The application of coal technologies for energy generation leads to high pollutant emissions. Thus, governmental and international organizations have created new programs and laws for monitoring emissions. Recently, the government of Kazakhstan has introduced regulations for the measurement of emissions produced by factories and power plants. However, the requirements and Corecommendations for the monitoring methods have not been defined. Therefore, this article addresses the problem and focuses on determining the measurement errors made by optical SGK510 and electrochemical POLAR devices used for coal power plants. The hypothesis is based on the fact that there are currently no systems for monitoring probe drying, and its implementation is expensive. The main methods are analyzed, namely their operation, taking into account the presence of water particles in samples, and the possibility of using adjustment coefficients is considered. The main pollutants chosen for analysis are CO, NO, NO2, NOx, SO2, and O2. Using the Broich–Pagan test, homoscedasticity was determined, and the Fisher test showed the possibility of using tuning coefficients. The data for the optical method were compared to measurements taken using Inspector 500. The error for SO2 determination was 7.19% for NO, 44.0985% for NO2, 733.26% for NOx, 7.39% for O2, 2.75% for CO, 60.81%. The comparison between SGK510 and POLAR demonstrated the following errors: for CO—1.5%, for NOx—82.4405%, for SO2—41.17%, for O2—11.61%. According to the Fisher criteria analysis of the optical method, only SO2 and CO values measured by SGK510 in comparison to Inspector 500 had close similarity, while others demonstrated high deviations. The significance tests were carried out by Fisher’s, t-test, and ANOVA methods. For the electrochemical measurement, only CO values had close similarity. In the future, methods will be proposed to improve the accuracy of the system while reducing maintenance costs, as well as cleaning sampling systems. The multicomponent analysis application for accuracy improvement with the exhaust gas humidity, temperature, and flow consideration was recommended as a possible solution.
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