Designation: D4458 − 15
Standard Test Method for
Chloride Ions in Brackish Water, Seawater, and Brines1 This standard is issued under the fixed designation D4458; the number immediately following the designation indicates the year of original origin al adoption or, in the case of revis revision, ion, the year of last revision. revision. A number in paren parenthese thesess indicates the year of last reappr reapproval. oval. A superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Sco Scope* pe*
3. Terminology
1.1 Thi Thiss tes testt meth method od2 is applicable to the measurement of chloride in highly mineralized waters such as oil field brines, seawater, and brackish water. The test method is based upon thee ti th titra tratio tion n of ch chlo lori ride de wit with h si silv lver er ni nitr trate ate,, us usin ing g a vi visu sual al indicator.
3.1 Definitions— For For definitions of terms used in this test method, refer to Terminology D1129 D1129..
1.2 Sample Sampless containing containing from 10 to 150 mg of chloride can be analyzed by this test method. These levels are achieved by dilution as described in the test method. 1.3 Th 1.3 Thee va valu lues es sta stated ted in SI un units its are to be re rega gard rded ed as standard. No other units of measurement are included in this standard. 1.4 It is the user’s responsibility responsibility to assure assure the validity of the method for untested types of water. 1.5 This standar standard d doe doess not purport purport to add addre ress ss all of the safet sa fetyy co conc ncer erns ns,, if an anyy, as asso socia ciate ted d wi with th its us use. e. It is th thee responsibility of the user of this standard to establish appro priate safety and health practices and determine the applicability of regulatory limitations prior to use. 2. Referenc Referenced ed Documents Documents 2.1 ASTM Standards:3 D1129 Terminology D1129 Terminology Relating to Water D1193 Specification for Reagent Water D1193 D2777 Practice D2777 Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on Water D3370 Practices for Sampling Water from Closed Conduits D3370 Practices D5810 Guide D5810 Guide for Spiking into Aqueous Samples D5847 Practice for Writing Quality Control Specifications D5847 for Standard Test Methods for Water Analysis
4. Summ Summary ary of Test Test Method 4.1 This test method is based upon upon the Mohr procedure procedure for determining chloride ion with silver nitrate. The chloride reacts with the silver ion before any silver chromate forms, due to the lower solubility solubility of silver chlor chloride. ide. The potas potassium sium chromate indicat ind icator or rea reacts cts with exc excess ess silver ion to for form m a red silver chromate precipitate. The end point is the appearance of the first permanent orange color. 4.2 This test method is suitable for analyzing analyzing solutions solutions with a pH between 6.0 and 8.5. 5. Signi Significanc ficancee and Use 5.1 Ch 5.1 Chlo lori ride de is pr pres esen entt in vi virt rtua ually lly all oi oill fie field ld br brin ines, es, seawaters, and many waste waters. Identification of the origin of the water and selection of its disposal method may be based upon the chloride content. The chloride content is also used to estimate the resisti resistivity vity of forma formation tion waters and to dif differen ferentiate tiate between subsurface formations. 6. Interfere Interferences nces 6.1 Sulfi Sulfide de,, br brom omide ide,, io iodid dide, e, thi thioc ocyan yanate ate,, cya cyanid nide, e, phosphate, sulfite, carbonate, hydroxide, and iron interfere in thiss tes thi testt meth method. od. Sulfide, Sulfide, sul sulfite fite,, and thiosulf thiosulfate ate can be removed with a peroxide treatment, but usually no attempt is made to remove bromide and iodide because they are usually presen pre sentt in ins insign ignific ificant ant qua quantit ntities ies com compar pared ed to chl chlori oride. de. If necessary, the pH can be raised and the hydroxides of several metals, including iron, can be filtered off. Iron, barium, lead, and bismuth precipitate with the chromate indicator.
1
This test method is under the juris jurisdictio diction n of ASTM Committee Committee D19 on Water and is the direct responsibility of D19.05 D19.05 on Inorganic Constituents in Water. Current Curre nt editio edition n appro approved ved Feb. 1, 2015. Publi Published shed March 2015. Origin Originally ally approved in 1985. Last previous edition approved in 2009 as D4458 – 09. DOI: 10.1520/D4458-15. 2 Hillebrand, W. F., Lundell, G. E. F., Bright, H. A., and Hoffman, J. I., Applied Inorganic Analysis, 2nd Ed., 732, John Wiley & Sons, Inc., New York, NY, 1953. 3 For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at
[email protected]. For Annual Book of ASTM Standards volume information, refer to the standard’s Document Summary page on the ASTM website.
7. Appar Apparatus atus 7.1 Laboratory Glassware. 7.2 Buret, 25-mL capacity. 7.3 Hotplate. 7.4 Magnetic Stirrer and TFE-fluorocarbon-Coated Stirring Bars.
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D4458 − 15 TABLE 1 Aliquot Size for Chloride Determination
8. Reag Reagents ents and Materials Materials 8.1 Purity of Reagents— Reagent Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all reagents shall conform to the specification of the Committee on Ana Analyt lytical ical Reag Reagent entss of the Ame Americ rican an Che Chemica micall Soc Society iety,, 4 where such specifi specification cationss are availab available. le. Other grades may be used us ed,, pr prov ovid ided ed it is fir first st as asce certa rtain ined ed th that at th thee re reag agen entt is of sufficiently high purity to permit its use without lessening the accuracy of the determination.
Specific Gravity
Sample Dilution
Equivalent Aliquot, mL
1.000 to 1.010
None—Take 50 mL for analysis None—Take 25 mL for analysis Dilute 25 mL to 100 mL, take 50 mL Dilute 25 mL to 100 mL, take 25 mL Dilute 25 mL to 500 mL, take 25 mL
50
8.2 Purity of Water— Unless Unless otherwise indica indicated, ted, refer reference ence to water shall be understood to mean reagent water conforming to Specification D1193 Specification D1193,, Type I. Other reagent water types may be us used ed pr prov ovid ided ed it is fir first st asc ascer erta tain ined ed th that at th thee wa water ter is of suffficie suf icientl ntly y hig high h pur purity ity to per permit mit its use with without out adv advers ersely ely affecting the precision and bias of the test method. Type III water was specified at the time of round robin testing of this test method.
1.120 to 1.150
8.3 Silver Nitrat Nitratee Soluti Solution, on, Stand Standard ard (equivalent to 5 mg Cl− /mL) — Dissolve Dissolve 23.9582 g of AgNO 3 in approximately 700 mL of water. Add 1 drop concentrated nitric acid (HNO 3) and dilute to 1 L in a volumetric flask. The HNO 3 will eliminate any precipitation of silver hydroxide which would change the concentration. Standardize against sodium chloride (NaCl) by theprotect procedure describedfrom in 8.4. in 8.4 . Store in an amber-brown bottle to the solution light. 8.4 Silver Nitrat Nitratee Soluti Solution, on, Stand Standard ard (equivalent to 2 mg Cl/mL) — For For lower chlor chloride ide concentrations, concentrations, this more dilute standard will give a more accurate titration. Dissolve 9.5834 g of AgNO3 in app approx roximat imately ely 700 mL of wate waterr. Add 1 dro drop p concen con centra trated ted nit nitric ric acid (HN (HNO O3) and dilute to 1 L in a volumetric flask. Standardize against sodium chloride (NaCl) by the procedure described below. Store in an amber-brown bottle to protect the solution from the light. 8.4.1 Dry 2 to 6 g of high purity (minimum (minimum 99.5 %) sodium sodium chloride crystals at 110°C for 2 h and cool in a desiccator to room temperature. 8.4.2 8.4 .2 Weig eigh h 1.6 1.6484 484 g of the NaC NaCll cry crysta stals. ls. Transfe Transferr the crystals into a 1-L volumetric flask, dissolve, dilute, and mix −
well. A quantity of 1 mL of this solution provides 1 mg of Cl . 8.4.3 Pipet 50 mL aliquots aliquots of the NaCl solution to standardstandard− ize the weaker AgNO3 solution (2 mg Cl /mL) and dilute to 100 10 0 mL with wa wate terr. Us Usee 10 100 0 mL of th thee Na NaCl Cl so solu lutio tion n to standardize the more concentrated AgNO3 solution (5 mg of Cl− /mL). 8.4.4 Add 1 mL of 5 % indicator indicator solution (see (see 8.5 8.5), ), 1 g of sodium bicarbonate powder, and titrate to the appearance of a perm pe rman anen entt or oran ange ge co colo lorr pr prec eced edin ing g a re red d pr preci ecipi pitat tate. e. Th Thee analystt must practice this titration to become familiar with this analys color. 8.4.5 Determi Determine ne the indicator blank by substituting substituting 100 mL of reagent grade water for the sample in 10.3 in 10.3 t to o 10.6 10.6.. 4
American an Reagent Chemicals, American Chemical Society Specifications, Americ
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not listed by the American American Chemi Chemical cal Society, Society, see Annual Standa Standards rds for Labor Laboratory atory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.
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1.010 to 1.025 1.025 to 1.050 1.025 to 1.090 1.090 to 1.120
Dilute 25 mL to 1000 mL, take 25 mL
25 12.5 6.25 1.25 0.625
8.4.6 The titre (T ) of the silver nitrate solution is given in the following equation: mg Cl2 used T 5 mL AgNO3 required 2 blank
8.4.7 If the the titre (T ) of the solutions are not exactly 2.0 or 5.0 mg of Cl− per mL AgNO3, it may be desirable to dilute the solutions if they are too concentrated or add more silver nitrate if too weak. In either case, restandardize restandardize the resulti resulting ng solution. 8.5 Potassium Potassium or Sodiu Sodium m Chr Chromate, omate, Indicator Solution— Prepare a 5 % solution (5 g/100 mL) and adjust the pH to 7.0 with HNO3 (1 + 19) or NaHCO3 powder described in in 8.6 8.6 a and nd 8.7.. 8.7 8.6 Sodium Bicarbonate (NaHCO3) — Powder Powder to adjust the sample pH to to 8.3 8.3.. 8.7 Nitri A dd 1 vo volu lume me of Nitricc Aci Acid d So Solut lutio ion n (1 + 19) — Add HNO3 (sp. gr. 1.42) to 19 volumes water. 8.8 Filter Paper Purchase suitable filter paper. paper. The user Paper— — Purchase must first ascertain that the filter paper is of sufficient purity to use without adversely affecting the bias and precision of the test method. 9. Sampl Sampling ing 9.1 Collect the sample sample in accordance accordance with Practices D3370 Practices D3370.. 10. Procedur Proceduree 10.1 Fi 10.1 Filte lterr (8.8 8.8)) th thee sam sampl plee to re remo move ve an any y in inso solu lubl blee or suspended materials. 10.2 Pipet an aliquot of sample into a 150-m 150-mL L Erlenmeyer Erlenmeyer flask.. Di flask Dilu lute te to 10 100 0 mL with wa water ter.. Re Refe ferr to Tabl Tablee 1 for approximate volume. 10.3 Measu Measure re the pH and adjust to near neutral. 10.4 Add 1 g of sodium bicarbonate bicarbonate and stir to dissolve. dissolve. The pH should be between 6.5 and 8.0. 10.5 Add 1 mL of 5 % chrom chromate ate indicator. indicator.
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10.6 Titr 10.6 itrat atee wi with th on onee of th thee sil silve verr ni nitr trate ate so solu lutio tions ns to a permanent orange color preceding the brick red colored precipitate.
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NOTE 1—Endpoint detection may be improved by selecting background and lighting conditions that enhance color contrast between the solution and precipitate. Number: 02238982 2Order Sold to:SERVICES INTER LAB DE MEXICO [700168] -
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D4458 − 15 TABLE 2 Determination of Precision and Bias of Chloride Ions in Synthetic Brines Amount Added, mg/L
994 48 324 143 524
Amount Found, mg/L
So mg/L
ST mg/L
% ± Bias
Statistically Significant (95 % Confidence Level)
995 47 868 142 959
0.0 130 740
0.0 340 1 450
+ 0.10 −0.94 0.39
no yes no
volume of of AgNO3 required to the end point 10.7 Record the volume and calculate the chloride content. 11. Calculation 11.1 11 .1 Calculat Calculatee the chlor chloride ide content as follo follows: ws: mg Cl2 / L 5
~ mL AgNO used 2 B ! 3 T 3 1000 3
mL sample
where: titre re,, mg mg Cl− /mL of AgNO3, and T = tit indicator tor blank, blank, as determine determined d in 8.4.5 in 8.4.5.. B = indica 12. Pre Precisi cision on and Bias5 12.1 Precision— The The overall and single operator precision of this th is te test st me meth thod od va vari ries es wi with th th thee qu quan antit tity y be bein ing g te teste sted d in accordance with Table with Table 2. 2. 12.2 Bias— Recover Recoveries ies of kno known wn amo amount untss of chlo chlorid ridee in synthetic brines are given in Table 2. 2. 12.3 The informatio information n in Table in Table 2 is 2 is derived from round robin testing in which five labora laboratories tories,, includ including ing eight operat operators, ors, participated. Of eight data sets ranked as described in Practice D2777,, none was rejected. One data point out of seventy-two D2777 was rejected. Three synthetic brines were analyzed, on each of three days, at chloride levels representative of the range of the test method. 12.4 These data may not apply to waters of other matrices. matrices. 12.5 12. 5 Pre Precisi cision on and bias of this test met method hod conforms conforms to Practice D2777 D2777 –ing. 77,., Und 77 whic wh ich wassallo wa inwances pla lace ce mad at th the time me collabo coll aborati rative ve test testing Under erh the allowan ces made eeinti 1.4 of of D2777 – 13, these precision and bias data do meet existing requirements for interlaboratory studies of Committee D19 test methods. 13. Qual Quality ity Control Control 13.1 In order to be cer 13.1 certain tain that ana analyt lytical ical values values obt obtain ained ed using usi ng thes thesee tes testt met method hodss are valid and accurate accurate with within in the confidence limits of the test, the following QC procedures must be followed when analyzing chloride. 13.2 Calibration and Calibration Verification: 13.2.1 13.2. 1 Standa Standardize rdize the titrant as directe directed d above. 5
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13.2.2 Verify titrant concen 13.2.2 concentratio tration n after standardization standardization by analyzing a standard at a mid-range concentration. The measured concentration of a mid-range sample should fall within 615 % of the known concentration. 13.2.3 13.2. 3 If standa standardizati rdization on canno cannott be verifi verified, ed, restan restandardi dardize ze the solution. 13.2.4 13.2. 4 It is recommended recommended to analyze a blank and continuing continuing calibration verification (CCV) at a 10 % frequency. The results should fall within the expected precision of the method or 615 % of the known concentration. 13.3 Initial Demonstration of Laboratory Capability: 13.3.1 13.3. 1 If a laboratory laboratory has not performed performed the test before, or if there has been a major change in the measurement system, for example, new analyst, new instrument, and so forth, a precision and bias study must be performed to demonstrate laboratory capability. 13.3 13 .3.2 .2 Analyz Analyzee se seve ven n re repl plic icate atess of a st stan anda dard rd so solu lutio tion n prepared from an Independent Reference Material containing a mid-range concentration of chloride. The matrix and chemistry of the solution should be equivalent to the solution used in the collaborative study. Each replicate must be taken through the complete analytical test method including any sample preservation and pretreatment steps. 13.3.3 13. 3.3 Calculate Calculate the mean and stan standar dard d dev deviati iation on of the seven values and compare to the acceptable ranges of bias in Table 2. 2. This study should be repeated until the recoveries are within the limits given in section Table 2. 2. If a concentration other oth er tha than n the rec recomm ommend ended ed con concen centrat tration ion is use used, d, ref refer er to Practice D5847 Practice D5847 for for information on applying the F test and t test in ev eval alua uatin ting g th thee acc accep epta tabi bilit lity y of th thee mea mean n an and d st stan anda dard rd deviation. 13.4 Laboratory Control Sample (LCS): 13.4.1 13.4. 1 To ensure that the test method is in contr control, ol, prepare and analyze a LCS containing a mid-range concentration of chlo ch lori ride de wi with th ea each ch ba batc tch h (l (lab abor orat ator ory y de defin fined ed or tw twen enty ty sample sam ples). s). The lab labora orator tory y con contro troll sam sample pless for a lar large ge bat batch ch should sho uld cov cover er the ana analyti lytical cal ran range ge whe when n pos possib sible. le. The LCS must be taken through all of the steps of the analytical method includ inc luding ing sam sample ple pre preser servat vation ion and pre pretre treatme atment. nt. The res result ult obtained for the LCS shall fall within 615 % of the known concentration. 13.4.2 13. 4.2 If the res result ult is not within within the these se limi limits, ts, analysis analysis of samples is halted until the problem is corrected, and either all the samples in the batch must be reanalyzed, or the results must be qualified with an indication that they do not fall within the performance criteria of the test method. 13.5 Method Blank: 13.5 13 .5.1 .1 Anal Analyz yzee a re reag agen entt wa wate terr te test st bl blan ank k wi with th ea each ch laboratorylabor atory-defined defined batch. The concen concentratio tration n of chlor chloride ide foun found d in the blank should be less than 0.5 times the lowest calibration standard. If the concentration of chloride is found above this level, analysis of samples is halted until the contamination is eliminated, and a blank shows no contamination at or above this level, or the results must be qualified with an indication that they do not fall within the performance criteria of the test method.
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D4458 − 15 13.6 Matrix Spike (MS): 13.6.1 To che 13.6.1 check ck for inte interfe rferen rences ces in the spe specific cific matr matrix ix being tested, perform a MS on at least one sample from each laboratory-defined batch by spiking an aliquot of the sample with a known concentration of chloride and taking it through the analytical method. 13.6.2 The spike concentration plus plus the background concentratio tra tion n of ch chlo lori ride de mu must st no nott ex exce ceed ed th thee hi high gh ca calib libra ratio tion n standard. The spike must produce a concentration in the spiked sample that is 2 to 5 times the analyte concentration in the unspiked sample, or 10 to 50 times the detection limit of the test method, whichever is greater. 13.6.3 13.6. 3 Calcula Calculate te the percen percentt recovery of the spike (P) using the follow following ing formu formula: la: P 5 100 @ A ~ V 1 V ! 2 BV # / CV CV s
where: A = B = C = Vs = V =
s
analyte conce concentratio ntration n (mg/L) (mg/L) in spiked spiked sample sample,, analyte conce concentratio ntration n (mg/L) (mg/L) in unspik unspiked ed sample, sample, concentratio concen tration n (mg/L) (mg/L) of of analyte analyte in spikin spiking g solution, solution, volume vol ume (mL (mL)) of sam sample ple used used,, and and volumee (mL) volum (mL) of spikin spiking g soluti solution on added added..
13.6.4 13.6. 4 The percent percent recovery of the spike shall fall within the limi limits, ts, , bas based ed on thetheana analyte lyte concentra concen tration tion, listed list ed in Gui Guide de D5810, D5810 Table 1. If percent recovery is , not within these limits, limi ts, a matr matrix ix inte interfe rferen rence ce may be pre presen sentt in the sample selected sele cted for spi spikin king. g. Und Under er thes thesee cir circum cumstan stances, ces, one of the following follow ing remedies must be emplo employed: yed: the matrix interference interference must be removed, all samples in the batch must be analyzed by a test method not affected by the matrix interference, or the
results must be qualified with an indication that they do not fall within the performance criteria of the test method. NOTE 2—Accepta 2—Acceptable ble spike recoveries recoveries are depen dependent dent on the concentration of the componen tion componentt of int intere erest. st. See Gui Guide de D5810 for additi additional onal information.
13.7 Duplicate: 13.7.1 13.7. 1 To check the precis precision ion of sample analyses, analyze analyze a sample in duplicate with each laboratory-defined batch. If the concentration of the analyte is less than five times the detection limit for the analyt analyte, e, a matrix spike duplicate duplicate (MSD) should be used. 13.7.2 13. 7.2 Calculate Calculate the sta standa ndard rd dev deviati iation on of the dup duplica licate te values and compare to the precision in the collaborative study using an F test. Refer to 6.4.4 of Practice D5847 Practice D5847 for for information on applying the F test. 13.7.3 13. 7.3 If the result result exceeds exceeds the precisio precision n limit, the batch batch must be reanalyzed or the results must be qualified with an indication that they do not fall within the performance criteria of the test method. 13.8 Independent Reference Material (IRM): 13.8.1 13.8. 1 In order to verify the quant quantitative itative value produced produced by the test method, analyze an Independent Reference Material (IRM (I RM)) su subm bmitt itted ed as a re regu gular lar sa samp mple le (i (iff pr pract actica ical) l) to th thee laboratory at least once per quarter. The concentration of the IRM should be in the concentration mid-range for the method chosen. The value obtained must fall within the control limits established by the laboratory. 14. Keyw Keywords ords
14.1 brack brackish ish water; brines; chloride ion; seawat seawater; er; silver nitrate
SUMMARY OF CHANGES Committ Comm ittee ee D1 D19 9 ha hass id iden enti tified fied th thee lo loca catio tion n of sel select ected ed ch chan ange gess to th this is st stan anda dard rd sin since ce th thee las lastt is issu suee (D4458 – 09) that may impact the use of this standard. (Approved Feb. 1, 2015.) (1) Added Added 8.8 8.8.. 11.1.. (2) Revised the equation in 11.1
(3) Revised Section Section 13 13..
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