Abstract:
Humidity- and temperature-dependent errors in concentrations reported by electrochemical sensors for atmospheric nitrogen dioxide significantly limit the reliability of the data. A basic understanding of the source of these errors has been missing. Empirical, software-based corrections are of limited reliability. The sensors feature a 40 wt % (≈4 molal) sulfuric acid electrolyte, and carbon working and quasi-reference (QRE) electrodes. We show that the sensor behaves as a truncated transmission line with resistance and capacitance elements varying with humidity. High-amplitude current fluctuations are due to humidity fluctuations, and are charging currents in response to fluctuations in interfacial capacitance. Baseline currents are due to very small differences in the open-circuit electrode potential between working and reference electrodes. We deduce that acid concentration changes in the meniscus within the porous electrode structure, in response to changes in the ambient temperature and humidity, cause both the capacitance fluctuations and the baseline changes. The open-circuit potential differences driving the baseline current variations are in part due to a difference in the liquid junction potential between the QRE and working electrode, dependent on humidity and temperature and caused by a gradient of acid concentration, and in part due to temperature- and acid-concentration-dependent variations in the rate of the potential-determining reactions. Based on the understanding obtained, we demonstrate a simple hardware change that corrects these unwanted errors.
