Operating Procedure F-5,Revision 1, "Chemical Control Limits."

PACIFIC GAS AND ELECTRIC COMPANY NUCLEAR GENERATION DEPARTMENT DIABLO CANYON POWER PLANT NO OPERATING PROC F r,

~ 4 TITLE: CHEMICAL CONTROL LIMITS

SCOPE

This procedure specifies the chemical control operating 1imits and where applicable, absolute limits for all the plant water systems. Procedures for making chemical adjustments to the various systems are not covered here.

PRERE UISITES

None

PROCEDURE

Chemical control 1'imits for normal"operation of the various plant water systems shown in the tables'hich follow. Process monitor instrumentation and periodic're sample analyses serve as the basis for checking the water quality. When the water quality is observed to be outside- the prescribed normal operating limits, prompt action should be taken to adjust the water quality to within the normal operating limits.

The tables included in this procedure are as follows:

'ABL'E'ND. TITLE

1 Accumulators 2 Auxiliary Boiler Water 3 Boric Acid Storage Tank and Boron Injection Tank Circulating Water Pump Motor Cooling System 5 Component Cooling Water 6 Condensate After Condensate Pumps '7 Condensate Storage Tank 8 Diesel Engine Jacket Cooling Water 9 Feedwater 10 Primary Water Storage Tank ll Reactor Coolant System 12 Refueling Mater Storage Tank 13 Residual Heat Removal System 14 Service Cooling Water 15 Spent Fuel Pool Mater 16 Spray Additive Tank 17 Stator Cooling Mater 18A Steam Generator Steam Side and Feedwater Chemistry Specifications for AVT 18B Steam Generato~ Blowdown Limiting AVT Specifications 19 Steam Purity

PAGE 1 OF 13 REYISION DATE 2/1/80

APPRO'IAL PLANT SUPERINTENDENT DATE

6 0041 60~ II L ' DIABLO. CANYON 1 ~ ",; POWER ANT UNIT NOS. AND 2 ~ 'PERATING PROCEDURE NO'. F-5 ': -'ITITLE: CHEMICAL'ONTROL LIMITS

a a ., TABLE C k ~ 1'CCUMULATORS

Par'ameter S ecification

Boric acid, ppm as boron 1900 to 2100

TABLE 2

'AUXILIARYBOILER WATER

S ecification Parameter erat>on ~et Layeu> pH, at 25'C 8.0 to 9.5 '=:.i'10.0 to 10.5 Dissolved 'oxygen, ppm Less than 0.10 Less'han 0.10 Hardness, ppm as CaC03 Less than 0.10 Chloride, ppm Less than 10 . 'Conductivity, at 25 C Less than 60 ymhos/cm Hydrazine, ppm Less than 1 75 to 1'50 Ammonia, ppm Less than 1.0 1 Iron and Copperz, ppm Less than 1.0

>Ammonia is to be added in sufficient quantity to adjust the pH to its specified range. This should normally require approximately 5 to 50 ppm aranonia.

2This is not intended as a control value; rather, it serves as an indicator of a system abnormality resulting from a crud burst, excessive corrosion rates, etc.

3The water level must be above the tubes and'he vapor space must be inerted with nitrogen during layup.

TABLE 3 BORIC ACID STORAGE TANK AND'ORON INJECTION TANK Parameter u if'0,000 Boric acid, ppm as boron to 22,500 Chloride~ ppm Less than 0.15 Fluoride~, ppm Less than 0.25 Silica, ppm Less than 2.1'ess Aluminum, ppm than 0.66 Calcium, ppm Less than 0.66 Magnesium, ppm Less than 0.66 Makeup Water Shall meet the specifications of Table 10, with the. exception for dissolved oxygen

Limit based on maximum limit of 0.00004$ Cl and 0.0002K F in boric acid crystals per W PDS 52205 AP, Rev. F.

2 PAGE OF 13 REVISION ~2''1'0 ~ .GATE $1

~ DIABLO CANYON POWER PLAh NIT NOS. 1 AND 2 OPERATING PROCEDURE NO. F-5 TITLE: CHEMICAL CONTROL LIMITS

TABLE 4

CIRCULATING WATER PUMP MOTOR COOLING SYSTEM

Parameter S ecification

Chromatei, ppm as CrO< 250 to 360 pH, at 25'Cz 9.0 to 9.7

iPotassium dichromate (KzCrq07) or potassium chromate (KqCrOq) must be used for makeup.

~The pH is controlled by the addition of potassium hydroxide (KOH) where the pH is less than 9.0, or by the addition of KzCrqOy when the pH is greater than 9.7.

TABLE 5

COMPONENT COOLING WATER

Parameter S ecification

Chromate>, ppm as CrO> 175 to 225 pHz 8.0 to 9.0 Chloride, ppm Less than 0.15 Fluoride, ppm Less than 0.15

>Potassium dichromate (KqCrqOq) or potassium chromate"(KqCrO<) must be used for makeup.

zThe pH is controlled by the addition of potassium hydroxide (KOH) when the pH is less than 9.0, or by the addition of KqCrq07 when the pH is greater than 9.7.

TABLE 6 CONDENSATE AFTER CONDENSATE PUMPS

Parameter S ecification Wet La u

Dissolved oxygen, ppb Less than 10 Less than 100 Hydrazine>; ppm I.O,] + 0.005 75-150 Ammonia, ppm Less than 1.0 Less than 1.0

i[0q7 means the concentration of dissolved oxygen, in the same units as hydrazine.

PAGE 3 OF 13 REVrsrON DATE 2/1/80 PAULO .CANYON POIPLANT UNIT NOS. I ANO 2 ,OPERATING PROCEDURE NO. F-5 TITLE: CHEMICAL CONTROL LIMITS

TABLE 7 CONDENSATE STORAGE TANK

Parameter Normal Limit's Absolute Limits

Cation Conductivity, at 25'C Less than 1.0 ymho/cm Less than 2.0 ymhos/cm " PH, at 25'C 6.0 to;8.0 5;-S.to 9;2 Total suspended solids~, ppm Less than O.l Less than 1.0 Dissolved oxygen'', ppm Less than O.l Less than 1.0 „ Free Hydroxide, ppm as OH Not detectable Less than 0.2 Sodium, ppm Less than 0.01 Less than 0.1 Silica, ppm Less than 0.2,. Less than 2.0

~Suspended solids are those which are retained on a 0.45 micron pore size filter.

zIn a practical sense, it may not be possible to maintain the oxygen at this level for all conditions of operation. However, it is imperative that maximum effort be made to maintain a low oxygen level at all times during wet layup and hydrostatic testing of the steam gen-. erators.

TABLE 8 DIESEL ENGINE JACKET COOLING WATER

Parameter S ecification

Chromate~, ppm as CrOq 790 to 1575 pH, at 25 Cz 8.5 to 10.0

>Potassium dichromate (KqCrz07) or potassium chr'ornate (KqCrOI,) must be used for makeup.

zThe pH is controlled by'the addition of potassium hydroxide (KOH) when the pH is less than 8.5, or by the addition of KqCrq07 when the pH is greater than 10.0.

'TABLE'

FEEDWATER

Parameter ~Met l.a u

Hydrazine, ppm [0>) + 0.005 75-'150'Less Dissolved Less than 5 than oxygen. ppb 100'ess Ammonia, ppm than 1.0

Dur ng power operat on (refer to Table 18 for limits during other modes of operation.

PAGE. 4 OF '13 NNYISION DATE 2/1/80' ) ~ DIABLO CANYON POMER PLANT IT.NOS. 1 AND 2 OPERATING PROCEDURE NO. F"

TITLE: CHEMICAL CONTROL LIMITS

TABLE 10 'PRIMARY MATER STORAGE TANK

Parameter

Cation conductivity Less than 1.0 gnho/cm at 25'C pH 6.0 to 8.0 at 25'C Dissolved Oxygen~, ppm Less than 0.10 Chloride and Fluoride (Total) ppm Less than 0.10 Total s'olidsz, ppm Less than 1.0 Suspended solids , ppm Less than O.l Silica, ppm Less than O.l Potassium, ppm Less than 0.01 Sodium, ppm Less than 0.01 Aluminum, total, ppm Less than 0.02 Calcium, ppm Less than 0.02 Magnesium, ppm Less than 0.02

>Oxygen concentration in the makeup water to the Reactor. Coolant System must not exceed 0.1 ppm when the coolant temperature is greater than 180'F. zExcluding boric acid in the Reactor Coolant System makeup. sSolids are defined as particles retained on a 0.45 micron pore size filter.

PAGE 5 OF 13 REVISION 1 DATE 2/1/80 DIABLO CANYON POWE NT UNIT NOS. 1 AND 2 OPERATING PROCEDURE NO. 'F-5 CHEMICAL .CONTROL. LIMITS

. TABLE ll REACTOR COOLANT SYSTEM

S ecifications Parameter tea tate on >talons

Conductivity, pnhos/cm Varies with boric acid and at 25'C alkali. Exp'ected range is from 1 to 40. pH Varies with boric acid and 9.8-10. 2 alkali, Expected range is from 4.2 to 10.5 at 25'C

Dissolved oxygen ~; ,3,ppm <0.10 <1. 0

Chloride ',4, ppm <0.15

Fluoride ~,", ppm <0.15 <1.5 <0.15 Hydrogen', cc(STP,)/kg power >1MWt 25-50 normal target band 30-40 Total suspended solids6, ppm

Lithium -77, ppm as Li 0.7-2.2 0.7-2.2

Boric acid, ppm's B Variable from 0-4000

Silica8, ppm <0.2

Al.Uminuma, ppm <0.05-

Calciums,. Ppm , <0;05

Magnesiums, ppm <0.05

e '! Wst t 1s c emsstry parameter in excess"'of its steady'state limit, but within its t'ransient limit, restore'the'pa'rameter; to within its steady'tate limit within 24 hours or be in't least HOT STANDBY within the next 6 hours,'and in COLD SHUTDOWN within, the follow'ing 30 hours. If a.transient limit is 'exceeded, be in at least HOT STANDBY within 6'hoiirs and in COL'D'HUTDOWN within the following 30 hours. 2Limits apply prior to heatup beyond-180'F. During power'peration with the specified hydrogen concentration maintained in the coolant, the'esidual oxygen concentration must not ex'ceed 0.005 ppm.

13 ' PAGE .6 OF REVISION .'. -1 'ATE'/1/80'--- tl l~

DIABLO CANYON POWER PLAN IT NOS. 1 AND 2 OPERATING PROCEDURE NO. F-5 TITLE: CHEMICAL CONTROL LIHITS

TABLE ll - (Continued)

sOuring startup, hydrazine may be used in concentrations up to 10 ppm when the coolant temperature is between 150'F and 180'F 'and the Oq exceeds O.l ppm.

"Halogen concentration must be maintained below the specified limits regardless of system temperature.

'Owing to changes in pressure in volume control tank during coolant letdown and charging to the RCS, the hydrogen concentration may exceed the normal operating range of 30 to 40 cc(STP)/kg.HqO. At power levels-above 1 NWt the hydrogen concentration in the coolant must be within the specified range of 25 to 50 cc(STP)/kg. Twenty-four hours prior to a scheduled shutdown, when the RCS is intended to be cooled down, the hydrogen concentration may be reduced to 15 cc(STP)/kg Hz0. The earlier reduction in hydrogen concentration facilitates hydrogen degasification following shutdown. This specification is not intended to include decay heat generated during subcritical operation.

Suspended solids are those which do not pass through a filter having 0.45 micron pore size. ~The lithium -7 limits apply prior to heatup beyond 150'F. aThese limits are included as recommended standards for monitoring coolant purity. Establishing coolant purity within the limits shown for these species is judged desirable with the current data base to minimize fuel clad crud deposition which affects the corrosion resistance and heat transfer of the clad.

PAGE 7 OF 13 REVISION DATE 2/1/80 DIABLO CANYON POM PLANT UNIT NOS. 1 AND 2 .OPERATING PROCEDURE:NO. F-5 TITLE: CHEMICAL CONTROL LIMITS

TABLE 12 REFUELING MATER STORAGE TANK

Parameter S ecification

Boric acid. ppm as boron 2000 to 2200 pH, at 25'C 4.0 to 4.7 Chloride, ppm Less than 0.15 Fluoride, ppm Less than „0.15 Suspended Solids', ppm Less than 2.0 . Silicaz, Less than 0.30 ppm'luminumz, ppm Less than 0.08 Calciumz ppm Less than 0.08 Magnesiumz,'pm Less -than 0.08 Makeup water Shall meet the specifications of Table 10,,with the exception for dissol.ved oxygen

are those which do not pass throughV'Solids a fil,ter having 0.45 micron pore size. zThese limits are included in the table of refueling water storage tank specifications as recommended standards for monitoring the refueling water purity. Since the refueling water becomes common with the reactor coolant during refueling, it is judged desirable with the current data base to establish refueling water limits shown, for these species to minimize fuel clad deposition which affects the corrosion resistance and heat transfer of the clad.

'PAGE 8 OF 13 REVISIDII 1 DATE.,2/1/80 ) 4 g3 DIABLO CANYON POWER PLA UNIT NOS. 1 AND 2 OPERATING PROCEDURE NO. F-5 CHEMICAL CONTROL LIMITS

TABLE 15

SPENT FUEL POOL WATER

Parameter S ecification

Boric acid, ppm as boron~ 2000 to 2500 pH, at 25'C 4.0 to 8.0 Chloride, ppm Less than 0.15 Fluoride, ppm Less than 0.15 Calcium, ppm Less than 1.0 Magnesium, ppm Less than 1.0 Makeup Water Shall meet the specifications of Table 10, with the exception for dissolved oxygen.

~The boron specification applies during periods when fuel transfer operations via the transfer canal are in progress. During initial fuel loading, the boron concentration limit does not apply.

TABLE 16 SPRAY ADDITIVE TANK Parameter ~Bi i ti

Sodium hydroxide, as NaOH 30 to 325 by weight Sodium carbonate, as NaqCOq Less than 1.0% by weight

TABLE 17 STATOR COOLING WATER

Parameter S ecification

Conductivity, pmhos/cm at 25'C Less than 1.5 Chloride, ppm Less than 0.15 Suspended solids Less than 1 FTU

PAGE 10 OF 13 >EVISION DATE 2/1/80 DIABLO CANYON POWE, E'LANT UNIT NOS. 1 AND 2 OPERATING PROCEDURE NO. F-5 TITLE:, CHEMICAL CONTROL LIMITS

TABLE 15 SPENT FUEL POOL WATER

Parameter S ecification

Boric as 2000 2500 acid, ppm boron'M, to at 25'C 4.0 to 8.0 Chloride, ppm Less than 0.15 Fluoride, ppm Less than 0.15 Calcium, ppm Less than 1.0 Magnesium, ppm Less than 1.0 Makeup Water Shall meet. the specifications of Table 10, with the exception for dissolved oxygen.

iThe boron specification applies during periods when fuel transfer operations via the transfer canal are in progress. During initial fuel loading, the boron concentration limit does not apply.

TABLE 16 SPRAY ADDITIVE TANK

Parameter S ecification

Sodium hydroxide," as NaOH 30 to 325 by weight Sodium carbonate, as Na~C03 less than 1.0Ã by weight

TABLE 17 STATOR COOLING WATER

Parameter S ecification

Conductivity, qmhos/cm at 25'C Less than 1.5 Chloride, ppm Less than 0.15 Suspended solids Less than 1 FTU

PAGE 10 'F 13 REVISION DATE 2/1/80 TABLE 18A

STEAM GENERATOR STEAM SIOE AHD FEED'ifATER CHEMISTRY SPECIFICATIONS FOR AVT Par~meter Cold Hydro, Hot Functional, Hot Hct Layup> Shutdown, Hot Standby Startup from Hot Standby Normal Power Operations Slowdown Blowdown Feedwater Blowdown Fccdwa ter Blowdown Control Expected Control Expected Control Expected Control Expected Control Expected pH at 25'C 10.0-10,5 8.8-9.2 8.8-9.2 N. 8.8-10.0s 8.5-10.0s 8.5-10.0s HA 8.8-9.2 8.5-9.0 8.5-9.0 Free OH. ppm Not detectable <0.05 <0.05 N N <0.05 «0.05 NA HA <0.05 <0.05 Cation Conductivity, NA <2.0 <2.0 HA 'A <77 <7z tlA .HA <2.0 «2.0 uml:os/cm at 25'C Specific Conductivity, N 'lA HA NA HA c4 >moos/cm at 25'C hA

Sodium, ppm HA -HA <0.1 N HA. HA . 'c0.5 HA HA NA '0.

Chloride,, ppm ~ <0.5 NA <0.15. HA HA tlA c0.5 HA HA HA «0.15 Arsconia, ppm As pH requires NA '«0. 5 HA HA HA <10.0 NA <0.5 tlA <0.25 . ~ Hydrazine, ppm 75-150z HA HA [Oz]+0.005s [Oz]<0.005s NA N [Oz]~0.005 'Oz]%.005 NA HA Dissolved Oxygen, <100 ~ . ppb HA c5 c100 c 100 HA' . c5 <5 c5 NA c5 Si0., . HA ppn HA <1.0 ttA HA HA c5 tlA, HA NA <1,0 Iron, ppm HA NA HA tlA '<0.1. NA HA llA <0.01 HA. NA Coppcri PPn HA HA HA HA c 0.05 .HA N HA c 0.005 HA HA Suspended Solids, ppm HA HA «14 HA NA HA HA HA HA ~ HA <1;0 Blcwdown Rate, gpm/SG N HA As HA ~ required HA Maximum Maximum HA NA As required HA ~ I O N r: ans not applicable. m >Ccndensate ~ « quality makeup water shall be used exclusively in achieving these conditions. Curing. Cold Hydro, scmc decomposition C7 of hydrazine is expected; sufficie'nt hydrazine should be added with the nakeup to reestablish the Cold itet ) Layup conditions at completion of .the test. m Fcedwater (Auxiliary Fcedwatcr) shall be of condensate makeup quality to which ammonium hydroxide and hydrazine are added at the inlet into the O steam generator for pH and oxygen control. The hydrazine shall be added at h rate to achieve a hydrazine concentration equivalent to three to . five times the oxygen concentration. O O g ~ " Curing hot functional testing, higher than normal suspended solids are expected. Blowdown should be maximized to reduce thc stean generator solids content to the concentration specified. r Vl OcParture from the normal 8.8-9.2 « PH range allows for increased HHs resulting from decomPosition of hydrazine used for feedwater system layuP. sHydrazinc level should exceed oxygen level by 5 ppb.

70uring startups. up to 48 hours from the initiation of plant loading, additional latitude from normal operating specifications is provided because increased levels of contaminants arc expected. "Operation outside the control par'amctcrs spccificd for. norcml power operation is governed I by the limiting conditions specifications (see Table 18B). - DIABLO CANYON POWE ANT UNIT NOS. 1 AND 2 ~ OPERATING PROCEDURE NO. F-5 TITLE: CHEMICAL CONTROL LIMITS

TABLE 188

STEAM:GENERATOR 'LOWDOWN 'IMITING AVT'SPECIFICATIONS Parameter Two Weeks~ 24 Immediate~ Hours'A pH at 25'C 8.0-8.5 or 9.0-9.2 <8.0 or >9.4 Cation Conductivi ty, >2.0 but <120 >120 pmhos/cm at 25'C

Free Hydroxide, ppm NA2 >0.05 but <0.35 >0.35

Blowdown Rate, gpm/SG - - - - Maximum available capacity - - --

~Corrective action including shutdown, if necessary, is recommended within the time periods indicated.

No relief for Free Hydroxide above the normal operating control limit of 0.05 ppm is provided in excess of 24 hours.

TABLE 19 STEAM'URITY S ecifications Norma L matin Con >talons Parameter Notes 0 erations 2 Weeks 24. Hours

Cation conductivity, <0. 3 0. 3-'0'. 5 0.5-1.0 pmhos/cm Dissolved oxygen, ppm <0. 0.01-0.03 01'0.'005 0.'03-0.10'.005-0.'010 Sodium,, ppm 0.010-0.020 Chloride, ppm <0.005 0.'005-0.010 0.010-0.020 Silica, ppm <0!010 0.010-0.020 0.020-'0.050 Copper,. ppm <0'.002 Iron, ppm <0:020 Sulfites and sulfates Not'etectable

>Yalue to be used as a cont'rol parameter. Either continuous direct analysis of condensed inlet steam, or as calculated from steam generator water and mechanical and vaporous carryover.

2Not a control parameter. The values represent typical levels which should be achieved under steady state conditions.

PAGE 12 OF 13, NNVrSrON DATE'/1/80' g ~

E AND'2 DIABLO CANYON POWER PLANT UNIT NOS. 1 OPERATING PROCEDURE NO. F-5 TITLE: CHEMICAL CONTROL LIMITS

REFERENCES

l. Diablo Canyon Power Plant FSAR, Table 10.4-2 2. "ChI.mistry Criteria and Specifications," Westinghouse Electric Corporation Document No. 5-1 (Previously WCAP-7452), Revision 2, March 1977, Nuclear Energy Systems, Water Reactor Divisions,'WR Systems Division. 3. .General Operating Orders, 5.301, 5.315, 8.201, 8.302

4. Standard Technical Specifications

5. "Steam -Side Water Chemistry Control Specifications," Westinghouse Electric Corporation Document No. 5-4 (Previously WCAP-8113), Revision 1, January 1975, Nuclear Energy Systems, Water Reactor Divisions, PWR Systems Division.

ATTACHMENTS

1. Appendix 1, Steam Cycle Process Sampling Points

2. Appendix 2

PAGE 13 OF 13 REVISION DATE 2~/1 80 0

l' DIABLO CANYON POWER PLA UNIT NOS. 1 AND 2 OPERATING PROCEDURE NO. F-5 TITLE: CHEMICAL CONTROL LIMITS

APPENDIX 1

STEAM CYCLE PROCESS SAMPLING'POINTS

The steam cycle process sampling system is provided for continuous, instrumented chemical analyses for certain important parameters. The steam cycle analyzer network ncompasses monitoring the following 'subsystems. 1. Main Condenser I The condensate in the main condenser is monitored for saltwater intrusion. Monitoring consists of measuring cation conductivity for the condenser tube sheet leak detection system, and specific conductivity for the condenser tray sample system. In addition, the east condenser half and the west condenser half are each sampled and ahalyzed for sodium ion. This particular sampling is accomplished through a header network from the samples on the tube sheet leak detection system and the condenser tray sample system. I

2. Condensate Pumps Discharge Header

Condensate downstream of the condensate pumps and the point where chemical addition takes place is sampled and analyzed for dissolved oxygen, specific and cation conductivity.

3. Feedwater

The feedwater is sampled downstream of feedwater heaters lA, B, and C on a common header. This water is analyzed for dissolved oxygen, hydrazine, pH, specific conductivity and cation conductivity.

4. Steam Generator Blowdown

Each steam generator's blowdown water is monitored for cation conductivity, pH, and sodium ion. In addition, the four steam generator samples header together, and the mixed sample is monitored for radioactivity (RE-19).

5. Steam Generator Steam

Each steam generator's steam is monitored for specific and cation conductivity.

This network of analyzers is'intended to provide the operator with a data base which serves as guidance for operation of the plant. The measurement value for a monitored parameter is to be compared to the limits specified in the appropriate tables in the main body of this procedure'.REVELS When a monitored parameter indicates a value which is outside the normal control value, corrective action must be taken without delay. THE INSTRUMENT READING IS TO BE CONSIDERED ACCURATE. The only exception to this admonition is when it is known for a fact that the instrument reading is actually in error. I The identification of the individual analysis instruments are shown in the following tables and figures.

PAGE 1 OF 5 NN DATE 2/1/80 I

DIABLO CANYON POW LANT UNIT NOS. 1 AND 2 OPERATING PROCEDURE NO. F-5

TITLE: CHEMICAL CONTROL LIMITS

APPENDIX 1 (Cont'd) TABLE Al-1 'AIN CONDENSER'SALTWATER INLEAKAGE INSTRUMENTATION

Sample Sam le Cell and Panel Nos. Sys tern Location Un 1 t ni t ane ane NW Inner 31 2A 29 Condenser Trays, Outer None 30 Specific Conductivity Inner 26 27 Measurement Outer 25 28 Inner 29 31 2A Outer 30 None SE Inner 27 26 Outer 28 25 NW Inlet 93 61 97 61 Tube Sheet Leak Outlet 94 61 98 61 Detection, Cation Inlet 91 61 95 61 Conductivity Outlet 92 . 61 96 61 Measurement Inlet 97 61 93 61 Outlet 98 61 94 .61 Inlet 95 61 91 61 Outlet 96 61 92 61 Condenser Inleakage West 99 63 Sodium Ion Measure- Half 99 63 ment East Half 100 63 100 63

Notes for Table Al-1: 1. Panel 2 is located in turbine building, East side of condenser. 2. Panel 2A is located in turbine building, West side of condenser. 3. Panel 4 is located in turbine building, East side of condenser. 4. Panel 5 is located in turbine building, West side of condenser. 5. Panel 61 is located in turbine building, Northeast of the condenser for Unit'.1, and Southeast of condenser for Unit 2. 6. Panel 63 is located in turbine building, Northeast of the condenser for Unit 1; and Southeast of condenser for Unit 2. 7. The sample supplied to cell 99 (sodium analysis) is a composite sample from samples supplying cell Nos. 25, 26, 27, 28, 91, 92, 95, and 96. The sample supplied to cell 100 (sodium analysis) is a composite from samples supplying cell Nos. 29, 30, 31, 93, 94, 97 and 98. 8. Refer to Figure A-1 for sample source location. 9. The signal from the condenser tray samples is recorded on the turbine board (VB3) in the control room; the signal from the condenser tube sheet samples is annunciated on high conductivity.

PAGE 2 OF 5 RtVtSrON DATE 2/1/80 -l a0 C7 NM W Pl 30 CÃ7 Pl 5 I 98 97 93 C) 29 O Q mm w O +O OUTLET INLET OUTLET W Pl I O Xl O % 26 XO ~ 91 + . 96 l I I w Ql

SE V)

UNIT 1

UNIT 2

30 93 29

OUTLET OUTLET INLET

FIGURE Al-1 'CELL NUMBERS FOR'BENIN CONDENSER SEAtlATER INLEAKAGE INSTRUMENTATION DIABLO CANYON POW LANT UNIT NOS. 1 AND 2 OPERATING PROCEDURE NO. F-5 TITLE: CHEMICAL .CONTROl LIMITS

APPENDIX 1 (Cont'd)

TABLE AJ-2 CONDENSATE WATER qUALITY INSTRUMENTATION

PARAMETER CELL,NUMBER PANEL,NUMBER

Dissolved 0 en 90 S ecific Conductivi,t ,88 Cation Conductivit 89

Notes for Table Al-2

1. Panels 1 and 3 are located in the auxiliary building sample room on the 85'levation.

2. The signals from these.moni,tors are, recorded, on the, turbine board (VB3).

TABLE Al-3 .FEEDWATER UALITY INSTRUMENTATION

PARAMETER CELL NUMBER PANEL, NUMBER

Dissolved Ox en 81

H drazine 35 S ecific Conductivit 59 Cation Conductivit 60 3 47

Notes for Table Al-3:

1. Panels 1 and 3,are located in the auxiliary, building sample room on the 85'levation.

2. The, signals from,the DOq, hydrazine, specific and cation conductivity are recorded on the turbine board (VB3).

3. The FW pH is recorded on panel 1, and annunciates in the control room on high or low pH.

5 ;PAGE .4 OF ,DATE ,2/1/80 ~ ~ ~ I ' I j g ~ ~ ' ''I 1 I 'I

~ > ) ~ ~

I' I II I

~ ~ ~ i ~ ' ~ ~

~ ~ ~ ~EMERGES%~ i ~ i ~

~ ~ ~iggQ

I ~ ~

~ ~ ~ ~ ~ ~ 0 ~

~ ~ ~ I ~ ~ ~ ~ ~ ~ ~ ~

~ I I ~ ~ ! ~ ~ ~ ~ ~ ~ ~

I ~ ~ ~ ~ ~ ~ ~ ~ I

i ~

i $ i

~ ~ ~ ~ ~ i ~ ~~R~~~

~ ~

~ ~ ~ ~

~ ~ ~ 1 ~ ~ ~ ~ ~ ~ ~ ~ ~

~ ~ ~ ~ ~ ~ ~ ~ ~ I ~ I ~ ~

I ~ ~ ~ ~

~ ~ I ~ 0 I. . DIABLO CANYON POWER PL UNIT NOS. 1 AND 2 OPERATING PROCEOURE NO. F-5 TITLE: CHEMICAL CONTROL LIMITS

APPENDIX 2 This appendix discusses the rationale for controlling'various chemical parameters for the major water systems. As part of this discussion, advisory comments are also provided for plant operation and shutdown associated with the power cycle chemical control parameters. It should be appreciated that some degree of corrosion or degradation of system materials will be taking place at all times. As such, the chemical control limits established in this procedure do not provide for a condition where "zero" corrosion rates exist; rather, the objective is to maintain the water quality to keep the corrosion rates tolerab')y low, and thereby extend the service life of system components.

1. REACTOR COOLANT SYSTEM

'. Electrical Conductivity and pH

These values will vary during fuel cycle lifetime and will be affected by the concentration of boric acid and alkali present. Observed variations in the electrical conductivity and pH, not associated with planned changes in system chemistry, may indicate deterioration of reactor coolant quality.

V b. Oxygen

Oxygen concentration of the reactor coolant is to be maintained below 0.1 ppm for plant operation above 180'F. The limit of 0.1 ppm is intended primarily as a guide to continuation of plant heatup from 180'F.to normal operating temperature. Plant operation with the specified hydrogen concentration will result in oxygen concentration below the detectable limit, that is less than 0.005 ppm. It has been observed that oxygen added to the system, for example, in makeup water will be consumed in the system. However, the consumption results in part from undesirable oxidation of metal surfaces with increased corrosion and corrosion product formation. Chloride

Chloride is well known to be detrimental to austenitic stainless steels in its role in stress corrosion cracking. The specified limit, acceptable for use. in these system materials, can readily be achieved with conventional water, treatment systems. d. Fluoride Fluoride concentration must be limited to the specified value to pre- clude the possibility of attack of the Zircaloy fuel cladding as well as the austenitic stainless steels. e. Suspended'olids

The concentration of suspended solids must be limited to minimize the

PAGE 14 ~ OF REVISION 1 DATE 2//120 0%4<" ~' "'l '

DIABLO CANYON POWE ANT UNIT NOS. 1 AND 2 OPERATING PROCEDURE NO. F-5 TITLE: CHEMICAL CONTROL LIMITS

APPENDIX 2 (Cont'd) presence of solid materials which could add,to fuel clad fouling 'and to an increase in the r'adioactivity level of the coolant as activated corrosion products.

f. pH Control Agent

The solution pH will vary with the concentration of. boric acid arid alkali present. The expected range measured at 25'0 is between'.2 and 10.5. Litliium hydroxide is added to the'oolant to'rov'ide'an alkaline envirohment at operating temperatures. As the reactor, coolant

temperature increases, dissociation of boric acid decreases allowing'he alkaline additive to control the coolaht pH,

g» Hydrogen

Owing to chang'es in pressure in the chemical and volume control kanPk during coolant letdown and charging to the, RCS', the hydrogen concen'-„ tration may exceed the normal operating range'f 30 to 40 cc (STP)'/kq H20. At power'evels abov'e 1 NMt the'ydrogen concentration-iri must- be within -the specified range of 25'o'0 cc (STP)'/kg.the'oolant Twenty-four'ours prior to a scheduled shutdown, whe'n the reactor coolant systeii is'nterided to be cooled down, th'e hy'drogen concentr'a'-

'tion may be''educed'o 15 cc (STP)/kg H20. The earlier reduction'n hydrogen concent'ration facilitates hydrogen dega'sification follow'ing shutdown. This specification is not intended to include: decay'eat generated during subcr'itical operation'.

The hydrogen excess in the'CS provides a mechanism for coPnverting oxygen (pro'duced from water rad'iolysis') back'to water (i.e.,"

2Hz+02~2H20).'eolite h. Forming, Elements

The thermal and'ydiraulic conditions in some Westinghouse cores'are conducive to a'imited:degree of subcooled nucleate boiling heat transfer; nucleate boiling, is, in turn, conducive: to'increased crud deposition. Conversely', cores with singgle phase heat transfer may'e subject to excessive'crud deposition due to high levels of impurities in the coolant',. or for'ther'r'e'asons; this may'ause initia'tion of boiling'eat transfer". In either"case, incorporation of ma'gnesium and calcium.hardne'ss"and aluminum and silica into th'is crud will cause (1) a signficant barrier to the'heat transfer, and, (2) densification of the crud; with the potential for*increased con'centration of lithium hydroxide at'he clad surface. Experience. with boiling heat tra'nsfer surfaces, generally, and with nuclear'uel, in particular, indicates both can lead to destructive corrosion and hydriding of the fuel c'ontrol of the'oolant purity, as indicated elements.. Thus, appropriate 'n table'l. is required to provide a high degree of core integrity. Furthermore, impro'ved control of c'rud buildup in the-core will help" limit the transport'of activation products-throughout the primary- system. ' " ''ll'(IO.t'I * 6 ' m 4 ' gal'0'lit 0

0'AG22 2 OF," 14',i 82P18108a 1 O'AT2-,2/1/80,, . DIABLO CANYON POWER PLANI'NIT NOS. 1 AND 2 OPERATING PROCEDURE NO. F-5 CHEMICAL CONTROL LIMITS

APPENDIX 2 (Cont'd)

2. TURBINE STEAM PURITY

The presence of unwanted corrosive impurities in steam can cause damage tn turbine components by corrosion, stress corrosion and corrosion fatigue. Deposition of impurities can also cause distress by lowering the efficiency of blades, upsetting pressure distributions and clogging seals and clear- ance in valves. If the extensive damage, lengthy outages and costly repairs caused by these occurrences are to be avoided, the purity of the steam throughout the turbine must be rigorously controlled. In addition, positive steps must be taken to assure that impurities from chemical cleaning procedures for plant piping and equipment do not get into the turbine.

From the point of view of steam turbine operation, ammonia, cyclohexylamine and morpholine may be used for pH adjustment. Water injections should utilize condensate quality water. Reconmended limits for impurities commonly found in turbine steam are given in Table 19. The normal values represent Westinghouse recommendations for reliable turbine operation. These values represent limits where the impurity concentration in steam is below its expected solubility limit everywhere in the dry regions of the turbine. The limiting conditions represent undesirable conditions which should be corrected to normal within the time periods indicated. In plants where better steam purity can be maintained, every effort should be made to do so.

3. STEAM SIDE WATER CHEMISTRY

Condenser leakage, makeup water flash evaporator carryover or demineralizer breakthrough and condensate feedwater systems corrosion products are the sources of chemical agents that have the potential for accumulating as sludge on the steam generator tube sheet, producing deposits on steam generator heat transfer surfaces and for being deleterious to the steam generator materials of construction. The feedwater is the means by which these chemical agents are transported to the steam generator. Recognition must be given to the fact that an All Volatile Treatment (AVT) chemistry provides no buffer against the effects of condenser leakage, that it is incapable of preventing the formation of scale should the chemical agents that, have the propensity for scale formation be present and that the ammonium hydroxide or the amines added to the system for feedwater pH control have minimum effectiveness as steam generator pH control agents at the operating temperature in the steam generator. Therefore, to accomplish the goal of maintaining a steam generator steam side all volatile chemistry environment which is innocuous to the steam generator materials, it is necessary through a rigorously controlled chemistry program to minimize the introduction of contaminants to the system and to minimize corrosion of the materials of construction of the condensate and feedwater systems. In addition to providing the proper environment for the steam generator, a well maintained AVT chemistry program will accomplish the following:

. Maintain a high integrity of all systems components.

PAGE 3 OF REVISION DATE 2/1/80 DIABLO CANYON 'POWER ~ANT UNIT NOS. 1 ANO 2 OPERATING PROCEDURE NO. F-5 TITLE: CHEMICAL CONTROL LIMITS

APPENDIX 2 (Cont'd)

- Avoid or minimize turbine deposits due to carryover and volatility from the steam generator. . Minimize sludge at its point of concentration, the steam generator. ~ Minimize scale deposits on the steam generator heat transfer surfaces. - Minimize feedwater oxygen content prior to entry into SG. -'Minimize corrosion of the condensate/feedwater systems materials..

These objectives can be achieved by proper selection of systems materials and by exercising careful chemistry control over the systems, including comprehensive sampling and analysis (in-line and laboratory), chemical injection at selected points, continuous system blowdown from the steam generator and effective protection of 'the steam generator and feedwater train internals during periods of inactivity. The details of are discussed in the following sections. these'rocedures. a. General Treatment Requirements

The steam system All Volatile Treatment chemistry specifications are addressed to the concerns of:

~ .Minimizing metal, corrosion ~ Limiting the accumulation of sludge in the steam generator ~ Minimizing scale formation (Ca-Mg) on the heat transfer surfaces ~ Minimizing the potential for the -formation of free caustic or acid ~ 'Maintaining "zero" dissolved oxygen level (particularly at points of contact with carbon steel and the steam generator heat transfer surfaces, viz., the Inconel 600 tubing.)

The above concerns will be minimized by meeting the three steam generator control parameter s identified in Table 18A, specifically the blowdown pH, cation conductivity and the Free Hydroxide Protection of the steam generators during inactive periods due to maintenance, refueling, etc. will require placing the steam generators in a layup condition. To ensure the long term performance of the steam system, it is essential that .the same degree of chemical control be exercised during these idle periods as that'xercised during normal plant operation.

PAGE 4 OF 14:- REVISION DAT,E ~2'Qgg ,DIABLO CANYON POWER PLAN NIT NOS. 1 AND 2 OPERATING PROCEDURE NO. F-5 TITLE: CHEMICAL CONTROL LIMITS

APPENDIX 2 (Cont'd)

Periods of hot shutdown and hot standby operati'on require that steam be released from the steam generators to provide heat release from the Reactor Coolant System due to heat input from core decay and reactor coolant pump heat. Chemistry control must be ap'plied during such operations similar 'to that exercised during normal operating conditions. Feedwater addition to the steam generators during this period may be from the condenser hotwell (if the condenser is being used as the heat sink and the condenser is being maintained under adequate vacuum), or the feedwater supply must be taken from a deaereated source (i.e. an appropriately designed condensate storage tank, etc.) in order to exclude oxygen from the system. Testing procedures should be instituted to check the steam generator water chemistry during hot shutdown and hot standby operating periods to maintain a proper chemical environment. Increased blowdown should be used as required to keep the steam generator water chemistry within specifications per Table 18A. It is imperative that the feedwater supply to the steam generators at all times have a low dissolved oxygen content. The only acceptable deviation from this rule is the water supplied to the steam generators during an emergency condition after the assured supply of deaerated condensate in the condensate storage tank has been exhausted and the alternate emergency sources of water are being utilized. The normal method of providing low dissolved oxygen content water to the steam generator is through the condensate and feedwater systems. The auxiliary feedwater system should also be capable of providing deaerated water to the steam generator for extended startup and hot standby operation. Therefore, the condensate storage tank must contain de-oxygenated water at all times in order to provide the desired quality water to the auxiliary feedwater pumps. The procedure to be followed in providing the protection mentioned above is discossed in greater detail in the following sections.

1) Steam Generator and Feedwater Chemistry "Control" Specifications

These specifications reflect a means for proper chemistry control in all of the steam cycle components. The possible occurrence of system contamination through condenser leakage, makeup water system mal- function or primary-to-secondary leakage is acknowledged. UNDER NO CIRCUMSTANCES SHOULD SODIUM PHOSPHATE OR OTHER CHEMICALS BE FED TO THE STEAM GENERATORS TO COMPENSATE FOR THE INTRODUCTION OF CONTAMIN- ANTS FROM THESE SOURCES. The bases for these specifications are more fully described below. Fundamental to the AVT approach to chemical control is the use of ammonium hydroxide or morpholine for for feedwater and steam pH control. Ammonium hydroxide is generally preferred; however, morpholine is acceptable provided it does not interfere with the sensitivity of the free hydroxide determination. Also, oxygen scavenging in the feedwater train is accomplished with non-catalyzed hydrazine. Under normal conditions, continuous blowdown'nd continuous chemical addition is maintained.

PAGE 5 OF 14 REVISION ~ DATE DIABLO CANYON POWER NT UNIT.NOS. 1 AND 2 OPERATING PROCEDURE NO. F-5 TITLE: CHEMICAL CONTROL LIMITS

'PPENDIX 2 (Cont'd) a) Feedwater Chemistry Control Parameters

Both the feedwater and steam systems are once-through systems requiring that any chemical treatment of these systeIIIs be based on the AVT concept regardless of the chemistry used in the steam generator. This concept has been adhered to by Westinghouse in its previous and present specifications relating to feedwater chemistry control.

(1) Dissolved Oxygen For corrosion prevention, oxygen must be eliminated as far as possible from the feedwater entering the steam generator. There must be no detectable oxygen (<0.005 ppm) present in the blowdown under any operating or test condition. Oxygen is controlled by the addition of hydrazine at the discharge of the condensate pumps. THE USE OF SULFITE FOR THIS PURPOSE IS PROHIBITED. For hot functional testing and hot standby, the concentra- 'ion of oxygen in the feedwater can be O.l ppm or less provided the concentration of hydrazine injected into the steam generator is 3 to 5 times the oxygen concentration in the feedwater source.

The principal source of oxygen intrusion into the secondary system is air inleakage into the main condenser and in the portions of the condensate and feedwater train which are at sub-atmospheric pressure. It should be recognized that the ,points where sub-atmospheric pressures occur varies with power level. The steam jet air ejector discharge flow .rate should be closely monitored for indications of abnormally high.air-inleakage flow rates. (2) Hydrazine Hydrazine is added to the feedwater to control oxygen as mentioned above. The concentration of hydrazine in the steam drum during hydro and,wet layup must be in the range 75 - 150 ppm. For hot functional testing and hot standby th'ydrazine concentration in the .feedwater should be maintained at 3 to 5 times the oxygen concentration in the feedwater source. For power operation, it is recommended that a hydrazine residual of >0.005 ppm in excess of the feedwater oxygen be maintained downstream of the highest pressure feedwater heater.

b) Steam Generator Chemistry Control Parameters

(1) pH

When controlling steam generator chemistry on,AVT chemistry

'AGE 14 EF IgGP ~ OF REIII GIGA I GATE rr r rt

DIABLO CANYON POWER PLANT NIT NOS. 1 AND 2 OPERATING PROCEDURE NO. F-5 CHEMICAL CONTROL LIMITS

APPENDIX 2 (Cont'd) it must be recognized that 1) AVT provides no buffering capacity for contaminants entering the steam generator and 2) the steam generator bulk water pH is at or slightly in excess of the neut'ral pH for water at the operating temperature of the steam generator. The ahsence of alkalin- ity in the steam generator at its operating temperature is due to the low ionization of the feedwater pH control amines at these temperatures. Therefore,.contaminants entering the steam generator .that are more strongly ionized than .the feedwater pH control amines have the potential for producing majol perturbations to the bulk water either in the form of acidity (sea water circulating cooling water).

Clearly then, the objectives of the steam generator pH control parameters stated in Tables 18A and 18B are to provide a means for controlling free acidity in the steam generator bulk water to minimize corrosion of the steam generator materials and turbine cycle and to provide a means whereby perturbations to the steam generator chemistry from sources such as condenser leakage can be recognized..

In the case of a sea water intrusion into a steam generator on AVT chemistry control a blowdown pH depression is expected. The magnitude of the pH depression at temperature was calculated from data developed by D.J. Turner. It was determined that for chloride concentration implied by the cation conductivity control parameter (10 ppm) for sea water plants (Table 188) the operation temperature (300'C) pH in the steam generator would be depressed approximately 0.5 pH units while the room temperature pH would be essentially unaffected. The data revealed that blowdown chloride concentrations in excess of approximately 40 ppm would be required to depress the room temperature pH. It is concluded, therefore, that in the case of sea water intrusions into the steam generator, pH alone is not an adequate monitor of water purity. Figure A2-1 depicts the expected effect of steam generator primary-to-secondary leakage (boric acid plus lithium hydroxide) on the ammonium hydroxide.pH at 25'C of the steam generator blowdown. These data were derived empirically in the laboratory and reveal that the presence of boric acid 'will cause a significant depression in the blowdown pH at 25'C. A lithium to boron weight ratio of 1/500 was selected for this study because it represents the primary coolant chemistry at mid-core life. It is significant to note that at the operating tempera-- ture of the steam generator, there is essentially no depression of the bulk water pH because of the low ionization of boric acid at these temperatures. The concentration of the lithium hydroxide, in the steam generator bulk water would not be of sufficient magnitude to affect the pH.

PAGE 7 OF 14 REYISION DATE 2/1/80 DIABLO CANYON POWER LANT UNIT NOS. 1 AND 2 OPERATING PROCEDURE NO. F-5 TITLE'HEMICALCONTROL LIMITS

APPENDIX 2 (Cont'd) (2)'ation Conductivity In the recirculating steam generator, the only bulk water losses from the steam generator ar the blowdown and the moisture that is entrained in the steam. Therefore, any contaminant entering'he steam generator will tend to concentrate until corrective action is taken. For this reason blowdown cation conductivity is one of the more sensitive methods available for monitoring contaminant input to the steam generator.

In analyzing a circulating water chemistry for purposes of calculating the steam generator blowdown cation conductivity as a function of condenser leakage, it is necessary to make the assumption that anything in the circulating water that has the potential for depositing on heat transfer surfaces will deposit or conversely, only the salts of sodium and potassium will remain soluble and are therefore the prime contributors to the blowdown cation conductivity; This is a'ery important point because the weight ratio of soluble sal'ts to tho'se that have a propensity for depositing on heat transfer surfaces is a significant variable in circulating water chemistries. An example of this variation is apparent wh'en comparing the chemistry of sea water, which has a ratio of approximately 7, to the chemistry of Lake Michigan, which has a ratio of approximately 0.05. From this analysis, it becomes apparent that the sea water has a significantly lower scaling potential than Lake Michigan and therefore, for a given blowdown cation conductivity attributable to condenser 1'eakage less deposition is occurring on the heat transfer surfaces of a plarit sited on the sea coast.

There is no question that cation conductivity is a valuable t'ool in the control of steam generator chemistry; however, recognition must be given to its total significance for proper'pplication. (3} Free Hydroxide It h'as been'established iri the laboratory and operating units that Inconel 600 steam generator tubing is susceptible to caustic stress assisted corrosion cracking and, because of this fact, every effort must be made to exclude Free Hydroxide from the steam generator environment. There are several potential, sources of free hydroxide. They'nclude condenser leakage from fresh water cooled plants (sea water inleakage tends to produce an acid condition in the steam g'ener'ator), makeup water systems and condensate polishing systems.

' ' PAGE 8 OF .14.. 'EVISION DATE 2/1/80 I)

C, ()

. DIABLO CANYON POWER PLANT UNIT.NOS. 1 AND 2 OPERATING PROCEDURE NO. F-5 TITLE CNEMICAL CONTROL LIMITS

APPENDIX 2 (Cont'd) l0.0

LI/O = I/ Joo MEI GHT

NH3 PPH 0 o.2 o.5 G I.O 0 2.o

9.0

CD 8.0 CD

CD l CC Lcs LU CQ

7.0

6.0 0 l0 20 30 QO 50

BORON (PPM) Figure A2-1 Boric Acid —Lithium Hydroxide Effect on Ammonio p H

PAGE 9 OF 14 RSViSrOR DATE '2 DIABLO CANYON POWER LANT UNIT NOS. 1 AND OPERATING PROCEDURE NO. F-5 CHEMICAL CONTROL LIMITS

APPENDIX 2 (Cont'd)

In cases where ion exchange is used to produce makeup water or condensate polishing, there is a potential for the accidental introduction of sodium hydroxide regenerant chemical into the system, and also the phen- omenon known as "sodium throw." The latter,may occur when the sodium inventory on the resin. bed is slowly replaced with another cation, such as ammonium ion which is normally present in the steam cycle. 2) Steam Generator and Feedwater Chemistry "Expected" Parameters

The following parameters are identified in Table 18A a's Expected Parameters. These parameters are identified for the'urpose of providing the operator a means for evaluating system chemistry perturbations.

a) Feedwater .

(1) Feedwater pH Control

The feedwater pH control ranges identified in Table lSA are based on guidelines established by the fossil boiler industry for minimizing corr'osion to the materials of construction normally utilized in these systems. of the feedwater specifications are to meetThe'bjectives or exceed the designed system component requirements and to minimize the amount of feedwater system corrosion products entering the steam generator.

The .pH of the feedwater system fluid is controlled'y continuous addition of ammonium hydroxide or an amine, added at the condensate pump discharge. Hydrazine added for oxygen suppression, may also contribute to the pH. The volatility of the amine enables it to be carried over :into the main steam system thus maintaining an alkaline pH in this system. (2) Iron and'opper These are reasonable allowances for contamination input to the'team generator during'ormal operation. They are not intended's control values, but are intended to indicate a point above which some system abnormality may exist (i.e. excessive corrosion resulting from improper chemical cohdi tions in the condensate and feedwater system).

b) Steam Generator Blowdown (1) Sodium Sod'ium is specified'or purposes of providing'a means of

PAGE~> OF 1'a REVISION'. DATE Ag

DIABLO CANYON POWER PLANT UNIT NOS. 1, AND 2 OPERATING PROCEDURE NO. F-5 CHEMICAL CONTROL L IHITS

APPENDIX 2 (Cont'd)

crosschecking the free hydroxide measurement and confirm- ing the source of a contaminant. The sources of sodium and their significance have been discussed previously. A (2) Chloride

Although Inconel 600 possesses good resistance to chloride stress corrosion cracking, steam generator chloride levels are restricted by the overall need of high water quality for AVT control. The presence of chloride in the blowdown is normally indicative of a condenser leak. The magnitude of the condenser leak can be calculated from the known chloride concentrations in the circulating water and blowdown and the total plant blowdown rate.

Chloride ion has been identified as the most active chemical species in an extremely complicated chemical process .that produces denting of the steam generator tubes in the vicinity of the carbon steel tube support plate.

At the recent Steam Generator Symposium, data was presented relative to the level of chloride ingress necessary to induce the tube support plate corrosion process that resulted in denting in plants with secondary systems containing copper alloys. Of particular note was the low level of chloride ingress required to produce denting at plants with circulating water chemistries capable of producing acid chloride environments in the steam generator, e.g., sea or brackish waters. The lant data stron 1 su ests that for sea water cooled lants havin co er-a loys in the secon ar s stem, continue o eration with nown ch ori e in ress- is not recommen ed, even t ou ow own ermits o servance of the norma s ecification. The cause of the contamination should e correcte immediately upon detection. At the same time, steam generator blowdown should be increased to the maximum rate, and action .should be taken to either temporarily arrest the leak source, or if it is in the condenser, isolate the affected condenser half for repairs of locatable leaks.

Dissolved Oxygen

The presence of oxygen in water has two effects:'t cor rodes metals by means of oxidation and in. many instances the corrosivity of'nown deleterious materials is in'creased due to the presence of oxygen. Therefore, in order to provide optimum protection to the steam generator materials of construction there must be no detectable oxygen ((0.005 ppm) present in the steam generator'blowdown under any operating or test condition.

PAGE ~ OF ~ REYISION 1 . DATE DIABLO CANYON POW LANT UNIT NOS. 1 AND 2

OPERATING PROCEDURE NO. F-5 TITLE: CHEMICAL CONTROL LIMITS

APPENDIX 2'Cont'd)

(,4)'i1,i ca Sil.ica is volatile and'ill'e present in the steam to an extent determined'y the boiler water pH, silica content and steam pressure. The objective in limiting Che silica content of the steam generator blowdown water is to minimize its concentration in the steam and avoid silica deposits on turbine blades and valves.

The present 1'imit of 1 ppm in the nuclear steam generator., reflecting the overall emphasis on good water quality, is conservative- relative to the "industrial standard" for current operation pressures and is believed, therefore, to avoid silica'eposition altogether. (5) Ammonium Hydroxide

The ammonium hydroxide entering the steam generator with the feedwater will undergo steam stripping to the extent that the ammonia concentration in the steam generator blowdown will be approximately one half of that in the feedwater .- This stripping action and a maximum feedwater pH of 9.2 are the bases for the expected blowdown ammonia concentrations identified in. Table 18A. (6) Suspended Solids Steam generator suspended solids should be minimized to prevent accumulation of excess sludge on the secondary side of the steam generator tube sheet. The operating limit of 1'pm is given to provide guidance as to acceptable and'achievable suspended solids input to the steam generator.

("7,) Blowdown Rate

To achieve optimum, effectiveness from the steam generator water chemistry control, the minimum continuous blowdown rate required to maintain the chemistry control parameters is required'during normal power operation. Such operation provides a dynamic system which is constantly removing any impurities from the steam generator. In addition, experience has shown conclusively that more stable steam generator chemistry control can be obtained with continuous blowdown than is obtained with an intermittent mode of operation. During periods of maintenance of the blowdown system or makeup. water treatment'ystem, blowdown may be reduced so long as the chemical specifications are not exceeded. To facili- tat'e maximum cleanup of the steam generator following a cold or hot shutdown, it is recommended that the maximum blowdown rate be instituted and maintained until full power operation is achieved. It is emphasized'that the blowdown rate should 14'' PAGE 12 PF REVISION . DATE 2/1/80 DIABLO CANYON POWER PLANT UNIT NOS. 1 AND 2 OPERATING PROCEDURE NO. F-5 TITLE: CHEMICAL CONTROL LIMITS

APPENDIX 2 (Cont'd)

be, increased, as required, to compensate for chemistry imbalances in the steam generator caused by factors such as condenser leakage, etc. during power operation. However, the causes of such imbalances should be corrected as soon as possible in order to keep the impurity input to the steam generator to a minimum.

During hot standby and hot functional testing, blowdown is employed as needed to maintain the steam generator water chemistry indicated in Table 18A.

3) Chemical Addition

The All Volatile Treatment method for steam side water chemistry control requires maximum attention to the prevention of contaminant input to the steam generators. This follows from the fundamental aspect of AVT control that it provides no chemical treatment for the steam generator itself, relying entirely on the exclusion of oxygen and contaminants resulting from condenser leakage, makeup water system malfunctions and chemicals used during such activities as pre- operation feedwater system cleaning, etc. The only chemicals injected into the steam side of the plant during operation are hydrazine, for oxygen suppression and an amine as required for feedwater and steam system pH control

Since no steam generator chemical treatment is provided, the introduction of impurities may result in the accumulation of high concentrations of contaminants in local areas and the formation of hardness scale on the heat transfer surfaces, i.e. the steam generator tubes. To minimize these possibilities, blowdown is increased as necessary to reduce the contaminant levels in the steam generator; failure to contain contaminant levels within the limits specified calls for immediate corrective measures. Corrective Actions

Remedial actions available to correct an abnormal chemical condition in the steam generator are as follows: a) Increase the steam generator blowdown rate. b) Overboard the affected hotwell, if condenser leakage is detected. c) Overboard the water from the tube sheet leak detection system, if this appears to be the contaminant source. d) Isolate the leaking condenser half and repair. e) Correct makeup water contamination, if indicated. If these corrective measures prove unsuccessful in controlling the steam generator chemistry, the unit must be shut down and repairs made to eliminate the source of the contaminant. The Limiting Control Specifications given in Table 18B have been established for

13 14 "- PAGE OF ' ISIQN DATE 2/1/80 DIABLO CANYON ER PLANT UNIT NOS. 1 AND 2 OPERATION PROCEDURE NO. F-5 TITLE: CHEHISTRY CONTROL LIHITS

APPENDIX 2 (Cont'd)

the purpose of allowing the operator a time frame during which a load reduction or shutdown can be scheduled for the purpose of making the repairs necessary to eliminate the source of contamination.

PAGE 14 OF 14 REVISIQN 1 ATE 2/1/80 0 DIABLO CANYON POWER PLANT UNIT NOS. 1 AND 2 OPERATING PROCEDURE NO. f-5 TITLE: CHEMICAL CONTROL LIMITS

APPENDIX 3

SECONDARY CYCLE CHEMISTRY CORRECTIVE ACTION GUIDANCE

This appendix provides corrective action guidance in summary fashion for situations when one or more secondary cycle chemical parameters are out of specification. Table A3-1 summarizes expected symptoms of certain operating upsets, such as condenser saltwater inleakage, excessive condenser air inleakage, incorrect chemical feed rates, etc. Table A3-2 suranarizes possible causes and corrective actions for off-control point chemical parameters.

1 PAGE OF 9 arvisroH DATE 2/1/80

APPENDIX 3 (Continued) O~ x) + TABLE A3-1 mr ~rca CHEMICAL SYMPTOMS OF ~ +o OPERATING UPSET CONDITIONS DURING POWER OPERATION ~o o UPSET CONDITION LIKELY SYMPTOMS1 ~ ~m m OO tHZ p)+ Leaking condenser .tube, defect not near tube sheet. 1. High specific conductivity on A m~O a. Condenser tray(s) r a> b. Condensate o mm c. Feedwater R ORr7~~ d. Steam generator blowdown 0 e. Steam generator steam (large leaks) r 2. High sodium concentration on Ng a. Condenser leak detection system Ch b. Feedwater C) m c. Steam generator blowdown C/l

3. Low cation conductivity on tube sheet leak C) detection.

4. High cation conductivity on a. Condensate b. Feedwater c. Steam generator blowdown d. Steam generator steam (large leak)

5. Low pH on steam generator blowdown, feedwater pH may trend downwards.

6. High chlorides* in steam aenerator blowdown.

Condenser'tube sheet leak. 1. High cation conductivity on a. Tube sheet leak detection b. Condensate c. Feedwater

l. Asterisked (*) items are indicated by grab sampling; all others are instrumented process monitors. 0, APPENDIX 3 (Continued) QD TABLE A3-1 Ctl ~ I CHEMICAL SYMPTOMS OF OPERATING UPSET CONDITIONS DURING PONER OPERATION o UPSET CONDITION LIKELY SYNPTONS1 m Mm Z O O Dl Condenser tube sheet leak (continued) d. Steam generator blowdown DO~ e. Steam generator steam (large leak) I C o m~R7 2. High sodium concentration on O~ a. Condenser leak detection system CD b. Feedwater I c. Steam generator blowdown Ul Q

3. High specific conductivity on C/7 a. Condensate O b. Feedwater c. Steam generator blowdown d. Steam generator steam (large leak)

4. Low specific conductivity on condenser trays D

5. Low pH on steam generator blowdown, feedwater may trend downwards

6. High clorides* on steam generator blowdown

Excessive condenser air inleakage. l. High dissolved oxygen (D02) in a. Condensate b. Feedwater 2. Higher than normal air ejector flow rate

3. High copper* and iron* in feedwater

Incorrect armonia (morpholine) feed rate. 1. Low pH (underfeed) or high pH (overfeed) in a. Feedwater b. Steam generator blowdown c. Steam generator steam l. Asterisked (*) items are indicated .by grab sampling; all others are instrumented process monitors. 0 O Cl APPENDIX 3 (Continued) Ill Xl TABLE A3-1 U7 CHEMICAL SYMPTOMS OF OPERATING UPSET CONDITIONS DURING POMER OPERATION O

UPSET CONDITION LIKELY SYMPTOMS1 Z O O Incorrect ammonia (morpholine) feed rate (continued) 2. High copper* (overfeed) in A CTIU I C a. Feedwater Kl O Pl b. Steam generator blowdown O O 3. High copper* and iron* (underfeed) in O I ll a. Feedwater I b. Steam generator blowdown I Ul

Incorrect hydrazine feed rate 1. High 002 (underfeed) in feedwater Vl Rl O1 2. High copper* and iron* (underfeed) in feedwater

O 3. High pH (overfeed) in a. Steam generator blowdown b. Steam generator steam

Primary-to-secondary leakage 1. High radi oacti vity on a. Steam generator blowdown monitor (RE-19) b. Air ejection discharge monitor (RE-15) c. Plant vent monitor(RE-14A 5 B, noble gases) d. Steam generator blowdown tank effluen't monitors (RE-23, liquid; RE-27, tank vent), during periods of SG blowdown when the blowdown cleanup demineralizer system is cut out

OCo

l. Asterisked (*) items are indicated by grab sampling; all others are instrumented process monitors. 0 APPENDIX 3 (Continued) OV TABLE A3-2 I ~CD Pl ~ I CORRECTIVE ACTIONS FOR OFF-CONTROL POINT CHEMICAL CONDITIONS IN THE SECONDARY CYCLE o A X U + REFERENCE Fl PARAMETER OUT OF OPERATING Z O SAMPLE POINT SPECIFICATION POSSIBLE CAUSES CORRECTIVE ACTION A PROCEDURE Pl~OO I C 1. MAIN CONDENSER X7 m O rn

a. Tray samples High specific Sal twa ter Locate X7 ~OP and plug leaking E-4 O ) conductivity inleakage icondenser tube(s) C-6 I I High specific Excessive feed Decrease feed rate of C-6 conductivity with rate of pH control ammonia (morpholine); D-2 C/I low cation ammonia O agent, overboard drains from steam C/) conductivity in (morpholine), or jet air ejector; verify e condensate and excessive feed rate~ correct hydrazine feed rate feedwater of hydrazine

b. Tube sheet High cation Saltwater Locate and plug leaking E-4 leak detec- conductivity inleakage condenser tube(s) C-6 tion samples

c. Tray and tube High sodium Saltwater For WEST condenser hal f E-4 sheet sample concentration inleakage sample header, cut out C-6 header circulating water pump 1-1 or (2-1) For EAST condenser half sample header, cut out circulating .water pump 1-2 (or 2-2)

2. CONDENSATE High dissol ved Excessive air . Increasehydrazine feed rate; D-2 PUMPS DISCHARGE oxygen leakage locate and secure inleakage C-7 HEADER pathway C-6

APPENDIX 3 (Continued) TABLE A3-2 o CORRECTIVE ACTIONS FOR OFF-CONTROL POINT CHEMICAL CONDITIONS IN THE SECONDARY CYCLE f Xl g7 REFERENCE m ~r ~ +o PARAMETER OUT.OF OPERATING SAMPLE POINT A SPECIFICATIONlow POSSIBLE CAUSES CORRECTIVE ACTION PROCEDURE IIl p 2. CONDENSATE High specific Excessive pH con- Decrease arrmonia (morpholine) D-2 z A+o~ PUMPS DISCHARGE conductivity with trol agent, ammonia feed rate; verify correct o m>O HEADER .cation (or morpholine) feed rate of hydrazine p- ~O (Continued) A Pl~m conductivity O C/l ~ High cation Saltwater Locate and plug leaking E-4 conductivity inleakage condenser tube(s) C-6

3. FEEDMATER pH (low) Underfeed of Increase ammonia (morpholine) D-2 ammonia (or mor- feed rate; terminate dis- m pholine) charge of steam jet air ( ejector after-condenser drains; verify correct hydrazine feed rate

pH (high) Overfeed of Decrease ammonia (morpholine) D-2 atmonia feed rate; increase overboard (morpholine) or of steam jet air ejector after- overfeed of. condenser drains; verify hydrazine correct feed rate of hydrazine

High 002 Excessive condense Increase hydrazine feed rate; D-2 air inleakage; locate and secure condenser C-6 underfeed of air inleakage pathway hydrazine High/Low Hydrazine Hydrazine feed Adjust hydrazine feed rate D-2 rate not in for target residual concen- CO C) balance with tration D02 levels

High specific Excessive ammonia Decrease ammonia (morphol ine) D-2 conductivity with (or'orpholine) or feed rate; veri fy correct low cation overfeed of hydra- hydrazine feed rate conductivity . zine

4 APPENDIX 3 (Continued) DO TABLE A3-2 m~ CORRECTIVE ACTIONS FOR OFF-CONTROL POINT CHEMICAL CONDITIONS IN THE SECONDARY CYCLE f R g) m ~o~r REFERENCE o PARAMETER OUT OF OPERATING o g) SAMPLE POINT SPECIFICATION POSSIBLE CAUSES CORRECTIVE ACTION PROCEDURE ~ ~m mz o> FEEDWATER and E-4 o 3. High cation Saltwater Locate plug leaking DOm~ (Continued) conductivity L'nleakage condenser tube(s) C-6 I C mm Oo High copper and Excessive corrosion Check condenser air inleakage, 0-2 O~I iron rate due to high pH, D02 levels, hydrazine feed C-6 DX7 ~ D02 or excessive rate f ammonia levels = -': D-2 I 4. STEAM GENERATOR High cation Saltwater Increase SG blowdown; check Vl BLOWDOWN conductivity inleakage; in- feedwater chemistry; check E-4 D sufficient SG performance of blowdown clean- C-6 CA blowdown; blow- up demineralizers; check for down cleanup condenser saltwater inleakage demineralizer exhaustion

High pH Excessive ammonia I Increase SG blowdown; check C-6 (morpholine) feed proper feed rates of amnonia 0-2 rate, excessive (morpholine) and hydrazine; ~ hydrazine feed increase discharge of air rate, insufficient I ejector after-condenser drains, discharge rate of check feedwater chemistry; air ejector after- 'heck S/G Free Hydroxide condenser drains

Low pH Condenser saltwater Increase SG blowdown and C-6 inleakage, insuf- increase aomonia (morpholine) D-2 ficient ammonia feed rate; terminate discharge E-4 (morpholine) feed of air ejector after. condenser rate, excessive drains; check for condenser discharge of air saltwater inleakage; check ejector after condensate and feedwater condenser drains. chemistry; verify correct hydrazine feed rate

CDO APPENDIX 3 (Continued) TABLE A3-2 I ~ CZ7 Pl ~ I CORRECTIVE ACTIONS FOR OFF-CONTROL POINT CHEMICAL CONDITIONS IN THE SECONDARY CYCLE A REFERENCE xn PARAMETER OUT OF OPERATING m Z CD CD SAMPLE POINT SPECI FICATION POSSIBLE CAUSES CORRECTIVE ACTION PROCEDURE A CTl D ~ r I= CD 4. STEAM GENERATOR High sodium Saltwater Increase SG blowdown; check C-6 n m~ BLO|IlDOMN inleakage; insuf- feedwater chemistry; check Z7 (Continued) ficient SG blow- performance of blowdown D-2 cD A ~ r down; blowdown cleanup demineralizers; check CD ~z cleanup deminera- for condenser saltwater r

lizer exhaustion 'nleakage. M High radioactivity Primary-to- Terminate discharge of SG D-2 CD secondary leakage blowdown; cut in blowdown OP-14 C/) cleanup demineralizers; check activity and leakrate for Tech Spec compliance/action

All other parameters,- Increase SG blowdown; check D-2 determined feedwater chemistry; check E-4 by laboratory feed rate C-6 analysis of grab. for correct of ammonia (morpholine) and C-6A samples hydrazine; check for condenser saltwater inleakage

5. STEAM GENERATOR High specific Excessive ammonia Check for correct pH control D-2 STEAM conductivity with (or morpholine) agent feed rate in condensate; C-2 low cation con- check for excessive hydrazine ductivity feed rate; check pH of steam generator. blowdown

High cation Excessive carry'- Increase SG blowdown; SG blow- 0-2 conductivity over of non- down cation conductivity should volatile impur- be too high (refer to actions ities in steam outlined above) generator

APPENDIX 3 (Continued) I m +r TABLE A3-2 ~ CD CORRECTIVE ACTIONS FOR OFF-CONTROL POINT CHEMICAL C) A CONDITIONS IN THE SECONDARY CYCLE Xo m x)~ REFERENCE Z o>CD CD PARAMETER OUT OF OPERATING Cl Pl SAMPLE POINT o> SPECIFICATION POSSIBLE CAUSES CORRECTIVE ACTION PROCEDURE I— C CD

n m~X7 6. CONDENSATE All control Makeup water out Check makeup water supply to F-4 R R STORAGE TANK parameters, except of specification; CST; if hotwell is out of CD P (CST) dissolved oxygen hotwell reject to specification (possibly due to CST out of speci- condenser saltwater inleakage), fication terminate hotwell rejection to CST, i.e., overboard excess water V) m CD ( C/l High dissolved Deaerator not Check makeup water deaerator F-4A CD oxygen functioning performance; check vacuum properly; poor or sea water evaporator vacuum on sea CD water flash evaporator

00 CD ~ l~~