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Calculation of pHt values at operating parameters of water coolant of the secondary circuit of NPPs with PWR

A.B. Larin, B.M. Larin, K.V. Zotova

Vestnik IGEU, 2024 issue 6, pp. 15—22

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Abstract in English: 

Background. The main issue of the water-chemical mode (WCM) of the secondary circuit of a nuclear power plant (NPP) is to ensure trouble-free operation of the main equipment by maintaining such physical and chemical properties of the coolant that would prevent corrosion and deposition of internal surfaces equipment. The rate of corrosion depends on the pH value, which is measured in cooled samples (at 25 °C) and taken at control points throughout the steam-water circuit. Temperature increasing leads to the change in dissociation of electrolytes, their activity coefficients, and the dissociation constants of water and dissolved electrolytes change. These changes lead to the fact that the pH values measured at 25 °C do not correspond to the real values of the pH value at the operation parameters of the coolant. Therefore, it is necessary to monitor pH value at the actual temperature (pHt) and, in case of indicator deviations, to correct a water chemistry mode. The problem may be solved semi-empirically, that is to calculate pHt values using developed mathematical models with some data obtained from chemical monitoring devices.

Materials and methods. Mathematical models to calculate pHt are based on equations of the theory of electrolyte solutions. Previously obtained temperature-dependent values of the ionic product of water, specific electrical conductivity and dissociation constants of electrolytes have been used.

Results. The authors have developed mathematical models of coolant ionic equilibria under conditions of hydrazine-ammonia water chemistry mode. pHt values in aqueous solutions of carbonic acid and ammonia have been calculated.

Conclusions. The determination of the high-temperature pH value is of great practical importance, especially for nuclear power plant units with PWR. The results obtained show that it is possible to monitor this indicator using the devices already available at the station for automatic chemical control. The values of thermal pH calculated according to the algorithms developed by the authors are comparable with the results of other studies. The results obtained may be used to develop complex algorithms to calculate pH for industrial conditions.

References in English: 

1. Tyapkov, V.F. Kompleksnyy podkhod k vyboru vodno-khimicheskogo rezhima II kontura v proektakh NPPs s VVER-1200 [An integrated approach to the selection of the water-chemical regime of the II circuit in nuclear power plant projects with PWR-1200]. Teploenergetika, 2011, no. 5, pp. 16–20.

2.   Golubev, B.P., Smirnov, S.N., Lukashov, Yu.M., Svistunov, E.P. Elektrofizicheskie metody issledovaniya svoystv teplonositeley [Electrophysical methods for studying the properties of heat carriers]. Moscow: Energoatomizdat, 1985. 184 p.

3.  Larin, A.B., Larin, B.M., Sorokina, A.Ya., Kiet, S.V. Izmerenie pH v usloviyakh sverkhchistoy sredy kondensata i pitatel'noy vody energoblokov [Measurement of pH in ultrapure environment of condensate and feed water of power units]. Teploenergetika, 2018, no. 11, pp. 97–102.

4.  Martynova, O.I. Mezhdunarodnye tablitsy i uravneniya dlya ionnogo proizvedeniya vody i para [International tables and equations for the ionic product of water and steam]. Teploenergetika, 1981, no. 1, pp. 74–75.

5.  Musinova, Yu.V., Smirnov, S.N. Raschet udel'noy elektroprovodnosti vodnykh rastvorov ammiaka [Calculation of the specific electrical conductivity of aqueous ammonia solutions]. Teploenergetika, 2000, no. 10, pp. 944–945.

6.  Lukashov, Yu.M., Komissarov, K.B., Golubev, B.P., Smirnov, S.N., Svistunov, E.P. Eksperimental'nye issledovaniya elektrofizicheskikh svoystv odno-odnovalentnykh elektrolitov pri vysokikh parametrakh sostoyaniya [Experimental studies of the electrophysical properties of single-monovalent electrolytes at high state parameters]. Teploenergetika, 1975, no. 12, pp. 76–79.

7.  Shcherbakov, V.N. Elektroliticheskie svoystva rastvorov ugol'noy kisloty i innovatsionnye metody operativnogo kontrolya kachestva vody tipa kondensata na TES [Electrolytic properties of carbonic acid solutions and innovative methods of operational quality control of condensate-type water at thermal power plants]. Vestnik DGTU, 2015, no. 4, pp. 24–30.

8. Marshall, W.L., Franck, E.U. Ion product of water substance, 0–1000 оC, 1–10,000 bars. New international formulation and its background. J. Phys. Chem. Ref. Data, 1981, vol. 10, p. 295.

9. Wright, J.M. The behavior of electrolytic solutions at elevated temperatures as derived from conductance measurements. WAPD–TM–204, June, 1961.

10. Ryzhenko, B.N. O velichinakh konstant dissotsiatsii ugol'noy kisloty pri povyshennykh temperaturakh [On the values of dissociation constants of carbonic acid at elevated temperatures]. Doklady AN SSSR, 1963, vol. 149, no. 3, pp. 639–641.

Key words in Russian: 
водно-химический режим, автоматический химический контроль, показатели качества теплоносителя, удельная электропроводность, водородный показатель рН, угольная кислота, аммиак
Key words in English: 
water chemistry, automatic chemical monitoring, coolant quality indicators, specific electrical conductivity, hydrogen pH, carbonic acid, ammonia
The DOI index: 
10.17588/2072-2672.2024.6.015-022
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