The item to which this evaluation is applicable represents:
Yes do 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 itembeing evaluated and an identification of the affected section(s) of the FSAR.
(4) SAFETY EVALUATION - PART B
,Yes No ill this item require a change to the station TechnicalSpecifications?
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 11 the probability of an accident previously evaluatedthe FSAR be increased?
/Will the consequences of an accident previously evaluatedYes No
je the FSAR be increased?Yes No V May the possibility of an accident which is different
j han any already evaluated in the FSAR be created?Yes No V Will the probability of a malfunction of equipment
important to safety previously evaluated in the FSARj p increased?| Yes No V Will the consequences of a malfunction of equipment
important to safety previously evaluated in the FSARincreased?
Yes No May the possibility of malfunction of equipmentinportant to safety different than any already evaluated
A the FSAR be created?Yes No V 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 safetyquestion is involved. Justify the conclusion that an unreviewed safety
|
| question is or is not involved. Attach additional pages as necessary.
Check those items below which were considered applicable during the preparationand review of this document.
Flushing and draining was used to minimize source - strength and con-tamination levels prior to performing an operation.
Permanent and/cr movable shielding was specified for reduction oflevels.
Use of pernanent or te=porary local exhaust ventilation syste=s wasused. for control of airborne contamination.
Operation was designed to be ccmpleted with the least practicable timespent in the radiation field.
{. v.:q Appropriate tools and equipment were specified for the operation to be--
_.. perrormee.
The operation was designed considering the minimum number of peoplenecessary for safe job completion.
Remote handling equipment and other special tools were specified toreduce external dose. ,
Contamination - control techniques were specified.
The operation was designed to be c.onducted in areas of as low anexposure as practicable.
/ Additicnal ALARA censiderations were:
|.sv Aust L- a'N= Ab ham d.xx anu - MM tica- ndiE./ ! W q
/ ALAPa Principles were not considered since the procedure did notinvolve work in a radiation area.
(5) Prepared by: N. [ 6 -N - [$Date=;- (6) Reviewed by: %Ob Date (- A 4- f a
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DUKE POWER COMPAhT
CHEMISTRY PROCEDURE FOR THE DETERMINATION OFCHLORIDE (MANUAL METHOD)
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1.0 Discussion
1.1 Scope
This procedure describes the manual colorimetric method forthe determination of chloride in high purity water.
1.2 Principle
The mercuric thiocyanate method of chloride analysis dependson the displacement of the thicrya2 ate ion from mercuric thio-cyanate by the chloride ion. The result of this reaction isthe formation of unionized, but soluble, mercuric chloride.In the presence of ferric ion, the liberated thiocyanateforms a highly colored ferric thiocyanate complex:
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Hg(SCN)2 + 2Cl HgCl +12SCN' (Reaction 1)+2
2SCN' + 2Fe+3 + 2 [Fe(SCN)] +2 (Reaction 2)
The intensity of its color, which is prop ~ortional to the originalchloride in concentration, is measured photometrically at awavelength of 463 ns.
Chlorides in water are significant since they contribute to;
j chloride stress corrosion of stainless steels. Chlorides alsocan accelernte pitting corrosion in all metals.
| 1.3 Precisions and Interferences
1.3.1 The precision of this method is 9 ppb. The accuracyis 20 ppb.,
1.3.2 Color, if present in the sample, will interfere withphotometric measurements where absorption occurs withinthe range of the selected wavelength.
1.3.3 Bromides, iodides, cyanides, thiosulfates and nitritesinterfere in this method by react 7ing with the mercuricthiocyanate. Chromates and hydrazine also interfere, butcan be removed. Hydrazine interferes over 1 ppm. Chromatesare precipitated with barium and filtered while hydrazineis oxidized by hydrogen peroxide at a pH of 9.2 with cupric
ion as a catalyst. Nitrite reduces the mercuric :niocyanateto mercurous thiocyanate which does not react as shownin reaction 1 in Section 1.2. Borax interferes due tothe buffer capacity of the borax. Calgon CS contains both '
nitrite and borax, therefore, samples containing CS cannot be analyzed without pretreatment to oxidize thenitrite to nitrate and convert the borax to boric acid.
1.4 Limits and Precautions -,
1.4.1 This se'thod is applicable for samples having a chlorideconcentration in the range of 50 to 2000 ppb.
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l.4.2 Care should be exercised in using mercuric thiocyanate, asit is highly toxic. Eye protection, lab coat, and rubbergloves should be used when handling nitric acid.
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1.4.3 Since the chloride ion is ubiquitous in nature, extremecare must be exercised in the collection and processing ofthe samples. All glassware should be nitric acid washedbefore use.
2.0 Apparatus,
l 2.1 Spectrophotometer
NOTE: Allow spectrophotometer to warm up for 20 minutes.
2.2 Two 100 mm light path optically matched sample cells.
| -2.3 Appropriate number of 125 ml erlenmeyer flasks, acid washed withnitric acid.
2.4 Ippendorf pipets with required tips.i
2.4.1 50 pl pipet (0.05 ml)
2.4.2 100 pl pipet (0.1 ml)
2.4.3 250 p1 pipet (0.25 ml)'
2.4.4 500 p1 pipet (0.50 ml),
2.4.5 1000 pl pipet (1.00 ml)
2.5 50 ml glass graduated cylinder, nitric acid washed.
2.6 Millipore filtration assembly.
2.7 Filters, 0.45 p.
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3.0 Reage.nts '
3.1 Ferric Nitrate, (10%)
Dissolve 30.0 1 0.1 g of reagent grade ferric nitrate [Fe(NO))39H 0) in 60 + 1 ml of demineralized water. Add 228 + 1 ml o.co$centrated nitric acid (HNO sp. gr.l.42). Dilute to 300 1 1
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ml with demineralized water. 3,his solution is stable indefinitely.T
3.2 Mercuric Thiocyanate, (0.3%)
Dissolve 0.900 1 0.001 g of mercuric thiocyanate [Hg(CNS),] in300 1 1 al of reagent grade methanol (CH 0H). Allow to stand forgat least 24 hours. -Filter and store in In amber reagent bottle.Do not use if more than 4 weeks old.
3.3 Stock Standard, (100 mg/1)
Dissolve 0.1648 1 0.0001 g, pre-dried at 105-110 C, of sodium chloridein demineralized water and dilute to one liter. This solution isstable for one year.
3.4 Cupric sulfate solution, (1000 mg/l Cu+2)
Dissolve 3.93 1 0.01g CuSO4 5H O in demineralized water and2dilute to 1 liter in a volumetrid flask. This solution is stableindefinitely.
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3.5 Sodium tetraborate solution, (0.lM)
Dissolve 20.1 1 0.lg Na B g in distilled water and dilute to-24one liter. This solution it stable indefinitely.3.6 Hydrogen peroxide, (H 0 , 30% by weight).22
3.7 Barium Nitrate solution, (4.3 %)
Dissolve 4311 g Ba(NO )? in demineralized water and dilute to31 liter in a. volumetric fIask. This solution is stable indefinitely.<
4.0 Procedure ,.
4.1 Standard Preparation
: Note: Generation of standard curve is not required if methodis in current use; however, a minimum of two standards(100 ppb and 200 ppb) which must fall within 1 20 ppb ofthe above standard curve are to be run daily. If these
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conditions are not met, a new staridard curve must beprepared. (Two 100 ppb Standards are to be run daily forQ Sum data.)
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4.1.1 Prepare a series of standards by adding suitablevolumes of stock standard solution (Section 3.3) to50 al of demineralized water in a 125 ml, nitric acidwashed erlenmeyer flask.
pl of 100 mg/l stock solution ml of 100 mg/l stock Final Chloride(Sectica 3.3) solution cone. ppb
NOTE: If no chromates are present or if hydrazine is <1 ppm,go to step 4.2.1. If chromates are present, go to step4.4. .If hydrazine is present and greater than 1 ppm, goto step 4.5.
4.2.1 Transfer 50 ml of the sample to a 125 m1, nitric acid washederlenmeyer flash.
4.2.2 Prepare a reagent blank by placing 50 0.5 ml of demin-eralized water into a 125 ml, nitric acid washed erlenmeyerflask.
4.2.3 To the samples, blank, and standards add successively5 + 0.1 ml of ferric nitrate solution (Section 3.1) and5.0 t 0.1 ml of mercuric thiocyanate solution (Section 3.2).Mix and allow to stand for 10 minutes.
4.3 Instrument Calibration and Sample Determination
4.3.1 Adjust the spectrophotometer to the 463 nm wave-length.
4.3.2 Fill a 100 mm sample cell with the reagent blank,place in the spectrophotometer, and set the zeroabsorbance.,
4.3.3 Analyze the standards, in order of increasing concentration,and subsequent samples using a 100 mm sample cell. Thesample cell is to be rinsed between each analysis with thenext sample to be analyzed. Check the zero absorbance withthe reagent blank before each sample.-
4.3.4 Prepare a standard curve by plotting absorbance vs. concen-tration of the chloride standards.
4.3.5 Determine the concentration of the unknown sample bycomparing the sample absorbance with the stand,ard curve.
4.4 Sample preparation - If chromates are present.
4.4.1 Add 50 ml of sample to a 125 m1 erlemeyer flask. Add 50M1 demineralized water to another flask (this is the reagentblank solution).
4.4.2 Add 5 ml barium nitrate solution (step 3.7) to each flaskand mix; allow to stand for 10 minutes.
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4.4.3 Decant each into nitric acid cleaned 50 m1 stoppered centri-fuge tubes and centrifuge for 5 minutes. Decant 50 ml fromeach tube into sample flasks.
4.4.4 Carry through steps 4.2.3 to 4.3.5.
4.5 Sample and Standard Preparation - If hydrazine is present greaterthan 1 ppa.
4.5.1 Add 50 ml of standards (step 4.1.1) and sample to individual125 ml erlenmeyer flasks. Also place 50 ml of demineralizedwater into a 125 ml erlenmeyer flask to be used as a reagentblank.,
4.5.2 Add 5.00 m1 sodium tetraborate solution (step 3.5) and2.00 ml cupric sulfate solution (step 3.4) and 1.0 ml of30% hydrogen peroxide (step 3.6) to each flask.
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4.5.3 Heat the solutions to gentle boiling on a hotplate andmaintain solutions at boiling temperature for 20 minutes.
4.5.4 Remove the solutions from the hotplate and cool them toroom temperature. Adjust the total volume of each solutionto exactly 50 ml with demineralized water.
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4.5.5.
After 10 minutes carry through steps 4.2.3 to 4.3.5.
| NOTE: Standards should go through chemical treatment when; removal of hydrazine method (Section 4.5) is involed.
When the chromate method (Section 4.4) or the nointerference species method (Section 4.2) are usedthe standards do not require this treatment.
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; 5.0 Referencest
(| 5.1 American Society for Testing and Materials, 1978 Book of ASTM
Standards, Part 31, D 512-67, Pages 295-300.
5.2 Standard Methods for Examination of Water and Wastewater,14th Edition, 1975, Part 408B, Pages 304"306.
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5.3 Steam Production Department System Power Chemistry ProcedureCP/19. '
The item to which this evaluation is applicable represents:
Yes No X A change to the station or procedures as described in the FSARt,'
or a test or experiment not described in the FSAR7
If the answer to the above is "Yes", attach a detailed description of the itembeing 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 TechnicalSpecifications?
If the answer to the above is "Yes," identify the specification (s) affectedand/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 X Will the probability of an accident previously evaluatedin the FSAR be increased?,
Yes No X Will the consequences of an accident previously evaluated'
in the FSAR be increased?Yes No X May the possibility of an accident which is different
than any already evaluated in the FSAR be created?Yes No X Will the probability of a malfunction of equipment
important to safety previously evaluated in the FSAR| be increased?| Yes No X Will the consequences of a malfunction of equipment
important to safety previously evaluated in the FSAR
| be increased?! Yes No X May the possibility of malfunction of equipmenti important to safety different than any already evaluated
( in the FSAR be created?Yes No X Will the margin of safety as defined in the bases to any
. Technical Specification be reduced?
iIf the answer.to any of the preceding is "Yes", an unreviewed safetyquestion is involved. Justify the conclusion that an unreviewed safetyquestion is or is not involved. Attach additional pages as necessary.
