Designation: D5373 − 13
Standard Test Methods for
Determination of Carbon, Hydrogen and Nitrogen in Analysis Samples of Coal and Carbon in Analysis Samples of Coal and Coke 1 This standard is issued under the ﬁxed designation D5373; the number immediately following the designation indicates the year of original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A superscript superscr ipt epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Sco Scope pe
D3180 Pra Practi ctice ce for Cal Calcul culati ating ng Coa Coall and Cok Cokee Ana Analys lyses es from As-Determined to Different Bases D5865 Test D5865 Test Method for Gross Caloriﬁc Value of Coal and Coke D7582 Test Meth Methods ods for Proxi Proximate mate Analysis Analysis of Coal and Coke by Macro Thermogravimetric Analysis 2.2 ISO Standard: ISO 5725-6 Accuracy 5725-6 Accuracy (Trueness and Precision) of Measurementt Met men Method hodss and Results Results Par Partt 6: Use in Pra Practi ctice ce of 3 Accuracy Values
1.1 Test Method Method A cover coverss the determina determination tion of carbon carbon in the range of 54.9 % to 84.7 %, hydrogen in the range of 3.25 % to 5.10 %, and nitrogen in the range of 0.57 % to 1.80 % in the analysis samples (7.1 ( 7.1)) of coal. 1.1.1 Test Method B cover coverss the determinat determination ion of carbo carbon n in analysis samples of coal in the range of 58.0 % to 84.2 %, and carbon in analysis samples of coke in the range of 86.3 % to 95.2 %. NOTE 1—The coals included in the interlaboratory study employed to derive the precision statement for this standard cover ASTM rank lignite A to low vola volatile tile bitu bitumin minous. ous. Additiona Additionall info informa rmation tion conc concern erning ing the composition of these coals appears in Annex in Annex A5. A5. The cokes used in the interlaborator interla boratory y study employ employed ed to derive the precision statement for coke included an equal number of met cokes and pet cokes.
3. Summ Summary ary of Test Test Methods 3.1 In Method A, A, carbon, hydrogen hydrogen and nitrogen nitrogen in coal are determined determin ed concu concurrent rrently ly in a singl singlee inst instrume rumental ntal proc procedure edure using a furnace operating at temperatures in the range of 900 °C to 105 1050°C 0°C.. The qua quanti ntitat tative ive con conver versio sion n of the car carbon bon,, hydrogen and nitrogen into their corresponding gases (CO 2, H2O, and NOx) occurs during combustion of the sample at an elevated temperature in an atmosphere of oxygen. Combustion products which can interfere with the subsequent gas analysis are rem remove oved. d. Oxi Oxides des of nit nitrog rogen en (NOx) ar aree re redu duce ced d to N 2 before detection. The carbon dioxide, water vapor and elemental nitrogen in the gas stream are determined by appropriate instrumental detection procedures.
1.2 Th 1.2 Thee va valu lues es st stat ated ed in SI un unit itss ar aree to be re rega gard rded ed as standard. No other units of measurement are included in this standard. standa ndard rd does not purport purport to add addre ress ss all of the 1.3 This sta safety safe ty co conc ncer erns ns,, if an anyy, as asso soci ciat ated ed wi with th it itss 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. Referenced Documents
3.2 In Method B, carbon in coal and coke is determined determined by combusting the sample in a 1350°C furnace. The H 2O in the combus com bustio tion n gas gases es is rem remove oved d and CO2 is det determ ermine ined d by infrared absorption.
2.1 ASTM Standards:2 D346/D346M Pra Practi ctice ce for Col Collec lectio tion n and Pre Prepar parati ation on of Coke Samples for Laboratory Analysis D2013 Practice for Preparing Coal Samples for Analysis D2013 D3173 Test D3173 Test Method for Moisture in the Analysis Sample of Coal and Coke D3176 Practice D3176 Practice for Ultimate Analysis of Coal and Coke
4. Signi Signiﬁcanc ﬁcancee and Use 4.1 Carbo Carbon n and hydro hydrogen gen values can be used to determine determine the amount of oxygen (air) required in combustion processes and for calculation of the efficiency of combustion processes.
1 These test methods are under the jurisdiction of ASTM Committee D05 Committee D05 on on Coal and Coke and are the direct responsibility responsibility of Subcommittee Subcommittee D05.21 on Methods of Analysis. Currentt edition approved Curren approved Oct. 15, 2013 2013.. Publi Published shed November 2013. Originally approved in 1993. Last previous edition approved in 2008 as D5373 – 08. DOI: 10.1520/D5373-13. 2 For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at [email protected] [email protected]
astm.org. g. For For Annual Annual Book of ASTM volume information, refer to the standard’s Document Summary page on Standards volume Standards the ASTM website website..
4.2 Car Carbon bon and hyd hydrog rogen en det determ ermina inatio tions ns can be use used d in calculations including material balance, reactivity and yields of products relevant to coal conversion processes such as gasiﬁcation and liquefaction. 3 Available from American National Standards Institute (ANSI), 25 W. 43rd St., 4th Floor, New York, NY 10036, http://www.ansi.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5373 − 13 4.3 Car Carbon bon and nit nitrog rogen en val values ues can be use used d in mat materi erial al balance balan ce calc calculat ulations ions empl employed oyed for emis emission sion accou accountin nting g purposes.
sufficiently high purity to permit its use without lessening the accuracy of the determination. 6.2 Carrier speciﬁ ciﬁed ed for the ins instr trume ument nt by the Carrier Gas, as spe manufacturer.
NOTE 2—The bulk composition of coal changes at a rate that varies from coal to coal during storage. As a result using coal for calibration can yield incorrect estimates of carbon, and hydrogen content in particular.
6.3 Oxygen, as speciﬁed for the instrument by the manufacturer.
5. Appar Apparatus atus
6.4 Additional Reagents, of types and qualities as speciﬁed for the instrument by the manufacturer.
Analyti ytical cal Ins Instru trumen mentt for CHN Ana Analys lysis is (Me (Metho thod d 5.1 Anal A)— An An instrument capable of analyzing a test portion of 6 mg or gre greate aterr. It inc includ ludes es a fur furnac nacee cap capabl ablee of mai mainta ntaini ining ng a temperature (900°C to 1050°C) in the range to ensure quantitative recovery of carbon, hydrogen and nitrogen in coal as their corresponding gases (CO 2, H2O, and NOx). The combustion gases or a representative aliquot shall be treated to remove, separate out or convert any components that can interfere with the measurement of carbon dioxide, water vapour or nitrogen. The detection system shall include provisions for evaluating the response in a manner that correlates accurately with the carbon car bon dio dioxid xide, e, wat water er vap vapour our and nit nitrog rogen en pre presen sentt in the treated combustion gases.
6.5 Calibration Materials— Calibrati Calibration on mate material rialss shal shalll be accompanied by a certiﬁcate of analysis stating the purity of the mat materi erial. al. If the cer certiﬁ tiﬁcat catee of ana analys lysis is doe doess not pro provid videe assigned values for carbon, hydrogen or nitrogen use the purity as stated on the certiﬁcate to establish carbon, hydrogen and nitrog nit rogen en fro from m the the theore oretic tical al val values ues.. Sto Store re the these se pur puree sub sub-stance sta ncess in a des desicc iccato atorr und under er con condit dition ionss tha thatt mai mainta ntain in the compounds in a dry state. 6.6 Referenc C ertiﬁed refe referenc rencee mate material rial Referencee Materials— Certiﬁed (CRM) coal(s) prepared by a recognized authority to monitor changes in instrument response that can be affected by constituents not present in the calibration materials ( Note 3) 3) and to verify the acceptability of nitrogen results. Coal(s) traceable to a certiﬁed reference material (CRM) coal(s) can also be used. Follow instructions on the reference material certiﬁcate with respect to storage of the reference material and use of assigned values. Use only those carbon, hydrogen and nitrogen values that have an assigned uncertainty or are traceable to a value with an assigned uncertainty.
Analytic tical al Ins Instru trumen mentat tation ion for Car Carbon bon in Coa Coall and 5.2 Analy An ins instru trumen mentt wit with h a fur furnac nacee Coke Ana Coke Analys lysis is (Me (Metho thod d B)— An capable of maintaining a temperature of at least 1350°C at all times during the analysis. The high temperature helps ensure the quantitative recovery of carbon from cokes. The infrared absorption detection system shall include provisions for evaluating the response in a manner that correlates accurately with the carbon dioxide present in the dry combustion gases. Follow the manuf manufactur acturer’ er’ss recom recommend mendatio ations ns for samp sample le mass (typi (typi-cally 50 mg to 300 mg).
NOTE 3—Coal contains mineral constituents as well as acid gas forming constituents that can affect the performance of chemicals used to ensure the consistent and uniform conversion and recovery of carbon, hydrogen and nitroge nitrogen. n. NOTE 4—The amount of nitrogen in the majority of coal employed for power production purposes is in the range of 0.5 % to 1.8 % . None of the calibrants yields percent nitrogen values within the ranges expected for coal. For this reason reference material (RM) coal is used to check the acceptability accep tability of nitroge nitrogen n results results..
5.3 Balance— A stand-alone balance or a balance integrated with the instrument, with a resolution of at least 0.1 % relative of the test portion mass. 6. Reage Reagents nts 6.1 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 speciﬁcations of the Committee on Analytical Reagents of the American Chemical Society, where such speciﬁcations are available. 4 Other grades may be used, use d, pro provid vided ed it is ﬁrs ﬁrstt asc ascert ertain ained ed tha thatt the reagent reagent is of
7. Pre Preparat paration ion of Anal Analysis ysis Sample 7.1 The sample shall shall be the analysis analysis sample prepared prepared to a top size of less than 250 µm (60 mesh). Coal samples shall be prepared prep ared in acco accordanc rdancee with Prac Practice tice D2013. D2013. Coke samples samples shall be prepared in accordance with Practice D346/D346M D346/D346M.. 8. Instrument Preparation
Reagent Chemicals, American Chemical Society Speciﬁcati Speciﬁcations ons , American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed by the American Chemical Society, Society, see see Analar Standards for Laboratory Chemicals,, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia Chemicals and National Formulary Formulary,, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville, MD.
8.1 Instrument Set-Up— Verify Verify all instrument operating parameters meet the speci rameters speciﬁcati ﬁcations ons in the inst instrume rument nt opera operating ting manual. manu al. Verif erify y the cond condition ition and quant quantitie itiess of all chem chemical icalss currently in use are satisfactory for the number of samples to be analyzed. anal yzed. Prior to any analysis, analysis, check for and, if necessary necessary correct any leaks in the combustion system, and the carrier gas system.
TABLE 1 Calibration Materials and Their Theoretical Contents of Carbon, Hydrogen and Nitrogen (Method A) Name EDTA Phenylalanine Acetanilide BBOT Graphite
Formula C10H16N2O8 C9H11NO2 C8H9NO C26H26N2O2S C
41.1 65.4 71.1 72.5 100.0
5..5 5 6.7 6.7 6.1
9.6 8.5 10.4 6.5
Analyses— ses— Perform 8.2 Blank Analy Perform blank analyses to esta establis blish h carbon, hydrogen and nitrogen levels in the combustion and carrier gases as required by the speciﬁc method. The level of carbon, hydrogen or nitrogen in these gases shall not exceed 1 % relative of the instrument response for the lowest mass of calibration material (8.4 ( 8.4)) for each analyte. Re-determine blank 2
D5373 − 13 analyses analys es whe whenev never er the car carrie rierr gas or oxy oxygen gen sup suppli plies es are changed or any chemicals are renewed.
basis to the nearest 0.1 % for carbon, 0.01 % for hydrogen and to the nearest 0.01 % for nitrogen.
8.3 Conditioning— Select Select a conditioning sample in the range of 75 % (or more) carbon dry basis. It is recommended that the moisture content be less than 3 %. Carry out four determinations on the conditioning sample. Discard the ﬁrst determination. If the range of the three retained determinations for either carbon, hydrogen or nitrogen values exceed 1.2 r where where r is is the repeatability of this standard, instrument stability is suspect. In this case take corrective action before proceeding with calibration.
10.2 Use the following following equations for the calculation calculation to dry basis: 10.2.1 For the carbon content: content: C d 5 C ad 3
N d 5 N ad 3
where: d = ad = C = N = H = M ad =
Ele lem men entt Carbon in Coke Carbon in Coal
0.45 0.10 0.05
1.00 0.25 0.15
Conce Conc ent ntra rattio ion n Range, % 86.3 to 95.4 57.7 to 84.0
Repeatability Limit, r r % % 0.87 0.55
Reproducibility Limit, R R % % 1.68 2.31
11.1.1 Repeatability Limit (r)— The The value below which the absolute difference between two test results calculated to a dry basis (Practices D3180 (Practices D3180 and and D3176 D3176)) of separate and consecutive testt det tes determ ermina inatio tions, ns, car carrie ried d out on the sam samee sam sample ple,, in the same laboratory, by the same operator, using the same apparatus on samples taken at random from a single quantity of homoge hom ogeneo neous us mat materi erial, al, may be exp expect ected ed to occ occur ur wit with h a probability of approximately 95 %. 11.1.2 Reproducibility The value below which Reproducibility Limit (R)— The the absolute difference between two test results calculated to a dry basis (Practices D3180 (Practices D3180 and and D3176 D3176), ), carried out in different labora lab orator tories ies,, usi using ng sam sample pless tak taken en at ran random dom fro from m a sin single gle quantity of material that is as homogeneous as possible, may be expected to occur with a probability of approximately 95 %.
TABLE 2 Concentrations Range and Limits for Repeatability and Reproducibility for Carbon, Hydrogen, and Nitrogen in Coal (Method A)
54.9 to 84.7 3.25 to 5.10 0.57 to 1.80
dry bas basis, is, as determ determined ined (as analy analyzed) zed) basis basis,, conten con tentt of car carbon bon,, % , conten con tentt of nit nitrog rogen, en, % , conten con tentt of of hydr hydroge ogen, n, % , and and moisture mois ture content content of of the sample sample as analyzed, analyzed, % .
TABLE 3 Concentration Range and Limits for Repeatability and Reproducibility for Carbon in Coal and Coke Determined Using 1350°C Combustion (Method B)
10.1 Rec 10.1 Record ord the tot total al carbon carbon,, hyd hydrog rogen en and nit nitrog rogen en as analyzed as a percentage by mass. Report the results on dry
Carbon Hydrogen Nitrogen
11.1 The precision 11.1 precision data for Test Test Method A for the dete determirmination of carbon, hydrogen, and nitrogen in coal are shown in Tabl ablee 2. Th Thee pr prec ecis isio ion n da data ta fo forr Tes estt Me Meth thod od B fo forr th thee determination of carbon in coal and coke are shown in Table 3. 3.
10. Calc Calculati ulation on
100 100 2 M ad
11. Prec Precisio ision n and Bias5
NOTE 5— 5—Appendi Appendix x X2 X2 provides provides guidance on the selection of the mass of a test portion that will yield for a mass of carbon similar to the mid range mass of the calibration material.
Reproducibility Limit, Reproducibility R %
100 2 M ad
H d 5 ~ H ad 2 0.1119 3 M ad ! 3
9.1 Determination: 9.1.1 Carry out a deter determina mination tion of the mois moisture ture content content of each analysis sample or each reference material coal, or both, in accordance with Test Method D3173 Method D3173 or or Test Methods D7582 Methods D7582 within wit hin 48 h of the determin determinati ation on of car carbon bon,, hyd hydrog rogen en and nitrogen on each analysis sample. 9.1.2 9.1 .2 Car Carry ry out the det determ ermina inatio tion n by wei weighi ghing ng out a tes testt portion of each analysis sample within a mass range recommended men ded by the man manufa ufactu cturer rer.. Con Conduc ductt det determ ermina inatio tions ns on consecutive test portions of an analysis sample as needed to meet quality control requirements. 9.1.3 9.1 .3 Veri erify fy the cal calibr ibrati ation on upo upon n com comple pletio tion n of all tes testt determinations and as needed to meet quality control requirements according to Annex A2. A2. 9.1.4 9.1 .4 Pri Prior or to con conduc ducti ting ng any tes testt det determ ermina inatio tions, ns, upo upon n completion of all test determinations and as needed to meet quality control requirements conduct determinations on consecutive test portions of a reference material (RM) coal ( 6.6 6.6). ). Verify the acceptability of results for the RM coal in accordance with Annex A3. A3.
Repeatability Limit, r r % %
10.2.3 For the hydrogen hydrogen content:
9. Proc Procedur eduree
Concentration Range, %
100 2 M ad
10.2.2 For the nitrogen content: content:
8.4 Calibration— If If the instrument has been previously calibrated bra ted in acc accord ordanc ancee wit with h Annex Annex A1 A1,, dete determin rminatio ations ns can proceed provided the calibration is veriﬁed in accordance with Annex A2. A2. Otherwise calibrate the instrument as described in Annex A1. A1. 8.4.1 Calibration for Carbon in Coal and Coke at 1350°C (Method B)— Use Use pure graphite to calibrate instruments operating at 1350°C that are used for determining carbon in coal and coke analysis samples.
NOTE 6—Additional information concerning precision statistics appears in Annex A4 in Annex A4 as well as the composition of the coals employed carbon, hydrogen, and nitrogen in the interlaboratory study (RR:D05–1034) that
5 Supporting Supp orting data have been ﬁled at ASTM International International Headquarters Headquarters and may be obtained obtained by request requesting ing Research Report RR:D05-1034 RR:D05-1034 and RR:D0 RR:D05-104 5-1042. 2.
D5373 − D5373 − 13 TABLE 4 Comparison of Reference EDTA and Reference Phenylalanine Certiﬁcate of Analysis Values with Interlaboratory Values for Carbon, Hydrogen, and Nitrogen Reference Pure Substance EDTA EDTA Phenylalanine Phenylalanine EDTA EDTA Phenylalanine Phenylalanine EDTA EDTA Phenylalanine Phenylalanine
Number of Results
Certiﬁcate of Analysis Val Value ue
Interlaboratory Study Valu Value e
1B 1C 1B 1C 1B 1C 1B 1C 1B 1C 1B 1C
Carbon Carbon Carbon Carbon Hydrogen Hydrogen Hydrogen Hydrogen Nitrogen Ni Nitrogen Ni Nitrogen Nitrogen
34 24 32 22 33 24 32 24 32 21 32 21
41.09 41.09 65.43 65.43 5.52 5.52 6.71 6.71 9.59 9.59 8.48 8.48
41.10 40.99 65.49 65.37 5.52 5.54 6.72 6.71 9.55 9.54 8.46 8.45
Bias 0.01 -0.10 0.06 -0.06 0.00 0.02 0.01 0.00 -0.04 -0.05 -0.02 -0.03
Signiﬁcant (95 % Conﬁdence) no no no no no no no no y es no no no
thesee bi thes bias ases es ar aree sh show own n in Tabl Tablee 5 and and bo both th bi bias ases es ar aree signiﬁcant at the 95 % conﬁdence level. The ruggedness testing was done with a carbon analyzer using ceramic boats in an open combustion tube. No accelerants or combustion aids, such as those used in some analyzers, were used. The carbon values from this study are shown in Annex Annex A6. A6.
appears in Annex in Annex A5. A5. Additional information collected during the determination mina tion of car carbon bon in coa coall and cok cokee at 1350 1350°C °C inte interla rlabor borato atory ry stud study y (RR:D05–1042) (RR:D0 5–1042) appears in Annex Annex Annex Annex A6. A6.
11.2 Bias— Two mate material rials, s, EDT EDTA A and pheny phenylalan lalanine, ine, distributed from a common source were included in the carbon, hydrogen hydro gen and nitr nitrogen ogen interlaborat interlaboratory ory study (Method A) as reference pure substances. Each participating laboratory calibrated bra ted their instrum instrument ent using one or mo more re of the pure sub sub-stances (6.5 (6.5)) obtained from a different source. The reference puree sub pur substa stance ncess wer weree ana analyz lyzed ed in two pha phases ses of the study conducted one year apart. A comparison of the certiﬁcate of analysis values and those obtained in the interlaboratory study for the reference pure substances are shown in Table 4. 4. 11.2.1 11. 2.1 Durin During g the interlaborat interlaboratory ory stud study y for the determinadetermination tio n of car carbon bon in cok cokee (Me (Metho thod d B) the ruggedne ruggedness ss tes testin ting g showed the analyses at 1350°C are biased high when compared to analyses at either 1150°C or 950°C. The average values of
NOTE 7—Guidelines for reporting test sample results that do not meet the rep repeat eatabi ability lity req requir uireme ements nts of this stan standar dard d whe when n all cal calibra ibration tion veriﬁcation and reference material check sample acceptance requirements are met are provided in Appendix in Appendix X3. X3.
12. Calc Calculati ulation on to Othe Otherr Bases 12.1 Report results from from the carbon, hydrogen, and nitrogen nitrogen determinations on any of the several common bases that differ solely with respect to moisture. Procedures for converting the as-determined concentrations to the other bases are speciﬁed in Practices D3176 Practices D3176 and and D3180 D3180..
TABLE 5 Relative Biases for Carbon in Coke Determined for 10 Coke Samples at Different Combustion Temperatures Parameter Carbon in Coke Carbon in Coke
Test Condition 1 Combustion Temperature 1350°C 1350°C
Test Condition 2 Combustion Temperature 1150°C 950°C
NOTE 1—Test Condition 2 is biased lower.
Average Bias % (Absolute) 0.44 0.96
Signiﬁcant (95 % Conﬁdence) y es y es
D5373 − D5373 − 13
ANNEXES (Mandatory Information) A1. NUMBE NUMBER R OF CALIBRATION CALIBRATION POINTS FOR METHODS A AND B
A1.1 To meet the precision precision requirement requirementss of this method method 6 calibration points are required for a linear ﬁt and 8 calibration points are required for a non linear ﬁt. These requirements are summarized for various ﬁts in Table A1.1. A1.1. A calibration point
consists of a determination on a single test portion of calibration material. NOTE A1.1—The interlaborator interlaboratory y study employed to validat validatee the precision of this test method required laboratories to employ 6 calibration points for a linear ﬁt and 8 for a non linear ﬁt. Additiona Additionall calibration points points can be used.
TABLE A1.1 Minimum Number of Calibration Points for Common Regressions Regression
A1.2 Guidance on the selection selection of masses of pure substance substance for calibration is given in Appendix X1. X1.
Number of Calibration Points Required
Linear Quadratic Power
6 8 8
A1.3 Verify the calibration according according to Annex A2. A2.
A2. CALIBRA CALIBRATION TION VERIFICATION VERIFICATION FOR CARBON, HYDROGEN AND NITROGEN (METHOD A)
A2.1 Some instruments instruments allow for calibration calibration drift corre correcction. Verify the acceptability of a drift correction immediately after conducting the drift correction.
veriﬁcation veriﬁcati on deter determina minations tions.. Use mass masses es of veri veriﬁcati ﬁcation on cali cali-brant that yield a mass of carbon within 5 mg of the calibration masses at the lower extreme, mid-point and upper extreme of the calibration (see Appendix (see Appendix X1). X1). If the additional veriﬁcation determin dete rminatio ations ns agre agreee with the valu values es from the cert certiﬁca iﬁcate te of analysis anal ysis within the limi limits ts speci speciﬁed ﬁed in Table A2.2 then it is acceptabl acce ptablee to cont continue inue with determinatio determinations ns on the anal analysis ysis samples. Otherwise reject the calibration as well as all determinat mi nation ionss bac back k to the las lastt acc accept eptabl ablee ver veriﬁc iﬁcati ation. on. Che Check ck instru ins trumen mentt set set-up -up ( 8.1 8.1), ), con conduc ductt bla blank nk ana analys lyses es (8.2 8.2)) and condition the instrument ( 8.3 8.3). ). Calibrate the instrument according to Annex to Annex A1 A1 before proceeding with analysis.
A2.2 Verify the acceptability acceptability of the calibration by determining the carbon, hydrogen and nitrogen in % of a calibration material (6.5 ( 6.5)) not used for calibration. Appendix X1 provides X1 provides guidance on selection of the mass of veriﬁcation material. A2.3 Table A2.1 lists the relative percentages the veriﬁcation determinations shall agree with the values of the carbon, hydrogen and nitrogen from the certiﬁcate of analysis. NOTE A2.1—These limits are from the calibration data supplied by the 14 laboratories that took part in the interlaboratory study (ILS) employed to validate this standard. The calibration data includes results from the pure substances listed in 6.5 in 6.5 and ﬁve instrument conﬁgurations covering two phases of the ILS conducted 1 year apart. These limits can serve as reasonable reason able performance performance criteria for calibra calibrations tions conducted in the same or different laboratories over an extended period of time.
A2.5 Since the absolute difference difference between the veriﬁcation veriﬁcation determination and the certiﬁcate of analysis value are within the abs absolu olute te lim limit it for car carbon bon,, hyd hydrog rogen en and nit nitrog rogen, en, the laboratory can continue with analysis of test samples without recalibrating the instrument.
A2.4 If any veriﬁcation determination determination does does not agree within the limits speciﬁed in Table A2.2, A2.2, condu conduct ct three additional additional
TABLE A2.1 Percent (%) Relative Calibration Acceptance Limits Carbon Hydrogen Nitrogen
1.20 % 2.10 % 1.80 %
D5373 − D5373 − 13 TABLE A2.2 Example of Calibration Veriﬁcation with EDTA Parameter
Certiﬁcate of Analysis %
Absolute Limit %
Veriﬁcation Result Veriﬁcation %
Absolute Difference %
41.08 5.51 9.60
1.20 % 2.10 % 1.80 %
0.49 0.12 0.17
41.27 5.59 9.50
0.19 0.08 0.11
Carbon Hydrogen Nitrogen
A3. ACCEPTA ACCEPTANCE NCE OF RESULTS FOR REFERENCE MATERIAL COAL(S)
A3.1 Cal A3.1 Calcul culate ate the as det determ ermine ined d car carbon bon,, hyd hydrog rogen en and nitrogen results to a dry basis (Section 10 10). ). Verify the dry basis results for consecutive carbon, hydrogen and nitrogen determinations agree within the repeatability limit (Section 11 11). ).
NOTE A3.2—For carbon and hydrogen it is recommended a record is kept of the dry basis results. Each dry basis carbon result should agree with the dry basis certiﬁcate value within 0.7 % . Each dry basis hydrogen result should agree with the dry basis certiﬁcate value within 0.2 % . The certifying agency should be notiﬁed when more than 7 consecutive dry basis results for carbon and/or hydrogen fall outside these limits. The certifying agency should be provided with the purchase date, in service date and expiry date of the reference material coal. The comparison limits for car carbon bon and hyd hydroge rogen n are der derive ived d fro from m the rep reprod roducib ucibilit ility y limi limitt (Section 11 11)) in acc accorda ordance nce with the section section on “Co “Compa mpariso rison n with a reference value for one laboratory” of ISO 5725-6.
A3.2 For nit A3.2 nitrog rogen en ver verify ify eac each h dry bas basis is nit nitrog rogen en res result ult agrees with the assigned value within 0.11 %. NOTE A3.1—The 0.11 % acceptance limit is derived from the reproducibility limit for nitrogen (Section 11 (Section 11)) in accor accordance dance with the section on “Comparison with a reference value for one laboratory” of ISO 5725-6.
A3.3 If any of the A3.3 these se acc accept eptanc ancee cri criter teria ia fai fails, ls, rej reject ect all determinations back to the last acceptable reference material determinations. Check instrument set-up ( 8.1 8.1), ), conduct blank analyses (8.2 (8.2)) and condition the instrument ( 8.3 8.3). ). Calibrate the instrumen instr umentt acco according rding to Annex A1 before before proce proceeding eding with determinations.
A4. PRECISION STATI STATISTICS STICS
A4.1 The precision of this standard’s Method A, characterized by repeatability ( sr , r ) and reproducibility ( s R, R ) has been determined for the materials listed in Tables A4.1-A4.3. A4.1-A4.3.
A4.2 The precision precision of this standard’ standard’ss Meth Method od B, chara character cter-ized by repeatability ( sr , r ) and reproducibility ( s R , R ), has been determined for the materials listed in Tables A4.4 and A4.5. A4.5.
TABLE A4.1 Repeatability (s r , r ) and Reproducibility (S R , R ) for Carbon % Coal Source Australia New Zealand Canada United Kingdom Australia Australia Australia Australia United States
hvAb hvAb Sub hvAb lvb hvAb hvAb Brown Coal hvAb
72.84 84.68 54.86 65.55 79.88 74.31 77.58 67.53 77.22
0.17 0.20 0.14 0.14 0.19 0.13 0.16 0.13 0.15
0.48 0.56 0.39 0.39 0.54 0.37 0.45 0.37 0.42
0.32 0.34 0.40 0.36 0.28 0.30 0.32 0.43 0.27
0.90 0.96 1.13 1.02 0.79 0.85 0.90 1.21 0.76
D5373 − 13 TABLE A4.2 Repeatability (s r , r ) and Reproducibility (S R , R ) for Hydrogen % Coal Source
Australia New Zealand Canada United Kingdom Australia Australia Australia Australia United States
hvAb hvAb Sub hvAb lvb hvAb hvAb Brown Coal hvAb
4.59 5.08 3.26 4.19 4.30 4.47 4.98 4.53 4.94
0.022 0.048 0.032 0.022 0.023 0.022 0.017 0.026 0.017
0.06 0.14 0.09 0.06 0.06 0.06 0.05 0.07 0.05
0.114 0.096 0.107 0.06 0.083 0.07 0.068 0.08 0.067
0.32 0.27 0.30 0.17 0.23 0.20 0.19 0.23 0.19
TABLE A4.3 Repeatability (s r , r ) and Reproducibility (S R , R ) for Nitrogen % Coal Source
Australia New Zealand Canada United Kingdom Australia Australia Australia Australia United States
hvAb hvAb Sub hvAb lvb hvAb hvAb Brown Coal hvAb
s r r
s R R
1.58 1.16 0.70 1.40 1.76 1.67 1.75 0.57 1.46
0.014 0.018 0.011 0.01 0.021 0.013 0.015 0.017 0.012
0.04 0.05 0.03 0.03 0.06 0.04 0.04 0.05 0.03
0.036 0.05 0.045 0.041 0.05 0.047 0.058 0.051 0.052
0.10 0.14 0.13 0.12 0.14 0.13 0.16 0.14 0.15
TABLE A4.4 Repeatability (s r , r ) and Reproducibility (S R , R ) for 1350°C Determination of Carbon in Coke, % Coke Sample Foundry Coke Furnace Coke DOF Coke 2017 3050 4070 5018 7009 NIST 2718a NIST 2776
Coke Type Met Coke Met Coke Met Coke Calcined Pet Coke Green Pet Coke Calcined Pet Coke Green Pet Coke Met Coke Green Pet Coke Met Coke
Average Carbon 89.68 89.62 87.69 95.42 88.37 86.27 86.73 87.74 89.30 89.40
sr 0.34 0.26 0.26 0.34 0.27 0.36 0.21 0.40 0.29 0.32
r 0.61 0.57 0.60 0.46 0.46 0.54 0.61 0.99 0.54 0.46
sR 0.95 0.73 0.74 0.96 0.76 1.02 0.60 1.11 0.81 0.91
R 1.71 1.60 1.68 1.28 1.27 1.51 1.70 2.78 1.51 1.28
TABLE A4.5 Repeatability (s r , r ) and Reproducibility (S R , R ) for 1350°C Determination of Carbon in Coal, % Coal Sample 89–2 89–4 89–6 89–7 89–8 89–9 90–1 91–2 91–5 NIST 2692c
Coal Rank subB hvCb ligA subA hvBb hvAb ligA lvb hvAb lvb
Average Carbon 67.87 67.05 60.37 69.15 69.05 69.37 57.74 84.03 71.45 82.63
sr 0.18 0.24 0.20 0.18 0.16 0.18 0.20 0.16 0.18 0.26
r 1.17 0.72 0.99 0.78 0.74 0.91 0.78 0.53 0.91 0.47
sR 0.52 0.68 0.55 0.51 0.43 0.52 0.57 0.44 0.49 0.72
R 3.29 2.01 2.78 2.17 2.08 2.54 2.18 1.49 2.54 1.31
D5373 − D5373 − 13 A5. COMPO COMPOSITIO SITION N OF COALS
A5.1 The composition composition of the coals employed employed to establish establish the precision of this standard’s Method A are listed in Table A5.1.. Thi A5.1 Thiss tab table le lis lists ts tho those se par parame ameter terss kno known wn to af affec fectt the determination of carbon, hydrogen and nitrogen in coal.
TABLE A5.1 Composition of Interlaboratory Study Coals Country
Australia New Zealand Canada United Kingdom Australia Australia Australia Australia United States
hvAb hvAb Sub hvAb lvb hvAb hvAb Brown Coal hvAb
Moisture % mm
Ash % Dry Basis
Sulfur % Dry Basis
Chlorine µg/g Dry Basis
3.27 0.96 10.24 2.97 1.40 3.20 3.10 10.20 1.61
10.71 1.76 24.23 19.18 9.81 11.05 6.50 1.22 8.51
0.52 1.50 0.25 1.90 0.59 0.56 0.45 0.31 0.92
225 830 37 4877 530 410 210 1220 1479
A6. CARBO CARBON N IN COKE SAMPLES TABLE A6.2 Percentages of Coke Carbon Determined Using Different Furnace Temperatures
A6.1 During the interlaboratory interlaboratory study for the determination determination of carbon in coke (Method B) the ruggedness testing showed there was a positive bias between the carbon determined in cokes using a 1350°C furnace and furnaces operated at lower temperatures. The positive bias between the carbon determined in cok cokes es usi using ng a 135 1350°C 0°C fur furnac nacee and tha thatt det determ ermine ined d wit with h lower temperatures are shown in Table A6.1 and and Table Table A6.2. A6.2.
Coke Co ke Sa Samp mple le 7009 Foundry Coke Furnace Coke DOF Coke 3050 5018 2017 4070 2776 2718a
TABLE A6.1 Percentages of Coke Carbon Determined Using Different Furnace Temperatures Coke Co ke Sa Samp mple le 7009 Foundry Coke Furnace Coke DOF Coke 3050 5018 2017 4070 2776 2718a A
Ave vera rage ge of 3 A Runs at 1350°C 88.17 89.73 90.32 88.30 88.78 87.43 94.71 86.35 89.78 89.83
Average of 3A Runs at 1150°C 87.73 89.44 89.33 87.67 88.26 87.08 94.95 86.30 89.03 89.24 Avera Av erage ge Dif Differ ferenc ence e
Difference 0.44 0.29 0.99 0.63 0.52 0.35 -0.24 0.05 0.75 0.59
0.44 0.4 4
Average of 3 runs performed on the same day.
Ave vera rage ge of 4A Runs at 1350°C 88.36 89.70 89.98 87.74 88.76 87.27 95.06 86.53 89.64 89.74
Average of 4A Runs at 950°C 87.58 88.78 88.49 87.23 88.29 86.47 93.89 85.68 88.34 88.44 Averag Ave rage e Dif Differ ferenc ence e
Average of duplicate runs on two different days.
Difference 0.78 0.92 1.49 0.51 0.47 0.80 1.17 0.85 1.30 1.30 0.96 0.9 6
D5373 − D5373 − 13 APPENDIXES (Nonmandatory Information) X1. PURE SUBSTANCE MASSES FOR CALIBRA CALIBRATION TION AND CALIBRATION VERIFICATION VERIFICATION
X1.1 This appendix appendix describes describes a proc procedure edure that can be used to calculate the range of calibrant masses from the expected range of carbon, % and hydrogen, % in the analysis sample (7.1).
Mc = = (75 × 5.3)/ 5.56 = 71 mg to the nearest mg
X1.8 Pick the smal smallest lest calculated calculated calibratio calibration n mass mass.. In this case it is 60 mg.
NOTE X1.1—Th X1.1—Thee hydr hydrogen ogen,, % det determ ermine ined d on a tes testt por portion tion of the analysis sample includes the hydrogen in the residual moisture of the test portion. NOTE X1.2—The amount of hydrogen in majority of coal employed employed for power production purposes is in the range of 4.5 % to 6.1 % when the hydrogen in the coal moisture is taken into account. This information is provided to assist in the selection of calibration and calibration veriﬁcation materials. NOTE X1.3—The amount of nitrogen in majority of coal employed for power production purposes is in the range of 0.5 % to 1.8 % . None of the calibration materials (6.5 (6.5)) yield percent nitrogen values within the ranges expected for coal.
X1.9 Pick the lar largest gest calculated calculated calibration calibration mass. In this case it is 155 mg. X1.10 Calcu Calculate late the differe difference. nce. In this case it is 95 mg. X1.1 X1 .11 1 Th Thee mi mid d ra rang ngee ca cali libr brat atio ion n ma mass ss of ED EDT TA is (60+155)/2 = 108 mg to the nearest mg. X1.12 The calibra X1.12 calibrant nt ma mass ss interv interval al for a lin linear ear ﬁt usi using ng 6 points is given by 95/5 or 19 mg the nearest mg. X1.13 The calibrant calibrant mass interval interval for a non linear ﬁt using 8 points is given by 95/7 mg or 14 mg to the nearest mg.
X1.2 A lab X1.2 labora orator tory y int intend endss to cal calibr ibrate ate an ins instru trumen mentt to cover carbon in the range of 55 % to 85 % and hydrogen in the range 4.5 % to 5.3 % . The laboratory uses a test portion mass of 75 6 5 mg.
X1.14 Table Table X1.1 X1.1 summarize summarizess the mass masses es EDT EDTA A for the TABLE X1.1 Masses of EDTA in mg for Calibration
X1.3 Calcu Calculate late to the neare nearest st milligram milligram the mass of cali cali-brant required for the lower and upper limits of carbon % as well as the lower and upper limits of hydrogen % using the following equation. Mc 5 ~ Mt 3 Av! / C C AC
Linear Non Linear
79 7 9 74
range of 55 % to 85 % carbon and 4.5 % to 5.3 % hydrogen for a test portion of 75 6 5 mg.
where: test portio portion n in milli milligram grams, s, Mc = mass of test C AC = mid range range mass of the the calibrati calibration on material material,, Mt = as determin determined ed heating heating value value of the analys analysis is sample, sample, and = heat heating ing value value of the the calibrat calibration ion mater material. ial. Av
X1.15 Calcu Calculate late the mass of the material material used for cali calibrabration veriﬁcation that will yield the same mass of carbon as a mass of the material within the range of the calibration using the following equation. Mv 5 ~ Mc 3 C AC ! / C C AV
X1.4 The mass of EDT EDTA A in milligrams milligrams with a cert certiﬁcat iﬁcatee of analysis value of 41.02 % carbon required to produce the same mass of carbon as a 75 mg test portion containing 55 % carbon is given by:
where: of veriﬁcati veriﬁcation on materia materiall in milligr milligrams, ams, Mv = mass of calibrant rant in milli milligram grams, s, Mc = mass of calib for carbon carbon or hydrogen hydrogen from the certiﬁca certiﬁcate te of C AC = value for analysis of the calibrant, % , and C AV = value for for carbon carbon or hydrogen hydrogen from the certiﬁca certiﬁcate te of analysis of the veriﬁcation material, % .
Mc = = (75 × 55)/ 41.02 = 101 mg to the nearest mg
X1.5 The mass of EDTA EDTA with a certiﬁcate of analysis analysis value of 41 41.0 .02 2 % ca carb rbon on re requ quir ired ed to pr prod oduc ucee th thee sa same me ma mass ss of carbon as a 75 mg test portion containing 85 % carbon is given by:
X1.16 The laboratory laboratory uses pheny phenylala lalanine nine as the calibration calibration veriﬁcation material.
Mc = = (75 × 85)/ 41.02 = 155 mg to the nearest mg
X1.17 The ma X1.17 mass ss of ph phen enyl ylal alan anin inee wi with th a ce cert rtiﬁ iﬁca cate te of analysis of 65.38 % carbon that will yield the same mass of carbon as the mid range mass of EDTA is given by:
X1.6 The mass of EDTA EDTA with a certiﬁcate of analysis analysis value of 5.5 5.56 6 % hyd hydrog rogen en req requir uired ed to pro produc ducee the same mas masss of hydrogen as a 75 mg test portion containing 4.5 % hydrogen is given by:
(108 × 41.02)/ 65.38 = 68 mg to the nearest mg
X1.18 X1 .18 The ma mass ss of ph phen enyl ylal alan anin inee wi with th a ce cert rtiﬁ iﬁca cate te of analysis of 65.38 % carbon that will yield the same mass of carbon as the smallest calculated calibration mass of EDTA is given by:
Mc = = (75 × 4.5)/ 5.56 = 60 mg to the nearest mg
X1.7 The mass of EDTA EDTA with a certiﬁcate of analysis analysis value of 5.5 5.56 6 % hyd hydrog rogen en req requir uired ed to pro produc ducee the same mas masss of hydrogen as a 75 mg test portion containing 5.3 % hydrogen is given by:
(60 × 41.02)/ 65.38 = 38 mg to the nearest mg
D5373 − D5373 − 13 X1.19 X1.1 9 Th Thee ma mass ss of ph phen enyl ylal alan anin inee wi with th a ce cert rtiﬁ iﬁca cate te of analysis of 65.38 % carbon that will yield the same mass of carbon as the largest calculated calibration mass of EDTA is given by:
(155 × 41.02)/ 65.38 = 98 mg to the nearest mg
X2. OPTI OPTIMUM MUM TEST SAMP SAMPLE LE MASS FOR THE DETERM DETERMINA INATION TION OF TOTAL TOTAL CARBON
X2.1 This appendix describes describes a procedure that can improve improve the reliability of carbon results. This can be important in cases where whe re car carbon bon res result ultss are emp employ loyed ed for car carbon bon acc accoun ountin ting g purposes.
X2.4 A laboratory laboratory empl employs oys EDT EDTA A to cali calibrat bratee an inst instrurument. X2.5 The test portion portion mass is 75
X2.2 The minimum minimum error of a resu result lt derived derived from a regre regresssion occurs near the mid range of the calibration. The mass of the test portion that produces a mass of carbon similar to the mid range mass of the calibration material can be estimated from fro m the as det determ ermine ined d hea heatin ting g val value ue (HV (HV)) of the analysis analysis sample, determined according to Test Method D5865 D5865 and and the heating value of the calibration material.
X2.7 Two ana X2.7 analys lysis is sam sample pless are to be tes tested ted for car carbon bon,, hydrogen and nitrogen. X2.8 The as determined heating heating value of analysis sample sample A is 23.88 MJ/kg. X2.9 The test portion portion mass mass for analysis analysis sample sample A that would would yield yiel d a ma mass ss of ca carb rbon on si simi mila larr to th thee mi mid d ra rang ngee ma mass ss of calibration material is given by:
M t = 108 × (16.91/23.88) = 76 mg to the nearest mg
where: = mass of test porti portion on in mill milligram igrams, s, Mt range mass of the the calibrati calibration on material material,, M CM = mid range determined ned heatin heating g value value of the analy analysis sis sample sample,, H VS = as determi and H VC = heati heating ng value value of the the calibra calibration tion mater material. ial.
X2.10 The as dete determin rmined ed heating value of analy analysis sis sample B is 34.03 MJ/kg. X2.11 X2. 11 The tes testt por portio tion n mas masss for analysis analysis sample sample B tha thatt would yield a mass of carbon similar to the mid range mass of calibration material is given by:
TABLE X2.1 Heating Value (HV) of Calibrants Calibrant EDTA Phenylalanine Acetanilide BBOT
X2.6 The mid range calibration calibration mass mass is 108 mg.
X2.3 The test portion mass mass equivalent to the mid range range mass of calibration material is given by: Mt 5 M CM 3 ~ H VC / H VS !
M t = 108 × (16.91/34.03) = 54 mg to the nearest mg
16.91 26.96 31.34 29.84
4038 6439 7485 7127
7268 11590 13473 12828
X3. CHECKING TEST RESULTS AND AND DETERMINING THE FINAL QUOTED RESULT RESULT
greater than 1.3 r , where r is is the repeatability limit (Section 11 11)) of this standard, report the median of the four determinations. Indicate the value reported is a median value.
X3.1 The procedures procedures described described in this appendix appendix are taken from the section on “Methods for checking the acceptability of test results and determining the ﬁnal quoted result,” of ISO 5725-6.
X3.3 Checking the Acceptability of Results Obtained Under Reproducibility Reproducibi lity Conditions:
X3.2 Checking the Acceptability of Results Obtained Under Repeatability Conditions:
X3.3.1 The cause for disc discrepan repancy cy between the ﬁnal quot quoted ed results from two different laboratories that exceeds the reproducibility limit (Section 11 11)) of this standard can be resolved by exchanging analysis samples and/or reference materials ( 6.6 6.6)) as well as calibrant(s) (6.5 ( 6.5). ). Where such an exchange is not prac pr acti tica call ea each ch la labo bora rato tory ry sh shou ould ld ob obta tain in te test st re resu sult ltss on a common sample preferably of known composition. Where use of a common material of known composition is not possible agreement should be reached between the two laboratories to refer to a third laboratory.
X3.2.1 For analysis samples samples that do not meet the the repeatability limit (Section 11 11)) of this standard conduct analysis of two additional addit ional consecutiv consecutivee test portions portions on the same day as the initial runs. Calculate the as determined carbon, hydrogen and nitrogen results to a dry basis (Section 10 10). ). Calculate the range of all four carbon, hydrogen and nitrogen values. X3.2.2 If the ran X3.2.2 range ge is les lesss tha than n or equal to 1.3 times times the repeatability limit report the mean of the four determinations. Indicate the value reported is a mean value. If the range is 10
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