POWER PLANT INSTRUMENTATION FOR MEASUREMENT OF HIGH-PURITY WATER QUALITY A symposium sponsored by ASTM Committee D-19 on Water AMERICAN SOCIETY FOR TESTING AND MATERIALS Milwaukee, Wis., 9-10 June 1980 ASTM SPECIAL TECHNICAL PUBLICATION 742 R W Lane, Illinois State Water Survey, and Gerard Otten, Puricons, Inc., editors ASTM Publication Code Number (PCN) 04-742000-16 • AMERICAN SOCIETY FOR TESTING AND MATERIALS 1916 Race Street, Philadelphia, Pa 19103 Copyright © by AMERICAN SOCIETY FOR TESTING AND MATERIALS 1981 Library of Congress Catalog Card Number: 81-65834 NOTE The Society is not responsible, as a body, for the statements and opinions advanced in this publication Printed in Baltimore, Md September 1981 Foreword The symposium on Power Plant Instrumentation for Measurement of High-Purity Water Quality was held on 9-10 June 1980 in Milwaukee, Wis The event was sponsored by the American Society for Testing and Materials, through its Committee D-19 on Water, and was also cosponsored by the American Society of Mechanical Engineers Gerard Otten of Puricons, Inc., and R W Lane of the Illinois State Water Survey presided as chairmen of the symposium and also served as editors of this publication Related ASTM Publications Analysis of Waters Associated with Alternative Fuel Production, STP 720 (1981), $23.00, 04-720000-16 Aquatic Invertebrate Bioassays, STP 715 (1980), $24.00, 04-715000-16 Aquatic Toxicology: Third Conference, STP 707 (1980), $39.50,04-707000-16 Aquatic Toxicology: Second Conference, STP 667 (1979), $37.75, 04-667000-16 Native Aquatic Bacteria: Enumeration, Activity, and Ecology, STP 695 (1979), $25.00, 04-695000-16 Disposal of Oil and Debris Resulting from a Spill Cleanup Operation, STP 703 (1980), $15.75, 04-703000-16 Aquatic Toxicology and Hazard Evaluation, STP 634 (1977), $30.75, 04-634000-16 A Note of Appreciation to Reviewers This publication is made possible by the authors and, also, the unheralded efforts of the reviewers—this body of technical experts whose dedication, sacrifice of time and effort, and collective wisdom in reviewing the papers must be acknowledged The quality level of ASTM publications is a direct function of their respected opinions On behalf of ASTM we acknowledge with appreciation their contribution ASTM Committee on Publications Editorial Staff Jane B Wheeler, Managing Editor Helen M Hoersch, Senior Associate Editor Helen P Mahy, Senior Assistant Editor Allan S Kleinberg, Assistant Editor Contents Introduction PANEL DISCUSSION Introduction to the Panel Discussion—J K RICE Monitoring Power Plant Water Chemistry—F J POCOCK Critical Overview of Power Station Sampling and Analysis of Water and Steam—o JONAS II A Consulting Engineer's Role in Power Plant Instrumentation for Measurement of High-Purity Water Quality—T C HOPPE 24 Power Plant Instrumentation for Measurement of High-Purity Water Quality—JAMES BROWN 30 GENERAL GUIDELINES AND REQUIREMENTS FOR MONITORING Status of Continuous Monitoring in Central Stations—D E NOLL 37 Power Plant Water Quality Instrumentation: A Guideline for Operation, Calibration, and Maintenance—K A SELBY 49 Program for Steam Purity Monitoring: Instrumentation and Sampling—D F PENSENSTADLER, S H PETERSON, J C BELLOWS, AND W M, HICKAM 55 Program for Steam Purity Monitoring: Results of Power Plant TestING—S H PETERSON, D F PENSENSTADLER, J C BELLOWS, AND W M HICKAM 71 NEWER TECHNIQUES AND INSTRUMENTATION FOR MONITORING Quantification of Sodium, Chloride, and Sulfate Transport in PowerGenerating Systems—T B WILLHITE, S G SAWOCHKA, AND W L PEARL 83 Detennination of Anions in High-Purity Water by Ion Chromatograpliy—J A RAWA 92 Recent Advances in Ion Chromatograpliy—J E GIRARD AND j A GLATZ 105 In-Plant System for Continuous Low-Level Ion Measurement in SteamProducing Water—J L SIMPSON, M N ROBLES, AND T O PASSELL 116 High-Purity Water Quality Monitoring Based on Ion-Selective Electrode Technology—A A DIGGENS, SUSAN LICHTENSTEIN, J C SYNNOTT, AND S J WEST 131 Evaluation of Power Plant Measurement of Sodium Ions in High-Purity Main Stream and Feedwater Utilizing In-Line Continuous Specific-Ion Electrodes—R F EHERTS 139 Use of On-Line Atomic Absorption in a Power Plant Environment—M C SKRIBA, G B GOCKLEY, AND J A BATTAGLIA Zero: The Unreachable Goal—s A FISHER 156 167 Resistivity of Very Pure Water and Its Maximum Value—T s LIGHT AND P B SAWYER Continuous Conductivity Monitoring of Anions in High-Purity Water— R W LANE, F W SOLLO, AND C H NEFF 185 Description and Evaluation of a Continuous Sample Water Evaporator— S J ELMIGER, N J MRAVICH, AND C C STAUFFER 196 Determination of Trace Chlorine and Oxidants in Seawater by Differential Pulse Polarography-GUY WASHINGER AND PEETER KARK 213 175 SUMMARY Summary 229 Index 233 STP742-EB/Sep 1981 Introduction This symposium was organized to present the need for power plant instrumentation in the measurement of high-purity water quality and to disclose the latest developments in this instrumentation Present water treatment techniques in high-pressure electric utility plants are complex, and monitoring the water quality assumes a very important role in ensuring continuous and efficient operation of these power plants Proper and efficient monitoring of water quality is necessary to avoid expensive plant outages (at reported costs of $1 000 000 per day) that can occur if the plant chemistry is allowed to vary from specified limits, possibly because of inadequate instrumentation The papers in this volume disclose the problems involved in monitoring the water quality of high-purity water and provide information on new instrumentation and the refinements that have been developed The information contained here should be helpful to engineers designing the instrumentation for new plants, for those charged with the responsibility of updating instrumentation for plants that not have adequate monitoring equipment, and for plant chemists who must continually monitor the water quality to ensure uninterrupted and economical maintenance-free operation Since as many as seven or more different general methods of measurement are described here, a full picture of the available instrumentation has been provided Techniques employing various methods of measurement, such as ion chromatography, atomic absorption spectrometry, specific-ion electrodes, ion-exchange columns, electrical conductivity, a gravimetric method, and differential pulse polarography, are covered in this volume Discussions on methods of sampling, desired points of sampling, and other details are included This publication should bring the reader up to date on the present methods available for monitoring the quality of high-purity water for utility power plant usage R W Lane Illinois State Water Survey, Urbana, III 61801; symposium chairman and editor Gerard Often Puricons, Inc., Berwyn, Pa 19312; symposium chairman and editor Copyright 1981 b y A S I M International www.astm.org WASHINGER AND KARK ON DIFFERENTIAL PULSE POLAROGRAPHY 221 rallel titration and polarographic runs against standards prepared from a 5-ppm sodium hypochlorite stock The sodium hypochlorite stock was standardized using the amperometric titration method Synthetic seawater electrolyte, described previously, was used for both methods The errors observed at low levels in the titration method are unexplained, however, dilution of the 0.00564 N PAO titrant by 50 percent served only to decrease the clarity of the end-point break The addition of a small amount of acid to the cell just prior to running the polarogram has recently been shown to give PAO calibration curves which are more sensitive (0.6 nA/ppb versus 0.4 nA/ppb) and cover a slightly broader concentration range Results obtained from parallel analyses of synthetic seawater samples by the DPP method and the amperometric titration method are given in Table Each sample was prepared by adding small volumes of a stock NaOCl solution to litre of percent NaCl solution The volumetric flask containing the sample was covered with aluminum foil and the analyses were run, in triplicate, as quickly as possible Titrations were carried out with a commercially available amperometric chlorine titrator using the manufacturer's recommended procedure The DPP analysis was carried out using the procedure described previously except that just prior to initiating the scan, 100 yul of Af HCL was added to the cell The resulting pH is about and the PAO peak occurs at about —0.4 V versus silver-silver chloride As the previous comparison indicates Table shows good agreement of the two methods at moderate to high chlorine levels, but at low levels (about 200 ppb) the amperometric titration lost accuracy and eventually sensitivity while the DPP method still gave good response at the 10 ppb level Seawater Samples Seawater from just off the New Jersey shore along with Barnagat Bay water samples were obtained for analysis by the method described Polarographic blanks were prepared by omitting Step (immobilization) from the procedure The polarographic data obtained for New Jersey seawater is shown on Figs 4, 5, and Calculation of the chlorine equivalent yields 24.09 ppb Table Similar curves were obtained for the bay water sample and resulted in a chlorine equivalent of 10.22 ppb The seawater sample was also analyzed under conditions where the less reactive oxidative species would not react The results are also given on Table and indicate that, of the 24.09 ppb total chlorine equivalent, about two thirds of the contribution is probably due to slower reacting species Reanalysis of a laboratory-spiked bay water sample for total chlorine 24 h after immobilization gave 99.2 percent of theoretical recovery at 79.9 ppb 222 POWER PLANT INSTRUMENTATION ^ & c u E E o O s s ^ *• a2 a u 'n v» ?Si •\i •c a, •5> "3 ^ III It e a a .r Đ"1" &< a ^ 11 o ô a^ ã p ^ 00 ^ ' rK CO -e i^i f*V f * l CN f S i^ ^1 II r-«n^^«n ^