ML100340284

NAI-1478-001, Revision 0, HNP CSAT Volume, Flow and Naoh Concentration Range Revisions

ML100340284
Person / Time
Site:	Harris
Issue date:	01/12/2010
From:	Harrell J Numerical Applications
To:	Office of Nuclear Reactor Regulation
References
HNP-10-006 NAI-1478-001, Rev 0
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Enclosure 2 to SERIAL: HNP-10-006 SHEARON HARRIS NUCLEAR POWER PLANT, UNIT NO. 1 DOCKET NO. 50-400/RENEWED LICENSE NO. NPF-63 APPLICATION FOR REVISION TO TECHNICAL SPECIFICATION CONTAINMENT SPRAY EDUCTOR FLOW RATES "HNP CSAT VOLUME, FLOW AND NaOH CONCENTRATION RANGE REVISIONS" Numerical Applications, Inc. Report Number NAI-1478-001 Revision 0 (Non-Proprietary)

(59 Pages)

HNP CSAT Volume, Flow and NaOH NAI-1478-001

• J APPLICATIONS.

NUMERICAL INC. Concentration Range Revisions Revision 0 1.LUTIONS 114 N~4GNRING ANOWFrWMG Page I of 59 Report Release Report Number: NAI- 1478-001 Revision Number: 0

Title:

HINP CSAT Volume, Flow and NaOH Concentration Range Revisions

Description:

The purpose of this report is to summarize the inputs, analyses and results associated with the proposed Harris Nuclear Plant Containment Spray Additive Tank (CSAT) maximum volume, eductor test flow range and sodium hydroxide concentration range revisions. The proposed maximum contained NaOH solution volume is 3768 gallons.

The proposed eductor test flow range is 17.2 gpm to 22.2 gpm. The proposed NaOH concentration range in the CSAT is 27 weight % to 29 weight %.

I- (-4 AMithor Date Jim Harrell ij - "--

Reviewer Date Sharon Thorne

(--I z - LO Project Manager Date Jim Harrell NAI Managerrgnt Dite Tom George

( NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-i478-001 APPLICATIONS. INC.

SOLUTIONS INCNGINO*RING AND90MNTARIE Concentration Range Revisions Revision 0 Page 2 of 59 Check items in the following lists to verify that project documentation and, engineering calculations that relate to this report are complete. It is the responsibility of the Report Author and Reviewer to confirm that the required Project documentationis completelto the extent, necessary to cover the release of this Report. The Report Author is responsible for archiving the report and the supporting documents.

Mark any items that. are not applicable with N/A notation.

Project Documentation-Checklist:,

d Project QA Requirements Fori.

C/ Project QAPlan.

Project OrgaizatioPa.

Y Project Work. Scope and Design Plan'.

• Project Calculation~and D'ocumentIndex including a listing for this report.

Project Engineer Training and Qualifi cation Forms for engineers involved wifh thils report.

Project QA Training Certification Forms for.engineers involved with, this :report,.

2/ Supporting documents reviewed and signed.

c, Report complies with relevant Purchase Ord'er. QA requirements-tReport and supporting documents to be archived by _ _ _ (not mote than -1 month fiom the final date on this Report).

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONMMDSO. NConcentration Range Revisions Revision 0 Page 3 of 59 Table of Contents

1. Purpose 5

2. Background and Introduction 5

3. Results 5

4. Proposed Technical Specification Revisions 7

5. pH Methodology .13 5.1 pH Calculations 13 5.2 Sump pH 19

6. Chemical Precipitate Methodology 21

7. Eductor Flow and Test Flow 22

8. Assumptions 22

9. Inputs 22 9.1 Common Inputs 23 9.2 Minimum Sump pH 26 9.3 Minimum Spray pH 43 9.4 Maximum Sump pH 46 9.5 Maximum Spray pH 55

10. References 58 List of Tables Table 1: Maximum and Minimum pH Results for HNP Cases ................................................. 8 Table 2: Chemical Precipitates with Proposed Revisions ........................................................ 12 Table 3: Eductor Flow Rate Proposed Technical Specification Test Values ........................... 12 Table 4: Param eters for log(Qx,y) equations .............................................................................. 16 Table 5: Param eter values for log (Q 4,2) ....................................................................................... 17 Table 6: W ater specific volum e ............................................................................................... 23 T able 7: W ater ion products .......................................................................................................... 24 Table 8: Debye-H tickel constants ............................................................................................ 25 Table 9: W ater Density for Palm er Equations ......................................................................... 26 Table 10: Gamma radiation signature and integrated energy releases ..................................... 27 Table 11: Beta radiation signature and integrated energy releases ........................................... 28 Table 12: Integrated containm ent air dose ................................................................................ 30

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. INC. Concentration Range Revisions Revision 0 Page 4 of 59 Table 13: Integrated containm ent sum p dose ........................................................................... 32 Table 14: Radioactive Cesium and Iodine ............................................................................... 35 Table 15: Integrated HI Added ................................................................ 36 Table 16: NaOH Molarity - Train A operating ................................... 37 Table 17: NaOH Molarity - Train B operating ................................... 38 Table 18: Maximum RCS inventory profile .................. 40 Table 19: Maximum RWST inventory profile - Train A ............................................................. 41 Table 20: Maximum RWST inventory profile - Train B ....................................................... 42 Table 21: Maximum Accumulator/SIT inventory profile ......................................................... 43 Table 22: Spray NaOH M olarity - Train A .............................................................................. 43 Table 23: Spray NaOH M olarity -Train B ............................................................................. 45 Table 24: Radioactive Cesium and Iodine ....... ......................................... 48 Table 25: Sump Volume .............................. ..................... 49 Table 26: Integrated CsOH Added ............... .......................  : ..................... 50 Table 27: NaO H M olarity ............. ........................................... ...................................... 51 Table 28: Maximum RCS inventory profile ............................................................................. 53 Table 29: Maximum RWST inventory profile ...................... .. ......................... 54 Table 30: Maximum Accumulator/SIT inventory profile.................................................... 55 Table 31: Spray N aOH M olarity - Train A .............................................................................. 55 Table 32: Spray N aOH M olarity - Train B .............................................................................. 57 List of Figures Figure 1: Minimum Sump and Spray A pH profile ................................. 9 Figure 2: Minimum Sump and Spray B pH profile .................................................................. 10 Figure 3: M aximum Sump and Spray pH profile ......................................................................... 11

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS.

ENGIRoNG INC. Concentration ConcentratioN Range Revisions Revision 0 Page 5 of 59

1. Purpose The purpose of this report is to summarize the inputs, analyses and results associated with the proposed Harris Nuclear Plant Containment Spray Additive Tank (CSAT) maximum volume, eductor test flow range and sodium hydroxide concentration range revisions. The proposed maximum contained NaOH solution volume is 3768 gallons. The proposed eductor test flow range is 17.2 gpmto 22.2 gpm. The proposed NaOH concentration range in the CSAT is 27 weight % to 29 weight %.

2. Background and Introduction Currently the Shearon Harris Unit 1Technical Specification Surveillance Requirements (Reference [10.22], Section 4.6.2.2.d) for the Containment Spray Additive System require that the eductor flow rate using the RWST as a test source be between 19.5 gpm and 20.5 gpm. This test range is very restrictive when uncertainties are considered. This test range is based in part on an historical requirement that the containment spray and sump pH both be greater than or equal 8.5 at the end of NaOH addition. Based on more recent data and regulatory documents (References [10.9], [10.13] and [10.20]), the historical pH requirement of 8.5 for the containment spray and sump is no longer applicable.

Additionally, the original pH analyses for Harris Nuclear Plant were performed utilizing boric acid equilibria data from a paper presented by R.E. Mesmer in 1971 (Reference [10.21]) which.

included minor errors. In order to correct the minor errors and to properly consider ionic strength dependence, the boric acid equilibria data of D.A. Palmer et. al. (Reference [10.2]) are utilized for the analyses supporting the proposed changes.

The currently applicable pH requirements for the Harris Nuclear Plant are based on prevention of iodine re-evolution, corrosion considerations and precipitate formation. These requirements dictate that the equilibrium containment sump pH be greater than 7 at the onset of the spray recirculation mode (Reference [10.20]) and that the maximum containment spray and sump pH profiles do not cause an increase in the mass of precipitates previously evaluated for Harris Nuclear Plant. The proposed eductor flow rate range (with the RWST as a test source), along with the other proposed changes, will assure these requirements are met.

3. Results The key pH results are documented in Table 1, Figure 1, Figure 2 and Figure 3. The results indicate that a CSAT concentration range of 27 wt.% to 29 wt.% NaOH with a CSAT volume range of 3268 gallons to 3768 gallons produces acceptable pH results. Acceptable pH results are defined as the containment sump minimum pH exceeding 7 by the time of recirculation to prevent iodine re-evolution and the containment sump and spray maximum pH profiles resulting in acceptable levels of precipitates as determined in Reference [10.19].

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS, INC. S;OF1VARE Sao.UONs INIENGJINEERING AND Concentration Range Revisions Revision 0 Page 6 of 59 Table 2 presents a comparison of the current licensing basis/tested precipitate amounts with those resulting from the proposed changes. The precipitate amounts resulting from the proposed changes are less than the currently analyzed/tested precipitate, amounts. Table 3 presents the new, test values for eductor flow. rates. These values are based on the proposed changes and result in acceptable pH values.

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS, INC. Concentration Range Revisions Revision 0 Page 7 of 59

4. Proposed Technical Specification Revisions The analyses discussed in this report consider and support the following Technical Specification revisions to Reference ,[10.22] (revisions are in bold and underlined):

CONTAINMENT SYSTEMS SPRAY ADDITIVE SYSTEM LIMITING CONDITION FOR OPERATION 3.6.2.2 The Spray Additive System shall be OPERABLE with:

a. A Spray Additive Tank containing between 27 and 29 weight % NaOH and a contained volume of between 3268 and 3768 gallons whi-h wi'l be en'sure ymaintaining

' an indicated lcvcl b*tweccn 90.7% and 93.9%, and

b. Two spray additive eductors each capable of adding NaOH solution from the chemical additive tank to a Containment Spray System pump flow.

APPLICABILITY: MODES 1, 2, 3, and 4.

ACTION:

With the Spray Additive System inoperable, 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 /> or be in at least HOT STANDBY within the next 6 hours6.944444e-5 days <br />0.00167 hours <br />9.920635e-6 weeks <br />2.283e-6 months <br />; restore the Spray Additive System to OPERABLE status within the next 48 hours5.555556e-4 days <br />0.0133 hours <br />7.936508e-5 weeks <br />1.8264e-5 months <br /> or be in COLD SHUTDOWN within the following 30 hours3.472222e-4 days <br />0.00833 hours <br />4.960317e-5 weeks <br />1.1415e-5 months <br />.

SURVEILLANCE REQUIREMENTS 4.6.2.2 The Spray Additive System shall be demonstrated OPERABLE:

a. At least once per 31 days by verifying that each valve (manual, power-operated, or automatic) in the flow path that is not locked, sealed, or otherwise secured in position, is in its correct position;

b. At least once per 6 months by:

1. Verifying the contained solution volume in the tank, and

2. Verifying the concentration of the NaOH solution by chemical analysis.

c. At least once per 18 months by verifying that each automatic valve in the flow path actuates to its correct position on a containment spray or containment isolation phase A test signal as applicable; and

d. At least once per 5 years by verifying each eductor flow rate is between 17.2 and 22.2 gpm, using the RWST as test source containing at least 436,000 gallons of water.

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS, INC. Concentration Range Revisions Revision 0 SMM-UIONS iNCNGING6CRIN ANDSOFWARe Page 8 of 59 Table 1: Maximum and Minimum pH Results for HNP Cases Time of Time of Maximum pH Maximum Case Recirc (sec) pH at Recirc (sec) pH Minimum Sump pH w/A train running 1973 7.146 17538 8.505 Spray A Minimum pH 1973 8.276 17538 9.107 Minimum Sump pH w/B train running 1973 7.196 17742 8.505 Spray B Minimum pH 1973 8.365 17742 9.077 Maximum Sump pH - 77F 1557 7.898 8237 9.420 Spray A Maximum pH -

77F 1557 9.014 8237 10.578 Spray B Maximum pH -

77F 1557 8.936 8237 10.433

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. INC. Concentration Range Revisions Revision 0 S*UIflONSINENGINCERING AID SOF"TWARE Page 9 of 59 Minimum Sump and Spray A 11 10 9

18 7

6 5

10 100 1000 10000 100000 Time (sec)

Figure 1: Minimum Sump and Spray A pH profile

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI- 1478-001 APPLICATIONS. INC.

Sa.UTOPJS PaCNGINERING SOlrWAR AND Concentration Range Revisions Revision 0 Page 10 of 59 Minimum Sump and Spray B 11 10 9

18 7

6 5

10 100 1000 10000 100000 Time (sec)

Figure 2: Minimum Sump and Spray B pH profile

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS, INC. Concentration Range Revisions Revision 0 NENGINEERING SOLUTiONS* ANDSOF"VARG Page 11 of 59 Maximum Sump and Spray 11 10 9

7 6

5 10 100 1000 10000 100000 Time (sec)

Figure 3: Maximum Sump and Spray pH proirde

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS, INC. Concentration Range Revisions Revision 0 S NS I NNCEPINGANOSOEFWV"D

ýoU Page 12 of 59 Table 2: Chemical Precipitates with Proposed Revisions Break Location NaS (kg) A1OOH (kg)

RCSdLoopibebrgs speces 107.40 (108.72) 0.00 (0.00)

RV nozzle (Microtherm the dominant 35.52 (35.53) 10.97 (11.33) dbris species)

PZR Safety Line (Min-K the 3 dominant debrig species) 33.80(33.81) 11.16(11.52)

Note: Current licensing/design basis and tested values in parentheses.

Table 3: Eductor Flow Rate Proposed Technical Specification Test Values Train A Train B Minimum test flow 17.2 gpm 17.2 gpm*

Maximum test flow 22.2 gpm 22.2 gpm The.Train B analysis actually supports a slightly lower value based on system configuration, but the more limiting Train A value is utilized.

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. INC. Concentration Range Revisions Revision 0 OSO AND SOUflONSINENGINEERING e RevisioAnR. 0 Page 13 of 59

5. pH Methodology 5.1 pH Calculations The hydrogen ion concentration ([H+]) in a solution is measured using the pH scale where:

pH = -log(H+. (1)

The concentration of hydrogen ions is based on the relative concentrations of acids and bases and other ions in the solution. For evaluating the post-LOCA sump pH the following chemical compounds are considered:

" Boron/Boric acid (B and B(OH) 3)

" Sodium Hydroxide (NaOH)

" Hydrochloric acid (HC1) 0* Nitric acid (HNO 3) 0 Hydriodic Acid. (HI)

• Cesium Hydroxide (CsOH)

The minor contributions%from any other acidic and basic species are assumed to offset and are negligible compared to the chemicals above. The boron/boric acid is introduced to the sump due to the borated water from the RCS, RWST, and accumulators which travels to the sump following a LOCA. In order to offset the effect of the boric acid, sodium hydroxide is added to the containment spray and then the sump to act as a buffer and raise the pH to 7.0. Hydrochloric acid is generated as a result of the irradiation of the cable insulation in containment and tends to reduce the sump pH. Nitric acid is formed due to the irradiation of water in the sump and also decreases the pH. Hydriodic acid is an iodine chemical form that may be released in containment after a LOCA. Cesium hydroxide is a cesium chemical form that may be released in containment after a LOCA. The relative concentration of these chemical species impacts the resulting sump pH.

The following sections provide the method for determining the pH of a solution with the chemical species identified above.

5.1.1 Conservation laws In order to determine the equilibrium conditions for a solution two general relationships are utilized. The law of conservation of charge and law(s) of conservation of mass can be combined into a single proton balance equation. This equation can be solved to determine [H+] and the resulting pH of the solution.

In general, a solution is macroscopically electro-neutral (law of conservation of charge). Thus, the sum of all cations and anions in the solution is zero. This relationship can be described mathematically for species A-, B2-, C+, and D 2' as:

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICTONE ,INC. Concentration Range Revisions Revision 0 Page 14 of 59

(- i)[A-]+ (-2)[B2- + (+1)[C+ + (+2)[D2+] 0 (2)

In a given solution, the mass of a single atomic species must also be conserved. For example, given an acid, HA, with a known stoichiometric concentration, C, the mass conservative law is written as:

[HA]+ [A-= C (3)

This equation conserves the quantity of [A- ] ions in the solution.

5.1.2 Equilibrium constants Many chemical species reach an equilibrium which takes the following form:

xX + yY + zZ +... :* aA + bB + cC +... (4)

For such chemical species, the mass action law specifies that a fixed relationship exists between the concentrations of the chemicals and their stoichiometric coefficients. This law can be written in equation form as:

K - [ B?[B][Cz (5) where K is defined as the equilibrium constant. For the example acid, HA, the equilibrium equation and mass action law can be written as:

HA <* H+ + A- (6)

_[H+IA-]

a [HA] (7) 5.1.3 Activity coefficients Direct use of the mass action law omits the impact of the interaction of solute particles on the equilibrium of the solution. To account for this interaction, an activity coefficient, y, is introduced which accounts for these effects on the equilibrium constant. The individual activity coefficients are based on the ionic strength of the solution, I, which is defined as:

I :lZz2C, (8) 2 where zi is the ionic charge and C, is the concentration of the ion.

The Debye-Htickel equation (p. 1.300 of Reference [10.5]) provides the activity for an ion of a specific valency (charge), z,, ionic radius, ai, and solution ionic strength, I, as:

J APPLICATIONS.

NUMERICAL SOCLrTJnS EN AN

• 'GINCEERIN

,=NO INC. HNP Concentration CSAT Volume, Range Revisions Flow and NaOH. -

Revision 0" NAI-1478-001 . ..

Page 15 of 59

_-AzZ,~fi log(r) 1+ BaZ i- (9)

These activity coefficients are included in the equilibrium equations which define the dissociation constants. For the example acid, HA , the dissociation constant from equation (7) is rewritten in the following manner:

Ka 7 HA[HA] (10) 5.1.4 Water speciation The equilibrium constant for water, K., is typically defined assuming the concentration of water is constant. Thus, the equilibrium equation and equilibrium constant can be defined as:

H 20 H+ + OH-K.w=[H+IoH-] .... .. (12)

As with other equilibrium constants, the value is dependent on temperature and ionic strength based on the activity coefficient. Thus, the equilibrium constant is rewritten as:

Kw =YH+H+ OH_[OH-1 (13) 5.1.5 Boron/boricacid speciation Using simple dissociation constants for boric acid from literature does not account' for polyborate species that typically form in borated water buffers. In order to determine the equilibrium concentrations of the boron species, equilibrium quotients from experimental data are utilized for this analysis. Reference [10.2] considers the formation of the following polymeric boric acid species: B(OH) 3 , B(OH)4, B2 (OH);, B3 (OH)7o, B 4 (OH)24. The general form of the equilibrium equation for the polymeric species formed by the boric acid is given below:

xB(OH) 3 +/-yOH Bx (OH )Y~-y 3 .. (14)

The molal equilibrium constant, Qx, is defined for the above equation as:

[Bx(OH)yZ(

[B(OH)3]X [OH-Y The equilibrium equation and molaliequilibrium quotients from Reference [10.2] are given below for each of the species considered. Additionally, the temperature and ionic strength dependent correlations for each of the equilibrium quotients are provided from Reference [10.2].

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. INC.

IN NEiNGERING S*0XUT!ONS AflO.OFIWAR Concentration Range Revisions Revision 0 Page 16 of 59 Species (1,1)

B(OH), + 0H_ B(OH)4 (16)

Q9 1-(OH)-*

(17)

=[B(OH) 31[OH-I log(Q,1]) p + + p 3 log(T) + (p 4 + p5 T)log(pw) - p 6 1 I p 8 12 log(pw)

T T 1- (1 + 2J exp(-2-i) 21 (18) where T is temperature in Kelvin, Pw is the density of water, I is the ionic strength, and PI-P8 are the parameters listed in Table 4.

Table 4: Parameters for log(Qx,y) equations.

Parameters Values p] -36.2605 P2 3645.18 P3 11.6402.

P4 16.4914 P5 -0.023917 p6 0.11902 P7 36.3613 Ps 0.72132 Species (2,1) 2B(OH) 3 + 0H- <= B2 (OH)7 (19)

[B 2(OH)7' Q21- [B(OH)3 ]2 [OH- (20) 1780.5 P4i log(Q 2 ,1 ) = -3.935 + + 0.95183 log(T) + p 61 + P7-I(fi) + P 812 log(pw) .(21)

T T Species (3,1)

NUMERICAL HNP CSAT Volume, F16W and NaOH NAI-1478-001 APPLICATIONS, INC. Concentration Range Revisions Revision.0 INENGINEERING 5]tMLrrWNS AND50G1WARC Page 17 of 59 3B(OH)3 +OH- 0H B3 (OH),o (22)

[B3 (OH)] [ 0I (23)

Q3,,

[B(oH)j3 0[H-3219.1 +P71(fi)+

log(Q 31 ) = -6.495 I+ý 39 T + 0.95186 log(T) + p 6I 81lg(. (24)

T Species (4,2) 4B(OH)3 + 20H- <* B 4 (OH)4 (25)

[B (O 4 1)"

(26) 2[B(OH) 3 4[oH-log(Q 4 2) =' -5.031 6001.3 IT + u3 1.3572 log(T) + u1I + U21T + u4TJ-T (27) where ul-u4 are the parameters described in Table 5.

Table 5: Parameter values for log (Q4,2).

Parameter Value ul 0.11830 u2 -0.0013078 u3 0.23298 u4 0.0021211 The mass balance for the boron is defined by the following equation:

CB = [B(OH)3 I + xQx,y [B(OH)3 ] [OH-] (28) where CB is the stoichiometric boron concentration in the solution. This equation can be rewritten for the boron species considered here as follows:

CB = [B(OH)3 ]+ Q,,, [B(OH)3 ][OH-]+ 2Q 2,,[B(OH)3 [OH-]

(29)

+ 3Q 3,1[B(OH)3f [OH- ]+ 4Q 4,2[B(OH)3 [OH-f r

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-00]

APPLICATIONS. INC. Concentrati6n Range Revisions Revision 0 Page 18 of 59 5.1.6 Sodium hydroxide and cesium hydroxide speciation Sodium Hydroxide (NaOH) is used to control the containment spray and sump pH. Sodium hydroxide is a strong base. The equation for the dissociation of sodium hydroxide in water may be written as follows: NaOH+ H20 z Na++ OH- + H0 Cesium hydroxide is created from fission product releases. Cesium hydroxide is a strong base.

The equation for the dissociation of cesium hydroxide in water may be written as follows:

CsOH+H 2 0 *Cs++OH-+H2 0 5.1.7 Hydrochloric,hydriodic and nitric acid speciation The impact of hydrochloric, hydriodic and nitric acid is also considered in this evaluation. For conservatism, these species are assumed to dissociate completely in the sump. This is equivalent to having a very small dissociation constant. Thus, the hydrochloric, hydriodic and nitric acid dissociate as follows:

HC!. HH + CI- (30)

HIr H+ + I-,  % (31)

HNO33... = H+ + N03 , *3 (32)

Thus, the mass balance equations for these acids are:

LCl-j= CHOl (33)

[LI= CHI, (34)

[No3 I-= CH 0 3 (35) where CHC1 CHI and CHN03 are the stoichiometric concentrations of hydrochloric, hydriodic and nitric acid, respectively.

5.1.8 EquilibriumpH determination Post-LOCA the containment sump contains a solution of the boric acid, sodium hydroxide, hydrochloric acid, hydriodic acid, nitric acid and cesium hydroxide. The pH of the sump is determined by balancing the charges of the individual species in the solution. By utilizing the equations developed above, [H- ].(and pH) can be determined. Generalizing equation (2) to consider the six chemical compounds in the sump, in addition to the hydrolization of water, gives the following equation:

[H'o[H

-[NO,-J [Cs+-[+/-(oL L [B2 (ao04 -[B (oH)10

]+[Na÷= 14 .0 (36) (6

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. INC. Concentration Range Revisions Revision 0 Page 19 of 59 The mass balance equations and equilibrium constants (with activity coefficients) calculated above can be substituted into equation (36)*to solve for [H+ ]. Due to the non-linearity of the boric acid speciation scheme and solution -ionic strength, this equation must be solved iteratively.

This process is completed using Microsoft Excel.

5.2 Sump pH.

As described in Section 5.1, the sump pH is calculated based on the relative concentrations of sodium hydroxide, boric acid, and other species contained in the sump. Note that the methods for determining minimum and maximum sump pH are identical; the inputs are simply biased in the appropriate direction to obtain the bounding results. The inputs for the minimum and maximum sump pH cases are given in Section 9. The followingdescribes the methodology for determining the pH for the Harris Nuclear Plant configuration..

5.2.1 Boron & water inventory In general, the methodology utilized allows for the use of time-dependent RCS, RWST, and Accumulator (or SIT) inventories in the sump. These inventories are time dependent based on assumptions regarding the vessel blowdown, number of ECCS pumps operating, etc. Boron concentrations for these sources are generally given in concentrations of parts-per-million (ppm).

The quantity of boron added to the sump from these sources is calculated based on the definition of concentration:

CBoron - MBoron.. (37) mBoron + mwaler Rearranging equation (37) gives:

C Boron m Boron - CBoron ) xm Waer (38)

The total boron and water inventory in the sump is determined and is used to determine boron concentrations for the pH and dissolution analyses.

5.2.2 Sump properties Sump properties including the boron concentration, temperature, volume, etc. impact the pH calculations. The sump boron concentration is calculated using equation (38) from above. A time-dependent sump temperature may be utilized and converted firom 'F to K for use in evaluating other chemical properties. This temperature conversion is given by:

0 ,:=

T[F]-32 T[K]=+ 273.15 (39)

. 1.8 The sump density is determined based on the sump temperature in. Reference [10.26]. The volume is calculated based on this density:

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. ,INC Concentration Range Revisions Revision 0 Page 20 of 59 m

m-(40)

P 5.2.3 Acid generation There are three additional sources beyond boric acid that can decrease the pH of the sump. The irradiation of cable insulation can generate hydrochloric acid which will affect the sump pH. In addition, irradiation of the sump water itself generates nitric acid which also decreases the pH.

Also, hydriodic acid is formed from reactions of the iodine released from post-LOCA fuel damage. To properly evaluate the pH of the sump, these sources must be considered in the pH analysis.

The amount of hydrochloric acid (HC1) produced by irradiation of electrical cable insulation is given in Section 2.2.5.2 of Reference [10.9] as 4.6E-4 g-mol HC1 / lbminsuiation-Mrad. The quantity of HC1 produced at any given time is given by the following equation:

Mi~1 -=4.6E -4 g-mol HGl M flation X (41) lbminsuation -7 Mrad Similarly, the nitric acid produced by irradiation of the sump water is given in Section,2.2.4 of Reference [ 10.9] as 7.3E-6 g-mol HN0 3 / L - Mrad. The quantity of nitric acid produced is given by the following equation:

MHNo 7.3E - 6 g - mol HN3XV M L - Mrad sump X Ysump (42)

The maximum potential amount of hydriodic acid is assessed based on the releases described in Reference [10.13].

5.2.4 Basic Fission Product Compounds Cesium hydroxide formed from reactions of the Cesium released from post-LOCA fuel damage can increase the pH of the sump. The maximum potential amount of cesium hydroxide is assessed based on the releases described in-Reference [10.13].

5.2.5 Basket/buffer dissolution Harris Nuclear Plant does notutilize trisodium phosphate, sodium tetraborate or any other dissolving solid for pH control, so dissolution is not applicable.

5.2.6 Species concentrations Using the water inventory calculated in Section 5.2.1, the concentrations of each of the chemical species in the sump is calculated according to the following equation:

NUMERICAL HNP CSAT Volume, Flow and NaOH . NAI-1478-001.

APPLICATIONS. INC. Concentration Range Revisions Revision 0 Page 21 of 59 MA (43)

[A]= MWA V.

Vsump where:

mA is the mass of species A MWA is the molecular mass of species A Vsump is the volume of the sump water These concentrations, are used to calculate the pH of the sump.

5.2.7 Activity coefficients.

Individual activity coefficients for the hydrogen ion and hydroxide ion are calculated using equation (9) from Section 5.1.3. Since this equation includes a term for ionic strength, an assumed value is used for this parameter which is verified at the end of the pH calculation.

Activity coefficients for the remaining species are either included in their respective solution methods (e.g., boric acid) or conservatively are assumed to be unity (e.g., sodium ion and nitric, acid ion).

5.2.8 EquilibriumpH determination The post-LOCA containment sump contains a solution of the boric acid, sodium hydroxide, hydrochloric acid, hydriodic acid, nitric acid and cesium hydroxide. The pH of the sump is calculated by balancing the charges on the individual ions as described in Section 5.1.8. This process is completed using Microsoft Excel.

6. Chemical Precipitate Methodology Westinghouse developed a methodology for predicting the species and quantities of chemical precipitates that could form in the post-accident containment environment by the reactions of the buffer agent (sodium hydroxide for HNP) with aluminum, insulation materials, and concrete.

This methodology is based on bench testing and is documented in Reference [10.23]. Along with this WCAP, Westinghouse developed an Excel spreadsheet for plants to predict the plant-specific chemical precipitates to use as an input into head-loss -testing for the replacement recirculation sump screens.

After appropriate benchmarking against Reference [10.24], 1-NP used this spreadsheet to predict the species and quantities of chemical precipitates that were used in the prototypical head-loss testing of the current sump screens. This testingis documented in Reference [10.25].

Based on the proposed HNP CSAT and eductor flow range changes, new pH profiles resulted for the containment sprays and sump. Any potential impact of the new pH profiles with respect to

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPU*ONS , INC. Concentration Range Revisions Revision 0 Page 22 of 59 chemical precipitates was assessed in Reference [10.19] using the methodology of Reference

,[10.23].

The new pH profiles resulting from the proposed HNP CSAT and eductor flow range changes were demonstrated to produce less than or equal to the chemical precipitate masses utilized in the testing documented in Reference [10.25].

7. Eductor Flow and Test Flow Reference [10.26] and Reference [10.27] determine the NaOH flow from the CSAT for pH determination and the RWST test flow through the eductor. NaOH flow from the CSAT is determined using eductor performance curves and system resistance. Conservative values are utilized for fluid properties, tank level/head and containment spray flow depending on whether minimum or maximum pH are being calculated. Once the minimum and maximum acceptable (with respect to pH criteria) NaOH flow rates are determined, those values are converted to RWST test flow values based on the RWST conditions, eductor performance curves and system resistance.

The minimum and maximum delivered concentration of NaOH are then input into the minimum and maximum pH calculations.

8. Assumptions The following section documents assumptions for the analysis.

8.1 All ionic species in the solution are assumed to be in equilibrium. Thus, the pH results at any given time are based on a steady-state analysis.

8.2 The individual activity coefficients are based on the Debye- Huickel theory which utilizes the effective ionic radius. The ionic radii utilized are provided at 25°C and the impact of temperature on the approximate ionic radii is assumed to be negligible.

8.3 The hydrochloric acid, hydriodic acid and nitric acid are assumed to fully dissociate in the sump.

8.4 The CSAT concentration range is 27 wt. % - 29 wt. %.

8.5 The CSAT maximum volume is 3768 gallons.

8.6 Although lithium hydroxide is used in the RCS for pH control, it was not credited in the minimum pH analyses nor modeled in the maximum pH analyses. A maximum sump sensitivity case with 5 ppm LiOH in the RCS indicated that the impact of LiOH on the maximum sump pH was small.

9. Inputs The following sections provide the development of inputs for determining the minimum and maximum sump pH.

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. INC. Concentration Range Revisions Revision 0 EýIERING ANDSOTWýARE SOLT1ONSNIN Page 23 of 59 9.1 Common Inputs The following section provides inputs that are common to both the minimum and maximum sump pH cases.

9.1.1 Water Density The temperature-dependent specific volume of water is taken from Appendix 24.A of Reference

[10.4] and is converted to density using the following relation:

_1*

V The table of specific volume is given as follows.

Table 6: Water specific volume Specific Temp. Volume (deg-F) (/ 3/Ibm) 40 0.01602 50 0.01602 60 0.01604 70 0.01605 80 0.01607 90 0.0161 100 0.01613 110 0.01617 120 0.01621 130 0.01625 140 0.01629

.150 0.01634 160 0.01639 170 0.01645 180 0.01651 190 0.01657 200 0.01663 210 0.0167 212 0.01672 220 0.01677 230 0.01685 240 0.01692 250 0.017 260 0.01708 270 0.01717 280 0.01726 290 0.01735 300 0.01745

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS, INC. Concentration Range Revisions Revision 0 Page 24 of 59 9.1.2 Water Ion Product The temperature-dependent ion product of water is from the equation given in Table 3.2 of Reference [10.10] which is as follows:

Slog(Kw ) _ 4470.99 T

_ 6.0875 + 0.01706T .

Note that the temperature, T, specified in the equation above is in units of Kelvin. This parameter is calculated for temperatures between 0°C and 150'C in 5°C increments. An additional data point for 148.88 0F (300*F) is also included.. The table generated using this equation is given as follows.

Table 7: Water ion products Temp.

(deg-C) -Iog(Kw) 0 14.941 5 14.732 10 14.533 15 14.345 20 14.165 25 13.995 30 13.833 35 13.679 40 13.532 45 13.393 50 13.261 55 13.136 60 13.016 65 12.903 70 12.796 75 12.694 80 12.598 85 12.506 90 12.420 95 12.338 100 12.260 105 12.187 110 12.118 115 12.053 120 11.992 125 11.934 130 11.880 135 11.830 140 11.783

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. INC. Concentration Range Revisions Revision 0 SMO.TON:TNENGINEERING AD SOF-TWARE Page 25 of 59 Temp..

(deg-C) -Iog(Kw) 145 11.738 148.88 11.706 150 11.697 9.1.3 Debye-Hiickel Constants The Debye-Hilckel constants that are used to calculate the activity coefficients are taken from Table 1.59 of Reference [10.5]. These parameters are given in the table below. Note that an additional point is added for 148.88°C (300'F) and the value of the constants are assumed to be the same as those at 100°C. This extra point is not utilized in the final, reported Harris Nuclear Plant pH analyses, but was utilized in sensitivity cases.

Table 8: Debye-Hfickel constants Temp.

(deg-C) A -B 0 0.4918 0.3248 5 0.4952 0.3256 10 0.4989 0.3264 15 0.5028 0.3273 20 0.507 0.3282 25 0.5115 0.3291 30 0.5161 0.3301 35 0.5211 0.3312 40 0.5262 0.3323 45 0.5317 0.3334

.50 0.5373 *0.3346

• 55 0.5432 0.3358 60 0.5494 0.3371

'65 0.5558 0;3384 70 0.5625 0.3397 75 0.5695 0.3411 80 0.5767 0.3426

85. 0.5842 0.3440 90 0.5920 0.3456 95 0.6001 0.3471 100 0.6086 0.3488 148.88 0.6086 0.3488

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. INC. Concentration Range Revisions Revision 0 SMtIUTONS ANDSO IN NGINEERING A Page 26 of 59 3

9.1.4 Water Density in gm/cm The water density is required in gm/cm 3 for solution. of the Palmer boric acid species equations.

This data is taken from Reference [10.1] as follows.

Table 9: Water Density for Palmer Equations Density of Water Temp Temp (deg Density (deg.C) K) (g/cm3) 0 273 0.9999 4 277 1.0000 20 293 0.9982 40 313 0.9922 60 333 0.9832 80 353 0.9718 100 373 0.9584 101 374 0.957662 103.00 376.15 0.956207 105.00 378.15 0.954733 107.00 380.15 0.95324 9.2 Minimum Sump pH For the minimum sump pH case, the current minimum volume and the new minimum sodium hydroxide concentration for the CSAT are considered (3268 gallons and 27 wt.% NaOH). This reduces the amount of base and decreases the pH. The maximum boric acid concentration is considered for the RCS, pressurizer, accumulators and RWST. This increases the amount of acid and decreases the pH. The maximum volume/mass of the RCS/pressurizer and RWST are also utilized to increase the amount of acid in the sump and decrease the pH. To minimize the pH, the generation of hydrochloric acid, nitric acid and hydriodic acid is considered in the minimum sump pH case. The generation of cesium hydroxide is conservatively not considered in the minimum sump pH case.

Only a single train of containment spray is credited to reduce NaOH addition, so the minimum sump pH calculation is completed twice, once for the A train of containment spray and once for the B train of containment

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS, INC. Concentration Range Revisions Revision 0 S0lUTKIWS ANMSOFIVARE INENGIWNEERING Page 27 of 59 9.2.1 ContainmentAir and Sump Water Dose In order to calculate the production of HCl -and HNO 3 in containment, the integrated doses must be calculated. Typical radiation release signatures for both gamma and beta radiation are given in Figures 1 and 2 of Reference [10.12], respectively. By integrating the area under each of these curves from the beginning of the event to 30 days post-LOCA, a time-dependent integrated dose fraction can be calculated for each time point. Table 10 gives the time, energy release rate, and integrated energy release for gamma radiation using the trapezoidal rule. For example, at time of 19 seconds, the integrated energy release is calculated as follows:

Ereease (Current Rate + PreviousRate) x (Current Time - PreviousTime) 2

+ PreviousEnergy Me Me VS-W+ 1.89E + 7 S-) *e Mee Ereease- 9.87E + 6 s-W s- (!..90E +IsI .80E Is)+ 8.90E+ y7e 2 W Erelease = 1.03E + 8 MeV W

Table 10: Gamma radiation signature and integrated energy releases Time Energy Release Rate Energy Release (sec) (MeV/secIW) (MeVIV) 1.80E+01 9.87E+06 8.90E+07 1.90E+01 1.89E+07 1.03E+08 4.61E+01 2.71E+08 4.04E+09 5.16E+01 3.36E+08 5.71E+09 5.59E+01 3.85E+08 7.23E+09 6.07E+01 4.30E+08 9.18E+09 9.53E+01 7.53E+08 2.97E+10 9.71E+01 7.60E+08 3.11E+10 1.88E+02 1.11E+09 1.16E+11 2.08E+02 1.09E+09 1.38E+11 4.65E+02 8.91E+08 3.93E+11 5.54E+02 8.59E+08 4.71E+11 9.30E+02 7.25E+08 7.69E+1 1 1.06E+03 7.02E+08 8.63E+ 11 1.86E+03 5.66E+08 1.37E+12

{NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478'001 APPLICATIONS. INC. Concentration Range Revisions Sa.UTONS[NENGINEERING ANDS*OF-1WAAE Revision 0 Page 28 of 59 Time Energy Release Rate Energy Release (sec) (MeV/sec/W) (MeV/W) 2.16E+03 5.41E+08 1.54E+12 3.39E+03 4.37E+08 . 2.14E+12 3.90E+03 4.06E+08 2.35E+12 4.71 E+03 3.56E+08 2.66E+12 5.23E+03 3.43E+08 2.84E+12 9.37E+03 2.37E+08 4.04E+12 1.09E+04 2.25E+08 4.40E+12 1.92E+04 1.64E+08 6.02E+12 2.08E+04 1.61E+08 6.28E+12 4.20E+04 1.15E+08 9.19E+12 4.48E+04 1.13E+08 9.51E+12 5.34E+04 1.07E+08 1.05E+13 8.14E+04 8.87E+07 1.32E+13 8.56E+04 8.81E+07 1.36E+13 1.02E+05 8.58E+07 1.50E+13 1.95E+05 7.31E+07 2.24E+13 2.02E+05 7.29E+07 2.29E+13 3.45E+05 6.91E+07 3.31E+13 3.48E+05 6.90E+07 3.32E+13 5.OOE+05 6.62E+07 4.35E+13 5.08E+05 6.61E+07 4.41E+13 8.37E+05 6.25E+07 6.52E+13 8.44E+05 6.25E+07 6.57E+13 1.96E+06 6.14E+07 1.35E+14 2.01E+06 6.14E+07 1.38E+14 2.59E+06 6.10E+07 1.73E+14 Table 11: Beta radiation signature and integrated energy releases Time Energy Release Rate Energy Release (sec) (MeV/sec/W) (MeV/W) 1.80E+01 9.36E+06 8.45E+07 1.90E+01 9.86E+06 9.38E+07 4.61E+01 1.75E+08 2.60E+09

'5 NUMERICAL HNP CSAT Volume, Flow and NaOH. NAI-1478-001 APPLICATIONS, INC. Concentration Range Revisions Revision 0 SOLI.TIONS SN ANDS*nARE ENGIINEERINS Page 29 of 59 Time Energy Release Rate Energy Release

,(sec). (MeV/sec/W) (MeV/W) 5.16E+01. 2.09E+08 3.66E+09 5.59E+01 .2.48E+08 4.63E+09 6.07E+01 2.92E+08 5.92E+09 9.53E+01 .. 5.41E+08 .. 2.04E+10 9.71E+01. . 5.54E+08 . 2.13E+10 1.88E+02 7.57E+08 - 8.09E+10 2.08E+02 8.02E+08 9.66E+10 4.65E+02 6.53E+08 2.83E+11 5.54E+02 6.OOE+08 3.39E+11 9.30E+02 4.90E+08 5.44E+11 1.06E+03 4.51 E+08 6.07E+11 1.86E+03 3.63E+08 9.30E+11 2.16E+03 3.29E+08 . 1.03E+12 3.39E+03 2.69E+08 1.40E+12 3.90E+03 2.44E+08 1.53E+12 4.71E+03 2.16E+08 .:1.72E+12 5.23E+03 1.99E+08 1.83E+12 9.37E+03 1.49E+08 2.55E+12 1.09E+04 1.30E+08 2.76E+12 1.92E+04 9.47E+07 3.70E+12 2.08E+04 8.79E+07 3.85E+12 4.20E+04 5.91 E+07 5.40E+12 4.48E+04 5.54E+07 5.56E+12 5.34E+04 5.10E+07 6.02E+12 8.14E+04 4.04E+07 7.30E+12 8.56E+04 3.89E+07 7.46E+12 1.02E+05 3.63E+07 8.09E+12 1.95E+05 2.85E+07. 1.11E+13 2.02E+05 2.80E+07 1.13E+13 3.45E+05 2.47E+07 1.51E+13 3.48E+05 2.46E+07 1.51E+13 5.OOE+05 2.28E+07 1.87E+13 5.08E+05 2.27E+07 1.89E+13

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS, INC. Concentration Range Revisions SOLMIONSU EflGNýEERING AMDSOp-*n Re Revision 0 Page 30 of 59 Time Energy Release Rate Energy Release (sec) (MeV/sec/W) (MeV/W) 8.37E+05 2.09E+07 2.61E+13 8.44E+05 2.09E+07 2.62E+13 1.96E+06 1.85E+07 4.82E+13 2.01E+06 1.84E+07 4.90E+13 2.59E+06 1.81E+07 5.97E+13 The tables above can be used to generate the general shape of the integrated dose for the containment air and sump. The total integrated dose at each time is divided by the 30 day integrated dose to obtain an integrated dose fraction. These fractions are multiplied by the Harris Nuclear Plant 30 day integrated doses for the containment air and sump from References [10.8]

and [10.18]. Conservatively, the containment sump integrated dose is assumed to be 9.03E06 rads gamma and 1.34E08 rads beta, which are the one month integrated accident dose in EQ zone C1 from Reference [10.8]. EQ zone Cl results in the highest one month accident integrated dose in the containment sump. Note that Attachment B of Reference [ 10.18] indicates that only 75.7% of the gamma dose in EQ zone ClIis to the sump. This reduction factor is not credited.

Conservatively, the containment air integrated dose is assumed to be 7.75E06 rads gamma and 1.34E08 rads beta, which are the one month integrated accident dose in EQ zone C2 from Reference [10.8]. EQ zone C2 results in the highest one month accident integrated dose outside of the sump in containment. Note that Attachment B of Reference [ 10.18] indicates that 55.9%

of the gamma dose in EQ zone C2 is to the sump and not the air. This reduction factor is not credited. An example of this calculation is completed below to obtain the integrated beta dose fraction to the containment air at 1.8E+l seconds..

8.45E + 07 Fbea --

5.97E + 13 x 1.34E + 8rad = 1.90E + 02rad This process is repeated for the sump and atmosphere beta and gamma doses. The total doses for the containment sump and containment atmosphere are added together and provided in the tables below.

Table 12: Integrated containment air dose Integrated Time Dose

• (sec) (Rads) 1.80E+01 1.94E+02 1.90E+01 2.15E+02 4.61E+01 6.02E+03 5.16E+01 8.47E+03 5.59E+01 1.07E+04

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS, -INC. Concentration Range Revisions SOCLITONS ANDSOTARqE iNENAIhNERINA Revision 0 Page 31 of 59 Integrated Time: Dose (sec) (Rads) 6.07E+01 1.37E+04 9.53E+01 4.71 E+04 9.71E+01 4.92E+04

• 1.88E+02 1.87E+05 2.08E+02 2.23E+05 4.65E+02 6.53E+05 5.54E+02 7.82E+05 9.30E+02 1.26E+06 1.06E+03 1.40E+06 1.86E+03 2.15E+06 2.16E+03 2.38E+06 3.39E+03 3.24E+06 3.90E+03 3.54E+06 4.71 E+03 3.98E+06 5.23E+03 4.23E+06 9.37E+03 5.90E+06 1.09E+04 6.39E+06 1.92E+04 8.57E+06 2.08E+04 8.92E+06 4.20E+04 1.25E+07 4.48E+04 1.29E+07 5.34E+04 1.40E+07 8.14E+04 1.70E+07 8.56E+04 1.74E+07 1.02E+05 1.88E+07 1.95E+05 2.59E+07 2.02E+05 2.64E+07.

3.45E+'05 3.54E+07 3.48E+05 3.54E+07 5.OOE+05 4.39E+07 5.08E+05 4.44E+07 8.37E+05 6.15E+07 8.44E+05 6.18E+07

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. INC.

SOq.LflIONS

• NENGINCERING ANOSOFnN/ARIE Concentration Range Revisions Revision 0 Page 32 of 59 Integrated Time Dose (sec) (Rads) 1.96E+06 1.14E+08 2.01E+06 1.16E+08 2.59E+06 1.42E+08 Table 13: Integrated containment sump dose Integrated Time Dose (sec) (Rads) 1.80E+01 1.94E+02 1.90E+01 2.16E+02 4.61E+01 6.05E+03 5.16E+01 8.51 E+03 5.59E+01 1.08E+04 6.07E+01 1.38E+04 9.53E+01 4.73E+04 9.71E+0i 4.94E+04 1:88E+02 1.88E+05 2.08E+02 2.24E+05 4.65E+02 6.56E+05 5.54E+02 7.85E+05 9.30E+02 1.26E+06 1.06E+03 1.41E+06 1.86E+03 2.16E+06 2.16E+03 2.39E+06 3.39E+03 3.25E+06 3.90E+03 3.56E+06 4.71 E+03 4.OOE+06 5.23E+03 4.26E+06 9.37E+03 5.93E+06 1.09E+04 6.42E+06 1.92E+04 8.62E+06 2.08E+04 8.97E+06 4.20E+04 1.26E+07

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. INC. Concentration Range Revisions Revision 0 AMDS N ENGINEERING SOLLrIONS rfTWARE Page 33 of 59 Integrated Time Dose (sec)- (Rads) 4.48E+04 1.30E+07 5.34E+04 1.41E+07

'8.14E+04 1.71E+07 8.56E+04 1.75E+07 1.02E+05 1.89E+07 1.95E+05 2.61E+07 2.02E+05 2.66E+07 3.45E+05 3.56E+07 3.48E+05 3.56E+07 5.OOE+05 4.42E+07 5.08E+05 4.47E+07 8.37E+05 6.20E+'07 8.44E+05 6.22E+',07 1.96E+06 1.15E+08 2.01 E+06 1.17E+08 2.59E+06 1.43E+08 9.2.2 Productionof Hydriodic Acid Iodine is released from the core as fuel failure occurs. Table 2of Reference [10.13] indicates that 5% of the core halogen inventory is discharged during the gap release phase while an additional 35% is discharged during the early in-vessel phase.

Consistent with Section 3.5 of Reference [10.1 3], the iodine exiting the reactor coolant system will be composed of 95% cesium iodide (CsI). This methodology will conservatively assume that all 5% of the remaining iodine release is in the form of HI in order to maximize the acid generation. This HI inventory is illustrated in the figure below.

NUMERICAL H[NP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. INC.

SOC*.O4 UN ANOSOFrTARE ENGINJEERING Concentration Range Revisions Revision 0 Page 34 of 59 Csl Cesium CsOH This release process is assumed to occur at a constant rate over the release period (i.e., 30 minutes and 1.3 hours3.472222e-5 days <br />8.333333e-4 hours <br />4.960317e-6 weeks <br />1.1415e-6 months <br /> for the gap and early in-vessel release phases, respectively). The core iodine inventory includes the stable 1127 species to maximize the amount of acid produced. The following equations describe this release.

d[I 0.05"0.05m, d 0.5V

• 0.05 h (Gap Release Phase) ti 0.05 *035m

[HI] = (Early In-Vessel Release Phase) dt VM .3h where:

m, = core iodine inventory (gram-mols), and Vpool= volume of the suppression pool (liters).

This release can be integrated considering the 1/2-hour PWR gap release duration to yield the following equations during the gap and in-vessel release periods.

[Ikt) - _ (, - tgap) (Gap Release Phase) 200

• Vsump 4[HI2t) 74.29.[t-(0.5-t

• V,,,,,p gap 4+

• mI 400 Vs,.mp, (Early In-Vessel Release Phase) where:

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. INC.

SO*{IJTrIONS INIENGINC*ENING AND,SOFIWfANE Concentration Range Revisions Revision 0 Page 35 of 59 t = time into accident (hrs), and.

tgap = onset of gap release (hrs).

For HNP, the iodine and cesium inventories are provided in Curies. in Table 2.0-1 of Reference

[ 10.10] for only the radioactive isotopes included in the source term. These values are converted to moles and grams using the following relationships.

10 n(atoms) =A _A(Ci) - 3.7 x10 (atoms/s/Ci) 0.693 n(atoms) n moles =

Avogadro'sNumber 6.02217E23 atoms/mole mass in grams = moles x-molar mass These relationships are implemented in the table below with half-life and molar mass information from Table A. I of Reference [ 10.17] and Reference [ 10.1 ], respectively Table 14: Radioactive Cesium and Iodine Ci Half-life (sec) Atoms Mol Grams 1-131 8.02E+07 6.947E+05 2.97E+24 4.94E+00 6.27E+02 1-132 1.16E+08 8.280E+03 5.13E+22 8.52E-02 1.08E+01 1-133 1.64E+08 7.488E+04 6.56E+23 1.09E+00 1.38E+02 1-134 1.80E+08 3.156E+03 3.03E+22 5.04E-02 6.39E+00 1-135 1.53E+08 2.380E+04 1.94E+23 3.23E-01 4.10E+01 Cs-134 1.53E+07 6.507E+07 5.32E+25 8.83E+01 ,1.17E+04 Cs-136 4.27E+06 1.132E+06 2.58E+23 4.28E-01 5.69E+01 Cs-137 9.17E+06 9.467E+08 4.64E+26 7.70E+02 1.02E+05 Using pages 18 through 20 of Attachment 4 of Reference [ 10.16], the grams of the stable isotopes 1127 and Cs' 33 are estimated *toconservatively include in the determination of CsOH and HI.

645/(1716-645) = 0.60,1 so the mass of the radioactive isotopes of Cesium will be increased by 60% to account for CS 33. Note that stable Cesium-133 is not included in the determination of minimum pH, as not including the stable isotope of Cesium increases the amount of HI.

29.83/(136.3-29.83) = 0.28, so the mass of the radioactive isotopes of iodine will be increased by 28% to account for 1127. Note that stable Iodine-127 is not included in the determination of maximum pH, as not including the stable isotope of Iodine increases the amount of CsOH.

For HI, the total moles of radioactive iodine are increased by 28% to account for stable 1-127 giving 1.82E+00 moles of 1-127 and 8.3 total moles of iodine.

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. INC. Concentration Range Revisions Revision 0 SMUTMIN ENGIHeAMflGMOSOFfA, Page 36 of 59 The table below presents the total HI added to the. sump as a function, of time based on the equations and data above.

Table 15: Integrated HI Added HI Time(sec) (gm-moles) 0 0.OOOOE+00

20. 0.OOOOE+00 30 0.0000E+00 50 2.3062E-04 100 8.0718E-04 200 1.9603E-03 300 3.1134E-03 400 4.2665E-03 500. 5.4196E-03 600, 6.5728E-03 650 7.1493E-03 700 7.7259E-03 800 8.8790E-03 900 1.0032E-02 1000 1.1185E-02 1100, 1.2338E-02 1200 1.3491E-02 1250 1.4068E-02 1300 1.4645E-02 1400 1.5798E-02 1500 1.6951E-02 1600 1.8104E-02 1973 2.5195E-02 2200 3.2242E-02 2400 3.8451E-02 2600 4.4660E-02 2800 5.0868E-02 3000 5.7077E-02 3500 7.2599E-02 4000 8.8121E-02 5000 1.1916E-01 6000 1.5021E-01 6480 1.6511E-01 9.2.3 NaOHMolarity The NaOH molarity is taken from Reference [10.26] depending upon which train of containment spray is assumed operating. The NaOH molarity is minimized by assuming the NaOH solution is at a maximum temperature of 104 'F (per input 4.5 of Reference [10.15]) and the CSAT NaOH

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS, INC. Concentration Range Revisions Revision 0 SDtIJTýONS ANDSOFARE INENGINt"RING Page 37 of 59 concentration is 27 wt.%. The values for NaOH-molarity from Reference [10.26] are given in the following tables.

Table 16: NaOH, Molarity - Train A operating NaOH Molarity In Sump Time Molarity (sec) 0.

0 0.0000 20 0.0004 30 0.0006 50 0.0009 100 0.0017 200 0.0028 "300 0.0036 400 0.0042

. 500 0.0046 600 0.0050 650 0.0052 700 0.0053 800 0.0056 900 0.0058 1000 0.0060 1100 0.0061 1200 0.0063

• 1250 0.0063 1300 0.0064 1400 0.0065 1500 0.0066 1600 0.0067 1973 0.0070 2200 0.0078 2400 0.0085 2600 0.0092

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS, INC. Concentration Range Revisions SOLUTiONS INENGIN*EERNG ANOSOFTAR1E Revision 0 Page 38 of 59 NaOH Molarity In Sump Time Molarity (sec) 2800 0.0099 3000 0.0106 3500 0.0123 4000 0.0141 5000 0.0176 6000 0.0211 7000 0.0246 8000 0.0281 10000 0.0350.

12000 0.0419-14000 0.0488 17538 0.0608 2.592E+06 0.0608*

• since the NaOH addition is complete at 17,538 seconds, there is no further increase in molarity after that point.

Table 17: NaOH Molarity - Train B operating NaOH Molarity In Sump Time Molarity (sec) ("

0 0.0000 20 0.0004 30 0.0006 50 .0.0010 100 0.0018 200 0.0031 300 . 0.0039 400 0.0046 500 0.0051 600 0.0055

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. INC. Concentration Range Revisions Revision 0 satnýoNs INCNGINECRING AMDSOFIVJARE Page 39 of 59 NaOH Molarity In Sump Time Molarity (sec) 650 0.0057 700 0.0058

.800 0.0061 900 0.0064 1000 0.0066 1100 0.0068 1200 0.0069 1250 0.0070 1300 0.0071 1400 0.0072 1500 0.0073 1600 0.0074 1973 0.0077 2200 0.0085 2400 0.0092 2600 0.0099 2800 0.0105 3000 0.0112 3500 0.0130 4000 0.0147 5000 0.0181 6000 0.0216 7000 .0.0250 8000 0.0284 10000 0.0352 12000 0.0419 14000 0.0486 17742 0.0609 2.592E+06 0.0609*

• since the NaOH addition is complete at 17,742 seconds, there is no further increase in molarity after that point.

( NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. INC.

S**UTO W NEGINERNG ANDSOFTWNARE Concentration Range Revisions Revision 0 Page 40 of 59 9.2.4 Water Inventory Boron Concentrations Maximizing boron concentrations in the RWST, RCS, pressurizer and accumulator water inventory requires that more NaOH be added to the sump and minimizes sump pH. The maximum boron concentrations are 2000 ppm boron for the RCS and pressurizer and 2600 ppm boron for the accumulators and 2600 ppm boron for the RWST per Reference [10.26].

CBoron, RCS, max = 2000 ppmi CBoron, RWST, max = 2600 ppm CBoron, accumulator,max = 2600 ppm.

9.2.5 Cable Insulation Mass The maximum cable insulation mass for Harris Nuclear Plant is assumed to be 20,000 Ibm based on Reference [10.14] giving a total of 17,350 ibm.

9.2.6 Sump Temperaturefor pH Based on a sensitivity study for the Harris Nuclear Plant minimum sump pH inputs, a higher sump temperature is conservative for the pH calculation. It should be noted that Reference

[ 10.26] maximizes the RCS, pressurizer and RWST liquid masses (by minimizing the temperature and maximizing the density), which consequently maximizes the associated boron masses; therefore, very conservative temperature biases are applied to the minimum sump pH cases. The temperature utilized for pH determination is 200 'F from Reference [ 10.26].

9.2.7 RCS Inventory in Sump The maximum RCS inventory (including pressurizer) is given as 424,480 ibm in Reference

[10.26]. Using the maximum inventory is conservative since it maximizes the mass of boric acid added to the sump from the RCS. This entire inventory is assumed to be deposited into the sump during the first second. This is accomplished using the following input table.

Table 18: Maximum RCS inventory profile Time Mass (sec) Im 0 0 1 424480 2.592E+06 424480 9.2.8 RWSTInventory in Sump The maximum RWST inventory delivered to the sump is given as 371,734 gallons from Reference [10.26]. The RWST temperature is assumed to be at the minimum value of 40 'F per Reference [10.26]. This inventory is added as per Reference [10.26] for the appropriate train.

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. INC. Revision 0 S*UlONS ANDS N ENGSWCNEERING ARE Concentration Range Revisions Page 41 of 59 This is accomplished using the following input tables for the A train and B train (note that the total injected RWST volume is conservatively higher than 3.71,734 gallons).

Table 19: Maximum RWST inventory profile - Train A RWST Inventory In Sump Time Mass (sec) (Ibm) 0 0 20 16180 30 32387 50 64897 100 146237 200 308696 300 470798 400 632429 500 793566 600 954223 650 1034375 700 1114410 800 1274126 900 1433401 1000 . 1592262 1100 1750794 1200 1909081 1250 1988129 1300 2067115 1400 2224896 1500 2382425 1600 2539714 1973 3134251 2.592E+06 3134251*

• corresponds to 372,569 total gallons

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. INC. Concentration Range Revisions N*ENGINCERtNG SOLJUTONS ANNSOFPNASSI Revision 0 Page 42 of 59 Table 20: Maximum RWST inventory profile - Train B RWST Inventorv In Sumn .

Time Mass (sec) (Ibm) 0 0

".20 16167 30 32360 50 64842 100 146115

• 200 308437 300 470405 400 631905 500 792915 600 953448 650 1033539

.700 1113514 800 1273112" 900 1432273 1000 1591022 1100 1749445 1200 1907625 1250 1986621 1300 2065554 1400 2223233 1500 2380661 1600 2537851 1973 3131968 2.592E+06 3131968**

• • corresponds to 372,569 total gallons

NUMERICAL HNP CSAT Volume, Flow and NaOH. NAI-1478-001 APPLICATIONS. INC.

Sr.llN,*INGr N *EERING AND 5OFPNA Concentration Range Revisions Revision 0 Page 43 of 59 9.2.9 Accumulator/SITInventory in Sump The accumulator/SIT mass is given as 197,871 lbms in Reference [10.26].This value is input using the following table.

Table 21: Maximum Accumulator/SIT inventory profile Time Mass (sec) (Ibm) 0 0 1 197871 2.592E+06 197871 9.3 Minimum Spray pH For the minimum spray pH cases, the following input changes are made to the minimum sump pH inputs described in Section 9.2.

• The addition of the RCS, pressurizer and accumulator inventory/mass was shifted to happen in the time step after recirculation began to prevent any effect of this inventory on the sprays prior to the sprays taking suction from the containment sump. The inventories remained the same. The boron concentration, therefore, remains at 2600 ppm until recirculation begins.

" The sump temperature at which pH is determined is changed to the maximum RWST temperature of 125 OF prior to recirculation, since the RWST is the source of the spray water.

The temperature remains at 200 °F after recirculation begins.

• The NaOH concentration/molarity is adjusted to the spray NaOH molarity from Reference

[ 10.26] for the appropriate train until the time the appropriate CSAT low level is reached and delivery of NaOH ends.

Table 22: Spray NaOH Molarity - Train A Time Molarity (sec) M 0 0.0000 20 0.0452 30 0.0451 50 0.0449 100 0.0450 200 0.0450

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. INC. Concentration Range Revisions Revision 0 Page 44 of 59 Time Molarity (sec) //

300 0.0452 400 0.0453 500 0.0454 600 0.0456 650 0.0456 700 0.0457 800 0.0458 900 0.0460 1000 0.0461 1100 0.0461 1200 0.0462 1250 0.0463 1300 0.0463 1400 0.0464 1500 0.0464 1600 0.0465 1973 0.0451 2200 0.0566 2400 0.0574 2600 0.0581 2800 0.0589 3000 0.0597 3500 0.0616 4000 0.0635 5000 0.0673

.6000 0.0711 7000 0.0749 8000 0.0787 10000 0.0862 12000 0.0937 14000. 0.1012 17538 0.1140

NUMERICAL HNP CSAT Volume, Flow and NaOH. NAI-1478-001 IýNAPPLICATIONS.

INC. Concentration Range Revisions Revision 0 Page 45 of 59 Table 23: Spray -NaOH Molarity - Train B "Time Molarity (sec) 0 0.0000 20 0.0499 30 0.0497 50 0.0496.

100 0.0496 200 0.0497

• 300 0.0499 400 0.0500 500 0.0502 600 0.0503-650 0.0504 700 0.0505 800 -0.0506 900 0.0507 1000 0.0509 1100 0.0510 1200 0.0510 1250 0.0511 1300 0.0511 1400 0.0512

• 1500 0.0513 1600 0.0513 1973. 0.0499 2200 0.0550 2400 0.0558 2600 0.0565 2800 0.0573 3000 0.0580 3500 0.0599 4000 " 0.0617 5000 0.0654

APPLICATIONS. INC. Concentration Range Revisions

{4 NUMERICAL ENGIRneRING HNP Cne CSAT Volume, tIONS oN FlowRevS and NaOH NAI-14785001 Revision 0 Page 46 of 59 Time Molarity (sec) M 6000 0.0691 7000 0.0728 8000 0.0765 10000 0.0838 12000 0.0910 14000 0.0981 17742 0.1110 The hydrochloric, hydriodic and nitric acid concentrations from the containment atmosphere and sump are set to 0 prior to recirculation since these acids do not exist in the RWST.

9.4 Maximum Sump pH For the maximum sump pH case, the new maximum volume and the new'maximum sodium hydroxide concentration for the CSAT are considered (3768 gallons and 29 wt.% NaOH). This increases the amount of base and increases the pH. The minimum boric acid concentration is considered for the RCS, pressurizer, accumulators and RWST. This'decreases the amount of acid and increases the pH. The minimum volume/mass of the RCS/pressurizer and RWST are also utilized to decrease the amount of acid in the sump and increase the pH. To maximize the pH, the generation of hydrochloric acid, nitric acid and hydriodic acid is not considered in the maximum sump pH case. The generation of cesium hydroxide is conservatively considered in the maximum sump pH case.

Both trains of containment spray are credited to increase NaOH addition, so the minimum sump pH calculation is completed once.

9.4.1 Productionof Cesium Hydroxide Cesium is released from the core as fuel failure occurs. Table 2 of Reference [10.13] indicates that 5% of the core alkali metal inventory (including cesium) is discharged during the gap release phase while an additional 25% is discharged during the early in-vessel phase. For iodine, Table 2 of Reference [10.13] indicates that 5% of the core halogen inventory is discharged during the gap release phase while an additional 35% is discharged during the early in-vessel phase.

Consistent with Section 3.5 of Reference [10.13], the iodine exiting the reactor coolant system will be composed of 95% cesium iodide (CsI). The cesium that is not in the chemical form of CsI is assumed to exit the RCS in the form of cesium hydroxide (CsOH) and be deposited into the containment sump. This CsOH inventory is illustrated in the following figure.

NUMERICAL H[NP CSAT Volume, Flow and NaOH. NAI-1478-001 APPLICATIONS. ,INC. .Concentration Range Revisions ' Revisi.on.0 INCNGIWIERING SOtUTIONS ANDSOFTWVAS Page 47 of 59 CsI Cesium HI Iodine CsOH This release process is assumed to occur at a constant rate over the release period (i.e., 30 minutes and 1.3 hours3.472222e-5 days <br />8.333333e-4 hours <br />4.960317e-6 weeks <br />1.1415e-6 months <br /> for the gap and early in-vessel release phases, respectively). The core Cesium inventory includes the stable Cs 133 species to maximize the amount of base produced..

The following equations describe this release. ...

d [CsOH] .5mc,- .95*.05mi (Gap Release Phase) dt V,,,

• 0.5 hr d-[CsOH] - 0.25mc, -0.95"0.35m 1 (Early In-Vessel Release Phase) dt . V,,mp 1.3 hr where:

mc, = core cesium inventory (gram-mols).

m1 = core iodine inventory (gram-mols).

Vsump = containment sump volume (liters)

This release can be integrated, considering the 1/2-hour PWR gap release duration to yield the following equations during the gap and in-vessel release periods.

Gap Release Phase:

[CsOHkt) O.lm* -0.095m 1 ,(t, -- gap)"

Vs.ump

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS, INC. Concentration Range Revisions Revision 0 SOCIUTJONS N ENGINEERING ANDOOFrWARE Page 48 of 59 Early In-Vessel Release Phase:

[CsOH] t) 0.1923 lmcs - 0.25577mi , - , +gp ]+

[-05ta 05mcs - 0.0475m, Vsump Vsump.

where:

t = time into accident (hrs), and tgap= onset of gap release (hrs).

For HNP, the iodine and cesium inventories are provided in Curies in Table 2.0-1 of Reference

[10.10] for only the radioactive isotopes included in the source term. These values are converted to moles and grams using the following relationships.

A A(Ci) 3.7 x 1010 (atoms/s/Ci)

A 0.693 n(atoms)=_ n moles -

Avogadro's Number 6.02217E23 atoms / mole mass in grams = moles x molar mass These relationships are implemented in the table below with half-life and molar mass information from Table A. 1 of Reference [10.17] and Reference [ 10.1 ], respectively.

Table 24: Radioactive Cesium and Iodine Ci Half4ife (sec) Atoms Mol Grams 1-131 8.02E+07 6.947E+05 2.97E+24 4.94E+00 6.27E+02 1-132 1.16E+08 8.280E+03 5.13E+22 8.52E-02 1.08E+01 1-133 1.64E+08 7.488E+04 6.56E+23 1.09E+00 1.38E+02 1-134 1.80E+08 3.156E+03 3.03E+22 5.04E-02 6.39E+00 1-135 1.5.3E+08 2.380E+04 1.94E+23 3.23E-01 4.10E+01 Cs-134 1.53E+07 6.507E+07 5.32E+25 8.83E+01 1.17E+04 Cs-136 4.27E+06 1.132E+06 2.58E+23 4.28E-01 5.69E+01 Cs-137 9.17E+06 9.467E+08 4.64E+26 7.70E+02 1.02E+05

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. INC. Concentration Range Revisions Revision 0 Page 49 of 59 Using pages 18 through 20 of Attachment 4 of Reference [10.16], the grams of the stable isotopes j127 and Cs133 are estimated to conservatively include in the determination of CsOH and HI.

645/(1716-645) = 0.60, so the massof the radioactiveisotopes of Cesium will be increased by 60% to account for Cs' 3 3. Note that stable Cesium-133 is not included in the determination of minimum pH, as not including the stable isotope of Cesium increases the amount of HI.

29.83/(136.3-29.83) = 0.28, so the mass of the radioactive isotopes of iodine will be increased by 28% to account for 1127. Note that stable Iodine-127 is not included in the determination of maximum pH, as not including the stable isotope of Iodine increases the amount of CsOH.

For CsOH, the total moles of radioactive cesium are increased by 60% to account for stable Cs-133 giving 5.15E+02 moles of Cs-133 and 1373.40 total moles of cesium.

The CSOH is added in terms of molarity, so the sump volume in liters must be determined. The sump voume in liters that was used for the conversion of the moles of CsOH to molarity is in the following table. Once the pH case is run, the resultant sump volume in liters must be ,compared to the the following table for reasonableness.

Table 25: Sump Volume Sump Volume Time(sec) (liters) 0 0 20 290076 30 297917 50 313715 100 353319 200 432413.

300 511293 400 589826 500 667987 600 745791 650 784565 700 823251 800 900363 900 977163 1000 1053682 1100 1130017 1200 1206264 1250 1244351

-1300 1282415 1350 1320455 1400 1358470 1500 1434430 1557 1477690 1650 1477690

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. INC. . Concentration Range Revisions Revision 0 U ElNGIWEERING SOC.TJONS ANDS ARC Page 50 of 59 Sump Volume Time(sec) (liters) 1660 1477690 1670 1477690 1680 1477690 1700 1477690 1800 1477690 2000 1477690 2500 1477690 3000 1477690 3500 1477690 4000 1477690 5000 1477690 6000 1477690 6480 1477690 The table below presents the CsOH added to the sump as a function of time based on the equations and data above.

Table 26: Integrated CsOH Added CsOH Time(sec) jM) 0 0.OOE+00 20 0.OOE+00 30 0.OOE+00 50 2.42E-06 100 7.52E-06 200 1.49E-05 300 2.01 E-05 400 2.38E-05 500 2.67E-05 600 2.90E-05 650 3.OOE-05 700 3.09E-05 800 3.25E-05 900 3.38E-05 1000 3.50E-05 1100 3.60E-05 1200 3.68E-05 1250 3.72E-05 1300 3.76E-05 1350 3.80E-05 1400 3.83E-05 1500 3.89E-05 1557 3.92E-05 1650 4.16E-05

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-601 APPLICATIONS. INC.

SOtLUTIONS ANDSc~fWAPNE INENGINEERING Concentration Range Revisions Revision 0 Page 51 of 59 CsOH Time(sec) (M) 1660.- 4.19E-05 1..'670 4.22E-05

,1680 4.24E-05 1700 4.29E-05 1800 4.55E-05 2000 5.47E-05 2500 7.93E 3000 .1.04E-04 3500 1.29E-04 4000 1.53E-04 5000 2.03E-04 6000 2.52E-04 6480 2.76E-04 9.4.2 NaOHMolarity The NaOH molarity is taken from Reference [ 10.26]. The NaOH molarity is maximized by assuming the NaOH solution is at a minimum temperature of 60 'F (per input 4.5 of Reference

[ 10.15]) and the CSAT NaOH concentration is 29 wt.%. The values for NaOH molarity from Reference [ 10.26] are given in the followingtables.'

Table 27: NaOH Molarity NaOH Molarity In Sump Time Molarity (sec) (Al) 0 -

• 0.0000 20 0.0011 30 0.0017.

50 .' 0.0027 100 0.0047 200 0.0078 300 0.0099 400 0.0115 500 . 0.0127 600 0.0136 650 0.0140 700 0.0144

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. INC. Concentration Range Revisions Revision 0 SOLtUL ANDSTý, ARE INENGUEERING Page 52 of 59 NaOH Molarity In Sump Time Molarity (sec) M 800 0.0151 900 0.0156 1000 0.0161 1100 0.0166 1200 0.0169 1250 0.0171 1300 0.0172 1350 0.0174 1400 0.0175 1500 0.0178 1557 0.0179 1650 0.0190 1660 0.0191 1670 0.0192 1680 0.0193 1700 0.0196 1800, 0.0207 2000 0.0229 2500 0.0286 3000 0.0342 3500 0.0398 4000 0.0454 5000 0.0565 6000 0.0677 7000 0.0787 8000 0.0898 8237 0.0924 2.592E+06 0.0924*

• since the NaOH addition is complete at 8,237 seconds, there is no further increase in molarity after that point.

NUMERICAL HNP CSAT Volume, Flow and NaOH. NAI-1478-001 APPLICATIONS, INC.

SO*f1,*ONS ANDS0T'PAM INENOINCERING Concentration Range Revisions Revision 0 Page 53 of 59 9.4.3 Water Inventory Boron Concentrations Minimizing boron concentrations in the RWST, RCS, pressurizer and accumulator water inventory requires that less NaOH be added to the sump and maximizes sump pH. The minimum boron concentrations are 15 ppm boron forthe RCS and pressurizer and 2400 ppm

'boron for the accumulators and 2400 ppm boron for the RWST from Reference [10.26].

CBoron, RCS, min 15 ppm CBoron, RWST, in = 2400 ppm CBoron, accumulator,mrin 2400 ppm 9.4.4 Sump TemperatureforpH Based on a sensitivity study for the Harris Nuclear Plant maximum sump pH inputs, a lower sump temperature is conservative for the pH calculation. It should be noted that Reference

[10.26] minimizes the RCS, pressurizer and RWST liquid masses (by maximizing the temperature and minimizing the density), which consequently minimizes the associated boron masses; therefore, very conservative temperature biases are applied to the maximum sump pH cases. The temperature utilized for pH determination is 77 °F,.which is much lower than the expected post-LOCA sump temperature, particularly for 8237 seconds (the time it takes to add all of the NaOH).

9.4.5 RCS Inventory in Sump The minimum RCS inventory (including pressurizer) is given as 416,768 lbm in Reference

[10.26]. Using the minimum inventory is conservative since it minimizes the mass of boric acid added to the sump from the RCS. This entire inventory is assumed to be deposited into the sump during the first 20 seconds. This is accomplished usingthe following input table.

Table 28: Maximum RCS inventory profile Time Mass (sec) (Ibm) 0 0 20 416768 2.592E+06 416768 9.4.6 RWST Inventory in Sump The minimum RWST inventory delivered to the sump is given as 313,195 gallons from Reference [10.26]. The RWST temperature is assumed to be at the maximum value of 125 'F per Reference [10.26]. This inventory is added as per Reference [10.26] for the appropriate' train. This is accomplished using the following input table.

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. INC. Concentration Range Revisions INENI*NaIRING SOIcUTK)N5 ANOS;OTflWARA* Revision 0 Page 54 of 59 Table 29: Maximum RWST inventory profile RWST Inventory In Sump Time Mass, (sec) .(Ibm) 0 0 20 17007 30 34080 50 68481 100 154719 200 326949 300 498710 400 669718 500 839915 600 1009336 650 1093765' 700 1178006 800 1345918 900 1513152 1000 1679773 1100 1845993 1200 2012023 1250 2094959 1300 2177843

.1350 2260676 1400 2343455 1500 2508859 1557 2603059*

2.592E+06 2603059

• corresponds to 313,816 total gallons, which is 0.2% higher than 313,195 gallons. This is based on minor rounding differences for properties and flows in Reference [10.26].

9.4.7 Accumulator/SIT Inventory in Sump The accumulator/SIT mass is given as 197,871 lbms in Reference [10.26].This value is input using the following table.

NUMERICAL HNP CSAT Volume, Flow and NaOH, NAI-1478-001 APPLICATIONS. INC. Concentration Range Revisions Revision 0 Page 55 of 59 Table 30: Maximum Accumulator/SIT inventory profile Time Mass (sec) (Ibm) 0 ___0 20 197871 2.592E+06 197871 9.4.8 Additional Maximum Sump pH casefor InitialpH The initial pH for the RCS, pressurizer and accumulator prior to any addition of RWST or CSAT water is determined .by running a single time step of the maximum sump pH case without the addition of NaOH or RWST water. This provides the event initiation/time 0 pH for use in precipitate determination.

9.5 Maximum Spray pH1 For the maximum spray pH cases, the following input changes are made to the maximum sump pH inputs described in Section 9.4.

" The addition of the RCS, pressurizer and accumulator inventory/mass was shifted to happen in the time step after recirculation began to prevent any effect of this inventory on the sprays prior to the sprays taking suction. from the containment sump. The inventories remained the same. The boron concentration, therefore, remains at 2400 ppm until recirculation begins.

" The NaOH concentration/molarity is adjusted to the spray NaOH molarity from Reference

[10.26] for the appropriate train until the appropriate CSAT low level is reached and delivery of NaOH ends.

Table 31: Spray NaOH Molarity - Train A Time Molarity (sec) (M) 0 0.0000 20 0.0733 30 0.0727 50 0.0722 100 0.0722 200 0.0723 300 0.0726 400 0.0729 500 1 0.0733

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS, INC. Concentration Range Revisions Revision 0 UN

.SO[.UTONS ENGINtERING SOFIW*ARn An*D Page 56 of 59 Time Molarity (sec) 600 0.0736 650 0.0737 I700 0.0739 800 0.0742 900 0.0745 1000 0.0747 1100 0.0748 1200 0.0748 1250 0.0749 1300 0.0749 1350 0.0749 1400 1 0.0750 1500 0.0750 1557 0.0750 1650 0.0934 1660 0.0935 1670 0.0936 1680 0.0938 1700 0.0940 1800 0.0953 2000 0.0978 2500 0.1040 3000 0.1103 3500 0.1165 4000 0.1228 5000 0.1352 6000 0.1475 7000 0.1597 8000 0.1717 8237 0.1745

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS. INC. Concentration Range Revisions Revision 0 Page 57 of 59 Table 32: Spray NaoH Molarity - Train B

• Time Molarity (sec) M 0 0.0000 20 0.0682 30 0.0676 50 0.0671 100 0.0672 200 0.0673 300 0.0676 400 0.0679 500 0.0682 600 0.0685 650 0.0687

,700 0.0688 800 0.0692 900 0.0694 1000 0.0697 1100 0.0697 1200 0.0698 1250 0.0698 1300 0.0699 1350 0.0699 1400 0.0700 1500 0.0701 1557 0.0701 1650 0.0841 1660 0.0843 1670 0.0844 1680 0.0845 1700 0.0848 1800 0.0861 2000 0.0886 2500 0.0950

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPWCATIONS..

SIM. -INC" Concentration Range Revisions Revision 0 Page 58 of 59 Time Molarity (sec) N 3000 0.1014 3500 0.1078 4000 0.1141 5000 0.1268 6000 0.1395 7000 0.1520 8000 0.1645 8237 0.1674 The cesium hydroxide concentrations/molarities from the containment atmosphere and sump are set to 0 prior to recirculation since they do not exist in the RWST.

10. References 10.1 CRC Handbook of Chemistry and Physics, 84' h-Ed.

10.2 D. A. Palmer, P. Benezath, D. J. Wesolowski, "Boric Acid Hydrolysis: A New Look at the Available Data," PowerPlant Chemistry, 2(5), 261-4 (2000).,;

10.3 Butler, James Newton, and David R. Cogley, "Ionic Equilibrium: Solubility and pH Calculations", 2 nd Ed.

10.4 Lindeburg, Michael R., Mechanical Engineering Reference Manual for the PE Exam, 12th Ed.

10.5 Speight, James G., "Lange's Handbook of Chemistry," 1 6 th Ed.

10.6 Faust, S. D. and 0. M. Aly, "Chemistry of Natural Waters," 1981.

10.7 De Levie, Robert, "How to Use Excel in Analytical Chemistry and in General Scientific Data Analysis," Cambridge University Press, 2004.

10.8 DBD-1000-V02, "Harris Nuclear Plant Environmental Qualification Design Basis Document," Revision 1.

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

10.10 Pankow, James F., "Aquatic Chemistry Concepts," 1991.

10.11 Westinghouse Electric Company Calculation CN-REA 13, "Shearon Harris Sources for Alternative Source Term Methodology Dose Evaluations," Revision 0.

10.12 NUREG/CR- 1237, "Best-Estimate LOCA (Loss-of-Coolant-Accident) Radiation Signature,"

June 1980.

NUMERICAL HNP CSAT Volume, Flow and NaOH NAI-1478-001 APPLICATIONS* INC. Concentration Range Revisions Revision 0 Page 59 of 59 10.13 USNRC, Regulatory Guide 1.183, "Alternative Radiological Source Terms for Evaluating Design Basis Accidents at Nuclear Power Plants", July 2000.

10.14 Shearon Harris Nuclear Power Plant FSAR, Table 6.1.2.-2 Amendment No. 48.

10.15 Carolina Power & Light Company Calculation HNP-I/INST-1037, "Containment Spray Additive Tank - Instrument Loops: L-7150; L-7166," Revision 3.

10.16 Numerical Applications Calculation NAI-1421-001, Rev. 4, "St. Lucie Units 1 & 2 EPU Source Term for AST Dose Calculations".

10.17 Federal Guidance Report No. 12, "External Exposure to Radionuclides in Air, Water, and Soil", September 1993.

10.18 Carolina Power & Light Company Calculation 3-C-03-049, "Integrated Doses for E-Q,"

Revision 5.

10.19 Nuclear Generation Group Calculation SD-0027, "Chemical Model Benchmarking,"

Revision 1.

10.20 NUREG-0800, "U.S. Nuclear Regulatory Commission Standard Review Plan, Section 6.5.2, Containment Spray as a Fission Product Cleanup System," Revision 4 dated March 2007.

10.21 R.E. Mesmer, C.F. Baes, Jr. and F.H. Sweeton, "Boric Acid Equilibria and pH in PWR Coolants, Thirty-Second International Water Conference Proceedings, Novemb6r 3, 1971, Pittsburgh, PA.

10.22 Technical Specifications for Shearon Harris Unit 1, NPF-63 through Amendment 129.

10.23 WCAP- 16530-NP, "Evaluation of Post-Accident Chemical Effects in Containment Sump Fluids to Support GSI-191," Revision 0.

10.24 Westinghouse Calculation Note CN-SEE-I-08-7, "Progress Energy Benchmark Package for Chemical Model and LOCA Deposition Model Spreadsheets,"Revision 0 (Proprietary).

10.25 SD-0026, "HNP GSI-191 Recirculation Sump Screen Debris Bed Head Loss," Revision 2.

10.26 Nuclear Generation Grooup Calculation 14.06.000-021, "pH Transient in the Sump and Containment Spray," Revision 6.

10.27 Calculation CT-0027, "Detail Calculation on NaOH Eductor Loop," Revision 9.