ML20058H520
| ML20058H520 | |
| Person / Time | |
|---|---|
| Site: | Grand Gulf  |
| Issue date: | 07/30/1982 |
| From: | MISSISSIPPI POWER & LIGHT CO. |
| To: | |
| Shared Package | |
| ML20058H456 | List: |
| References | |
| RTR-NUREG-0737, RTR-NUREG-737, TASK-2.B.3, TASK-TM 08-S-04-316, 8-S-4-316, NUDOCS 8208030607 | |
| Download: ML20058H520 (10) | |
Text
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PLANT OPERATIONS MANUAL Attachment 2 to AECM-82/339 Volume 08 08-S-04-316 Section 04 Revision 4 o" * :
! DRAFT CHEMISTRY INSTRUCTION
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DEVELOPMENT AND USE OF CALIBRATION CURVES FOR CHLORIDE DETERMINATIONS 1
UTILIZING CHLORIDE ELECTRODES SAFETY RELATED I' .
Prepared: / go d , . /
/.
Reviewed: /
. Tecnnical Review Independent Review r, Q.. . ;-
.y
?iRC .
Approved:
Plant Chemist Concurrence:
Chemistry / Radiation Control Superintendent List of Ef fective Pages:
Page '
1-8 Artschsent I _
4 List of TCN's Incorporated:
P.evisien TON No.
O None 1 None .-
2 None -
3 None 8208030607 820730 PDR P
ADOCK 05000416 PDR
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GRAND GULF NUCLEAR STATION CHEMISTRY INSTRUCTION
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Title:
D2velop. 6 Use of Calibration Curves No.: 08-S-04-316 Revision: 4 Pego: I for Chlor. Deter. Utilizing Chlor. Electr.
1.0 PURPOSE .
.For development and use of calibration curves for chloride deter =inations using the Graphic Controls Ultra-sensitive (or egivalent) and the Lazar Micro
- - Cnloride eletrodes. This instruction pertains to Chloride concentration from 20pph fo-1000 ppm.
2.0 REFERENCES
2.1 Standard Methods, 14th Edition, 1975 -
2.2 Chemistry Procedure 08-S-03-1, Qualification of Chemistry Program 2.3 Chemistry Instruction 08-S-04-109, Operation of Orion 701 Ipn Analyzer I
2.4 Chemistry Instruction 08-S-04-466, Potassium Chloride Standard 2.5 Applicable Manufacturer's Technical Manuals . for Instruments and Electrodes 3.0 DEFINITIONS .
3.1 Immersion depth - Immersion depth, with the Lazar micro ion electrode should be adjusted to confor= to the sample size. For samples of one ml er greater, the electrode sensing element can be completely immersed.
For extremely small samples, the electrode can just barely be i=mersed to ellow contact between the solution being measured and the electrode sensing element.
3.2 Ionic Strength Adjuster (ISA) - ISA should be added to both sa=ples and standards whenever possible. If sample size is in the low microliter.
range, making the addition of ISA very difficult, then standards should also not conta'in any ISA. ,
3.3 Standard solutions - Volume of standards should be close to that of the s ample s . Standard solutions which are as much as an order of magnitude larger in volume than samples will not greatly effect results.
3.4 Stirring - Stirring with a stirring bar becodes i= practical for samples below 10 ml and, enerefore, should not be done. Response time in unstirred solutions will be somewhat longer than in stirred solutions.
If sample solutions are not stirred, tnen standard solutions should also not be stirred.
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GRAND GULF NUCLEAR STATION , CHEMISTRY INSTRUCTION
Title:
Drvelop. 6 Use of Calibration curves No.: 08-5-04-316 Revision: 4 Pege: 2 for Chlor. Deter. Utilizing Chlor. Electr.
NOTE
. hen 'using the Chloride - Analysis Chamber in conjuntion with the Lazar electrodes, sa=ple and standard solutions can be shaken for mixing.
Also, sa=ple and standard solutions in micro dishes may be gently agitated except where there is a possibility of radioactive contamination, should a high radiation sample be spilled.
4.0 PREREQUISITIES '
4.1 Apparatus Required 4.1.1 Graphic Controls Ultra-Sensitive Chloride electrode .and i Reference electrode 4.1.2 Lazar Micro Chloride electrode and Lazar Micro Ref,erence electrode 4.1.3 pH/mV meter 4.1.4 Orion Electrode switch 4 .1.'S Chloride Analysis Chamber
- 4.1.6 Beakers, various sizes 4.1.7 Micro dishes 4.1.6 Pipets, various sizes 4.2 Reagents Required .
4.2.1 Potassium Nitrate, KNO3 , 102 ,
, 4.2.2 Sodium Nitrate, NANO3 , 5M 4.2.3 Ultrex Nitric Acid, HNO 3, concentrated Acypf +, ,
4.2.4 Chloride Standards,,G-1000 ppm
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4.2.5 Demineralized water ~ ~ ~~
4.3 Attachments .
Attachment I - Lazar DJH-146 Micro Double Junction Electrode
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Grid *D GULF NUCLEAR STATION CHEMISTRY INSTRUCTION
Title:
Dzvelop. & Use of Calibration Curves No.: 08-S-04-316 Revision: 4 Pege: 3 for Chlor. Deter. Utilizing Chlor. Electr.
t^
t 5.0 PRECAUTIONS 5.1 The outer solution of the double junction reference electrode must be changed daily (10% KNO3 ). Initial card attached to instrument for daily. verification. g,y ,
TA s enc: p:e~ L j.s gue e.te eko de h c. .tsacco'st ?c/ lect M U6s.
5.2 The Cl- and reference electrodes must be stored separately.
5.2.1 Store the Cl-electrodes in a solution made from 100 ml demineralized H 2O and 100 ml ultrex HNO3 .
5.2.2 Store the double junction electrodes 'in demineralized H 20-5.3 Do not use the Cl-electrodes.in the presence of silver or , sulfide.
~T 5.4 The Graphic Controls, or equivalent, electrode is designed for very low levels of chloride. It should not be used in ramples if the chloride concentration is expected to be greater than 1 ppm. Instead, use the Lazar Micro electrode, or another procedure.
6.0 INSTRUCTIONS . .
'6.1 Calibration Curve for the Graphic
- Controls; or equivalent, electrode 6.1.1 Ensure startup of the Orion 701-A Ion analyzer in accordance with '
Re ference 2.3. , .
6.1.2 "erify functional check performed within the proper time frame as stated in the Calibration Functional Check Log Sook.
6.1.3 Verify outer solution of the double junction reference electr. ode has been changed and the inner solution is at the required level.
l l 6.1.4 Select the channel corresponding to the electrode' to be used and l ensure Orion 605 electrode switch is energized.
l 6.1.5 Rinse the specific ion and ref erence electrode in demineralized I water.
- 6.1.6 Place 100 ml of demineralized H2O int a 150 ml beaker containing a magnetic stirring bar.
6.1.7 Immerse the chloride and cou:le junction reference electrode in t
- the water.
l G.I.d Tair. the 0.ica 701 -A selecter saitch tc the Ir.' pccitien, : tert tne
< magdetic stirrer, and pipatQJ,00 ml of Ultrex E"03 into the water. Stir for 30 seconds. The solution is now adjusted to pH of approximately 2.0.
i
. CRAND GULF NUCLEAR STATION CHEMISTRY INSTRUCTION
Title:
Dsvelop. & Use of Calibration Curves No.: 08-S-04-316 Revision: 4 page: a for Chlor. Deter. Utilizing Chlor. Electr.
6.1.9 The' curve can be genera ted up to 1 ppm; 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 area, limit the curve to 1 ppm.
6.1.10 The lower limit of the curve should be that level that can be proven repeatable. The electrode is most reproducible at a lower level of 20 ppb, therefore,the lower chloride concentration should be established enere.
soppM * '
6.1.11 From thedchloride standard ' r-*-
pipet with
, Eppendorf (or equivalent) pipets,0100 e%L to the beaker of step 6.1.8. Stir for 30 seconds and record MV. Each additional c.100,dincrease chloride concentration by 20 ppb. .
6.1 12 Repeat step 6.1.11 over the range desired.
Example:
4 1st addition oft.100,tsf 20 ppm Cl- to the solution = 20 ppb
. -.2 2nd addition ofC200/of 20 ppm Cl- to the solution = 60. ppb d
. 3rd addition of0.200isf 20 ppm Cl to tne solution = 100 ppb d
4th addition ef..50C.isf 20. ppm Cl- to the solution = 200' ppb -
6.1.13 plot the mV potential versus concentration on appropriate graph paper, with mV reading along the X-axis, and concentration along the Y-axis.
6.2 Refill the outer chamber of the Lazar double j' unction reference electrode as follows: '
NOTE
, Exercise care to prevent contaminating the electrode tip with chloride from hands.
6.2.1 Remove the silicone gasket and wash the bottom chamber ich deionized or distilled water. (See Attachment I.)
thejelied KNO$ -
6.2.2 With the electrode held upcide down, slevly add g filling solution to the bot tom chamberj bein; ref a! not :: trcp cir hgabier.
6.2.3 Fill the chamber to approximately.1/S of an inch from the ooening.
6.2.4 Remove the cap from the clactr.,da tip nd carefully repl:ce the silicone gasket.
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GRAND CULF b'UCLEAR STATION CHEMZSTRY 2NSTRUCTION Tiele: Develop. 6 Use of Calibration Curves No.: 08-S-04-316 Revision: 4 page: 5 for Chlor. Deter. Utilizing Chlor. Electr.
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.
NOTE '
s 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 bybbles are I present.
6.2.7 Rinse the electrode and tip with demineralized water, wipe the tip with tissue, and insert the electrode plug into the reference electrode jack in the pH/mV meter.
6.3 Calibration Curve for~ the Lazar Micro electrode 6.3.1 Do steps 6.1.1 through 6.1.4.
6.3.2 Soak the chlor,ide electrode in a 100 ppm chloride solution for 10 minutes. .
&;w e. +h e elc e n c a'e l- c.% k e en..'l= e d uc'e r .
6.3.3 NOTE 1 4
( Calibration curves using larger volumes (to 100 ml) than those that follow may be generated simply by adjusting, proportionately, the volume of Ultrex
- HNO3 . When total volume of sample plus Ultrex HNO3 is 10 ml, add l
0.2 ml of ISA (5M NANO3 ). Increase the addition of ISA proportionately with increasing volume.
NOTE 2 ,
The purpose of the Chloride Analysis Chamber (CAC) is to prevent exposing high haa(AJU samples to the atmosphere. When preparing a calibration curve for the CAC, the s:eps performed should duplicate those s:eps taken during tne analysis.
t l NOTE 3 l c l
- 'he Cel l's i .L ict. ..u r. e to be gct.erated is to be d:nc using a tiere dish,
- ~
proceed to step s. 7..f . ,
l l
, GRAND GULF NUCLEAR STATION CHEMISTRY INSTRUCTION
Title:
D2velop. & Use of Calibration Curves No.: 06-5-04-316 Revision: 4 pego: 6 for Chlor. Deter. Utilizing Chlor. Electr.
. \
f.3,y h g 4. c a c. -
3, 9 00afn$100n.!y;,e p J 9 M c/ / Q
.b. f4f;79 HNO 3 hjtne pipet portey.e4. Cw c ,
- c. Place a rubber septa onto the pipet port.. .
C.lCC
- d. Using a gas tight syringe, evacuate C.44cc (or greater)) ,
of air from the chamber.
Al oms eeM a."l,? m ot s x& k "I n A M -(M -
.go
- e. Using the gas tight syringe, pipet'O.J!m1 f of.t.at. 0.15 ppmm standard into the CAC. . -
f* Netu C % n D e. ~O~ .
7 o. ' . Gently shake the CAC to mix the standard wtih U1' trex HNO3
.C
- f. Allow 5 minutes for the mV reading to stabilize.
NOTE Stabilization time . allowance i:r.sst be exactly the same for all standards and samples.
- j. . Record the reading, remove the septa and rinse the CAC with demineralized water.
, p . Repeat steps 6.3.4 ib nrough 6.3.4.2 over the range desired.
/ Do step 6.1.13.
NOTE ."
To avoid rinsing the micro dish between each measurement, use as many micro dishes as necessary to cover the desired range. - -
l 6.3.5 Using micro-dishes a.
% 9w 4 ofp,r.J,tw& '?; & 'I!W Ultex 1C:03 and 0.l:: r.fof the 0.15 ppmpa '
l chloride standard into tne micro dish.
Note the time or siart a timer.
- ~
b.
NOTE _
If a high radiation sampie in to b'e anal 5 sed, skip S cp
- 6.3.5.c t: cvcid .:::i':lc t:r.:: 3 .ti r l
O.
. . GRAND GULF NUCLEAR STATION CREMfSTRY INSTRUCITON
Title:
Develop. & Use of Calibration Curves Ne.: 08-S-04-316 Revision: 4 PagG: 7 for Chlor. Deter. Utilizing Chlor. Electr. l
- c. Agitate gently, being careful not to spill any of the solution.
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- d. Lower the electrodes into the solution, wait at least 5 minutes from step 6.3.5.4, then read the mV value. (See Note following step 6.3.4.hi
. c.. .
- e. Record the mV reading.
- f. Repeat steps 6.3.5.a through 6.3.5.e over the desired range.
s
- g. Do step 6.1.13.
6.4 Sample Analysis ,
T -
6.4.1 Graphic Controls (or equivalent) Electrodes
- a. Do 6.1.1 through 6.1.4.
NOTE High conductivity water may indicate ggH that will not be adjusted to HNU Y Yhis, 2 with the addition off 3 s ample mus t first be pH tested, then an appropriate quantity of HNO3 must ce added to a separate sa=ple to adjust the pH to 2 (pH measurements add enloride, tnerefore, the same s ample cannot be used).
- b. Prior to running an analysis, standardize the meter / electrode by analyzingE*" 20 p pb s t a nd ard . Adjust the standardization knob fof#ftespective electrode channel to the reading of th'e
/.
standard. -
d'
- c. Rinse 4 electrodes thoroughly with demin water. Immerse the electrodes in 100 ml of sacple to which you have added 100 ml Ultrex HNO3 .
- d. Stir for 30 seconds and record the, MV reading. ,
mV
- e. Convert to ppb Cl- by using the calibration curve.
6.4.2 Lazar Electrode o a. Using the CAC (1) Oc ytces 6.1.l throu;h 0.1.'.
(2) Do step 6.3.2. .
h ol US-gy & , /n T - tmi (3) '
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- CRAND GU?J NUCLEAR STATION CEEMISTRY INSTRUCTION
Title:
Div21op. 6 Use of Cclibration Curves No.: 06-5-04"316 Revision: 4 Page: 6 for Chlor. Deter. Utilizing Chlor. Electr.
(4) Using a standard with a chloride concentration approximating that of the expected concentration of the s ample, do steps 6.3.'4.a through 6.3.4 h s
(5) Adjust the mV reading to the specific value of the standard's known concentration as taken froo the most recent calibration curve generated for this analysis.
(6) Remove the septa and rinse tne CAC with demineralized water. .
.. s (7) Using a b.IO3m1 aliquot of th'e sample in Lieu of the s tandard , do steps 6.3.4.b through 6.3.4.f. .
- p. (8) Read ppm chloride from the calibration curve.
- b. Using a micro dish (1) Do $teps'6.1.1 through 6.1.4.
(2) Do Step 6.3.2.
t]z. k? : h1 a . 7l & dWS (3) - w .- s (4) Using a standard with a chloride concentration approximating that of th,e expected concentration of the sample, de steps 6.3.5.a through 6.3.5.e.
(5) De step 6. N. 2. a. ( 5)
, ',., (6) Using a c.100 ml alignot of'the sample in lieu ,-
of the standard, do steps 6.3.5.a through 6.3.5.e.
l (7) Read ppm chloride from the calibration 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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Ibdel D3M-146 Micro Double Jtneti , oferenca Electrode r m .
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-' cccoartrent CAUlI73: Da not push siliccne easlet into
' electrode so deen that it beccces hard to remove. Instead re::nve gasket and add core filling solutionc
. ~Y
- bottom ccrpertrent. - p l j. silicone gasket A
narrow teflon tubing
' Push to force reference soluticn out of electrode tip -
electrode tip N
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electrode cap
-. .