ML20080P488
| ML20080P488 | |
| Person / Time | |
|---|---|
| Site: | Catawba  |
| Issue date: | 08/14/1979 |
| From: | Chaust R, Evans L, Tuckman M DUKE POWER CO. |
| To: | |
| Shared Package | |
| ML20080P419 | List:
|
| References | |
| CP-O-A-8100-11, NUDOCS 8402220561 | |
| Download: ML20080P488 (14) | |
Text
..--.m o Form SPD-1002-1 DUKE POWER COMPANY (1) ID No: CP/0/A/8100/11 PROCEDURE PREPARATION Change (s)_ o to PROCESS RECORD 0 Incorporated (2) STATION: Catawba (3) PROCEDURE TITLE: Cher.iste Precedure for the Determination of Dissolved Oxygen (4) PREPARED BY: k, DATE: 7-1[.3-7i (5) REVIEWED BY: m , [.3A DATE: ~ 2' 2 7 Cross-Disciplinary Review By: te A 6!?h1 N/R:ddd'7i-2/
(6) TEMPORARY APPROVAL (IF NECESSAR1 :
By: (SRO) Date:
By: Date:
(7) APPROVED BY: N[ ocE m [ b Date: F//yh1 (8) MISCELLANEOUS:
l Reviewed /Apptoved By: Date:
Reviewed / Approved By: Date:
l MASTER FILE i
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8402220561 840215 PDR ADOCK 05000413 E PDR l
- ., m FOPJi SPD-1001-2 DUKE POWER COMPANY j NUCLEAR SAFETY EVALUATION CHECK LIST (1) STATION
- Catawba UNIT: 1 X 2 X 3 OTHER:
(2) CHECK LIST APPLICABLE TO: CP/0/A/8100/11 (3) SAF53 EVALUATION - PART A The item to which this evaluation is applicable represents:
Yes No X A change to the station or procedures as described in the FSAR or a test or experiment not described in the FSAR?
If the answer to the above is "Yes"', attach a detailed description of the item being evaluated and an identification of the affected section(s) of the FSAR.
(4) SAFETY EVALUATION - PART B Yes No X Will this item require a change to the station Technier!
Specifications?
If the answer to the above is "Yes," identify the specification (s) affected and/or attach the applicable pages(s) with the change (s) indicated.
(5) SAFETY EVALUATION - PART C As a result of the item to which this evaluation is applicable:
Yes No 1 Will the probability of an accident previously evaluated
( in the FSAR be increased?
Yes No _ % Will the consequences of an accident previously evaluated in the FSAR be increated?
Yes No % May the possibility of an accident which is different than any already evaluated in the FSAR be created?
Yes No % Will the probability of a malfunction of equipment important to safety previously evaluated in the FSAR be increased?
l Yes No % Will the consequences of a malfunction of equipment l important to safety previously evaluated in the FSAR i be increased?
Yes No % May the possibility of malfunction of equipment important to safety different than any already evaluated in the FSAR be created?
Yes No N Will the margin of safety as defined in the bases to any Technical Specification be reduced?
If the answer to any of,the preceding is "Yes", an unreviewed safety question is involved. Justify the conclusion that an unreviewed safety l question is or is not involved. Attach additional pages as necessary.
(6) PREPARED BY: . DATE: 7-2b~7i (7) REVIEWED BY: (LN . tb DATE: b ~ 87
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(8) Page 1 of I
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m _. ENCLO5G2 9 DUi:E PO*IR CO.SANT
) AIAPa EVALUATION CECrlIST (1) Station: Catawba Unit: 1 X 2 X 3 0 her:
(2) Checklist Applicable to: C8 o !A ! P/00 //
(3) AI).PA Evaluation Check those ite=s below which were censidered applicable during the preparation and review of this document.
Flushing and draining was used to minimize source - strength and con-ta=ination levels prior to perforcing an operation.
Pe:manent and/or c:ovable shielding was specified for reduction of levels. .
Use of pernanent or te=porary local exhanst ventilation syste=s was used for control of airborne contamination.
Operation was designed to be completed with the least practicable time spent in the radiatics field.
Appropriate tools and ecuipment were specified for the operaticn to be 7;.,. perforned.
The operation was designed considering the minimum number of people necessary for safe job completion.
Renote handling'ecuipment and other special tools were specified to i
reduce external dese.
I Conta=ination - centrol technicues were specified.
l The operition was designed to be conducted in areas of as low en exposure as practicable.
Additienal AI.AFA considerstiens were:
- AD.?A Principles were not censidered sis:e the procedure did no:.
t involve work in a radiation area.
(5) Prepared by: ]
- k. ~8 Date _ 2 - f $ " hd
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(6) Reviewed by: k%, a . knm Date J./9-fd
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CP/0/A/8100/11 DUKE POWER COMPANY CATAWBA NUCLEAR STATION CHEMISTRY PROCEDURE FOR THE DETERMINATION OF DISSOLVED OXYGEN i
1.0 DISCUSSION 1.1 Scope This procedure covers three methods (Indigo Carmine, medit _.d Winkler, and Chemets) for the determination of dissolved crygen.
j 1.2 Principle 1.2.1 Indigo Carmine - Dissolved oxygen reacts with a solution of indigo carmine dye to produce color changes. The concentration of dissolved oxygen can be determined by the f
color produced.
1.2.2 Winkler - Dissolved oxygen can be determined by an indirect titration method. Direct titration of dissolved oxygen in water would be difficult since no indicator of adequate sensitivity is known. To overcome this difficulty, the oxygen is quantitatively reacted with iodide to form iodine. The concentration of iodine is more easily determined.
The quantitative reaction taking place for dissolved oxygen determination is:
4H+ + 41' + O 2---4>
2I2 + 2H 2O 1.2.3 Chemets - Dissolved oxygen Chemets, using indigo carmine or Rhodazine D reagents, react'to produce a progressive l color change when oxygen is present.
1.3 Interferences 1.3.1 Indigo Carmine - Hydrazine up to 1 ppm and ferric ion up to 4 ppm will not interfere. Boric acid does not interfere up to 250 ppm as boron. Above 250 ppm additional potassium
( hydroxide must be added as shown in Enclosure 6.1.
l_ 1.3.2 Winkler - The azide modification to this method is used to l
eliminate interferences from less than 5 ppb nitrate .
[
i nitrogen and less than 1 ppm ferrous ion. Other oxidizing or reducing agents should not be present. Oxidizing agents will. tend to cause high results while reducing
, agents lead to low results. Boric acid can interfere if an insufficient amount of caustic is added.
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CP/0/A/8100/11 Pega 2 of 10 1.3.3 Chemets - No interferences should occur when this method is used where applicable.
1.4 Limits and Precision 1.4.1 Indigo Carmine - Dissolved orygen can be detectined by this method from 0 ppb to 60 ppb. The precision ranges from i I ppb at 5 ppb to 13.8 ppb at 60 ppb.
1.4.2 Vinkler - The lower limit of this method is apprcximately 50 ppb with no upper limit. The precision of this method varies with the type of sample to be analyzed. Precision of i 20 ppb can be expected with distilled water to : 60 ppb in waste water.
1.4.3 Chemets - Dissolved oxygen can be determined froc 0 to 1000 ppb with the low range kit and fron 100 ppb to 12,C30 ppb with the high range kit.
1.5 Precautions Analysts should wear eye protection when ha'ndling chemicals.
2.0 APPARA7US 2.1 Indigo Carcine 2.1.1 25 ml buret
. 2.1.2 300 ml BOD sample bottles 2.1.3 Color chart or standards 2.2 Winkler 2.2.1 Sewage sampler with rope 2.2.2 300 ml BOD bottle 2.2.3 500 ml Erlenmeyer flask 2.2.4 10 ml buret 2.2.5 3 pipets to deliver 2 ml each 2.3 Chemets - All equipment needed is supplied with the dissclved oxygen Chemets kit. .
3.0 REAGENTS 3.1 Indigo Car:ine
CP/0/A/8100/11 Pagn 3 of 10 3.1.1 Indigo Carmine Solution - Add 0.45 t 0.005 grams of indigo '
carmine and 4.5 t 0.1 grams of dextrose to a one liter volumetric flask. Add 500 t 5 ml of glycerin, dilute to 1 liter with demineralized water and mix thoroughly. This solution is stable for 30 days when refrigerated.
4 3.1.2 Potassium Hydroxide Solution - Dissolve 530 1 1 gram of potassium hydroxide in water and dilute to 1 liter. Store in a polyethylene bottle. This solution is stable inde-finitely.
3.1.3 Color Reagent - In a 150 ml beaker, mix 4010.5 al of indigo carmine solution (Section 3.1.1) with 10 1 0.1 ml of potassium hydroxide solution (Section 3.1.2) and pour into a buret. Allow the solution to stand until red color changes to bright yellow. Eenew daily.
5 NOTE: When the sample contains more than 250 ppm boron, adjust KOH according to Enclosure 6.1.
3.1.4 Hydrochloric Acid Solution (1%) - Pipet 10 ml of contentrated hcl into a 1 liter volumetric flask containing demineralized water and dilute to volume with demineralized water.
3.1.5 Red Stock Solution - In a 250 n1 volumetric flask, dissolve 14.82 grams of cobaltous 6H 0 200 ml chloride hexabydrate (CoCl2 in approximately of 1% v/v hcl and dilute to 250 ml )
with 1% v/v hcl. Store in an amber bcttle. This solution is stable indefinitely.
l 3.1.6 Yellow Stock Solution - In a 250 ml volumetric flask,
- i. dissolve 11.26 grams of ferric chloride hexahydrate (FeCl . 6H3 0) in approximately 200 ml of 1% v/v hcl and dilut$to230ml. Store in an acber bottle. This solution is stable indefinitely. .
j 3.1.7 Blue Stock Solution - In a 250 ml volumetric flask, dissolve 1 -
15.61 grams of cupric sulfate pentahydrate (Cus04 5H 0)
{ in approximately 200 ml of 1% v/v hcl and dilute to 2509 ml.
i Store in an amber bottle. This solution is stable indefinitely 3.1.8 Standard Color Solutions - Prepare a series of color standards by placing the following amounts in a 500 ml volumetric flask.
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Final Color Equivalent Dissolved M1 of Stock Solution j of Solution Oxygen in PPB Tellcw Red Blue Yellow 0 58.35 1.25 Orange 5 33.35 8.35
, Orange pink 10 20.85 10.1 Pink -
15 16.55 15.65 Pink-red 25 6.35 24.0 Red purple 50 2.85 30.5 13.5 L Blue purple 94 1.25 50.85 70.45 l -
Blue > 100 47.5 86.7 l
CP/0/A/8100/11 Page 4 of 10 Add 2.3 al of concentrated hcl to each bottle and dilute to the neck with water. Stopper, seal, label (including date prepared) and retain for 1 year.
3.2 Winkler 3.2.1 Winkler Method Using Powder Pillows 3.2.1.1 Phenylarsine oxide (PAO) 0.0375N, commercially available.
NOTE: This must be standardized according to Section 3.2.2.3.2. If the normality is high, dilute according to Section 3.2.2.3.4. If the normality is low, the calculation in Section 4.2.2.S can be adjusted to compensate for the low normality.
3.2.1.2 Powder pillows (alkaline-iodide-szide , manganous sulfate, and sulfamic acid) premeasured, commercially available.
3.2.1.3 Potassium hydrexide, solid, reagent grade.
3.2.1.4 Starch Solution - Dissolve 1 gram of soluble starch in 100 ml of boiling water while stirring.
Boil for 1 minute after addition of starch.
Cool and use.
NOTE: This must be made daily since aquecus-starch suspensions decompose within a few days due to bacterial action.
3.2.2 Winkler Method Using Laboratory Chemicals 3.2.2.1 Manganous sulfate solution - Dissolve 364 2 0.5 grams of manganous sulfate' (MnSO4 . 3H 0) in decineralized l water. Filter and dilute to 1 Iiter.
1 NOTE: 400 1 0.5 grams of MnSO, . 2H 0 or 2
i 480 1 0.5 gramsofMnSO{.4H0canbe 2
used.
3.2.2.2 Iodide-azide Solution - Dissolve 700 1 0.5 grams of potassium hydroxide (KOH) in sufficient de-mineralized water to make approximately 700 ml of solution in a 1 liter volumetric flask and
- cool to room temperature. Dissolve 150 0.5 grams l
of iodate-free potassium iodide (KI) in 200 cl of demineralized water and mix with the KOH l
solution in the volumetric flask. Dilute to 1 liter.~
To this solution add 10 1 0.1 gram of l
sodium azide (nan,) dissolved in 40 cl of de=ineraliz water. Mix the s51ution and store in a dark polyethylene bottle.
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m CP/0/A/8100/11
. Pcan 5 of 10 3.2.2.3 Phenylarsine Oxide (PAO) 0.0375N 3.2.2.3.1 Dissolve 45 2 0.1 grams of PA0 (C H As0) in 750 ml of demineralized water 6S containing 12 1 0.1 grams of sodium hydroxide.
NOTE: Some of the PA0 will not dissolve.
However, after 1 to I hours of stirring (magnetic stirrer), enough will have dissolved to continue.
Decant 650 ml of this solution into a 1500 ml beaker. Verv slowly adjust the pH between 6 and 7 with 50% v/v hcl (6N E 40 mis), then dilute to about 1100 ml with decineralized water and stir for about 5 ninutes (at this point, there will be a fluffy white precipitate). Filter this solution through qualitative filter paper and add 1 nl of chloroform to the filtrate as a preservative. Standardize this solution according to Section 3.2.2.3.2.
Commercial PA0 can be used, but it must also be standardized.
3.2.2.3.2 Standardization of 0.0375N PA0 Solution -
Dissolve 1.2188 2 0.0005 grams of potassium biniodate (KH(IO 2 )3) in demineralized water and dilute to 1 liter. This is a 0.0375N solution of [KH(IO3 )2]. Dissolve 2 2 0.1 grams of iodate .,ree potassium iodide (KI) r in an Erlenmeyer flask with about 150 ml of ' demineralized water. Add exactly 20.00 ml of 0.0375N standard biniodate solution followed by 10 1 0.5 ml l of 10% v/v H3 SO 4 . Dilute to 300 ml j and titrate the liberated iodine with l
the 0.03755 PA0 titrant. When a pale yellow color appears, add approximately 2 al of starch solution. If the l
prepared PA0 solution (Section 3.2.2.3.1) is exactly 0.0375N, then it will require exactly 20 ml of biniodate to
! reach the end point.
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! 3.2.2.3.3 Calculate the ner=ality of the PA0 solution by rhe following formula:
g PA0 or 0.75
,20mlmlPA0 x 0.0375N used n1 PA0 used l
NOTE: If the PA0 solution is less than 0.0375N, discard and start over.
CP/0/A/8100/11 Page 6 of 10 3.2.2.3.4 If the normality of the PA0 is greater than 0.0375, prepare 1 liter of working solution by the following formula:
_ 0.0315N x 1000 ml
- Normality of PA0 (Section 3.2.2.3.37 where X = the number of milliliters of PA0 to be diluted to 1 liter 3.2.2.4 Sulfuric Acid - concentrated (36N) 3.2.2.5 Starch Solution - Prepare according to Section 3.2.1.4.
3.3 Chemets - all reagents necessary are supplied with the dissolved oxygen Chemets kits.
4.0 PROCEDURE 4.1 Indigo-Carmine 4.1.1 Determine that reagents 3.1.1, 3.1.3 and 3.1.8 have not expired.
4.1.2 C.11ect a sample in a 300 ml BOD bottle by running the sample line to the bottoc of the BOD bottle with a sample flow of 500 - 1000 ml per cinute. Allow for 10 changes of sample bottle volume while sample is flowing. Extreme care must be taken to prevent entrapment of air in the sample. Maintain BOD bottle full to overflowing while removing the sample line.
4.1.3 Insert the tip of the buret containing the color reagent (Section 3.1.3) below the neck of the bottle and add 2 ml of the color reagent. .
, 4.1.4 Remove the buret tip from the BOD bottle and stopper the L BOD bottle exercising care in preventing the entrapment of l air in the sample.
4.1.5 Invert the bottle several times and compare the color of the sample with the color of the standards (Section 3.1.8) or color chart.
, 4.2 Winkler 4.2.1 Collection of Sample 4.2.1.1 Sample Collection Using Sewage Sampler 4.2.1.1.1 Secure 300 ml BOD bottle in the sampler.
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CP/0/A/8100/ll Paga 7 of 10 4.2.1.1.2 Place the sampler under water and hold there until no air bubbles can be seen escaping from the sampler (about 2 minutes).
4.2.1.1.3 Lift the sampler out of the water and remove the top.
4.2.1.1.4 Place glass stopper into the BOD bottle and remove the bottle from the sampler.
4.2.1.2 Sample Collection at Sample Panel 4.2.1.2.1 Collect a sample in a 300 ml BOD bottle by running the saeple line to the botto: cf the BOD bottle with a sample flow of 500 - 100C cl per minute. Allow for 10 changes of sample bottle volume while sample is flowing. Extreme care must be taken to prevent entrapcent of air in the sample. Maintain BOD bottle full to overflowing while removing the sample line.
4.2.1.2.2 Recove the saeple line frot the BOD bottle and s:cpper the BC3 bcttle exercising care in prever. ting the entrapnent of air in the sample.
4.2.2 Determination of Dissolved Oxygen Using Powder Pillows 4.2.2.1 Empty one premeasured Hach capsule of manganous sulfate and one capsule of alkaline-iodide-azide into the BOD bottle.'
NOTE: Add 3 grams of solid KOM if the sample is borated.
4.2.2.2 Shake bottle well and allow the contents to settle.
NOTE: Water high in chlorides requires a 10 minute contact with the precipitate.
4.2.2.3 Empty one (1) premeasured capsule cf sulfamic acid into the BOD bottle and again shake well.
NOTE: Use two powder pillows if the sacple is borated.
4.2.2.4 Transfer the entire 300 ml into a 50C ml Erlenmeyer flask.
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CP/0/A/8100/ll Pega 9 of 10 NOTE: High iodine concentrations decompose starch to products which do not have good indicator properties. The light yellow color indicates that most of the iodine has been reduced.
4.2.3.7 Add 1 - 2 ml of starch solution and continue titration until the blue color disappears.
4.2.3.8 The number of ml of titrant used equals the dissolved oxygen content in ppm according to the formula:
D.O. in ppm = (8000)(0.0375)(ml of tigant) 300 where 8000 = milliequivalents for cxygen 0.0375 = nor:ality of titrant (PA3)
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300 = volume of sample in ml 4.3 Chemets 4.3.1 Procedure for Sewage Waters Using High Range Chemets Kit 4.3.1.1 Fill the sample cup to 25 ml with sacple.
4.3.1.2 Add 2 - 3 drops cf neutralizer solution and stir.
4.3.1.3 Snap Chemet tip in sample and mix con ents.
4.3.1.4 Compare with colcr standards to deter =ine 0 i*
ppm. 2 4.3.2 Procedure for Secondary Systems Using Low Range Chemets Kit 4.3.2.1 Place Chemet in sa=ple.
4.3.2.2 Snap Chemet tip and mix contents.
4.3.2.3 Compare with color standards to deter =ine 0 i" ppm. 2 t
5.0 PIFERI.NCES 5.1 American Society for Testing and Materials, 1978. Annual . Book of ASTM Standards, Part 31, D 88866, Pages 445-454.
5.2 Standard Methods for the Examination of Water and Wastewa er, 14th Edition, 1975, Part 442, Pages 440-4!.9.
5.3 Skoog, D.A. and West, D.M , 1965. Analy-ical Che=istry, An Introductica; Holt, Phinehart, and Winston, pp 393 and 398.
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CP/0/A/8100/ll Paga 8 of 10 4.2.2.5 Titrate the sample with 0.0375N PA0 until the sample is light yellow. Add a few cl of starch solution to the sample, then titrate until the blue color disappears.
NOTE: High iodine concentrations decompose starch to products which do not have good indicator properties. The light yellow color indicates that most of the iodine has been reduced.
4.2.2.6 Since the PA0 solution is 0.0375N, then the i
' number of ml used equals the dissolved oxygen content in ppm.
D.O. in ppm = (8000)(0.0375)(ml of titrant) 300 where 8000 = mg/l milliequivalents fcr oxygen 300 = volume of sample (ml) 0.0375 = normality of titrant (PAO) 4.2.3 Determination of Dissolved Oxygen Using Laboratory Chemicals 4.2.3.1 To the sample collected in a 300 ml 20D bottle, add 2 ml of MnSO 4 solution followed by 2.0 ml of the alkaline-iodide-azide solution, well below the surface of the liquid.
NOTE: Add 3 grams of KOH for berated samples.
4.2.3.2 Replace the stopper, carefully excluding air bubbles, and mix.
4.2.3.3 Repeat the mixing a second time after the floc has settled, leaving- a clear suparnate solution.
NOTE: Water high in chlorides requires a 10 minute contact with the precipitate.
4.2.3.4 When the floc has settled, leaving at least t
100 ml of clear supernate, remove the stopper
! and add 2.0 ml of H3 SO
! 4 and mix. Allow this solution to stand f8r a minimum of 5 minutes before proceeding. Do not allow it to stand more than 2 hours2.314815e-5 days <br />5.555556e-4 hours <br />3.306878e-6 weeks <br />7.61e-7 months <br />.
NOTE: Add 4 el of H 2SO4 for borated samples.
4.2.3.5 Transfer the entire contents of the E3D bottle into a 500 ml Erlenmeyer flask.
4.2.3.6 Titrate the sample with 0.0375N PA0 solution to a pale yellow.
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CP/0/A/8100/11 Pege 10 cf 10 I
5.4 McGuire Nuclear Station Ch.mistry Procedures CP/0/A/8100/17A and CP/0/B/8100/18A.
5.5 Oconee Nuclear Station Chemistry Procedure CP/0/A/300/17.
5.6 Steam Production Department System Power Chemistry Procedures CP/31 and CP/33.
6.0 ENCLOSURES 6.1 Graph for KOH Addition la The Presence Of Boric Acf.d.
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.P/0/A/8100/11 Inclosure 6.1 Graph for KOH Addition in the Presence of Boric Acid 2200 --
--= _ _ _ . . . - .
2000 .- - - . . - - - - - - - . - - - -.
1800 - -- - -- - - - - - . - -- - - .
Borie 1600 . - - . - - . - . - - - . - - - - -
Acid - - - . .- -
g . . - _ - . . . - . . . . . - - _ __ . . . _
Ppm 1400._._ . ....._ _.... _._ ..- - -- . - -- . . ~ . . - . . .--.
Boron 12 0 0 - - -- - - - -- ---- -
1000 -
! 800 - - - - - -
6 00 - ---- - - - - - - -- -
400 - - - - - - - - --
- - - - - ~
200 - - - - - - - - - --- - - - - - - .
0 10 20 30 40 50 60 70 "O CS 1 "-
Milliliters KOH Solution per 10 =illiliters Indigo Car ine Solutica .