ML20128N150

Rev 1 to CP 807/2807/3807AR, Determination of Hydrazine by Titration

ML20128N150
Person / Time
Site:	Millstone
Issue date:	05/15/1996
From:	Peters J NORTHEAST NUCLEAR ENERGY CO.
To:
Shared Package
ML20128N126	List: ML20128N122 ML20128N150 ML20128N167 ML20128N173 ML20128N226 ML20128N280
References
CP-807-2807-380, NUDOCS 9610160304
Download: ML20128N150 (11)

Text

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CHEMISTRY PROCEDURE E

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Determination Of Hfdrazine by Titration p:

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Approval: !J' N1 'S Vice President - Nuclear Operations SORC Mtg. No: 94-/8 Date: 5- /- 94 Effective Date: 5-/S-94 3 9610160304 961004 l PDR ADOCK 05000245 P PDR

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Level of Use Subject Matter Expert:

J. Peters lnform8 tion

Millstone All Units Chemistry Procedure

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j Determination of Hydrazine by Titration TABLE OF CONTENTS

1. PURPO SE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

2. PREREQUISITES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

3. PRECAUTIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

4. INSTRUCTIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 4.1 Preparation of Sodium Bicarbonate Solution . . . . . . . . . . . . . . . . . . 4 4.2 Preparation of Iodine 'Iltrating Solution . . . . . . . . . . . . . . . . . . . . . . 4 4.3 Preparation of Sodium Thiosulfate Solution . . . . . . . . . . . . . . . . . . . 4 4.4 Weekly Standardization of Iodine 'I1trant . . . . . . . . . . . . . . . . . . . . . 5 4.5 Sample Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

5. . REVIEW AND SIGNOFF . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

6. REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

7.

SUMMARY

OF CHANGES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 ATTACHMENTS AND FORMS Chem Form 807/2807/3807AR-1,"Hydrazine Titration Log" Chem Form 807/2807/3807AR-2," Iodine Titrant Weekly Standardization Log" i

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L,evel of Use by . ,rd,, y ky im CP M7/2MMM7AR Rev. 2 nformation g ug pg 3 of g

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1. PURPOSE 1.1 Oldective Provide instructions for the analysis of hydrazine in water at

concentrations greater than 1 ppm by titration.

1.2 Discussion j Hydrazine is readily oxidized by iodine. In this analysis, a measured i

aliquot of sample is titrated with a standard iodine solution. When all of the hydrazine is consumed, the excess iodine reacts with the starch to form j an intensely colored blue complex, indicating the endpoint of the titration. I

2. PREREOUISITES  ;

i 2.1 General j N/A 2.2 Documents j

] 2.2.1 NUC CHM 01," Chemistry Quality Control Program" i

2 2.3 Tools and Consumables 2.3.1 Euret,10.0 mL 2.3.2 Buret,25.0 mL 1

2.3.3 Cylinder, graduated 100 mL 1

2.3.4 Flask Erlenmeyer 250 mL l 2.3.5 Buret clamp 2.3.6 Buret base i

2.3.7 Flask, Volumetric 1000 mL 2.3.8 Watch glass 2.3.9 Potassium Iodide (KI)

. 2.3.10 Sublimed Iodine i

Level of Use k , , _/m i CP 807/2807/3807AR

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SodiumThiosulfate 5-hydrate (Na2SO 2.3.11 2 3

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I 2.3.12 Sodium Thiosulfate N/40 - vendor supplied 2.3.13 Sodium Bicarbonate - Reagent Grade 2.3.14 Stable Starch solution - vendor supplied

3. PRECAUTIONS 3.1 Other oxidizable materials if present, including ferrous iron, sulfite and sulfide will be titrated, resulting in erroneously high values.

3.2 A watch glass must be used when weighing sublimed iodine to prevent the loss of analyte during transfer from the reaction ofiodine with various

, materials other than glass.

3.3 Samples must be analyzed immediately after collection to prevent the hydrazine from reacting with atmospheric oxygen resulting in erroneously low values.

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4. INSTRUCTIONS

) 4.1 Preparation of Sodium Bicarbonate Solution i

4.1.1 DISSOLVE 50.0 grams of reagent grade sodium bicarbonate in 950 mL of demineralized water.

4.1.2 Refer Tb NUC CHM 01, " Chemistry Quality Control Program,"

and LABEL bottle.

4.2 Preparation ofIodine"Iltrating Solution 4.2~ In a 500 mL volumetric flask, DISSOLVE 20.0 grams of potassium iodide in 50 mL of demineralizer water. j 4.2.2 ADD 1.60 grams of sublimed iodine to volumetric flask l containing potassium iodide solution. l J l l 4.2.3 MIX solution until iodine is completely dissolved.

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4.2.4 DILUTE to 500 mL with demineralized water and MIX solution j thoroughly.

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. 4.2.5 TRANSFER iodine titrating solution to a bottle.

4.2.6 LABEL bottle with a 1 month expiration date.

! 4.3 Preparation of Sodium Thiosulfate Solution I

4.3.1 In a 1 liter volumetric flask, DISSOLVE 6.20 grams of reagent grade soidum thiosulfate in approximately 500 mis of

, demir.eralized water.

4.3.2 DILUTE to 1 liter with demineralized water and MIX solution thoroughly.

4 4.3.3 TRANSFER solution to an amber bottle.

i 4.3.4 Refer 'Ib NUC CHM 01, " Chemistry Quality Control Program,"

and LABEL bottle.

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Level of Use b k d CP 8W280M807AR informeuon K N_ . .f A ' y_ ,R;.1 ,

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4.4 Weekly Standardization ofIodine Tltrant

4.4.1 ADD the following solutions to a 250 mL Erlenmeyer flask

• 10.0 mL of sodium thiosulfate solution i

OR 10.0 mL of sodium thiosulfate N/40 solution

• 2.0 mL of vendor supplied stable starch solution I

• 90 mL of demineralized water

! 4.4.2 MIX solution thoroughly, NOTE When color of the sample remains blue and does not fade with swirling, j the titration should be stopped, the end point has been reached.

4.4.3 SWIRL flask and TITRATE with the iodine titrating solution until a blue color end point is obtained.

4.4.4 READ the mL of iodine solution required to reach the end point from the burette.

4.4.5 RECORD the following information on Chem Form 807/2807/3807AR-2:

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• Date

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• mL of titrant for standardization

• . Week ending date

• Tbchnician initials 1

I g Level of Use gy jr 5 {. y -[% CP 807/2807/3807AR g3 Information g ~. jf% M4 5 of 8

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4.5 Sample Analysis

{ 4.5.1 ADD the following solutions to a 250 mL Erlenmeyer flask.

• 100 mL of sample a

2.0 mL of vendor supplied stable starch solution 5 mL of sodium bicarbonate solution NOTE When color of the sample remains blue and does not fade with swirling, the titration should be stopped, the end point has been reached.

4.5.2 SWIRL flask and TITRATE with the iodine titrating solution until a blue color end point is obtained.

4.5.3 READ the mL of iodine solution required to reach tlic end point from the burette.

4.5.4 CALCULATE the ppm hydrazine as follows:

PPM hydrazine = 20 (mi of titrant - 0.1 mi3 D

^ l D = Dilution Factor = 100/ number of mL of sample used in dilution.

A = number of mL required for weekly standardization (Chem Form 807/2807/3807AR-2).

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4 4.5.5 RECORD the following information on Chem Form 807/2807/3807AR-1:

• Date

• Tune

• Sample point

• mL of titrant for sample

• Dilution factor

• ppm Hydrazine

• Tbchnician initials e

i A A- /t A ce so7/2807/38074R K" ~K iq"yy Level of Use information g.1, l

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5. REVIEW AND SIGNOFF E

5.1 The x niew and signoff for this procedure is located on:

i i 5.1.1 Chem Form 807/2807/3807AR-1, "Hydrazine 'Iitration IAg" 5.1.2 Chem Form 807/2807/3807AR-2, " Weekly Iodine 'Iitrating Solution Standardization Img" l 6. REFERENCES I 6.1 Calgon Corporation," Determination of Hydrazine in Boiler Water (Direct Iodine Titration Method),"'Ibst No. 35-166-C, March 1989

6.2 NUC CHM 01, " Chemistry Quality Control Program," Rev. O

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SUMMARY

OF CHANGES i

7.1 The content of this procedure was modified to incorporate new format l criteria specified in Revision 1 of DC-2," Developing and Revising i Millstone Procedures and Forms."

i 7.2 Incorporated a hydrazine titration log sheet.

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'- 7.3 Incorporated an iodine tritrant weekly standardization log sheet.

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r 3 r 3 WATER 6Edih MANAGEMENT ANALYTICAL sv.s_omacoco..mc. DIVlSlON PROCEDURES L J L J

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DETERMINATION OF HYDRAZINE IN BOILER WATER (Direct lodineTitration Method)

SUMMARY

OF METHOD ment items are obtainable from Calgon Corporation, Hydrazine is readily oxidized by iodine. In this test, a Pittsburgh, Pennsylvania. When ordering, include de.

measured aliquot of sample is titrated with a standard scription and catalog number.

iodine solution. When all of the hydrazine is consumed, Description Unit Size Catalog No.

the excess iodine reacts with starch to form an intensely N/40 Thiosulfate Solution qt R5095 colored blue complex, mdicating the endpomt of the Stable Starch Solution pt R5096 titration. The test, which is applicable to waters con- Clamp for Buret, Single Each E1029 tamm, g more than 1 mg/L N H4, must be performed Cylinder, Graduated 100 mL E1038 immediately after sampling for results to be meanmg-(Glass) ful. For measurement of hydrazine concentrations be-low 1 mg/L, refer to test No.35-241'. Cylinder, raduated 100 mL E1351 SAMPLING REQUIREMENTS (Plastic)

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Cool the sample upon ecuection to 70*F or lower and fj,8h , P reela,

analyze immediately after collection. Hydrazine tends Graduate, Conical 10 mL E1057 to react with oxygen m the atmosphere and delay of Stirring Rod, glass 6 in. E1089 analysis may result m erroneously low values. Suppon, Rectangular Base Medium E1094 Buret, Geissler 25 mL E1186 INTERFERENCES Buret, Geissler 10 mL E1434 The test is not specific to hydrazine but will measure a S '

variety of oxidizable compounds. Certain organic com- uio pounds, ferrous iron, sulfite and sulfide are positive Standard lodine Solution

• N.A.

mterferences, Flask, Volumetric 10C0 mL N.A.

• see Reagents section tor information en preparation or these ORDERING REAGENTS AND EQUIPMENT solutions.

Reagents, certified by Calgon Corporation, and equip. NA. -Not available PROCEDURE J

Standardization of lodine Solution Add 90 mL of distilled water and 2 mL of Stable Starch Solution to 10 mL of N/40 Thiosulfate Solution in a porcelain dish. Titrate with iodine to the blue starch color. The net volume of iodine required for the titration should be approximately 20 mL. Adjustment of the reagent is not necessary if compensation is made in the calculation. Since this solution is not stable, only an amount sufficient to last a month should be made at one time. Standardize daily.

Sample Analysis I 1.1b a 250 mL Erlenmeyer flask, add about 2 mL of Stable Starch Solution and 5 mL of

< . Sodium Bicarbonate Solution.

(Procedure Continued)

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2. Measure 100 mL of the decanted boiler water sample in a 100 mL graduated cylinder and

, pour into the 250 mL flask.

3. Slowly add Standard Iodine Solution from a buret, while constantly shaking the sample.

Stop the titration when a blue color, which is not removed by further stirring, first appears.

j From the buret read the mL of Iodine Solution used.

4. The blank on this titration is about 0.1 mL. Calculate the hydrazine concentration in the following manner.

20 mg/L Hydrazine (N H.) = (mL titration - 0.1 mL) X 7 where A = actual mL of Iodine Solution required to titrate 10 mL of N/40 Thiosulfate Solution.

Reagents Sodium Bicarbonate Solution - Dissolve 50 grams of reagent grade sodium bicarbonate (NaHCO3) in 950 mL of distilled water.

Standard Iodine Solution - Dissolve 20 grams of reagent grade potassium iodide crystals, in as little water as possible. Weigh on a watch glass 1.6 grams of iodine crystals then add the iodine crystals to the solution. Shake or stir the contents until all of the iodine is dissolved.

Dilute to 1 liter.

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l Detersnination of Hydrazine W

SUSSIDIARY OF IAERCM & CO.,1NC.

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in Boiler Water (Direct Iodine Titration Method)

Test No. 35466-C L A

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