ML20080P605
| ML20080P605 | |
| Person / Time | |
|---|---|
| Site: | Catawba  |
| Issue date: | 07/29/1982 |
| From: | Bolin C, Cox J, Painter R DUKE POWER CO. |
| To: | |
| Shared Package | |
| ML20080P419 | List:
|
| References | |
| CP-O-A-8150-07, CP-O-A-8150-7, NUDOCS 8402220595 | |
| Download: ML20080P605 (11) | |
Text
. . m _
Form 34731 (1041)
(Formerly SPD lo021)
DUKE POWER COMPANY (1) ID No: CP/0/A/8150/07 PROCEDURE PREPARATION Change (s) O to PROCESS RECORD 0 Incorporated I
(2) STATION: Catawba (3) PROCEDURE TITLE: Chemistry Procedure for the Determination of Chloride - Auto Analyzer (4) PREPARED BY: (h M DATE: 9- / S -l'd (5) REVIEWED BY: ,
8/ f DATE: 7-A.P-f2-Cross-Disciplinary Review By: U.
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(6) TEMPORARY APPROVAL (IF NECESSAR :
By: (SRO) Date:
By: Date:
(7) APPROVED BY: .b. Date: 7IL\ IL l
! (8) MISCELLANEOUS:
l Reviewed / Approved By: Date: __
l l Reviewed / Approved By: Drte:
l l
MASLR RE i
B402220595 840215 PDR ADOCK 05000413 E PDR
FORM SPD-1001-2 !
DUKE POWER COMFANY f NUCLEAR. SAFETY EVALUATION CHECK LIST (1) STATION: Catawba UNIT: 1 X 2 X 3 OTHER:
(2) CHECK LIST APPLICABLE TO: CP/0/A/8150/07 (3) SAFETY EVALUATION - PART A The item to which this evaluation is applicable represents:
Yes No / A change to the station or procedures as described in the FSAF or a test or experiment not described in the FSAR?
If the answer to the above is "Yes", attach a detailed description of the ite being evaluated and an identification of the affected section(s) of the FSAR.
i (4) SAFETY EVAIUATION -' PART B Yes No / Will this item require a change to the station Technical 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 / 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 increased?
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?
Yes No / Will the consequences of a malfunction of equipment important to safety previously evaluated in the FSAR be increased?
Yes No / May the possibility of malfunction of equipment important to safety different than any already evaluated n the FSAR be created?
Yes No 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
_ question is or is not involved. Attach additional pages as necessary.
(6) PREPARED BY: &L M DATE: '/-/3-fL (7) REVIEWED BY: A DATE: 7- J P- E2- _
i (8) Page 1 of I
' Fom 18855 (3-80) -
DUKE POWER COMPANY ALARA EVALUATION CHECKLIST Catawba (1) Station Unit: 1, 2 3 Other:
(2) Checklist Applicable to: CP/0/A/8150/07 (3) ALARA Evaluation Check those items below which were considered applicable during the preparation and review of this document.
Flushing and draining were used to minimize source - strength and con-tamination levels prior to performing an operation.
Permanent and/or movable shielding was specified for reduction of levels.
Use of permanent or temporary local exhaust ventilation systems was used for control of airborne contamination.
/ Operation was designed to be completed with the least practicable time spent in the radiation field.
Appropriate tools and equipment were specified for the operation to be performed.
/ The operation was designed considering the minimum number of people necessary for safe job completion.
Remote handling equipment and other special tools were specified to reduce external dose.
Contamination - control techniques were specified.
The operation was designed to be conducted in areas of as low an exposure as practicable.
Additional ALARA considerations were:
ALARA Principles were not considered since the procedure did not involve work in a radiation area.
(5) Prepared by: dadd Date 9-/3-90 (6) Reviewd by: /f M Date 7 - LP- P 2- i
5 CP/0/A/8150/07 DUKE POWER COMPANY CATAWBA NUCLEAR STATION CHEMISTRY PROCEDURE FOR THE DETERMINATION OF CHI,0 RIDE - AUTO ANALYZER 1.0 DISCUSSION 1.1 Scope This procedure describes the automated colorimetric method for the determination of chloride in high purity water.
1.2 Principle The mercuric thiocyanate method of chloride analysis depends on the displacement of the thiocyanate ion from mercuric thiocyanate by the chloride ion. The result of this reaction is the formation of un-fonized, but soluble, mercuric chloride. In the presence of ferric ion, the liberated thiocyanate forms a highly colored ferric thiocyanate complex. The intensity of its color is proportional to the original chloride ion concentration:
~ ~
Hg(SCN)2 + 2C1 + HgC12 + 2SCN
~
3
- 2SCN + 2Fe ++ 2 (Fe(SCN))2+
l The wet colorimetric analysis of chloride is automatea using a j modified Technicon Auto Analyzer II. Samples to be analyzed are l poured into cups and loaded on the sample module. A peristaltic l
proportioning pump, operating continuously, pumps samples and l reagents through the analytical cartridge. Air bubbles segment the flowing stream, maintaining sample integrity and eliminating the cross-mixing of samples. After mixing, the solutions are routed to a delay coil where the color reaction is completed. The analytical l stream is then directed to'the flow cell where it is de-bubbled and l pumped through the optical path of thc colorimeter. The optical
! density of the solution at a select wavelength is determined and a signal from the detector ir transmitq The color intensity of the (Fe(SCN))~gd to a strip complex chart obeys recorder.
Beer's law, so the absorbance increases linearly with an increase in chloride concentration.
1.3 Precision and Interference L The precision and accuracy of this procedure will be determined by l Q-Sum data.
l Bromides, iodides, cyanides, thiosulfates, chreraates, nitrates, and hydrazine interfere in this method by reacting with the mercuric l thiocyanate.
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l
- -~ -
CP/0/A/8150/07 Paga 2 of 6 Color, if present in the sample, will interfere with photometric measurements where absorption occurs within the range of the selected bandpass.
1.4 Limits and Precautions This method is applicable over the concentration range of 25 ppb to 1000 ppb chloride.
Since chloride and fluoride are determined simultaneously, some references to fluoride will be made in this procedure. A general understanding of procedure CP/0/A/8150/08 (Chemistry Procedure for the Determination of Fluoride-Auto Analyzer) should be achieved before beginning this analysis.
All reagents required for this procedure must be reviewed to insure that they are current with regard to shelf life. If this condition is not met, remake the dated reagents.
Care should be exercised in handling mercuric thiocyanate, as it is highly toxic. Face shield and rubber gloves must be used in handling nitric acid.
Since chloride ion is a very common contaminant, extreme care must be exercised in the collection and processing of samples. All labware must be nitric acid washed.
When handling radioactive samples, good laboratory practices and techniques are essential to prevent radioactive contamination of personnel, equipment, and physical structures.
2.0 APPARATUS 2.1 Technicon Auto Analyzer II consists of:
2.1.1 Sampler IV with a 40/hr. adjustable cam ,
2.1.2 Ismatec - Brinkman proportioning pump 2.1.3 Analytical Cartridge, see Enclosure 6.1 for manifold description 2.1.4 Single channel colorimeter with:
2.1.4.1 1.5 - 50 mm flow cell 2.1.4.2 Interference filter for 480 nm wavelength 2.1.5 Strip chart recorder 2
2.2 Three Nalgene 100 ml volumetric flasks properly acid cleaned ith 4
nitric acid.
2.3 1000 p1 Eppendorf pipet with appropriate tip
CP/0/A/8150/07 Paga 3 of 6 2.4 Sample cups 2.5 Waste chemical receptacle 3.0 REAGENTS NOTE: The preparation date for each reagent must be compared to the designated shelf life and determined valid prior to use or remake as necessary.
3.1 Ferric Nitrate
.l In a one gallon carboy, dissolve 122 t 2 grams of ferric nitrate
, (Fe(NO3 )3
- 9H2 O) in 2400 1 50 al of Super Q water. Slowly add 1600 ml of concentrated Nitric Acid (HNO3 ). Mix, then add 2.0 : 0.1 ml of Brig - 35 wetting agent and remix. Shelf life is two months.
3.2 Mercuric Thiocyanate Dissolve 0.70 1 0.005 grams of mercuric thiocyanate Gig (SCN)2), in
'350 1 20 al of reagent grade methanol. Then slowly add 650 2 20 ml of Super Q Water. Shelf life is one month.
3.3 Stock Chloride Solution (1000 ppa)
'In a 1000 ml nalgene volumetric flask dissolve 1.6485 1 0.0002g of-oven dried ($105*C for one hour and desiccator stabilized) sodium chloride in Super Q water and dilute to voluge. Discard after 12 months.
3.4 Stock Fluoride Solution (1000 ppm)
In a 1000 al nalgene volumetric flask, dissolve 2.2100 t 0.0002g of oven dried (*105'C for one hour and desiccator stabilized) anhydrous sodium fluoride, NaF, in Super Q water and dilute to volume. Discard after 12 months.
3.5 Stock Fluoride and Chloride Standards l
Prepare a series of mixed stock standards by diluting suitable volumes of both stock solutions (Section 3.4 and 3.5) to 1 liter in a nalgene volumetric flask, using Super Q water. Discard after one
- month,
~ ~ ~
al of F Stock Solution el of CL" Stoch Solution Conc. F ppm Conc. CL ppm 1000 ppm 1000 ppm 10 + 50 = 10 50 100 + 5 = 100 5 10 + 10 = 10 10 I
1 l
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CP/0/A/8150/07 Paga 4 of 6 4.0 PROCEDURE 4.1 Instrument Calibration Set up the Technicon Auto Analyzer II as shown on Enclosure 6.1.
Allow recorder and colorimeter to warm up for 30 minutes. During warmup, run Super Q water through the sample line to check the flow pattern and hydraulics of the system. Obtain a resgent baseline with
' the sample probe in the wash receptacle. Once the bubble pattern has been established and the 30 minute warmup time has elapsed, calibration may begin.
4.1.1 Recorder Calibration
- a. Rotate colorimeter display rotary switch to "Zero" position and place the recorder pen span control to the .1 volt position.
NOTE: Use the .1 volt position when using the recorder output from the colorimeter. When using the telemetry output, place the recorder pen span control to the 5 volt position.
- b. Adjust Recorder "Zero" Control Knob (on recorder) until recorder reads 0% on chart paper,
- c. Rotate colorimeter display rotary switch to " Full Scale" position.
, d. Adjust Recorder " Cal" (on recorder) until recorder reads 100% on chart paper. !
, e. Recheck 0% on chart paper by placing the colorimeter
+
display rotary switch to the "Zero" position and repeat steps "4" through "d" if necessary.
- f. Place colorimeter display rotary switch in the
" Normal" position and place the recorder pen span control to the 50 Milli Volt position.
NOTE: This position is to be used when using th recorder output from the colorimeter. When using the telemetry output, place the recorder pen span control to the 2 volt position.
- g. Set the reagent base line to 10% of full scale using first (if necessary) the Aperture Adjustment (on colorimeter) for gross deflection, and then the Baseline Trimpot for fine adjustment.
- h. Place the colorimeter display rotary switch to the
" Damp 2" position.
4.2 Preparation of Standards and Samples Prepare a series of standards by diluting 1.00 ml of each mixed stock standard solution (Section 3.6) to 100 ml with Super Q water:
Prepare fresh daily.
. + , - - - , , - - , - , , ,_ ,e , . . , , - . _ _ _
- , _ . , - _ . , , - . , - _ _ - . . , n,_ _ . , _ - _ , - , _ _ _ _ - - , , _ . ,
CP/0/A/8150/07 Paga 5 of 6
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Stock Standard Solution Conc. F ppb Conc. CL ppb F ppm CL ppm 10 50 100 500 100 5 1000 50 10 10 100 100 Prepare sample cups containing samples, standards, and Super Q water.
Load these onto the sampler as shown in Enclosure 6.2. Set the alarm pin for the.last sample and begin analysis. After every four
' samples, run three cups of a 100 ppb standard. Two 100 ppb standards will be re:orded daily for "Q-Sun".
4.3 Instrument Standardization While the three 500 ppb standards (Section 4.2) are being analyzed, allow the first standard to peak without calibrating. During the second steady state adjust the colorimeter "Std Cal" to obtain a recorder deflection of 54 chart divisions (10 ppb /dev). The final standard steady state should fall on the proper chart division.
The 50 ppb standard should peak at 5 t .5 chart divisions. Fine tune ,
the second 50 ppb standard if necessary.
The 100 ppb standard should peak at 10 chart divisions without adjustment. Fine tune the second 100 ppb standard to 10 chart divisions if necessary.
After standardizing the instrument, run 3 cups of 100 ppb standard.
'If the standards are not within Q-Sum limits, repeat the entire standardization.
NOTE: Iftheinstrumenthasbeeninstandbyfor}1 hour,run three cups of 100 ppb standard, and verify that they are within Q-Sum limits. If not, repeat the entire standardization.
4.4 Determination of Unknown Concentration NOTE: If chromates or other interferring species are present the sample should be run as per CP/0/A/8100/05, Chemistry Procedure for the Determination of Chloride (Manual Method).
Unknown sample concentration will be determined directly from the strip chart paper by averaging the three peaks. Example, 2.5 divisions times 10 ppb /div. equals 25 ppb, and 25 divisions times 10 ppb /div. equals 250 ppb.
Some baseline drift may be encountered while samples and standards are being acalyzed. For this reason the reagent baseline will be interpreted for each sample.
CP/0/A/8150/07 Pagn 6 of 6 Should one peak appear to be contaminated, use the average of the remaining two peaks for calculating sample concentration. If at least 2 peaks do not agree within 10 ppb, reanalyze the sample.
4.5 Standby Operation.
When analyses are completed for the day, switch the pump speed regulator from "10" to "1". Place the recorder and recorder power in the "Off" position and rotate the colorimeter display rotary switch to the "Zero" position.
4.6 Termination of Instrument Operation.
When analyses are completed for the day, turn off the recorder and the pump, unplug the colorimeter, release the pump platen, and install the pinch bar.
5.0 REFERENCES
5.1 McGuire Nuclear Station Chemistry Procedure CP/0/A/8150/07.
5.2 Stear "roduction Department System Power Chemistry Procedure CP/20.
6.0 ENCLOSURES _
6.1 Technicon Auto Analyzer II Analytical System 62 Cutaway of Technicon Sample Tray
Enclosure 6.1 CP/0/A/8150/07 Technicon Auto Analyzer II Analytient System To sampler IV Wash Receptacle Sampler y ,- i Ise tiodule ""'"
A j
g purple / white Ise waste f I
I white / white From ISE dehubh11
) To dehubbler tube black / black Air ,'
grey / grey Tisab ;
$- litr. a _00000 ,1, se grey / grey sample (Fluoridef To itecorder -
O d e a a_ yellow / yellow sample (Chloride) 20 *I' urn A#
m Igr ' black / black air Mixing Coil orange / white Trom debubbler w
. green / orange Hecuric Thia ,'
white / white sarsple pull throur,h '
To pull throi4gh '
- 7 . orange / white Ferric Nitrate ,
To waste g blue / blue purple /wh it e From Color waste Super Q wash water
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(,olo r ime t e r ,
s V Peristaltic Pump y
To debubbler llaste Tube Tube Color & Flow Rates purple / white 3.90 ml/ min blue / blue 1.60 ml/ min yellow / yellow 1.20 ml/ min grey / grey 1.00 ml/ min white / white 0.60 ml/ min black / black H.32 ml/ min orange / white 0.23 ml/ min orange / green 0.10 ml/ min
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CP/0/A/8150/07 CUTAWAY OF TECHNICON SAMPLE TRAY U.
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