of pH value is an urgent need for environmental water quality monitoring without calibration of pH electrodes. The nonlinearity and potential drift of pH electrode is the main problem which restricts long-term continuous monitoring. The characteristic rules including electrode potential, zero value, electrode slope coefficient, and electrode potential drift for pH electrode are analyzed in detail under the condition of long-term continuous use. The exponential smoothing potential drift prediction model with self-adaptive dynamic optimization smoothing order and smoothing coefficient is established. Combining electrode potential drift threshold judgment and Nernst equation, calibration-free dynamic calculation mathematical model of pH long-term monitoring is established. Indoor simulation and field test indicate that the measurement absolute error caused by electrode drift is within 0.01 pH and the specified measurement error for pH monitoring instrument is always within 0.1 pH. The proposed method is very suitable for the terminal of pH detector with the advantages of good portability for the MCU chip, small samples, high-precision and fast running speed. Furthermore, the life of pH electrode can be prolonged significantly. It is also proved that the proposed method has a good application prospect.
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