ML072070257

Technical Specification Change Request No. 337 - Reactor Building Emergency Sump Ph Control System Buffer Change

ML072070257
Person / Time
Site:	Three Mile Island
Issue date:	06/29/2007
From:	Cowan P AmerGen Energy Co
To:	Document Control Desk, Office of Nuclear Reactor Regulation
References
5928-07-20097
Download: ML072070257 (134)

Text

AmerGenM AmerGen Energy Company, LLC www.exeloncorp.com An Exelon Company 200 Exelon Way Kennett Square, PA 19348 10 CFR 50.90 June 29, 2007 5928-07-20097 U. S. Nuclear Regulatory Commission ATTN: Document Control Desk Washington, DC 20555-0001 Three Mile Island Nuclear Station, Unit 1 Facility Operating License No. DPR-50 NRC Docket No. 50-289

Subject:

Technical Specification Change Request No. 337 - Reactor Building Emergency Sump pH Control System Buffer Change In accordance with 10 CFR 50.90, "Application for amendment of license or construction permit,"

AmerGen Energy Company, LLC (AmerGen) proposes changes to Appendix A, Technical Specifications (TS), of the Three Mile Island Nuclear Station, Unit 1 (TMI Unit 1) Facility Operating License. Enclosure 1 contains AmerGen's description and assessment of the change. Enclosure 2 contains the proposed. TS changes.

The proposed change would revise TMI Unit 1 Technical Specification 3.3.1.3, "Reactor Building Spray System and Reactor Building Emergency Core Cooling System." The current capability to add sodium hydroxide (NaOH) to the Reactor Building spray system as a buffer during the initial phase of a loss-of-coolant accident will be replaced with trisodium phosphate dodecahydrate (TSP) stored in baskets located inside the Reactor Building containment. Related changes to Technical Specifications 3.3.2.1 and 4.1, and the Bases are also proposed.

As part of this license amendment request, AmerGen proposes to modify the current UFSAR licensing basis methodology for calculating the iodine removal coefficients for the Reactor Building spray system to be consistent with NUREG-0800, Standard Review Plan 6.5.2.

The proposed amendment has been reviewed by the TMI Unit 1 Plant Operations Review Committee and approved by the Nuclear Safety Review Board in accordance with the requirements of the AmerGen Quality Assurance Program.

Using the standards in 10 CFR 50.92, AmerGen has concluded that these proposed changes do not constitute a significant hazards consideration, as described in the enclosed analysis performed in accordance with 10 CFR 50.91 (a)(1). Pursuant to 10 CFR 50.91 (b)(1), a copy of this Technical Specification Change Request is provided to the designated official of the Commonwealth of Pennsylvania, Bureau of Radiation Protection, as well as the chief executives of the township and county in which the facility is located.

9r9

U.S. Nuclear Regulatory Commission June 29, 2007 Page 2 We request approval of the proposed change by December 1, 2007, with the amendment being implemented within 30 days of issuance. This will allow an orderly implementation of these changes following approval in accordance with the December 31, 2007 containment emergency sump modification compliance requirements specified in NRC Generic Letter 2004-02.

Regulatory commitments established by this submittal are identified in Enclosure 3. If you have any questions or require additional information, please contact Mr. David Distel at (610) 765-5517.

I declare under penalty of perjury that the foregoing is true and correct. Executed on the 2 9 th day of June, 2007.

Respectfully,.

Pamela B. dowan Director - Licensing and Regulatory Affairs AmerGen Energy Company, LLC

Enclosures:

1) TMI Unit 1 Technical Specification Change Request No. 337 - Reactor Building Emergency Sump pH Control System Buffer Change Description and Assessment

2) TMI Unit 1 Technical Specification Change Request No. 337 - Markup of Proposed Technical Specification and Bases Page Changes

3) List of Commitments cc: S. J. Collins, Administrator, USNRC Region I D. M. Kern, USNRC Senior Resident Inspector, TMI Unit 1 P. J. Bamford, USNRC Project Manager, TMI Unit 1 D. Allard, Director, Bureau of Radiation Protection - Pennsylvania Department of Environmental Protection Chairman, Board of County Commissioners of Dauphin County, PA Chairman, Board of Supervisors of Londonderry Township, Dauphin County, PA TMI Unit 1 File No. 07029

ENCLOSURE 1 TMI Unit 1 Technical Specification Change Request No. 337 Reactor BuildingoEmergency Sump pH Control System Buffer Change Description and Assessment

Subject:

Reactor Building Emergency Sump pH Control System Buffer Change - TS Sections 3.3.1.3, 3.3.2.1, and 4.1

5.0 REGULATORY ANALYSIS

5.1 No Significant Hazards Consideration 5.2 Applicable Regulatory Requirements/Criteria 5.3 Precedent

7.0 REFERENCES

ATTACHMENTS: : AmerGen/Exelon Calculation C-1 101-1 53-E410-036, Revision 0, "Reactor Building Spray pH Prior to the Start of Recirculation Spray" : AmerGen/Exelon Calculation C-1 101 -153-E410-040, Revision 0, "Reactor Building Sump Post-LOCA pH and TSP Quantity" : AmerGen/Exelon Calculation C-1 101 -900-EOOO-087, Revision 2, "Post-LOCA EAB, LPZ, TSC, and CR Doses Using AST and RG 1.183 Requirements" (Electronic CD)

Enclosure 1 Description and Assessment Page 1 of 19 ENCLOSURE 1 DESCRIPTION AND ASSESSMENT 1.0 Description In accordance with 10 CFR 50.90, "Application for amendment of license or construction permit," AmerGen Energy Company, LLC (AmerGen) is requesting an amendment to Facility Operating License No. DPR-50 for Three Mile Island Nuclear Station, Unit 1 (TMI Unit 1). The proposed change would revise TMI Unit 1 Technical Specification (TS) 3.3.1.3, "Reactor Building Spray System and Reactor Building Emergency Core Cooling System." The current capability to add sodium hydroxide (NaOH) to the Reactor Building spray system as a buffer during the initial phase of a loss-of-coolant accident (LOCA) will be replaced with trisodium phosphate dodecahydrate (TSP) stored in baskets located inside the Reactor Building containment. As part of the modification, the sodium hydroxide addition tank will be isolated from the Reactor Building spray system, but will physically remain in place.

The reason for this change is to minimize the potential for exacerbating sump screen blockage under post-LOCA conditions. As a result of AmerGen's efforts to address Generic Safety Issue 191 (Assessment of Debris Accumulation on PWR Sump Performance) for TMI Unit 1, concerns have been identified relating to potential adverse chemical interactions between NaOH and certain insulation materials used in the TMI Unit 1 containment. Related changes to Technical Specifications 3.3.2.1 and 4.1, and the Bases are also proposed.

AmerGen requests that the following changed replacement pages be inserted into the existing Technical Specifications:

Revised TMI Unit 1 TS Pages: 3-22, 3-23, 3-24, 4-2b, 4-7, 4-10, and 4-1Oc.

2.0 Proposed Change The proposed amendment changes the method of pH control for the water in the Reactor Building emergency sump after a postulated LOCA. This change deletes the specification for sodium hydroxide (NaOH) spray addition and adds a specification for the use of trisodium phosphate dodecahydrate (TSP) as the chemical for pH control. In addition, to support the buffer change, the Updated Final Safety Analysis Report (UFSAR) methodology for calculating the iodine removal coefficients for the Reactor Building spray system is modified to be consistent with NUREG-0800, Standard Review Plan 6.5.2.

2.1 Revise TMI Unit 1 TS 3.3.1.3, Reactor Building Spray System and Reactor Building Emergency Cooling System, (page 3-22) to delete the sodium hydroxide tank requirements and insert TSP requirements:

Enclosure 1 Description and Assessment Page 2 of 19 OLD TS 3.3.1.3

b. The sodium hydroxide (NaOH) tank shall be maintainedat 8 ft. +/-6inches lower than the BWST level as measured by the BWST/NaOH tank differentialpressureindicator. The NaOH tank concentrationshall be 10.0 +/- .5 weight percent (%). Specification 3.3.2.1 applies.

c. All manual valves in the discharge lines of the NaOH tank shall be locked open.

Specification 3.3.2.1 applies.

NEW 3.3. 1.3.b The Reactor Building emergency sump pH control system shall be maintained with > 18,815 lbs and <28,840 lbs of trisodium phosphate dodecahydrate (TSP).

Specification 3.3.2.1 applies.

2.2 Revise TMI Unit 1 TS Section 3.3.2.1 to delete the reference to the NaOH tank on page 3-23, and to read as follows:

"If the CFT boron concentrationis outside of limits, or if the TSP baskets contain amounts of TSP outside the limits specified in 3.3.1.3.b, restore the system to operable status within 72 hours8.333333e-4 days <br />0.02 hours <br />1.190476e-4 weeks <br />2.7396e-5 months <br />. If the system is not restored to meet the requirements of Specification 3.3.1 within 72 hours8.333333e-4 days <br />0.02 hours <br />1.190476e-4 weeks <br />2.7396e-5 months <br />, the reactorshall be placed in a HOT SHUTDOWN condition within six hours."

2.3 Revise TMI Unit 1 TS Table 4.1-1 (page 4-7), item 40, for the BWST/NAOH Differential Pressure Indicator, and item 41, for the Sodium Hydroxide Tank Level Indicator, to delete these line items from the table. Revise Table 4.1-3 (page 4-10), item 10, for the Sodium Hydroxide concentration, to delete this line item from the table.

2.4 Revise TMI Unit 1 TS Table 4.1-5 (page 4-10c), System Surveillance Requirements, to add surveillance testing for the TSP buffer and to read as follows:

NEW Item Test Frequency

2. ReactorBuilding a. Verify the TSP baskets contain R Emergency Sump > 18,815 lbs and s 28,840 lbs of pH Control TSP.

System

b. Verify that a sample from the TSP R baskets provides adequate pH adjustment of borated water 2.5 Bases Changes:

The Bases Section 3.3 will be revised to delete discussion of NaOH addition and add the following discussion:

Enclosure 1 Description and Assessment Page 3 of 19 The Reactor Building emergency sump pH control system ensures a sump pH between 7.3 and 8.0 during the recirculationphase of a postulatedLOCA. A minimum pH level of 7.3 is requiredto reduce the potentialfor chloride induced stress corrosioncracking of austenitic stainlesssteel and assure the retention of elemental iodine in the recirculatingfluid. A maximum pH value of 8.0 minimizes the formation of precipitatesthat may migrate to the emergency sump and minimizes post-LOCA hydrogen generation. Trisodium phosphate dodecahydrateis used because of the high humidity that may be present in the Reactor Building during normal operation. This form is less likely to absorb large amounts of water from the atmosphere.

All TSP baskets are located outside of the secondary shield wall in the Reactor Building basement (El. 281 -0"9. Therefore, the baskets are protected from the effects of credible internal missiles inside the shield wall. The designated TSP basket locations ensure that the baskets are not impacted by the effect of potential LOCA jet impingement forces and pipe whip.

The Bases Section 3.3 (TS page 3-24) will also be revised to state that the iodine removal function of the Reactor Building spray system requires one spray pump and TSP in baskets located in the Reactor Building basement. In addition, Bases Section 4.1 (TS page 4-2b) will be revised to add information related to surveillance testing for the TSP in the baskets.

2.6 Licensing Basis Methodology Change As part of the proposed buffer change, the UFSAR methodology for calculating the iodine removal coefficients for the Reactor Building spray system is modified to be consistent with NUREG-0800, Standard Review Plan 6.5.2, Revision 4 (March 2007), "Containment Spray as A Fission Product Cleanup System." This methodology is recommended in Regulatory Guide 1.183 (Reference 2), which is applicable to TMI Unit 1 for accident analysis using alternative radiological source terms.

3.0 Background Under LOCA conditions, a buffering agent must be added to the Reactor Building sump recirculation water to increase the sump solution pH to between 7.3 and 8.0. Buffering agent addition is required to reduce re-evolution of iodine fission products from the sump solution to the containment atmosphere as iodine gas. Thus, pH adjustment is primarily a control measure for offsite and control room doses. Increasing the coolant pH also reduces the corrosion rates of materials in the containment, most notably metal structural members and components. Traditionally, both sodium hydroxide (NaOH) and trisodium phosphate dodecahydrate (TSP) have been used as buffering agents at many plants. NaOH is stored in liquid form in a tank and is fed into the containment spray system post-LOCA. In plant designs that use TSP, the TSP is stored in baskets that become submerged within the containment sump pool (as the post-LOCA water level rises) and release the buffering agent by dissolution.

The present method of buffering the sump water at TMI Unit 1 is through the addition of NaOH to the Reactor Building (RB) spray system. The NaOH solution is stored in the sodium hydroxide tank (BS-T-2) located outside the RB. The tank is isolated from the RB spray system piping by two normally closed motor-operated valves BS-V-2A and 2B. The valves

Enclosure 1 Description and Assessment Page 4 of 19 open on receipt of an engineered safeguards actuation signal, and the NaOH mixes with Borated Water Storage Tank (BWST) injection supply water. The RB spray solution mixes with the spilled reactor coolant from the LOCA and the buffered water makes its way to the emergency sump where it is available for recirculation. In the current design, the buffered water has a pH of at least 8.0 prior to initiating recirculation. However, NRC Standard Review Plan (SRP) 6.5.2, Revision 4 permits the spraying of a boric acid solution during the initial injection phase when the spray solution is being drawn from the borated water storage tank (BWST). The SRP also states that-the pH of the spray solution should be adjusted to at least 7.0 by the onset of recirculation.

This TS change will allow the use of TSP, a highly water-soluble basic chemical, to buffer the acidic spray/reactor coolant mixture in the RB emergency sump. This method uses plain boric acid as the spray solution during the post-LOCA injection phase. Other than isolating the NaOH tank and associated recirculation pump from the RB spray system, there are no, changes in RB spray system operation required by the use of TSP.

TSP is used as a post-LOCA buffering agent at other stations because 6f its many favorable characteristics. In particular, it dissolves rapidly and the quantity needed to increase the coolant pH above 7.3 is reasonable. It also. has corrosion inhibitor properties beyond its

'ability to moderate pH. For example, carbon steel corrosion is inhibited through the formation of iron phosphate conversion coatings. Also, aluminum corrosion is inhibited. In the dodecahydrate form, TSP has a good storage life and'is readily available.

TSP has been.successfully used in a wide variety of applications that are relevant to use in a containment spray solution. The proposed amendment to change the method of pH control Will improve personnel safety by eliminating the caustic chemical sodium hydroxide from the RB.

Proposed Design The Reactor Building emergencysump pH control system will be a passive system using 23 stainless steel storage baskets filled with TSP. No active means of Reactor Building emergency sump pH control are required. TMI Unit 1 has determined by analyses the amount of TSP required to adjust the sump pH to a proposed minimum value of 7.3. These analyses considered a range of quantities for the boric acid and TSP.

The minimum pH is produced by the maximum amount of boric acid and the minimum amount of TSP. Conversely, the maximum pH is produced by the minimum amount of boric acid and the maximum amount of TSP. The proposed TS surveillance requirement of

> 18,815 lbs and < 28,840 lbs of TSP will result in a pH between 7.3 and 8.0 during the long-term recirculation phase. A maximum pH value of 8.0 minimizes theformation of precipitates that may-migrate to the emergency sump and minimizes post-LOCA hydrogen generation.

The sump pH baskets will be~located outside of the secondary shield wall in the Reactor Building basement (El. 281'-0"), so that they' are in the flow path of the RB spray/reactor coolant mixture flowing to the emergency sump. A total of 23baskets will be installed to assure that adequate TSP is dissolved in the water, given the flow paths and allowable floor space in the Reactor Building. The sides of the baskets will be stainless steel mesh screen to allow the spray/reactor coolant mixture to dissolve the TSP. The baskets are designed to

Enclosure 1 Description and Assessment Page 5 of 19 withstand seismic loads. The TSP chemical is technical grade, granular TSP dodecahydrate, which contains 12 waters of hydration and has the chemical formula of Na 3 PO 4 .12H 20.

4.0 Technical Analysis The following topics associated with the proposed change are discussed further below:

1. Radiological Consequences

2. Chemical effects

3. Corrosion of containment materials

4. Hydrogen generation

5. Environmental qualification (EQ) of equipment

6. TSP basket design and isolation of sodium hydroxide tank

7. UFSAR accident analysis 4.1 Radiological Consequences 4.1.1 Effect of pH Change The present method of buffer addition is to add NaOH to the RB spray during the emergency core cooling system (ECCS) injection phase of the LOCA. The NaOH is mixed with water from the BWST prior to being sprayed into the containment atmosphere. The proposed change to replace this method with TSP stored in baskets will reduce the rate of buffer addition during the ECCS injection phase. Initially, the RB spray mixture will consist of plain boric acid solution. The spray pH during the injection phase may be as low as 4.6 as documented in Attachment 1 (Calculation No. C-1101-153-E410-036, Revision 0, "Reactor Building Spray pH Prior to the Start of Recirculation Spray"). As indicated in Standard Review Plan (SRP), Section 6.5.2, "Containment Spray as A Fission Product Cleanup System", fresh sprays (i.e., sprays with no dissolved iodine) are effective at scrubbing elemental iodine and thus a spray additive is unnecessary during the initial injection phase when the spray solution is being drawn from the BWST. As described in the SRP, research has shown that elemental iodine can be scrubbed from the atmosphere with borated water, even at low pH. The SRP provides an equation for calculating a first-order removal coefficient that is not dependent on pH.

However, since long-term use of a plain boric acid spray could increase the potential for elemental iodine re-evolution and long-term stress corrosion during the recirculation phase of the LOCA, the equilibrium sump solution pH must be increased. The current licensing basis for TMI Unit 1 credits the Alternative Source Term (AST) with guidance from Regulatory Guide (RG) 1.183 (Reference 2) for calculating radiological dose consequences post-LOCA.

The RG 1.183 guidance indicates that if sump pH is above 7.0, then a licensee does not need to evaluate revolatization of iodines for dose consequences. RG 1.183 also recommends an iodine flashing fraction of 10% as applied to Engineered Safety Feature (ESF) recirculation leakage outside primary containment, unless a lower value can be justified. The TMI Unit 1 AST calculations currently justify a calculated iodine flashing fraction of 5% during 'ESF recirculation for the first 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> following a LOCA and 2% for the remainder of the 30-day accident evaluation; however, these values are pH-dependent (Reference Attachment 3). The supporting analysis indicates that use of these values requires that the sump pH be > 7.3. The NRC accepted use of the 5% and 2% flashing

Enclosure 1 Description and Assessment Page 6 of 19 fraction values in Reference 3. In the current design, use of NaOH injection results in a calculated pH > 8.0. With the proposed change to TSP, continued use of the 5% and 2%

iodine flashing fractions will require that the long-term sump pH be > 7.3. The TSP baskets will be designed and located with the objective of ensuring rapid dissolution of the TSP. The baskets will be located on the RB floor (El. 281'-0") around the RB, but outside the secondary shield wall. All baskets will be submerged by the post-LOCA flood inventory. There will be a sufficient quantity of TSP to adjust the pH range to > 7.3 to 8.0, as documented in (Calculation No. C-1 101 -1 53-E410-040, Revision 0, "Reactor Building Sump Post-LOCA pH").

4.1.2 Change to UFSAR Methodology for Spray Removal Coefficient When applying the AST guidance, the chemical forms of radioiodine released to the containment are assumed to be 95% cesium iodide (particulate form), 4.85 percent elemental iodine, and 0.15 percent organic iodide. As part of the proposed change, AmerGen will use the methodology in SRP Section 6.5.2, Revision 4 for calculation of RB spray removal coefficients. The current TMI Unit 1 spray removal coefficients, which are developed in UFSAR Appendix 14B, "Iodine Removal Capabilities of the TMI-1 Reactor Building Spray System," are based on the methodology in ANSI/ANS-56.5-1979, "American National Standard for PWR and BWR Containment Spray System Design Criteria."

Separate spray removal coefficients are developed for elemental, organic and particulate forms of iodine. The ANSI formulation for the elemental spray removal coefficient is directly.

proportional to the iodine partition coefficient, which is a strong function of thespray pH.

Regulatory Guide 1.183 states that the iodine removal models in SRP Section 6.5.2 are acceptable (ANSI/ANS-56.5 was withdrawn in 1993). The formulation for the elemental iodine spray removal coefficient in SRP Section 6.5.2 is independent of spray pH, and results in a larger removal coefficient than that used in the current design basis. For the particulate iodine, the formulation for spray removal coefficient in SRP Section 6.5.2 is essentially the same as currently described in the UFSAR. The SRP also states that no credit should be taken for the removal of organic iodine, which is consistent with the approach used in the current TMI Unit 1 dose calculations, so an organic iodine removal coefficient is not applied.

Calculation C-1 101 -900-EOOO-087, Revision 2, "Post-LOCA EAB, LPZ, TSC, and CR Doses Using AST and RG 1.183 Requirements" (provided in Attachment 3) has been prepared to evaluate the proposed change. This calculation uses the NRC sponsored computer code RADTRAD, version 3.03 (Reference 5) and determines the containment spray elemental and particulate (i.e., aerosol) iodine removal coefficients and the elemental iodine decontamination factor in accordance with SRP 6.5.2. It shows that use of the SRP 6.5.2 methodology results in larger elemental iodine removal coefficients than those calculated using ANS-56.5 methodology. This means the elemental iodine is removed faster from the RB atmosphere and, therefore, for a given elemental iodine decontamination factor, there will be less airborne elemental iodine available for leakage from containment atmosphere, as compared to the current calculation. The reduced minimum RB sump water pH (i.e., 7.3 for the proposed change using TSP versus 8.0 for the current design using NaOH) results in a smaller elemental iodine decontamination factor. A smaller elemental iodine decontamination factor means there will be greater residual airborne elemental iodine activity in the containment building atmosphere at the point in the analysis when credit for

Enclosure 1 Description and Assessment Page 7 of 19 RB spray is cut off, as compared to the current calculation. Revision 2 of the calculation includes an adjustment to the assumed RB sprayed volume that is unrelated to the proposed change discussed in this amendment. The combined effect of these calculation changes results in slightly smaller post-LOCA doses to the control room, the Exclusion Area Boundary (EAB), and the Low Population Zone (LPZ), as compared to the current licensing basis values.

The calculated total effective dose equivalent (TEDE) for the control room, EAB, and LPZ are summarized below for the proposed change. The allowable dose limits from 10 CFR 50.67, "Accident Source Term", and the TMI Unit 1 current licensing basis dose analysis results are also provided. All calculated dose consequence results remain below the acceptance criteria of 10 CFR 50.67 and General Design Criterion (GDC) 19.

Large Break Loss-of Coolant Accident) Accident TEDE Dose (Maximum (Rem) Hypothetical H ti Control Room EAB LPZ Current Licensing 4.75 24.37 7.72 Basis TEDE Dose Reanalyzed TEDE 4.74 22.58 7.45 Dose Results Allowable TEDE 5 25 25 Dose Limit

.4.2 Chemical Effects As part of a PWR Owners Group chemical effects resolution effort, Westinghouse has evaluated several compounds as potential replacement buffers that would minimize the potential for chemical precipitate formation following a LOCA (Reference 1). The type of thermal insulation used in the TMI Unit 1 RB is predominantly reflective metallic. The NaOH spray, reacting with significant quantities of aluminum in the RB, has the potential to produce chemical precipitates such, as sodium aluminum silicate (NaAISi 3O8 ) and aluminum oxyhydroxide (AIOOH), especially at higher pH values. The Westinghouse study determined that trisodium phosphate in granular form is a good candidate for replacing NaOH in plants, such as TMI Unit 1, that do not generate calcium silicate debris. TSP inhibits aluminum corrosion, which provides an advantage over the present use of NaOH.

Further evaluation of the effect of the proposed buffer change from NaOH to TSP on the TMI Unit 1 resolution of GSI-191 is being addressed separately by AmerGen. As discussed in Reference 4, TMI will validate that adequate margin exists to bound the impact of

Enclosure 1 Description and Assessment Page 8 of 19 chemical effects once the vendors' tests results to quantify chemical debris effect on head loss have been published.

4.3 Corrosion of Containment Materials NRC Branch Technical Position MTEB 6-1, "pH for Emergency Coolant Water for PWRs",

states that in order to reduce the probability of stress-corrosion cracking of austenitic stainless steel components, the pH of the recirculation fluid should have a minimum pH of 7.0. TSP is presently used as a buffering agent in other U.S. PWRs (e.g., Crystal River-3) to establish a post-LOCA sump pH of > 7.0. The application of TSP at TMI Unit 1 will be similar to that of other plants, establishing sump pH of > 7.3 to 8.0. TSP inhibits aluminum corrosion and corrosion to carbon steel is low (Reference 1).

For the proposed change, the pH of the spray solution during the post-LOCA initial injection phase will be acidic. The TMI Unit 1 coatings for the containment liner and concrete have been evaluated for a spray pH of 4.0 with an exposure time of 7.5 hours5.787037e-5 days <br />0.00139 hours <br />8.267196e-6 weeks <br />1.9025e-6 months <br />. The coatings were determined to beacceptable for the proposed change since the exposure is for short duration, the coatings used exhibit satisfactory resistance to chemical exposure from acids, and the primers are protected by the topcoat, so they are not directly exposed to spray.

4.4 Hydrogen Generation As stated in UFSAR Section 6.5.3, corrosion of zinc and aluminum are accounted for in the production of hydrogen post-LOCA. However, research has shown that aluminum corrosion from exposure to water at higher pH values generates more hydrogen than water at lower pH values. The production of hydrogen by aluminum corrosion is based on aluminum surface area within the containment and the surface corrosion rate according to the reaction:

2AI + 3H 20 -+ 3H2 + A120 3. One pound of aluminum reacts to produce 19.93 scf H2. The TSP chemical buffers the RB emergency sump water at a lower pH range than the current NaOH buffer (7.3 to 8.0 for TSP versus 8.0 to 11.0 for NaOH). As such, the post-LOCA hydrogen generation rate will not increase as a result of the proposed change.

4.5 Environmental Qualification (EQ) of Equipment The EQ Program for TMI Unit 1 meets the requirements of 10 CFR 50.49. All equipment within the scope of this program has been evaluated for compliance with either the Division of Operating Reactors (DOR) Guidelines or 10 CFR 50.49 with guidance from Regulatory Guide 1.89.

In the current design, the RB spray solution is alkaline due to the direct addition of sodium hydroxide to the boric acid solution from the. BWST. Equipment in the EQ program is qualified for a chemical spray with a pH range of 8.0 - 11.0. In the proposed design, the spray solution during the injection mode will be acidic, consisting of spray solution from the BWST, only. The EQ components in the RB needed to function after RB spray has initiated were identified and evaluated for the effects of an acidic RB spray. DOR Guidelines allow environmental qualification by analysis. These components were evaluated for an exposure to RB spray with a pH of 4.0 for an initial 7.5 hours5.787037e-5 days <br />0.00139 hours <br />8.267196e-6 weeks <br />1.9025e-6 months <br />. This pH value bounds the minimum pH determined in the calculation provided in Attachment 1. After 7.5 hours5.787037e-5 days <br />0.00139 hours <br />8.267196e-6 weeks <br />1.9025e-6 months <br />, an alkaline spray is assumed, with a long term pH of 7.3 - 8.0. The age sensitive materials (non-metallic parts)

Enclosure 1 Description and Assessment Page 9 of 19 covered under the requirements of 10 CFR 50.49, and the metallic parts of these EQ components (such as metal housings of components) were evaluated for this spray condition. Evaluation was based on utilizing and analyzing available industry and technical research data. This included chemical resistance of materials, effect of aging on materials that will be exposed to spray, and the duration of acidic and alkaline spray. The analysis concluded that all EQ equipment located inside the RB is qualified for the revised RB spray chemical conditions resulting from the proposed change.

4.6 TSP Basket Design and Isolation of Sodium Hydroxide Tank TSP Basket Design The TSP baskets will be fabricated with stainless steel framing and wire mesh. Based on the structural analysis, the baskets will not need anchorage to the basement floor to prevent movement or overturning. This will reduce the radiation exposure during installation and will allow for temporary relocation, as needed, during refueling outages without the need to remove anchor bolts. The baskets will be located outside of the secondary shield wall in the RB basement (El. 281'-0"). Therefore, the baskets will be protected from the effects of credible internal missiles generated by failure of reactor coolant piping or control rod drive equipment components that are located inside of the shield wall. The basket locations will be selected such that they are not adversely impacted by the effects of LOCA jet impingement forces and pipe whip.

The proposed installation of TSP baskets will result in a minor decrease in net free volume of the RB. This decrease has been reviewed for effects on the RB peak pressure analysis and the post-LOCA radiological analysis. The proposed change will not affect the calculated Sp~ost-accident RB peak pressure or the RB pressure profile used for EQ analysis, as reported in UFSAR Appendix 6B. Also, the radiological analysis is unaffected. The volume of steel added by the proposed basket design has been assessed for the effect on maximum RB post-LOCA flood level, and there is no adverse impact.

NaOH Tank Isolation As discussed above, NaOH tank BS-T-2 will be isolated from the RB spray system. The proposed change will not alter the seismic classification of the RB spray system or the NaOH tank (both Seismic Class I). The existing ESAS signal circuitry and electrical power will be removed from the NaOH tank isolation valves, and at least one manual valve in each supply train will be locked closed providing permanent isolation of the NaOH tank. The existing TS associated with the NaOH tank instruments will no longer be required and are deleted in the proposed change.

Isolation of the tank will remove the NaOH tank liquid inventory (1451 ft) from the post-accident emergency sump water inventory. This results in a minor reduction in calculated RB post-LOCA flood level. The reduced level has been evaluated for impact on net positive suction head (NPSH) available for the ECCS pumps. Sufficient NPSH margin will remain available.

Enclosure 1 Description and Assessment Page 10 of 19 4.7 UFSAR Accident Analysis UFSAR Section 14.2.2.3 discusses the large break LOCA analysis and Section 14.2.2.3.4 discusses the consequences of LOCA radioactive releases to the environment. The NRC-sponsored computer code RADTRAD, is used to determine TEDE doses at the EAB, LPZ and in the control room. UFSAR Appendix 14B, "Iodine Removal Capabilities of the TMI-1 Reactor Building Spray System", discusses the RB spray effectiveness in reducing airborne iodine. Appendix 14C, "Evaluation of Accident Dose", discusses radioactive dose analysis and results based on implementation of AST per Regulatory Guide 1.183 and 10 CFR 50.67.

As discussed in Section 4.1 above, the post-LOCA radiological consequences and the methodology for calculating RB spray removal coefficients are revised for the proposed change.

Summary The proposed change to remove the existing RB emergency sump pH buffer (sodium hydroxide) and replace it with TSP will reduce precipitate formation in the RB post-LOCA, while maintaining an acceptable long-term sump pH range for minimizing radioactivity releases and corrosion of the RB materials. The proposed change to the methodology for calculating RB spray removal coefficients will be consistent with SRP 6.5.2. Evaluation has determined that the proposed change will not have adverse effects on the radiological analysis, hydrogen generation, or the functional capability of Reactor Building systems, structures, and components following a postulated LOCA.

5.0 Regulatory Analysis 5.1 No Significant Hazards Consideration AmerGen has evaluated whether or not a significant hazards consideration is involved with the proposed amendment by focusing on the three standards set forth in 10 CFR 50.92, "Issuance of amendment," as discussed below:

1., Does the proposed amendment involve a significant increase in the probability or consequences of an accident previously evaluated?

Response: NO.

For the'proposed change, trisodium phosphate dodecahydrate (TSP) will be used as a buffer for post-accident pH control and will replace the existing buffer. The buffer material and means of storage and delivery are not initiators for previously analyzed accidents. The accident mitigation function of the replacement buffer is the same as the existing buffer. The pH of the water in the emergency sump following a loss of coolant accident (LOCA) will be adjusted with TSP rather than sodium hydroxide (NaOH) to be within a range that will reduce the potential for elemental iodine re-evolution and long-term stress corrosion during the recirculation mode of emergency core cooling system (ECCS) operation. In addition, the replacement buffer will reduce the formation of

Enclosure 1 Description and Assessment Page 11 of 19 precipitates resulting from chemical reactions between the recirculating spray solution and insulating materials in the Reactor Building (RB), thus reducing the. potential for ECCS emergency sump intake screen blockage. The proposed sump pH range will not result in an increase in post-LOCA hydrogen generation. The proposed isolation of the sodium hydroxide tank, and the installation of TSP in baskets has been evaluated for impacts on accident effects and the safety functions of required systems, structures, and components (SSCs). The RB emergency sump solution pH profile resulting from the proposed change has been evaluated for impacts on environmental qualification of SSCs. The accident mitigation functions of required SSCs will not be affected by the proposed change.

As a part of the proposed change, the radiological consequences of a postulated LOCA have been reanalyzed using Standard Review Plan (SRP) 6.5.2, "Containment Spray as a Fission Product Cleanup System", and the Alternate Source Term (AST) guidance in Regulatory Guide 1.183. The analysis considered the use of a plain borated water spray during the post-LOCA injection phase and a spray mixture with a minimum pH of 7.3 during the recirculation phase. The results of the reanalysis show that the consequences of the accident are not increased. The calculated doses at the Exclusion Area Boundary, Low Population Zone boundary, and in the Control Room remain within 10 CFR 50.67 AST dose limits.

Therefore, the proposed change does not involve a significant increase in the probability or consequences of an accident previously evaluated.

2. Does the proposed amendment create the possibility of a new or different kind of accident from any accident previously evaluated?

Response: No.

The proposed change will replace the existing spray additive design using sodium

'hydroxide solution stored in a tank with TSP contained in baskets located on the floor of the RB. The TSP storage and delivery method is passive. The baskets are constructed of stainless steel to resist corrosion and are seismically qualified. The existing sodium hydroxide tank, associated piping, and valves will no longer be used and will be permanently isolated, but their structural integrity will be maintained. The RB spray system will perform the same function and operate in the same manner for the proposed change; however, the sodium hydroxide tank isolation valves will no longer be required to open on an engineered safeguards actuation signal. The accident mitigation function of TSP will be the same as the existing buffer, sodium hydroxide. The TSP will act as a buffering agent to raise the pH of the water in the containment emergency sump to greater than 7.3 for long-term post-LOCA RB spray recirculation. The SSCs required for post-LOCA accident mitigation have been evaluated for the proposed change including the effects of the modified emergency sump solution pH profile. No new accident scenarios, failure mechanisms, or single failures are introduced as a result of the proposed change.

Therefore, the proposed change does not create the possibility of a new or different kind of accident from any accident previously evaluated.

Enclosure 1 Description and Assessment Page 12 of 19

3. Does the proposed amendment involve a significant reduction in a margin of safety?

Response: No.

The proposed change from sodium hydroxide to TSP will not reduce the effectiveness of the post-LOCA pH control buffer. The TSP will buffer the sump water sufficiently to assure that the resulting mixture pH is > 7.3 and < 8.0. This pH level will be effective in reducing the potential for iodine re-evolution during the recirculation phase of a LOCA, preventing long-term stress corrosion cracking of austenitic stainless steel, and minimizing post-LOCA hydrogen generation. In addition, the use of TSP will reduce the formation of precipitates resulting from chemical reactions between the recirculating spray solution and insulating materials in the RB, thus reducing the potential for ECCS emergency sump intake screen blockage. The proposed use of SRP 6.5.2 guidance, which is an NRC-approved methodology, for post-LOCA dose calculations does not result in a reduction in a margin of safety. The proposed change does not adversely

• affect the performance of SSCs required for post-LOCA mitigation, and does not affect an operating parameter or setpoint used in the accident analyses to establish a margin of safety. Also, the proposed change does not affect a margin of safety associated with containment functional performance.

Therefore, the proposed change does not involve a significant reduction in any margin of safety.

Based on the above, AmerGen concludes that the proposed amendment to change the Reactor Building emergency sump pH control method from NaOH to TSP, and to revise the related TS, presents no significant hazards consideration under the standards set forth in 10 CFR 50.92(c), and, accordingly, a finding of "no significant hazards consideration" is justified.

5.2 Applicable Regulatory Requirements/Criteria Design Criteria TMI Unit 1 has been designed and constructed taking into consideration the general criteria for nuclear power plant construction permits as listed in proposed Atomic Energy Commission General Design Criteria, dated July,1967.

Criterion 11 - "Control Room." The proposed amendment complies with this criterion.

Criterion 11 states that the facility shall be provided with a Control Room from which actions to maintain safe operational status of the plant can be controlled. Adequate radiation protection shall be provided to permit access, even under accident conditions, to equipment in the Control Room or other areas as necessary to shut down and maintain safe control of the facility without radiation exposure of personnel in excess of 10CFR20 limits. It shall be possible to shut the reactor down and maintain it in a safe condition if access to the Control Room is lost due to fire or other cause.

Calculated post-accident control room doses for the proposed change are within

Enclosure 1 Description and Assessment Page 13 of 19 10 CFR 50.67 limits, which is applicable to the alternative source term methodology implemented for TMI Unit 1.

Criterion 37 - "Engineered Safety Features Basis for Design." The proposed amendment complies with this criterion. Criterion 37 states that engineered safety features shall be provided in the facility to back up the safety provided by the core design, the reactor coolant pressure boundary, and their protection systems. As a minimum, such engineered safety features shall be designed to cope with any size reactor coolant pressure boundary break up to and including the circumferential rupture of any pipe in that boundary assuming unobstructed discharge from both ends.

The required capability to control the pH of the post-LOCA emergency sump fluid is maintained. The small reduction in RB post-LOCA cooling water volume due to isolation of the NaOH tank will not affect the design capability of engineered safety features.

Criterion 38 - "Reliability and Testability of Engineered Safety Features." The proposed amendment complies with this criterion. Criterion 38 states that all engineered safety features shall be designed to provide high functional reliability and ready testability. In determining the suitability of a facility for a proposed site, the degree of reliance upon and acceptance of the inherent and engineered safety afforded by the systems, including engineered safety features, will be influenced by the known and the demonstrated performance capability and reliability of the systems, and by the extent to which the operability of such systems can be tested and inspected where appropriate during the life of the plant.

(

The proposed pH control system design using TSP is passive and no single failures are assumed. The capability for testing and inspection is provided.

Criterion 41 - "Engineered Safety Features Performance Capability." The proposed amendment complies with this criterion. Criterion 41 states that engineered safety features, such as emergency core cooling and containment heat removal systems, shall provide sufficient performance capability to accommodate partial loss of installed capacity and still fulfill the required safety function. As a minimum, each engineered safety feature shall provide this required safety function assuming a failure of a single active component.

The proposed pH control system design using TSP is passive, so'no new single failures are assumed. In addition, the quantity of TSP in the storage baskets accounts for material densification and all baskets will be submerged by the post-LOCA sump fluid. Therefore, partial loss of installed capacity is not considered a credible failure.

Criterion 42 - "Engineered Safety Features Components Capability." The proposed amendment complies with this criterion. Criterion 42 states that engineered safety features shall be designed so that the capability of each component and system to perform its required function is not impaired by the effects of a loss of coolant accident.

All TSP baskets will be submerged by the post-LOCA sump fluid, which will promote dissolution of the TSP. The effects of a LOCA will not impair the TSP function.

\

Enclosure 1 Description and Assessment Page 14 of 19 Criterion 52 - "Containment Heat Removal Systems." The proposed amendment complies with this criterion. Criterion 52 states that where active heat removal systems are needed under accident conditions to prevent exceeding containment design pressure, at least two systems, preferably of different principles, each with full capacity, shall be provided.

The proposed change to add TSP in baskets, and isolate the NaOH tank, will not affect the RB cooling design function of the RB spray system.

Criterion 70 - "Control of Releases of Radioactivity to the Environment." The proposed amendment complies with this criterion. Criterion 70 states that the facility design shall include those means necessary to maintain control over the plant radioactive effluents, whether gaseous, liquid, or solid. Appropriate holdup capacity shall be provided for .

retention of gaseous, liquid, or solid effluent, particularly where unfavorable environmental conditions can be expected to require operational limitations upon the release of radioactivity effluents to the environment. In all cases, the design for radioactivity control shall be justified: (1) on the basis of 10CFR20 requirements for normal operations and for any transient situation that might reasonably be anticipated to occur, and (2) on the basis of 10 CFR 100 dosage level guidelines for potential reactor accidents of exceedingly low probability of occurrence except that reduction of the recommended dosage levels may be required where high population densities or very large cities can be affected by the radioactive effluents.

TMI Unit 1 calculated post-LOCA doses for the proposed change comply with 10 CFR 50.67, "Accident Source Term."

Regulations 10 CFR 50.36, 'Technical Specifications." The proposed change is consistent with the criteria specified in 10 CFR 50.36(c)(2)(ii) for inclusion of items in TS..

10 CFR 50.44, "Combustible Gas Control for Nuclear Power Reactors." As discussed in Section 4.4, the proposed change will not result in an-increase in post-LOCA hydrogen generation.

10 CFR 50.49, "Environmental Qualification of Electric Equipment Important to Safety for Nuclear Power Plants." As described in Section 4.5, environmentally qualified components were analyzed and the evaluation concluded that all components analyzed will be capable of performing their safety functions underthe short-term and long-term post-accident Reactor Building pH conditions.

10 CFR 50.67, "Accident Source Term." As described in Section 4.1, with the proposed buffer change from sodium hydroxide to trisodium phosphate, and the proposed change to the UFSAR methodology for calculation of the spray removal coefficient, the post-LOCA offsite radiological consequences at the Exclusion Area Boundary (EAB), the Low Population Zone (LPZ) boundary, and the control room, comply with 10 CFR 50.67.

Enclosure 1 Description and Assessment Page 15 of 19 Other Guidance Standard Review Plan (SRP) 6.5.2, "Containment Spray as a Fission Product Cleanup System." As described in Section 4.1, the proposed change uses the methodology of SRP 6.5.2 to replace the current UFSAR methodology for calculating the post-LOCA spray removal coefficients.

Summary AmerGen has determined that the proposed change does not require any exemptions or relief from regulatory requirements and does not affect conformance with any General Design Criteria.

5.3 Precedent Emergency sump pH control using TSP stored in baskets is presently implemented at a number of operating plants, including Crystal River Unit 3, which is a B&W NSSS plant of the same vintage as TMI Unit 1. Other plants that use TSP include: Palisades, Palo Verde Units 1, 2, and 3, Waterford-3, Arkansas Nuclear One Unit 2, and Millstone Unit 2.

Conclusion In conclusion, based on the considerations discussed above, (1) there is reasonable assurance that the health and safety of the public will not be endangered by operation in the proposed manner, (2) such activities will be conducted in compliance with the Commission's regulations, and (3) the issuance of the amendment will not be inimical to the common defense and security or to the health and safety of the public.

6.0 Environmental Consideration A review has determined that the proposed amendment would change a requirement with respect to installation or use of a facility component located within the restricted area, as defined in 10 CFR 20, or would change an inspection or surveillance requirement. However, the proposed amendment does not involve (i) a significant hazards consideration, (ii) a significant change in the types or significant increase in the amounts of any effluent that may be released offsite, or (iii) a significant increase in individual or cumulative occupational radiation exposure. Accordingly, the proposed amendment meets the eligibility criterion for categorical exclusion set forth in 10 CFR 51.22(c)(9). Therefore, pursuant to 10 CFR 51.22(b), no environmental impact statement or environmental assessment need be prepared in connection with the proposed amendment.

7.0 References

1. WCAP 16596-NP, Revision 0, "Evaluation of Alternative Emergency Core Cooling Buffering Agents," July 2006.

2. Regulatory Guide 1.183, Alternative Radiological Source Terms for Evaluating Design Basis Accidents at Nuclear Power Reactors, July 2000.

Enclosure 1 Description and Assessment Page 16 of 19

3. TMI Unit 1 License Amendment No. 235, Engineered Safety Feature (ESF) Systems Leakage Outside Containment, dated September 19, 2001.

4. Letter from P. B. Cowan (Exelon Generation Company, LLC and AmerGen Energy Company, LLC) to U. S. Nuclear Regulatory Commission, Exelon/AmerGen Response to NRC Generic Letter 2004-02, "Potential Impact of Debris Blockage on Emergency Recirculation During Design Basis Accidents at Pressurized-Water Reactors," dated September 1, 2005.

5. "RADTRAD, A Simplified Model for RADionuclide Transport and Removal And Dose Estimation," S&L Computer Program Number 03.7.720-3.03, Version 3.03.

6. NUREG-0800, Standard Review Plan 6.5.2, Revision 4 (March 2007), "Containment Spray as A Fission Product Cleanup System."

Enclosure 1 Description and Assessment Page 17 of 19 Attachment 1 AmerGen/Exelon Calculation C-1101-1 53-E410-036, Revision 0, "Reactor Building Spray pH Prior to the Start of Recirculation Spray"

Attachment 1 CC-AA-309-1 001 Design Analysis Major Revision Cover Sheet Design Analysis (Major Revision) Last Page No. I Att. B pg. 4 Analysis No.: C-1101-153-E410-036 Revision: 2 0

Title:

' Reactor Building Spray pH Prior to the Start of Reclrculation SpISl ECVECR No.: 4 07-00174 Revision: 1 0 7

Station(s): TMI Component(s): 14 Unit No.: 1I Discipline: 9 TEDM__

Descrip. Code/Keyword: spray, pH TS P SafetylQA Class: 11 Q0 AF'ET'j k.LAIE __

System Code: "2 2107.-I_

Structure: Reactor Building CONTROLLED DOCUMENT REFERENCES _

Document No.: From[To Document No.: rrom/To I VI~IIJlI It I I A 111-I.I

" 14.I 1J-,.QIIIt.lU1*III¢,

t IZ ~

IVIILJIIII 2 RAui,~I FC.

From Section 3.3, Amendment 227 Update 18 From CaIc. C-1 101 -823-5450-001, TMI-1 LBLOCA EQ Temperature Profile Using From the GOTHIC Computer-Code, Rev. 9 Is this Design Analysis Safeguards Information? "6 Yes E] No X If yes, see SY-AA-101-106 Does this Design Analysis contain Unverified Assumptions?"1 Yes I-. No X If yes, ATI/AR#:

This Design Analysis SUPERCEDES: C-1101-210-5340-005, Rev. 0 and in part.

C-1101-210-5340-007, Rev. 1 Note: The remainder of these calculations will be superseded by the original revision of C-1101-153-E410-040, being issued in conjunction with this calculation, per ECR 07-00174. The approval of ECR 07-00174, and its associated calculations, will supersede C-1101-210-5340-005, revision 0, and C-1 101-210-5340-007, Revision 1, in their entirety.

Description of Revision (list affected pages for partials): 19 TMI-1 is changing the buffering chemical for the post-LOCA reactor building sump water ffom sodium hydroxide (NaOH) to trisodium phosphate dodecahydrate (TSP) via ECR 07-00174. This modification will result in a change in the reactor building spray pH prior to recirculation spray.

This original (Revision 0) calculation indicates the range of pH in the reactor building prior to recirculation spray is limited to 4.6 pH minimum. It is recommended in the calculation that a conservative estimate of 4 pH be utilized where low pH Is a limiting factor and pH 5.5 where high pH is liming factor =to jrvide reasonable margin.

Preparer." Robert A. Nelson (  ;;VA o?

Pdnt NOM Ae Method of Review: 2" Detailed Review X Alternate Calculations (attached) [E Testing El Reviewer:" Jeri C. Penrose ,-C. G b0.*o,,,T Pdfnt Name sign rami Da*

Review Notes: 2 Independent review E2 Peer review El (For External Analyses Only) -

External Approver.' /4.. /. [(

.0 .)

Exelon Reviewer" 23 -*.F kalol trd&?L Print Name sign Name Independent 3r Party Review Reqd?21 Yes E] No X Exelon Approver:" P.4A .i ,,sr _ __-______-_________--

Pin-t Name S1i~nNgn Da

Cac. No. C-1101-153-E410-036 Sheet 2 of 19 Review Checklist for External RevisionC6 Owners Acceptance Design Analysis Page 17 of 17 Design Analysis No. C-1 101-153-E410-036 Rev. 0 Yes No N/A

1. Do assumptions have sufficient rationale? ['2 [] El

2. Are assumptions compatible with the way the plant is operated and with the licensing ID Li basis?

3. Do the design inputs have sufficient rationale? [ 1. EL

4. Are design inputs correct and reasonable? a ' Li Ei

5. Are design inputs compatible with the way the plant is operated and with the licensing . [ []

basis?

6. Are engineering Judgments clearly documented and justified? Li I]

7. Are Engineering Judgments compatible with the way the plant is operated and with the [

licensing basis?

8. Do the results and conclusions satisfy the purpose and objective of the design analysis? F1i El

9. Are the results and conclusions compatible with the way the plant is operated and with the

• Li m licensing basis?

10. Does the design analysis include the applicable design basis documentation? [] Li

11. Have any limitations on the use of the results been identified and transmitted to the i El Eý appropriate organizations?

12. Are there any unverified assumptions? Li 2 'El

13. Do all unverified assumptions have a tracking and closure mechanism in place? Li i [Er

14. Have all affected design analyses been documented on the Affected Documents List (ADL) Li m for the associated Configuration Change.

15. Do the sources of inputs and analyses methodology used meet current technical requirements and regulatory commitments? (If the input sources or analysis methodology are based on an out-of-date methodology or code, additional reconciliation may be required E L L' i3 if the site has since committed to a more recent code)

16. Have 'vendor supporting technical documents and references (including GE DRFs) been [L reviewed when necessary?

Exelon Reviewer: i( /1//'4 6 Date:

A er!en Calc. No. C-1101-153-E410-036 Sheet 3 of 19 TITLE Reactor Building Spray pH Prior to the Start of Recirculation Spray REV

SUMMARY

OF CHANGE APPROVAL DAT'E 0 Initial Issue OA4,f ý1&1001A 6 P/0-4 0.

60'f ý,ý

£ I

CALCULATION SHEET AmerGen Sheet

Subject:

Reactor Building Spray pH Calculation No. Rev. No. System Nos.

Prior to the Start of Recirculation Spray C-1101-153-E410-036 0 210 4 of 19 Table of Contents Section

1. P UR P OS E :............................................ 1................................................... ......... 5

2. INP UT S : .............................................. 5...................

5

3. ASSUMPTIONS: ............ .................................................... 7

4.

REFERENCES:

................................................................................ 7

5. COMPUTER PROGRAMS: ............................................................................. 7

.6. METHOD OF ANALYSIS: ..................................... .......................................... 8

7. NUMERIC ANALYSIS ...................................................................................... 8

.8. R ES ULTS: ..... ................................................................................................ 10

9. C O NC LUS IO N S : ............................................... ............................................ 11

10. ATTA C HME NT S : ...................................................................................... ......... 11 Attachment A, US Borax Inc., Optibor Product Profile, PP1 -AB1 2-646-US Attachment B, Cover and pages 8-10 from NUREG/CR-6875, Boric Acid Corrosion of Light Water Reactor Pressure Vessel Materials, July 2005 (Total Pages = 19)

CALCULATION SHEET

Subject:

Reactor Building Spray pH AmerGen Calculation No. Rev. No. System Nos. Sheet Prior to the Start of Recirculation Spray C-1101-153-E410-036 0 210 5 of 19

1. PURPOSE:

TMI-1 is changing the buffering chemical for the post-LOCA reactor building sump water from sodium hydroxide (NaOH) to trisodium phosphate dodecahydrate (TSP) via ECR 07-00174 [Ref. 4.5].

Historically, when NaOH was utilized as a chemical buffer, it was mixed with a borated water solution from the Borated Water Storage Tank (BWST) upstream of the reactor building spray headers. This spray would be injected into the Reactor Building via the spray headers, prior to recirculation. Limits on the contained water volume, NaOH concentration, and Boron concentration, were established in Technical Specification 3.3 [Ref. 4.1] to ensure a pH value between 8.0 and 11.0 in the solution spray within containment after a Design Basis Accident (DBA).

Utilizing TSP as a buffering chemical prohibits the introduction of the chemical buffer prior to reactor building spray. The TSP is located in baskets on the reactor building floor (elevation 281'). As the sprayed borated water solution from the BWST accumulates in the reactor building, prior to start of recirculation, the TSP buffer will dissolve and begin mixing. Prior to dissolution and mixing of the TSP, the spray will consist of the borated water solution from the BWST. Following the start of recirculation spray, and continual mixing, the pH of the reactor building spray will be the same as the pH of the water in the reactor building sump.

This calculation is a determination of the anticipated range of tie Reactor Building spray pH prior to recirculation.

2. INPUTS:

The specific inputs used for this calculation"is summarized in this section.

2.1 Minimum BWST boron 2,500 ppm [Ref. 4.1, Section concentration. 3.3.1.1]

2.2 Maximum BWST boron 2,800 ppm [Ref. 4.2, Table concentration 6.2-1]

CALCULATION SHEET

Subject:

Reactor Building Spray pH AmerGenCalculation No. Rev. No. System Nos. Sheet Prior to the Start of Recirculation Spray C-1101-153-E410-036 0 210 6 of 19 2.3 Boric Acid Solution [Ref. 4.3]

Concentration vs. pH

% H3BO 3 by weight of solution pH at 20 'C (68 OF) 0.1 6.1 0.5 5.6 1 5.1 2 4.5

3. 4.2 4 3.9 4.72 3.7 (saturated) 2.4 Molecular weight of boron 10.811 g/g-mole [Ref. 4.4]

2.5 Molecular weight of boric acid 61.833 g/g-mole [Ref. 4.4]

(H 3B0 3) 2.7 Maximum Containment 138 °C [Ref. 4.7, Sheet temperature (280 OF) 25, Figure 3]

2.8 Minimum BWST temperature 4.4 0C [Ref. 4.1]

(40 OF)

(

CALCULATION SHEET AmerGen Calculation No. Rev. No.. System Nos. Sheet

Subject:

Reactor Building Spray pH Prior to the Start of Recirculation Spray C-1101-153-E410-036 0 210 7 of 19

3. ASSUMPTIONS:

3.1 The maximum in the containment is 138 0C (280 OF) [Ref. 4.7, Sheet 25, Figure 3]. It is assumed that the spray fluid temperature is in equilibrium with the containment temperature.

3.2 The pH of boric acid solutions increases very slightly, -0.1 pH unit between -30 and -95 OC (86 and 203 OF), with increasing temperatures

[Ref. 4.6, pg 9-10, Figure 9.a]. It is assumed that this trend continues for the range of temperatures of interest -4.4 to 138 0C (40 to 280 OF).

3.3 For the purposes of this calculation it is assumed that (a) the pH of boric acid solutions at various concentrations that was provided by a major boric acid supplier (US Borax, Inc.) [Ref. 4.3] are accurate and (b) interpolation between the data points is sufficiently accurate for the concentration range of interest (i.e., the difference between different interpolation methods, such as logarithmic and polynomial, is small compared to other potential variations including the range of concentrations in the BWST).

4.

REFERENCES:

4.1 TMI Unit 1 Technical Specifications, Section 3.3 4.2 TMI-Unit 1 FSAR, Update 18 4.3 US Borax Inc., Optibor Product Profile, PPl-AB12-646-US (see Attachment A) 4.4 CRC Handbook of Chemistry and Physics, 78th Ed.

4.5 AmerGen ECR No. 07-00174, RB Buffer Replacement Modification (NaOH to TSP) 4.6 NUREG/CR-6875, Boric Acid Corrosion of Light Water Reactor Pressure Vessel Materials, July 2005 (see Attachment B) 4.7 CaIc. C-1 101-823-5450-001, TMI-1 LBLOCA EQ Temperature Profile Using the GOTHIC Computer Code, Rev. 9

5. COMPUTER PROGRAMS:

None.

CALCULATION SHEET

Subject:

Reactor Building Spray pH AmerGen Calculation No. Rev. No. System Nos. Sheet Prior to the Start of Recirculation Spray C-1101-153-E410-036 0 210 8 of 19

6. METHOD OF ANALYSIS:

The method for performing this calculation is to use the design basis range of boron concentrations in the BWST to determine the pH of the boric acid solution.

This will involve the following steps:

1. Calculate the conversion between ppm boron and wt% boric acid.

2. Calculate the boric acid concentrations associated with the upper and lower boron concentrations in the BWST.

3. Determine the pH of the boric acid solutions associated with the upper and lower boron concentrations in the BWST based on published data of the concentration and temperature dependence of the pH of boric acid solution.

7* NUMERICAL ANALYSIS:

1. Calculate the conversion between ppm boron and wt% boric acid.

• ~ ~ ~ ~ ~ (10wt% ,-,o-~p~ "1*8 *'

6.3gm~boricacid= "pbrn

~wt% boricacid= X ppm boron x I 10 xl6.3 lmlbrcai

ý1,000,000 ppm) 10.811 lgmole boron

-or wt% boricacid = Xppm boron 1749 ppmboron

2. Convert BWST boron concentrations in ppm to wt% boric acid.

a. Upper concentration limit 2,800 ppm Boron =

1.60wt% Boric Acid 1,749 ppm Boron

b. Lower concentration limit

• 2,500ppm Boron

= 1.43 wt% Boric Acid 1,749 ppmBoron

CALCULATION SHEET

Subject:

Reactor Building Spray pH AmerGen Calculation No. Rev. No. System Nos. Sheet Prior to the Start of Recirculation Spray C-1101-153-E410-036 0 210 9 of 19

3. Estimate the pH of the boric acid solutions at 200C (68 OF):

The boric acid concentration in BWST is between I and 2 wt%. Estimate the pH at the intermediate concentrations using a Lagrange Interpolation polynomial for 3 points. The Lagrange Interpolation polynomial is based on the following boric acid concentration and pH values from Section 2.3:

% H3 B0 3 by weight of pH at 20 °C (68 OF) solution 1 5.1 2 4.5 3 4.2 2

pH = 6.0 -1.05 xwt% + 0.15 xwt%

a. Upper concentration limit (minimum pH) pH = 6.0 -1.05 x 1.60 + 0.15 x 1.602= 4.70

b. Lower concentration limit (maximum pH) pH = 6.0 -1.05 x 1.43 + 0.15 x 1.432 = 4.81

4. Estimate the pH of the boric acid solutions at lower and higher temperatures.

The maximum temperature inside the reactor building following LOCA is 138 0C (280 OF) [See Input 2.7 and Assumption 3.1]. The minimum BWST temperature is 4.4 'C (40 OF) [See Input 2.8].

Based on information provided in NUREG/CR-6875 (Figure 9.a) the pH of boric acid solutions are not change significantly with changes in temperature.

This figure is a plot of the pH of a room temperature saturated boric acid solution between - 30 0 C and -95 °C (86 and 203 OF). It shows that the pH is increases by - 0.1 over the -65'C (-30 °C and -95 °C) range for an air purged solution. Other sections of this report suggest that this trend is consistent for higher temperatures (e.g., Figure 44) indicated that the corrosion rate of steel decreases as the temperature increases from - 100 to

- 250 'C (212 and 480 °F).

CALCULATION SHEET

Subject:

Reactor Building Spray pH AmerGen Calculation No. Rev. No. System Nos. Sheet Prior to the Start of Recirculation Spray 1 C-1101-153-E410-036 0 210 110 of 19 To conservatively account for temperature variations, the pH will be reduced by 0.1 for the lower temperature (4.4 'C) and the pH will be increased by 0.2 for the higher temperature (138 0C).

a. Upper concentration limit (minimum pH) and low temperature pH= 4.70 - 0.1 4.6 b.. Upper concentration limit (minimum pH) and high temperature pH= 4.70 + 0.2 =4.9

c. Lower concentration limit (maximum pH) and low temperature pH = 4.81 - 0.1 = 4.7

d. Lower concentration limit (maximum pH) and low temperature pH = 4.81 + 0.2 = 5.0

8. RESULTS:

The pH of the Containment Building spray prior to recirculation spray will be the pH of the water from the BWST. The pH of the water in the BWST depends on the boric acid concentration in the water.

The design basis range of the BWST boron and boric acid concentration is:

Boron Boric Acid pH pH pH Concentration Concentration at-20 'C at 4.4 °C at 138 °C (ppm) (wt%) (68 OF) (40 OF) (280°F) 2,500 1.43 4.81 4.7 5.0 2,800 1.60 4.70 4.6 4.9 At higher temperatures (during the first several hours following the LOCA), the pH may be slightly greater (i.e., closer to neutral).

CALCULATION SHEET

Subject:

Reactor Building Spray pH AmerGen Calculation No. Rev. No. System Nos. Sheet.

Prior to the Start of Recirculation Spray C-1101-153-E410-036 0 210 11 of 19

9. CONCLUSIONS:

The pH of the Containment Building Spray prior to Recirculation Spray will be between 4.6 and 5.0.

For analyses where a low pH is a limiting factor (e.g., Equipment Qualification) a pH of 4 should be used to provide a reasonable margin. For analyses where a high pH is a limiting factor (e.g., Chemical Effects) a pH of 5.5 should be used to provide a reasonable margin.

10. ATTACHMENTS:

Attachment A, US Borax Inc., Optibor Product Profile, PPI-AB12-646-US.

(4 pages)

Attachment B, Cover and pages 8-10 from NUREG/CR-6875, Boric Acid Corrosion of Light Water Reactor Pressure Vessel Materials, July 2005 (4 pages)

Attachment A Page 1 of 4 to C-1101-153-E410-036, Rev. 0

.20 M#L-.E TEAM Bortiborc Product Profile Opaibor Boric Adds are a pure, multiftinctional source of boric omdde (%W.. .Apart from borax pentahydrate. they are the most widely used industrial borate.

H3B03 Optilior Boric Acids (ll3tl0ý are theoretically composed of boric ooide and water.

Orthoboric Add Cryialline in composition, white in appearance, they can be used as gr*mules or as a CASrSCA Nebe I0043O3S.3 powder. B.oth forms are stable under normal condition, free.lowin, and easily handled by means of air or mechanical convesing. In solution, they art mildly acidic.

Technical Grade:

Granular and Powder Fibs, Glas :resells National Formulary (NF): Crepmn et: VW/

• Granular and Powder Spedal Quality (SQ):

Granular Applications and Benefits Glass and glass fiber

.I0 5 Is both a flux and a network former; it assists the melt and influences the final product properties. In fibor glam for example, it reduces melting tenmperlures and helps the fibeizing process. Generally, BL, lowers viscosity, controls thermal expansion, inhibits devitrification, increases durability and chemical resisance, and reduces susceptilbry to mechanicas or thermal slhoX.

Optifr Boric Acds mraybe used in combination with a soditu borate (borax pentabydrate or anhydrous borax) in order to adjust the sodium to boron ratio in glasses which require low sodium levels. Ti6 is Important in borosiliceae glass where BJ*, provides essential fuxing properties at low sodium and high alumina level P'its, glazes, and enamels For the glassy surfaces of ceramics and enamels boric oxide acts as both network former and flu- It initiates glass formation (at low temperatures), ensures 'thermal tiCbetween glaze and body, reduces Aiscosilty and surface tension, incre-es refractive indet, enhances strength, durability and scratch resistance, and facilitates lead-free formulatons. Wigh boron frits mature rapidly, Improve.the speed at which smooth, even glaze surfaces develop, and provide good bases for coloring oxides.

Opti' Boric Adds are used is the F0.%source In the formulation of fast ire fits for tiles because of their requirement for low sodium levels.

Flame retardancy Incorporated into cellulose materials, borates change the oxidation reactions and promote tile formation of 'char', thereby inhlsibtlng combustion. Op fir Boric Acds, alone or in combination with borax, are particularly effective in reducing the flammability of cellulose insulation, wood composites, and the cotton baltin" used ROIjZ41J in mattresses.

(

Attachment A Page 2 of 4 to C-1101-153-E410-036, Rev. 0 Optibor Product Profile Metallurgy OpIfirir Boric Aids prevet the oxidation of metal suraaces In welding brazn, or soldkn 'They are also used as a source of boron for strengthening metal alloys and steel Corrosion inhibition Oph'kr Boric Acids armincorporated in many aqueous and non-aiqueous systems requiring corrosion inhibition. lubrication or thermal oxidative stabilization. Optibor Boric Acids find use in the manufacture of lubricants, brake fluids, metalworking fluids, water treatment chemicals. and fuel additives.

Adhesives

• As part of the starch adhesive formulation"for corrugated paper and pajerboard, and as a pepting agent in the manufacture of casein-based and dexrin-based adhesives.

Optibor Boric Acids greatly improve the tack and green strength of the adhesive by, crossfinking eonjugated hydroxyl groupjp Personal care products NF' grade Opibor Boric Acid findmapplications in coaisetics, toiletries mad pharmaceuticals.

It is used in conjunction with sodium burates for pH buffering, atd as a croallukiug agent to emusit waxes and other paraffins.

Nuclear energy Being a highly effective absorber of thermal neutrons, The boron-lO isotope is essential to the safely and control systems of nuclea power stations. OplUor SQ Boric Acid is made for dte nuclear industry, and can be isotopically enriched Io increase the available proportion of boron-]0.

Chemical reactions Siffeck of 5203 ont glass ePanalon In the manudscturng of nylon intermediates, Optibor Boric Acids catlzes the oxidation of hydrocarbons and increases the yield of alcohols by forming esters that prevent further oxidation of hydroxyl groups to ketones and carboxylic acds.

121 Trey are also used in preparing various important industrial pioducts such as boron haltde%borohydride.

fluoborotes&metallic borates, borate esters. and boron

• 0 AlA containing ceramics.

0 10 20 30 40 Some other applicatio Wetioht d.s added Dye stabilation Paints Reduction in linear woeffident of ex"asion in glae when Electroplating fiand-casting (magnesium) silica is replaced proprortionatey by boric add. This fedlitates lectrolylic capacitors Textile firshring

• thermal lit Inceramckglares ands heat resistance In Leather proessing borosilkiate,qWa ru n Gm by Heot sfhfde.i and finishing

Attachment A Page 3 of 4 to C-1101-153-E410-036, Rev. 0 Optibor Product Profile Chemical and Physical Properties When healed above l00VC (22) in the open. Opfi/rBoric Acids gradually lose water tirst chanin to metaboric add, HBOQ,of which three monotropic forms edst. Those have ineiting polins respeca*el of 176TC (348lfD, 201*C (39WF8). and 236TC k4.5W]'F.

Dehydration stoep at die composition MB02 unless thdetTe of heating is extended or the temperature raised above ISM0C00O2'F). On continued heating and at higher terperatures all water is removed leaving the Caarsc anhllrous oxide, B-O4. the r cystalline ferm of which t nelts at Mluarlht:S 6.3 45V (8,) leaopus 'Spedffir Graiy15 form has no definite melting p0et,soen.ng at about 35C ng ont (6Q?*F) and becoming fully Ilud Heat of solutron (,btorbeco',' 16xas8u at obout WC 0 WC(92F).

Stability Optlbr Boric acids ares stable Tem'p *C(,) .N crytdalne product hih does not chang chemicailly undler .-A2 normal storage conditiona (42) 2(42 Wide fluctuations in temperature 10, (50) 349 and humidity can cause (68) r*cryertllsation at particle 2' .(77)..  %' .,. '4 r contact points, resulting in 5.46 .

catting. Care should therefore be (8) takten to avMsuchlfluctusalons (5 7:1235 during starage of the product 40 (I4).........,

Also, It Is, of course, essntiallto.................. . 1 mainlan Ithe integrity of the 50 (1222.9 65 (149)'ý 14A2 70,, (158). . 15ý75 90 (194). . 23.27 9.(203). . . 25221 10 (222).. 25 a,3'(179§)!. 22

• Boiling point of solution

Attachment A Page 4 of 4 to C-1101-153-E410-036, Rev. 0 Optibor Product Profile I Solubility in other solvents Hydrogen Ion concentration Aqueous soltions of Ojdbor Biodc Acids are rildly

.Or~au~1c~olvkuTepe) ork add by' acidic, the pH dect-asng with icrmeasing

• etuae solutions conce*tmrlon.

Goi~8$% -,202(68)' 19.90

%HyBO~yA6:1 rEtlylenebyCoi f,25 (M7 1160.

tlys~glycol., 25 (M7 13.60 .

actat Ethy ~.25 (77),, 1.30 Acotope25 , 2(77) 0.60c GýIacialcetfc add 30(86),, 6.30 4.2

~.

Metanl , 25 (77), 22.66, A-72  :-J, 17" l~ropan2S 2(M7 7.34' 2.ehl1Propanol -25(77),, -5.32

'34. 1-butaisol~ 25(77)'

4.36 's" Notlce:

Before using these producM please read the Product Spedificationsm the Safety Data Sheets and any other applicable product literature.

The de*eriptdos of potentil own for theseopredut are eroolded only b-yey oftconplede.e prod*ct% ar not Intended or rceo=ieuneded for snyula*f* orprohbibt.-d use twlunidrgT wittuet linilladon. any use that wouldconsttlute Infrvie.ee ofanysppikable puttrses.NwrIsIt Intended o reesurunendled that Idtflupduent be usWed faray desbed purposes without vorilostion bythe user of *he prsdsets kand offus? for tub purpmoses, iswell usensuring eli upllebleou. r.oasedrer.stttls allptsis-cwttt nJorressiAeo use orthe oreducts Aeebased o0 data b olieedb reto e . 'The sellerfi have norAbIlW r-solting ",einuisse of the products sod provIdese ao uAsuft. wboer ll- pvmd or WAliM.a to tirerus*s.ht*obained seaod Inwodwocxe withdirections or e psudiens, f the *foductsra not fnobuyer msueouneal responsWIb-tIintudity.say iijury or dasese, resuhlio ftommia oftebbprodom whetherusudstoneorlin esuubigustio uwith atlur oustv dusTHEMIUERtMAMtS NO61CPIVSS OR IN(PURD WARRAT*,tES OF MEiRCHANTADJnTY a 15 FORA PART1CUtI OR AR PURPOSL 'IRE SELMR SIIALLHAVENO U.WitMfY FOR CONSEQ*0ETIAL IMMAaL BoraxAstaPut.Ltd. BorSax Europe Umtted U.. BoresItre 501 Orcharod foRwd IA GCtlord BRusineoPat 247 Tourucy Road 5550 WhedG&e Place Guildford. GU26XG Vkdsaci.Clffrouns. 9233..1847.

oSuaporv73MM United ,M;uedmn Unted States 7b): M6)MOMtttt T (444)143 2421O1 Tel: (1) G6M 29 540 FeI MW l 8V7 M Fm. (44) 1i4M242001 Fee ia) 6l1 2V71W$

A member of the Rio Tinto Group wwr~oru.com

-Au'--

Attachment B Page 1 of 4 to C-1101-153-E410-036, Rev. 0.

NIJREGICR-68775 ANL-04/09 Boric Acid Corrosion of Light Water Reactor Pressure Vessel Materials Argonne National Laboratory U.S. Nuclear Regulatory Commission Un, Office of Nuclear Regulatory ReSearch A, Washington, DC 20555-0001

Attachment B , Page 2 of 4 to C-1101-153-E410-036, Rev. 0 Figure 6.

Ring samples fabricated from the Type 308 SMA

.7 weld overlay.

Figure 7..

Assembled low-alloy steel andring set of samples Type 308 SSof A533 SMA -Gr.-8 weld overlay for corroslonlwastage tests.

2.2 Test Environments The various test environments simulate the postulated conditions in the RPV head/nozzle crevice. Thie environment in the crevice between the RPV head and the Alloy 600 penetration above the J-groove weld (see Fig. 3) depends on what the leak rate is, and whether the nozzle/head annulus Is. plugged or open. The following three environmental conditions have been Investigated in. the present study: I) low-temperature (=95"C1 saturated boric acid solution deserated and aerated; i1) high-temperature. high-pressure aqueous environment with a range of boric acid solution concentrations; and 111)high-teoperature I 150-300'C) boric acid powder at atmospheric pressure with and without addition of water.

2.2.1 Low-Temperature Saturated Boric Acid Solutions Near the end of the overall progression of damage, high leak rates through the CRDM cracks provide suffeienl ,cooling of the metal ,surfaces to allow liquid boric acid solutions to form In the crevice. These solutions will become concentrated In boric acid througlh boiling and more reactive by Infusion of Oxygen available directly from the ambient atmosphere.

7 The solubillty of boric acid6. at temperatures up to )f00C 1212*F) is shown in Fig. 0.

The solubility increases by a factor of --8 when temperature Is increased from room 0

temperature (RT) to I 00 C.

a

Attachment B Page 3 of 4 to C-1101-153-E410-036, Rev. 0 S0000f 42&o 40000 -

'35000 24.0

=000I -20.0 250 16D Figure 82 2Fiue p o ,a -Solubility of boric acid 8 or awppm t 000eat wte% boric acid) In water vs.

f ay .

00 To .e temperature (Ref. 6,7).

scoot-14.0 0 20 AO so so 100 Teelafatw ('C)

Figures ga-d show the measured pH-of aerated and deaerated solutions of boric acid atI temperatures up to 100-C. The RT-saturatted boric acid solution was prepared by adding more than the required amount of boric acid to uitra-high pure lUll?) water at itT and storing It for a few daya. The temperature was measured using a three-digit Omrega-digital K-type thermometer which was calibrated. The boiling point for the Saturated boric acid solution was measured to be =-03"C, but the experiments were conducted at 97,5*C, The ]00IC-saturawed solution was prepared by adding boric acid to UHP waler at 100lC until excess boric acid crystals for agglomerated powder) were presented In the solution. Boric acid solutions saturated at any other temperature between 25 and 1001C were obtained by cooling the tO0C'-

saturated solution. The solutions were purged with N2 plus 1% H 2 gas for deaerated condition and were open to air environment for the aerated condition. "The exact concentration of DO.

measured by CHEMets ampoules. in the deaerated and aerated solutions was <5 and =30 ppb, respectively. The DO measurement was made .by inserting a glass tip into the solution.

opening the tip quickly at temperature to suck the solution, and closing the tip with a rubber cap. The test glass was air cooled to room temperature and DO measured by CHEMets capsules.

The pli of RT-saturated solutUon of boric acid Is plotted as a function of temperature in Fig, 9a. The measured pH of both aerated and deacrated solutions show little or no change with temperature at 25.-I0O0C. The pH of boric acid solutions that were saturated at temperature Is plotted as a function of temperature in Fig. 9b and boron concentration In Fig. 9c; the pH decreased with increasing temperature or boron concentration. The pH and solubility of boric acid (wppm B) in water are plotted as a function of inverse temperature in Fig. 9d to gain an understanding of the solution enthalpy for the boric acid In the water and formation nerg*y for the ionization, i.e., 21H20 + BlOI4fs = IHs301 + [BIOM 4 l'. The results indicate that the IB(OHl4]" ion is stable in the temperature range 25-100"C, and boric acid may be treated to be totally Ionized In solutions that are saturated at test temperature.

Another scenario can also create low-temperature saturated solutions of boric acid. Slow leakage into an open crevice or annulus leaves deposits of boric acid in the crevice and also on top ofRPV head surfaces (Fig. 4). The annulus between the nozzle and head Is then plugged by deposits and/or corrosion products. In the absence of moisture, these deposits wil be relatively dry and a layer of molten HB0 2 and solid B 2 03 will form next to the hot metal surface. Later moisture may be Introduced to this pile of deposits either due to unplugging of 9

Attachment B Page 4 of 4 to C-1101-153-E410-036, Rev. 0 the nozzle/head annulus or leakage from the. CRDM nozzle flange or continued leakage through the crack. The heat of evaporation will provide cooling and. If the rate at which moisture is added to the pile or deposits is equal to the rate at which moisture evaporates, a concentrated solution of boric acid will form under the pile: the solution temperature may be as high as 150 or 170'C.

3.0 2S 2.5 2.0 2.0 rA, po 1.5 ArPauso D 30 40 50 6D 70 50 90 I GoI *. .. . . . ..

10i 20 30 40 0 W0

?a .80 R. .

g0 100 (a) (b)

__6__ DOSO.W . 10000 a Aeowd AA 9 2-5 A -

3' 1.0 S-OkM1'YC-1b-GftA-cW

1 * .' . .

i10.000 . .2 . X000 0.W. . . 40A0D0 1.2.7

. -,.. .2.8. . Z,9 .

.i l. 3.0.. .3.1. . 3.2 .32. 2.4 WPM).a 100011(K)

(Cl (d)

Figure 9. Plots of pH' vs. temperature in the oxygen and argon gas environments <a) for the RT-saturated solution and (b) the boric acid saturated at T; (c) pH-r vs. wppm B for temperalure between RT and 100C; and ,d) pHT and wppm Bvs. Inverse temperature.

2.2.2 High-Temperature High-Pressure PWR Environments Initially, extremely low leak rates result In complete flashing of the coolant to steam.

Under this condition. two scenarios are possible based on whether the nozzle/head annulus is plugged by deposits and/or corrosion products or is open to the atmosphere. A plugged nozzle/head annulus will result in a high-temperature. high-pressure aqueous environment In the annulus. i.e.. on the OD of the CRDM nozzle. The PWR environment used in the present study consisted of 1000ppm B. 2ppm Li. <10ppb dissolved oxygen (DO), and =2ppm

(=23 cc/kg) dissolved hydrogen. However, depending on how long after the leak that the crevice gets plugged, the concentrations of B and Lt In the solution may be slgnlifcantly greater than the typical nalues in the PWR environment. Continued leakage, into an open crevice will cause a buildup of boric acid deposits in the crevice.

10

Enclosure 1 Description and Assessment Page 18 of 19 Attachment 2 AmerGen/Exelon Calculation C-1 101-153-E410-040, Revision 0, "Reactor Building Sump Post-LOCA pH and TSP Quantity"

CC.-AA-309-1001 Revision 3 Cover followed by page 1a Design Analysis (Major Revision) I Last Page No. 075 Analysis No.:' C-1101-153-E410-040 Revision: 2 0

Title:

RB Sump Post-LOCA pH and TSP Quantity ECIECR No.:' 07-00174 Revision: 0 Station(s): 7 TMI Component(s): 14 1

Unit No.: '

Discipline: 9 TEDM Descrio. Code/Keyword: 10 TSP, Sump pH SafetylQA Class: Safety Related System Code: 12 214 Structure: Reactor Building CONTROLLED DOCUMENT REFERENCES *'

Document No.: FromlTo Document No.: From/To TMI Unit I UFSAR From C-1101-211-E610-060 From TMI Technical Specification From C-1i101-212-5450-040 From SDBD-TI-211 From C-1101-212-E610-069 From SDBD-TI-212 From C-1101-220-E610-054 From SDBD-TI-213 From C-1 101-823-5450-001 From C-1101-202-E620-415 From C-1101-900-E610-070 From C-1101-210-E610-010 From Drawing 1E-153-02-011 sht2 From Is this Design Analysis Safeguards Information? 10 Yes [] No o If yes, see SY-AA-0i1-106 Does this Design Analysis contain Unverified Assumptions? '7 Yes [] No 0 if yes, ATI/AR#:

This Design Analysis SUPERCEDES: 18 C-ilOl-900-E610-070, C-1101-210-E741-012 C-1101-210-5340-005, C-1101-210-5340-007 Description of Revision (list affected pages for partials): , TMI-1 is changing the buffering chemical for the post-LOCA reactor building sump water from sodium hydroxide (NaOH) to trisodium phosphate dodecahydrate (TSP) via ECR 07-00174. This modification will result in a change in the reactor building sump pH.

This Reisone4 ca cufa iron Indicates the range of pH in the reactor building sump limited to pH 7.3 to pH 8.0. It also indicates the amount of TSP required to achieve this pH range and the required storage volume.

Jeri C. Penrose (S&L) 6/26/07 Preparer: 2*

Print Narne ~hLc -~Lw *1* . .......

nnlO Method of Review: 21 Detailed Review 0 Alten nate CalculationsjLpttach ad) E3 Testing El Reviewer:. Robert A. Nelson (S&L)

PedntNorne 1A4j . / ulgn Name 6/26/07 Date Independent review []F Review Notes:" Peer review Ml (For ExternaAn*Jyses COry)

External Approver: 2" W.F. Bartling (S&L)

- ~A' PrintName Exelon Reviewer: "

Independent 3rd Party Review Reqd?2" I Exelon Approver: " R

CC-AA-309 Owners Acceptance Review Checklist for Revision 6 External Design Analysis Page 17 of 17 Page la followed by page lb Design Analysis No. C-1101-153-E410-040 Rev. 0 Yes No N/A

1. Do assumptions have sufficient rationale? El

2. Are assumptions compatible with the way the plant is operated and with the E'E licensing basis? Li 2-' li

3. Do the design inputs have sufficient rationale? El Li

4. Are design inputs correct and reasonable? El

5. Are design inputs compatible with the way the plant is operated and with the licensing basis?

6. Are engineering Judgments clearly documented and justified? i Li M-

7. Are Engineering Judgments compatible with the way the plant is operated and with the licensing basis? E] El IT

8. Do the results and conclusions satisfy the purpose and objective of the design analysis?

9. Are the results and conclusions compatible with the way the plant is operated and with the licensing basis?

• 'li Li El

10. Does the design analysis include the applicable design basis documentation?

ff' El

11. Have any limitations on the use of the results been identified and transmitted to the El El Li appropriate organizations?

El 8Li

12. Are there any unverified assumptions?.

ELi 1-1 Li

13. Do all unverified assumptions have a tracking and closure mechanism in place?

14. Have all affected design analyses been documented on the Affected Documents LriLi List (ADL) for the associated Configuration Change.

15. Do the sources of inputs and analyses methodology used meet current technical requirements and regulatory commitments? (Ifthe input sources or analysis, methodology are based on an out-of-date methodology or code, additional ffi Li 1

reconciliation may be required if the site has since committed to a more recent code)

16. Have vendor supporting technical documents and references (including GE DRFs) been reviewed when necessary?

Exelon Reviewer: Date: LA Sign I

7c

AmerGen cac.No.

Sheet I b TITLE RB Sump Post-LOCA pH and TSP Quantity

SUMMARY

OF CHANGE APPROVAL DATE 0Initial Issue ./2/O, 7' /

AmerGen CALCULATION SHEET

Subject:

Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 2 of 75 TABLE OF CONTENTS Section Page

1. PURPOSE: 3

2. INPUTS: 4

3. ASSUMPTIONS: 9

4.

REFERENCES:

10

5. 'COMPUTER PROGRAMS: 12

6. METHOD OF ANALYSIS: 13

7. NUMERIC ANALYSIS: 15

8. RESULTS: 29

9. CONCLUSION: 31

10. ATTACHMENTS:

Attachment A - Iodine add Cesium Released from Core Inventory 32 Attachment B - Spreadsheets (including formulae) 35 Attachment C - FORTRAN Program Listings 38 Attachment D - Benchmarks of FORTRAN Programs 53 Attachment E - Reference Materials 72

A ,merGen CALCULATION SHEET

Subject:

Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 3 of 75 1.0 PURPOSE Following a design basis accident, the contents of the Reactor Coolant System (RCS), the Borated Water Storage Tank (BWST), the Core Flood Tanks (CFT), and the Makeup Tank (MUT) mix in the Reactor Building. These waters are borated and generally have an acidic pH. To maintain the pH of the mixture within the required limits, sodium hydroxide has been injected into water pumped from the BWST to raise the pH of borated water collecting in the RB sump.

ECR TM 07-00174 replaces the sodium hydroxide (NaOH) buffer with trisodium phosphate (TSP) buffer. The TSP will be stored in baskets in containment and will dissolve to raise the pH of the borated water mixture.

This calculation determines the minimum required amount of TSP which will raise the pH to a minimum level of 7.3 and the maximum allowable amount of TSP which will limit the sump pH to a maximum level of 8.0.

AmerGen CALCULATION SHEET

Subject:

Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 4 of 75 2.0 INPUTS 2.1 The minimum injected BWST volume is 40,684 ft 3 (304,344 gal) per calculation C-1 101-212-5450-040 (Reference 4.29). The minimum mass of water for this volume is conservatively determined by the maximum BWST temperature of 1200 F (SDBD-TI-212 Reference 4.19). The corresponding minimum mass is calculated at 2,510,738 lb in calculation C-1 101-210-E610-010 (Reference 4.25) using a specific volume of 0.016204 ftP/lb from the ASME steam tables (Reference 4.7).

2.2 The maximum injected BWST volume is 47,983 ft3 (358,936 gal) per calculation C-1 101-212-E610-069 (Reference 4.31). This volume is based on an initial tank level of 59.0 ft and a final tank level of 1.354 ft.

The Initial 59.0-ft tank level is the high level alarm of 58.0 ft plus 1.0 ft instrumentation uncertainty; and it coincides with the bottom of the overflow pipe. The final level is at the bottom of the 24-inch outlet nozzle (2'-4" centerline level). The maximum mass of water for this volume is conservatively determined by the minimum BWST temperature of 400 F required by TMI Tech Spec, Section 3.3.1.1 .a (Reference 4.17).

2.3 The minimum BWST boron content is 2500 ppm as B as required by the Tech Spec (Reference 4.17). The maximum BWST boron concentration is 2800 ppm as B per the UFSAR (Reference 4.16). The maximum boron content limit of 2800 ppm as B is based on a maximum 2750 ppm measured plus 50 ppm sampling error to prevent boric acid precipitation in the core per calculation C-1 101-220-E610-054 (Reference 4.32) and description in the Decay Heat Removal System Design Basis (Reference 4.19).

2.4 Reactor coolant (RC) is contained in the reactor, two steam generators (OTSG), pressurizer, four RC pumps, and interconnecting piping. The RC volumes of these components and RC temperatures are listed in the UFSAR (Reference 4.16).

Component RC volumes are as follows:

• Reactor 4058 ft3 0 OTSG (ea) 2030ft3 Pressurizer 800 ft3

• RC pumps (ea) 56 ft3

• Piping:

Reactor inlet 1102 ft33 Reactor outlet 979 ft Pressurizer 20 f 3 Pressurizer spray. 2 ft3 The Pressurizer contains both RC and steam, and the listed volumes are for RC only. The normal steam volume is 702 ft3 and is in addition to the normal RC volume.

The reactor coolant temperatures are as follows:

• Reactor inlet 5540 F e Reactor outlet 6040 F

• Pressurizer 6480 F 2.5 The normal RC pressure is 2155 psig measured at the reactor outlet pipe per the UFSAR (Reference 4.16).

2.6 The boric acid content of RC varies during the fuel cycle and from cycle to cycle. A bounding maximum boric acid content is conservatively taken as 2800 ppm as B based on the BWST maximum boric acid level.

This boron content will not be exceeded provided the power rate (2568 MWt) does not increase and the

ArnerGen CALCULATION SHEET

Subject:

Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E41.0-040 0 214 5 of 75 cycle duration (2 years) does not increase (See Assumption 3.4). It also conservatively exceeds the refueling boron limit. The minimum RC boron content is 0 ppm as B (Ref. not required).

2.7 The two Core Flood Tanks (CFT) contain a volume of 940 +/- 30 ft 3 each. [Tech Spec 3.3.1.2.a] gReference 4.17). Therefore the maximum CFT volume is 1940 ft3 and the minimum CFT volume is 1820 ft .

.2.8 The CFT normal operating temperature is 900 F per UFSAR Table 6.1-1 (Reference 4.16) 2.9 The CFT boric acid content is required to be a minimum of 2270 ppm as B by the Tech Spec [TS 3.3.1.2.b]

(Reference 4.17). The maximum CFT boric acid content is limited to 2850 by the Operating Procedure chemistry requirements (Reference 4.20).

2.10 The volume of the Makeup Tank is calculated to be 574 ft3 in calculation C-1101-21 1-E610-060 (Reference 4.27).

2.11 The Makeup Tank normal operating temperature is 1200 F [SDBD-T1-211] (Reference 4.18) 2.12 The Makeup Tank system (MUT) mirrors the RC system and has the same chemistry. The maximum boric acid content is 2800 ppm as B consistent with Input 2.6. The minimum boric acid is 0 ppm as B.

2.13 The bounding maximum RB sump temperature is 2800 F based on the EQ temperature profile in the Gothic LB LOCA calculation C-1 101-823-5450-001 (Reference 4.33). A bounding minimum RB sump temperature of 40' F is used based on the minimum BWST temperature of 400 F consistent with Input 2.2.

2.14 The Reactor Building containment has an inside diameter of 130 ft and a free volume of 2.126 x 106 ft3 per UFSAR (Reference 4.16).

2.15 Radiation Doses The specific gamma and beta doses inside containment were not calculated at TMI-I. LOCA radiation conditions were developed based on bounding requirements of DOR Guidelines and NUREG-0588. As a

• result, radiation doses for equipment qualification are not affected by reload core inventory changes.

The UFSAR (Reference 4.17) establishes radiation service conditions applicable to equipment in the containment vapor space and applicable to equipment submerged in the containment sump fluid. The total gamma dose radiation service condition inside containment is 2 x 107 Rad. The total beta dose radiation service condition inside containment is 2 x 108 Rad. Because beta radiation is non-penetrating, one-half this value or I x 108 Rad will be used for surface exposures to account for self-shielding. These doses are 6-month integrated doses and are conservative for a 30-day exposure in this calculation.

2.16 Electrical Cable Insulation The total volume of chlorine-bearing electrical cable insulation in containment is 146.5 ft3 of hypalon per GPUN memo E550-98-055 (Reference 4.36). A copy of this memo was not available, but it is used as input in approved calculation C-1101-900-E610-070 (Reference 4.35) for calculation of hydrochloric acid generation by radiolysis in containment. Calculation C-1 101 -900-E610-070 is being superceded by this calculation, but the input remains valid.

2.17 The core inventory of iodine and cesium is determined in Calculation C-1 i01-202-E620-415 (Reference 4.24). End-of-Cycle (EOC) conditions produce higher overall iodine and cesium concentrations and were used as bounding in this calculation. The mass of each isotope is tabulated in Tables 1 and 2 in Attachment

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Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 6 of 75 2.18 The density of water as a function of temperature is abstracted from the ASME Steam Tables (tabulated in Reference 4.3, p. A-6) and is presented below. These densities are used for linear interpolation in the program TSP.

Temperature Density, ?H20 Temperature Density, ?H20 Temperature Density, {?H20 OF Ibm/ft OF Ibm/ft OF Ibm/ft 32 62.414 120 61.713 210 59.862 40 62.426 130 61.550 212 59.812 50 62.410 140 61.376 220 59.613 60 62.371 150 61.188 240 59.081 70 62.305 160 60.994 260 58.517 80 62.220 170 60.787 280 57.924 90 62.116 180 60.569 300 57.307 100 61.996 190 60.343 350 55.586 110 61.862 200 60.107 400 .53.648 2.19 The molecular weights of species used in this calculation are given below. For the compounds, the molecular weight is the sum of the molecular weights of the individual elements in their respective quantities.

Species Molecular Weight I Reference Boron, B 10.81 Ref. 4.1, front cover Water, H2 0 18.02 Ref. 4.1, front cover Boric Acid, H3BO3 61.83 Ref. 4.1, front cover Technical-grade TSP, Na3 PO4o12H 2Oo1/4NaOH 390.12* Ref. 4.1, front cover

• Consistent with ICL Product Data Sheet provided in Reference 4.38.

2.20 The ionic activity product of water, Kw, is as follows (Reference 4.4):

4470.99 pKw =-Iog(K,)= - 6.0875 + 0.01706 .T T

where: T = temperature, degrees K 2.21 The molal equilibrium quotients for boric acid, Q1,1, Q2.1, Q3,1, and Q4,2, are as follows (Reference 4.5):

log(Q 1 ) 1573.21 +28.6059 + 0.012078. T - 13.2258- log(T) +

T (0.3250 - 0.00033- T)-I - 0.0912.13/2 2756.

log(Q 21)= -18.966 + 5.835-log(T)

T 3339.5 Iog(Q 3 '1 ) = T 8.084 + 1.497-log(T)

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Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 7 of 75 12,820 -134.56 + 42.105 log(T)

T where: Q,y = molal equilibrium quotient (see Section 7.7)

T = Temperature, deg K I = Ionic strength 2.22 The approximate effective ionic radii of H÷ and 0H- in aqueous solutions at 25°C are presented below (Reference 4.1, Table 5-2, p. 5-5). Ionic radii of other species are not required because activity coefficients are determined for only H÷, 0H, H2PO4, HP0 42 , and PO 43 in this calculation.

Species Effective Ionic Radius, A (A)

H+ 9.0 0H- 3.5 H2P0 4" 4.0 HPO" 4.0 PO 41 4.0 2.23 The constants A and B for the Extended Debye-HOckel equation are taken from Table 5-3 of Reference 4.1 (p. 5-6) and are given below.

Temperature Unit Volume of Water Temperature Unit Volume of Water 0C °F A B °C OF A B 0 32 0.4918 0.3248 55 131 0.5432 0.3358 5 41 0.4952 0.3256 60 140 0.5494 0.3371 10 50 0.4989 0.3264 65 149 0.5558 0.3384 15 59 0.5028 0.3273 70 158 0.5625 0.3397 20 68 0.5070 0.3282 75 167 0.5695 0.3411 25 77 0.5115 0.3291 80 176 0.5767 0.3426 30 86 0.5161 0.3301 85 185 0.5842 0.3440 35 95 0.5211 0.3312 90 194 0.5920 0.3456 40 104 0.5262 0.3323 95 203 0.6001 0.3471 45 113 0.5317 1 0.3334 100 212 0.6086 0.3488 50 122 0.5373 0.3346 2.24 Mass attenuation coefficients for gamma and beta radiation in air and in Hypalon are taken from NUREG-1081 (Reference 4.9). As described in NURE--1 081, the gamma coefficients are based on the average gamma radiation energy from post-accident fission products of 1.0 MeV and the beta coefficients are based on the maximum beta radiation energy from post-accident fission products of 0.55 MeV.

Mass attenuation coefficients for air are:

p7/p = 0.0636 cm 2/g for 1 MeV gamma radiation I.LIp = 33.6 cm 2/g for maximum beta radiation of 0.55 MeV where: .t= linear attenuation coefficient, 3

cm"1 p = density of air, gram/cm

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Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 1 214 8 of 75 Mass absorption coefficients for Hypalon electrical cable jacketing (which has carbon as the major ingredient) are:

gyp = 0.0637 cm 2/g for 1 MeV gamma radiation p/p = 33.6 cm 2/g for maximum beta radiation of 0.55 MeV where: pt = linear absorption coefficient, 3cm"r p = density of hypalon, gram/cm The density of Hypalon is 1.55 g/cm 3 per NUREG-1 081.

2.25 The TSP baskets provided as part of ECR TM 07-00174 are as shown in Drawing I E-153-02-011 (Reference 4.40). Each basket provides a storage chamber 3'-0" x 3'-0" x 3'-0" high. The uppermost 2-1" is visually obscured by a 2-/" square tubular rim, so the usable (visible) storage height is 2'-91". Deducting the space occupied by the four 2-1/" x 2-/" comer posts and the double 2-1A" x 2-1/2" horizontal brace on each side, each basket contains a net maximum volume of 24.51 ft3 to the bottom of the top rim. A total of 23 baskets are provided.

22.6 The bulk density of granular TSP dodecahydrate is 51 lb per ft 3 as reported by the manufacturer ICL Performance Products (Reference 4.41)

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Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 9 of 75 3.0 ASSUMPTIONS 3.1 All species in the containment sump solution are assumed to be in equilibrium. Therefore, the results for the amount of TSP required are based on a steady state analysis.

3.2 The density of pure water is used for all solutions analyzed herein. This is considered acceptable and within the accuracy of this calculation as the containment sump solutions analyzed are dilute.

3.3 Electrical cable is represented by a single cable construction consistent with the NRC model used in NUREG-1081 (Reference 4.9) and NUREG/CR-5950 (Reference 4.12). The cable is a 0.89-inch diameter single-conductor cable witha 158 mil insulation/jacket thickness. The jacket thickness is 72 mil. The jacket material is Hypalon (chlorine-bearing) and the insulation material is ethylene propylene rubber (EPR) or other non-chlorine bearing material. All cable is assumed to be routed in cable tray because of the large quantity used in this calculation.

3.4 The maximum RC boron content varies from fuel cycle to fuel cycle. A bounding value was selected (Input 2.6) assuming the power rate (2568 MWt) does not increase and the cycle duration (2 years) does not increase.

L

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Calculation No. JRev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 10 of 75

4.0 REFERENCES

4.1 Dean, J. A., Editor, Lange's Handbook of Chemistry, 11th Edition, McGraw-Hill Book Company, New York, NY, 1973. ISBN 0-07-016190-9

,)

4.2 Pavlyuk, L. A. and P. A. Kryukov, "Spectrophotometric Determination of the First and Second Ionization Constants of Phosphoric Acid from 25 to 1750C," Institute of Inorganic Chemistry, Novosibirsk, USSR, 1978.

4.3 Crane Technical Paper No. 410, "Flow of Fluids through Valves, Fittings, and Pipe," 25th Printing, Stamford, CT, 1991.

4.4 Faust, S. D. and 0. M. Aly, Chemistry of Natural Waters, Ann Arbor Science Publishers, Inc., 1981.

4.5 Mesmer, R. E., C. F. Baes, Jr., and F. H. Sweeton, "Acidity Measurements at Elevated Temperatures. VI.

Boric Acid Equilibria," Inorganic Chemistry, Volume 11, Number 3, pp. 537-543, 1972.

4.6 Grenthe, I. and Wanner, H, "TBD-2: Guidelines for the Extrapolation to Zero Ionic Strength", AEN-NEA, Issy-les-Moulineaux, France, (2000) 4.7 ASME Steam Tables, 4th Edition, The American Society of Mechanical Engineers, New York, NY, 1979.

4.8 NUREG-0800, "Standard Review Plan for the Review of Safety Analysis Reports for Nuclear Power Plants",

Section 6.5.2, Revision 4 4.9 NUREG-1081, Post-Accident Gas Generation from Radiolysis of Organic Materials", published September 1984.

4.10 NUREG-1465, "Accident Source Termsfor Light-Water Nuclear Power Plants," February 1995.

4.11 NUREG/CR-5732 (ORNLITM-1 1861), Revision 3, "Iodine Chemical Forms in LWR Severe Accidents," April 1992.

4.12 NUREG/CR-5950, "Iodine Evolution and pH Control," December 1992.

4.13 U.S. Nuclear Regulatory Commission Regulatory Guide 1.183, Revision 0, "Alternative Radiological Source Terms for Evaluating Design Basis Accidents at Nuclear Power Reactors", dated July 2000 4.14 GE Document APED-5398-A, "Summary of Fission Product Yields for U-235, U-238, Pu-239, and Pu-241 at Thermal, Fission Spectrum.and 14 MeV Neutron Energies" 4.15 Radiological Health Handbook, U.S. Department of Health, Education, and Welfare, Public Health Service, Compiled and Edited by the Bureau of Radiological Health and the Training Institute Environmental Control Administration, Revised Edition, 1970 4.16 TMI Unit 1 USFAR 4.17 Three Mile Island Technical Specification 4.18 SDBD-Tl-211, Rev 4, "System Design Basis Document for Makeup and Purification (#211)"

4.19 SDBD-T1 -212, Rev 4, "System Design Basis Document for Decay Heat Removal System (#212)"

\

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Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 11 of 75 4.20 SDBD-T1-213, Rev 4, "System Design Basis Document for Core Flood System (#213)"

4.21 SDBD-TI-214, Rev 4, "System Design Basis Document for Reactor Building Spray System (#214)"

4.22 SDBD-T1 -220, Rev 4, "System Design Basis Document for Reactor Coolant System (#220)"

4.23 C-1101-153-5310-022 Rev 5A, "TMI Unit I Reactor Building Maximum Flood Level" 4.24 C-1101-202-E620-415 Rev 3, "TMI-1 Isotopic Core Inventory" 4.25 C-1101-210-E610-010 Rev 4, "Reactor Building Minimum Level During Recirculation Following LBLOCA" 4.26 C-1101-210-E741-012 Rev 1, "Estimated Reactor Building Sump pH Following a LOCA" MHA 4.27 C-1101-211-E610-060 Rev 0, "Makeup Tank Volume" 4.28 C-1101-212-5360-028 Rev 0, "Water Level Limit in BWST During a OTSG Tube Rupture""

4.29 C-1101-212-5450-040 Rev 2, "BWST Minimum Usable Volume" 4.30 C-1101-212-E510-057 Rev 0, "TMI BWST Level Loop Accuracy" 4.31 C-1101-212-E610-069 Rev 0, "BWST Maximum Usable Volume" 4.32 C-1101-220-E610-054 Rev 1, "Boron Concentration Following a Large Break LOCA" 4.33 C-1101-823-5450-001 Rev 9, "TMI-1 LBLOCA EQ Temp Profile Using the GOTHIC Computer Code" 4.34 C-1101-900-E000-087, Rev 2, ".Post-LOCA EAB, LPZ, TSC, and CR Doses Using AST and RG 1.183 Requirements" 4.35 C-1101-900-E610-070 Rev 0, "Minimum Sump pH Following a MHA" 4.36 GPUN Memo E550-98-055, M.G. Acosta to A. Irani "Response to ETTS No: 12256, Chloride Bearing Cables in Reactor Building TMI-1" 4.37 C-1101-901-5360-007 Rev 9A, "TMI-1 Hydrogen Generation Inside Containment" 4.38 Trisodium Phosphate Crystalline (TSPc) Product Data Sheet, ICL Performance Products LP 4.39 Computer Programs 4.39.1 Microsoft Excel 97 SR-2, S&L Program No.. 03.2.081-1.0, dated 04/28/1999.

4.39.2 Lahey/Fujitsu FORTRAN 95 - LF95 Version 5.70c, S&L Program No. 03.5.044-5.7c, dated 01/07/2003.

4.39.3 Mathcad 11.2, S&L Program No. 03.7.548-11.2, dated 6/28/2004 4.40 Drawing 1 E-1 53-02-011, Sht 2, Rev 0, "Reactor Building/TSP Basket Location and Fabrication" 4.41 E-mail from Robert Allison (ICL) to Stephen Eichfeld (S&L),

Subject:

TSPc bulk density, dated 5/2/200 (included in Attachment F)

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Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 12 of 75 5.0 COMPUTER PROGRAMS The FORTRAN 95 computer language is utilized to write the computer program TSP. The source code is compiled using the Lahey/Fujitsu FORTRAN 95 compiler, Version 5.7c. The computer program TSP was validated using Mathcad 11.2.

All spreadsheets developed for this calculation are created using Microsoft Excel 97 SR-2. The validation of the spreadsheets is implicit in their detailed review.

These programs were run under the Windows XP Professional Version 2002, SPI operating system on S&L PC No.

ZD2480.

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Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 13 of 75 6.0 METHOD OF ANALYSIS 6.1 Summary This calculation determines the amount of TSP required to neutralize borated waters in the Reactor Building (RB) containment following a LOCA design basis accident. A required minimum amount of TSP is determined which will raise the pH to a required lower limit over the post-LOCA range of conditions. A limiting maximum amount of TSP is determined which will not exceed a required upper pH limit over the post-LOCA range of conditions.

Following a design basis accident, borated waters from the Reactor Coolant System (RCS), the Borated Water Storage Tanks (BWST), the Core Flood Tanks (CFT), and the Makeup Tank (MUT) mix in the Reactor Building. Failure of the core releases iodine and cesium to containment which: form hydriodic acid, cesium hydroxide, and cesium iodide in the sump solution. In addition, nitric acid is contributed to the mixture from radiolysis of air and water and hydrochloric acid is contributed from radiolysis of chlorine-bearing electrical cable insulation. TSP stored in baskets in containment dissolves and contributes trisodium phosphate plus water of hydration and sodium hydroxide impurities to the mixture.

Equilibrium chemistry is computed as a function of TSP addition and as a function of temperature to determine the resulting pH of the combined solution. The required amount of TSP is found by iteratively solving for the amount of TSP necessary to achieve the acceptance.criteria pH. These evaluations were based on a steady state analysis of equilibrium conditions for each condition.

6.2 Analytical Methods Calculation of equilibrium conditions considers the following:

• Borated water mass

• Nitric acid addition

• Hydrochloric acid addition Iodine release from core inventory.

• Cesium release from core inventory

• Boron speciation

• TSP speciation

• Water dissociation The total amount of water and boric acid is determined from a mass balance of the RCS, BWST, CFT, and MUT volumes added to containment. Two bounding conditions were determined: the minimum water mass and minimum boric acid content and the maximum water mass and maximum boric acid content. The minimum water mass was determined using the minimum volume and maximum specific volume, while the maximum water mass was determined using the maximum volume and minimum specific volume. The concentration of boric acid for each condition was determined by mass balance.

The generation of nitric acid (HNO3) is determined following the methodolgy of NUREG/CR-5950 (Reference 4.12). This method calculates HNO 3 as a function of gamma and beta radiation doses and as a function of the water mass.

The generation of hydrochloric acid (HCI) is determined following the methodology of NUREG-1081 (Reference 4.9) and NUREG/CR-5950 (Reference 4.12). This method calculates HCI as a function of gamma and beta radiation doses and as a function of the mass of chlorine-bearing insulation/jacketing.

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Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214. 14 of 75 Iodine and cesium are released when the core fails. The fractions of iodine and cesium in the core inventory that are released to containment are determined as discussed in Regulatory Guide 1.183 (Reference 4.13).

In the resulting solutions, boric acid dissociates to form equilibrium amounts of various borate species.

Trisodium phosphate also dissociates to form equilibrium amounts of various phosphate species. The speciation of each is a function of equilibrium constants, temperature, ionic strength and pH. Water also dissociates to form H+ and OH- as a function of dissociation constant, temperature, and ionic strength.

The overall equilibrium conditions are computed for the mixture and the pH is determined from the equilibrium hydrogen ion concentration. The TSP requirements are found iteratively.

6.3 Acceptance Criteria

1. A minimum sump pH of 7.3 is required to prevent iodine evolution from the sump. This pH value is specified in the Tech Spec (Reference 4.17) and has been updated as a part of ECR TM 07-00174.

2. A maximum sump pH of 8.0 is required to limit chemical effects of materials dissolved in, containment which can subsequently collect on the sump strainers. This is a consideration for evaluation of chemical effects as part of GSI-191.

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Calculation No. Rev. No.. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 15 of 75 7.0 NUMERICAL ANALYSIS 7.1 Summary This analysis determines the mass of trisodium phosphate dodecahydrate (TSP) required to raise the pH of the borated water in the containment sump to within a design range of 7.3 to 8.0 for post-LOCA conditions.

A parametric analysis was performed to determine the required TSP mass as a function of the quantity of borated water in the sump, the boron concentration in the sump, the sump water temperature, and the desired equilibrium pH value. The analysis is performed using equilibrium equations derived in this calculation which were iteratively solved with a computer algorithm, TSP, which has been developed specifically for this purpose.

The detailed analysis is described in subsequent sections.

The pH resulting from dissolution of TSP in borated water was evaluated to determine the minimum amount of TSP required to raise the post-LOCA pH in the containment sump to a minimum of 7.3 and the maximum amount of TSP required to limit the pH to 8.0. This analysis included computation of:

• Borated water mass

• Nitric acid addition from radiolysis

• Hydrochloric acid addition from radiolysis

• Iodine addition from core inventory

• Cesium addition from core inventory

• Boron speciation

• TSP speciation

• Water dissociation

• Equilibrium conditions and pH The analysis is performed for both the maximum and the minimum quantities of borated water in the sump with corresponding maximum and minimum boron concentrations. The analysis is repeated for equilibrium pH values ranging from 7.0 to 8.5 for sump temperatures between 40°F and 280°F. This pH range encompasses the design range and shows the pH sensitivity to TSP addition.

The equilibrium conditions for the resulting solution were determined as a function of TSP addition and as a function of temperature. These evaluations were based on a steady state analysis of equilibrium conditions for each condition.

7.2 Borated Water The amounts of borated water and boric acid concentrations are determined as follows.

The minimum boric acid mass and boric acid concentration are determined by the following data (Inputs 2.1 through 2.12). The minimum mass of borated water is 3,148,801 lb and the boric acid concentration is 2073 ppm as B based on the total mass of boric acid of 6528 lb as B.

Minimum Maximum Specific Minimum Minimum Volume Temperature Volume Mass Boric acid J

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Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 -0 214 16 of 75 ft3 dejaF ft3/Ib lb Dom as B lb BWST 40648 120 0.016204 2508516 2500 6271 Reactor Coolant:

Reactor 4058 579 0.022609 179486 0 0 OTSG (2) 4060 579 0.022609 179575 0 0 Pressurizer 800 648 0.026552 30130 0 0 RC pumps (4) 224 579 0.022609 9908 0 0 RC piping - inlet 1102 554 0.021692 50802 0 0 RC piping - outlet 979 604 0.023818 41103 0 0 Pressurizer piping 20 648 0.026552 753 0 0 Pressurizer spray piping 2 648 0.026552 75 0 0 Core Flood Tank 1820 90 0.016102 113029 2270 257 Makeup Tank 574 120 0.016204 35423 0 0 TOTALS 3148801. 6528 The maximum boric acid mass and boric acid concentration are determined by the following data (Inputs 2.1 through 2.12). The maximum mass of borated water is 3,643,118 lb and the boric acid concentration is 2802 ppm as B based on the total mass of boric acid of 10207 lb as B.

Minimum Maximum Specific Minimum Minimum Volume Temperature Volume Mass Boric acid

..ft! deqF fe/lb lb ppm as B lb BWST 47983 40 0.016019 2995380 2800 8387 Reactor Coolant:

Reactor 4058 579 0.022609 179486 2800 503 OTSG (2) 4060 579 0.022609 179575 2800 503 Pressurizer 800 648 0.026552 30130 2800 84 RC pumps (4) 224 579 0.022609 9908 2800 28 RC piping - inlet 1102 554 0.021692 50802 2800 142 RC piping - outlet 979 604 0.023818 41103 2800 115 Pressurizer piping 20 648 0.026552 753 2800 2 Pressurizer spray piping 2 648 0.026552 75 2800 0 Core Flood Tank 1940 90 0.016102 120482 2850 343 Makeup Tank 574 120 0.016204 35423 2800 99 TOTALS 3643118 10207 7.3 Nitric Acid from Radiolysis

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Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 17 of 75 Nitric acid (HN03) is formed by irradiation of air and water in the containment sump. Per Section 2.2.4 of NUREG/CR-5950 (Ref. 4.12), the generation rate of HNO 3, G, is 0.007 molecules HNO 3 per 100 eV absorbed in the sump. This generation rate converts to 7.3x10"6 g-mole/liter per MegaRad as follows:

G= 0.007 molecule

• mole

• 6.241x 1011 eV

• 100x10 6 erg 1000.g 100 eV 6.022 x 1023 molecule erg MegaRad g kg G=7.3x10-6g-mole/kgperMegaRad The 30-day total integrated dose (TID) of radiation in the containment sump is:

30-day gamma TID = 0.2 x 108 rad 30-day beta TID = 1.0 x 108 rad 1._2 x 1_03 rad total Although beta radiation has a limited penetration, the beta dose is conservatively applied to the entire mass of water. This accounts for any mixing or spray that could expose waters to beta radiation.

The concentration of HNO 3 in the sump after 30 days is:

[HNO, ] = G

• TID = 8.71xil0 -4g-mole per kg water Because the formation is HNO 3 is dependent on the amount of water that is irradiated, the total mass of HNO 3 is directly proportional to the mass of water. Consequently, the resulting concentration of HNO 3 in the sump after 30 days will be constant and not vary with the mass of water.

For the minimum and maximum amounts of borated water calculated in Section 7.2, the corresponding amounts of HNO 3 added to the sump are 173 lb and 200 Ib, respectively.

TSP. dodecahydrate contains water of hydration which is released when the TSP dissolves. Asmall amount of HNO 3 will also be formed from TSP water of hydration and is 3.04 x 10.- lb HNO 3 per pound of TSP.

7.4 Hydrochloric Acid from Radiolysis Hydrochloric acid (HCI) is formed by radiolysis of chloride-bearing electrical cable insulation in containment Hydrochloric acid production was computed using the methodology described in NUREG/CR-5950 (Ref. 4.12) and NUREG-1081 (Ref. 4.9).

There are many sizes of electrical cable in containment ranging from small control cable to large power cable. A cable inventory by size and by weight was not readily available, so a typical cable size is utilized in this calculation as representative of the total combination of cables. A single electrical cable size and construction description from NUREG/CR-5950, Appendix B was used as a representative size for this

.calculation The NUREGICR-5950 electrical cable description was based on the model developed by the NRC in NUREG-1081. This model utilized a single-conductor power cable with an OD of 2.2608 cm (0.89 in) and with an EPR insulation layer and a Hypalon jacket. The conductor diameter is 1.4580 cm (0.574 inches) and the insulation O.D./jacket I.D. is 1.8948 cm (0.746 inches). These dimensions result in a total insulation/jacket thickness of 0.4014 cm (158 mils). Of this total insulation and jacket thickness, the outer portion that is Hypalon is 72 mil thick.

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Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 18 of 75 The outside cable diameter and jacket thickness used in this calculation are:

" Outside cable diameter, D,, = 2.2608 cm = 0.89 in

• Jacket thickness, y, = 0.183 cm = 0.072 in Hydrochloric acid generation in chlorine-bearing material in the cable is determined based on the following equation from Appendix B of NUREGICR-5950 (Ref. 4.12):

R=G* 3*S*A where: R = HCI production rate G = radiolysis yield

= radiation energy flux on the cable jacket S = cable jacket surface area A = absorption fraction of energy flux in the cable jacket The values for each of these parameters used in this calculation are determined in the following paragraphs.

Radiolysis yield, G Per NUREG/CR-5950 (Ref. 4.12) the G value for Hypalon is 2.115 molecules HCI per 100 eV (in a vacuum). This corresponds to 3.512x1 0-20 g-mole HCI/MeV:

2.115 molecule mole 1x106eV 100eV 6.022 x 1023 molecule MeV G = 3.512 x 10-20 g-mole HCl / MeV Radiation flux at the surface of the cable iacket.

The exposure of the cable jacket to radiation energy is represented by the energy flux applied to the cable surface (4). The term 4 is derived in NUREG-1081 (Ref. 4.9) from the radiation source term (energy release per unit volume of containment), diminished by attenuation in air between the source and the cable surface:

In this calculation, input data was available in the form of Total Integrated Dose (TID) instead of the radiation source term. Consequently, an energy flux in containment is determined from the radiation dose (TID) and the mass attenuation coefficient in air.

The TID calculations used as input are conservatively treated as an infinite cloud. For an infinite cloud, the energy absorbed equals the energy emitted so the volumetric energy emission is related to TID by:

E

= TID

• Pair

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Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 19 of 75 The energy flux at the cable surface is determined by integrating the air-attenuated radiation over the distance from the cable.

The flux at the cable surface is determined in NUREG-1 081 to be:

E 1 - e(-4*r) .1- e(-PiI*r)

• = TID *Pa~rlr a V I.t, air where: = cumulative radiation flux at cable surface (for 30 days)

TID = 30-day total integrated dose in air Pair = density of air pI=r linear attenuation coefficient for air r = distance from surface The linear attenuation coefficient p.for air is determined from the mass attenuation coefficient pip as discussed in NUREG-1081 (Ref. 4.9):

plip = constant, k, or p=kp Consistent with treatment as an infinite cloud, the distance r is infinite and the term e(W) reduces to zero.

Substituting,

• =TID

• Pair * --

4 pk

• Pair The air density terms cancel leaving:

TID k

where: 4 = cumulative radiation flux at cable surface (30-day)

TID = 30-day total integrated dose k.= mass attenuation coefficient for air The TID for gamma radiation and beta radiation are as follows (Input 2.15):

30-day gamma (y) TID = 2.0 x l0e Rad 30-day beta (0) TID = 1.0 x 108 Rad (includes 50% reduction for self-shielding)

Mass attenuation coefficients for air per NUREG-1081 are:

- pýp/P = 0.0636 cm 2/g for I MeV gamma radiation (ky)

.p/p = 33.6 cm 2/g for maximum beta radiation of 0.55 MeV (kp)

This leads to a gamma surface flux of:

. I

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Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 20 of 75 2.0xl07Rad . 100erg ,6.2415x10 erg 5

MeV =1.9627x 10MeVpercm2

=0.0636cm /gram gram Rad 2

0 and a beta surface flux of:

1.0xl0 8 Rad

• 100erg *6.2415x10MeV=l.85 76 x10,MeVpercm'

'=33.6cm2/gram gramRad erg Surface area of cable *acket,S The amount of cable insulation in containment subject to radiolysis at TMI is 146.5 ft3 of hypalon (Input 2.16). The insulation is considered to be composed of an ethylene propylene rubber (EPR) insulator with a hypalon jacket based on typical electrical cable construction in NUREG/CR-5950. Hypalon is the portion of insulation which. releases HCI during radiolysis.

Using the cable construction and dimensions as described in NUREG/CR-5950, the Hypalon jacket has an outside diameter of 0.89 in and a thickness of 72 mil while the EPR insulation has an outside diameter of 0.746 in and a thickness of 86 mil. The combined jacket and insulation has a thickness of 158 mil.

The density of Hypalon is given in NUREG-1081 as 1.55 g/cm 3. This results in a mass of 14,176 lb of Hypalon jacket.

The jacket surface area is determined from the jacket volume and cross-sectional area. The jacket volume is 146.5 ft 3 (4148418 cm 3). The jacket cross-sectional area based on the 0.89 in (2.2608 cm) OD and 0.746 in (1.8948 cm) ID is 1.19455 cm 2 .

The jacket surface area is:

S =n D

• Length = D* Volume jacket x - sectional area 3

4,148,418cm S = zt*2.2608cm* = 24,665,500cmý 1.19455cm' 50m Hypalon absorption coefficient, A The absorption fraction of the energy Is calculated as follows per Section 4.2 of NUREG-1081 (Ref. 4.9):

A= 1e-py where: A = fraction of radiation energy absorbed by cable jacket p = linear absorption coefficient of cable jacket y = thickness of cable jacket Linear absorption coefficients for Hypalon are determined as discussed in NUREG-1 081 (Ref. 4.9) using the following mass absorption coefficients:

l.jp = 0.0637 cm2/g for gamma radiation in carbon material (e.g. Hypalon)

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Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 21 of 75

,p/p = 33.6 cm2/g for beta radiation 3

The density of Hypalon is given in NUREG-1 081 as 1.55 g/cm This results in the following gamma radiation and beta radiation linear absorption coefficients for Hypalon:

3 pr = 0.0637cm 2 /g x 1.55g/cm = 0.0987cm-1 Pp = 33.6cm2 /g x 1.55glcm 3 = 52.08cm-1 Using the jacket thickness of 0.183 cm as determined from cable construction, the absorption coefficient for gamma radiation in hypalon is:

Ay =1-e-ly =1-e(m-00987l.018 3 ) = 0.0179 And the absorption coefficient for beta radiation In hypalon is:

08 A= 1- e-gy = 1 - e - *°18 3 ) = 0.9999 Resulting HCI production rate These values are substituted in the preceding HCI generation equation:

R=G*ý*S*A The following results are calculated:

HCI production from gamma radiation = 304 g-mole HCI production from beta radiation = 161 g-mole Total HCI production = 465 g-mole 7.5 Hydriodic Acid from Core Inventory Hydriodic acid is formed by the post-LOCA release of elemental iodine (I) and hydrogen iodide (HI) from the reactor core and its absorption in the containment sump water.

Per Regulatory Guide 1.183, Table 2 (Ref. 4.13), 5% of the iodine core inventory is released into containment during the Gap Release Phase and an additional 35% of the iodine core inventory is released into containment during the Early In-Vessel (EIV) Phase. This occurs during the first 1.8 hours9.259259e-5 days <br />0.00222 hours <br />1.322751e-5 weeks <br />3.044e-6 months <br /> of the LOCA. The Gap Release Phase has an onset of 30 seconds and a duration of 30 minutes and is followed by the EIV Phase with a duration of 78 minutes per Table 4 of Regulatory Guide 1.183 (Ref. 4.13). No further iodine is released after the EIV phase, so the total release is the sum of the Gap Release Phase and the EIV Phase The reactor core inventory of iodine, the Gap Release Phase iodine release, and the EIV Phase iodine release and the total iodine release are determined in Table 1, Core Iodine Inventory Determination, from the activities of iodine radionuclides listed in Input 2.17.

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Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 22 of 75 Per Section 3.5 of Regulatory Guide 1.183 (Ref. 4.13), 95% of the iodine released from the RCS is in the form of cesium iodide, 4.85% is in the form of elemental iodine, and 0.15% is in the form of organic iodide.

Section 3.5 of NUREG-1465 (Ref. 4.10) and Section 4.2 of NUREG/CR-5732 (Ref. 4.11) indicate that at least95% of the iodine entering containment from the RCS is in the form of cesium iodide with no more than 5% as I plus HI. For this calculation, it will be conservatively assumed that the combined I plus HI is the maximum 5% in order to maximize the acid contribution from iodine to the containment sump. The amount of iodine release that forms HI is 3.76 g-mole.

As shown in Table I (Attachment A), the core iodine inventory released in containment during the LOCA is 75.22 g-mole. The amount of iodine release that forms cesium iodide is 71.46g-mole. This compound is a soluble salt and dissolves in the sump to form cesium ions and iodide ions. These ions contribute to the ionic strength of the sump solution. Because activity coefficients of chemical species are functions of ionic strength, cesium iodide influences chemical equilibria. Consequently, cesium iodide is included in the computation of solution ionic strength.

Considering the above, the amount of iodine used in this calculation is 75.22 g-mole released in containment.

7.6 Cesium Hydroxide from Core Inventory Cesium hydroxide is formed by the release of cesium from the reactor core and its absorption in the suppression chamber water.

Per Regulatory Guide 1.183, Table 1 (Ref. 4.13), 5% of the cesium core inventory is released into containment during the Gap Release Phase and an additional 25% of the cesium core inventory is released into containment during the Early In-Vessel (EIV) Phase.. This occurs during the first 1.8 hours9.259259e-5 days <br />0.00222 hours <br />1.322751e-5 weeks <br />3.044e-6 months <br /> of the LOCA. The Gap Release Phase has an onset of 30 seconds and a duration of 30 minutes and is followed by the EIV phase with a duration of 78 minutes per Table 4 of Regulatory Guide 1.183 (Ref. 4.13).

The reactor core inventory of cesium, the Gap Phase cesium release, and the EIV Phase cesium release are determined in Table 2 (Attachment A), Core Cesium Inventory Determination, from the activities of cesium radionuclides listed in Input 2.17.

As shown in Table 2 (Attachment A), the core cesium inventory released in containment during the LOCA is a total of 677.98 g-mole.

Cesium released in the form of cesium iodide does not contribute to formation of cesium hydroxide. The quantity of cesium iodide is 71.46 g-mole (95% of the molar quantity of iodine released) consistent with the determination of hydriodic acid production (see Section 7.5). The amount of cesium as cesium iodide is subtracted from the cesium release to obtain the quantity of cesium hydroxide in the post-LOCA suppression chamber water. The cesium release that forms cesium hydroxide is 606.52 g-mole.

Cesium iodide is a soluble salt and dissolves in the sump to form cesium ions and iodide ions. These ions contribute to the ionic strength of the sump solution. Because activity coefficients of.chemical species are functions of ionic strength, cesium iodide influences chemical equilibria. Consequently, cesium iodide is included in the computation of solution ionic strength.

Considering the above, the amount of cesium used in this calculation is 677.98 g-rnole released in containment.

7.7 Boron Speciation

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I Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 23 of 75 Specific values of pH, sump temperature, borated water quantity, and boron concentration are considered in this analysis. Based on the borated water quantity and the boron concentration, the total quantity of boric acid in gram-moles per liter, as boron, is calculated.

Based on the total quantity of boron and the temperature-dependent molal equilibrium quotients reported by Mesmer et al. (Ref. 4.5), the equilibrium concentrations of the boron species are determined. The boron species considered in the containment sump solution are B(OH) 3 (boric acid, H3BO3), B(OH) 4 , B2(OH)7",

B3(OH) 10c,and B4(OH) 142-. Reference 4.5 presents two dissociation schemes wherein the only difference is that Scheme I contains the B4(OH) 142" species and Scheme II contains the B5(OH) 1 3-species instead.

However, the contributions of the B4(OH) 142 species and the Bs(OH) 18 3-species are minimal and are so similar that replacement of one by the other has no significant effect on the formation of quotients of the other species (Ref. 4.5). Therefore, Scheme I with the B4(OH)1 42-species was selected for convenience.

The dissociation equilibrium equations and their molal equilibrium quotients are as follows (Reference 4.5).

The species, B.(OH) 3x.yy', are defined by (x,y).

Species (1.1):

B(OH) 3 + OH- <= B(OH)4

[B(OH);]

Q[B(OH) 3 ].[OH-]

log(Q1 1)=, 1573.21

' T +28.6059+0.012078. T-13.2258.log(T)+

(0.3250 - 0.00033. T)-I -0.0912.13/2 Species (2.1):

2B(OH) 3 +OH-

• B2 (OH);

Q= [B2 (OH);]

[B(OH) 3]2 .[OH-]

log(Qz 1)= 2756.1 -18.966 + 5.835-log(T)

T Species (3.1):

3B(OH) 3 +OH- c* B3(OH),-

[B3 (OH)' 0 ]

Q3.1 [B(OH) 3]3 .[OH-]

log(Q 31 ) = T 8.084 + 1.497- log(T)

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Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 24 of 75 Species (4.2):

4B(OH) 3 +20-- 4* B4 (OH)21

[B4 (0H)11 14 Q4,2 = [B(OH) 3 14 .[OH_] 2 '

12820 log(Q 4 2 )'= 12T - 134.56 + 42.105 .log(T) where IX] concentration of species X [gram-moles/liter]

T solution temperature [K]

Qxy molal equilibrium quotient I ionic strength of the solution, defined as follows (Ref. 4.1, p. 5-3):

I = 0.5(CIZ1+C2Z22. ...... +CnZn2)

Cl molarity of species I [gram-moles/liter]

zI ionic charge of species I It should be noted that individual activity coefficients are not used to define the molal equilibrium quotients for the boron species since the quotients already account for the individual activity coefficients (Ref. 4.5).

The equilibrium quotient Q 1,1 for B(OH) 4 includes terms using ionic strength I. Although Q is based on ionic strength derived from molal concentrations, the ionic strength used in this calculation is based on molar solutions. In dilute solutions molality and molarity are approximately equal. This calculation involves only dilute solutions, so molality and molarity are used interchangeably.

To determine the concentrations of all boron species, the total B(OH)3 concentration is iterated until the total boron concentration is the same when calculated in both of the following manners.

[B] ms"=

MWB , VHO

[B] = [B(OH) 3 ] + [B(OH);] + 2-[B2 (OH);] + 3. [B3 (OH)" 0] + 4. [B4(OH);"]

where

[X] concentration of species X [gram-moles/liter]

ma mass of boron in containment sump [grams]

mB = mH20,I

• ppmB / 106 MWB molecular weight of boron VH20 total volume of water in containment sump [liters]

7.8 TSP Phosphate Speciation Technical grade TSP dodecahydrate, Na3PO4*12H 20*11/4NaOH, is used to raise the pH of borated water in containment. The amount required is iteratively varied to achieve a specified pH.

In aqueous solution, the TSP dissociates into phosphoric acid, negatively charged phosphate ions and positively charged sodium ions. Based on the quantity of TSP and the temperature-dependent dissociation

AmnerGen CALCULATION SHEET

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Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 25 of 75 constants of phosphoric acid reported by Palvlyuk et al. (Ref. 4.2), the equilibrium quantities of the dissociation products of phosphoric acid are determined. These products are H3 PO4 , H2PO4, HPO 42 , and Po 43".

The dissociation equilibrium equations and their dissociation constants are given as follows (Ref. 4.2).

Dissociation Constant K1 :

H3P0 4 C> H2PO4 + H*

K1 YH2Po[H2PO4 .H,[]

YH3P 4[H3PO 4 ]

where Kt is defined by (Ref. 4.2):

pK1 =-Iog(K1) = 583.01 5 -2.715 + 0.009801. T T

Note that the activity of a non-ionic species such as H3PO 4 in dilute solutions is the same as the molar concentration; thus, the activity coefficient, y, is unity.

Dissociation Constant K-,:

HIPO4 <* HP02 +H`

YHOI- [HPO2]'YH÷ [H*Ii YHpo; [IH2PO 4]

where K2 is defined by (Ref. 4.2):

pK 2 =-Iog(K2 )= 1272.7 1.154+0.01368-T T

DQssociation Constant K3.:

HPO- <* PO +H+

3 'K-= -]YH+1H+ ]

yP -POO4 K3 .PO- [HPO2-]

where K3 is defined by (Ref. 4.1, p. 5-15):

pK 3 = -log(K 3) = 12.36 where

[X] concentration of species X [gram-moles/liter]

T solution temperature [K]

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Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 26 of 75 K, dissociation product constant 71 individual activity coefficient for a species Since phosphoric acid is a triprotic acid, the concentration of H3PO4 can be determined in terms of the three dissociation constants (K1, K2, K3) and the total mass of TSP in the containment sump. Once the concentration of H3PO4 is known, the concentrations of the other species can be determined. The concentration of TSP in the sump is given by:

[TSP]- mTSP MWTSP

• VMO

[TSP] = [H 3 PO,]+ [H2PO [HPO4+ 4]+[PO]

Realizing that [H2POP-1 is dependent on [H3PO4], that [HP0 421 is dependent on [H2Po 41 and that [PO43] is dependent on [HP0 4 1 leads to the following:

[H3PO K,

K

,J{1 tYllPo; "H'H.[ ] +2"K0%2 K-K 2

• (,-"( "H

+ Kl K K 2.K 3 JH+]y= y~,,.- 1"(y,-H+

.- 1]y

[TSP] . 7HpO2 where: pg concentration of species X [gram-moles/liter]

mTSP mass of.TSP in containment sump [grams]

MWTsp molecular weight of TSP VH20 total volume of water in containment sump [liters]

Thus, given a mass of TSP and a desired pH, the H-1 3P0 4 concentration can be determined.

7.9 Water Dissociation Based on the desired equilibrium pH and the temperature-dependent ionic activity product constant of water, Kw, the equilibrium concentrations of OH and H*ions in water are determined using the following equations.

K. =yH.[H]'yOH-[OH-]

where

.H.[H*] =10-PH and the ionic activity product constant of water, Kw, is calculated as follows (Ref. 4.4).

pK. = -log(K) =4470.99 -6.0875 + 0.01706.T T

where T solution temperature [K]

yJ individual activity coefficient for a species

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Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-0401 0 214 27 of 75 The individual activity coefficients, yi, are estimated using the extended form of the Debye-Hcckel theory (Ref. 4.1, p. 5-3):

-og(y) A-z 0.5 1 +(B. a, .°10.5) where A temperature dependent constant of the Debye-HUckel equation B temperature dependent constant of the Debye-HLckel equation zi ionic charge of species I a, effective ionic radius of species I I ionic strength of solution defined as follows (Ref. 4.1, p.*5-3):

n2 I = 0.5(c1z1 2+2z. ...... +c.

The Debye-HOckel constant 'A" is a function of temperature and density; and the Debye-HOckel constant "B" is a function of temperature and water dielectric constant which is itself a function of temperature. Readily available tabulations of the Debye-HOckel constants lie in the temperature range of 320 F to 2120 F to cover typical water conditions from freezing to boiling at atmospheric pressure. The.functions are well behaved (as shown in a plot of temperature vs. constants included in Attachment F) and the curve fit of the existing data shows excellent agreement with an R2 of 0.99999. Extrapolation from 2120 F to the maximum sump temperature of 2800 F is reasonable given the excellent data trend.

The effective ionic radii, ah, used in this analysis were taken at a temperature of 250 C (770 F). The effect of temperature on the approximate ionic radii, and thus on the individual activity coefficients, is considered negligable.

Debye-Huckel constants A'and B are recognized to be temperature dependant, but the ionic radius "a," is not treated as temperature dependant in the literature. No reference could be found for values of "a" at temperatures other than 25 degrees C. The tabulation of ionic radii used in this calculation were listed at 25 degrees C following conventional practice and-are applicable to other temperatures. It is thought that any temperature dependence of the Debye Huckel product B*a is lumped in the term B. Therefore the effect of temperature on the approximate ionic radii is considered to be negligible.

7.10 TSP When TSP dodecahydrate (Na 3PO 4 .12H 2 0.1/4NaOH) dissolves in the containment sump, it dissociates to form phosphate ions and sodium ions. TSP also contributes additional water to the sump from its water of hydration.

Sodium contributed to the sump from TSP is determined by:

[Na] = (3+ 0.25).m.

MWrsp VHZo TSP is available as anhydrous trisodium phosphate (i.e., no water of hydration) and as trisodium phosphate dodecahydrate (12 moles of water of hydration). The amount of hydration can vary, and at least one chemical vendor reports the product as a decahydrate (10 moles of water of hydration) based on chemical assays. For this calculation, the fully hydrated TSP dodecahydrate is used.

The mass of water added by TSP is:

AmerGen CALCULATION SHEET

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Calculation No. Rev. No. System Nos. -Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 28 of 75 mX *N. -MWH 2 o mH2 o = *v[MWNB where N = the number of moles of water of hydration in the TSP formula Using the fully hydrated form of TSP (trisodium phosphate dodecahydrate), N = 12.

This water is added to the mass of water initially present in the sump.

7.11, Determination of Equilibrium Conditions Equilibrium conditions are determined for the mixture of borated water, nitric acid, hydrochloric acid, hydriodic acid, cesium hydroxide, cesium iodide, and TSP. Equilibrium amounts of each chemical species in solution are simultaneously solved as described in preceding sections.

At equilibrium, the concentration of negatively charged species' (anions) must equal the concentration of positively charged species (cations) for electroneutrality.

The sum of negative charges is determined from the concentrations of the anions B(OH) 4 B2(OH) 7",

B3(OH) 10 , B4(OH)1 42 ", OH', Cl', N03-, I, H2 PO4", HP0 4 2 and PO 43. The species B4(OH) 142" and HP0 42 "

have charges of negative2 and PO 43 has a charge of negative 3, so contributions to the sum of negative charges from these ions are adjusted accordingly.

Neg Charge = [B(OH)-] + [B2 (OH)-] + [B, (OH)j] + 2. [B4(OH)'-]

+ [OH-] + [crI] + [N03] + [r] + [HPO-]+ 2. [HPO-] + 3. [PO3-The sum of positive charges is determined from the concentrations of H+, Na*, and Cs*.

Pos Charge =[H+] + [Na+] + [Cs+]

7.12 Determination of pH The equilibrium concentrations of borate, phosphate, and hydroxyl anions are functions of pH and temperature. For a given temperature, the pH is iteratively adjusted until electroneutrality is achieved.

Electroneutrality is verified when the ratio of positive to negative charges is unity.

-The pH resulting from addition of a fixed amount of TSP is determined from the H+ concentration after electroneutrality is achieved. By definition, pH is:

pH = -log(yH, [H*])

where: YH = activity coefficient for the species H*

The mass of TSP required to achieve a selected pH is determined by iteratively varying the mass of TSP until the selected pH is achieved.

The computer program TSP-R is used to iteratively solve the simultaneous equilibrium, mass balance, and charge balance equations. This program is capable of determining either the pH resulting from a specified mass of TSP or the mass of TSP required for a specified pH.

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. Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 29 of 75 8.0 RESULTS 8.1 Mass of TSP Required for Containment Sump pH Control The parametric analysis performed in this calculation determines the mass of TSP required for post-LOCA containment sump pH control.

The results of iterative computations are provided in the following tables.

Required Minimum Mass of TSP (Ib)

Maximum Boron and Borated Water f 3,643,118 lb water in sump Temperature 2802 ppm B (net sump concentration)

OF pH=7.2 pH=7.3 pH=7.4 pH=7.5 40 15431 18815 22710 27096 100 15396 18793 22699 27100 150 14286 17674 21661 26256 200 12322 15496 19357 23954 250 9922 12640 16069 20312 280 8474 10838 13879 17731 Required Maximum Mass of TSP (Ib)

Minimum Boron and Borated Water 3,148,801 lb water in sump Temperature 2073 ppm B (net sump concentration) oF pH=7.9 pH=8.0 pH=8.1 40 24993 28840 32933 100 26467 30674 35240 150 27895 32766 38133 200 27955 33388 39455 250 26130 31810 38253 280 24176 29810 36283 The lower limit for the required TSP mass is the maximum required TSP mass (over the range of.

temperatures) at the low pH limit (pH = 7.3) for the maximum boron concentration and borated water mass.

The lower limit TSP mass requirement of 18,815 lb ensures that the post-LOCA containment sump pH will be at least 7.3, regardless of sump temperature.

Similarly, the upper limit for the required TSP mass is the minimum required TSP mass (over the range of temperatures) at the high pH limit (pH = 8.0) for the minimum boron concentration and borated water mass.

The upper limit TSP mass requirement of 28,840 lb ensures that the post-LOCA containment sump pH will not be greater than 8.0, regardless of sump temperature.

8.2 Based on the above results, a mass of TSP within the range of 18,815 to 28,840 lb would maintain the post-LOCA containment sump pH value within the range of 7.3 to 8.0 for both the maximum and minimum quantities of boron and borated water at all sump temperatures. TSP requirements for other pH limits are included in the analysis to indicate the sensitivity of these results.

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Calculation No. F.Re No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 j 0 214 30 of 75 This range of required TSP mass is applicable provided the following post-LOCA containment sump

• conditions are met:

• boron concentration between 2073 ppm and 2802 ppm

• temperature between 40°F and 280°F 0 borated Water mass between 3,148,801 Ibm and 3,643,118 Ibm 8.3 Each TSP basket has a usable storage capacity of 24.51 ft3 (Input 2.25). At the bulk density of 51 lb/ft3 (Input 2.26), each basket can contain up to 1250 lb TSP. Installation of 23 baskets (see Input 2.25) is required and will store a total of 28,750 lb when filled to the bottom of the upper rim. This is a filled depth of 33.5 inches. The minimum 18,815 lb TSP will fill the baskets to a depth of 22 inches.

8.4 Because TSP will be provided in the fully hydrated dodecahydrate form, the volume will not expand during storage. Some TSP compaction or dehydration may occur during storage which will decrease the required volume.

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Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 31 of 75

9.0 CONCLUSION

9.1 A minimum of 18,815 lb fully-hydrated TSP (dodecahydrate) is required to meet the acceptance criteria of a sump pH of 7.3 mihimum. This conclusion applies to the full range of-expected sump conditions and temperatures.

9.2 A maximum of 28,840 lb fully-hydrated TSP (dodecahydrate) is required to meet the acceptance criteria of a sump pH of 8.0 maximum. This conclusion applies to the full range of expected sump conditions and temperatures.

9.3 A total of 23 TSP baskets will contain the required amount of TSP. The baskets have a capacity of 28750 lb TSP when filled to a depth of 33.5 inches (bottom of upper rim). The minimum 18815 lb TSP will fill the baskets to a depth of approximately 22 inches. Because TSP will be provided in the fully hydrated dodecahydrate form, the volume will not expand during storage. Some TSP compaction or dehydration may occur during storage which will decrease the required volume.

9.4 The sump pH will be 7.3 to 8.0 using TSP as the buffer.

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Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 32 of 75 Attachment A Iodine and Cesium Released from Core Inventory Table 1 - Iodine Core Inventory ...................................................................................................... 33 Table 2 - Cesium Core Inventory........................................................................................................ 34

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Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-04 0 214 33 of 75 Table A Iodine Core Inventory K

Neutron Mass 1.008665 amu (Ref. 1) Core Inventory Fraction Released In Contatlnment for Halooens 1 CurIe 3.70E+10 dis/sec (Ref. 1) Gap Release Phase 0.05 (Ref. 4, Thl 2)

Avogadro's Number 6.022137E+23 atoms/mole (Ret. 2) Early In-Vessel Phase 0.35 (Ref. 4, Thl 2)

Fuel Assemblies per Core (Ref. 3) Fraction as Csl 0.95 (ref. 4)

BOC Core EOC Core Atomic Mass Half Life Specific Inventory Inventory Gap EIV Total Isotope (Ref. 1) (Ref. 2) tIl units Half Life Activity (Ref 3) (Ref 3) Release Release Release

[aamu ac] [Cl/gm] [gmn/core] [gm/core] [mole] Lmole mole]

1-127 12.9'04470 stable stable I2.82E+03 524E+03 2.06E+00 1,47001 1.68E+0 1-128 127.905838 25.00 m 1,500 5.88E+07 6.00E-03 1.46E-02 5.71E-06 4.00E-05 4.57E-05 1-129 128.904987 1.57E+07 a 4.95E+14 1.77E-04 9.98E+03 1.81E+04 7.02E+00 4.91E+01 5.62E+01 1-130 129.906676 12.36 h 44,496 1.95E+06 5.32E-01 1.24E+00 4.77E-04 3,34E-03 3.82E-03 1-130M 129.906676 9.0 m 540 1.61E+08 2.54E-03 5.95E-03 2.29E-06 1.60E-05 1.83E-05 1-131 130.906127 8.020 d 692,928 1.24E+05 5.33E+02 5.49E+02 2.10E-01 1.47E+00 1.68E+00 1-132 131.907981 2.28 h 8,208 1.04E+07 9.35E+00 9.52E+00 3.61E-03 2.53E-02 2.89E-02 1-133 132.907750 20.8 h 74,880 1.13E+06 1.26E+02 1.23E+02 4.63E-02 3.24E-01 3.70E-01 1-133M 132.907750 9 a 9 9.43E+09 3.97E-04 4.34E-04 1.63E-07 1.14E-06 1.31E-06 1-134 133.909850 52.6 m 3,156 2.67E+07 5.93E+00 5.77E+00 2.15E-03 1.51 E-02 1.72E-02 I-134M 133.909850 3.7 m 222 3.79E+08 3.31E-02 3.80E-02 1.42E-05 9.93E-05 .1.14E-04 1-135 134.910020 6.57 h 23,652 3.54E+08 3.78E+01 3.73E+01 1.38E-02 9.68E-02 1.11E-01 1-136 135.914740 1.39 m 83 9.95E+08 6.40E-02 6.24E-02 2.30E-05 1.61E-04 1.84E-04 1-136M 135.914740 47 a 47 1.77E+09 2.16E-02 2.06E-02 7.58E-06 5.30E-05 6.06E-05 1-137_1' 136.923405 24.5 a 24.5 3.36E+09 1.95E-02 1.83E-02 6.68E-06 4.68E-05 5.35E-05 1-138(') 137.932070 6.5 s 6.5 1.26E+10 2.58E-03 2.39E-03 8.66E-07 6.06E-06 6.93E-06 1-1397F 138.940735 2.30 s 2.30 3.53E+10 4.38E-04 4.OOE-04 1.44E-07 1.01E-06 1.15E-06 1-140T4) 139.949400 0.86 a 0.88 9.37E+10 4.60E-05 4.09E-05 1.46E-08 1.02E-07 1.17E-07 1-141rr 140.958065 0.45 a 0.45 1.78E+11 3.39E-06 3.10E-06 1.10E-09 7.70E-09 8.80E-09 1-142__ 141.966730 0.2 a 0.2 3.97E+11 1.97E-07 2.05E-07 7.22E-11 5.05E-10 5.78E-10 1-143 142.975395 n/a 1.98E-08 2.21E-08 7.73E-12 5.41E-11 6.18E-11 1-14401) 143.984060 n/a 6.06E.10 7.12E-10 2.47E-13 1.73E-12 1.986-12 1-145") 144.992725 n/a 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.OOE+00 Totals (g-mole) 9.36E+00 6.58E+01 7.52E+01 Fraction as Csl Totals (p-mole) 8.89E+00 6.25E+01 7.15E+01 1

~

Fraction as HI Totas (g-mole) 4.68E-01 3.29E+00 3.76E+00

1) Atomic mass not given for these isotopes In Reference 1;therefore, a multiple of the neutron mass Is added to the atomic mass of 1-136M.

2) Fraction as HI conservatively Includes organic Iodides

1. Radiological Health Handbook, 1970.

2. Chart of the Nuclides, 15th Edition.

3. TMI Calcula*lon C-1101-202-E620-415, Rev 3 -Table 5

4. Reg Guide 1.183.

AmnerGen CALCULATION SHEET

Subject:

Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 34 of 75 Table A Cesium Core Inventory Neutron Mass 1.008665 arnu (Ref. 1) Core Inventory Fraction Released in Contatinment for Alkalis 1 Curie 3.70E+10 dis/sec (Ref. 1) Gap Release Phase 0.05 (Ref. 4, Thl 2)

Avogadro's Number 6.022137E+23 atoms/mole (Ref. 2) Early In-Vessel Phase 0.25 (Ref. 4, Thl 2)

Fraction Iodine as Cal 0.95 (Ref. 4)

BOC Core EOC Core Atomic Mass Half Uifa Specifti Inventory Inventory Gap EWV Total Isotope (Ref. 1) (Ref. 2) tia units Half Life Activity (Ref 3) (Ref 3) Release Release Release

-amu- [sec] (C/*gm] [am/cora] [gin/cor] [mole] [mole] [mole]

CS-132 131.906393 6.48 d 559,872 1.53E+05 5.040E-02 1.12E-01 4.25E-05 2.12E-04 2.55E-04 CS-133 132.905355 stable 8.870E+04 1.17E+05 4A0E+01 2.20E+02 2.64E+02 CS-134 133.906823 2.085 a 65,121,840 1.29E+03 5.950E+03 1.26E+04 4.70E+00 2.35E+01 2.82E+01 CS-134M 133.906823 2.90 h 10,440 8.07E+06 2.030E-01 4.49E-01 1.68E-04 8.38E-04 1.01E-03 CS-135 134.905770 2.30E+06 a 7.25E+13 1.15E-03 2.760E+04 4.92E+04 1.82E+01 9.12E+01 1.09E+02 CS-135M 134.905770 53 m 3.180 2.63E+07 2.600E-02 7.09E-02 2.63E-05 1.31E-04 1.58E-04 CS-136 135.907340 13.16 d 1.137,024 7.30E+04 2.930E+01 6.15E+01 2.26E-02 1.13E-01 1.36E-01 CS-137 136.908770 30.07 a 9.48E+08 8.69E+01 7.160E+04 1.26E+05 4.60E+01 2.30E+02 2.78E+02 CS-138 137.910800 32-2 m 1,932 4.23E+07 3.200E+00 3.04E+00 1.10E-03 5.51E-03 6.61E-03 CS-138M 137.910800 2.9 m 174 4.70E+08 1.210E-02 .1.26E-02 4.57E-06 2.28E-05 2.74E-05 CS-139 138.912900 9.3 m 558 1.46E+08 8.910E-01 8.47E-01 3.05E-04 1.52E-03 1.83E-03 CS-140 139.917110 1.06 m 64 1.27E+09 9.180E-02 8.89E-02 3.11E-05 1.55E-04 1.86E-04 CS-14111 140.925775 24.9 a 24.9 3.22E+09 2.730E-02 2.55E-02 9.05E-06 4.52E-05 5.43E-05 CS-142(1 141.934440 1.8 a 1.8 4.42E+10 1.170E-03 1.07E-03 3.77E-07 1.88E-06 2.26E-06 CS-143') 142.943105 1.78 a 1.78 4.43E+10 6.070E-04 5.34E-04 1.87E-07 9.34E-07 1.12E-06 CS-144 143.951770 1.01 a 1.01 7.76E+10 9.160E-05 8.90E-05 3.09E-08 1.55E-07 1.85E-07 CS-145 144.960435 0.59 a 0.59 1.322+11 1.240E-05 1.22E-05 4.21E-09 2.10E-08 2.52E-08 CS-146 145.969100 0.322 s 0.322 2.40E+11 5.740E-07 5.93E-07 2.03E-10 1.02E-09 1.22E-09 CS-14"/' 146.977765 0.227 a 0.227 3,38E+11 2.420E-07 2.73E-07 9.29E-11 4.64E-10 5.57E-10 CS-14 147.98,430 0.15 a 0.15 5.08E+11 5.290E-09 6.25E-09 2.11E-12 1.06E-11 1.27E-11 CS-149") 148.995095 n/e 0.00+E00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 CS-1"50* 150.003760 n/a 2.95E-12 3.61E-12 1.20E-15 6.02E-15 7.22E-15 Totals (g-mole) 1.130E+02 5.650E+02 6.780E+02 Fraction as Cl Totals (g.role) 8.893E+00 6.253E+01 7.146E+01 Fraction as CsON Totals -mole) 1.041E+02 5.025E+02 6.065E+02

1) Atomic mas not given for these isotopes in Reference 1; therefore, a multiple of the neutron mass is added to the atomic mass of CS-140.

1. Radiological Health Handbook, 1970.

2. Chart of the Nuclides, 15th Edition.

3. TMI Calculation C-1 101-202-E620-415, Rev 3 - Table 5

4. Reg Guide 1.183.

AnerGen CALCULATION SHEET

Subject:

Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 35 of 75 Attachment B Excel Spreadsheets (including formulae)

Table 1 - Iodine Core Inventory .................................................................................................................. 36 Table 2 - Cesium Core Inventory ............................................. ........................................ ........

................. 37

- C.. Wc.wfh~Cam*.. ~flflt.0dICt-tfl6WO 0-s 1311C- -~ AZ I - I n- Iz I~.- I I = I. I=.I= I -

t 00 4.~O-'S Omn bi--- -~

nIUtllI m*1,1 m ' I *0144S e.C*,,n mew,m as in.tu

- I I -~

.cc~ II as-lele B-4.A..0.,.a

'a.----m bd

AmerGen CALCULATION SHEET

Subject:

Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 38 of 75 Attachment C FORTRAN Program Listings This attachment contains the FORTRAN code used to compile the TSP-R.exe program.

File Name Description I Page tsp.for File contains the code for determination of pH/mass of TSP 39 - 45 openf.for Sub-routine for user supplied input and output file names 46-47 rhoh2ofcn.for Sub-routine determines the density of water via linear interpolation 48 faint.for Sub-routine determines the Debye-HOckel constant 'A' via linear 49 ninterpolation fbint.for Sub-routine determines the Debye-HOckel constant B' via linear 50 interpolation To compile TSP-R.exe, the following programs are used: tsp.for, openf.for, rhoh2ofcn.for, faint.for and fbint.for.

This attachment also includes instructions for creating the input file required for TSP-R.exe. The instructions are included after the FORTRAN code (pages 51 - 52).

AmerGen CALCULATION SHEET

Subject:

Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quanfty C-1101-153-E410-040 0 214 39 of 75 Tsp.for C CONTAINMENT SUMP pH CONTROL USING TRISODIUM PHOSPHATE C

IMPLICIT REAL *8 (A-H,O-Z)

REAL *8 MWB,MWTSP,NA,LQB11,LQB11I,LQB21,LQB31,LQB42 REAL *8 IST,IS,PPMB,PPMTSP,LGH,LGOH,LGP REAL *8 MWH3BO3, MWH20,NHYDRATE,NNAOH,MH2OADD REAL *8 IODINE INTEGER

• 4 OPTN1, OPTN2, OPTN3, OPTN4, OPTN5 CHARACTER *60 TITLE CALL OPENF READ (8, 100) TITLE READ (8, *) PH, TF,A,B READ (8, *) OPTN1,OPTN2,OPTN3,OPTN4,OPTN5 READ(8, *) TMH2OI,ROH20,PKH20,MH2OADD READ(8, *) TMB,PPMB,LQBIII,LQB21,LQB31,LQB42 READ(8, *) TMTSP,MWTSP,NHYDRATE,NNAOH,PKPI,PKP2,PKP3 READ(8,*)GMI,GMCS,GMCL,TID MWB - 10.81 MWH3BO3 = 61.83 MWH20 = 18.02 aH= 9.0 aOH = 3.5 alxPOx = 4.0 IF (OPTN4.EQ.0) GOTO 5 A = FAINT (TF)

B = FBINT(TF) 5 IF (OPTN1.EQ.0) GOTO 10 T = (TF-32)/1.8+273.15 PKH20 = 4470.99/T-6.0875+0.01706*T PKP1 = 583.01/T-2.715+0.C09801*T PKP2 = 1272.7/T-1.154+0.01368*T PKP3 = 12.36 LQB11I = 1573.21/T+28.6059+0.012078*T-13.2258*DLOG10(T)

LQB21 = 2756.1/T-18.966+5.835*DLOG10(T)

LQB31 3339.5/T-8.084+1.497*DLOGI0(T)

LQB42 = 12820/T-134.56+42.105*DLOG10(T)

ROH20 = RHOH2OFCN(TF) 10 IF (OPTN2.EQ.0) GOTO 50 20 IF (OPTN3.EQ.0) TMB = TMH2OI*PPMB/10**6 IF (OPTN3.EQ.1) PPMB = 10**6*TMB/TMH2OI PPMTSP = 10**6*TMTSP/(TMH2OI+TMTSP)

PPMH3BO3 = PPMB*MWH3BO3/MWB

AmerGen. CALCULATION SHEET

Subject:

Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 40 of 75 TMH3BO3 = TMH2OI*PPMH3BO3/10**6 TMH20 = TMH2OI+TMTSP* (NHYDRATE*MWH20/MWTSP)-TMH3BO3+MH2OADD TLH20 = (TMH20/ROH20)*(12**3)*(2.54**3)/1000 GMPLI=GMI/TLH20 GMPLCS=GMCS/TLH20 GMPLCL=GMCL/TLH20 GMPLNO3=(7.3E-06)*TID/1.0E06 PKOH = PKH20-PH

'PHT= 7.0, LQB11 = LQBI1 IST = 0.01 GOTO 40 30 PH =PHT PHT = PHT+(CBEP+CBEB)

PKOH = PKH20-PHT IF (OPTN1.EQ.0) GOTO 40 IST = IS IS = (BOH4+B2OH7+B3OHI0+4*B4OHI4+H2PO4+4*HPO4+9*PO4+NA+H+OH)/2 IS = IS + 0.5*(GMPLI+GMPLCS+GMPLCL+GMPLN03)

LQB11 = LQB11I+(0.325-0.00033*T)*IS-0.0912*IS**1.5 LGOH -A*IS**0.5/(I+B*aOH*IS**0.5)

PKOH = PKH20-(PH-LGOH) 40 GMPLB = TMB*453.59/(MWB*TLH20)

H3B03 = 0.95*GMPLB GOTO 44 42 H3BO3 = H3BO3*(GMPLB/TGMPLB) 44 RB11 = 10**(LQB11-PKOH)

RB21 = 10**(LQB21-PKOH)

RB31 = 10**(LQB31-PKOH)

RB42 = 10**(LQB42-2*PKOH)

BOH4 = H3BO3*RB11 B20H7 = H3BO3**2*RB21 B3OH10 = H3BO3**3*RB31 B40H14 = H3BO3**4*RB42 TGMPLB = H3BO3+BOH4+2*B20H7+3*B30HIO+4*B40HI4 ERR = ABS((TGMPLB-GMPLB)/GMPLB)

IF (ERR.GT.0*.00001) GOTO 42 LGH = -A*IS**0.5/(1+B*aH*IS**0.5)

H = 10**(-PHT-LGH)

OH = 10**(-PKOH)

CBEB = H-(OH+BOH4+B2OH7+B3OHl0+2*B4OH14)

GMPLTSP = TMTSP*453.59/(MWTSP*TLH20)

LGP = -A*IS**0.5/(I+B*aHxPOx*IS**0.5)

RPIJ= 10**(PHT-PKPI-LGP)

AmerGen CALCULATION SHEET

Subject:

Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 .41 of 75 RP2 = 10**(PHT-PKP2-3*LGP)

RP3 = 10**(PHT-PKP3-5*LGP)

'NA = (3+NNAOH)*GMPLTSP H3P04 = GMPLTSP/(I+RP1+RP1*RP2+RPI*RP2*RP3)

H2PO4 = H3PO4*RPI HP04 = H2PO4*RP2 P04 = HP04*RP3 CBEP = NA-(H2PO4+2*HP04+3*PO4)

CBEP=CBEP-GMPLI+GMPLCS-GMPLCL-GMPLNO3 ERR = ABS((CBEB+CBEP)*2/(CBEB-CBEP))

IF (ERR.GT.0.000001) GOTO 30 ERR = ABS(.(IS-IST)*2/(IS+IST))

IF (ERR.GT.0.000001) GOTO 30 GOTO 90 50 TLH20 = (TMH2OI/ROH20)*(12**3)*(2.54**3)/1000 IF (OPTN3.EQ.0) TMB = TMH2OI*(PPMB/10**6)

IF (OPTN3.EQ.1) PPMB = 10**6*TMB/TMH20I PPMH3BO3 = PPMB*MWH3BO3/MWB TMH3BO3 = TMH2OI*PPMH3BO3/10**6

.TMTSP = TMB PKOH = PKH20-PH LQB11 = LQB11I IST = 0.01 GOTO 70 60 TMH20 = TMH20I+TMTSP*(NHYDRATE*MWH20/MWTSP)-TMH3BO3+MH20ADD TLH20 = (TMH20/ROH20)*(12**3)*(2.54**3)/1000 GMPLI=GMI/TLH20 GMPLCS=GMCS/TLH20 GMPLCL=GMCL/TLH20 GMPLNO3=(7.3E-06)*TID/1.0E06 TMTSP = TMTSP*ABS(CBEB/CBEP)

IF (OPTN1.EQ.0) GOTO 70 IST = IS IS = (BOH4+B20H7+B3OHI0+4*B40HI4+H2PO4+4*HPO4+9*PO4+NA+H+OH)/2 IS = IS + 0.5*(GMPLI+GMPLCS+GMPLCL+GMPLN03)

LQB1I LQB11I+(0.325-0.00033*T)*IS-0.0912*IS**1.5 LGOH = -A*IS**0.5/(1+B*aOH*IS**0.5)

PKOH = PKH20-(PH-LGOH) 70 GMPLB = TMB*453.59/(MWB*TLH20)

H3BO3 = 0.95*GMPLB GOTO 74 72 H3B03 = H3BO3*(GMPLB/TGMPLB) 74 RB11 = 10**(LQB11-PKOH)

AmerGen CALCULATION SHEET

Subject:

Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 42 of 75 RB21 = 10**(LQB21-PKOH)

RB31 = 10**(LQB31-PKOH)

RB42 = 10**(LQB42-2*PKOH)

BOH4 = H3BO3*RB1I B20H7 = H3BO3**2*RB21 B3OH10 = H3BO3**3*RB31 B4OH14 = H3BO3**4*RB42 TGMPLB = H3BO3+BOH4+2*B2OH7+3*B3OHIO+4*B4OHI4 ERR = ABS((TGMPLB-GMPLB)/GMPLB)

IF (ERR.GT.0.000001) GOTO 72 LGH = -A*IS**0.5/(I+B*aH*IS**0.5)

H = 10**(-PH-LGH)

OH = 10**(-PKOH)

CBEB = H- (OH+BOH4+B2OH7+B3OHlO+2*B4OHI4)

GMPLTSP = TMTSP*453.59/(MWTSP*TLH20)

LGP = -A*IS**0.5/(l+B*aHxPOx*IS**0.5)

RPI = 10**(PH-PKPI-LGP)

RP2 = 10**(PH-PKP2-3*LGP)

RP3 = 10**(PH-PKP3-5*LGP)

NA = (3+NNAOH)*GMPLTSP H3PO4 = GMPLTSP/(I+RPI+RPI*RP2+RP1*RP2*RP3)

H2PO4 = H3PO4*RP1 HP04 = H2PO4*RP2 P04 = HPO4*RP3 CBEP = NA-(H2PO4+2*HPO4+3*PO4)

CBEP=CBEP-GMPLI+GMPLCS-GMPLCL-GMPLNO3 ERR = ABS ((CBEB+CBEP) *2/(CBEB-CBEP))

IF (ERR.GT.0.000001) GOTO 60 ERR = ABS((IS-IST)*2/(IS+IST))

IF (ERR.GT.0.000001) GOTO 60 PPMTSP = 10**6*TMTSP/(TMH2OI+TMTSP)

GOTO 90 90 WRITE(10,100) TITLE WRITE (10, *) , -- ----......... ...........

IF (OPTNI.EQ.0)

&WRITE(10,*) 'Option 1 = 0 (pK values are entered)'

IF (OPTN1.EQ.1)

&WRITE(10,*) 'Option 1 = 1 (pK values are calculated)'

IF (OPTN2.EQ.0)

&WRITE(10,*)'Option 2 = 0 (quantity of TSP is calculated)'

IF (OPTN2.EQ.1)

&WRITE(10,*) 'Option 2 = 1 (equilibrium pH is calculated)'

IF (OPTN3.EQ.0)

&WRITE(10,*) 'Option 3 = 0 (input boron quantity is in PPM)'

IF (OPTN3.EQ.1)

&WRITE(10,*) 'Option 3 = 1 (input boron quantity is in ibm)'

AmnerGen CALCULATION SHEET

Subject:

Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 43 of 75 IF (OPTN4.EQ.0)

&WRITE(10,*) 'Option 4 = 0 (Debye-Hickel constants are entered)'

IF (OPTN4.EQ-.i)

&WRITE(10,*) 'Option 4 - 1 (Debye-Hilckel constants are calculated)'

IF (OPTN5.EQ.0)

&WRITE(10,*) 'Option 5 = 0 (Formatted results)'

IF (OPTN5.EQ.1)

&WRITE(10,*) 'Option 5 =.1 (Unformatted results)'

IF (OPTN5.EQ.0) THEN WRITE (10, *) '.........................

WRITE (10,102) 'Temperature, OF =',TF WRITE(10,105)'A (constant of activity) =',A WRITE(10,105)'B (constant of activity) ,B WRITE(10,106) 'Solution ionic strength =.,Is WRITE (10,*) '.........................

WRITE(10,102)'Initial mass of borated water, lbm =',TMH201 WRITE(10,102)'Final mass of pure water, ibm =',TMH20 WRITE(10,104)'Density of water, lb/ft' =',ROH20 WRITE(10,106)'pK (water) =',PKH20 WRITE(10,106)'pK (OH) =' ,PKOH WRITE(10,108)'Log (gamma OH) =',LGOH WRITE (10,102) 'Equilibrium pH =',PH WRITE(10,108)'Log (gamma H) =',LGH WRITE (10,*) '.........................

WRITE(10,102)'Total mass of Boron, Ibm =',TMB WRITE(10,101)'PPM of Boron =',PPMB WRITE(10,103)'MW of Boron =',MWB WRITE(10,102)'Total mass of Boric acid, ibm =',TMH3BO3 WRITE(10,101)'PPM of Boric acid =',PPMH3BO3 WRITE(10,106)'Log Q1,1 (Boric acid) =',LQBII WRITE(10,106)'Log Q2,1 (Boric acid) =',LQB21-WRITE(10,106)'Log Q3,1 (Boric acid) =',LQB31 WRITE(10,106)'Log Q4,2 (Boric acid) =',LQB42 WRITE(10,108)'H3BO3 =',H3BO3 WRITE(10,108)'B(OH)4 =',BOH4 WRITE (10,108) 'B2(OH)7 =', B2OH7 WRITE(l0,108) 'B3(OH)10 =',B3OH10 WRITE (10,108) 'B4 (OH) 14 =',B40Hl4

.WRITE(10,107)'CBEB =',CBEB WRITE (10, *) '..........................

WRITE(10,102)'Total mass of TSP, lbm =',TMTSP WRITE(10,101)'PPM of TSP =',PPMTSP WRITE(10,103)'MW of TSP =',MWTSP WRITE(10,101) '# of Hydrates(X), Na3PO4*XH20*YNaOH =',NHYDRATE WRITE(10,104)'# of NaOH(Y), Na3PO4*XH20*YNaOH =',NNAOH WRITE(10,10S6)'Log (gamma H2PO4) =',LGP WRITE(10,106)'Log (gamma HP04) =',LGP WRITE(10,106)'pKl (Phosphoric acid) =',PKPI

A* 1erGen. CALCULATION SHEET

Subject:

Calculation No. Rev. No. i System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 44 of 75 WRITE(10,106) 'pK2 (Phosphoric acid) =',PKP2 WRITE(10,103) 'pK 3 (Phosphoric acid) =',PKP3 WRITE(10,108) 'H3P04 =',H3P04 WRITE(10,108) 'H2P04 =',H2P04 WRITE (10,108) 'HPO4 =',HPO4 WRITE (10,108) 'P04 =',P04 WRITE(10,108)'NA NA WRITE(10,107)'CBEP =',CBEP WRITE (10,*)' -- '- - - - - - - - - -- - - - - - - - - - - -

WRITE(10 108) '[I] =',GMPLI WRITE(10,108) '([Cs =',GMPLCS WRITE(10,108) '(Cl] =',GMPLCL WRITE(10,108) ' [NO3] =' ,GMPLNO3 WRITE (10, *)---------------------------------------------------... .. ..

WRITE(10,107)'Charge balance error =',ERR WRITE (10,*) '. . . . . . . . . . . . . . . . . . . . . . . . .

ELSE IF (OPTN5.EQ.1) THEN WRITE (10, *) -

&------ U WRITE(10,*)'Temperature, OF =',TF WRITE(10,*)'A (constant of activity) =',A WRITE(10,*)'B (constant of activity) =',B WRITE (10,*) 'Solution ionic strength =',"IS WRITE (10, *) '. . . . . . . . . . . . . . . . . . . . . . . . . .

WRITE(10,*) 'Initial mass of borated water, lbm =',TMH2OI WRITE(10,*)UFinal mass of pure water, lbm =',TMH20 WRITE(10,*) Density of water, lb/ft 3 - =',ROH20 WRITE(10,*) pK (water) =',PKH20 WRITE(10,*) 'pK (OH) =',PKOH WRITE(10,*)ULog (gamma OH) =',LGOH WRITE (10,*) 'Equilibrium pH =',PH WRITE(10,*) 'Log (gamma H) =',LGH WRITE (10,*) - - - - - - - - - - - - - - -- - - - - - - - - - - -

WRITE(10,*)'Total mass of Boron, lbm =',TMB WRITE(10,*)!PPM of Boron =,PPMB WRITE(10,*)'MW of Boron =',MWB WRITE(10,*)'Total mass of Boric acid, ibm =',TMH3BO3 WRITE(10,*)'PPM of Boric acid =',PPMH3BO3 WRITE(10,*) 'Log Q1,1 (Boric acid) =',LQBll WRITE(10,*)'Log Q2,1 (Boric acid) =',LQB21 WRITE(10,*) 'Log Q3,1 (Boric acid) =',LQB31 WRITE(10,*)'Log Q4,2 (Boric acid) =',LQB42 WRITE (10, *).'H3BO3 =',H3B03 WRITE (10,*) 'B (OH) 4 =' ,BOH4 WRITE(i0,*) 'B2(OH)7 =',B20H7 WRITE (10,*) 'B3 (OH) 10 =' ,B3OH10 WRITE(I0,*) 'B4 (OH) 14 =' ,B4OHl4

ArmerGen CALCULATION SHEET

Subject:

Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity I C-1101-153-E410-040 0 214 45 of 75 WRITE (10,*) 'CBEB =',CBEB.

WRITE (10,*) '

WRITE(10,*)'Total mass of TSP, ibm =', TMTSP WRITE(10,*)'PPM of TSP =',PPMTSP WRITE(10,*)'MW of TSP -', MWTSP WRITE (10,*) '# of Hydrates (X), Na3PO4*XH20*YNaOH =',NHYDRATE WRITE(10, *) '# of NaOH(Y), Na3PO4*XH20*YNaOH =',NNAOH WRITE(10,*) 'Log (gamma H2PO4) =',LGP WRITE(10,*) 'Log (gamma HPO4) =',LGP WRITE (10,*) 'pKl (Phosphoric acid) =',PKPI WRITE (10, *) 'pK2 (Phosphoric acid) =',PKP2 WRITE(10,*)'pK3 (Phosphoric acid) =',PKP3 WRITE (10,*) 'H3PO4 =', H3PO4

-' ,H3PO4 WRITE (10, *) 'H2PO4 =',H2P04 WRITE (10,*) 'HPO4 =,HPO4 WRITE (10,*) 'P04 =',P04 WRITE (10, *) 'NA =' ,NA WRITE (10,*) 'CBEP =',CBEP WRITE (10, *) '------------------

WRITE (10, *) [I] =',GMPLI WRITE (10, *) '[Cs] =',GMPLCS

-WRITE (0,*) '[Cl] =',GMPLCL WRITE (10, *) '[N03 -',GMPLNO3 WRITE (10, *) -------------------------------------------------------

- ,-)

WRITE (10,*) 'Charge balance error =', ERR WRITE (10, *),I------------------------------------------------------

END IF

.100 FORMAT (A60) 101 FORMAT (A38,F16.0) 102 FORMAT (A38, FI6. 1) 103 FORMAT (A38,F16.2) 104 FORMAT (A38,F16.3) 105 FORMAT (A38, FI6.4) 106 FORMAT (A38, F16.6) 107 FORMAT (A38,ES16.8E2) 108 FORMAT (A38,ES16.6E2)

END

AmerGen, CALCULATION SHEET

Subject:

Calculation No. Rev. No. System Nos.' Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 46 of 75 Open . for SUBROUTINE OPENF()

C C subroutine to open files C

INTEGER INPUT, OUTPUT DATA INPUT/8/

DATK OUTPUT/10/

C CHARACTER*60 IFNAME,OFNAME CHARACTER RESP LOGICAL EXISTS INTEGER ICODE CHARACTER*256 ERRMSG C

10 PRINT *, 'Enter input file name:

READ(*, '(A)') IFNAME IF (IFNAME .EQ. ' ') GO TO 10 NRE=I INQUIRE(FILE=IFNAME,EXIST=EXISTS)

IF (EXISTS) THEN OPEN (INPUT,FILE=IFNAME, STATUS='OLD',IOSTAT=ICODE,ERR=50)

ELSE PRINT*,'File does not exist!'

GO TO 10 END IF C

20 WRITE(*,*) 'Enter output file name:

READ(*,'(A)I) OFNAME IF (OFNAME .EQ. ' !) GO TO 20 NRE=2 INQUIRE(FILE=OFNAME,EXIST=EXISTS)

IF (EXISTS) THEN PRINT *, 'File already exist. Overwrite? Y or N:

READ(*,'(A)I) RESP IF (RESP.EQ.'Y' .OR. RESP.EQ.'y') THEN OPEN (OUTPUTFILE=OFNAME, STATUS='UNKNOWN')

ELSE GO TO 20 END IF ELSE OPEN (OUTPUT, FILE=OFNAME,fSTATUS='NEW',IOSTAT=ICODEERR=50)

END IF C

RETURN C

50 CALL IOSTATMSG(ICODE,ERRMSG)

PRINT*,'File open error!'

PRINT*,'Error-Code : ',ICODE PRINT*,'Error Msg : ',ERR MSG IF (NRE.EQ.1) THEN

AmerGen CALCULATION SHEET

Subject:

Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 47 of 75 GO TO 10 ELSE GO TO 20 END IF c

END

AmerGen CALCULATION SHEET Subjecti Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 48 of 75 rhoH2Ofcn. for double precision function rhoH2Ofcn(tfx)

C c Calculate Density of water C

implicit double precision (a-h,o-z)

C double precision-tf(27), rho(27)

C data tf/

12 32., 40., 50., 60., 70., 80., 90., 100., 110., 120.,

3 130., 140., 150., 160., 170., 180., 190., 200., 210., 212.,

220., 240., 260., 280., 300., 350., 400./

data rho/

2 62.414, 62.426, 62.410, 62.371, 62.305, 62.220, 62.116, 61. 996, 61.862, 61.713, 61.550, 61.376, 61.188, 60.994, 60.787, 60.569, 3 60.343, 60.107, 59.862, 59.812, 59.613, 59.081, 58.517, 57.924, 44 57.307, 55.586, 53.648/

C if (tfx.lt.tf(l)) rhoH2Ofcn = rho(1) do 10 i=2,27 if (tfx.ge.tf(i-l) .and. tfx.le.tf(i)) then rhoH2Ofcn=rho (i-I) +

&(tfx-tf (i-1)) * (rho (i) -rho (i-i)) / (tf(i) -tf (i-i))

end if 10 continue if (tfx.gt.tf(27)) rhoH2Ofcn = rho(27)

C return C

end

ArnerGen CALCULATION SHEET

Subject:

Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 49 of 75 faint, for double precision function faint(tfx) c c Calculate Debye-Hickel Coefficient A c

implicit double precision (a-h,o-z) c double precision tf(21), fa(21)

C data tf/

1 32.,ý 41., 50., 59., 68., 77., 86., 95., 104., 113.,

2 122., 131., 140., 149., 158., 167., 176., 185., 194., 203.,

3 212./

data fa/

11 0.4918, 0.4952, 0.4989, 0.5028,'0.5070 0.5115, 0.5161, 0.5211, 2 0.5262, 0.5317, 0.5373, .0.5432, 0.5494 0.5558, 0.5625, 0.5695, 3 0.5767, 0.5842, 0.5920, 0.6001, 0.6086 /

C if (tfx.lt.tf(1)) faint = fa(1) do 10 i=2,21 if (tfx.ge.tf(i-1) .and. tfx.le.tf(i)) then faint=fa (i-1) +

&(tfx-tf (i-l)) *(fa (i) -fa (i-l)) /(tf (i) -tf (i-l))

end if 10 continue if (tfx.gt.tf(21)) then faint = (0.00000158486*tfx+0.000260119)*tfx+0.48195' end if C

return c

end

AmerGen CALCULATION SHEET

Subject:

Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 50 of 75 fbint. for double precision function fbint(tfx)

C c Calculate Debye-Hfickel Coefficient B C

implicit double precision (a-h,o-z)

C double precision tf(21), fb(21)

C data tf/

1 32., 41., 50., 59., 68., 77., 86., 95., 104., 113.,

2 122., 131., 140., 149., 158., 167., 176., 185., 194., 203.,

3 212./

data fb/

1* 0.3248, 0.3256, 0.3264, 0.3273, 0.3282, 0.3291, 0.3301, 0.3312, 2 0.3323, 0.3334, 0.3346, 0.3358, 0.3371, 0.3384, 0.3397, 0.3411, 3 0.3426, 0.3440, 0.3456, 0.3471, 0.3488/

C if (tfx.it.tf(l)) fbint = fb(l) do 10 i=2,21 if (tfx.ge.tf(i-l) .and. tfx.le.tf(i)) then fbint=fb (i-l).+,

&(tfx-tf(i-l))*(fb(i)-fb(i-1))/(tf(i)-tf(i-l))

end if 10 continue if (tfx.gt.tf(21)) then fbint = (0.000000271613*tfx+0.0000668289)*tfx+0.322388 end if C

return C

end

ArnerGen CALCULATION SHEET

Subject:

Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 51 of 75 TSP-R.exe INPUT DESCRIPTION Each 'Card' listed below is a separate line of input in the input file.

Each 'Word' on a 'Card' is an input entry on that line. The Words beloware all followed-by the corresponding variable in the FORTRAN computer code.

Card 1:

TITLE Run title Card 2:

Word 1 PH Equilibrium pH (set to zero if OPTN2=I)

Word 2 TF Sump temperature, OF Word 3 A Debye-HOckel constant, A (set to zero if OPTN4=I)

.Word 4 B Debye-HOckel constant, B (set to zero if OPTN4=I)

Card 3:

Word 1 OPTN1 Option 1 0 = pK values entered in input deck 1 = pK values calculated Word 2 OPTN2 Option 2 0 = TSP mass is calculated I = equilibrium pH is calculated Word 3 OPTN3 Option 3 0 = input quantity for boron is in ppm 1 = input quantity for boron is in Ibm Word 4 OPTN4' Option 4

-o = Debye-HOckel constants (A,B) entered in input deck 1 = Debye-HOckel constants (A,B) calculated Word 5 OPTN5 Option 5 0 = Formatted results 1 = Unformatted results Card 4:

Word 1 TMH201 initial borated water mass in sump, Ibm Word 2 ROH20 water density, Ibm/fW (set to zero if OPTN1=1)

Word 3 PKH20 pK water (set to zero if OPTN1=I)

Word 4 MH20ADD Additional non-borated water mass added to total water mass, Ibm Card 5:

Word 1 TMB initial boron mass, Ibm (set to zero if OPTN3=0)

Word 2 PPMB initial boron concentration, ppm (set to zero if OPTN3=I)

Word 3 LQBWI I log (Q1,1) (set to zero if OPTNI=1)

Word 4 LQB21 log (Q2,1) (set to zero if OPTN1=l)

Word 5 LQB31 log (Q3,1) (set to zero if OPTNI=I)

Word 6 LQB42 log (Q4,2) (set to zero if OPTNI=I)

AmerGen CALCULATION SHEET

Subject:

Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 52 of 75 Card 6:

Word I TMTSP TSP mass when determining pH, Ibm (set to zero if OPTN2=0)

Word 2 MWTSP molecular weight of TSP molecule Word 3 NHYDRATE Number of hydrates (X) in TSP molecule, Na3PO4*XH20*YNaOH Word 4 NNAOH Number of NaOH molecules (Y) in TSP molecule, Na3PO4*XH20*YNaOH Word 5 PKPI pKl for phosphoric acid (set to zero if OPTNI =1)

Word 6 PKP2 pK2 for phosphoric acid (set to zero if OPTN=I1)

Word 7 PKP3 pK3 for phosphoric acid (set to zero if OPTNI==1)

Card 7:

Word 1 GMI g-moles Iodine added to suppression pool Word 2 GMICS g-moles Cesium added to suppression pool Word 3 GMCL g-moles Chloride added to suppression pool Word 4 POOLTID Suppression pool TID, Rad

AmerGen CALCULATION SHEET

Subject:

Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 53 of 75 Attachment D Mathcad Validation of FORTRAN Program TSP-R This attachment contains the Mathcad files used to benchmark the FORTRAN program TSP-R as well as the input and output files for the benchmarked FORTRAN runs.

Page TSP-R Benchm ark Input File (val-test.in) .................................................................................................... 54 TSP-R Benchmark Output File (val-test.out) .................................... 55-56 Mathcad Benchm ark of TSP-R ............................... ............................................................................... 57-71

AmerGen CALCULATION SHEET

Subject:

Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-110-153-E410-040 0. 214 54 of 75 TSP-R Validation Input File Min pH 7.5,100, 0, 0 1,0,0,1,1 3643118, 0, 0, 0 0, 2802, 0, 0, 0, 0 0, 390.12, 12, 0.25, 0, 0, 0 75.22, 677.98, 465,120000000.

AmerGen CALCULATION SHEET

Subject:

I Calculation No. Rev.No.' System Nos, Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 C 214 5 of 7 TSP-R Validation Output Min pH Option 1 = 1 (pK values are calculated)

Option 2 = 0 (quantity of TSP is calculated)

Option 3 = 0 (input boron quantity is in PPM),

Option 4 = 1 (Debye-H~ickel constants are calculated)

Option 5 = 1 (Unformatted results)

Temperature, *F = 100.0000000000000 A (constant of activity) = 0.5239333245489333 B (constant of activity) = 0.3318111168013679 Solution ionic strength = 7.885496259347409E-02 Initial mass of borated water, lbm = 3643118.000000000 Final mass of pure water, lbm = 3599752.491113404, Density of water, lb/ft 3 = 61 99599838256836 pK (water) = 13.59644176324590 pK (OH) = 5.985496521216293 Log (gamma OH) = -0.1109452420296030 Equilibrium pH = 7.500000000000000 Log (gamma H) = -8.002145236355966E-02 Total mass of Boron, lbm = 10208.01663600000 PPM of Boron = 2802.000000000000 MW of Boron = 10.81000041961670 Total mass of Boric acid, ibm = 58386.83282102004 PPM of Boric acid = 16026.61039829620 Log Q1,l (Boric acid) = 4.469115785953613 Log Q2,1 (Boric acid) = 4.442785580375762 Log Q3,1 (Boric acid) = 6.387948113890130 Log Q4,2 (Boric acid) = 11.62487084571569 H3B03  : 0.1942850817799009 B(OH) 4 5.916416222735322E-03 B2(OH)7 - i.081852288589077E-03 B3(OH)10 = 1.852550075920406E-02 B4(OH) 14 = 6.421487200431189E-04, CBEB = -2.680906264918021E-02 Total mass of TSP, ibm = 27100.07930103181 PPM of TSP = 7383.779033150214 MW of TSP = 390.1200000000000

1. of Hydrates(X), Na3PO4*XH20*YNaOH = 12.00000000000000

1. of NaOH(Y), Na3PO4*XH20*YNaOH = 0.2500000000000000 Log (gamma H2PO4) = -0.1071798789634814 Log (gamma HP04) = -0.1071798789634814 pKl (Phosphoric acid) = 2.207469022593649 pK2 (Phosphoric acid) = 7.192725264958558 pK3 (Phosphoric acid) = 12.35999965667725 H3P04 = 1.452948980353735E-08 H2PO4 = 3.647213786897662E-03 HPO4 = 1.551585072958415E-02

AmerGen CALCULATION SHEET

Subject:

Calculation No. Rev. No. System Nos. I Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 56 of 75 P04 - 7.356569308583342E-07 NA 6.228239778443303E-02 CBEP - 2.680906113528796E-02

[I] = 4.574877588447088E-05

[CS] = 4.123471825864606E-04

[CIl = 2.828128261935517E-04

[N031 = 8.760000127949752E-04 Charge balance error = 7.7126663046114,98E-07

AmerGen Attachment D Caic. C-1 101-153-E410-040, Rev. 0 TMI Unit 1 Page 57 grammole:= I gm Input Values Description TF:= 100 OF Sump temperature (TF - 32)

Z= 1.-- + 273.15 T = 310.93 K Sump temperature A:= 0.5239333245489333 Debye-H0ckel Constant

'VW B := 0.3318111168013679 Debye-HOckel Constant M12Oi := 3643118 -lb Total initial mass of borated water M2Oadd:= 0 lb Additional non-borated water mass added to total water mass ppmB := 2802 ppm Post-LOCA sump boron concentration Nhydrate:= 12 Number of hydrates in TSP molecule Number of NaOH molecules per TSP NNaOH := 0.25 molecule MWTSP := 390.12 -cl Molecular weight of TSP mol gi Molecular weight of'boron MWB := 10.81 tool gm MWBOH3:= 61.83 Molecular weight of boric acid tool MWH20:= 18.02 gm Molecular weight of water mol ibm-

• w := 61.99599838256836 Density of water ft3

-2 I:= 7.885496259347409 x 10 (1) Assume a solution ionic strength, I MTSP:- 27100.07930103181 Ibm (2) Assume a TSP mass EQBOH3 := 1.942850817799009.10- 1 grammole .(3) Assume B(OH) 3 concentration liter pH:= 7.500000 Equilibrium pH

AmerGen Attachment D Calc. C-1l101-1 53-E410-040, Rev. 0 TMI Unit 1 Page 58

/

aiH:= 9.0 angstroms Approximate effective ionic radius of H*

ion in aqueous solotion aioH:= 3.5 angstroms Approximate effective ionic radius of OH- ion in aqueous solotion aiH2PO4:= 4.0 angstroms Approximate effective ionic radius of H2 PO4 - ion in aqueous solotion aiBIiO4:= 4.0 angstroms Approximate effective ionic radius of HP0 42 - ion in aqueous solotion aiP0 4:= 4.0 angstroms Approximate effective ionic radius of 3

P0 4 - ion in aqueous solotion GMI:= 75.22 grammole Moles of Iodine (I-) from HI GMCs:= 677.98 grammole' Moles of Cesium (Cs+)

GMci:= 465 grammole Moles of Chlorine (CI-) from HCI TID 120000000 rad Total Integrated Dose

AmerGen Attachment D Calc. C-1101-153-E410-040, Rev. 0 TMI Unit I Page 59 Assumption (1): Assume a solution ionic strength, I.

The individual activity coefficient,- yl, is

-gTi) (A.zi2.I05

-1g(i)=1 + (B..aii.5)]

or solved for yj equivalently, where zi is the charge of the ion being evaluated in this equation.

The activity coefficient of H*, YH' is:

Given: Calculation:

ziH:= I A = 0.5239333 B = 0.3318111 YH:= 12-11+Bi I = 0.078855 YH = 0.831722686 The activity coefficient of 0H-, YOH, is:

Given: Calculation:

ZiOH := -1 S[A (ýioH 2 A = 0.5239333 10.5]1 B = 0.3318111 I = 0.078855 YOH:= 10 YOH = 0.774559452 The activity coefficient of H 3 P0 4 , YH3PO4' is by definition unity since the molecule has no charge.

Given: Calculation:

ZiH3PO4 0 (no charge for a molecule) yH3PO4 := 1

AmerGen Attachment D CaIc. C-1101-153-E410-040, Rev. 0 TMI Unit I , Page 60 The activity coefficient of H 2 P04", YH2PO4, is Given: Calculation:

ZiH2P04 := -1 A= 0.5239333

[*

[ E= P14 )2 '.I]

• B = 0.3318111 YHP4=10 1 I( i2jPO4I.)]J I = 0.078855 YH2P04 = 0.781304132

" The activity coefficient of HPO4 2 -, yHPO4, is:

iiP0:= -2 Given: Calculation: [AE(*oi 2o*04 A= 0.5239333 B = 0.3318111 YI-P04 := 101 L1I+(BaiI-0 4 I')] J r = 0.078855 Y7po4 = 0.372632289 The activity coefficient of P0 4 -, YP04, is:

Given: Calculation:

z iP0 4 := -3 ) 210.]

A= 0.5239333 [A ('iP04 B =-0.3318111 1PO4" aiPo4 1'5)]

I = 0.078855 YPO4 = 0.108487847

AmerGen Attachment D Calc. C-1 101-1 53-E410-040, Rev. 0 TMI Unit 1 Page 61

• The ionic activity product constant of water, Kw, is:

Given: Calculation:

T =310.9277778 K 447O9 PKw:= 6.0875 + (0.01706)(T)

T pKw = 13.5964408

-pKw 101 Kw = 2.5325567 x 10-14

" The equilibrium quantity of H+ is:

Given: Calculation:

TH = 0.8317227 Solved equivalently for [H+],

YH [H[H] = 10"PH EQ11 := PI YH

'EQH = 3.8020818 x 10-8 '

Note that '[H+]' is denoted as 'EQH; in mathematical form, to represent the equilibrium concentration of the ion.

" The equilibrium quantity of OH- is:

Given: Calculation:

TH = 0.8317227 Solved equivalently for [OH-],

I/OH

= 0.7745595 Kw EQ1 1 3.8020818 x 1o8 EQo01 Kw= 2.5325567 x 16-14 YOH PH-]

• YH* [H+] Kw 6 EQOH 1.0339616 x 106 Note that '[OH']' is denoted as 'EQOH' in mathematical form, to represent the concentration of the ion.

AmerGen Attachment D, Calc. C-1'101-153-E410-040, Rev. 0 TMI Unit I Page 62 Assumption (2): Assume a TSP mass.

• The total mass of Boron in pounds is:

Given: Calculation:

MB PPmB (ppm)

MH20i=3.643118 x 106 lb 106 (ppm)

MB 1.0208017 x 10lb MWBOH3 MB.

MBOH3:=

MWB MBOH3 = 5.8386833 x 104

• The total final mass of water in pounds is:

Given: Calculation:

MH2i = 3.643118 x 10 lb N]

Of := MH2Oi + MTSP-MIOadd = 0 lb 390 12 fl, MWTSP = . +-MBOH3 + MH2O MTSP = 2.7100079 x 104 Ib MH2Of= 3.5997525 x 106 lb

• The total final volume of water in liters is:

Given: Calculation:

MH2Of= 3.5997525 x 10 Ib VH2O MH2Of lb Pw = 61.9959984 lb Pw"(l ft° VH2Of= 1.6441971 x 106liter Concentration of Boron in grammoles per liter is:

Given: Cal culation:

MB = 1.0208017 x 10r lb ( MB'Ib "* m*

Cot M'WB = 10.81 YVIUO fMWffB jib)

Co0 ICB = 0.2605105 graimmole VH2Of= 1.6441971 x 106 liter liter

AmerGen Attachment D Calc. C-1101-153-E410-040, Rev. 0 TMI Unit 1 Page 63 Concentration of Iodine in grammoles per liter is:

Given: Calculation:

VH2Of= 1.6441971 x 10 6liter GM-grammole VH20f Coney = 4.5748773 8 x 10-5 rml liter Concentration of Chlorine in grammoles per liter is:

Given: Calculation:

VH20f= 1.6441971 x 106 liter GMct1 grammole oncc:= VH2f Conccl = 2.82812813 x 10-4 olte liter Concentration of Cesium in grammoles per liter is:

Given: Calculation:

VH2Of.= 1.6441971 x 106 liter GM0 8 *grarnmole 0011008:= ,VH2Qf Conccs = 4.12347163 x 10-4 grammole liter 0Concentration of Nitric Acid in grammoles per liter is:

Given: Calculation:

6 VH2Of = 1.6441971 x 10 lie ConciO 3  :=7.3.10-6 grarnmole TID)

• TIiD= 1.2 x 1 rad liter 1.106 ConCNo3 := ConcN0O3 COneN03 = 8.76 x 1- 4 grammole liter Note that the units on G [7.3x1 0-6 grammole/liter] are actually incorrect [they should be grammole/(liter*MRad)] in the above equation since the radiation unit 'Rad' is not available in Mathcad. Therefore, it is left out of the equation. The correct values are computed, however.

AmerGen Attachment D Calc. C-1 101-153-E410-040, Rev. 0 TMI Unit I Page 64 Concentration of TSP in grammoles per liter is:

Given: Calculation:

VH2Of = 1.644197.1 x 10. liter MTSp.(lb).453 .59.(ýlb COcTSP VH2fMWTsP COncTSP = 0.0191638 grammole liter The dissociation constants of phosphoric acid are:

T = 310.9277778 K 583.01 pK 1 T 2.715 + (0.009801)(7)

S 27T pK1 2.2074688

- pK1 K1 := 10 K1 = 6.2019918 xxl0-pK 2 1.154 + (0.01368)(T) pK2 = 7.1927255

- pK2

)

K2 := 10 K2= 6.4161497 x 16- 8 pK3 := 12.36

- pK 3 K3 :=10 K 3 = 4.3651583 x 10--13

• The equilibrium quantity of phosphoric acid is:

'ConcT. r( liter EQH3PO4:=

. H K1 KI"K 2 KI_'__"3 1+ + +

EQH3PO4 = 1.4529489 x 16-8

AmerGen Attachment D Caic. C-1101-153-E410-040, Rev. 0 TMI Unit I Page 65 The equilibrium quantities of phosphoric acid species are:

Given: Calculation:

YH3P04 = 1 Solved equivalently for [H2 PO4-1, 7

H2P04 = 0.7813041 4 )

YH= 0.8317227 EQr 2P0 4 := K1 . EQ ,..ryPO 4 /

K, = 6.2019918 x 10-3 EM04 = 1.4529489 x 10-8 EQH2pO4 =3.6472153xx EQH = 3.8020818 x 108 YH2PO4 * [H2 PO 4 -]

• YH * [H+] I (YH3PO4 * [H3 PO4]) = K1 Note that '[H2P0 41 is denoted as 'EQH2P 0 4' in mathematical form, to represent the equilibrium concentration of the ion Given: Calculation:

P0 4 = 0.781.3041 2 Solved equivalently for [HP0 4 -,

YHyQ4 = 0.3726323 S=0.8317227 (H2Po4"EQH2PO4'2 K2 = 6.4161497 x 10 8 9Efy'P EQH2P 0 4 = 3.6472153 x 10-3 EQPO4 = 0.0155158 EQH=3.8020818 x 108 YHPO4 * [HPO 4 2 "]

• YH * [H+] I ('YH2PO4 * [H2 PO 4 "])= K2 Note that '[HP0 4 2 -], is denoted as 'EQHP04 in mathematical form, to represent the equilibrium concentration of the ion Given: Calculation:

Y-PO4 = 0.3726323 Solved equivalently for [P0 4 3 -1, YH = 0.8317227

.ypo4 = 0.1084878 EQp0 4 := ýK, 3 HYHPO4.EQPO4

/

K 3 = 4.3651583 x 10- 13 EQH =3.8020818 x 10 8 -8 EQP 04 7.3565624x 10-7 EQHPO4= 0.0155158 I (YHPO4 * [HP0 2 YPO4 * [PO43-]

• VH * [H*] 4 1) = K3 3

Note that '[P0 4 -' is denoted as 'EQP0 4 ' in mathematical form, to represent the equilibrium

AmerGen Attachment D Calc. C-1101-153-E410-040, Rev. 0 TMI Unit I Page 66 concentration of the Ion The TSP concentration based on the above quantities is:

MolahityTSP:= EQH3PO 4 + EQH2P 0 4 + EQHpO4 4 EQP0 4 MolalityTsp = 0.0191638

'MolalityS..( grarnmole") -~ C~

ErrorTSP :=CocTSP ErrorTsP = 0

AmerGen Attachment D Calc. C-1101-153-E410-040, Rev. 0 TMI Unit 1 Page 67 The molal equilibrium quotients of boric acid are:

Given:

T = 310.9277778 K I = 0.078855 Calculation:

1573.21 1 logQ1 1 + 28.6059 + 0.012078T- 13.2258 log(T) + (0.3250 - 0.00033T)I - 0.09121"5 T

logQl11 4.4691148 Qll := 10 1OgQ11 x 10 4 Q1 = 2.9452002 2756*1 logQ21 := 6. - 18.966 + 5.835-log(T)

T logQ21 = 4.4427847 Q2 := 10o~1gQ21 Q21= 2.7719454 x 104 logQ31:= 3339.5 - 8.084 + 1.497.log(T)

T logQ31 = 6.3879476 Q31 10logQ31 Q31 = 2.443136 x 106 12820.0 logQ42 =- 134.56 + 42.105.log(T)

T logQ42= 11.6248692 Q42:= 10o1°gQ42 Q42 = 4.2156949 x 10

AmerGen Attachment D Caic. C-1101-153-E410-040, Rev. 0 TMI Unit 1 Page 68 Assumption (3): Assume H3 BO 3 concentration.

EQBOH3 = 0.1942851!

• The equilibrium quantities of boric acid species are:

Given: Calculation:

Q1 = 2.9452002 x 104 Solved equivalently for [B(OH) 4 -1:

EQBOH3 = 0.1942851 EQBOH4i!- (Q11)(EQBOH3)(EQOH)

EQOH = 1.0339616 x 10 EQBOH4 = 5.9164159 x 10-3

• EQBOH4 i (EQBOH)EQOH Given: Calculation:

Q2, = 2.7719454 x le Solved equivalently for [B2 (OH)7-]:

EQOH =, 1.0339616 x 10- 6 EQ2H7 (Q2,)(EOH3)2 (EQOH)

EQBOH3 = 0.1942851 EQB2OH7 EQB2OH7 = 1.0818524 x 10

=Q21 (EQBOH3) 2 EQOH Given: Calculation:

Q3 1 = 2.443136 x 106 Solved equivalently for [B3 (OH)10 :

3 EQOH = 1.0339616 x 10-6 EQB30H10 (Q3 l)(EQBO) (EQOH)

EQBOH3 = 0.1942851 EQB301110 = 0.0185255 EQB3OH10O EQB30HI Q31 3

(EQBoH3) EQoH Given: Calculation:

Q4 2 = 4.2156949 x 1011 Solved equivalently for [B4(OH) 142-1:

EQOH = 1.0339616 x 10- 6 2 EQB4oH14 := (Q42)(EQBOH3)4 (EQoH)

AmerGen Attachment D Calc. C-1101-153-E410-040, Rev. 0 TMI Unit I Page 69 EQBOH3 = 0.1942851 x 10- 4 EQ4 0 oH14 = 6.4214904 2-(EQBo3)4 EQoH2

• The Boron concentration based on the above quantities Is:

MolalityBoron:= EQBOH3 + EQBoH4 + 2EQB2OH7 + 3 EQB3OH1O + 4 EQB4OH14 MolalityBoro.. 1 -- 0.2605104 granxole. liter

• The error due to Assumption (4) above is ErrorBEI~B-:lteMolalityBoron.( gmro1CI) COncB ConeB ErrorB 6.3312843 x 10-7 Therefore. Assumption (3) above Is verified.

• Na concentration Is:

Given: Calculation:

MolalityT 8 P = 0.0191638 COnCNa:= (3 + NNaOH).MolalityTSp NNaOH = 0.25 COnCNa 0.0622824 grammole liter Charge balance error, due to assumption (2) is:

Given:

Concentrations of I-, Cl-, Cs+, and NO3- need to be redefined without units for charge balance.

HI:= Con liter U 45748774 x 105 grammole Cs := Concs. grarmole liter Cs = 4.1234716 x 10-4 CIHC1 := Concc1" liter C1HC1 2.8281281 x I0- 4 grammole N03IINO3  := C~nCHNO3 liter N03HN03 8.76 x 10- 4 IN~03  := ConcN 03

• grammole COnCNa = 0.0622824 EQH.= 3.8020818 x 10 8

AmerGen Attachment D Calc. C-1101-153-E410-040, Rev. 0 TMI Unit 1 Page 70 EQOH= 1.0339616 x 10-6

-3\

10 EQ_2P 0 4 = 3.6472153 x EQHp 0 4 = 0.0155158.

EQpo4 = 7.3565624 x 10-7 3

EQBOH4 = 5.9164159 x 10, EQB2OH7 = 1.0818524 x 10-3 EQB3OH1O = 0.0185255 EQB4OH14 = 6.4214904 x 104 Calculation:

2 CBEB :=EQH - EQOH - EQBOH4 - EQB20H7 - EQB3OH1O - EQB4OH14 CBEB = -0.0268091 0

CBEP:= COnCNa - EQHpo 4 - 2.EQBPo 4 - 3.EQpo 4 + Cs - IMp- C HC1 - N03HN 0 3 CBEP = 0.0268091 CBE := F2. (CBEB + CBEP)

L (CBEB - CBEP)ii CBE = 7.9402646 x 10-7 Therefore, Assumption (2) above is verified.

The ionic strength of the solution is:

(C1.Z 12 + C2.Z 2 2+ +....+C 2) 2 2 2 ConcNa + EQH + EQoH + EQH2pO4 + 2 EQPOp 4 + 3 EQpo 4 + EQBOH4 + EQB2oH7 ...

+ EQB3H1O + 2 EQ 2 + Cs +I + 0 HC1+ NO3H 0 3 IS 2 Is= 0.078855 EMTor := -

AmerGen Attachment D Calc. C-1 101-153-E410-040, Rev. 0 TMI Unit 1 Page 71 Error = 4.1956195 x 1-7 Therefore.[ Assumption m I I above is verified.

(1)

AmerGen CALCULATION SHEET Subject, Calculation No. Rev. No. System Nos. Sheet RB Sump Post-LOCA pH and TSP Quantity C-1101-153-E410-040 0 214 72 of 75 Attachment E Reference Materials

1. E-mail from Robert Allison (ICL) to Stephen Eichfeld (S&L),

Subject:

TSPc bulk density, dated 5/2/200 ....... 73

2. Debye-Huckel Constants vs. Temperature ......................................... 75

/'\

AmerGen Calculation C- 1101-1 53-E410-040 TMI Unit 1 Rev 0 Page 73

<Stephen.Elchfeld@exeloncor To <jedr.c.penrose@sargentlundy.com>

p.com> cc <william.f.bartlng@sargentlundy.com>,

06/11/2007 08:51 AM <william.bartling@exeloncorp.com>

bcc Subject FW: TSPc bulk density

Jeri, Here is the email from ICL on the density of the bulk TSPc powder, and the latest basket drawing file. The drawing still lacks the total number of baskets, otherwise the drawing is done.

Steve 717-948-8125 (TMI)

Message -----

Original-----

From: Robert.Allison@icl-pplp.com [1]

Sent: Wednesday, May 02, 2007 5:04 PM To: Eichfeld, Stephen

Subject:

TSPc bulk density Stephen, According to our records, the sample you received was:

Product Trisodium Phosphate Dodecahydrate (TSPC) MED Accordingly, the bulk density would be:

TSPc powder = 0.82 g/cc, 51 lb/cu.ft.

Should you need any further information please call.

Thanks, Rob 908 832 0819 Confidentia lity Notice: This email is confidential, may be legally privileged, and is for the intended recipient only. Access, disclosure, copying, or distribution by or to unauthorized persons is prohibited and may be a criminal offense. Please delete if obtained in error and notify the sender of your receipt of this email.

AmerGen Calculation C-1 101-153-E410-040 TMI Unit 1 Rev 0 Page 74 This e-mail and any of its attachments may contain Exelon Corporation proprietary information, which is privileged, confidential, or subject to copyright belonging to the Exelon Corporation family of Companies.

This e-mail is intended solely for the use of the individual or entity to which it is addressed. If you are not the intended recipient of this e-mail, you are hereby notified that any dissemination, distribution, copying, or action taken in relation to the contents .of and attachments to this e-mail is strictly prohibited and may be unlawful. If you have received this e-mail in error, please notify the sender immediately and permanently delete the original and any copy of this e-mail and any printout.

Thank You.

1EI 53-02-011S2a.tif

AmerGen Calculation C-1101-153-E410-040 TMI Unit I Rev 0 Page 75 Debye-Huckel Constants 0.7 - V P

,-12 04 0.2 c0.

. hems2 1 .4Ed N 2S0 29 31 33 35E-0

7) 21ý x+3740 3900 2037 I

Temperature (deg K)

Enclosure 1 Description and Assessment Page 19 of 19 Attachment 3 AmerGen/Exelon Calculation C-1101-900-EOOO-087, Revision 2, "Post-LOCA EAB, LPZ, TSC, and CR Doses Using AST and RG 1.183 Requirements" (Electronic CD)

ENCLOSURE 2 TMI Unit 1 Technical Specification Change Request No. 337 Markup of Proposed Technical Specifications and Bases Page Changes Revised Technical.Specifications'& Bases Pages, 3-22 3-23 3-24 4-2b 4-7

.4-10 4-1 Oc

CONTROLLE COP 3.3 EMERGENCY CORE COOLING, REACTOR BUILDING EMERGENCY COOLING.

AND REACTOR BUILDING SPRAY SYSTEMS (Contd.)

b. CFT boron concentration shall not be less than 2,270 ppm boron.

Specification 3.3.2.1 applies.

c. The electrically operated discharge valves from the CFT will be assured open by administrative control and position indication lamps on the engineered safeguards status panel. Respective breakers for these valves shall be open and conspicuously marked. A one hour time clock is provided to open the valve and remove power to the valve. Specification 3.0.1i applies.

d. DELETED

e. CFT vent valves CF-V-3A and CF-V-3B shall be closed and the breakers to the CFT vent valve motor operators shall be tagged open, except when adjusting core flood tank level and/or pressure. Specification 3.0.1 applies.

3.3.1.3 Reactor Building Spray System and Reactor Building Emergency Cooling System The following components must be OPERABLE:

a. Two reactor building spray pumps and their associated spray nozzles headers and two reactor building emergency cooling fans and associated cooling units (one in each train). Specification 3.0.1 applies.

3.3.1.4 Cooling Water Systems - Specification 3.0.1 applies.

a. Two nuclear service closed cycle cooling water pumps must be OPERABLE.

b. Two nuclear service river water pumps must be OPERABLE.

c. Two decay heat closed cycle cooling water pumps must be OPERABLE.

d. Two decay heat river water pumps must be OPERABLE.

e. Two reactor building emergency cooling river water pumps must be OPERABLE.

3.3.1.5 Engineered Safeguards Valves and Interlocks Associated with the Systems in Specifications 3.3.1.1, 3.3.1.2, 3.3.1.3, 3.3.1.4 are OPERABLE. Specification 3.0.1 applies.

3-22 Amendment No. 33, 80, 98,4.1-, 4-74, 4,-, 244., 22,-

INSERT A - TS PAGE 3-22 The Reactor Building emergency sump pH control system shall be maintained with

> 18,815 lbs and < 28,840 lbs of trisodium phosphate dodecahydrate (TSP).

Specification 3.3.2.1 applies.

CONTRlOLL.ED COAPY 3.3 EMERGENCY CORE COOLING. REACTOR BUILDING EMERGENCY COOLING AND REACTOR BUILDING SPRAY SYSTEM[S (Contd.)

3.3.2 Maintenance or testing shall be allowed during reactor operation on any component(s) in the makeup and purification, decay heat, RB emergency cooling water, RB spray, BWST level instrumentation, or cooling water systems which will not remove more than one train of each system from service. Components shall not be removed from service so that the affected system train is inoperable for more than 72 consecutive hours. If the system is not restored to meet the requirements of Specification 3.3.1 within 72 hours8.333333e-4 days <br />0.02 hours <br />1.190476e-4 weeks <br />2.7396e-5 months <br />, the reactor shall be placed in a HOT SHUTDOWN condition within six hours.*

3.3.2.1 If e CFT boron concentration is outside of limits, r NO taN i outid t l1 rf

.3..3. or ny an IvIve n t N 1OH4ankdishgeine ar no oe oe r system to operable status within 72 hours8.333333e-4 days <br />0.02 hours <br />1.190476e-4 weeks <br />2.7396e-5 months <br />. If the system is not restored to meet the requirements of Specification 3.3.1 within 72 hours8.333333e-4 days <br />0.02 hours <br />1.190476e-4 weeks <br />2.7396e-5 months <br />, the reactor shall be placed in a HOT SHUTDOWN condition within six hours. 1`6 1- "'1i TSP0 A'ts Ao'_ coan l73ait 3.3.3 Exceptions to 3.3.2 shall be as follows:, ,sfec,';a, " 3. 3.1. 3,

a. Both CFTs shall be OPERABLE at all times.

b. Both the motor operated valves associated with the CFTs shall be fully open at all times.

c. One reactor building cooling fan and associated cooling unit shall be permitted to be out-of-service for seven days.

3.3.4 Prior to initiating maintenance on any of the components, the duplicate (redundant) component shall be verified to be .OPERABLE.

• In accordance with AmerGen License ChangeApplication dated February 14, 2001, and any requirements in the associated NRC Safety Evaluation, a portion of the Nuclear Service Water System piping between valves NR-V-3 and NR-V-5 may be removed from service and Nuclear Services River Water flow realigned through a portion of the Secondary Services River Water System piping for up to 14 days. This note is applicable for one time use during TMI Unit 1 Operating Cycle 13.

Bases The requirements of Specification 3.3.1 assure that, before the reactor can be made critical, adequate engineered safety features are operable. Two engineered safeguards makeup pumps, two decay heat removal pumps and two decay heat removal coolers (along with their respective cooling water systems components) are specified. However, only one of each is necessary to supply emergency coolant to the reactor in the event of a loss-of-coolant accident. Both CFTs are required because a single CFT has insufficient inventory to reflood the core for hot and cold line breaks (Reference 1).

The operability of the borated water storage tank (BWST) as part of the ECCS ensures that a sufficient supply of borated water is available for injection by the ECCS in the event of a LOCA (Reference 2).

The limits on BWST minimum volume and boron concentration ensure that 1) sufficient water is available within.containment to permit recirculation cooling flow to the core, and 2) the reactor will remain at least one percent subcritical following a Loss-of-Coolant Accident (LOCA).

The contained water volume limit of 350,000 gallons includes an allowance for water not usable because of tank discharge location and sump recirculation switchove set oint. Te li thi 0r*

3-213 Amendment No. 449, 45-7, 4-65, 4-7-, 28,-2-.9.i

CONTROLLED COPY 3.3 EMERGENCY CORE COOLING, REACTOR BUILDING EMERGENCY COOLING AND REACTOR BUILDING SPRAY SYSTEMS (Contd.)

Bases (Contd.)

en *.0 d1.ofhsotio s~rayd thictamntaer deignbas'a cidet.)

Vi.o1 .*irmiaesfheLotenti~l fdrcajqt ddma:e tbm~chinic lssters ard cmptn~s Redundant heaters maintain the borated water supply at a temperature greater than 409F.

Maintaining MUT pressure and level within the limits of Fig 3.3-1 ensures that MUT gas will not be drawn into the pumps for any design basis accident. Preventing gas entrainment of the pumps is not dependent upon operator actions after the event occurs.

The plant operating .limits (alarms and procedures) will include margins to account for instrument error.

The post-accident reactor building emergency cooling may be accomplished by three emergency cooling units, by two spray systems, or by a combination of one emergency cooling unit and one spray system. The specified requirements assure that the required post-accident components are available.

The iodine removal function of the reactor building spray system requires one spray pumprio ,+

~~6~~~6~~~7r ,

Asi ~

I'A'~~' &t5 loc&A d i-i AAc . 4eedor The spray system utilities common suction lines with the decay heat removal system. If a single train of equipment is removed from either system, the other train must be assured to be operable in each system.

When the reactor is critical, maintenance is allowed per Specification 3.3.2 and 3.3.3 provided requirements in Specification 3.3.4 are met which assure operability of the duplicate components. .The specified maintenance times are a maximum. Operability of the specified components shall be based on the satisfactory completion of surveillance and inservice testing and inspection required by Technical Specification 4.2 and 4.5.

The allowable maintenance period of up to 72 hours8.333333e-4 days <br />0.02 hours <br />1.190476e-4 weeks <br />2.7396e-5 months <br /> may be utilized if the operability of equipment redundant to that removed from service is verified based on the results of surveillance and inservice testing and inspection required by Technical Specification 4.2 and 4.5.

In the event that the need for emergency core cooling should occur, operation of one makeup pump, one decay heat removal pump, and both core flood tanks will protect the core. In the event of a reactor coolant system rupture their operation will limit the peak clad temperature to less than 2,200 *F and the metal-water reaction to that representing less than 1 percent of the clad.

Two nuclear service river water pumps and two nuclear service closed cycle cooling pumps are required for normal operation. The normal operating requirements are greater than the emergency requirements following a loss-of-coolant.

REFERENCES (1) UFSAR, Section 6.1 - "Emergency Core Cooling System" (2) UFSAR, Section 14.2.2.3 - "Large Break LOCA" 3-24 Amendment No. 89, 449, 1-57, 465, 47-.8, -2

INSERT B - TS PAGE 3-24 (Bases for Section 3.3)

The Reactor Building emergency sump pH control system ensures a sump pH between 7.3 and 8.0 during the recirculation phase of a postulated LOCA. A minimum pH level of 7.3 is required to reduce the potential for chloride induced stress corrosion cracking of austenitic stainless steel and assure the retention of elemental iodine in the recirculating fluid. A maximum pH value of 8.0 minimizes the formation of precipitates that may migrate to the emergency sump and minimizes post-LOCA hydrogen generation.

Trisodium phosphate dodecahydrate is used because of the high humidity that may be present in the Reactor Building during normal operation. This form is less likely to absorb large amounts of water from the atmosphere.

All TSP baskets are located outside of the secondary shield wall in the Reactor Building basement (El. 281'-0"). Therefore, the baskets are protected from the effects of credible internal missiles inside the shield wall. The designated TSP basket locations ensure that the baskets are not impacted by the effect of potential LOCA jet impingement forces and pipe whip.

CONTROLLED COPY Bases (Cont'd)

The equipment testing and system sampling frequencies specified in Tables 4.1-2, 4.1-3, and 4.1-5 are considered adequate to maintain the equipment and systems in a safe operational status.

REFERENCE (1) UFSAR, Section 7.1.2.3(d) - "Periodic Testing and Reliability" (2) NRC SER for BAW-10167A, Supplement 1, December 5, 1988.

(3) BAW-10167, May 1986.

(4) BAW-10167A, Supplement 3, February 1998.

C 4-2b Amendment No. 181,225,-2466

INSERT C - TS PAGE 4-2b (Bases for Section 4.1)

Reactor Building Emergency Sump PH Control System

Background

TSP baskets are placed on the floor (281 ft elevation) in the containment building to ensure that iodine, which may be dissolved in the recirculated primary cooling water following a Loss of Coolant Accident (LOCA), remains in solution. Recirculation of the water for core cooling and containment spray provides mixing to achieve a uniform pH.

TSP also helps inhibit Stress Corrosion Cracking (SCC) of austenitic stainless steel components in containment during the recirculation phase following an accident.

Fuel that is damaged during a LOCA will release iodine in several chemical forms to the reactor coolant and to the containment atmosphere. A portion of the iodine in the containment atmosphere is washed to the sump by containment sprays. The Borated Water Storage Tank water is borated for reactivity control. This borated water, if left untreated, would cause the sump solution to be acidic. In a low pH (acidic) solution, dissolved iodine will be converted to a volatile form. The volatile iodine will evolve out of solution intothe containment atmosphere, significantly increasing the levels of airborne iodine. The increased levels of airborne iodine in containment contribute to the radiological releases and increase the consequences from the accident due to containment atmosphere leakage.

After a LOCA, the components of the safety injection and containment spray systems will be exposed to high temperature borated water. Prolonged exposure to hot untreated sump water combined with stresses imposed on the components can cause SCC. The rate of SCC is a function of stress, oxygen and chloride concentrations, pH, temperature, and alloy composition of the components. High temperatures and low pH, which would be present after a LOCA, tend to promote SCC. This can lead to the failure of necessary safety systems or components.

TSP Quantity The quantity of TSP placed in containment is designed to adjust the pH of the sump water to be between 7.3 and 8.0 after a LOCA. The hydrated form (dodecahydrate) of TSP is used because of the high humidity in the containment building during normal operation. Since the TSP is hydrated, it is less likely to absorb large amounts of water from the humid atmosphere and will undergo less physical and chemical change than the anhydrous form of TSP. A pH > 7.3 is necessary to prevent significant amounts of iodine released from fuel failures and dissolved in the recirculation water from converting to a volatile form and evolving into the containment atmosphere. Higher levels of airborne iodine in containment may increase the release of radionuclides and the consequences of the accident. A pH > 7.3 is also necessary to prevent SCC of austenitic stainless steel components in containment. SCC increases the probability of failure of components. The pH needs to remain < 8.0 to minimize the formation of precipitates that may migrate to the emergency sump and minimize post-LOCA hydrogen generation. The minimum acceptable amount of TSP is that weight which will ensure a sump solution pH ? 7.3 after a LOCA, with the maximum amount of water at the minimum initial pH possible in the containment sump; a maximum acceptable

I, amount of TSP is that weight which will ensure a sump solution pH of < 8.0 with a minimum amount of water at a maximum initial pH.

The TSP is stored in wire mesh baskets placed inside the containment at the 281 ft elevation. Any quantity of TSP between 18,815 lb and 28,840 lb. will result in a pH in the desired range. If it is discovered that the TSP in the containment building is not within limits, action must be taken to restore the TSP to within limits. The Completion Time of 72 hours8.333333e-4 days <br />0.02 hours <br />1.190476e-4 weeks <br />2.7396e-5 months <br /> is allowed for restoring the TSP within limits, where possible, because 72 hours8.333333e-4 days <br />0.02 hours <br />1.190476e-4 weeks <br />2.7396e-5 months <br /> is the same time allowed for restoration of other ECCS components.

Surveillance Testing Periodic determination of the mass of TSP in containment must be performed due to the possibility of leaking valves and components in the containment building that could cause dissolution of the TSP during normal operation. A Refueling Frequency is required to determine that > 18,815 lbs and < 28,840 lbs are contained in the TSP baskets. This requirement ensures that there is an adequate mass of TSP to adjust the pH of the post LOCA sump solution to a value > 7.3 and < 8.0. The periodic verification is required every refueling outage. Operating experience has shown this Surveillance Frequency to be acceptable due to the margin in the mass of TSP placed in the containment building.

Periodic testing is performed to ensure the solubility and buffering ability of the TSP after exposure to the containment environment. Satisfactory completion of this test assures that the TSP in the baskets is "active." Adequate solubility is verified by submerging a representative sample, taken via a sample thief or similar instrument, of TSP from one of the baskets in containment in un-agitated borated water heated to a temperature representing post-LOCA conditions; the TSP must completely dissolve within a 4 hour4.62963e-5 days <br />0.00111 hours <br />6.613757e-6 weeks <br />1.522e-6 months <br /> period. The test time of 4 hours4.62963e-5 days <br />0.00111 hours <br />6.613757e-6 weeks <br />1.522e-6 months <br /> is to allow time for the dissolved TSP to naturally diffuse through the un-agitated test solution. Agitation of the test solution during the solubility verification is prohibited, since an adequate standard for the agitation intensity (other than no agitation) cannot be specified. The agitation due to flow and turbulence in the containment sump during recirculation would significantly decrease the time required for the TSP to dissolve. Adequate buffering capability is verified by a measured pH of the sample solution, following the solubility verification, between 7.3 and 8.0. The sample is cooled and thoroughly mixed prior to measuring pH. The quantity of the TSP sample, and quantity and boron concentration of the water are chosen to be representative of post-LOCA conditions. A sampling Frequency of every refueling outage is specified.

Operating experience has shown this Surveillance Frequency to be acceptable.

-I

TABLE 4.1-1 (Continued)

CHANNEL DESCRIPTION CHECK TEST CALIBRATE REMARKS

38. OTSG Full Range Level W NA R

39. Turbine Overspeed Trip NA R NA 4

.1 40. r s O

°"r I ffe/e 7 0

3 S

I) n 42. Diesel Generator NA NA R

-J Protective Relaying 7'

43. 4 KV ES Bus Undervoltage Relays (Diesel Start)

a. Degraded Grid NA M(1) A (1) Relay operation will be checked by

-4 local test pushbuttons.

b. Loss of Voltage NA M(1) R (1) Relay operation will be checked by local, test pushbuttons.

44. Reactor Coolant Pressure S(1) M R (1) When reactor coolant system is DH Valve Interlock Bistable pressurized above 300 psig or Tave is greater than 200 0 F.

45. Loss of Feedwater Reactor Trip S(1) S/A(1) R (1) When reactor power exceeds 7% i .

power.

46. Turbine Trip/Reactor Trip S(1) S/A(1) F (1) When reactor power exceeds 45%

power.

47. a. Pressurizer Code Safety Valve S(1) NA F (1) When Tare is greater than 5250F...

and PORV Tailpipe Flow Monitors

b. PORV - Acoustic/Flow NA M(1) R (1) When T.. is greater than 5250 F.

• 48. PORV Setpoints NA M(1) R (1) Per Specification 3.1.12 excluding valve operation.

TABLE 4.1-3 Cont'd Item Check Fremuency

4. Spent Fuel Pool Boron Concentration greater than Weekly Water Sample or equal to 600 ppmb I 4 5. Secondary Coolant Isotopic analysis for DOSE EQUIVALENT 1-131 concentration At least once per 72 hours8.333333e-4 days <br />0.02 hours <br />1.190476e-4 weeks <br />2.7396e-5 months <br /> when reactor coolant system pressure is greater than 300 psig or Tav is greater than 200 0 F.

6. Deleted z

7. Deleted I

8. Deleted

9. Deleted 10.

11. Deleted

12. Deleted

1. Until the specific activity of the primary coolant system is restored within its limits.

• Sample to be taken after a minimum of 2 EFPD and 20 days of POWER OPERATION have elapsed since the reactor was last subcritical for 48 hours5.555556e-4 days <br />0.0133 hours <br />7.936508e-5 weeks <br />1.8264e-5 months <br /> or longer.

• • Deleted

• Deleted I

TABLE 4.1-5 SYSTEM SURVEILLANCE REQUIREMENTS Item Test Frequency

1. Core Flood Tank a. Verify two core flood tanks S each contain 940 + 30 ft3 borated water.

b. Verify that two core flood tanks each contain 600 + 25 psig. S

c. Verify CF-V-1A&B are fully open. S.

d. Verify power is removed from CF-V-1A&B and CF-V-3A&B M valve operators Amendment No. 4-10c

INSERT D - TS PAGE 4-10c

2. Reactor Building a. Verify the TSP baskets R Emergency Sump contain > 18,815 lbs and pH Control < 28,840 lbs of TSP.

System

b. Verify that a sample from R the TSP baskets provides adequate pH adjustment of borated water.

ENCLOSURE 3 List of Commitments

Enclosure 3 List of Commitments Page 1 of 1

SUMMARY

OF AMERGEN COMMITMENTS The following table identifies regulatory commitments made-in this document by.AmerGen. (Any other actions discussed in the submittal represent intended or planned actions by AmerGen. They are described to the NRC for the NRC'S information and are not regulatory commitments.)

COMMITMENT TYPE COMMITMENT COMMITTED DATE ONE-TIME OR "OUTAGE" ACTION PROGRAMMATIC (Yes/No) (Yes/No)

Install TSP buffer modification Within 30 days of and isolate NaOH tank BS-T-2. approval of the TSP Yes No buffer license amendment request.

At least one manual valve in Within 30 days of each supply train will be locked approval of the TSP No Yes closed providing permanent buffer license isolation of the NaOH tank. amendment request.