ML082480679
| ML082480679 | |
| Person / Time | |
|---|---|
| Site: | Calvert Cliffs  |
| Issue date: | 08/27/2008 |
| From: | Calvert Cliffs, Constellation Energy Group, Constellation Generation Group, MPR Associates |
| To: | Office of Nuclear Reactor Regulation |
| Shared Package | |
| ML082480669 | List: |
| References | |
| 0090-0148-01, 0090-0807-0148-01, GL-04-002 | |
| Download: ML082480679 (76) | |
Text
Calvert Cliffs Nuclear Power Plant, Inc.
August 27, 2008 ATTACHMENT (3)
MASS OF SODIUM TETRABORATE DECAHYDRATE BUFFER REQUIRED FOR POST-LOCA CONTAINMENT BUILDING SUMP pH CONTROL
Tom King July- 18-2008 Jim Hibbard July- 18-2008 Tom King August-4-2008 MMPR MPR Associates, Inc.
320 King Street Alexandria, VA 2231 4 CALCULATION TITLE PAGE MPR-QA Form QA-3.1-1, Rev. 1 Client: Constellation Energy Power Generation Group Project: CCNPP EQ Analyses and Buffer Quantity Calculation Title: Mass of Sodium Tetraborate Decahydrate Buffer Required for Post LOCA Containment Building Sump pH Control Page 1 of 36 + Appendices A-G (75 Total Pages) Task No. 0090-0807-0148-01 Calculation No. 0090-0148-01 Preparer / Date Manvan Charrouf July- 18-2008 Marwan Charrouf August-4-2008 Marwan Charrouf August-1 8-2008 4 Jim Hibbard QUALITY ASSURANCE DOCUMENT This document has been prepared, checked, and reviewed/approved in accordance with the Quality Assurance requirements of lOCFR5O Appendix B, as specified in the MPR Quality Assurance Manual.
Reviewer & Approver / Date Jim Hibbard August-4-2008 Jim Hibbard August- 18-2008 Checker / Date Tom King August-1 8-2008
- t. Rev. No.
MPR QA Form QA-3.1-2, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 RECORD OF REVISIONS Calculation No. level of the calculation in effect at the time that page was last revised. Prepared By Revision - 0 1 0090-0148-01 Affected Pages All All Note: The revision Description
/ Initial Issue Summary of Changes from Revision 0: Revised Section 1.0 to incorporate new scope. Revised Section 3.0 to discuss new results. Changed Input 14 equilibrium quotients. Revised Section 7.1 to use option I reaction scheme. Revised Sections 7.2,7.3, and 7.4 to define limiting cases. Revised Sections 7.5.1 to 7.5.3 to describe option I balance equations. Revised Section 7.5.6 to modify validation results. Revised Sections 8.1 and 8.2. Added Section 8.3 to calculate required buffer mass and pH for new limiting cases. Added Section 8.4 for pH as a function of time. Added new references in Section 9.0. Revisedgrouped Appendices B and C to incorporate several temperatures.
Added new Appendices C, D, E, F, & G. General revisions to incorporate comments provided by CCNPP. number found on each individual page of the calculation carries the revision Checked By r 4 6- Page: 2 MPR QA Form QA-3.1-2, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 RECORD OF REVISIONS Page: 3 Calculation No. 0090-0148-01 k:ar&> / J. Description
/ Summary of Changes from Revision 1: Changed label of ionic product constant of water 'K,' in Input 5. Inserted two new temperature points for water density evaluation in Input 7. Removed last three rows. Inserted appropriate units for borated water density expression in Input 8. Changed the temperature values in Inputs 27 and 28.
Removed "and Pressurizer water" from first paragraph of Section 7.2.
Changed rninimum/maximum temperatures for RCS and Pressurizer in Table 7-1. Corrected borated water density units on page 20. Updated the following calculations in Sections 7.3,7.4, 8.1, 8.2, 8.3, 8.4 and Appendices B, C & D. Updated titlelsignatures page for Revision 3. Updated this page to indicate changes from Revision 2. Updated Table of Contents (Appendix F title). Updated Summary of Results section. Changed RCS coolant maximum Boron concentration from 2300 to 2700 ppm (Input 18).
This increase will make the determination of the quantity of NaTB bounding for Operational Modes 1 to 4. Updated Table 7-1 for RCS/Pressurizer maximum Boron concentration. Calculation updates to maximum Boron in water cases. Calculation updates to mass of buffer and resultant concentrations.
Updated Table 8-2 for pH as a function of time. Updated calculations. Updated title. number found on each individual page of the calculation carries the revision Revision 2 3 level of the calculation in effect at the time that page was last revised. Affected Pages All 1,3,5 6'7 15 19 20 - 25 29 - 31 33 Appendices B & C F- 1 Note: The revision MPR QA Form: QA-3.1-3, Rev . 0 MMPR MPR Associates.
Inc . 320 King Street Alexandria.
VA 22314 Calculation No . 0090-0 148-01
/ Table of Contents 1.0 Purpose .................................................................................................................
6 2.0 Acceptance Criteria
..............................................................................................
6 3.0 Summary of Results .............................................................................................
6 4.0 Background
...........................................................................................................
7 4.1 General Review of Sodium Tetraborate Decahydrate Qualities
...................................
8 5.0 Assumptions
.........................................................................................................
9 6.0 Input
.....................................................................................................................
10 7.0 Methodology
.......................................................................................................
16 7.1 Boric Acid and Borax Equilibria
................................................................................
17 7.2 Containment Sump Water Mass
..........................................................................
18 7.3 Containment Sump Boron and Boric Acid Concentrations
........................................
22 7.4 Acids Produced by Radiolysis
....................................................................................
25 7.5 System of Equations
...................................................................................................
26 7.5.1 Mass Balance
....................................................................................................
26 7.5.2 Charge Balance
.................................................................................................
26 7.5.3 Ionic Strength Balance
......................................................................................
27 7.5.4 Water Dissociation
............................................................................................
27 7.5.5 Determination of pH .........................................................................................
27 7.5.6 Chemical Model Validation
..............................................................................
28 8.0 Results
................................................................................................................
29 8.1 Maximum Boric Acid Concentration
.........................................................................
29 8.2 Minimum Boric Acid Concentration
..........................................................................
31 8.3 Current Design Basis Case
.........................................................................................
32 ................................................................................................................
8.4 pHvs.Time 33 I Prepared By &* &/ Checked By -l Page: 4 Revision:
2 MPR QA Form: QA-3.1-3, Rev . 0 MPR Associates.
Inc . BMPR 320 King Street Alexandria.
VA 2231 4 Calculation No . 0090-0148-01 r 9.0 References
.............................................................................
..........................
34 .........
A pH Predictions of Solutions with Boric Acid and Borax Decahydrate A-1 ................................... B Containment Sump pH as a Function of Temperature B-1 C Containment Sump pH with Borax Decahydrate Buffer - Case IV (no strong acids) ...........................................................................................................................
C- 1 D Containment Sump pH with Borax Decahydrate Buffer - Case V .................
D-1 E Reference 27 - Record for Iodine in Containment
..........................................
E-1 ...................................................
F Reference 29 - Record for Radiation Doses F-1 G Reference 22 - Temperature Profile to 30 Days Following LOCA ................
G-1 Checked By x:dh>&IPj Page: 5 Revision:
3 MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0148-01
/ 1 .O PURPOSE The purpose of this calculation is to determine the minimum required mass of the buffer Sodium Tetraborate Decahydrate (Na2B407.
10H20), commercially known as Borax Decahydrate, needed to raise the pH of the containment building sump at Calvert Cliffs Nuclear Power Plant (CCNPP) to above or equal to
7.0 following
a Loss of Coolant Accident (LOCA).
This calculation includes a determination of sump water pH as a function of time during the recirculation phase. 2.0 ACCEPTANCE CRITERIA 1. A minimum sump pH of 7.0 is required to limit radioactive Iodine (I2) from being released from the irradiated water pool to the containment atmosphere.
The higher pH decreases the level of airborne Iodine in containment and reduces the radiological consequences from containment atmosphere leakage following a LOCA. (Reference 1 - B 3.5.5) 2. A maximum sump pH of 8.0 is required to prevent excessive corrosion of materials in the containment building, especially the dissolution of Aluminum which could lead to the formation of chemical precipitates that could increase the head loss of the sump strainers (References 25 and 26). 3.0
SUMMARY
OF RESULTS The analysis calculates that 13,448 lb of Borax Decahydrate is the minimum mass required to raise the containment sump pH following a LOCA to 7.0.
This result was obtained for an accident scenario that injects the maximum possible concentration of boric acid into the containment building with the maximum possible amount of water. The resultant concentration of buffer solution using 13,750 lb of Borax Decahydrate in an alternate accident scenario that injects the minimum possible concentration of boric acid delivered by the minimum possible amount of water into containment was determined to produce a final pH of approximately 7.6. The addition of margin to the calculated required minimum mass (13,448 increased to 13,750 lb) provides reasonable conservatism for potential minor changes in plant design. Therefore, it is concluded that 13,750 lb of buffer mass satisfies the acceptance criteria for this evaluation.
It should be noted that the equilibrium pH calculation assumes 100% chemical assay of buffer material present in the containment basement. Plant personnel must determine the chemical assay of buffer material that is to be placed in containment baskets and adjust the mass accordingly. Therefore, the amount of 100% Borax Decahydrate that conservatively meets the criteria for pH control is 13,750 lb.
i Prepared By &&hW(d Checked By - 67 Page: 6 Revision:
Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0 148-01 The pH variation as a function of time during the recirculation phase was modeled as a pH variation as a function of sump water temperature.
The effect of temperature on the pH of the containment sump water was evaluated using the complete dissolution of the required mass of buffer. The analysis shows that the effect of temperature is not very significant. As calculated, the decrease in temperature from 194°F (1 hour1.157407e-5 days <br />2.777778e-4 hours <br />1.653439e-6 weeks <br />3.805e-7 months <br /> after the accident) to 125OF (30 days after the accident) results in a drop in pH from 7.12 to 7.05 for the highest boric acid case, and 7.61 to 7.60 for the lowest boric acid case. The calculation determines that the effect of nitric and hydrochloric acids, generated by radiolysis, on the pH or the mass of buffer needed is negligible. Table 8-1 indicates that approximately 3% of the borax decahydrate mass will be used to neutralize the strong acids.
4.0 BACKGROUND
In the event of a Loss of Coolant Accident at Calvert Cliffs Nuclear Power Plant, cooling of the reactor core will be provided by the Safety Injection System (SIS). During the injection mode, the Ngh Pressure Safety Injection (HPSI) pumps and Low Pressure Safety Injection (LPSI) pumps start automatically and take suction from the Refueling Water Tank (RWT). The Containment Spray (CS) pumps will also take suction from the RWT. Coolant lost from the Reactor Coolant System (RCS) rupture will drain to the containment sump and mix with the borated spray water. When the borated water level in the RWT reaches the Recirculation Actuation Signal (RAS) setpoint, the two containment sump isolation valves will open and the LPSI pumps will shut down.
As a result, the SIS continues to operate in the recirculation mode with the HPSI and CS pumps taking suction from the containment sump through a set of sump strainers that filter any large pieces of debris. The water in the RWT contains dissolved boric acid which yields a solution with a pH of approximately 5.0 at 80°F. When the alkaline reactor coolant from the break mixes with spray water, the resulting solution will have a pH of 5.05 (Reference 2 - Section 6.4). The acidic containment spray water will contact most surfaces in the containment building, including the equipment, which will make the metals susceptible to chloride stress corrosion cracking.
Furthermore, at low pH levels Iodine may come out of solution as Iodine gas, and eventually be released to the environment, resulting in increased off site radiation exposure (Reference 3).
To achieve passive pH control, CCNPP currently uses trisodium phosphate dodecahydrate (TSP) stored in baskets placed in the containment basement.
As the water level in the containment pool rises, the TSP dissolves and flows out of the stainless steel mesh screens on the sides of baskets. Mixing will be achieved as the fluid is recirculated. The TSP increases the pH to greater than or equal to 7.0. Prepared By Checked By 4z2-77 Page: 7 Revision:
3 MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 22314 Calculation No. 0090-0 148-0 1 / The dissolution of TSP into the post-LOCA containment pool and its interaction with other chemicals or corrosion byproducts that may have entered the pool from wetted or submerged surfaces can lead to the formation of precipitates such as calcium phosphate (Reference 4). These precipitates may potentially combine with other types of debris (for example: fiber insulation) accumulated near the sump screens and impede the flow through the sump strainers. Due to the presence of Calcium-Silicate insulation at CCNPP, a possibility for an alternative buffering agent is being considered to alleviate the impact of chemical precipitate that may be produced from the reaction of the dissolved calcium, silicate, and other species with TSP. Sodium tetraborate (NaTB) decahydrate has been evaluated by the Pressurized Water Reactors Owners Group (PWROG) experimental program, and was demonstrated to have very similar qualities to TSP (Reference 5).
The main findings for NaTB properties as a buffering agent are summarized in the following section. 4.1 General Review of Sodium Tetraborate Decahydrate Qualities The candidate buffering agents selected in Reference 5 were chosen based on a set of criteria that satisfy different conditions that not only reduce precipitate generation but also insure that the candidates have similar performance characteristics to those buffering agents currently in use. It was shown that NaTB is an acceptable alternative to TSP for the following reasons:
- 1. NaTB exhibited a very similar dissolution time as TSP in water around 67°C (153OF) (Reference 5, Table 5-1). 2. The mass of NaTB required to raise the pH of boric acid solution is comparable to that of TSP (Reference 5, Table 5-2)
- 3. At increasing temperatures, NaTB exhibited a faster dissolution rate in boric acid solution than TSP (Reference 5, Table 5-3).
- 4. Buffered solutions of boric acid with NaTB around pH of 8.0, produced less precipitates when dissolved Calcium or Aluminum was added, than with TSP (Reference 5, Tables 5- 4/55) 5. Buffered solutions of boric acid with NaTB around pH of 8.0 produced comparable Steel corrosion as with TSP. Higher corrosion of Aluminum, however, was recorded for NaTB than for TSP (Reference 5, Table 5-8).
Overall, the above list of conclusions makes NaTB a reasonable alternative buffering agent to TSP for purposes of reducing the risk of producing deleterious chemical precipitates in a design basis accident.
Prepared By &lo- -4 Checked By &e7 Page: 8 Revision:
2 MPR QA Form: QA-3.1-3, Rev. 0 WMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0 148-0 1 5.0 ASSUMPTIONS The following assumptions are made in this analysis: 1. All chemical species dissolved in the containment sump solution are assumed to be in equilibrium. Therefore, the results for the mass of NaTB required to achieve the target pH are applicable for steady state conditions.
- 2. The contribution of Hydriodic acid (HI) to lowering the pH of the containment sump pool is assumed to be negligible. Reference 3, Section 2.2.2 states that the total amount of iodine in containment would be of the order of 100 moles with roughly 5% given off as HI. Because of this expected low concentration for iodine ions, they are not accounted for in this analysis.
- 3. The contribution of Cesium Iodide (CsI) to the containment pool buffer chemistry is assumed to be negligible.
Reference 6, Section 3.5 states that 95% of the iodine released should be assumed to be CsI. End-of-Cycle Total Integrated Dose information for Iodine is given in Reference 27 as 14260 grams, or approximately 112 moles. This is comparable to the estimated value given in Assumption 2. Hence, 95% of 112 moles does not yield a significant concentration for iodine or cesium ions in the sump water volume. 4. In a dilute aqueous solution, the addition of a solute makes a negligible change in the volume of the solution.
Therefore, in this calculation molality and molarity are assumed to be equivalent.
The units for molarity are moles of solute per liter of solution, denoted as 'M'. 5. The total liquid mass in the containment sump at the start of recirculation is determined by adding the amount of water provided by the following sources: a. Reactor Coolant System (RCS)
- b. Pressurizer Water Volume
- c. Safety Injection Tanks (SIT) d. Boric Acid Storage Tanks (BAST) e. Refueling Water Tank (RWT) f. Initial Sump Inventory
- 6. The piping between the various tanks (namely SIT, BAST, and RWT) and the RCS is assumed to hold a negligible amount of water compared to the storage capacity of the tanks. Prepared By hew,& Checked By \ CT Page: 9 Revision:
Rev. 0 MMPR MPR Associates, Inc.
320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0 148-01
- 7. The amount of water in the containment atmosphere is assumed to remain unchanged before and after the accident and thus will not contribute to the liquid mass delivered to the containment sump.
This is conservative since the relative humidity inside the containment building will be higher following a LOCA.
- 8. The initial amount of water in the containment sump is assumed to be 50 gallons from condensation and unidentified leaking water from pipes.
This value is higher than the sump level alarm setpoint of 49 gallons (Reference 2, Section 4.3.3).
This water is conservatively assumed to be at 0 psig and 70°F, which is below the maximum average ambient air temperature (120°F according to Design Input 23 of Reference 13-part 2). Additionally, this water is assumed to have the same limits of Boron concentration as the RWT (Input 15).
- 9. The Boron concentration of the water held by the RCS and the Pressurizer is assumed to be the same. 10. The water volume of the condensed steam in the Pressurizer is assumed to be negligible compared to the other water sources.
- 11. The temperature of the sump water between 19 and 30 days following the accident is linearly extrapolated from the temperature at times less than 19 days provided as design input (Reference 22). The containment pressure at 30 days is assumed to be atmospheric. 12. During the recirculation phase, the containment sump fluid is assumed to be fully mixed with the buffer solution.
- 13. The pH of the sump water is assumed to be influenced only by the chemistry of boric acid, nitric acid, hydrochloric acid, and borax decahydrate.
6.0 INPUT
- 1. The approximate effective ionic radii of Hydrogen and Hydroxide ions, Hf and OH', are taken from Reference 7, Table 8.2 in aqueous solution at 25°C. The following values are used in the computation of the ionic activity coefficient:
aH+ = 9.0 Angstrom, aOH- = 3.5 Angstrom.
- 2. The individual ionic activity coefficient, y, is estimated from the following equation of the Debye-Hiickel theory (Reference 7, Section 8.1): - log y, = AZ: fi l+~a,& Prepared By Checked By &h- Page: 10 Revision:
Rev. 0 MPR Associates, Inc.
MMPR 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0148-01
/ where A and B are the Debye-Hiickel constants, z is the ionic charge, a is the effective ionic radius, and I is the ionic strength of the solution.
- 3. The constants
'A' and 'B' for the Debye-Hiickel equation from 0°C to 100°C are taken from Reference 7, Table 8-3. 4. The ionic strength of the solution, 'I', is defined as the summation of the product molarity 'C' times ionic charge
'2' squared for all the ionic species present in the solution (Reference 12, Chapter 6): n I = 0.5Cclz: I Checked By 7 &>&/L7 . Prepared By ,' Page: 11 Revision:
Rev. 0 MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0148-01
- 6. The molar weights of compounds used in the calculation are given/below (Reference 7 for atomic weights):
- a. Boron: MWB = 10.81 g/mol b. Boric Acid:
MWB(OH)3 = 61.83 glmol c. Borax Decahydrate:
mNa2B407,1()~20
= 38 1.37 g/mol 7. The density of pure water as a function of temperature and pressure is taken from Reference 8. The following values are used in the calculation. 8. The density of borated water is approximated using the following expression from Reference 9, which incorporates the effect of boric acid concentration
'Cboric7 on water density. Cboric is evaluated as the ratio of mass of boric acid to mass of fluid: P(T,C,,,~)
= P,(T) + 315C ,,,, + 100C,2,,, where p is the density of borated water, p, is the density of pure water in kg/m3, and T is the temperature. Converting to lb/ft3:
p(T, C ,,,, = p, (T) + 19.665CbOric
+ 6.243~;~~
- 9. The total gamma dose at the surface of the sump is taken from Reference
- 29. This value will be used in the calculation of nitric acid (HN03) produced from irradiation of water: y,O,T, = 16.84MegaRad Prepared By &&+ Checked By M~ -< Page: 13 Revision:
2 MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0148-01
/ 10. The total gamma and beta doses at the surface of the iodine removal filter are taken from Reference 29.
This value will be used in the calculation of the hydrochloric acid (HCl) produced from irradiation of Hypalon cable in containment:
ypdose = 567.63MegaRad
- 11. The mass of chloride bearing cable that contributes to the formation of HCl is taken from Reference 10 as Mcable = 550 Kg or approximately 1213 Lb. This mass is the maximum for the two units at Calvert Cliffs. 12. The nitric acid generation rate is from Reference 3, Section 2.2.4.
The generation rate in moles of HN03 is a function of the total gamma dose and volume of sump water: mol G,,, = 7.3 x L MegaRad ' Ydose 13. The hydrochloric acid generation rate is from Reference 3, Section 2.2.5.2. The generation rate in moles of HCl is a function of the total gamma and beta doses and mass of electrical cable exposed to radiation:
mol GHU = 4.6 x lb MegaRad . ~Pdosse 14. The molal equilibrium quotients
'Q,,,' for boric acid-borate dissociation schemes are taken from Reference 13, page A-8, and reproduced below as a function of Temperature
'T' in units of Kelvin, and Ionic strength 'I' in units of mole/L: 1573'21 +28.6059 + 0.012078.T
-13.2258.log(T)
+ f (I) a. logQl,l= 2756'1 19.1998+0.00033.T
+ 5.835-log(T)+
f (I) b. log Q,, =y- 3339'5 8.3178 +0.00033 -T + 1.497 .log(T) + f (I) C. log Q,,, = 7 - 12820 134.7938 + 0.00033 -T + 42.105.log(T)
+ f (I) d. log Q,,, =-- T where f (I) = (0.325 -0.00033.T) .I - 0.0912.1' Prepared By &&-,,/A? Checked By , Page: 14 Revision:
2 MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0 148-01 Page: 15 Revision:
3 , 15. The minimum RWT Boron concentration considered in this calculation is 2300 ppm, while the maximum RWT Boron concentration is 2700 pprn (Reference 14 - SR 3.5.4.4). 16. The minimum SIT Boron concentration considered in this calculation is 2300 ppm, while the maximum SIT Boron concentration is 2700 pprn (Reference 14 - SR 3.5.1.4). 17. The minimum BAST Boric Acid concentration considered in this calculation is 6.25%
by weight. The maximum BAST Boric Acid concentration is 8% by weight (Reference 20). 18. The minimum RCS coolant Boron concentration is 0 pprn (towards the end of the fuel cycle). The maximum RCS coolant Boron concentration is 2700 ppm, based on limit for Boron precipitation in the core following a LOCA (Reference 1 - B 3.5.4). 19. The minimum RWT borated water volume that is injected to the containment sump is 360,000 gallons (Reference 2, Section 6.4.2).
The maximum RWT borated water available for injection is taken as 420,000 gallons, which is equivalent to the total tank volume (Reference 2, Table 6-4). 20. The minimum SIT borated water volume considered in this calculation is 11 13 ft3, while the maximum SIT borated water volume is 1179 ft3 in each tank (Reference 14 - SR 3.5.1.2).
There are four SITs at CCNPP (Reference 31 -Input 3.1). 21. The maximum BAST borated water volume per tank is taken as 1270 ft3 (Reference 13 - Design Input 3 of part 2). The minimum BAST borated water volume is calculated based on the minimum tank level given in Figure 15.1.2-1 of Reference 2 1 as 107 inches (at 8 w.t.%). The maximum tank level is given as 130 inches (at 6.25 w.t.%). Therefore, the minimum BAST liquid volume is 1270 ft3 x (1071130)
= 1045 ft3.
There are two BASTS at CCNPP. 22. The RCS water volume excluding the Pressurizer is 9576 ft3 (Reference 2, Table 4-1). 23. The minimum Pressurizer water volume considered in this calculation is 600 ft3, while the maximum Pressurizer water volume is 800 ft3 (Reference 2, Table 4-7). 24. The minimum temperature of the RWT is 40°F, while the maximum temperature is 100°F (Reference 1 - B 3.5.4). Atmospheric pressure (Reference 2, Table 6-4) will be used to evaluate the density of water at those temperature extremes.
- 25. The operating temperature of 120°F and the design pressure of 250 psig for the SIT will be used to evaluate the density of water in the SITs (Reference 2, Table 6-3). 26. The temperature limits of water in the BAST are from Reference 21, Figure 15.1.2-1. The minimum temperature in the BAST is 103.5"F (at 8 w.t.%), and maximum temperature is MPR QA Form: QA-3.1-3, Rev. 0 BMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0148-01 C 115°F (at 6.25 w.t.%). The design pressure of 15 psig will be used to evaluate the density of water at those temperature extremes (Reference 13 -Design Input 4 of part 2). 27. The RCS normal operating pressure of 2250 psia (Reference 2, Table 4-1) will be used to evaluate the density of coolant at the lowest average coolant temperature of 200°F to cover Operational Modes 1 to 4 (Reference 13 - Design Input 19). 28. The Pressurizer normal operating pressure of 2250 psia (Reference 2, Table 4-7) will be used to evaluate the density of coolant at the lowest average coolant temperature of 200°F (Reference 13 - Design Input 19). 29. The sump water temperature as a function of time following the LOCA is extracted from Reference
- 22. The input temperatures are graphically shown in Appendix G. 30. In accordance with Reference 29, the Boric Acid Storage Tanks are isolated for the calculation of the lowest possible Boron concentration case in the containment post LOCA sump. This is a conservative approach.
7.0 METHODOLOGY
The solubility of boric acid in water has been studied extensively in the literature.
At very low concentrations (5 0.025 M), only the mononuclear species produced by the following reaction were found (Reference 15, p. 297):
B(OH), + H,O ++ &OH); + Hf In relatively concentrated solutions (2 0.025 M), such as the boric acid concentration expected at CCNPP following a LOCA with several thousand ppm Boron concentration sump water, polymeric ions (Borates containing BX(OH),, where x>l) from the acceptance of OH- ions by B(OH)3 are formed. The determination of the exact structure of those polynuclear species of Boron has been the subject of several experiments (References 11, 16, 17, 18, and 19). All of those studies present data and analyses that support the formation of polyborate ions. Moreover, the data presented in Reference 11 was collected at three different temperatures (50°, 100°, and 200°C). This calculation uses the dissociation schemes identified in Reference
- 11. A verification of the method was performed by comparing pH predictions with the Reference 11 dissociation scheme to the pH of buffered boric acidfborax solutions from the literature. The results of the comparison are given in Appendix A. Prepared By Ccr/ Checked By 4 f L Page: 16 Revision:
2 MPR QA Form: QA-3.1-3, Rev. 0 mMPR MPR Associates, Inc. 320 King Street Alexandria, VA 22314 Calculation No. 0090-0148-0 1 7.1 Boric Acid and Borax Equilibria The dissolution of Borax Decahydrate whose molecular formula is Na2B405(OH)4.8H20, releases two positively charged Sodium ions, Naf, and one doubly negatively charged Tetraborate ion into the solution. However, the tetraborate ion will break down to produce the mononuclear ion B(OH)4, and at equilibrium will only be present to a minute extent (References 15 and 17). Therefore, the boric acidhorax equilibrium equations can be written in the following scheme.
The subscripts on the equilibrium quotients Q,,, satisfy the formation of -Y borate ions of the form Bx(OH)3,+, . The brackets [ ] denote the equilibrium concentration in mole/L of a given species, so the quotients are assigned based on the thermodynamic equilibrium relationship (Reference 28, pg. 77): Main Reactions Scheme (Reference 11) - Steps 1,2, and 3 B(OH), +OH- w- B(0H); [B(OH), I = [B(OH3)][OH
-1 2B(OH), +OH- w- B, (OH); Q2,1 = [B, (OH); I [B(OH, )I2 [OH -1 3B(OH), +OH - w- B, (OH), [B, (OH), I Q3'1 = [B(oH,)]~[oH-]
Step 4 - Option I 4B(OH), + WH- w- B,(OH);; [B, (OH);: I Q4'2 = [B(oH~)]~[oH-]~ Step 4 - Option 11 [B, (OH);;] Q55.3 = [B(oH,)]~[oH-]~
Prepared By A& &A,,& Checked By I C7 Page: 17 Revision:
2 MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0148-0 1 According to Reference 11, the contribution of the (4,2) and the (5,3) species are so similar that replacement of one by the other for modeling the fourth dissociation step has no significant impact on the formation quotients of the other species.
This analysis relies on the equilibrium quotients given in Input 14 for the Option I scheme. Furthermore, the methodology is validated in Appendix A, and it is demonstrated that the dissociation scheme with Option I gives very good results in modeling the measured pH values when compared to experimental data.
Thus, the calculation of the NaTB mass required to achieve the target pH at CCNPP is conducted using the Option I scheme. 7.2 Containment Sump Water Mass Table 7-1 below summarizes the different borated water sources identified in the Input Section, their corresponding volumes, temperatures, pressure, and Boron concentrations. Note that only the operating temperature was available for the SIT, and only one volume was considered for the RCS. The computation of the BAST content of Boron in ppm is obtained from the weight
% of boric acid concentration as such: Boron (ppm) = Mass of Boron 1 Mass of Liquid x lo6 = MWB I MWecoH,, x w.t.% x lo4, where w.t.% = 6.25 or 8.0 (Input 17). Thus:
g m 10.81- mol BAST-MinBoronppm
- = .6.25 lo4 g m 61.83- mol BAST-MinBoronppm
= 10927 gm 10.81- mol BAST-MaxBoron
.- PPm '- .8.0104 P-' 61.83- mol BAST-MaxBoronppm
= 13987 The above Boron concentrations are inserted into Table 7-1. Prepared By &&W,* Checked By LT Page: 18 Revision:
0 I Minimum Temperature (OF) 40 120 103.5 200 200 70 Source RWT SIT BAST RCS Pressurizer Initial Inventory MPR Associates, Inc.
MMPR Alexandria, 320 King Street VA 2231 4 Temperature (OF) 100 120 115 200 200 120 Calculation No.
0090-0 148-0 1 Pressure (psis) 14.7 264.7 29.7 2250 2250 14.7 Minimum Boron (ppm) 2300 2300 10927 0 0 2300 Minimum Volume (ft3) 481 25 1113 1045 9576 600 6.68 Maximum Boron (PP~) 2700 2700 13987 2700 2700 2700 Maximum Volume <ft3) 561 46 1179 1270 9576 800 6.68 Prepared By &- CL& Table 7-1. Containment Sump Water Sources Note: Minimum and maximum volumes are given per each tank for SIT and BAST.
In the following evaluations, the tabulated input from Table 7-1 along with the minimum density of fluid (at maximum temperature), and maximum density (at minimum temperature) based on the corresponding Boron concentration is used to calculate the limiting sump water mass and total Boron content. Furthermore, water sources that will be used or isolated in the most limiting cases are incorporated in the analysis.
INPUT g m MWBoron := 10.81- g m g m MW~oric~cid
- = 61.83z MWBorax := 381.37- mol mol lb p, := 61.63- Pure Water Density at 125 F & 14.7 psia ft3 (lower bound temperature for long term cooling) f "RWT" \ f 48125) Checked By Page: 19 Revision:
3 Water,,, := ("Initial Inventory" ) \ 6.68 "SIT" "BAST" "RCS" "Pressurizer" 3 ft MinWatervol
- = 11 13 1045 9576 600 MPR QA Form: QA-3.1-3, Rev. 0 MPR Associates, Inc. MMPR Alexandria, 320 King Street VA 2231 4 Calculation No. 0090-0148-01 prepare% b~w/&2=7*
Checked By Page: 20 Revision:
3 at max. temperature at min. temperature (Input 7) (Input 7) f 62.00) f 62.43) MinPureWater
- = 61.76 61.79 60.55 60.55 ~61.71) (62.31) f 2300\ f 2700) MinBoronpp, := lb - ft3 lb - MaxPureWater
.- ft3 '- 61.76 61.96 60.55 60.55 2300 10927 0 0 \ 2300) \ 2700 j (1) (11 .- MaxBoronpp, .- The isolation of BASTS is considered a Single Point Failure. This gives the lower bound for sump Boron concentration MinFactor
- = (See Assumption 5 & Input 30). 2700 13987 2700 2700 4 0 1 1 COMPUTE (1) ( 1 j MW BoricAcid
MinAcidMassRatio
- = .MinBoron
MaxAcidMassRatio
- = .MaxBoron
-6 ppm . l O MW Boron (0.0132) f 0.01 54\ MaxFactor
- = 4 2 1 1 MinAcidMassRatio
= (0.0132) (0.0154) 0.0132 0.0625 0 0 MaxAcidMassRatio
= 0.0154 0.08 0.0154 0.0154 Total Sump Water Mass: - MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 MPR QA Form: QA-3.1-3, Rev. 0 Calculation No. 0090-0 148-01 J / Borated Water Density as a function of Boric Acid Mass Ratio (Input 8): MinBWaterp
- = MinPureWater
+ 19.665MinAcidMassRatio
+ 6.243MinAcidMassRatio - P (( 2j) Ib ft MaxBWaterp
- = MaxPureWater
+ 19.665MaxAcidMassRatio
+ 6.243MaxAcidMassRatio P &+ear&- ,' Checked By - Page: 21 Revision:
3 MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 22314 Calculation No. 0090-0 148-0 1 / I Checked By
- 4257 Page: 22 Revision:
3 d' 7.3 Containment Sump Boron and Boric Acid Concentrations Based on the calculated individual contribution from each borated water source, the collective containment sump Boron concentration can be calculated as: - Cc,M1 csump - ' , where Ci and Mi are the Boron concentration, and water mass from each CMI 1 source. Given, the possibility for accident scenarios that generate a combination of minimum Boron/minimum Liquid, minimum Boron/maximum Liquid, maximum Boron/minimum Liquid, or maximum Boron/maximum Liquid, four collective containment sump Boron concentrations are analyzed to determine the range of expected boric acid concentrations that will influence the pH calculation.
Calculate Boron Mass in each Case from each source: -----------
Case1 Bmass := (Min~oron PPm . MinWater mass -1.10- Case11 Bmass := (MinBoron
-6 PPm . MaxWater mass )- 10 Case111 Bmass := (MaxBoron
-6 PPm .MinWater mass ), 10 -----------
CaseIV Bmass := MaxBoron ( -6 ppm .Mawater mass ) 10 (6891) /810l\ - lb Bmass - - Bmass - 673 1764 0 635 0 0 0 lb \I/ \I) f 8090) f 9510) lb \1/ (1; 790 2259 1573 131 - Case111 Bmass - 746 0 1566 98 - lb Bmass -
MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0148-01 x Case' Bmass Bmass Case1 pp, := . lo6 Case11 ppm . - . lo6 .- MinWater ,,, MaxWater mass CaseI PPm = 1936 Case11 ppm = 2287 Bmass 6 case'v Bmass Case111 pp, := .lo CaseIV .I0 6 MinWater mass ppm := x~an~ater
,,, Case111 ppm = 2700 CaseIV PPm = 3095 Therefore, in summary: Case I: Minimum Boron concentration delivered via minimum water mass: Csump = 1936 ppm. Case 11: Minimum Boron concentration delivered via maximum water mass:
C,,,, = 2287 ppm. Case III: Maximum Boron concentration delivered via minimum water mass:
Csump = 2700 ppm.
Case IV: Maximum Boron concentration delivered via maximum water mass: C,,,, = 3095 ppm. Case V: Design Basis for TSP Buffer (Reference 13, considered here for comparison):
C,,, = 3 105.5 ppm. Consequently, the two extremes for Boron concentration (Case I
& Case IV), and the current licensing case for TSP (Case V) are used to calculate the un-dissociated Boric acid concentrations which will be used in the pH buffer calculation.
Checked By , Page: 23 Revision:
3 MPR Associates, Inc.
320 King Street Alexandria, VA 2231 4 Converting from Boron ppm, the concentration of boric acid in moles/L is: I [B(OH)3]0
= (MWscoH,, I MWB x Boron ,,, x lo6) x Mass of Liquid I MWB(OH)3 x Density of Liquid / Mass of Liquid. Grouping the limiting cases, we get: Page: 24 Revision:
3 CaseIppm L,imitingcaseppm
- = [ 1 CaseIVppm Calculate corresponding Boric acid mass ratio / / Checked By 6 -7 Calculation No. 0090-0148-01
.- MW BoricAcid
.LimitingCases
-6 boric-acid
.- ppm .lo MW Boron Prepared By +~~& For conservatism, the long term cooling density is used Un-dissociated Boric acid concentration BOH3 := I[ .LimitingCases PPm ))lo- MW Boron 1 MPR QA Form: QA-3.1-3, Rev. 0 MPR Associates, Inc.
320 King Street Alexandria, VA 2231 4 Based on Input 9 and 12, the amount of Nitric acid produced as
~03- is calculated for Case 1 and IV. Similarly, based on Input 10, 11, and 13 the amount of Hydrochloric acid as C1 is calculated.
Page: 25 Revision:
3 . - RadWater mass .- MaxWater mass 7.4 Acids Produced by Radiolysis Checked By , fl( Calculation No. 0090-0148-0 1 mass := 12131b Prepared By ,/&f~@ Lz@?!?c? Y 4 6 mol RadWater mass GHNO3 := 7.3.10- -. L 'Ydose P GHCl = 316.726 mol Concentration quantities considering the volume of the water are HCI := 'HC~ RadWater,,,, MPR QA Form: QA-3.1-3, Rev. 0 MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0 148-01 J 7.5 System of Equations The analysis of the boric acidlborax dissolution and dissociation mechanism is governed by three independent equations which relate the concentrations of the different species in the solution to the pH. The following sections describe the setup of the analytical equations.
7.5.1 Mass Balance The mass balance for the ionic species is one of the conservation laws that the buffered solution must satisfy (Reference 12, Section 1.5).
The dissociation of the initial molecules of boric acid and borax decahydrate produces several ions as discussed in Section 7.1.
Therefore, the sum of concentrations of all species of Boron at equilibrium must equal the initial concentration of Boron supplied by both boric acid and sodium tetraborate decahydrate:
[B(OH)3I0
+ 4[Na2B4Or(0H)4.8H20]O
= [B(OH)3] + [B(oH)~-]
+ ~[B~(oH)~-]
+ 3[~3(0~)10-1
+ 4[~4(0~)1i~1.
The left-hand side terms are known from the initial concentration of boric acid in the sump, and the mass of borax decahydrate which is a parameter.
The terms on the right-hand side are substituted with their corresponding equilibrium quotient expressions, so that only the term [B(OH)3] remains in the equation.
The substitution involves the following relationships from Section 7.1:
[B(OH);I = QI,I [OH-] [B(OH),I, 2 [BI(OH)?-I
= Q2,1 [OH-] [B(OH)3I , 3 [J33(0~)161
= Q3,1 [OH-] [B(OH)3I , 4 [B~(OH)II-~I
= Q4,2 10H-l~ [B(OH)3I . 7.5.2 Charge Balance The charge balance for the ionic species is the second conservation law that the buffered solution must satisfy (Reference 12, Section 1.5). Therefore, electroneutrality of the solution as a whole requires that the sum of all the positive and negative charges add up to zero as such: [H'] + [~a'] = [OH-] + [B(oH)~-]
+ [B~(oH)~-]
+ [B~(oH)~~-]
+ 2[84(0H)~i~]
+ [CI-]+[~03-]
L Prepared By Checked By ,&A- - Page: 26 Revision:
2 MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0 148-0 1 Y / The concentration of sodium ions is taken to be constant and is determined as twice the concentration of sodium tetraborate decahydrate, since there are two sodium atoms per molecule of sodium tetraborate decahydrate.
The concentrations of hydrogen and hydroxide ions are covered in Section 7.5.4 and 7.5.5. 7.5.3 Ionic Strength Balance The ionic strength I is a measure which counts the ions in solution, with each ionic concentration weighed by the square of its valence (Reference 12, Section 6.1), as formulated in Input 4. Similar to the pH, the Ionic strength is a property of the final equilibrium state of the buffer solution.
The ionic strength also comes into play in the activity coefficients of the cations and anions as described by the Debye-Hiickel theory (see Input 2).
For this reason, in this analysis the ionic strength balance is imposed as a third equation to solve the coupled system of equations, as follows:
I = Y' ([HI] + [N;] + [OH-] + [c<] + [NO?] + [B(oH)~-]
+ [B~(oH)~-]
+ [B~(oH)~~-]
+ 4[~4(0~)14-~1).
7.5.4 Water
Dissociation When accounting for activity corrections in the equilibrium constant for water, the following relationship must be satisfied (Reference 12, Section 6.4):
K, = Y,+[H'IY,,-[OH-I.
K, is a function of temperature, and its value at the analysis temperature (see Input 29) is interpolated from the data referenced in Input 5. The activity coefficients for H+ and OH- are computed from Inputs 1 and 2. 7.5.5 Determination of pH By definition, the pH of the solution is PH = - log(y,+ [H + I). The pH in this analysis is unknown along with the ionic strength
'I7, and the equilibrium concentration of boric acid
[B(OH)3].
To start the analysis, a guess is first made for all three variables and the three balance equations are examined to determine the magnitude of the error.
The process is iterated until convergence is achieved and a solution pH has been calculated.
The mass of sodium tetraborate decahydrate is adjusted until a calculated pH is achieved that satisfies the acceptance criteria.
Prepared By &-!g!!?g!!?&
I/ Checked By - <F/ Page: 27 Revision:
2 1. Model V- Resub MPR -. Im. F-YPR ~le~~nctritt, 320 ~[ng sw VA =I4 CdculaUon No. -148-01 7.54 ClmlnIcal MdeJV~ &m~f)~befwe,~p~~f~eredw~lrti~
Of~~~id&bCE&Xd*!&ydrateha~b~
reported in the literature at varying mixture concemtrBt4ms.
To verify the adqu~t~-y of the chemical analysis model MW above, the balance quadons wee solved for a number of input cormnuations of initial Mc acid and bm. Forth eightexpimentai data points that wleremOde~tbean~pH~atmostO.~unitsfirom~~~pH~~t.
h~pHtaa~btwem7.0d75,~mOde1~antmrrof~i~lyO.XplriImi~.
Fv 7-1 Ww campmm tb dts of the validation to li- da& The ddh of the validation analysis are given in Am A. 9.0 . 0.0 -- - I - - I - - C - - - - MCW/ 0.- 1 0.1WWTI 023291 MI 0B7M I 0.23fM4 a231MI M3lM I 0.OOSM D.OWM o.oeSM IIPOIM 0.- 0.01PM 0.mM 0.- Bode Acid I Borax A pmm BY &-,&+ CMkael By Paw 28 Rwkbn: 2 MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0 148-01
8.0 RESULTS
8.1 Maximum Boric Acid Concentration Solving for a target pH of 7.0 using the higher initial boric acid concentration of Case IV, the required borax decahydrate concentration that should enter in the containment sump to neutralize the solution is determined to be [Na2B405(OH)4-8H20]0
= 0.0074 M.
The calculation steps and the balance equations are given in Appendix B. The borax decahydrate concentration was obtained by trial-and-error to achieve the target pH of 7.0. The absolute mass balance error, the charge balance error, and the ionic strength balance error from the governing equations are each less than 0.0001. The relative errors are also of the same order of magnitude. Therefore, the analytical pH prediction of 7.0 satisfies the first acceptance criterion. This pH value is consistent for 77°F (25OC). Given the required buffer concentration, the corresponding buffer mass is calculated as such: [buffer] = moles of boradliters of solution where: moles of borax = MassBorax 1 MW~orax , and liters of solution = (Massliquid
+ mass^^^,^)
/ Density of Sump Liquid.
The density of the sump liquid for the buffer mass calculation is determined at the temperature when the recirculation phase starts (at 30 minutes T = 196OF - Reference 30, and Appendix G). This provides a conservative result since the temperature will decrease at later times. Thus, rearranging to solve for MassBo, using the maximum mass of water from Section 7.2 yields: mol CaseIVBorax
- = 0.0074- g m 'boric-acid
= O.O1 77 MWBorax = 38 1.37- L mol Ib pw,,, := 60.2- (Input 7) x MaxWater ,,,, = 46083561b ft3 P ras := pwras + 19.665Cboric-acid
+ 6.243 (cboric-acid - t TI ft I; (Input 8) Ib pra, = 60.55- ft3 x Max~ater mass CaseIV Borax~ass
- = CaseIV B~~~~. 'MW Borax P ras - Borax CaseIV BoraxMass
= 13448 1b Prepared By Checked By ,/A7 Page: 29 Revision:
Rev. 0 aMPR MPR Associates, Inc. 320 King Street Alexandria, VA 22314 Calculation No. 0090-0148-01 To determine the corresponding equilibrium Boron concentration that resudfrom the addition of the borax decahydrate buffer, the total mass of Boron must be summed. One mole of NaTB, contains four moles of Boron, and one mole of boric acid contains one mole of Boron. Thus, Concentration of Boron = 4 x Concentration of Borax + 1 x Concentration of Boric Acid.
The limiting total Boron concentration given in Appendix B as part of the pH calculation occurs for Case IV conditions (for pH =7.0 to 7.1). Simplifying:
TotalBoroncon, := EQBoron mol TotalB~ron,~~~
= 0.3 13% L TotalBoron cone .- 'MW Bomn , 106 TotalBoron PPm .- P ras TotalBoron
= 3498 PPm Appendix C provides a similar pH calculation for Case IV without the contribution of the radiolysis generated acids.
The results are reported here to aid in the surveillance testing of the buffering agent.
mol CaseIV-noaBOrax
- = 0.0072- L x~ax~ater
,,,, CaseIV-noa B~~~~M~~~
- = CaseIV-noa B~~~~. Borax p ras - CaselV-noa ora ax'^^
Borax CaseIV-noa Borax~ass
= 13083 1b Table 8-1 below summarizes the mass of buffer needed to neutralize the different acids, and provides the units in grams per liter. g m CaseIVBOra;MW Borax = 2.822- g m CaseIV-noa Borax.MW Borax = 2.746- L L Prepared By Checked By bdpY &> t' Page: 30 Revision:
3 Acid Type Boric Radiolysis Generated Total MPR QA Form: QA-3.1-3, Rev. 0 BMPR MPR Associates, Inc. 320 King Street Alexandria, VA 22314 Calculation No. 0090-0 148-01 NaTB Quantity Required to Neutralize mol/L 0.0072 0,0002(1) 0.0074 / Table 8-1. Borax Decahydrate Concentration and Mass for pH = 7.0 Note (1): Effective concentration estimated as 'Total' minus 'Boric'. 8.2 Minimum Boric Acid Concentration To insure that the predicted amount of buffer does not violate the second acceptance criterion under less acidic sump conditions, the pH for Case I using the above buffer mass must be calculated. First, the initial concentration of borax decahydrate in the Case I water volume must be determined. For conservatism, the higher density of water at 125OF is used. The mass of Borax is conservatively rounded up to establish an upper bound:
Deploy Borax~ass
- = 137501b Min~ater mass = 3888935 1b lb p 1 = 61.848- ft3 .- Deploy BoraxMass
'P 1 Case1 Borax .- Mw 130rax.(Dep10y BoraxMass
+ x~~~~~~~~
mass 1 mol CaseIBOra, = 0.0092- L The above initial buffer concentration is entered into the pH calculation in Appendix B. The results indicate that the pH is 7.6 at a temperature of 77OF (25°C). Therefore, the calculated buffer mass of 13,750 lb results in a containment sump pH that satisfies the second acceptance criterion.
Prepared By && u g/L 2.74 0.08 2.82 Checked By Ib 13,083 365 13,448 Page: 31 Revision:
3 CBA = 0.01776 pure water density MMPR MPR Associates, Inc.
320 King Street Alexandria, VA 2231 4 MPR QA Form: QA-3.1-3, Rev. 0 Calculation No. 0090-0 148-0 1 8.3 Current Design Basis Case To compare the mass of NaTB from Case IV required to achieve a final sump pH equal to 7.0 to that of TSP, the current licensing basis case is used to calculate the mass of NaTB for the latter conditions of boric acid concentration and sump water mass.
Solving for a target pH of 7.0 using the initial boric acid concentration of Case V, the required borax decahydrate concentration that should enter in the containment sump to neutralize the solution is determined to be [Na2B405(OH)4-8H20]0
= 0.0075 M. Fluid properties are evaluated at 25OC (77°F) to reflect the conditions used in Reference 13, Part 1, neglecting the participation of nitric and hydrochloric acids. The input boric acid concentration is calculated in this section.
The pH calculation steps and the balance equations are given in Appendix D. The borax decahydrate concentration was obtained by trial-and-error to achieve the target pH.
The absolute mass balance error, the charge balance error, and the ionic strength balance error is each less than 0.00001. CaseV := 3105.5 Reference 13, PPm M SUM^ := 4503500 lb pg. 18 of Calc. No. 00081 1 (293-02 Boric Acid mass ratio is MW BoricAcid
.10 - 6 CBA := CaseV ppm . MW Boron lb P W77F := 62.251- ft3 P ,u,p77 := P W77F + ( 19.665CBA
+ 6.243CB2)lb ft3 borated water density lb P sump77 = 62.602- Initial Boric Acid Concentration is ft3 P sump77 - 6 InitBoricAcid
= 0.2881- L mol output from pH calc - Appendix D CaseVBorax
- = 0.0075- L SUMP BoraxMass
- = Borax ' 'MW Borax P sump77 - Borax Borax CaseV Borax~ass
= 12882 lb Prepared By &~<,fl6-77 Checked By Page: 32 Revision:
Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0 148-0 1 Page: 33 Revision:
3 8.4 pH vs. Time The containment sump pH as a function of time is calculated for the recirculation phase in a postulated LOCA. The recirculation phase begins roughly 30 minutes from the start of the accident (Reference 30). It is assumed that borax granular material would have already dissolved due to the relatively elevated temperature of the water and the rising pool level. The analysis performed in this section, assumes that the buffer mass obtained in Section 8.1 is fully dissolved and mixed with the fluid (Assumption 12). Therefore, the effect of the sump water temperature on the pH can be evaluated.
In order to minimize the sump pH transient, Case IV sump conditions with the full acid load of the radiolysis generated acids, which in reality are produced over time, are considered at the start of the transient.
In order to maximize the sump pH transient, the production of radiolysis generated acids in Case I sump conditions is considered to occur 12 hours1.388889e-4 days <br />0.00333 hours <br />1.984127e-5 weeks <br />4.566e-6 months <br /> after the start of the transient, with the maximum attainable concentrations released into the water. The sump water temperatures are selected from Input 29.
The following set of times and temperatures are evaluated for the pH transient calculations.
The pH computations for Case I and Case IV transients are performed in Appendix B, and the results are summarized in Table 8-2. Table 8-2. Sump water temperature and pH as a function of time Note (1): Strong acids included in the pH calculation at each time.
Note (2): Strong acids included in the pH calculation from 12 hours1.388889e-4 days <br />0.00333 hours <br />1.984127e-5 weeks <br />4.566e-6 months <br />.
MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 22314 Calculation No. 0090-0148-0 1 , / f As shown in the above table, the initial higher temperature of the sump water will result in a slightly larger value for the equilibrium pH than at lower temperatures.
This can be explained from the dynamics of the equilibrium quotient relationships of Section 7.1.
Since 'Q,,' is inversely proportional to temperature (See Input 14), the decrease of water temperature with time leads to higher values for Qxy, thus an increase in the equilibrium concentrations of some dissociated borates in the temperature range of interest.
In simple terms, the concentration of positively charged hydrogen ions must increase to maintain electro-neutrality with the negatively charged borate ions, effectively reducing the pH as temperature declines.
In conclusion, the temperature impact on the pH of the sump water is negligible. The results obtained in Sections 8.1 and 8.2 are conservative since the mass or concentration of sodium tetraborate decahydrate fulfills the requirement of pH greater than or equal to 7.0 at ambient temperature. Moreover, at the highest temperature shortly after the initiation of recirculation, the resultant pH is below the upper limit of pH = 8.0.
9.0 REFERENCES
- 1. Calvert Cliffs Units 1 and 2, Technical Specification Bases.
- 2. Calvert Cliffs Updated Final Safety Analysis Report, Revision
- 38. 3. NUREGICR-5950, "Iodine Evolution and pH Control", December 1992.
- 4. LA-UR-05-6996, "Integrated Chemical Effects Test Project: Test
- 3 Data Report", October 2005. 5. WCAP-16596-NP, Revision 0, "Evaluation of Alternative Emergency Core Cooling System Buffering Agents", July 2006.
- 6. U.S. NRC Regulatory Guide 1.183, "Alternative Radiological Source Terms for Evaluating Design Basis Accidents at Nuclear Power Reactors", July 2000.
- 7. Dean, J. A., "Lange7s Handbook of Chemistry", 14" Edition, McGraw-Hill, 1992.
- 8. ASME Steam Tables, Sixth Edition.
- 9. Tuunanen J., Tuomisto H., and Raussi P., "Experimental and Analytical Studies of Boric Acid Concentrations in a VVER-440 Reactor During the Long-Term Cooling Period of Loss-of-Coolant Accidents", Nuclear Engineering and Design 148 (1994) 2 17-23 1. 10. Calvert Cliffs Calculation DCALC No. CA04602, Revision 0, "Additional TSP Required to Compensate for Production of Nitric And Hydrochloric Acid".
Prepared By &&- Checked By /&?' Page: 34 Revision:
Rev. 0 MMPR MPR Associates, Inc.
320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0148-01
- 11. Mesmer R. E., Baes C. F., and Sweeton F. H., "Acidity Measurements at Elevated Temperatures.
VI. Boric Acid Equilibria", Inorganic Chemistry, Vol. 11, No. 3, 1972. 12. Robert de Levie, "Aqueous Acid-Base Equilibria and Titrations", Oxford University Press, 1999. 13. BG&E Calculation No. M-93-33, Revision 0, "Mass of TSP Required to Ensure a Minimum Sump pH of 7.0 in the Event of a LOCA". 14. Calvert Cliffs Units 1 and 2, Technical Specifications.
- 15. Cotton F.
A., and Wilkinson G., "Advanced Inorganic Chemistry - A Comprehensive Text", John Wiley & Sons, 1980. 16. Smith H. D., and Wiersema R. J., "Boron-11 Nuclear Magnetic Resonance Study of Polyborate Ions in Solution", Inorganic Chemistry, Vol.
11, No. 5, 1972. 17. Heller G., Janda R., Mathieu J, "Investigation of the Polyborate Equilibria in Aqueous Solutions by "B-NMR and Raman Spectroscopy", Inorganica Chemica Acta. Vol. 40, 1980 pg. X107 - X108. 18. Ingri N., "On the First Equilibrium Steps in the Acidification of B(OH)4, An Application of the Self-Medium Method", Acta Chemica Scandinavica, Vol. 17, 1963, pg. 573-580. 19. Ingri N., "Equilibrium Studies of Polyanions Containing B", siN, ~e~ and vV", Svensk Kemisk Tidskrift 75:4 (1963). 20. Calvert Cliffs Units I and 2, Tech Spec Action Value Basis Document, "Module 13 - BAST Boric Acid Concentration", TS 80.02, Revision
- 1. 21. Calvert Cliffs Nuclear Power Plant, Technical Requirements Manual (TRM), Revision
- 13. 22. Email from Mahmoud Massoud (Constellation) to Steve Kinsey (MPR),
Subject:
"RE: Data File7', dated July 24, 2008. Attached to this calculation as Appendix G. 23. Li Y., Shimada H., Sakairi M., Shigyo K., Takahashi H., Seo M., "Formation and Breakdown of Anodic Oxide Films on Aluminum in Boric AcidlBorate Solutions", Journal of Electrochemical Society, Vol.
144, No. 3, March 1997. 24. Gieskes J. M., "Effect of Temperature On The pH of Seawater", Limnology and Oceanography, Vol. 14, No. 5 (Sep., 1969), pp. 679-685.
Prepared By &&& CheckedBy
&Qd/&<Z Page: 35 Revision:
Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0 148-0 1 25. Bahn C. B., Kasza K. E., Shack W. J., and Natesan K., "Technical Letter Report on Evaluation of Long-term Aluminum Solubility in Borated Water Following a LOCA", Argonne National Laboratory, February 25,2008, NRC Contract
- JCN 3216. 26. WCAP-16530-NP, Revision 0, "Evaluation of Post-Accident Chemical Effects in Containment Sump Fluids to Support GSI-191", February 2006.
- 27. Email from John Massari (Constellation) to Steve Kinsey (MPR),
Subject:
"Iodine in Containment", dated: July 16,2008. Attached to this calculation as Appendix E. 28. Fogler H. S., "Elements of Chemical Reaction Engineering", Third Edition, Prentice Hall, 2000. 29. Email from John Massari (Constellation) to Steve Kinsey (MPR),
Subject:
"RE: Buffer Calc", dated: July 24,2008. Attached to this calculation as Appendix F. 30. Calvert Cliffs Calculation CA04903, Revision 0002, "Evaluation of Minimum Time to RAS". 3 1. BG&E Calculation No. CA0377 1, Revision 002, "Determination of Minimum Water Level in Containment During Containment Sump Recirculation".
Prepared By fifi &d , Checked By &L7 Page: 36 Revision:
2 MPR QA Form: QA-3.1-3, Rev. 0 aMPR MPR Associates, Inc. 320 King Street Alexandria, VA 22314 Calculation No. 0090-0148-01 I A pH Predictions of Solutions with Boric Acid and Borax Decahydrate The chemical analysis methodology described in Section 7 was used to predict the theoretical pH value of buffer systems of boric acid and borax decahydrate whose pH was known experimentally.
Table A-1 below summarizes the results of the validation analyses. Note that the Reference 5 borax decahydrate concentration was given in g/L (See Figure A-1), so it was converted to molar units and reported in Table A-1 . Table A-1. Results of Validation Using Option I Dissociation Scheme at 298OK (25°C I 77OF) The worksheet in this appendix presents the analysis steps undertaken to validate the chemical dissociation methodology.
The inputs of this model correspond to the data points in Table A-1. The exact values for pH, equilibrium B(OH)3 concentration, and ionic strength obtained from the iterative program are used to compute the error in the balance equations.
The dissociation scheme with option I is used. Individually, the mass balance error, the charge balance error, and the ionic strength balance error is less than 0.0001. The relative errors are also of the same order of magnitude.
&e Prepared By f Page: A-1 Revision:
2 MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No.
0090-0148-01 35 - I I -- 0.09 I 1 I I I I I t I I -- 0.07 --I-- ---- - -- 0.06 z -- 0.03 -- 0.02 -- 0.01 t 0.00 6.0 6.5 7.0 7.5 8.0 8.5 9.0 PH Figure A-1. Adjustment of pH with addition of sodium tetraborate decahydrate to 2500 ppm Boron solution (reproduced from Reference
- 5) Prepared By fi~-+je!5f Checked By /A7* Page: A-2 Revision:
2 Initial Total Boron Concentration EQBoron := 4.Borax + BoricAcid MPR Associates, Inc.
MMPR 320 King Street Alexandria, VA 2231 4 MPR QA Form: QA-3.1-3, Rev. 0 Calculation No.
0090-0 148-0 1 Prepared By @&* Checked By I 6- Page: A-3 Revision:
2 INPUT Room Temperature Tk := 298.15 K Initial Concentrations (Each row represents a validation case): / 0.5 1 f 0.005\ mol - L BoricAcid
- = 0.5 0.1 0.231 0.231 0.23 1 0.23 1 k0.231) (0.083) Na := %.Borax Sodium ion concentration f 0.01 \ Na = mol - Borax := L 0 05 0.025 0.001 0.003 0.010 0.029 0.1 0.05 0.002 0.006 0.02 0.058 Remove units on variables L BoricAcid
- = BoricAcid
.- mol m01 - L L Borax := Borax- mol L Na := Na.- k0.166) mol Tk TK := - K f 0.52\ - E%oron - 0.7 0.2 0.235 0.243 0.27 1 0.347 (0.5631 CONSTANTS GUESSES effective ionic radius of H+ effective ionic radius of OH- Debye-Huckel Constants water equilibrium constant COMPUTE MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc.
320 King Street Alexandria, VA 22314 Calculation No.
0090-0148-01 r I Prepared By AWb @&/ Checked By I /4&zI-7 Page: A-4 , Revision:
2 Hplus = MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 ' 7.643~ 10 7' 7.464~ 10 4.195~ lo9 4.15~ 10 1.453~ 10- 4.656~ 10 1.709~ 10 (6.596~ 10- 91 Calculation No.
0090-0148-01 Prepared By &www,&--f Checked By , Page: A-5 Revision:
2 E f 0.9131 YH = 0.823 0.85 0.954 0.928 0.888 0.845 k0.799) ___j lo Hplus := - YH YY OYninus := Hpi~~ .YH.YoH MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0148-01 logQl I := + 28.6059+ 0.012078TK - 13.22581og(TK)
+ (0.325 - 0.00033TK).Ionicstrength 1.5 + -0.09 1210nicstrength - hQl 1 Qll := 10 > 10gQ~~ := - 19.1998+ 0.00033TK
+ 5.8351og(TK)
+ (0.325 - 0.00033TK).Ionicstrength 1.5 __j log& 1 Q21 := 10 > 10gQ~~ := 3339'5 - 8.3118+ O.00033TK
+ 1.4971og(TK)
+ (0.325 - 0.00033TK)-Ionicstrength 1.5 log4 1 Q31 := 10 Prepared By Checked By Page: A-6 Revision:
2 MPR QA Form: QA-3.1-3, Rev. 0 BMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No.
0090-0148-01 Prepared By &dlirp Checked By I &e7 Q11= Page: A-7 Revision:
2 '5.746~ lo4' 5.995~ lo4 5.865~ lo4 4 5.723~ 10 5.734~ lo4 4 5.775~ 10 5.886~ lo4 (6.207~ lo4) Q21 = '3.829~ lo4' 3.996~ lo4 3.909~ lo4 3.814~ lo4 3.822~ lo4 3.849~ lo4 3.923~ lo4 k4.136~ lo4) ' 3.1~ 10 12 ' 3.235~ 1012 3.165~ 1012 3.087~ 1012 3.094~ 1012 3.116~ 1012 3.176~ 1012 (3.349~ 1012) Q31 = '4.872~ lo6' 6 5.084~ 10 6 4.974~ 10 4.853~ lo6 4.863~ lo6 4.897~ lo6 6 4.992~ 10 6 k5.263~ 10 / Q42 =
MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 22314 Calculation No. 0090-0148-01 Prepared By hd*w / BOH4 := m) ) B20H7 := ( Q21~0~i,,,-BOH~
> B30H10:= (Q31~0Yninur.BOH33)
B401II4:= (QZOYninut.BOH;j CheckedBy , /AL9 BOH4 = Page: A-8 Revision:
2 '1.489~ 10- 4' 1.549~ 10- 1.443~ 10- 5.407~ 10 1.612~ lo4 5.261~ lo4 1.44~ 10 k3.591~ 10- 3, '4.548~ 10- 4' 5.504~ 10- 2.115~ 10 3.531~ lo4 1.064~ 10- 3.59~ 10 1.058~ lo2 ~3.007~ 10 2, B30H10= B20H7 = ' 9.304~ 10- " 8.323~ 10 1.879~ 10- 1.581~ lo3 4.665~ 10 1.472~ 10 3.741~ 10 k8.188~ 10 2, ' 4.685~ 10 5' B40H14 = 4.861~ 4.309~ 10 6.206~ 10 5.507~ 10 5.822~ 4.28~ 10 ~2.524~ 10 2, MPR QA Form: QA-3.1-3, Rev. 0 WMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0148-01 Prepared By Checked By &cA/... Page: A-9 Revision:
2 MASS BALANCE ERROR Sum Boron := BOH + BOH4 + 2.B20H7 + 3.B30H10 + 4.B40H14 MBE := EQ~oron - S"%oron f 0.520001) 0.700009 0.199992 0.234999 0.243002 0.270997 0.347 MBE = -2.466~ 10 2.602~ 10 15 5.869~ 10 (-3.346~ 10- 5, '-8.463~ 10 7' -9.471~ lov6 7.949~ 10 1.294~ 10 (0.563033)
Sumgoron = CHARGE BALANCE ERROR charge := Hplus + Na .- Neg charge .- OHminus + BOH4 + B20H7 + B30H10 + 2.B40H14 CBE:= POscharge - Negcharge f 0.01 ) ~0.01000l\ - Poscharge - CBE = 0.100003 0.049998 0.002 0.006001 0.02 0.058 0.1 0.05 0.002 0,006 0.02 0.058 2.805~ 10- -3.838~ 10- L-1.298~ 10 51 '-2.557~ 10- 7' -2.738~ 10- 1.848~ 10- -7.811~ 10- -4.614~ 10- - Negcharge - (0.166) \0.166013/
SBE := Ionicstrength - SumIons SBE = MPR QA Form: QA-3.1-3, Rev. 0 1 mMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0148-01 IONIC STRENGTH BALANCE ERROR 1 Sumlons := -.(~a + HplUs + OHminus + BOH4 + B20H7 + B30HlO + 4.~40~14) 2 I Prepared By &we Checked By I /&Z Page: A-10 Revision:
2 MPR QA Form: QA-3.1-3, Rev. 0 BMPR MPR Associates, Inc.
320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0148-01 zy&>,/N/-7 B Containment Sump pH as a Function of Temperature This appendix implements the methodology discussed in Section 7.5. The temperature of the fluid determines the constants to be used. The input concentrations are obtained from Sections 7.3 and 7.4. The two limiting cases for boric acid concentration are analyzed via a horizontal array containing two elements, while vertical arrays are used for the temperature vanation, whereby each pH column representing a boric acid concentration.
INPUT Temperature Array Checked By . Tk := Page: B-1 Revision:
3 Chloride ion concentration Remove units on variables
- 4) mol Cl:= (1.504-10-4 1.779.10- - BoricAcid
- = Boric L L Acid ',,1 Nitrate ion concentration L 4) mol NO3 := ( 1.224 10- 1.229 10- - Borax := Borax- L rnol L Na := Na.- L Initial Total Boron Concentration C1 := C1.- mol mol EQBoron := 4.Borax+ BoricAcld Tk L TK := - NO3 := N03.- K mol EQBoron = (0.3139 0.2142) L /363.34\ 362.70 360.95 358.96 353.77 349.68 34 1.42 344.70 340.61 335.99 325.20 t298.15) Initial Case IV and Case I Concentrations:
rnol Boric Acid := ( 0.2843 0.1774 ) - L rnol K Borax := ( 0.0074 0.0092 ) - L Sodium ion concentration Na := 2.Borax rnol Na = (0.015 0.018 )- L MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc.
320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0 148-0 1 Prepared By &cn/H Checked By &A/&&/ f -7 Page: B-2 Revision:
3 CONSTANTS aH := 9 effective ionic radius of H+ OH := 3.5 effective ionic radius of OH- Debye-Huckel Constants at each water equilibrium constant at each temperature temperature 3.735 10 l3 ' 3.639 10 l3 3.387.10 l3 3.12210 l3 2.503 10 l3 2.084 10 l3 1.409 10 1.65210 l3 1.354 10 l3 1.07210 l3 5.963 10 l4 k~.o~1610-14, DHA := GUESSES f0.5923) 0.5913 0.5886 0.5855 0.5776 0.5717 0.5602 0.5647 0.5591 0.5530 0.5397 k0.5 115) := DHB := f0.28101 0.17983) 0.28094 0.17975 0.28076 0.17952 0.28055 0.17926 0.28000 0.17856 0.27957 0.17854
0.27872 0.17737 0.27906 0.17784 0.27863 0.17726 0.27816 0.17659 0.27710 0.17498 (0.27484 0.17104) f 0.3457) 0.3455 0.3449 0.3443 0.3428 0.3416 0.3393 0.3401 0.3390 0.3378 0.335 1 (0.3291) .- Ionicstrength
'- (0.01485 0.01849) 0.01485 0.01849 0.01485 0.01849 0.01486 0.01850 0.01486 0.01851 0.01487 0.01852 0,01488 0.01855 0.01487 0.01853 0.01488 0.01855 0.01489 0.01857 0.01491 0.01863 (0.01504 0.01900) pH := BOH3 := (7.1 1927 7.61491) 7.11809 7.61481 7.11482 7.61455 7.11051 7.61370 7.09966 7.61207 7.09182 7.60203 7.07618 7.60170 7.08246 7.60184 7.07462 7.60 167 7.06587 7.60169 7.0461 8 7.60273 (7.00780 7.61 179)
Rev. 0 WMPR MPR Associates, Inc.
320 King Street Alexandria, VA 22314 Calculation No. 0090-0148-0 1 Prepared By Checked By Page: B-3 Revision:
3 7 I COMPUTE > > - (DH - (DH*. JZ) l+DHB.aH.
JG YH-C~S~IV
- = YOH-case1~
- = lo ~+DHB.%H.
Jq > > - (DH*.J~) - (DH*. JC) 1t DHB.aH. Ionicstrength YH-CaseI := r YOH-C~S~I
- = l+~~e.~oH.
Jz - - (1) (9 lo 1 o- Hplus-~ase~~
- = %lus-~ase1
- = YH-C~S~IV YH-caseI > Kw O%inus-case~v
'= ~I~~-c~~~IV.YH-C~~~IV~YOH-C~~~IV
> Kw OYninus-case~
- = Hplus-case1
'YH-c~~~I'YoH-c~~~I (0.8781 0.878 0.878 0.879 0.88 0.881 0,883 0.883 0.883 0.885 0.887 ~0.8911 YOH-C~S~I
= (0.853) 0.853 0.854 0.854 0.856 0.857 0.86 0.859 0.86 0.861 0.864 (0.869) YH-C~S~IV
= YOH-case~v
= f 0.886) 0.887 0.887 0.888 0.889 0.89 0.892 0.891 0.892 0.893 0.895 (0.8991 f 0.865) 0.865 0.866 0.866 0.868 0.869 0.872 0.87 1 0.872 0.873 0.876 \0.881/ YH-case1 '
MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 22314 Calculation No.
0090-0148-01 Prepared By Hplus~~ase~~
= Checked By FA7 Page: B-4 Revision:
3 '5.682~ 10 6' 5.519~ 10 5.095~ 10- 4.647~ 10- 3.627~ 10 2.962~ 10 1.927~ 10 2.294~ 10 1.844~ 10 1.429~ 10 7.573~ 10 (1.169~ '8.572~ 10- " 8.593~ 10 ' 8.654~ 10 ' 8.736~ 10 ' 8.943~ 10 9.097~ 10 9.41 x 10 9.283~ 10 ' 9.442~ 10 9.624~ 10 ' 1.005~ 10 ( 1.092~ 10 7, Hplus-~ase~
= O%~nus-~ase~~
= '2.765~ 10 " 2.765~ 10 ' 2.765~ 10 ' 2.769~ 10 ' 2.775~ 10 2.837~ 10 ' 2.833~ 10 ' 2.834~ 10 ' 2.832~ 10 2.829~ 10 ' 2.815~ 10 ' \2.743x 10- 8, O%,nus-~ase~
= '1.805~ 10 5' 1.757~ 10- 1.633~ 10 1.502~ 10 1.197~ 10 9.724~ 10- 6.551~ 10 7.691~ 10 6.293~ 10 4.975~ 10 2.765~ 10 ( 4.76~ 10- )
MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc.
320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0 148-0 1 )\ l"gQ1 1-case1~ :' + 28.6059+ 0.012078TK - 13.22581og(TK)
... (1) + (0.325 - 0.00033TK)~Ionicstrengt~
... + -0.09 12 Ionicstrength IF( _____j logQ1 1 -CaseI\ Q1 1-case1~ := lo I, 1573.21 1 lase = [ + 28.6059+ 0.012078TK - 13.22581og(TK)
... (2) + (0.325 - 0.00033TK).Ionicstrength
... + a.~g~a(~onic~~~~~~~
(2)) A logQl 1-case] Qll-case~
- = lo - ) 2756.1 - 19.1998+ 0.00033TK
+ 5.8351og(TK)
... 1 l0gQ21-~ase~~
- = ( 1) + (0.325 - 0.00033TK).IonicStrength
... + -0.09 12 Ionicstrength - ( (1)) A log& 1-~ase1\ Q2 I-C~S~IV := lo i - ) 2756.1 logQ21-~~~~1
- = - - 19.1998+ 0.00033TK
+ 5.83510g(TK)
TK (2) + (0.325 - 0.00033TK).Ionicstrength
... + -0.0912 Ionicstrength - ( ' log(& l-~asel Q21-~ase1:=
Prepared By Checked By . Page: B-5 Revision:
3 MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 MPR QA Form: QA-3.1-3, Rev. 0 Page: B-6 Revision:
3 ./ Checked By , -w,&2Z=-Z=-, Calculation No. 0090-0148-01 Prepared By MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc.
320 King Street Alexandria, VA 22314 Calculation No.
0090-0148-01 Prepared By / Checked By 6- \ Page: B-7 Revision:
3 Q1 I-C~S~IV ' Q2 1-case1~ = f 3 ' 2.917~ 10 2.985~ lo3 3 3.181~ 10 3.424~ lo3 4.167~ lo3 4.889~ lo3 3 6.849~ 10 5.977~ lo3 7.087~ lo3 8.642~ lo3 4 1.41~ 10 \ 5.76~ lo4 1 3 \ '2.805~ 10 2.861~ lo3 3.024~ lo3 3.223~ lo3 3 3.822~ 10 4.392~ lo3 5.889~ lo3 5.231~ lo3 6.067~ 12 7.213~ 13 1.107~ lo4 i3.838~ lo4) Qll-case~
= f 3' 2.921~ 10 3 2.989~ 10 3.186~ lo3 3.429~ lo3 4.173~ lo3 3 4.897~ 10 6.86x lo3 5.987~ lo3 7.099~ lo3 8.657~ lo3 1.412~ lo4 (5.771~ lo4) '6.754~ lo4' 4 6.989~ 10 7.68~ lo4 4 8.559~ 10 5 1.142~ 10 5 1.443~ 10 2.356~ lo5 5 1.933~ 10 5 2.475~ 10 3.296~ 10' 5 6.654~ 10 6 ~3.846~ lo4) Q3 1-C~S~IV = '6.744~ lo4' 6.978~ lo4 7.668~ lo4 8.545~ lo4 5 1.14~ 10 5 1.441~ 10 5 2.352~ 10 5 1.93~ 10 2.471~ lo5 3.291~ 12 6.643~ lo5 Q21-case1
= Q31-case1
= '2.809~ lo3' 2.866~ lo3 3.029~ lo3 3.228~ lo3 3.828~ lo3 4.399~ lo3 3 5.899~ 10 5.239~ lo3 6.077~ lo3 7.225~ lo3 1.109~ lo4 (4.884~ lo6) (4.894~ 10 MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc.
320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0 148-01 Prepared By Checked By t - Page: 13-8 Revision:
3 f 8 \ 2.603~ 10 2.788~ 10' 8 3.37~ 10 4.195~ 10 8 7.563~ lo8 9 1.226~ 10 3.434~ lo9 9 2.261~ 10 9 3.814~ 10 9 7.042~ 10 3.261~ 10 10 (3.113~ 10 ) 12 Q42-case1~
= > BOH4CaseIV
- = ( Q1 - Case~~~~inus-~ase~~.~~~:
I)) > BOH4-CaseI
- = (Q~ 1-CaseI.~%inus-CaseI.~~~:2))
> B2OH7-CaseIV:=
f B40H14-Case1V:=
C~S~IV OGinus-C~S~IV
- 2. (B OH; I)) 4] B4OHl4-CaseI :=
f 8 \ 2.599~ 10 2.783~ 10' 3.364~ 10 8 4.189~ lo8 7.551~ lo8 9 1.224~ 10 9 3.428~ 10 9 2.258~ 10 3.808~ 12 7.03~ lo9 3.255~ lolo (3.107~ l0l2) Q42-~ase1=
MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0148-01 Prepared By +d..u/g I 1 Checked By 6-7 BOH4-CaseIV
= Page: B-9 Revision:
3 ' 4.656~ 10 3' 4.628~ 10- 4.551~ 10- 4.463~ 10 4.231~ 10 4.048~ 10- 3.678~ 10 3.826~ 10 3.642~ 10- 3.435~ 10 2.959~ 10- ( 1.85~ 10- / B20H7-CaseIV
= (4.698~ 10- 3, BOH4-Case1
, (9.479x 10 3' 9.443~ 10 9.343~ 10 9.23~ 8.92~ 10 8.501~ 10 7.971~ 10 8.189~ 10 7.918~ 10- 7.605~ 10 6.833~ 10 '1.258~ 10 3' 1.246~ 10- 1.215~ 10 1.179~ 1.087~ 10 1.017~ 10 8.814~ 9.344~ 8.687~ 7.976~ 10 6.436~ 10- (3.389~ 10- *) B20H7_CaseI
'1.639~ 10 3' 1.627~ 10 1.594~ 10 1.558~ 10- 1.461~ lo3 1.364~ 10 1.216~ 10- 1.274~ 10- 1.202~ 10 1.121~ lo3 9.386~ 10- \5.356x 10- 4/
MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc.
320 King Street Alexandria, VA 2231 4 Calculation No.
0090-0148-01 Prepared By ."I" - / Checked By ,&e7' - B30H10-CaseIV
= Page: 13-10 Revision:
3 '8.502~ 10- " 8 54x 10 8.647~ 10- 8.769~ 10- 9.08~ 10 9.324~ 10- 9.81~ 9.623~ 10- 9.857~ 10 1.012~ 10 1.07~ lo2 ,l.lSSx 10- 2, B30HlO_CaseI=
'8.863~ 10 5' 8.986~ 10- 9.338~ 10 9.768~ 10- 1.102~ 1.178~ 1.458~ 1.338~ 10 1.491~ lo4 1.695~ 10- 2.337~ 10- k6.038~ 10 4, B40H14-CaseIV=
'7.088~ 10- 3' 7.133~ 10 7.258~ 10 7.403~ 10 7.784~ 10- 7.986~ 10 8.611~ 8.364~ 10 8.675~ 10- 9.03~ 10 9.857~ 10 kl.166~ lo2) ' 5.23~ ' 5.281~ lo5 5.427~ 10 5.603~ 10 6.106~ 10 6.561~ 7.679~ 10- 7.205~ 10- 7.805~ 10 8.594~ 10 l.l~lx 10 12.423~ 10 41 B40H14_CaseI=
MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0 148-0 1 Prepared By &4&/ 1 REGROUP BOH4 := (BOH4-CaseIV BOH4-CaseI)
Hp~us := ( ~plus-case~v Hp~us-~ase~)
B20H7 := (B20H7CaseIV B20H7-CaseI)
'%inus := (~%inus-~ase~~
OYninus-case1 ) B30H10:= (B30H10-CaseIV B30H10-CaseI)
B40H14 := ( B40H14-CaseIV B40H14-CaseI)
MASS BALANCE ERROR S~rnlV~,~~~
- = BOHil) + BOH4 + 2.B20H7 + 3.B30H10 + 4.B40H14 1,l 1,1 1,1 1,1 SllIIlIBOron
- = BoH:~) + BOH41 ,2 + 2.8203171,2
+ 3.B30H14 + 4.B40H14 1,2 MBE1~ := EQ~oron , - SurnlV~oron MBE~ := EQ~oron - Suml~oron Checked By ,,/A ,-, C L Page: B-11 Revision:
3 MBEIV = ' 2.069~ 10- ti ' 7.349~ 10 ti 2.99~ 10 -1.391~ 10 ti 1.109~ lo5 1.325~ 10 9.719~ -1.2~ 6.911~ 3.431~ 1.124~ k 5.379~ 10- ti 1 MBEI = '-5.887~ 10 " -6.172~ 10- ti 5.018~ lo-' -5.975~ 10- ti 6.288~ 10 2.413~ 10- ti 1.166~ lo5 -4.353~ 10- -1.56~ 10 -5.84~ 10 ti 2.83~ lo6 ( 6.277~ 10- ti ) Sumlv~oron
= 10.313898\
0.313893 0.313897 0.313901 0.313889 0.313887 0.313899 0.313912 0.313893 0.313897 0.313899 (0.313895)
Sud~oron = f 0.2142061
0.2 14206
0.2142 0.2 14206 0.214194 0.214198 0,214188 0.2 14204 0.214202 0.2 14206 0.214197 (0.214194)
MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0148-01 Prepared By +-W,/-g CHARGE BALANCE ERROR POSIV~~,~, := Hplus l, + Na 1,1 Poslcharge
- = Hplus + Na 1, 2 NegIVcharge
- = OGinus + BOH41, + B20H71,, + B30H1Ol, + 2.B40Hlf, + CI1, + N031, 1,l Neglcharge
- = O%inusl, + BOH41,2 + B20H71,2 + B30H101,2
+ 2.B40Hlf Neg1-12~rcharge
- = '%inus + BOH4,, + B20H71, + B30H10, ,2 + 2.B40Hlf + C1 1,2 + NO3 1,2 Checked By . Page: B-12 Revision:
3 f 0.0148) 0.0148 0.0148 0.0148 0.0148 0.0148 o,o148 0.0148 0.0148 0.0148 0.0148 k0.0148) CBq~ := PoslVcharge - Neg~~charge CBq := Poslchage - Neglcharge s12i := 6.. 12 CBq-12~r := Poslcharge - Neg~-12~rcharge - CBEI ~121 := CBE1-l2~r 2i pOslv~hxg, - '-1.176~ lo7' 1.015~ 10 1.105~ lo-6 '-1.624~ 10 6' -4.421~ 10- 1.039~ CBqV = \0.0184/ -9.196~ 2.958~ 10 ti 3.511~ 1.69~ 10 -3.153~ 1.209~ 10 -1.782~ 10- -8.326~ 10- \ 4.805~ 10- , CBq = -1.434~ 3.355~ 10- 3.098~ 10- 3.392~ 10- -2.974~ 10- 3.388~ 10 -1.12~ 10 -2.5~ \ 7.955~ 10- / - POslcharge - (0.01 84) 0.01 84 0.0184 0.0 184 0.0184 0.0 184 o.ol 84 0.01 84 0.01 84 0.01 84 0.01 84 MPR QA Form: QA-3.1-3, Rev. 0 WMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0 148-0 1 Prepared By Checked By +- Page: B-13 Revision:
3 - Neglvcharge - /0.0187\ 0.0187 0.0187 0.0187 0.0187 0.01 84 O.O1 84 0.0184 0.0184 0.0184 0.0184 \0.0184/ f 0.0148 \ 0.014799 0.014799 0.014801 0.014797 0.014797 0.014798 0.014803 0.014799 0.0148 0.014801 ( 0.0148 / f 0.0184) 0.0184 0.01 84 0.01 84 0.0184 0.0181 0,018 0.0181 0.0181 0.0181 0.0181 \0.0181/ IONIC STRENGTH BALANCE ERROR SumIVIons
- = -. 2 Nal.l + Hpl~s,,~ 'r + 4.B40H141, t C1 1,1 + N031, 1 Suqons := :.(~a~, + Hplus ,2 + OGinusl ,2 + BOH4 1,2 + B20H7 1,2 + B30H10 1,2 t 4.B40H14 1.2) SU~~~~~~~~~
- = ; Na l, + HplUS + OHminusl, + BOH41, + B2OH7 + B30HlO1, ... [ 1,2 + 4.B40Hlf + C11,2 + N03,,2 - Neg~charge - - Neg1-12Hrcharge - (1) SBqV := Ionicstrength - SumIVIons (2) SBq := Ionicstrength - SudIons (2) SB?i - 12Hr := Ionicstrength - Sum112Hr10ns SumIVIons
= SBE := 1-12~r s12i Is121 /0.014852) 0.014852 0.014854 0.014857 0.01486 0.014864 0.014876 0.014874 0.014878 0.014886 0.014911 (0.0150421 Sudlons = f 0.01 8489) 0.01849 0.01 8493 0.01 8498 0.018509 0.018366 0.018394 0.018385 0.01 8399 0.01842 0.01 8483 \0.018853/
MPR QA Form: QA-3.1-3, Rev. 0 BMPR MPR Associates, Inc.
320 King Street Alexandria, VA 223 14 Calculation No.
0090-0 148-0 1 Prepared By Checked By Page: 13-14 Revision:
3 SBqV = '-2.449~ 10 6' -2.391~ 10 -3.805~ 10 3.419~ 10 3.331~ 10- 6.053~ 10 3.964~ 10 -3.722~ 10 2.456~ 10 ti 3.87~ 10 -5.983~ loW7 \ -2.12~ 10- , SBq = ' 5.304, 10- ' -1.122~ 10- -2.891~ 10 1.579~ 10 1.493~ 10 3.7~ 10 5.832~ 10- -5.323~ 10 1.034~ 10 -7.218~ 10 -3.861~ 10 j-3.444~ 10- 6/
Corresponding to 3095 ppm Boron Sodium ion concentration WMPR MPR Associates, Inc.
320 King Street Alexandria, VA 2231 4 Chloride ion concentration set to zero Calculation No. 0090-0148-01 Nitrate ion concentration set to zero L Borax := Borax- rnol C Containment Sump pH with Borax Decahydrate Buffer - Case IV (no strong acids) This appendix implements the methodology discussed in Section 7.5. The temperature of the fluid determines the constants to be used. Input concentrations are obtained from Section 7.3. INPUT Temperature Tk := 298.15 K Initial Concentrations:
BoricAcid
- = 0.284e L rnol Borax := 0.0072- L Na := 2.Borax rnol Na = 0.0144- L rnol C1 := 0.0- L rnol NO3 := 0.0- L Remove units on variables L BoricAcid
- = BoricAcid
.- rnol L Na := Na-- rnol L Cl := C1.- rnol Initial Total Boron Concentration EQBoron := 4.Borax + BoricAcid EQsoro, = 0.3131 Prepared By L NO3 := N03.- rnol MPR QA Form: QA-3.1-3, Rev. 0 Checked By &//..% I Page: C-1 Revision:
3 effective ionic radius of H+ effective ionic radius of OH- Debye-Huckel Constants water equilibrium constant MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0148-01 CONSTANTS "H := 9 OH := 3.5 DH A := .5115 DH B := 3291 K, := 1.0116.10-14 GUESS pH := 7.00675 Ionic := 0.01464 BOH 3 := 0.27439 COMPUTE - (DHA d-) YH := 10 ~+DHB.~H.,/=
YH = 0.9 lo Hplus := - YH '%inus := K, Hpi~s.Y~.Y~~ - 7 Os,n,s = 1.164~ 10 Prepared B *& Checked By l Page: C-2 Revision:
3 MPR Associates, Inc.
320 King Street Alexandria, VA 2231 4 Calculation No. Prepared By Checked By Page: C-3 I MPR QA Form: QA-3.1-3, Rev. 0 0090-0148-01 Revision:
3 /
CHARGE BALANCE ERROR PosCharge
- = Hplus + Na Poscharge
= 0.0144 Neg charge := OHminus + BOH4 + B20H7 + B30H10 + 2.B40H14 + CI + NO3 NegCharge
= 0.0144 -7 Poscharge - Negcharge
= 2.18~ 10 IONIC STRENGTH BALANCE ERROR 1 Suqons := -.(~a + Hplus + OGinus + BOH4t B20H7+ B30HIO+ 4.B40H14+
Cl + ~03) 2 Suqons = 0.01464 Ionicstrength - Suqons = 1.25~ 10- MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, lnc.
320 King Street Alexandria, VA 22314 Calculation No.
0090-0148-01 0' MASS BALANCE ERROR Sum Boron := BOH 3 + BOH4 + 2.B20H7 + 3.B30H10 + 4.B40H14 Sumgoro, = 0.313 1 EQBoron - Sumgoron = 4.0282~ 10- 6 Prepared By &*&* ,'/ Checked By 6 I / L- Page: C-4 Revision:
3 Corresponding to 31 05.5 ppm Boron Sodium ion concentration MPR Associates, Inc.
aMPR Alexandria, 320 King Street VA 2231 4 Chloride ion concentration set to zero Nitrate ion concentration set to zero Calculation No. 0090-0 148-0 1 L Borax := Borax- mol L NO3 := N03.- mol D Containment Sump pH with Borax Decahydrate Buffer - Case V This appendix implements the methodology discussed in Section 7.5. The temperature of the fluid determines the constants to be used. Input concentrations are obtained from Section
8.3. INPUT
25C Temperature Tk := 298.15 K Initial Concentrations:
rnol BoricAcid
- = 0.2881- L rnol Borax := 0.0075- L Na := 2.Borax rnol Na = 0.015- L rnol C1 := 0.0- L rnol NO3 := 0.0- L Remove units on variables L BoricAcid
- = BoricAcid
.- rnol L Na := Na.- mol L C1 := C1.- rnol Initial Total Boron Concentration EQBoron := 4.Borax + BoricAcid EQBoron = 0.3 18 1 Prepared By 4- MPR QA Form: QA-3.1-3, Rev. 0 Checked By > ,.jpZ!&7 Page: D-1 Revision:
2 effective ionic radius of H+ effective ionic radius of OH- Debye-Huckel Constants water equilibrium constant MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc.
320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0148-01 1 CONSTANTS aH := 9 OH := 3.5 DH A := .5115 DH B := ,3291 K, := 1.0116.10-14 GUESS pH := 7.00888 Ionic strength := 0.01525 BOH 3 := 0.27771 COMPUTE - (.HA.,,-) 1 I+DH,.~,.,/=
YH := 10 YOH := 10 ~+DHB.~~H.
J- YH = 0.899 YOH = 0.88 lo 5lus := - Hplus = 1.09~ 10 YH 'sinus := Kw Hp~~~ .YH.YoH OGinus = 1.173~ 10- 7 Prepared By fifdflw i Checked By L7 Page: D-2 Revision:
2 MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0148-01 , logQl 1 := - 1573.21 + 28.6059+ 0.012078TK - 13.22581og(TK)
+ (0.325 - 0.00033TK).Ionicslrength
... TK 1.5 + -0.09 1 '210nicseength logQ* 1 Qll := lo 4 Ql 1 = 5.76~ 10 2756.1 10gQ~~ := - - 19.1998+ 0.00033TK
+ 5.8351og(TK)
+ (0.325 - 0.00033TK)~Ionicstrength
... TK 1.5 + -0.09 1210nicstrength log%! 1 4 Q21 := 10 Q2i = 3.839~ 10 3339 5 := - - 8.3178+ 0.00033TK
+ 1.49%log(TK)
+ (0.325 - 0.00033TK).Ionicstrength
... TK 1.5 + -0.09 12IonicStrength log4 1 Q3i := 10 6 Q3i = 4.885~ 10 12820 10gQ~~ := - - 134.7938+
0.00033TK
+ 42.1051og(TK)
+ (0.325 - 0.00033TK)~Ionicstrength
... TK 1.5 + -0.09 1210nicstrength logQ42 Q2 := 10 Q42 = 3.108~ 10 12 BOH4 := Q1 1.0%inus.BOH3 BOH4 = 1.876~ 10 2 B20H7 := Q2 l.0~in,s.BOH3 B20H7 = 3.472~ 10 B30H10:= Q31.0Ginus.BOH3 3 B30H10= 1.227~ 10 4 B40H14 := Q4Z~Yninus2.~~~3 B40H14= 2.542~ 10- Prepared By &p Checked By ,/A7* Page: D-3 Revision:
2 Sum Boron := BOH3 + BOH4 + 2.B20H7 + 3.B30H10 + 4.B40H14 Sumgoron = 0.3181 - 6 EQBoron - SU~~,,, = -3.6339~ 10 CHARGE BALANCE ERROR 'Oscharge
- = Hplus + Na PosCharge
= 0.015 Neg charge := OHminus + BOH4 + B20H7 + B30H10 + 2.B40H14 + C1 + NO3 Negcharge
= 0.015 - 7 P0sCharge - Negcharge
= -3.624~ 10 IONIC STRENGTH BALANCE ERROR 1 SuqonS := ;.(~a + Hplus + OGinus + BOH4 + B20H7+ B30HlO+ 4-B40H14+
Cl + ~03) Suqons = 0.01525 Ionicstrenglh - Suqons = -4.496~ 10- MPR QA Form: QA-3.1-3.
Rev. 0 WMPR MPR Associates, Inc.
320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0 148-01 MASS BALANCE ERROR Prepared By &,*W Page: D-4 Revision:
2 MPR QA Form: QA-3.1-3, Rev. 0 BMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0148-01 v E Reference 27 - Record for Iodine in Containment From: Massari, John Sent: Wednesday, July 16, 2008 5:54 PM To: 'Kinsey, Steve'; KINSEY, STEPHEN P Cc: Swailes, John
Subject:
Iodine in Containment Steve, Here's the info you wanted on mass of iodine released to containment post-LOCA.
The core inventories (in moles) come from the SAS2H/ORIGEN case CDCB.out in calculation CA06358 if you need a reference. I've covered both TID-14484 (current) and AST (NRC approved but not implemented until 201 0 RFO) methods, and included decay and BOC/EOC effects to give you an idea of the range during the cycle.
Decay actually doesn't do much for you since the bulk of the iodine is stable 1-127 and long-lived 1-129. What's not considered is removal mechanisms that don't lead to the sump such as iodine filters or plate-out in the unsprayed region.
John zrG</A9 Checked By Page: E-1 Revision:
Rev. 0 MMPR MPR Associates, Inc.
320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0 148-01 16000 Z 14000 E s 9 12000 +-' 8 a, E 10000 .- a +-' 8 8 8000 8 .- 6000 .- u 0 - i5 4000 V) 2 2 2000 0 0.1 1 10 100 1000 10000 Time Since Start of Accident (hours)
<<Iodine in containment for sump pH.xls>> Prepared By &&- Checked By Page: E-2 Revision:
2 MPR QA Form: QA-3.1-3, Rev. 0 BMPR MPR Associates, Inc.
320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0148-01 P / F Reference 29 - Record for Radiation Doses From: Massari, John [ma~lto:John.Massari@conste11ation.com]
Sent: Thu 2008-07-24 17:04 To: Kinsey, Steve Cc: Wilson, William J; Swailes, John; Massoud, Mahmoud; Furio, Patricia S
Subject:
RE: Buffer Calc Steve, I can confirm the first 2 bullets and I've added in the adjusted doses for the last one below and the associated references needed. Mahmoud, please add in the 30-day sump temperature.
John ----- Original Message-----
From: Kinsey, Steve
[mailto:skinsey@mpr.coml Sent: Thursday, July 24, 2008 2:55 PM To: Massari, John Cc: Wilson, William J; Swailes, John; Massoud, Mahmoud; Furio, Patricia S
Subject:
Buffer Calc
Dear Mr. Massari:
Please confirm the design inputs below by return email as discussed today in our 12:30 PM Conference.
There are four items for you to address. Please confirm the first two items. Please fill in information on the last two items
The upper bound of the RCS concentration during power operations is less than the minimum shutdown boron concentration.
Therefore, the bounding maximum RCS boron concentration is the 2300 ppm mlnlmum boron concentration required in the RWT. The lower bound RCS boron concentration is 0 ppm boron. These limits will be used to evaluate the required sodium tetraborate decahydrate to achieve pW7.0 in the ECCS sump pool post LOCA and post RAS .
- BAST boric acid load not delivered to the ECCS sump pool. MPR will use a minimum boric acid load which does not include the contents of the BAST to develop the upper bound on pH for the total NaTB load.
- Sump Water Temperature at 30 Days The sump water temperature at 30 days is {Please fill in) MPR is adding a pH versus Time section to the calculation which will Provide Licensing with needed input for the Buffer LAR. pH is affected L Prepared By Checked By be,,&&=- I Page: F-1 Revision:
3 MPR QA Form: QA-3.1-3, Rev. 0 WMPR MPR Associates, Inc. 320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0148-01 Prepared By &--@ 1 MPR is adding a pH versus Time section to the calculation which will Provide Licensing with needed input for the Buffer LAR. pH is affected by temperature.
The sump water temperature varies with time. Therefore, the sump pH will Vary with time. The current design calculation, CA06774, Revision 1 provides sump water temperature to 1,000,000 seconds or about 11 days. The pH versus Time results will be based on the temperature provided here.
- The dose rate for HC1 and H2N03 formation The new dose adjustments for determining radiologically generated acids are {Please fill in) The dose calculation changed about 2004 but was not carried into CA04602, Revision 0. The new generation rates will be based on the adjustments that you provide here. Sump Surface (50' from filter) Checked By 4/-,+ Atborne Plateout Finer Sum p Total Page: F-2 Revision:
2 18-m cycle I-year intetrated doses beta +gamma beta gamma 141.5 133.9 7.6 88.57 88 0.57 0.45 0 0.45 8 0 8 238.52 221.9 16.62 Finer Housing Surface M 18m-24m beta gamma I I 1 I 1 1 1 I Atborne Plateout Finer Sump Total M 24m VN beta gamma I .0327 1.0178 I ,0097 1.0097 1 1.0097 1 I ,0096 18-monthcycle 1yint.dosesfrom CA03879(Be&telCalcM-81-27sh.26,32,33) 18m to 24m-cycle multiplier for 1 y int. dose from NEU 335 (Bed7tel M 44 sh 48b 8 48c) Ppp K + VAP 1 y int. dose multiplier from CA06188 p. 48 18-mcyclel-yearintetrateddoses beta +gamma beta gamma 141.5 133.9 7.6 88.57 88 0.57 321 0 3 21 8 0 8 559.07 221.9 337.1 7 24m VPP vrd nbPpp K adjusted beta+gamma beta ga nrrm 146.01 138.28 7.74 89.43 88.85 0.58 0.45 0 .OO 0.46 8.08 0 .OO 8.08 243.97 227 .I 3 16.84 M18m-24m beta gamma I I 1 1 1 1 1 1 M24mV.W beta gamma 1.0327 I .01 78 1 .OD97 1.0097 1 1 .DO97 1 I .OD96 24m VW vrd Ppp K adjusted beta+gam beta gamma 146.01 138.28 7.74 89.43 8 8.85 0.58 324.11 0 .OO 324.1 1 8.08 0.00 8.08 567.63 227.13 3 40 .50 MPR QA Form: QA-3.1-3, Rev. 0 MMPR MPR Associates, Inc.
320 King Street Alexandria, VA 2231 4 Calculation No. 0090-0 148-0 1 G Reference 22 - Temperature Profile to 30 Days Following LOCA From: Massoud, Mahrnoud Sent: Thursday, July 24, 2008 10:43 AM To: KINSEY, STEPHEN P; Swailes, John; Massari, John; 'Kinsey, Steve'
Subject:
RE: Data File Gentlemen I've attached the result of extended GOTHIC analysis. The analysis runs for an additional 660,000 seconds (about 8 days). The code predicts that the sump water temperature at 19.2 days would be about 140 F. Although I extended the decay heat to beyond 1 month, the code did not run to 2,592,000 seconds due to the lack of sufficient data for the containment air coolers. -Mahmoud Prepared By Checked By bG@f&9b Page: G-1 Revision:
2 MPR QA Form: QA-3.1-3, Rev. 0 MPR Associates, Inc. WMPR Alexandria, 320 King Street VA 2231 4 Calculation No. 0090-0 148-01
/ , 21 Sump Water Temperature TL'I 0- h b @ 3 +d F a, E ? 0 0 34 0.68 -1.02 '1.38 .1 .7 Time {sec) Xle6 GOTHIC 7 2a(QR) J~11/2312C108 16 05 59 - END OF EMAIL MESSAGE Extrapolation The above temperature profile is used for a linear least-squares polynomial fit supplying the data only from 10 days to 19 days. The figure below shows the onginal temperature profile with the superimposed linear fit extending to 30 days. The extrapolated temperature value at 30 days is 125.763 OF. Prepared By W& Checked By 7 7 Page: (3-2 Revision:
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