ML20080E135
| ML20080E135 | |
| Person / Time | |
|---|---|
| Site: | Grand Gulf  |
| Issue date: | 01/07/1983 |
| From: | Whitney G MISSISSIPPI POWER & LIGHT CO. |
| To: | |
| Shared Package | |
| ML20080E069 | List:
|
| References | |
| 08-S-04-316, 8-S-4-316, NUDOCS 8308300738 | |
| Download: ML20080E135 (16) | |
Text
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PLANT OPERATIONS MANUAL em s!$.e
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Volume 08 08-S-04-316 i
Ssetion 04 Revision 5 Date: 1-7-83
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_ CHEMISTRY INSTRUCTION DEVELOPMENT AND USE OF CALIBRATION'CURVIS'FOR CHL'ORIDE DETERMINATIONT
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UTILIZING CHLORIDE ELECTRODES SAFETY RELATED Prepared:
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Technical fview Ind'ependyInt'Revies/
Approved:
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Pl' ant Chemist List of Effective Pages:
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1-13 Atts. I-II List of TCN'a Incorporated:
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Ravision TCN No, i
WORK [PROCbSSilhG 2
None 3
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8308300738 830825 DR ADOCK 05000
m-GRAND GUL'F NUCLEAR STATION CHEMISTRY INSTRUCTION
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Title:
Develop. & Use of Calibration Curves No.: 08-S-04-316 Revision: 5 Page:
1
('N for Chlor. Deter. Utilizing Chlor. Electrs.
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i 1.0 PURPOSE For development and use of calibration curves for chloride determinations using the Graphic Controls ultra-sensitive (or eqivalent) and the Lazar micro
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chloride eletrodes. This instruction pertains to chloride concentration from N
20 ppb to 1000 ppe.
2.0 REFERENCES
2.1 Standard Methods, 15th Edition, 1980 2.2 Chemistry Procedure 08-S-03-1, Qualification of' Chemistry Program 2.3 Chemistry Instruction 08-S-04-109, Operation, of Orion 701 Ion Analyzer 2.4 Chemistry Instruction 08-S-04-466, Potassium Chloride Standard 2.5 Applicable Manufacturer's Technical Manuals for Instruments and Electrodes 2.6 Chemistry Instruction 08-S-04-443, Ionic Strength Adjsst'er -(ISA) and l
Filling Solution with FSIE and Double Junction Reference. Electrode
- 2.7 Chemistry Instruction 08-S-04-468, ~ Potassium Nitrate 1
2 3.0 DEFINITIONS 3.1 Immersion Depth - Immersion depth, with the Lazar micro; ion electrode, should be adjusted to conform to the sample size.
For samples of I al or I
greater, the electrode sensing element can be completely immersed.
For extremely small samples, the electrode can just barely be immersed to allow contact between the solution being measured and the electrode sensing element.
3.2 Ionic Strength Adjuster (ISA)
'ISA should be added to both samples and standards whenever possible.' If sample size is in the lo'w miciol, iter range, making the addition of ISA very difficult,.then stacdards should not contain any ISA.
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3.3 Standard Solutions - Volume of standards should ' be close to that of the samples.
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GRAND GULF NUCLEAR STATION CHEMISTRY INSTRUCTION
Title:
Develop.s & Usa of Calibration Curves No.: 08-S-04-316 Revision: 5 Page:
2) for Chlor. Detar. Utilizing Chlor. Electrs.
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,)'9 3.4 Stirring - Stirring with a stirring bar becomes impractical for samples below 10 m1 and, therefore, should not be done. Response time in unstirred solutions will be somewhat longer than in stirred solutions.
If saeple solutions are not stirred, then standard solutions should not be stirred.
3.5 Shaking - Shaking is possible when using the chloride analysis chamber in conjunction with the Lazar electrodes. Also, sample and standard solutions in micro dishes may be gently agitated except where there is a possibility of radioactive cancentration, should a-high ~ radiation sample -
he spilled.
4.0 PREREQUISITES 4.1 Apparatus Rcquired 4.1.1 Graphic Controls (or equivalent) ultra-sensitive chloride electrode and Orion (or equivalent) double junction reference electrode 4.1.2 Lazar micro chloride electrode and Lazar micro, double junction reference electrode 2
4.1.3 pH/mV meter 4.1.4 Orion electrode swit h
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4.1. 5 - Chloride anaiysis chamber 4.1.6 liaakers, various sizes
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4.1.7. Micro dishes 4.1.8 Pipets, various sizes 4.2 Reagents Required 4.2.1 Potassium nitrate, KNO, 10% (pH adjusted to 12 with KOH)
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GRAND CULF NUCLEAR STATION CHEMISTRY INSTRtiCTION
,Tiglke" Develop.&UseofCalibrationCurvesNo.: 08-S-04 'J16 Revision: 5 Page:
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fer Chlor. Deter. Utilizing Chlor. Electra.
C I
f 4.2.2 Sodium nitrate, NANO, SM 3
l 4.2.3 Ultrex nitric acid, RNO, concentrated 3
f 4.2.4 Chloride standards, 20 ppb to 1000 ppe I.
i 4.2.5 Demineralized water 4.3 Attachments 4.3.1 Attachment I - Orion 90-02 Double Junction Reference Electrode 4.3.2 Attachment II - Lazar DJM-146 Micro Double Junction Reference Electrede 5.0 PRECAUTIONS 5.1 The outer solution (10% KNO ) of the double junction refere: tee 3
electrode must be changed daily. Check pH of outer solution (pH = 12).
Initial card attached to instrument for daily verification.
NOTE
_The KNO3 for the Lazar electrode is a special gelled KNO.
3 5.2 The Cl-and reference electrodes aust be stored separately.
5.2.1 Store the Cl-electrodes in a solution made from 100 ml desineralized H O and 100 ?\\ ultrex HNO.
2 3
5.2.2 Store the Graphic Controls' reference electrode in desineralized
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H 0.
2 5.2.3 Store the Lazar's reference electrode in 10%F.NO.
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5.3 Do not use the Cl-electrodes in the presence of silver or sulfide.
5.4 The Graphic Controls, or equivalent, electrode is designed for very low levels of chloride.
It should not be used in samples or dilutions if the chloride concentration is expecced to be greater than 1 ppe.
- Instead, dilute farther, or use the La~zar micro electrode.
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GRAND CULF NUCLEAR STATION CHEMISTRY INSTRUCTION
Title:
Develop. & Use of Calibration Curves No.: 08-S-04-316 Revision: 5 Page:. 4 fer Chlor. Deter. Utilizing Chlor. Electra.
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5.5 Exercise care when handling the electrodes to prevent contaminating the electrodes with chlorida or greasy substances.
6.0 I,NSTRUCTIONS 6.1 Refill the chambers of the Orion (or equivalent) double junction reference electrode as follows:
6.1.1 Outer Chamber (Refill Daily When in Use) a.
Tip the electrode so that the filling solution moistens the green 0-ring (see Attachment I) on the electrode'o body.
b.
Holding the electrodes by the cap in one hand, push the outer sleeve up into the cap with the other hand, allowing the filling solution to drain out.
c.
With the outer sleeve pushed up into the cap, flush the chamber once or twice with 10% KNO3 through the outer chamber filling hole.
d.
Assure the outer sleeve is flurb with the inner cone.
e.
Fill the outer chenber with 10% KNO.
3 NOTE The level of the outer chamber filling solution must be at least one inch above the sample solution in the beaker, and the level of the inner solution must always be at least one inch above the level of the outer solution.
6.1.2 Inner Chamber (Refill weekly when in use) a.
Unscrew the electrode cap and remove the two springs and contact assembly.
r e e CRAND CULF NUCLEAR STATION CHEMISTRY INSTRUCTION T.
l Tit tg4 Dpvelop. & Use of Calibration Curves No.: 08-S-04-316 Revision: 5 Page:
5 for Chlor. Deter. Utilizing Chlor. Elecers.
NOTE It is not necessary to remove the outer sleeve to drain the inner chamber.
b.
Remove the inner chamber filling solution by:
I (1)
Inserting the spout of a partially emptied flip-spout bottle into the inner chamber filling hole, holding the bottle upright,-the tiectrode bpside down with the vent hole pointed in the desired direction of dispersal, and squeezing the flip spout bottle to cause the inner solution to spurt out of the chamber vent, or (2) Turn the electrode upside down, insert the needle of a hypodermic syringe into the filling hole and withdraw the filling solution into the syringe.
c.
Refill the inner chamber through the filling hole with fresh 90-00-02 Orion (or equivalent) filling solution.
d.
Replace the syringe and contact assembly, then screw the cap on to finger tightness.
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6.2 Refill the outer chaeber of the Lazar double junction reference electrode as follows:
6.2.1 Remove the s{1icone gasket and wash the bottom chamber with deionized or distilled water (see Attscheent II).
6.2.2 With the electrode held upside down, slowly add the jelled KNO3 filling solution to the bottom chamber, being careful not to trap air bubbles.
6.2.3 Fill the chamber to approximately 1/8 of an inch from the opening.
6.2.4 Remove the cap from the electrode tip and carefully replace the silicone gasket.
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GRAND GULF NUCLEAR STATION CwEMISTRY INSTRUCTION
Title:
Develop. & Use of Calibration CurvesjNo.: 08-S-04-316 Revision: 5 Page: -6kg-
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for Chlor. Deter. Utilizing Chlor. Electrs.l
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6.2.5 Using the silicone gasket in a manner similar to using a hypodermic syringe plunger, push some solution out of the electrode tip.
6.2.6 Check the teflon tubing for air bubbles and remove the air bubbles by continuing to press the gasket inward until the air bubbles are expelled, being careful not to push the gasket so deep that it becomes difficult to remove.
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If the air bubbles could not be removed without jamming the gasket, remove the filling solution from the electrode chamber and repeat steps 6.2.3 through 6.2.6 until no air bubbles are present.
6.2.7 Rinse the electrode and tip with domineralized water, wipe the tip with tissue, and insert the electrode plug into the reference electrode jack in the pH/mV meter or the appropriate jack in the Orion electrode switch.
6.3 Calibration Curves 6.3.1 Ensure startup of the Orion 701-A Ion Analyser in accordance with Reference 2.3.
.)
6.3.2 Verify functional check performed within the proper time frame as stated in the Calibration Functional Check Log Book.
6.3.3 Verify outer solution of the double junction reference electrode has been changed and the inner solution is at the required level.
4 6.3.4 Select the channel corresponding to the electrode to be used and ensure Orion 605 electrode switch is energized.
6.3.5 Rinse the specific ion and reference electrode in demineralized water.
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CRAND CULF NUCLEAR STATION CHEMISTRT INSTRUCTION TitJ4,4 Develop. & Use of Calibration Curves No.: 08-S-04-316 Revision: 5 Page:
7 far Chlor.-Deter. Utilizing Chlor. Electrs.
b_
6.3.6 Graphic Controls (or equivalent) Chloride Electrode and Orion (or equivalent) Reference Electrode a.
Place 100 ml of demineralized H O into a 150 ml beaker 2
containing a magnetic stirring bar.
b.
Immerse the chloride and double junction reference electrode in the water.
I c.
Turn the Orion 70b-A selector switch to-the MV position, start -
the magnetic stirrer, and pipet 0.100 ml of Ultrex HNO3 into the water.
Stir for 30 seconds. The solution is now adjusted to a pH of approximately 2.0.
NOTE The curve can be generated up to 1 ppe; however, as the amount of standard is added to the beaker, the volume and, consequently, the pH of the solution may be affected. To preclude problems in this aEea, limit the curve to 1 ppe.
l NOTE The lower limit of the curve should be that level that can be proven repeatable. The electrods is most reproducible at a lower level of 20 ppb, therefore the lower chloride concentration should be established there.
d.
At exactly 30 seconds after step 6.3.6.c, pipet 0.100 ml of the 20 ppa chloride standard to the breaker of step 6.3.6.c.
e.
Stir for 30 seconds and record mV.
NOTE Each additional 0.100 ml increases the Cl-concentration by 20 b
PP.
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GRAND GULF NUCLEAR STATION CHEMISTRY INSTRUCTION
Title:
Develop. & Use of Calibration Curves No.: 08-S-04-316 Revision: 5 Page:. -8 fer Chlor. Deter. Utilizing Chlor. Electrs.
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f.
Repeat steps 6.3.6.d and 6.3.6.e over the range desired.
Example:
1st addition of 0.100 ml of 20 ppe Cl-to the solution = 20 ppb 2nd addition of 0.200 ml of 20 ppe Cl-to the solution = 60 ppb 3rd addition of 0.200 mi of 20 ppe Cl-to the solution = 100 Ppb 4th addition of 0.500 al of 20 ppe C1-to the solution = 200 pbb g.
Plot the mV potential versus concentration on appropriate graph paper, with mV reading along the X-axis, and concentration along the Y-axis.
6.3.7 Lazar Micro Chloride and Reference Electrodes a.
Do steps 6.3.1 through 6.3.4.
b.
Soak the chloride electrode in a l'00 ppe chloride solution for
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10 minutes.
c.
Rinse the electrodes in domineralized water.
NOTE Calibration curves using 1"arger volumes (to 100 ml) than those that follow may be generated simply by adjusting, proportionately, the volume of Ultrex HNO. Wen total 3
volume of sample plus Ultrex HNO3 is 10 mi, add 0.2 al of ISA (5M NANO ).
Increase the addition of ISA 3
proportionately with increasing volume.
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j GRAND GULF NUCLEAR STATION CHEMISTRY INSTRUCTION TiqAe) Dgvelop. & Use of Calibration Curves No.: 08-S-04-316 Revision: 5 Page:
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far Chlor. Deter. Utilizing Chlor. Electrs.
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4 NOTE The purpose of the Chloride Analysis Chamber (CAC) is to prevent exposing high radiation samples to the atmosphere.
When preparing a calibration curve for the CAC, the steps performed should duplicate those steps taken during the analysis.
NOTE 1
If the calibration curve to be generated is to be done using a micro dish, proceed to step 6.3.7.e.
d.
Using the CAC (1) Assure that the pH/mV meter is set to STANDBY.
(2) Screw the cap containing the Lazar chloride electrode and reference electrode onto the CAC.
(3) Using a 0.025 to 0.100 31 pipet, carefully add I drop of Ultrex HNO3 through the piper. port of the CAC.
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(4) Place a rubber septa onto the pipet port.
(5) Using a gas tight syringe, evacuate 0.100 cc (or greater) l of air from the chamber.
NOTE Always evacuate a volume of air equal to or greater than the volume of sample.
(6) Using the gas tight syringe, pipet 0.100 al of the 0.15 ppa standard into the CAC.
(7) Note the time or start a timer.
(8) Gently shake the CAC to mix the standard with the Ultrex HNO3 kd
GRAND GULF NUCLEAR STATION CHEMISTRY INSTRUCTION
Title:
Develop. & Use of Calibration Curves No.: 08-S-04-316 Revision: 5 Page:,10 far Chlor. Deter. Utilizing Chlor. Electra.
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(9) Turn the select switch to mV and allow 3 minutes (starting with step 6.3.7.d(7)) for the mV reading to stabilize.
NOTE Stabilization time allowance must be exactly the same for all standards and samples.
(10) Record the reading, remove the septe and rinse the-CAC with desineralized water.
(11) Repeat steps 6.3.7.d(2) through 6.3.7.d(9) over the range desired.
(12) Do step 6.3.6.g.
NOTE To avoid rinsing the micro dish between each measurement, use as many micro dishes as necessary to cover the desired range.
e.
Using Micro-Dishes (1) Using a micro pipet, carefully pipet I drop of Ultrex RNO3,and 0.100 ml of the 0.15 ppe chloride standard into the micro dish.
(2) Note the time or start a timer.
NOR If a high radiation sampla is to be analyzed, skip step 6.3.7.e(3) to avoid possible contamination.
(3) Agitate gently, being careful not to spill any of the solution.
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GRAND GULF NUOLEAR STATION CHEMISTRY INSTRUCTION l
l Title; Develop. & Use of Calibration Curves No.: 08-S-04-316 Revision: 5 Page: 11 l
fer* Calot. Deter. Utilizing Chlor. Electra.
i (N 9
(4) Lower the electrodes into the solution, wait at least 5 minutes from step 6.3.7.e(1), then read the mV value (see note following step 6.3.7.d(9)).
(5) Record the mV reading.
(6) Repeat steps 6.3.7.e(1) through 6.3.7.e(5) over the desired range.
i (7) Do s tep 6.3. b.g.-
6.4 Sample Analysis 6.4.1 Graphic Controls (or equivalent) Chloride Electrode and Orion (or equivalent) a.
Do steps 6.3.1 through 6.3.5.
NOTE High conductivity water may indicate a pH that will not be adjusted to pH 2 with the addition of 0.100 ml of Ultrex HNO. This sample must first be pH tested, then an 3
k appropriate quantity of HNO3 must be added to separate sample to adjust the pH to 2 (pH measurements add chloride, therefore, the samt sample cannot be used).
b.
Measure the 20 ppb standard as per section 6.3.6 and adjust the mV reading to the value taken from the most recent calibration curve for this standard, Rinse the electrodes thoroughly with domineralized water.
c.
d.
Add 100 ml of sample or sample dilution to a clean 150 al beaker and start the stirrer.
Add 0.100 ml of Ultrex HN0. note the time and lower the e.
2 electrodes into the solution.
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GRAND GULF NUCLEAR STATION CHEMISTRY INSTRUCTION
Title:
Develop. & Use of Calibration Curves No.: 08-S-04-316 Revision: 5 Paget 12 fer Chlor. Deter. Utilizing Chlor. Electrs.
9 f.
At exactly 30 seconds after the previous step, observe and record the mV reading.
g.
Convert mV to ppb Cl-by using the calibration curve.
6.4.2 Lazar Electrodes a.
Using the CAC (1) Do steps 6.-3.t through 6:3.4.- *
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(2) Do neep 6.3.7.b.
(3) Rinse the electrodes in domineralized water.
(4) Using a standard with a chloride concentration approximating that of the expected concentration of the sample, do steps 6.3.7.d(1) through 6.3.7.d(9).
(5) Adjust the mV reading to the specific ralue of the standard's known concentration as taken from the most recent calibration curve generated for this analysis.
(6) Remove the septa and rinse the CAC with domineralized
}
water.
(7) Using a 0.100 al aliquot of the sample in lieu of the standard, do steps 6.3.7.d(3) through 6.3.7.d(10).
(8) Read ppa chloride from the calibration curve.
b.
Using a Micro Dish (1) Do steps 6.3.1 through 6.3.4.
(2) Do step 6.3.7.b.
(3) Rinse the electrodes with desineralized water.
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GRAND GULF NUCLEAR STATION CHEMISTRY INSTRUCTION Tic,lej Develop. & Use of Calibration Curves No.: 08-S-04-316 Revision: 5 Page: 13 far Chlor. Deter. Utilizing Chlor. Elecers.
O N.
(4) Using a standard with a chloride concentration approximating that of the expected concentration of the sample, do steps 6.3.7.e(1) through 6.3.7.e(4).
(5) Do step 6.4.2.a(5).
(6) Using a 0.100 mi aliquot of the sample in lieu of the standard, do steps 6.3.7.e(1) through 6.3.7.e(5).
(7) Read ppe chiaridt fr0m the cal'ibration curve.
7.0 DOCUMENTATION / CORRECTIVE ACTION Document results on appropriate reporting forms as per Chemistry Procedure 08-S-03-10.
Process completed forms in accordance with Chemistry Procedure 08-S-03-3, Document Control.
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dRAhDGULFNUCLEARSTATION CHEMISTRY INSTRUCTION
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08-s-04-316 Rev. 5 Attachment II Page 1 of 1 0
PAGE RTYPE XREF. NO.
DATE LAZAR DJM-146 MICR0 DOUBLE JUNCTION REFERENCE ELECTRODE o
CAUTION: Do not push silicone gasket into electrode so deep that it becomes hard to remove.
Instead remove tasket and add more filling solution.
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Push to force reference solution out of electrode tip.
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GRAND GUT.F NUCLEAR STATION CHEMISTRY INSTRUCTION A...
, s 08-S-04-316 Rev. 5 Attachment I Page 1 of 1
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