1、Designation: D 5827 09Standard Test Method forAnalysis of Engine Coolant for Chloride and Other Anionsby Ion Chromatography1This standard is issued under the fixed designation D 5827; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision,
2、 the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope*1.1 This test method covers the chemical analysis of enginecoolant for chloride ion by high-performance ion
3、chromatog-raphy (HPIC). Several other common anions found in enginecoolant can be determined in one chromatographic analysis bythis test method.1.2 This test method is applicable to both new and usedengine coolant.1.3 Coelution of other ions may cause interferences for anyof the listed anions. In th
4、e case of unfamiliar formulations,identification verification should be performed by either orboth fortification and dilution of the sample matrix with theanions of interest.1.4 Analysis can be performed directly by this test methodwithout pretreatment, other than dilution, as required by thelinear
5、ranges of the equipment. Table 1 indicates severalapplicable anions and approximate detection limits.1.5 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.6 This standard does not purport to address all of thesafety concerns, if
6、 any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to its use.2. Referenced Documents2.1 ASTM Standards:2D 1193 Specification for Reagent WaterD 117
7、6 Practice for Sampling and Preparing Aqueous So-lutions of Engine Coolants or Antirusts for Testing Pur-posesE 691 Practice for Conducting an Interlaboratory Study toDetermine the Precision of a Test MethodE 177 Practice for Use of the Terms Precision and Bias inASTM Test Methods3. Summary of Test
8、Method3.1 A small volume of working sample is prepared bydilution of the sample with the method eluant. This dilutedsample is filtered and pumped through two ion exchangecolumns and a suppressor and into a conductivity detector. Ionsare separated based on their affinity for exchange sites of theresi
9、n with respect to the resins affinity for the eluant. Thesuppressor increases the sensitivity of the method by bothincreasing the conductivity of the analytes and decreasing theconductivity of the eluant. The suppressor converts the eluantand the analytes to the corresponding hydrogen form acids.Ani
10、ons are quantitated by integration of their response com-pared with an external calibration curve and are reported asmilligrams per litre (mg/L).4. Significance and Use4.1 This test method provides for the qualitative and quan-titative determination of common anions in engine coolant inthe milligram
11、s per litre to low percent range and requires onlya few millilitres or microlitres of sample per test, with resultsavailable in less than 30 min.Acceptable levels of chloride andother anions vary with manufacturers blending specificationsand applicable ASTM minimum or maximum specifications.5. Inter
12、ferences5.1 Interferences can be caused by substances with similarretention times, especially if they are in high concentrationcompared to those of the analyte of interest. Sample dilutionwill be used to minimize or solve most interference problems.1This test method is under the jurisdiction of ASTM
13、 Committee D15 on EngineCoolants and is the direct responsibility of Subcommittee D15.04 on ChemicalProperties.Current edition approved March 1, 2009. Published April 2009. Originallyapproved in 1995. Last previous edition approved in 2002 as D 5827-95(02).2For referenced ASTM standards, visit the A
14、STM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.TABLE 1 Analytes and Minimum Detection LimitsAnalyte Detection Limit, mg/LAChloride (Cl)2.0Nitrite (NO2)
15、5Bromide (Br) 4.0Nitrate (NO3)71o-Phosphate (HPO4)220.0Sulfate (SO4)28.0Oxalate (C2O4)212.0ADetermined using 100-L sample volume. Sample diluted 99 + 1 (v/v) withchromatographic eluant 30-S/cm full scale, suppressed conductivity detection.Dionex AS4ASC column with AG4ASC guard columns. Other systems
16、 will requireMDL determinations using chosen dilution factors, eluants, columns, and detector.1*A Summary of Changes section appears at the end of this standard.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.5.2 A water dip (solvent
17、system peak) can cause interfer-ence with some integrators. This is eliminated by dilution withthe eluant if the sample dilution factor is 49 + 1 (v/v) or greater.Below this dilution, it is best to add a spike of eluantconcentrate to the sample such that the sample is not dilutedsignificantly and th
18、e resulting test solution matches the eluantused in the system. One method is the addition of 100 L of100X eluant concentrate to 10.0 mL of sample or standard.5.3 Method interferences can be caused by the contamina-tion of glassware, eluant, reagents, etc. Great care must betaken to ensure that cont
19、amination, especially by chloride, iskept at the lowest possible levels.5.4 Pre-rinsing of the sample preparation containers withdeionized water is mandatory.5.5 The use of latex gloves is highly recommended toprevent contamination.6. Apparatus6.1 Analytical Balance, capable of weighing accurately t
20、o0.0001 g.6.2 Ion ChromatographAnalytical system with all re-quired accessories including syringes, columns, suppressor,gasses, and detector. Column life and performance are en-hanced by the use of a two-eluant channel gradient pump, ifavailable.6.3 Guard Column, for protection of the analytical col
21、umnfrom strongly retained constituents. Better separations areobtained with additional plates.6.4 Anion Separator Column, capable of producing analyteseparation equivalent to or better than that shown in Fig. 1.6.5 Anion Suppressor DeviceMicro membrane suppressoror equivalent. A cation exchange colu
22、mn in the hydrogen formhas been used successfully, but it will periodically need to beregenerated as required, being indicated by a high backgroundconductivity and low analyte response.6.6 Conductivity Detector, low volume (2 L) and flow,temperature compensated, capable of at least 0 to 1000 S/cmon
23、a linear scale.6.7 Integrator or Chromatography Data System Software,capable of obtaining approximately the same detection limitsas are listed in Table 1.6.8 Drying Oven, controlled at 105, 150, and 600 6 5C.6.9 Desiccator.7. Reagents7.1 Purity of ReagentsReagent grade or higher puritychemicals shal
24、l be used for the preparation of all samples,standards, eluants, and regenerator solutions. Unless otherwiseindicated, it is intended that all reagents conform to thespecifications of the Committee on Analytical Reagents of theAmerican Chemical Society, where such specification areavailable.3Other g
25、rades may be used, provided it is firstascertained that the reagent is of sufficiently high purity topermit its use without lessening the accuracy of the determi-nation.7.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water as definedby Type II of
26、 Specification D 1193. It is recommended that allwater be filtered through a 0.2-m filter. For eluant preparation,degas the water by sparging with helium or vacuum degassingand sonication.7.3 Eluant Buffer Stock SolutionSodium bicarbonate(NaHCO3) 1.5 mM and sodium carbonate (Na2CO3) 1.2 mM.Dissolve
27、2.5203 6 0.0005 g of NaHCO3and 2.5438 6 0.0005gofNa2CO3in reagent water in a 1000-mLTypeAvolumetricflask and dilute to 1 L. Dilute 100.0 mL of this stock solutionto 2000 mL in a 2-L Type A volumetric flask with degassedreagent water. The pH of the stock solution is 10.1 to 10.3(based on pKacalculati
28、on). The eluant solution used may bedifferent if other system or analytical columns are used.7.4 Stock Bromide SolutionDry approximately2gofsodium bromide (NaBr) for6hat150C and cool in adesiccator. Weigh and dissolve 1.2877 g of the dried salt inreagent water and dilute to 1 L (1.00 mL = 1.00 mg br
29、omide).7.5 Stock Chloride SolutionDry approximately2gofsodium chloride (NaCl) for1hat600C and cool in adesiccator. Weigh and dissolve 1.6485 g and dilute to 1 L withreagent water (1.00 mL = 1.00 mg Cl).7.6 Stock Formate SolutionDry approximately2gofsodium formate (NaHCO2) at 105C for 6 h and cool in
30、 adesiccator. Weigh and dissolve 1.4775 g of the salt in reagentwater and dilute to 1 L (1.00 mL = 1.00 mg formic acid).7.7 Stock Glycolic Acid SolutionWeigh and dissolve1.0000 g of the solid acid in reagent water and dilute to 1 L(1.00 mL = 1.00 mg glycolate).3Reagent Chemicals, American Chemical S
31、ociety Specifications , AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmac
32、opeial Convention, Inc. (USPC), Rockville,MD.FIG. 1 Sample RunChloride Peak at 1.7 minD58270927.8 Stock Nitrate SolutionDry approximately2gofso-dium nitrate (NaNO3) for 24 h at 105C and cool in adesiccator. Weigh and dissolve 1.3707 g and dilute to 1 L withreagent water (1.00 mL = 1.00 mg NO3).7.9 S
33、tock Nitrite SolutionDry approximately 2 g of so-dium nitrite (NaNO2) for 24 h in a desiccator containingconcentrated sulfuric acid (relative density of 1.84). Weigh anddissolve 1.4998 g and dilute to 1 L with reagent water (1.00mL = 1.00 mg NO2). Refrigerate and prepare weekly becausenitrite is oxi
34、dized easily.7.10 Stock Oxalic Acid SolutionWeigh and dissolve1.4002 g of oxalic acid dihydrate (C2H2O42H2O) in reagentwater and dilute to 1 L (1.00 mL = 1.00 mg oxalic acid).7.11 Stock Phosphate SolutionWeigh and dissolve 1.4330g of potassium dihydrogen phosphate (KH2PO4) and dilute to1 L with reag
35、ent water (1.00 mL = 1.00 mg PO43).7.12 Stock Sulfate SolutionDry approximately2gofanhydrous sodium sulfate (Na2SO4)for1hat105C and coolin a desiccator. Weigh and dissolve 1.4790 g and dilute to 1 Lwith reagent water (1.00 mL = 1.00 mg SO42).7.13 Suppressor Solution for Membrane Suppressor0.025N H2S
36、O4. Carefully add 13.7 mL of reagent sulfuric acid(relative density of 1.84) to approximately 500 mL reagentwater in a 1-Lvolumetric flask. Dilute to 1000 mLwith reagentwater. Dilute 100 mL of this concentrate to 2000 mL withreagent water for the final working suppressor solution.7.14 StabilityStand
37、ard stock solutions are stable for atleast one month when stored at 4C. Fresh nitrite and phos-phate standards must be prepared weekly.8. Sampling8.1 Collect the sample in a scrupulously clean glass orpolyethylene bottle in accordance with Test Method D 1176.Collect at least 100 mL of sample.9. Cali
38、bration and Standardization9.1 Analyze each standard solution separately to determinethe analytes retention time.9.2 Set the chromatograph up in accordance with the con-ditions specified in Table 2 and Fig. 2. The use of otherequipment, eluants, or flows requires calculation of suitabledilution fact
39、ors and instrument settings that permit the analystto obtain the resolution and detection limits given in Fig. 1 andTable 1, respectively.9.3 Prepare concentrations of chloride at 0.08, 0.4, 0.8, and4.0 mg/L from the stock solution. All final solutions should bemade with eluant as described in 5.2.
40、Calibrate the ionchromatograph with at least five levels of the analyte, startingnear but above the minimum detection limit (MDL) and furtherdefining the working range in samples subsequent to dilution.These chloride analyte examples reflect a dilution of 99 + 1(v/v) with eluant. If it is desirable
41、to calibrate for another anionspecies, these may be combined in the preceding five calibra-tion standards once the retention times have been establishedindividually. Concentrations of these other anions in thecalibration solutions must bracket the expected range for thesespecies and include a level
42、near the MDL for each species.NOTE 1Ion chromatography equipment other than that described inthis test method may require that standards be prepared at higher or lowerlevels.9.4 Analyze a blank containing only the eluant as describedin Section 10.9.5 A mid-range standard must be used to verify there
43、solution of anions, regardless of a desire to quantitate all ofthem.9.6 Analytical curves must be established at only onedetector scale setting in order to prevent a change of slopeaffecting the analytical curve.9.7 The analytical calibration curve and an eluant blankshall be verified daily prior to
44、 the analysis of samples to verifythe system resolution, calibration, and sensitivity.9.8 The analytical calibration curve, analyte retention timesand resolution, and an eluant blank shall be verified subsequentto a change of the system eluant.9.9 Conditions:Column: ion chromatography Flow: 2 mL/min
45、Detector: see 6.6 Suppressor flow: 2 mL/minEluant: see 7.3 Sample loop: 50 LNOTE 2If a gradient pump is available, refer to Fig. 2 for an exampleof a step gradient that has proven successful for cleaning the column ofstrongly retained species such as polyphosphates and molybdate, whichwould otherwis
46、e elute in subsequent runs.NOTE 3The sample loop volume will vary based on the columncapacity, sensitivity, and other factors. Refer to ion chromatographyequipment manuals and column information for machine-specific details.10. Procedure10.1 Set the ion chromatograph up in accordance with themanufac
47、turers instructions.10.2 Equilibrate the system by pumping eluant for 15 to 30min, until a stable baseline is obtained. Sample preparation isusually performed by 99 + 1 (v/v) dilution with eluant.10.3 Flush the injection loop with 2 to 3 mLof sample usinga 10-mL disposable plastic syringe fitted wit
48、h a 0.2-m syringefilter.410.4 Start the chromatographic run in accordance with themanufacturers instructions.10.5 At least one duplicate and one fortified coolant samplemust be analyzed with each batch of ten or fewer samples.Results must be recorded in the laboratory manual. Thefortified sample is
49、to be prepared by addition of a mixedanalyte mid-range standard.Addition of 100 L of fortification4Nalgene Catalogue No. 190-202, or equivalent.TABLE 2 Chromatographic ConditionsAnalyte Peak No. Retention Time, minChloride 2A1.7Nitrite 3 2.1Bromide 4 3.3Nitrate 5 3.7Phosphate 6 7.7Sulfate 7 10.5Oxalate 8 13.3AFluoride, acetate, formate, and glycolate will all elute before chloride, and poorresolution of these species often precludes the quantitation of any, or all four, ofthem.D5827093standard solution to 10 mL of prepared sample in
